JP6744877B2 - Solid electrolyte composition, solid electrolyte-containing sheet and all-solid secondary battery, and method for manufacturing solid electrolyte-containing sheet and all-solid secondary battery - Google Patents

Description

The present invention relates to a solid electrolyte composition, a solid electrolyte-containing sheet and an all-solid secondary battery, and a method for manufacturing a solid electrolyte-containing sheet and an all-solid secondary battery.

A lithium ion secondary battery is a storage battery that has a negative electrode, a positive electrode, and an electrolyte sandwiched between the negative electrode and the positive electrode, and is capable of charging and discharging by moving lithium ions back and forth between both electrodes. Organic electrolytes have been conventionally used as electrolytes in lithium-ion secondary batteries. However, the organic electrolyte is liable to leak, and there is a risk of short circuit inside the battery due to overcharging and overdischarging, which may cause ignition, and further improvement in reliability and safety is required.
Under these circumstances, an all-solid secondary battery using an inorganic solid electrolyte in place of the organic electrolytic solution has been receiving attention. The all-solid secondary battery consists of a solid negative electrode, electrolyte, and positive electrode, which can greatly improve the safety and reliability, which are the challenges of batteries using organic electrolytes, and also enable longer life. Will be. Furthermore, the all-solid-state secondary battery may have a structure in which electrodes and electrolytes are directly arranged and arranged in series. Therefore, higher energy density can be achieved as compared with a secondary battery using an organic electrolytic solution, and it is expected to be applied to an electric vehicle, a large storage battery, and the like.

Due to each of the above advantages, the development of an all-solid-state secondary battery as a next-generation lithium-ion battery is being advanced (Non-Patent Document 1). In these all solid state secondary batteries, any one of the negative electrode active material layer, the solid electrolyte layer, and the positive electrode active material layer is used as an inorganic solid electrolyte and/or active material and binder particles such as a specific polymer compound. It has been proposed to form a material containing (binder). For example, in Patent Document 1, 99% or more of carbon-carbon double bonds are hydrogenated, and a solid electrolyte composition containing a crystalline norbornene ring-opening polymer hydride having a specific melting point as a binder, and An all solid state secondary battery is described. In addition, Patent Document 2 contains a solid electrolyte material obtained by applying a composition containing a monomer or oligomer having a double bond and a radical polymerization initiator as a binder composition, radically polymerizing the composition, and curing the composition. Sheets and solid state batteries are described.

JP, 2011-233422, A International Publication No. 2010/898918

NEDO Technology Development Organization, Fuel Cell/Hydrogen Technology Development Department, Energy Storage Technology Development Office "NEDO Next-generation Storage Battery Technology Development Roadmap 2013" (August 2013)

In recent years, the development of all-solid-state secondary batteries has progressed rapidly, and the performance required for all-solid-state secondary batteries has also increased. In particular, in an all-solid secondary battery in which the electrode active material layer and the solid electrolyte layer are formed of solid particles, it is desired to enhance the binding property between the solid particles in order to improve the cycle characteristics of the battery.

An object of the present invention is to provide a solid electrolyte composition capable of improving binding properties between solid particles and improving cycle characteristics in an all solid state secondary battery. Another object of the present invention is to provide a solid electrolyte-containing sheet and an all solid state secondary battery using the above solid electrolyte composition. Further, it is an object of the present invention to provide a method for manufacturing each of the solid electrolyte-containing sheet and the all solid state secondary battery.

As a result of intensive investigations by the present inventors, by using a solid electrolyte composition containing a specific compound capable of undergoing a metathesis reaction and gelation and a metathesis catalyst, it has a high binding property between solid particles and high cycle characteristics. It was found that an all-solid-state secondary battery having The present invention has been completed through further studies based on these findings.

That is, the above problem was solved by the following means.
(1) An inorganic solid electrolyte having ion conductivity of a metal belonging to Group 1 or Group 2 of the periodic table, a compound having a non-aromatic carbon-carbon unsaturated bond, and a metathesis catalyst . A solid electrolyte composition for an all-solid secondary battery .
(2) The solid electrolyte composition according to (1), wherein the non-aromatic carbon-carbon unsaturated bond is a terminal vinyl group or a terminal ethynyl group.
(3) The solid electrolyte composition according to (1) or (2), wherein the compound having a non-aromatic carbon-carbon unsaturated bond has at least one functional group selected from the following functional group group.
<Functional group>
Hydroxy group, mercapto group, carboxy group, sulfonic acid group, phosphoric acid group, amino group, cyano group, isocyanate group, acid anhydride group, epoxy group, oxetanyl group, alkoxy group, carbonyl group, 3 or more ring structure group having group, a group having an amide bond, a group having a urea bond, a group having a urethane bond, a group having an imide bond, isocyanurate bond with.
(4) The compound having a non-aromatic carbon-carbon unsaturated bond is any one of (1) to (3) having two or more non-aromatic carbon-carbon unsaturated bonds in one molecule. The solid electrolyte composition described.
(5) The compound having a non-aromatic carbon-carbon unsaturated bond has a structure of any one of a star type, a hyperbranched type and a dendrimer type, and is described in any one of (1) to (4). Solid electrolyte composition.
(6) The solid electrolyte composition according to (1), wherein the compound having a non-aromatic carbon-carbon unsaturated bond is represented by the following general formula (1a) or (2a).

In the above formula, R ^{11 to} R ¹³ , R ¹⁴ , R ^{21 to} R ²³ and R ²⁴ represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group or an aryl group, and R ³¹ and R ³⁴ represent a hydrogen atom or an alkyl group. Represents an alkenyl group, an alkynyl group or an aryl group. L ¹¹ , L ²¹ and L ³¹ represent a single bond or a divalent linking group. n and m are integers of 1 to 20, and l is an integer of 0 to 20. X represents an organic group having a valence of n+m+1.
(7) The solid electrolyte composition according to (6), wherein R ³¹ and R ³⁴ have at least one functional group of the following functional group group.
<Functional group>
Hydroxy group, mercapto group, carboxy group, sulfonic acid group, phosphoric acid group, amino group, cyano group, isocyanate group, acid anhydride group, epoxy group, oxetanyl group, alkoxy group, carbonyl group, 3 or more ring structure group having group, a group having an amide bond, a group having a urea bond, a group having a urethane bond, a group having an imide bond, isocyanurate bond with.
(8) The solid electrolyte composition according to any one of (1) to (7), wherein the compound having a non-aromatic carbon-carbon unsaturated bond has a mass average molecular weight of less than 10,000.
(9) The solid electrolyte composition according to any one of (1) to (8), wherein the metathesis catalyst is a ruthenium catalyst.
(10) The solid electrolyte composition according to any one of (1) to (9), wherein the metathesis catalyst is a catalyst in which an oxygen atom and/or a nitrogen atom is bound to and/or coordinated with a ruthenium atom.
(11) The solid electrolyte composition according to any one of (1) to (10), in which the content of the metathesis catalyst in the total solid content of the solid electrolyte composition is 0.001% by mass to 1% by mass. ..
(12) The solid electrolyte composition according to any one of (1) to (11), which contains an active material.
(13) The solid electrolyte composition according to any one of (1) to (12), wherein the inorganic solid electrolyte is a sulfide-based inorganic solid electrolyte.
(14) The solid electrolyte composition according to any one of (1) to (13), which contains a dispersion medium.
(15) A step (1a) of applying the solid electrolyte composition according to any one of (1) to (14) above to a substrate to obtain a coated sheet,
A solid electrolyte for an all-solid secondary battery, including a step (2a) of heating the coated sheet to 50° C. or higher to crosslink and cure it by a metathesis reaction of a compound having a non-aromatic carbon-carbon unsaturated bond. Sheet manufacturing method.
(16) Conditions for starting the metathesis reaction of the compound having a non-aromatic carbon-carbon unsaturated bond by heating the solid electrolyte composition according to any one of (1) to (14) above 50°C. The step (1b) below,
A method for producing a solid electrolyte-containing sheet for an all-solid secondary battery, which comprises a step (2b) of applying the composition obtained in the step (1b) onto a base material and crosslinking-curing the composition.
(17) An inorganic solid electrolyte having ion conductivity of a metal belonging to Group 1 or 2 of the periodic table and a non-aromatic carbon-carbon unsaturated bond represented by the following general formula (3). A solid electrolyte-containing sheet for an all-solid secondary battery , comprising a compound having the structural unit having and a metathesis catalyst residue having Ru, Mo and/or W metal elements of 10 ppm or more.

In the above formula, Z ¹ represents the following general formula (3-1), and Z ² represents the following general formula (3-2). R ³ represents a hydrogen atom, an alkyl group or an aryl group. L ³ represents a single bond or a divalent linking group. n and m are integers of 1 to 20, and l is an integer of 0 to 20. X represents an organic group having a valence of n+m+1.

In the above formula, R ¹ and R ² represent a hydrogen atom, an alkyl group, an alkenyl group or an aryl group. L ¹ and L ² represent a single bond or a divalent linking group. * Indicates a binding site with X.
(18) The unsaturated bond ratio calculated by the following formula (5) of the compound having a structural unit having a non-aromatic carbon-carbon unsaturated bond represented by the general formula (3) is The solid electrolyte-containing sheet according to (17), which satisfies 1%<unsaturated bond rate<90%.
Unsaturated bond ratio=(sum of the number of non-aromatic carbon-carbon unsaturated bonds in the compound)/
(Sum of the number of all carbon-carbon bonds in the compound)×100 Formula (5)
( 19 ) The solid electrolyte-containing sheet according to (17) or (18) , which contains an active material.
( 20 ) An all-solid secondary battery comprising a positive electrode active material layer, a solid electrolyte layer, and a negative electrode active material layer in this order,
An all-solid secondary battery in which at least one layer of a positive electrode active material layer, a negative electrode active material layer, and a solid electrolyte layer comprises the solid electrolyte-containing sheet according to any one of (17) to (19) .
( 21 ) A method for producing an all-solid secondary battery, which comprises producing an all-solid secondary battery through the method for producing a solid electrolyte-containing sheet according to (15) or (16).

In the present specification, the numerical range represented by "to" means a range including the numerical values before and after "to" as the lower limit value and the upper limit value.
In the present specification, when simply described as “acrylic” or “(meth)acrylic”, it means methacrylic and/or acrylic.
In the present specification, when there are a plurality of substituents and linking groups and the like (hereinafter, referred to as substituents and the like) represented by specific symbols, or when a plurality of substituents and the like are defined simultaneously or alternatively, It means that the substituents and the like may be the same or different from each other. The same applies to the definition of the number of substituents and the like.

In the present specification, the weight average molecular weight can be measured by GPC as a polystyrene-equivalent molecular weight unless otherwise specified. At this time, GPC device HLC-8220 (manufactured by Tosoh Corporation) is used, G3000HXL+G2000HXL is used as a column, and the flow rate is 1 mL/min at 23° C. and detection is performed by RI. The eluent can be selected from THF (tetrahydrofuran), chloroform, NMP (N-methyl-2-pyrrolidone), and m-cresol/chloroform (manufactured by Shonan Wako Pure Chemical Industries, Ltd.), and it dissolves. If so, use THF.

The solid electrolyte composition of the present invention, when used as a material for a solid electrolyte layer and/or an active material layer of an all-solid secondary battery, enhances the binding property between solid particles, and is a solid resulting from repeated charging and discharging. It has an excellent effect of suppressing an increase in interfacial resistance between particles and improving cycle characteristics. In addition, the solid electrolyte-containing sheet and the all-solid secondary battery of the present invention utilize the solid electrolyte composition having the above-mentioned excellent effects and exhibit excellent performance.
Moreover, according to the manufacturing method of the present invention, the solid electrolyte-containing sheet and the all-solid secondary battery of the present invention can be preferably manufactured.
The above and other features and advantages of the present invention will become more apparent from the following description with reference to the accompanying drawings as appropriate.

FIG. 1 is a vertical cross-sectional view schematically showing an all solid state secondary battery according to a preferred embodiment of the present invention. FIG. 2 is a vertical cross-sectional view schematically showing the all-solid-state secondary battery (coin battery) produced in the example.

[Solid electrolyte composition]
The solid electrolyte composition of the present invention comprises an inorganic solid electrolyte (A) having ion conductivity of a metal belonging to Group 1 or 2 of the periodic table, and a compound having a non-aromatic carbon-carbon unsaturated bond. It contains (B) and a metathesis catalyst (C). The preferred embodiments will be described below.

(Inorganic solid electrolyte (A))
The solid electrolyte composition of the present invention contains an inorganic solid electrolyte.
The solid electrolyte of the inorganic solid electrolyte is a solid electrolyte in which ions can move. Since it does not contain an organic substance as the main ionic conductivity material, it is an organic solid electrolyte (a polymer electrolyte typified by polyethylene oxide (PEO), an organic typified by lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), etc. Electrolyte salt) is clearly distinguished. Further, since the inorganic solid electrolyte is solid in the steady state, it is not dissociated or liberated into cations and anions. In this respect, it is clearly distinguished from inorganic electrolyte salts (LiPF ₆ , LiBF ₄ , lithium bis(fluorosulfonyl)imide (LiFSI), LiCl, etc.) in which cations and anions are dissociated or released in the electrolytic solution and the polymer. .. The inorganic solid electrolyte is not particularly limited as long as it has ion conductivity of a metal element belonging to Group 1 or Group 2 of the periodic table, and generally has no electron conductivity. When the all-solid-state secondary battery of the present invention is a lithium ion battery, the inorganic solid electrolyte preferably has lithium ion ionic conductivity.
As the above-mentioned inorganic solid electrolyte, a solid electrolyte material usually used for all solid state secondary batteries can be appropriately selected and used. Representative examples of the inorganic solid electrolyte include (i) a sulfide-based inorganic solid electrolyte and (ii) an oxide-based inorganic solid electrolyte. In the present invention, a sulfide-based inorganic solid electrolyte is preferably used from the viewpoint that a better interface can be formed between the active material and the inorganic solid electrolyte.
(I) Sulfide-based inorganic solid electrolyte The sulfide-based inorganic solid electrolyte contains a sulfur atom (S) and has an ionic conductivity of a metal element belonging to Group 1 or 2 of the periodic table, Moreover, those having electronic insulation are preferable. The sulfide-based inorganic solid electrolyte preferably contains at least Li, S and P as elements and has lithium ion conductivity, but other than Li, S and P depending on the purpose or case. It may contain an element.
For example, a lithium ion conductivity inorganic solid electrolyte satisfying the composition represented by the following formula (1) can be mentioned, which is preferable.

L _a1 M _b1 P _c1 S _d1 A _e1 (1)

In the formula, L represents an element selected from Li, Na and K, and Li is preferable.
M represents an element selected from B, Zn, Sn, Si, Cu, Ga, Sb, Al and Ge. Among them, B, Sn, Si, Al or Ge is preferable, and Sn, Al or Ge is more preferable.
A represents I, Br, Cl or F, preferably I or Br, and particularly preferably I.
Each of L, M and A may be one kind or two or more kinds of the above elements.
a1 to e1 represent the composition ratio of each element, and a1:b1:c1:d1:e1 satisfies 1 to 12:0 to 1:1:2 to 12:0 to 5. Further, a1 is preferably 1 to 9, and more preferably 1.5 to 4. b1 is preferably 0 to 0.5. Further, d1 is preferably 3 to 7, and more preferably 3.25 to 4.5. Further, e1 is preferably 0 to 3, and more preferably 0 to 1.

In the formula (1), the composition ratio of L, M, P, S and A is preferably such that b1 and e1 are 0, more preferably b1=0, e1=0 and the ratio of a1, c1 and d1 is a1:c1:d1=1-9:1:3-7, more preferably b1=0, e1=0 and a1:c1:d1=1.5-4:1:3.25-4. It is 5. The composition ratio of each element can be controlled by adjusting the compounding quantity of the raw material compound at the time of manufacturing a sulfide type inorganic solid electrolyte, as mentioned later.

The sulfide-based inorganic solid electrolyte may be amorphous (glass) or crystallized (glass-ceramic), or only part thereof may be crystallized. For example, Li-P-S based glass containing Li, P and S, or Li-P-S based glass ceramics containing Li, P and S can be used.
The sulfide-based inorganic solid electrolyte is composed of [1] lithium sulfide (Li ₂ S) and phosphorus sulfide (for example, phosphorus pentasulfide (P ₂ S ₅ )), [2] lithium sulfide and at least one of elemental phosphorus and elemental sulfur, Alternatively, it can be produced by a reaction [3] of lithium sulfide with phosphorus sulfide (for example, phosphorus pentasulfide (P ₂ S ₅ )) and at least one of elemental phosphorus and elemental sulfur.

The ratio of Li ₂ S and P ₂ S _{5 in the} Li—P—S based glass and the Li—P—S based glass ceramics is a molar ratio of Li ₂ S:P ₂ S ₅ , and preferably 65:35. It is 85:15, more preferably 68:32 to 77:23. By setting the ratio of Li ₂ S and P ₂ S ₅ in this range, the lithium ion conductivity can be further increased. Specifically, the lithium ion conductivity can be preferably 1×10 ⁻⁴ S/cm or more, more preferably 1×10 ⁻³ S/cm or more. There is no particular upper limit, but it is practically 1×10 ⁻¹ S/cm or less.

Specific examples of the sulfide-based inorganic solid electrolyte include, for example, those using a raw material composition containing Li ₂ S and a sulfide of an element belonging to Group 13 to Group 15. it can. More _{specifically, Li 2 S-P 2 S} 5, Li 2 S-LiI-P 2 S 5, Li 2 S-LiI-Li 2 O-P 2 S 5, Li 2 S-LiBr-P 2 S _{5, Li 2 S-Li 2} O-P 2 S 5, Li 2 S-Li 3 PO 4 -P 2 S 5, Li 2 S-P 2 S 5 -P 2 O 5, Li 2 S-P 2 S _{5 -SiS 2, Li 2 S-} P 2 S 5 -SnS, Li 2 S-P 2 S 5 -Al 2 S 3, Li 2 S-GeS 2, Li 2 S-GeS 2 -ZnS, Li 2 S- _{Ga 2 S 3, Li 2 S} -GeS 2 -Ga 2 S 3, Li 2 S-GeS 2 -P 2 S 5, Li 2 S-GeS 2 -Sb 2 S 5, Li 2 S-GeS 2 -Al 2 _{S 3, Li 2 S-SiS} 2, Li 2 S-Al 2 S 3, Li 2 S-SiS 2 -Al 2 S 3, Li 2 S-SiS 2 -P 2 S 5, Li 2 S-SiS 2 - _{P 2 S 5 -LiI, Li 2} S-SiS 2 -LiI, such as _{Li 2 S-SiS 2 -Li 4} SiO 4, Li 2 S-SiS 2 -Li 3 PO 4, Li 10 GeP 2 S 12 and the like .. Among _{them, Li 2 S-P 2 S} 5, Li 2 S-GeS 2 -Ga 2 S 3, Li 2 S-SiS 2 -P 2 S 5, Li 2 S-SiS 2 -Li 4 SiO 4, Li 2 _{S-SiS 2 -Li 3 PO 4} , Li 2 S-LiI-Li 2 O-P 2 S 5, Li 2 S-Li 2 O-P 2 S 5, Li 2 S-Li 3 PO 4 -P 2 S ₅ , the crystalline, amorphous or crystalline and amorphous mixed raw material composition of Li _2, S—GeS ₂ —P ₂ S ₅ , and Li ₁₀ GeP ₂ S ₁₂ has high lithium ion conductivity. preferable. An example of a method for synthesizing a sulfide-based inorganic solid electrolyte material using such a raw material composition is an amorphization method. Examples of the amorphization method include a mechanical milling method and a melt quenching method, and among them, the mechanical milling method is preferable. This is because the treatment can be performed at room temperature and the manufacturing process can be simplified.
Among _{them, Li 2 S-P 2 S} 5, LGPS (Li 10 GeP 2 S 12), Li 2 S-P 2 S 5 -SiS 2 and the like are preferable.

(Ii) Oxide-based inorganic solid electrolyte The oxide-based inorganic solid electrolyte contains an oxygen atom (O) and has the ionic conductivity of a metal element belonging to Group 1 or 2 of the periodic table, Moreover, those having electronic insulation are preferable.
The ionic conductivity of the oxide-based inorganic solid electrolyte is preferably 1×10 ⁻⁶ S/cm or more, more preferably 5×10 ⁻⁶ S/cm or more, and 1×10 ⁻⁵ S. /Cm or more is particularly preferable. The upper limit is not particularly limited, but it is practically 1×10 ⁻¹ S/cm or less.

As a specific compound example, for example, Li _xa La _ya TiO ₃ [xa satisfies 0.3≦xa≦0.7, and ya satisfies 0.3≦ya≦0.7. ] (LLT); Li _xb La _yb Zr _zb M ^bb _{mb Onb} (M ^bb is one or more elements selected from Al, Mg, Ca, Sr, V, Nb, Ta, Ti, Ge, In and Sn). Xb satisfies 5≦xb≦10, yb satisfies 1≦yb≦4, zb satisfies 1≦zb≦4, mb satisfies 0≦mb≦2, and nb satisfies 5≦nb≦20. Li _{xc Byc} M ^cc _{zc Onc} (M ^cc is one or more elements selected from C, S, Al, Si, Ga, Ge, In and Sn. xc is 0≦xc≦5. , Yc satisfies 0≦yc≦1, zc satisfies 0≦zc≦1, and nc satisfies 0≦nc≦6.); Li _xd (Al,Ga) _yd (Ti,Ge) _zd Si _ad P _md O _nd (xd satisfies 1 ≦ xd ≦ 3, yd satisfies 0 ≦ yd ≦ 1, zd satisfies 0 ≦ zd ≦ 2, ad satisfies 0 ≦ ad ≦ 1, md is 1 ≦ md≦7, and nd satisfies 3≦nd≦13.); Li _(3-2xe) M ^ee _xe D ^ee O (xe represents a number of 0 or more and 0.1 or less, and M ^ee is divalent) Represents a metal atom, D ^ee represents a halogen atom or a combination of two or more kinds of halogen atoms); Li _xf Si _yf O _zf (xf satisfies 1≦xf≦5, yf satisfies 0<yf≦3) , Zf satisfies 1≦zf≦10); Li _xg S _yg O _zg (xg satisfies 1≦xg≦3, yg satisfies 0<yg≦2, and zg satisfies 1≦zg≦10). _{); Li 3 BO 3; Li} 3 BO 3 -Li 2 SO 4; Li 2 O-B 2 O 3 -P 2 O 5; Li 2 O-SiO 2; Li 6 BaLa 2 Ta 2 O 12; Li 3 PO _(4-3/2w) N _w (w is w<1); Li _3.5 Zn _0.25 GeO ₄ having a LISION (Lithium superionic conductor) type crystal structure; La _0.55 having a perovskite type crystal structure. Li _0.35 TiO ₃ ; LiTi ₂ P ₃ O ₁₂ having a NASICON (Naturium super ionic conductor) type crystal structure; Li _1+xh+yh (Al,Ga) _xh (Ti,Ge) _2-xh Si _yh P _3-yh O ₁₂ (xh satisfies 0≦xh≦1 and yh satisfies 0≦yh≦1. _{); Li 7 La 3 Zr 2} O 12 having a garnet-type crystal structure (LLZ), and the like.
A phosphorus compound containing Li, P and O is also desirable. For example, lithium phosphate (Li ₃ PO ₄ ); LiPON in which part of oxygen of lithium phosphate is replaced by nitrogen; LiPOD ¹ (D ¹ is preferably Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zr, Nb, Mo, Ru, Ag, Ta, W, Pt, and Au are one or more elements selected from the above).
Further, LiA ¹ ON (A ¹ is one or more elements selected from Si, B, Ge, Al, C and Ga) and the like can also be preferably used.
Among _them, (is as M bb, xb, yb, zb , mb and nb ^{_{above.) LLT, Li xb La yb}} Zr zb M bb mb O nb, LLZ, Li 3 BO 3, Li 3 BO 3 -Li ₂ SO ₄ , Li _xd (Al, Ga) _yd (Ti, Ge) _zd Si _ad P _md O _nd (xd, yd, zd, ad, md and nd are as described above) are preferable, and LLZ and LLT are preferable. , LAGP(Li _1.5 Al _0.5 Ge _1.5 (PO ₄ ) ₃ ) or LATP([Li _1.4 Ti ₂ Si _0.4 P _2.6 O ₁₂ ]-AlPO ₄ ) are more preferable.

The inorganic solid electrolyte is preferably particles. The volume average particle diameter of the particulate inorganic solid electrolyte is not particularly limited, but is preferably 0.01 μm or more, more preferably 0.1 μm or more. The upper limit is preferably 100 μm or less, more preferably 50 μm or less. The volume average particle size of the inorganic solid electrolyte is measured by the following procedure. The inorganic solid electrolyte particles are prepared by diluting a 1% by mass dispersion liquid in a 20 mL sample bottle with water (heptane in the case of a substance which is unstable to water). The diluted dispersion sample is irradiated with ultrasonic waves of 1 kHz for 10 minutes, and immediately thereafter, used for the test. Using this dispersion sample, a laser diffraction/scattering particle size distribution analyzer LA-920 (trade name, manufactured by HORIBA) was used, and data was captured 50 times using a measurement quartz cell at a temperature of 25° C. Obtain the volume average particle size. For other detailed conditions and the like, refer to the description of JISZ8828:2013 "Particle size analysis-dynamic light scattering method" as necessary. Five samples are prepared for each level, and the average value is adopted.

The content of the inorganic solid electrolyte in the solid electrolyte composition is preferably 5% by mass or more at a solid content of 100% by mass, in consideration of compatibility between battery performance and reduction of interfacial resistance and maintenance effect. % Or more, and more preferably 20% by mass or more. From the same viewpoint, the upper limit is preferably 99.9% by mass or less, more preferably 99.5% by mass or less, and particularly preferably 99% by mass or less.
However, when the positive electrode active material or the negative electrode active material is contained, the content of the inorganic solid electrolyte in the solid electrolyte composition is such that the total content of the positive electrode active material or the negative electrode active material and the inorganic solid electrolyte is in the above range. Is preferred.
In the present specification, the solid content means an inorganic solid electrolyte (A), a compound (B) having a non-aromatic carbon-carbon unsaturated bond, a metathesis catalyst (C), and drying at 170° C. for 6 hours under a nitrogen atmosphere. A component that does not disappear by volatilization or evaporation when treated. Typically, it refers to components other than the dispersion medium described below.
The inorganic solid electrolytes may be used alone or in combination of two or more.

(Compound (B) having a non-aromatic carbon-carbon unsaturated bond)
The compound having a non-aromatic carbon-carbon unsaturated bond (hereinafter, also simply referred to as compound (B)) is a non-aromatic carbon-carbon unsaturated bond (hereinafter, also simply referred to as non-aromatic unsaturated bond). Is not particularly limited as long as it is a compound having. Non-aromatic means having no aromaticity.

-Group having a non-aromatic unsaturated bond-
Examples of the non-aromatic unsaturated bond include a carbon-carbon double bond and a carbon-carbon triple bond having no aromaticity, which are preferable.
The non-aromatic unsaturated bond may be present at any position in the molecule of the compound (B), and has a group having a non-aromatic unsaturated bond (hereinafter, simply referred to as a non-aromatic unsaturated group). The term ")" may be chain-like or branched, or may further form a ring.

The non-aromatic unsaturated group is a group in which at least one hydrogen atom or an alkyl group of the compound represented by the following general formula (1) or (2) is replaced with a bond “−” (hereinafter, represented by the general formula (1 ) Or (2) is also referred to as a group).

In the above formula, R ^{1a to} R ^4a , R ^5a and R ^6a are each a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, an acyl group, an acyloxy group, an alkoxycarbonyl group or an aryloxycarbonyl group. Alternatively, it represents a carbamoyl group. R ^{1a to} R ^4a may form a ring structure with any organic group. R ^5a and R ^6a may form a ring structure with any organic group. Note that at least one of R ^{1a to} R ^4a is a hydrogen atom or represents a group having an alkyl group. Further, at least one of R ^5a and R ^6a is a hydrogen atom or represents a group having an alkyl group.

The substituent in which at least one hydrogen atom or an alkyl group of the compound represented by the general formula (1) or (2) is replaced with a bond "-" is represented by the general formula (1) or (2). Any substituent may be used as long as it has a partial structure. For example, when R ^1a is a hydrogen atom, it is a substituent in which the hydrogen atom in R ^1a is replaced with a bond “−”, and when R ^1a is alkoxycarbonyl, an alkyl group or a hydrogen atom in R ^1a is a bond. It is a substituent that is replaced with "-".

The alkyl group, alkenyl group, alkynyl group, aryl group, heteroaryl group, acyl group, acyloxy group, alkoxycarbonyl group, aryloxycarbonyl group and carbamoyl group for R ^{1a to} R ^4a , R ^5a and R ^6a are the substituents described below. The preferred statements of radical Z can be applied.

Among them, in the general formula (1), R ^1a and R ^2a are hydrogen atoms, R ^3a is a hydrogen atom or an alkyl group, and R ^4a is a hydrogen atom, an alkyl group, an alkoxycarbonyl group or an aryloxy group. A carbonyl group in which a hydrogen atom or an alkyl group in R ^3a or R ^4a is replaced with a bond “−” is preferable. Further, in the general formula (2), a group in which R ^5a is a hydrogen atom, R ^6a is a hydrogen atom or an alkyl group, and a hydrogen atom in R ^6a is replaced with a bond “−” is preferable.

As the specific non-aromatic unsaturated group, any one selected from a terminal vinyl group, an allyl group, a (meth)acryloyl group and a terminal ethynyl group is preferable.
When the compound (B) has a non-aromatic unsaturated bond at its molecular end, the reactivity of the metathesis reaction described later is further enhanced, and the compound (B) can be crosslinked at a low temperature. In addition, since the crosslinking efficiency is further increased, the binding property between solid particles is improved. From these viewpoints, the non-aromatic unsaturated group is more preferably a terminal vinyl group or a terminal ethynyl group.
The compound (B) preferably has two or more non-aromatic unsaturated groups, more preferably three or more.

-Functional group-
The fact that the compound (B) has at least one kind of functional group selected from the following functional group group means that the interaction between the compound (B) and the inorganic solid electrolyte, or the compound (B) and the inorganic solid electrolyte and the active material. It is preferable from the viewpoint of enhancing the interaction between the above and the binding property.
<Functional group>
Hydroxy group, mercapto group, carboxy group, sulfonic acid group, phosphoric acid group, amino group, cyano group, isocyanate group, acid anhydride group, epoxy group, oxetanyl group, alkoxy group, carbonyl group (>C=O), 3 A group having a ring structure of at least a ring, a group having an amide bond, a group having a urea bond, a group having a urethane bond, a group having an imide bond, and a group having an isocyanurate bond.

The acid anhydride group means a group (group in which at least one hydrogen atom is replaced with a bond “−”) obtained from an acid anhydride of dicarboxylic acid.

The amino group preferably has 0 to 12 carbon atoms, more preferably 0 to 6 carbon atoms, and particularly preferably 0 to 2 carbon atoms.
The sulfonic acid group may be an ester or salt thereof. In the case of an ester, it preferably has 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, and particularly preferably 1 to 6 carbon atoms.
The phosphate group may be its ester or salt. In the case of an ester, it preferably has 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, and particularly preferably 1 to 6 carbon atoms.
For the other functional groups, the preferred description of the substituent Z described below can be applied.
The functional group may be present as a substituent or a linking group. For example, the amino group may be present as a divalent imino group or a trivalent nitrogen atom.

Among the above functional groups, polar groups are preferably used from the viewpoint of affinity for the inorganic solid electrolyte and/or the positive electrode active material. Specifically, a hydroxy group, a mercapto group, a carboxy group, a sulfonic acid group, a phosphoric acid group and an amino group are preferred, and a carboxy group is more preferred.
From the viewpoint of affinity for the negative electrode active material and/or the conductive additive, a nonpolar group is preferably used. Specifically, a group having a ring structure with three or more rings is preferred.

As the group having a ring structure of three or more rings, at least one hydrogen atom of an aromatic hydrocarbon, an aliphatic hydrocarbon or an unsaturated hydrocarbon represented by the following general formula (A) is replaced with a bond “−”. And a group in which at least one hydrogen atom of the aliphatic hydrocarbon represented by the general formula (B) described later is replaced with a bond “−” is preferable.
The aromatic hydrocarbon, unsaturated hydrocarbon or aliphatic hydrocarbon represented by the following general formula (A), and the aliphatic hydrocarbon represented by the following general formula (B) are carbonaceous materials which are negative electrode active materials. Excellent compatibility with materials. Therefore, while further improving the dispersion stability of the compound (B) having a group in which at least one hydrogen atom of these compounds is replaced by a bond “−” in the solid electrolyte composition, the solid electrolyte-containing sheet of The binding property can be improved. Further, as the dispersion stability and the binding property are improved, it is possible to improve the cycle characteristics of the all-solid secondary battery produced by using this solid electrolyte composition.

In the general formula (A), CHC represents a benzene ring, a cyclohexane ring, a cyclohexene ring or a cyclohexadiene ring. n _A represents an integer of 0-8. R ^{A1 to} R ^A6 each independently represent a hydrogen atom or a substituent. When CHC is other than a benzene ring, the ring structure may have a hydrogen atom in addition to R ^{A1 to} R ^A6 . X ^A1 and X ^A2 each independently represent a hydrogen atom or a substituent. Here, in R ^{A1 to} R ^A6 , X ^A1 and X ^A2 , adjacent groups may be bonded to each other to form a 5- or 6-membered ring. However, if _{n A} is ^0, any one substituent of R A1 ^{to R A6 _{is, - (CHC 1) m A}} -R Ax or where any two of ^R A1 ^{to R A6} each other bonds _{^{and, - (CHC 1) m a}} - form a. Here, CHC ¹ represents a phenylene group, a cycloalkylene group, or a cycloalkenylene group, m _A represents an integer of 2 or more, and R ^Ax represents a hydrogen atom or a substituent. When n _A is 1, in R ^{A1 to} R ^A6 , X ^A1 and X ^A2 , at least two adjacent to each other are bonded to each other to form a benzene ring, a cyclohexane ring, a cyclohexene ring or a cyclohexadiene ring.

As the substituent represented by R ^{A1 to} R ^A6 , an alkyl group, an aryl group, a heteroaryl group, an alkenyl group, an alkynyl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an alkylthio group, an arylthio group, a heteroarylthio group, Acyl group, acyloxy group, alkoxycarbonyl group, aryloxycarbonyl group, alkylcarbonyloxy group, arylcarbonyloxy group, hydroxy group, carboxy group or salt thereof, sulfo group or salt thereof, amino group, mercapto group, amide group, formyl Examples thereof include a group, a cyano group, a halogen atom, a (meth)acryl group, a (meth)acryloyloxy group, a (meth)acrylamide group, an epoxy group and an oxetanyl group.

n _A is more preferably an integer of 0 to 6, an integer of 1 to 4 is particularly preferred.

The aromatic hydrocarbon represented by the general formula (A) is preferably a compound represented by the following general formula (A-1) or (A-2).

In the general formula (A-1), Ar is a benzene ring. R ^A1 ~R ^{A6, X A1} and ^{X A2} of the general formula (A) have the same meaning as ^{R A1 ~R A6, X} A1 and ^{X A2} in, and the preferred range is also the same. n _A 1 represents an integer of 1 or more. However, when n _A 1 is 1, at least two adjacent to each other in R ^{A1 to} R ^A6 , X ^A1 and X ^A2 are bonded to each other to form a benzene ring.
In the general formula (A-2), R ^Ax has the same meaning as R ^Ax in the general formula (A), and the preferred range is also the same. R ^A10 represents a substituent, and n _A x represents an integer of 0 to 4. m _A 1 represents an integer of 3 or more. ^RAy represents a hydrogen atom or a substituent. Here, R ^Ax and R ^Ay may be bonded.

n _A 1 is preferably an integer of 1 to 6, more preferably an integer of 1 to 3, particularly preferably 1 to 2 integer.
m _A 1 is preferably an integer of 3 to 10, more preferably an integer of 3 to 8, and particularly preferably an integer of 3 to 5.

Specific examples of the aromatic hydrocarbon represented by the general formula (A) include naphthalene, anthracene, phenanthracene, pyrene, tetracene, tetraphene, chrysene, triphenylene, pentacene, pentaphene, perylene, pyrene, benzo[a]pyrene. , Coronene, anthanthrene, corannulene, ovalen, graphene, cycloparaphenylene, polyparaphenylene or a compound containing a structure of cyclophene. However, the present invention is not limited to these.

In the general formula (B), Y ^B1 and Y ^B2 each independently represent a hydrogen atom, a methyl group or a formyl group. R ^B1 , R ^B2 , R ^B3 and R ^B4 each independently represent a substituent, and a _B , b _B , c _B and d _B represent an integer of 0 to 4.
Here, ring A may be a saturated ring, an unsaturated ring having 1 or 2 double bonds or an aromatic ring, and rings B and C may be an unsaturated ring having 1 or 2 double bonds. May be In addition, in each of a _B , b _B , c _B or d _B , when each is an integer of 2 to 4, adjacent substituents may be bonded to each other to form a ring.

The aliphatic hydrocarbon represented by the general formula (B) is a compound having a steroid skeleton.
Here, the carbon number of the steroid skeleton is as follows.

The substituents in R ^B1 , R ^B2 , R ^B3 and R ^B4 may be any substituents, but an alkyl group, an alkenyl group, a hydroxy group, a formyl group, an acyl group, a carboxy group or a salt thereof, (meth) An acryl group, a (meth)acryloyloxy group, a (meth)acrylamide group, an epoxy group, and an oxetanyl group are preferable, and an =O group in which two substituents having the same carbon atom are jointly formed is preferable.
The alkyl group is preferably an alkyl group having 1 to 12 carbon atoms and may have a substituent. As such a substituent, any substituent may be used, and examples thereof include an alkyl group, an alkenyl group, a hydroxy group, a formyl group, an acyl group, a carboxy group, an alkoxycarbonyl group, a carbamoyl group and a sulfo group. It is further preferable that the alkyl group contains an unsaturated carbon bond of a double bond or a triple bond inside.
The alkenyl group is preferably an alkenyl group having 2 to 12 carbon atoms and may have a substituent. As such a substituent, any substituent may be used, and examples thereof include an alkyl group, an alkenyl group, a hydroxy group, a formyl group, an acyl group, a carboxy group, an alkoxycarbonyl group, a carbamoyl group and a sulfo group.
R ^B1 is preferably substituted at carbon number 3, R ^B2 is preferably substituted at carbon number 6 or 7, R ^B3 is preferably substituted at carbon number 11 or 12, and R ^B4 is carbon. It is preferable to substitute the number 17.

Y ^B1 and Y ^B2 are preferably a hydrogen atom or a methyl group.

a _B , b _B , c _B and d _B are preferably integers of 0 to 2.

When the ring A is an unsaturated ring, the double bond is preferably a bond with carbon numbers 4 and 5, and when the ring B is an unsaturated ring, the double bond is a bond with carbon numbers 5 and 6 or 6 and 7. When the C ring is an unsaturated ring, the double bond is preferably a carbon number 8 or 9 bond.

The compound represented by the general formula (B) includes all stereoisomers. When the binding direction of the substituent is represented by α in the downward direction of the paper and β in the upward direction of the paper, it may be either α or β, or a mixture thereof. The arrangement of A/B rings, the arrangement of B/C rings, and the arrangement of C/D rings may be either trans arrangement or cis arrangement, or may be a mixed arrangement thereof. Absent.

In the present invention, the sum of a _{B to} d _B is preferably 1 or more, and any of R ^B1 , R ^B2 , R ^B3 and R ^B4 is preferably a hydroxy group or an alkyl group having a substituent.

Specific examples of the aliphatic hydrocarbon represented by the general formula (B) include cholesterol, ergosterol, testosterone, estradiol, erdosterol, aldosterone, hydrocortisone, stigmasterol, timosterol, lanosterol, 7-dehydrodesmosterol, 7 -Dehydrocholesterol, colanic acid, cholic acid, lithocholic acid, deoxycholic acid, sodium deoxycholic acid, lithium deoxycholic acid, hyodeoxycholic acid, chenodeoxycholic acid, ursodeoxycholic acid, dehydrocholic acid, foquecholic acid or hyocholic acid Examples include compounds that include a structure. However, the present invention is not limited to these.

The group having 3 or more ring structures is particularly preferably a group having a cholesterol ring structure or a structure in which 3 or more aromatic groups are condensed, and most preferably a deoxycholic acid residue or a pyrenyl group.

The compound (B) may be a monomer, an oligomer, or a polymer as long as it is dissolved in the solid electrolyte composition, and may be a gas or a liquid at room temperature. It may be solid.
The molecular weight is not particularly limited, but the molecular weight or the mass average molecular weight (Mw) is preferably less than 10,000, more preferably less than 1,000. The lower limit is not particularly limited, but is preferably 20 or more. The compound name is ethylene for a double bond and acetylene for a triple bond. When the compound (B) has any of the following star-type, hyperbranch-type, and dendrimer-type structures, the molecular weight means the molecular weight of the core part.

In the case of polymers, the non-aromatic unsaturated bond may be in the main chain or in the side chain, but is preferably in the side chain.
It is preferable that the compound (B) has a structure of any of a star type, a hyperbranched type and a dendrimer type, since the crosslink density of the compound (B2) formed by the metathesis reaction can be increased.

The star type is one structure of a multi-branched polymer and has a core portion and at least three arm portions coupled to the core portion.
The core portion is preferably an atomic group having a molecular weight of 200 or more, and more preferably an atomic group having a molecular weight of 300 or more. The upper limit is preferably 5,000 or less, more preferably 4,000 or less, and particularly preferably 3,000 or less. It is preferred that this core is not the only tetravalent carbon atoms. The core part is preferably the organic group X in the following general formula (1a) or (2a).
The molecular weight of the arm portion is preferably 500 or more, more preferably 1,000 or more. The upper limit is preferably 1,000,000 or less, and more preferably 500,000 or less.
As the monomer capable of forming the arm portion, Polymer Handbook 2nd ed. , J. For example, those described in Brandrup, Wiley linterscience (1975) Chapter 2 Pages 1-483 can be used.

The hyperbranched type and the dendrimer type are also one structure of a multibranched polymer, and have a branched structure in the arm portion.
Here, the dendrimer refers to a polymer having good symmetry and a regular branched structure extending three-dimensionally from the core part. Dendrimers consist of repeating chemical bonds, called dendrons, between branches. It is different from the hyperbranched polymer and other polymers in that the branching has a regular and clear structure and no molecular weight distribution, that is, a single molecular weight.
The hyperbranched polymer has a structure in which a repeating unit corresponding to an arm portion branches from the core portion and extends. The branching of repeating units occurs randomly and has a molecular weight distribution.

The compound (B) preferably has a non-aromatic unsaturated bond at the arm portion in the star type, hyperbranched type and dendrimer type structures described above, and more preferably at the end of the arm portion.

The compound (B) preferably has two or more non-aromatic unsaturated bonds in one molecule, and the compound (B) is more preferably represented by the following general formula (1a) or (2a). ..

In the above formula, R ^{11 to} R ¹³ , R ¹⁴ , R ^{21 to} R ²³ and R ²⁴ represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group or an aryl group, and R ³¹ and R ³⁴ represent a hydrogen atom or an alkyl group. Represents an alkenyl group, an alkynyl group or an aryl group. L ¹¹ , L ²¹ and L ³¹ represent a single bond or a divalent linking group. n and m are integers of 1 to 20, and l is an integer of 0 to 20. X represents an organic group having a valence of n+m+1.

The description of the substituent Z described below can be applied to the alkyl group, alkenyl group, alkynyl group and aryl group in R ^{11 to} R ¹³ , R ¹⁴ , R ^{21 to} R ²³ and R ²⁴ . Hereinafter, preferred forms of the applicable substituent Z will be described.
The alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and specifically, methyl, ethyl or octyl is preferable.
The alkenyl group preferably has 2 to 10 carbon atoms, more preferably 2 to 8 carbon atoms, and specifically, ethenyl, 2-octenyl, 2,5-heptadienyl, 2,5-octadienyl or 9-decenyl is preferable.
The alkynyl group preferably has 2 to 10 carbon atoms, more preferably 2 to 8 carbon atoms, and specifically, ethynyl is preferable.
The aryl group preferably has 6 to 18 carbon atoms, and specifically, phenyl is preferable.

In the compound represented by the general formula (1a), it is preferable that R ¹¹ , R ¹² , R ²¹ and R ²² are all hydrogen atoms, and the compound represented by the general formula (2a) includes R ¹⁴ and R It is preferable that both ²⁴ are hydrogen atoms.

For the alkyl group, alkenyl group, alkynyl group and aryl group for R ³¹ and R ^34, the preferred descriptions for R ^{11 to} R ¹³ , R ¹⁴ , R ^{21 to} R ²³ and R ²⁴ can be applied.
It is also preferable that R ³¹ and R ³⁴ have a functional group selected from the above-mentioned functional group group (hereinafter, also referred to as a specific functional group).

L ¹¹ and L ²¹ link X with the non-aromatic unsaturated group (for example, —C(R ¹³ )═C(R ¹¹ )(R ¹² )) in the general formulas (1a) and (2a). Any group may be used as long as it does not affect the reaction between the non-aromatic unsaturated group and the metathesis catalyst.
L ³¹ is a group connecting R ³¹ and X in the general formula (1a) and R ³⁴ and X in the general formula (2a), and influences the reaction between the non-aromatic unsaturated group and the metathesis catalyst. Any group may be used as long as it does not give.
That is, L ¹¹ , L ²¹ and L ³¹ are linking groups having no non-aromatic unsaturated bond.

The divalent linking group for L ¹¹ , L ²¹ and L ³¹ is an alkylene group (preferably having a carbon number of 1 to 18 and preferably 1 to 10) and an arylene group (preferably having a carbon number of 6 to 18). And a heteroarylene group (a 5-membered or 6-membered heteroarylene group having at least one of an oxygen atom, a sulfur atom and a nitrogen atom as a ring-constituting atom is more preferable. The ring to be cycled is preferably a benzene ring or an alicyclic ring, and the number of carbon atoms constituting the heteroarylene group is preferably 2 to 20. The heteroaryl ring in the heteroarylene group includes an aromatic ring and an aliphatic ring. ^{), - O -, - NR} N -, - C (= O) -, - C (= O) -O- or -C (= O) NR ^N - or combinations thereof are preferred. ^RN represents a hydrogen atom, an alkyl group (preferably having a carbon number of 1 to 8) or an aryl group (preferably having a carbon number of 6 to 12).
L ^{11, L 21} and ^{L 31} represents a single bond, an alkylene group, -C (= O) -O - , - C (= O) - alkylene, -O- alkylene, -C (= O) -O- alkylene Alternatively, -OC(=O)-alkylene is more preferable.

L ¹¹ , L ²¹ and L ³¹ may be bound to X on either side. For example, in the case of -C(=O)-O-, it may be bonded to X by an oxygen atom or may be bonded to X by a carbonyl group.
It is also preferable that L ¹¹ , L ²¹ and L ³¹ have a specific functional group.

Having a specific functional ^group, the group represented by -L 31 ^{-R 31} or ^-L 31 ^{-R 34,} specifically, the following of the group are preferably exemplified, as limiting the present invention by this interpretation It is not something that will be done. In addition, * indicates a binding site with X.

n and m are preferably integers of 1 to 10.
l is preferably an integer of 1 to 10, more preferably an integer of 2 to 5.
As for n+m, the integer of 2-40 is preferable and the integer of 3-8 is more preferable.
X is preferably a 2- to 60-valent organic group, and more preferably a 3- to 12-valent organic group.

The m+n+1 valent organic group in X is, for example, a polycyclic organic group represented by any one of the following general formulas (Q-1) to (Q-19) or the following general formulas (Q-20) to (Q-36). ) A pentaerythritol residue, a dipentaerythritol residue, a diaminoalkylene residue and a trimethylolalkane residue represented by any of the following general formulas (H-1) to (H-3) Preferred examples thereof include a cyclic siloxane residue and a silsesquioxane residue represented by any of the following general formulas (P-1) to (P-8).
When X is a silsesquioxane residue, the compound (B) is a sol-gel body of the compound represented by the general formula (1a) or (2a) and a trialkoxysilane having a non-aromatic unsaturated bond. It may be a mixture with. In this case, the content of the compound represented by the general formula (1a) or (2a) in the compound (B) as a mixture is preferably 10 to 99% by mass, more preferably 50 to 95% by mass.
In addition, Y in the following general formulas (Q-1) to (Q-36) and (H-1) to (H-3) and R in the following general formulas (P-1) to (P-8) are arbitrary. And a binding site with L ¹¹ , L ²¹ or L ³¹ .
The arbitrary linking group is, for example, a single bond, an alkylene group (having 1 to 18 carbon atoms, more preferably 1 to 10 carbon atoms), -O-, -C(=O)-, -C(=O). ) O-, -C(=O)NR-, -S- and -NR- (R represents a hydrogen atom, an alkyl group or an aryl group, preferably a hydrogen atom), a single bond, an alkylene group, -O-, -S- or -NR- is preferred. It should be noted that either side may be combined with X.
In the following general formula, a to f represent a repeating number, preferably 2 to 20, and more preferably 3 to 10.

The compound (B) represented by the general formula (1a) or (2a) can be synthesized by the following method. That is, a compound in which the terminal portion of X, which is the mother nucleus of the multi-branched skeleton (star type, hyperbranched type and dendrimer type), is a nucleophilic functional group such as a hydroxy group, a carboxy group, an amino group and a mercapto group, Alternatively, for a compound having a leaving group such as a halogen atom (Cl, Br, I), -OTs and -OMs, a non-aromatic unsaturated bond and a reactive functional group (hydroxy group, carboxy group, amino group) And a compound having a mercapto group, etc.). Here, Ts represents a tosyl group and Ms represents a mesyl group.
For example, the compound (B) is obtained by forming an ester bond from the reaction of a hydroxy group and a carboxy group, an amide bond from a reaction of an amino group and a carboxy group, and a thioester bond from a reaction of a mercapto group and a carboxy group.
For leaving groups such as halogen atom (Cl, Br, I), -OTs and -OMs, a hydroxyl group, an amino group and a mercapto group are reacted to form an ether bond, an amide bond and a thioether bond, respectively. Formed to give compound (B).

Examples of the compound (B) include those described below, but the present invention is not limited thereto.
In addition, in the exemplary compounds b-1 to 24, Y or R in X is described in the column of the structure of parentheses with n, m or l to be bonded (for example, the structure of () _n ). L ¹¹ and L ²¹ are bonded to Y or R by the left bond (for example, a carbonyl bond in b-1) described below.
In addition, in the exemplified compounds b-25 to 52, the number of subscripts in () or [] represents mol %. However, the number in parentheses () in [] indicates the number of repeating units.

As the compound (B), one type may be used alone, or two or more types may be used in combination.

The content of the compound (B) in the solid electrolyte composition is 0.05% by mass to 30% by mass at a solid content of 100% by mass in consideration of both battery performance and reduction in interfacial resistance and maintaining effect. Is preferred, 0.1% by mass to 20% by mass is more preferred, and 1% by mass to 10% by mass is even more preferred.

In the present invention, the mass ratio of the total mass (total amount) of the inorganic solid electrolyte and the electrode active material to be optionally contained to the mass of the compound (B) [(mass of inorganic solid electrolyte+mass of electrode active material)/compound (B Mass]] is preferably in the range of 1,000 to 1. This ratio is more preferably 500 to 2, and even more preferably 100 to 10.

(Metathesis catalyst (C))
As the metathesis catalyst, atoms of groups 5, 6, and 8 (long-periodic periodic table, hereinafter the same) are used as transition metal atoms. Although the atoms of each group are not particularly limited, the atoms of the preferred group 5 are tantalum, the atoms of the preferred group 6 are molybdenum and tungsten, and the preferred atoms of the group 8 are ruthenium and osmium. The metathesis catalyst is preferably a ruthenium catalyst (that is, a ruthenium-containing catalyst).
For example, JP-B-41-20111, JP-A-46-14910, JP-B-57-17883, JP-B-57-61044, JP-A-54-86600, and JP-A-58-127728. Living ring-opening metathesis catalysts described in JP-A No. 1-240517 and the like. Specifically, a shrock type polymerization catalyst (Japanese Patent Laid-Open No. 7-179575, Schrock), which is a general metathesis polymerization catalyst essentially consisting of (a) a transition metal compound catalyst component and (b) a metal compound promoter component. et al., J. Am. Chem. Soc., 1990, Vol. 112, p. 3875-etc. and Grubbs type polymerization catalyst (Fu et al., J. Am. Chem. Soc., 1993, 115). Vol., 9856-; Nguyen et al., J. Am. Chem. Soc., 1992, Vol. 114, 3974-; Grubbs et al., WO98/21214 pamphlet) and the like.

As the metathesis catalyst (C) used in the present invention, a Grubbs type polymerization catalyst is preferable, and a ruthenium carbene complex is more preferable. Specifically, the following catalysts can be preferably used, and products described in catalogs manufactured by Aldrich, catalogs manufactured by Wako Pure Chemical Industries, Ltd., etc. can be obtained.
The following catalysts are typical.
First generation Grubbs catalyst benzylidene bis(tricyclohexylphosphine)dichlororuthenium(II)
Second generation Grubbs catalyst benzylidene [1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro(tricyclohexylphosphine)ruthenium(II)
First generation Hoveyda-Grubbs catalyst (tricyclohexylphosphine)dichloro(2-isopropoxyphenylmethylene)ruthenium(II)
Second generation Hoveyda-Grubbs catalyst [1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro(2-isopropoxyphenylmethylene)ruthenium(II)

In addition to the above, the following catalysts can be preferably used.
-Benzylidene[1,3-bis(2-methylphenyl)-2-imidazolidinylidene]dichloro(tricyclohexylphosphine)ruthenium(II)
-Benzylidene[1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro(bis(3-bromopyridine))ruthenium(II)
-3-Methyl-2-butenylidene[1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro(tricyclohexylphosphine)ruthenium(II)
-[1,3-Bis(2-methylphenyl)-2-imidazolidinylidene]dichloro(2-isopropoxyphenylmethylene)ruthenium(II)
-(Tricyclohexylphosphine)dichloro(2-isopropoxy-5-N,N-dimethylaminosulfonylphenylmethylene)ruthenium(II)
-[1,3-Bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro(2-isopropoxy-5-N,N-dimethylaminosulfonylphenylmethylene)ruthenium(II)
-Dichloro(tricyclohexylphosphine)[(tricyclohexylphosphoranyl)-methylidene]ruthenium(III) tetrafluoroborate-[1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro (Tricyclohexylforanyl)methylidene ruthenium(III) tetrafluoroborate

Among them, the metathesis catalyst (C) is more preferably a catalyst in which an oxygen atom or a nitrogen atom is coordinated or bonded to a ruthenium atom.

The content of the metathesis catalyst (C) in the solid electrolyte composition is 0.001% by mass to 5% by mass when the solid content is 100% by mass in consideration of compatibility between the battery performance and the reduction and maintenance effect of the interface resistance. %, more preferably 0.01% by mass to 2% by mass, still more preferably 0.1% by mass to 1% by mass.

In the solid electrolyte composition of the present invention, the content mass ratio of the metathesis catalyst (C) to the compound (B) is, from the viewpoint of reactivity, the compound (B): metathesis catalyst (C)=1:0.05 to 1 Is preferable, and 1:0.1-0.5 is more preferable.

When the compound (B) is a liquid capable of dissolving the metathesis catalyst (C) at -50 to 40°C, the solid electrolyte composition of the present invention does not need to contain a dispersion medium.

In the present specification, with respect to a substituent which is not specified as substituted or unsubstituted (the same applies to a linking group), it means that the group may have an appropriate substituent. This is also synonymous for compounds that do not specify substitution or substitution. The following substituent Z is mentioned as a preferable substituent.
Examples of the substituent Z include the followings.
Alkyl group (preferably alkyl group having 1 to 20 carbon atoms, for example, methyl, ethyl, isopropyl, t-butyl, pentyl, heptyl, 1-ethylpentyl, benzyl, 2-ethoxyethyl, 1-carboxymethyl, etc.), alkenyl A group (preferably an alkenyl group having 2 to 20 carbon atoms, for example, vinyl, allyl, oleyl, etc.), an alkynyl group (preferably an alkynyl group having 2 to 20 carbon atoms, for example, ethynyl, butadiynyl, phenylethynyl, etc.), Cycloalkyl group (preferably a cycloalkyl group having 3 to 20 carbon atoms, for example, cyclopropyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, etc. However, when the alkyl group is used in the present specification, it is usually meant to include a cycloalkyl group. ), an aryl group (preferably an aryl group having 6 to 26 carbon atoms, for example, phenyl, 1-naphthyl, 4-methoxyphenyl, 2-chlorophenyl, 3-methylphenyl, etc.), an aralkyl group (preferably having 7 carbon atoms). To 23 aralkyl groups, for example, benzyl, phenethyl and the like, provided that the term "alkyl group" as used in the present specification usually means an aralkyl group.), a heterocyclic group (preferably a heterocyclic group having 2 to 20 carbon atoms, A 5- or 6-membered heterocyclic group having at least one selected from an oxygen atom, a sulfur atom and a nitrogen atom as a ring-constituting atom is preferable, and examples thereof include tetrahydropyranyl, tetrahydrofuranyl, 2-pyridyl, 4 -Pyridyl, 2-imidazolyl, 2-benzimidazolyl, 2-thiazolyl, 2-oxazolyl, pyrrolidone group, etc.), alkoxy group (preferably alkoxy group having 1 to 20 carbon atoms, for example, methoxy, ethoxy, isopropyloxy, benzyloxy). Etc.), an aryloxy group (preferably an aryloxy group having 6 to 26 carbon atoms, for example, phenoxy, 1-naphthyloxy, 3-methylphenoxy, 4-methoxyphenoxy, etc., provided that an alkoxy group is usually referred to in the present specification. It is meant to include an aryloyl group), an alkoxycarbonyl group (preferably an alkoxycarbonyl group having 2 to 20 carbon atoms, for example, ethoxycarbonyl, 2-ethylhexyloxycarbonyl, etc.), an aryloxycarbonyl group (preferably having a carbon atom number). 6 to 26 aryloxycarbonyl groups such as phenoxycarbonyl, 1-naphthyloxycarbonyl, 3-methylphene Nonoxycarbonyl, 4-methoxyphenoxycarbonyl and the like), an amino group (preferably an amino group having 0 to 20 carbon atoms, an alkylamino group, an arylamino group, for example, amino, N,N-dimethylamino, N, N-diethylamino, N-ethylamino, anilino, etc.), sulfamoyl group (preferably sulfamoyl group having 0 to 20 carbon atoms, for example, N,N-dimethylsulfamoyl, N-phenylsulfamoyl), acyl group (Preferably an acyl group having 1 to 20 carbon atoms, for example, acetyl, propionyl, butyryl and the like), an aryloyl group (preferably an aryloyl group having 7 to 23 carbon atoms, for example, benzoyl and the like, but an acyl group in the present specification) In that case, it is usually meant to include an aryloyl group. ), an acyloxy group (preferably an acyloxy group having 1 to 20 carbon atoms, for example, acetyloxy and the like), an aryloyloxy group (preferably an aryloyloxy group having 7 to 23 carbon atoms, for example, benzoyloxy and the like, In the present specification, an acyloxy group usually means an aryloyloxy group), a carbamoyl group (preferably a carbamoyl group having 1 to 20 carbon atoms, for example, N,N-dimethylcarbamoyl, N-phenylcarbamoyl, etc. ), an acylamino group (preferably an acylamino group having 1 to 20 carbon atoms such as acetylamino, benzoylamino and the like), an alkylthio group (preferably an alkylthio group having 1 to 20 carbon atoms such as methylthio, ethylthio, isopropylthio). , Benzylthio, etc.), an arylthio group (preferably an arylthio group having 6 to 26 carbon atoms, for example, phenylthio, 1-naphthylthio, 3-methylphenylthio, 4-methoxyphenylthio, etc.), an alkylsulfonyl group (preferably carbon atoms). An alkylsulfonyl group having 1 to 20 carbon atoms, such as methylsulfonyl, ethylsulfonyl, etc., an arylsulfonyl group (preferably an arylsulfonyl group having 6 to 22 carbon atoms, such as benzenesulfonyl etc.), an alkylsilyl group (preferably carbon). An alkylsilyl group having 1 to 20 atoms, for example, monomethylsilyl, dimethylsilyl, trimethylsilyl, triethylsilyl, etc., an arylsilyl group (preferably an arylsilyl group having 6 to 42 carbon atoms, for example, triphenylsilyl, etc.), An alkoxysilyl group (preferably an alkoxysilyl group having 1 to 20 carbon atoms, for example, monomethoxysilyl, dimethoxysilyl, trimethoxysilyl, triethoxysilyl, etc.), an aryloxysilyl group (preferably having 6 to 42 carbon atoms) aryloxy silyl group, for example, triphenyl oxysilyl etc.), a phosphoryl group (preferably phosphoryl group of 0-20 carbon atoms, for ^{example, -OP (= O) (R} P) 2), a phosphonyl group (preferably a carbon phosphonyl group atoms from 0 to 20, for ^{example, -P (= O) (R} P) 2), a phosphinyl group (preferably a phosphinyl group having 0 to 20 carbon atoms, for _{^{example, -P (R P) 2)}} , (Meth)acryloyl group, (meth)acryloyloxy group, (meth)acryloylino group ((meth)acrylamide group), hydroxy group, mercapto Examples thereof include a group, a carboxy group, a phosphoric acid group, a phosphonic acid group, a sulfonic acid group, a cyano group, and a halogen atom (eg, fluorine atom, chlorine atom, bromine atom, iodine atom, etc.).
In addition, the above-mentioned substituent Z may further be substituted on each of the groups exemplified as the substituent Z.
When the compound, the substituent, the linking group, etc. include an alkyl group, an alkylene group, an alkenyl group, an alkenylene group, an alkynyl group, an alkynylene group, etc., these may be cyclic or chain, and may be linear or branched. , And may be substituted as described above.

(binder)
The solid electrolyte composition for all-solid secondary battery of the present invention preferably also contains a binder.
The binder used in the present invention is not particularly limited as long as it is an organic polymer.
The binder that can be used in the present invention is preferably a binder that is usually used as a binder for a positive electrode or a negative electrode of a battery material, and is not particularly limited, and for example, a binder made of the resin described below is preferable.

Examples of the fluorine-containing resin include polytetrafluoroethylene (PTFE), polyvinylene difluoride (PVdF), and a copolymer of polyvinylene difluoride and hexafluoropropylene (PVdF-HFP).
Examples of the hydrocarbon-based thermoplastic resin include polyethylene, polypropylene, styrene butadiene rubber (SBR), hydrogenated styrene butadiene rubber (HSBR), butylene rubber, acrylonitrile butadiene rubber, polybutadiene and polyisoprene.
Examples of acrylic resins include methyl poly(meth)acrylate, ethyl poly(meth)acrylate, isopropyl poly(meth)acrylate, isobutyl poly(meth)acrylate, butyl poly(meth)acrylate, and poly(meth)acrylate. ) Hexyl acrylate, octyl poly(meth)acrylate, dodecyl poly(meth)acrylate, stearyl poly(meth)acrylate, 2-hydroxyethyl poly(meth)acrylate, poly(meth)acrylic acid, poly(meth) ) Benzyl acrylate, poly(meth)acrylic acid glycidyl, poly(meth)acrylic acid dimethylaminopropyl, and copolymers of monomers constituting these resins.
Copolymers with other vinyl monomers are also preferably used. Examples thereof include poly(meth)acrylate-polystyrene copolymer, poly(meth)acrylate methyl-acrylonitrile copolymer, poly(meth)acrylate butyl-acrylonitrile-styrene copolymer, and the like.

In addition to the radical polymerization type polymer, polycondensation type polymer can be used. As the polycondensation polymer, for example, urethane resin, urea resin, amide resin, imide resin, polyester resin and the like can be preferably used.
The polycondensation polymer preferably has a hard segment portion and a soft segment portion. The hard segment site represents a site capable of forming an intermolecular hydrogen bond, and the soft segment site generally represents a flexible site having a glass transition temperature (Tg) of room temperature (25±5° C.) or lower and a molecular weight of 400 or more.
These may be used alone or in combination of two or more.

The upper limit of the glass transition temperature of the binder is preferably 50°C or lower, more preferably 0°C or lower, and most preferably -20°C or lower. The lower limit is preferably −100° C. or higher, more preferably −70° C. or higher, particularly preferably −50° C. or higher.

The glass transition temperature (Tg) is measured under the following conditions using a differential scanning calorimeter "X-DSC7000" (trade name, manufactured by SII Nanotechnology Co., Ltd.) using a dry sample. The measurement is performed twice on the same sample, and the result of the second measurement is used.
Atmosphere in measurement chamber: Nitrogen (50 mL/min)
Temperature rising rate: 5°C/min
Measurement start temperature: -100°C
Measurement end temperature: 200°C
Sample pan: Aluminum pan Mass of measurement sample: 5 mg
Calculation of Tg: Tg is calculated by rounding off the decimal point of the intermediate temperature between the descending start point and the descending end point of the DSC chart.

The water content of the polymer constituting the binder used in the present invention is preferably 100 ppm (mass basis) or less, and Tg is preferably 100° C. or less.
Further, the polymer constituting the binder used in the present invention may be crystallized and dried, or the polymer solution may be used as it is. It is preferable that the amount of metal-based catalyst (urethane-forming or polyester-forming catalyst = tin, titanium, bismuth) is small. The metal concentration in the copolymer is preferably 100 ppm (mass basis) or less by reducing the amount during the polymerization or removing the catalyst by crystallization.

The solvent used in the polymerization reaction of the polymer is not particularly limited. It is desirable to use a solvent that does not react with the inorganic solid electrolyte and the active material and that does not decompose them. For example, hydrocarbon solvents (toluene, heptane, xylene), ester solvents (ethyl acetate, propylene glycol monomethyl ether acetate), ether solvents (tetrahydrofuran, dioxane, 1,2-diethoxyethane), ketone solvents (acetone) , Methyl ethyl ketone, cyclohexanone), a nitrile solvent (acetonitrile, propionitrile, butyronitrile, isobutyronitrile), a halogen solvent (dichloromethane, chloroform) and the like can be used.

The weight average molecular weight of the polymer constituting the binder used in the present invention is preferably 10,000 or more, more preferably 20,000 or more, still more preferably 50,000 or more. The upper limit is preferably 1,000,000 or less, more preferably 200,000 or less, still more preferably 100,000 or less.
In the present invention, the molecular weight of a polymer means the weight average molecular weight unless otherwise specified.

The content of the binder in the solid electrolyte composition for an all-solid secondary battery is 100% by mass of the solid component in view of the good interfacial resistance reduction property and its maintainability when used in the all-solid secondary battery. 0.01 mass% or more is preferable, 0.1 mass% or more is more preferable, and 1 mass% or more is further preferable. From the viewpoint of battery characteristics, the upper limit is preferably 20% by mass or less, more preferably 10% by mass or less, and further preferably 10% by mass or less.
In the present invention, the mass ratio [(mass of the inorganic solid electrolyte+mass of the electrode active material)/mass of the binder] of the total mass (total amount) of the inorganic solid electrolyte and the electrode active material to be contained as necessary with respect to the mass of the binder is The range of 1,000 to 1 is preferable. This ratio is more preferably 500 to 2, and even more preferably 100 to 10.

It is also preferable that the binder used in the present invention is polymer particles that retain the particle shape. In the present invention, poly(meth)acrylate (PMMA), poly(methyl methacrylate-methacrylic acid) copolymer (PMMA-PMA) or poly(methyl methacrylate-ethyl methacrylate) copolymer (PMMA) is used. -PHM) is preferably used.
Here, the term “polymer particles” refers to particles which are not completely dissolved even when added to a dispersion medium described later, are dispersed in the dispersion medium in a particle state, and have an average particle diameter of more than 0.01 μm.

The shape of the polymer particles is not limited as long as the polymer particles remain solid. The polymer particles may be monodisperse or polydisperse. The polymer particles may have a spherical shape, a flat shape, or an amorphous shape. The surface of the polymer particles may be smooth or may have an uneven shape. The polymer particles may have a core-shell structure, and the core (inner core) and the shell (outer shell) may be made of the same material or different materials. It may be hollow, and the hollow ratio is not limited.

The polymer particles can be synthesized by a method of polymerizing in the presence of a surfactant, an emulsifier or a dispersant, and a method of precipitating in a crystalline form as the molecular weight increases.
Also, a method of mechanically crushing an existing polymer or a method of reprecipitating a polymer solution into fine particles may be used.

The average particle diameter of the polymer particles is preferably 0.01 μm to 100 μm, more preferably 0.05 μm to 50 μm, further preferably 0.1 μm to 20 μm, and particularly preferably 0.2 μm to 10 μm.

Unless otherwise specified, the average particle size of the polymer particles used in the present invention is based on the measurement conditions and definitions described below.
The polymer particles are prepared by diluting a 1% by mass dispersion liquid in a 20 ml sample bottle using an arbitrary solvent (dispersion medium used for preparation of a solid electrolyte composition for all solid state secondary batteries, for example, heptane). The diluted dispersion sample is irradiated with ultrasonic waves of 1 kHz for 10 minutes, and immediately thereafter, used for the test. Using this dispersion liquid sample, using a laser diffraction/scattering particle size distribution analyzer LA-920 (trade name, manufactured by HORIBA), data was captured 50 times using a measuring quartz cell at a temperature of 25° C., Let the obtained volume average particle diameter be an average particle diameter. For other detailed conditions and the like, refer to the description of JISZ8828:2013 “Particle size analysis-dynamic light scattering method” as necessary. Five samples are prepared and measured for each level, and the average value is adopted.
Incidentally, the measurement from the prepared all-solid-state secondary battery, for example, after disassembling the battery and peeling the electrode, perform the measurement according to the measuring method of the average particle diameter of the polymer particles for the electrode material, in advance, This can be performed by excluding the measured value of the average particle size of particles other than the polymer particles that have been measured.

The binder used in the present invention may be a commercially available product. It can also be prepared by a conventional method.

(Dispersion medium)
The solid electrolyte composition of the present invention also preferably contains a dispersion medium.
The dispersion medium may be any one as long as it can disperse each of the above components, and examples thereof include various organic solvents, and those which dissolve the metathesis catalyst (C) are preferable.
Specific examples of the dispersion medium include the following.
Examples of the alcohol compound solvent include methyl alcohol, ethyl alcohol, 1-propyl alcohol, 2-propyl alcohol, 2-butanol, ethylene glycol, propylene glycol, glycerin, 1,6-hexanediol, cyclohexanediol, sorbitol, xylitol, Examples thereof include 2-methyl-2,4-pentanediol, 1,3-butanediol, and 1,4-butanediol.
As the ether compound solvent, alkylene glycol alkyl ether (ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol, dipropylene glycol, propylene glycol monomethyl ether, diethylene glycol monomethyl ether, triethylene glycol, polyethylene glycol, propylene glycol monomethyl ether, dipropylene glycol Glycol monomethyl ether, tripropylene glycol monomethyl ether, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether, etc.), dialkyl ether (dimethyl ether, diethyl ether, diisopropyl ether, dibutyl ether, etc.), alkylaryl ether (anisole, etc.), cyclic ether (tetrahydrofuran, dioxane) (Including 1,2-, 1,3- and 1,4-isomers) and the like).
Examples of the amide compound solvent include N,N-dimethylformamide, N-methyl-2-pyrrolidone, 2-pyrrolidinone, 1,3-dimethyl-2-imidazolidinone, 2-pyrrolidinone, ε-caprolactam, formamide, and N. -Methylformamide, acetamide, N-methylacetamide, N,N-dimethylacetamide, N-methylpropanamide, hexamethylphosphoric triamide and the like can be mentioned.
Examples of the amino compound solvent include triethylamine, diisopropylethylamine, tributylamine and the like.
Examples of the ketone compound solvent include acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone.
Examples of the aromatic compound solvent include benzene, toluene, xylene, mesitylene and the like.
Examples of the aliphatic compound solvent include hexane, heptane, octane, decane and the like.
Examples of the nitrile compound solvent include acetonitrile, propyronitrile, isobutyronitrile and the like.
Examples of the ester compound solvent include ethyl acetate, butyl acetate, propyl acetate, butyl butyrate, and butyl pentanoate.
Examples of the non-aqueous dispersion medium include the above aromatic compound solvents and aliphatic compound solvents.

In the present invention, among them, an amino compound solvent, an ether compound solvent, a ketone compound solvent, an aromatic compound solvent and an aliphatic compound solvent are preferable, and an ether compound solvent, an aromatic compound solvent and an aliphatic compound solvent are more preferable. In the present invention, it is preferable to use the sulfide-based inorganic solid electrolyte and further select the above specific organic solvent. By selecting this combination, a functional group active to the sulfide-based inorganic solid electrolyte is not contained, so that the sulfide-based inorganic solid electrolyte can be stably handled, which is preferable. In particular, a combination of a sulfide-based inorganic solid electrolyte and an aliphatic compound solvent is preferable.

The dispersion medium has a boiling point at atmospheric pressure (1 atm) of preferably 50°C or higher, and more preferably 70°C or higher. The upper limit is preferably 250°C or lower, more preferably 220°C or lower.
The dispersion medium may be used alone or in combination of two or more.

In the present invention, the content of the dispersion medium in the solid electrolyte composition can be appropriately set in consideration of the balance between the viscosity of the solid electrolyte composition and the drying load. Generally, 20 to 99 mass% is preferable, 25 to 70 mass% is more preferable, and 30 to 60 mass% is particularly preferable in the solid electrolyte composition.

(Active material)
The solid electrolyte composition of the present invention may contain an active material capable of inserting and releasing ions of a metal element belonging to Group 1 or 2 of the periodic table. Examples of the active material include a positive electrode active material and a negative electrode active material, which will be described below. A transition metal oxide that is a positive electrode active material or a metal oxide that is a negative electrode active material is preferable.
In the present invention, the solid electrolyte composition containing the active material (positive electrode active material, negative electrode active material) may be referred to as an electrode layer composition (positive electrode layer composition, negative electrode layer composition).

-Cathode active material-
The positive electrode active material that may be contained in the solid electrolyte composition of the present invention is preferably one that can reversibly insert/release lithium ions. The material is not particularly limited as long as it has the above characteristics, and may be a transition metal oxide, an element such as sulfur that can be complexed with Li, or the like.
Among them, as the positive electrode active material, a transition metal oxide having preferably used a transition metal oxide, a transition metal element ^M a a (Co, Ni, Fe, Mn , Cu, and one or more elements selected from V) The thing is more preferable. Further, the element M ^b (elements of Group 1 (Ia) other than lithium, elements of Group 2 (IIa), elements of Group 2 (IIa), Al, Ga, In, Ge, Sn, Pb, Elements such as Sb, Bi, Si, P and B) may be mixed. The mixing amount, 0~30mol% is preferred for the amount of the transition metal element ^{M a (100mol%).} It is more preferable that the mixture is synthesized so that the molar ratio of Li/Ma is 0.3 to 2.2.
Specific examples of the transition metal oxide include (MA) a transition metal oxide having a layered rock salt type structure, (MB) a transition metal oxide having a spinel type structure, (MC) a lithium-containing transition metal phosphate compound, (MD) ) Lithium-containing transition metal halogenated phosphoric acid compounds, (ME) lithium-containing transition metal silicic acid compounds, and the like.

Specific examples of the transition metal oxide having a (MA) layered rock salt structure include LiCoO ₂ (lithium cobalt oxide [LCO]) and LiNi ₂ O ₂ (lithium nickelate) LiNi _0.85 Co _0.10 Al _0.05. O ₂ (lithium nickel cobalt aluminum oxide [NCA]), LiNi _1/3 Co _1/3 Mn _1/3 O ₂ (lithium nickel manganese cobalt oxide [NMC]), LiNi _0.5 Mn _0.5 O ₂ (manganese) Lithium nickelate).
Specific examples of the transition metal oxide having a (MB) spinel structure include LiCoMnO _4, Li ₂ FeMn ₃ O ₈ , Li ₂ CuMn ₃ O ₈ , Li ₂ CrMn ₃ O _{8, and} Li ₂ NiMn ₃ O _8. ..
Examples of the (MC) lithium-containing transition metal phosphate compound include, for example, olivine-type iron phosphate salts such as LiFePO ₄ and Li ₃ Fe ₂ (PO ₄ ) ₃ , iron pyrophosphates such as LiFeP ₂ O ₇ and LiCoPO _4. Cobalt phosphates, Li ₃ V ₂ (PO ₄ ) ₃ (lithium vanadium phosphate), and other monoclinic nasicon-type vanadium phosphate salts.
The (MD) lithium-containing transition metal halogenated phosphate compound, for _example, Li 2 FePO ₄ F such fluorinated phosphorus iron _salt, Li 2 MnPO ₄ hexafluorophosphate manganese salts such as _F, Li 2 CoPO ₄ F And the like, such as cobalt fluorophosphates.
Examples of the (ME) lithium-containing transition metal silicic acid compound include Li ₂ FeSiO ₄ , Li ₂ MnSiO ₄ , and Li ₂ CoSiO ₄ .
In the present invention, a transition metal oxide having a (MA) layered rock salt structure is preferable, and LCO or NMC is more preferable.

The shape of the positive electrode active material is not particularly limited, but a particle shape is preferable. The volume average particle diameter (sphere-converted average particle diameter) of the positive electrode active material is not particularly limited. For example, it can be 0.1 to 50 μm. A normal crusher and/or a classifier may be used to make the positive electrode active material have a predetermined particle size. The positive electrode active material obtained by the firing method may be used after washing with water, an acidic aqueous solution, an alkaline aqueous solution, or an organic solvent. The volume average particle diameter (sphere-converted average particle diameter) of the positive electrode active material particles can be measured using a laser diffraction/scattering particle size distribution measuring device LA-920 (trade name, manufactured by HORIBA).

The positive electrode active material may be used alone or in combination of two or more.
When forming the positive electrode active material layer, the mass (mg) (unit weight) of the positive electrode active material per unit area (cm ² ) of the positive electrode active material layer is not particularly limited. It can be appropriately determined according to the designed battery capacity.

The content of the positive electrode active material in the solid electrolyte composition is not particularly limited and is preferably 10 to 95% by mass, more preferably 30 to 90% by mass, and further preferably 50 to 85% by mass in 100% by mass of the solid content. It is preferably 70 to 80% by mass, and particularly preferably.

-Negative electrode active material-
The negative electrode active material that may be contained in the solid electrolyte composition of the present invention is preferably one that can reversibly insert/release lithium ions. The material is not particularly limited as long as it has the above-mentioned characteristics, and carbonaceous materials, metal oxides such as tin oxide and silicon oxide, metal composite oxides, simple lithium and lithium alloys such as lithium aluminum alloys, and Sn. , Si and In, and other metals capable of forming an alloy with lithium. Among them, carbonaceous materials or lithium composite oxides are preferably used from the viewpoint of reliability. Further, the metal composite oxide is preferably capable of inserting and extracting lithium. The material is not particularly limited, but it is preferable that titanium and/or lithium is contained as a constituent component from the viewpoint of high current density charge/discharge characteristics.

The carbonaceous material used as the negative electrode active material is a material consisting essentially of carbon. For example, petroleum pitch, carbon black such as acetylene black (AB), graphite (natural graphite, artificial graphite such as vapor-grown graphite) and various synthetic resins such as PAN (polyacrylonitrile) resin and furfuryl alcohol resin. The carbonaceous material obtained by firing can be mentioned. Further, various carbon fibers such as PAN-based carbon fibers, cellulose-based carbon fibers, pitch-based carbon fibers, vapor-grown carbon fibers, dehydrated PVA (polyvinyl alcohol)-based carbon fibers, lignin carbon fibers, glassy carbon fibers, and activated carbon fibers. Examples thereof include mesophase microspheres, graphite whiskers, and tabular graphite.

As the metal oxide and the metal composite oxide applied as the negative electrode active material, an amorphous oxide is particularly preferable, and chalcogenite which is a reaction product of a metal element and an element of Group 16 of the periodic table is also preferably used. To be The term "amorphous" as used herein means an X-ray diffraction method using CuKα rays, which has a broad scattering band having an apex in the region of 20 to 40° at a 2θ value, and a crystalline diffraction line. May have. The strongest intensity of the crystalline diffraction lines seen at 2θ values of 40° or more and 70° or less is 100 times or less than the diffraction line intensity of the apex of the broad scattering band seen at 20° or more and 40° or less of 2θ Is more preferable, it is more preferably 5 times or less, and it is particularly preferable not to have a crystalline diffraction line.

Among the compounds consisting of the above amorphous oxides and chalcogenides, amorphous oxides of metalloid elements and chalcogenides are more preferable, and elements of Group 13 (IIIB) to 15 (VB) of the periodic table, Al , Ga, Si, Sn, Ge, Pb, Sb, Bi, or a combination of two or more thereof, and chalcogenide are particularly preferable. Specific examples of preferable amorphous oxides and chalcogenides include Ga ₂ O ₃ , SiO, GeO, SnO, SnO ₂ , PbO, PbO ₂ , Pb ₂ O ₃ , Pb ₂ O ₄ , Pb ₃ O ₄ , and _{Sb 2 O 3, Sb 2 O} 4, Sb 2 O 8 Bi 2 O 3, Sb 2 O 8 Si 2 O 3, Bi 2 O 4, SnSiO 3, GeS, SnS, SnS 2, PbS, PbS 2, Sb 2 Preferable examples are S ₃ , Sb ₂ S ₅ , and SnSiS ₃ . Further, these may be composite oxides with lithium oxide, for example, Li ₂ SnO ₂ .

It is also preferable that the negative electrode active material contains a titanium atom. More specifically, Li ₄ Ti ₅ O ₁₂ (lithium titanate [LTO]) is excellent in rapid charge/discharge characteristics because the volume change during storage and release of lithium ions is small, and deterioration of the electrode is suppressed, and lithium ion secondary It is preferable in that the life of the battery can be improved.

In the present invention, hard carbon or graphite is preferably used, and graphite is more preferably used. In the present invention, the carbonaceous materials may be used alone or in combination of two or more.

The shape of the negative electrode active material is not particularly limited, but a particle shape is preferable. The average particle diameter of the negative electrode active material is preferably 0.1 to 60 μm. A normal crusher and/or a classifier are used to obtain a predetermined particle size. For example, a mortar, a ball mill, a sand mill, a vibrating ball mill, a satellite ball mill, a planetary ball mill, a swirling airflow type jet mill and a sieve are preferably used. At the time of pulverization, wet pulverization in which water or an organic solvent such as methanol is allowed to coexist can be carried out as necessary. It is preferable to perform classification in order to obtain a desired particle size. The classification method is not particularly limited, and a sieve, an air classifier, or the like can be used as necessary. Classification can be carried out both dry and wet. The average particle diameter of the negative electrode active material particles can be measured by the same method as the method for measuring the volume average particle diameter of the positive electrode active material described above.

The chemical formula of the compound obtained by the above-mentioned calcination method can be calculated from the mass difference of the powders before and after calcination as a simple method, and as a simple method.

Examples of the negative electrode active material that can be used together with the amorphous oxide negative electrode active material centered on Sn, Si, or Ge include carbon materials capable of inserting and extracting lithium ions or lithium metal, lithium, lithium alloys, and lithium. A metal that can be alloyed is preferable.

In the present invention, it is also preferable to apply a Si-based negative electrode. Generally, a Si negative electrode can occlude more Li ions than a carbon negative electrode (graphite, acetylene black, etc.). That is, the storage amount of Li ions per unit weight increases. Therefore, the battery capacity can be increased. As a result, there is an advantage that the battery drive time can be lengthened.

The negative electrode active material may be used alone or in combination of two or more.
When forming the negative electrode active material layer, the mass (mg) (unit weight) of the negative electrode active material per unit area (cm ² ) of the negative electrode active material layer is not particularly limited. It can be appropriately determined according to the designed battery capacity.

The content of the negative electrode active material in the solid electrolyte composition is not particularly limited, and is preferably 10 to 80% by mass, more preferably 20 to 80% by mass, and 30 to 80% in terms of solid content of 100% by mass. It is more preferably mass%, and further preferably 40 to 75 mass%.

(Conductive agent)
The solid electrolyte composition of the present invention may optionally contain a conductive auxiliary agent used for improving the electronic conductivity of the active material and the like, if necessary. As the conductive auxiliary agent, a general conductive auxiliary agent can be used. For example, electron conductive materials such as graphites such as natural graphite and artificial graphite, carbon blacks such as acetylene black, Ketjen black and furnace black, amorphous carbon such as needle coke, vapor grown carbon fiber and carbon nanotube. Carbon fibers such as, carbonaceous materials such as graphene and fullerene, metal powders such as copper and nickel, metal fibers may be used, and conductive polymers such as polyaniline, polypyrrole, polythiophene, polyacetylene, and polyphenylene derivatives. May be used. One of these may be used, or two or more may be used.
When the solid electrolyte composition of the present invention contains a conduction aid, the content of the conduction aid in the solid electrolyte composition is preferably 0 to 10% by mass.

(Lithium salt)
The solid electrolyte composition of the present invention also preferably contains a lithium salt (supporting electrolyte).
The lithium salt is preferably a lithium salt that is usually used in products of this type, and is not particularly limited, and examples thereof include the lithium salts described for the binder particles.
This lithium salt is not contained in the binder particles (the polymer forming the binder particles) (existing alone in the solid electrolyte layer composition), and thus the lithium salt contained in the binder particles. Is different from.
The content of the lithium salt is preferably 0 parts by mass or more and more preferably 5 parts by mass or more with respect to 100 parts by mass of the solid electrolyte. The upper limit is preferably 50 parts by mass or less, and more preferably 20 parts by mass or less.

(Dispersant)
The solid electrolyte composition of the present invention may contain a dispersant. By adding a dispersant, even if the concentration of either the electrode active material or the inorganic solid electrolyte is high, the aggregation thereof can be suppressed, and a uniform active material layer and solid electrolyte layer can be formed.
As the dispersant, those usually used in all solid state secondary batteries can be appropriately selected and used. For example, it is composed of a low molecular weight or oligomer having a molecular weight of 200 or more and less than 3000 and contains a functional group represented by the functional group group (I) and an alkyl group having 8 or more carbon atoms or an aryl group having 10 or more carbon atoms in the same molecule. Those are preferable.
Functional group (I): acidic group, group having basic nitrogen atom, (meth)acryloyl group, (meth)acrylamide group, alkoxysilyl group, epoxy group, oxetanyl group, isocyanate group, cyano group, mercapto group and hydroxy Group (acidic group, group having basic nitrogen atom, alkoxysilyl group, cyano group, mercapto group and hydroxy group are preferable, and carboxy group, sulfonic acid group, cyano group, amino group and hydroxy group are more preferable.)
In the all solid state secondary battery of the present invention, when there is a layer containing a dispersant, the content of the dispersant in the layer is preferably 0.2 to 10% by mass.

(Preparation of solid electrolyte composition)
The solid electrolyte composition of the present invention is prepared by mixing or adding an inorganic solid electrolyte (A), a compound (B) and a metathesis catalyst (C), and optionally other components such as an active material and a dispersion medium, Can be prepared. For example, it can be produced by mixing the above components using various mixers. The mixing conditions are not particularly limited, and examples thereof include a ball mill, a bead mill, a planetary mixer, a blade mixer, a roll mill, a kneader, and a disc mill.
In the method for producing a solid electrolyte composition, the timing of introducing the metathesis catalyst may be before mixing (for example, ball mill) or during preparing slurry after performing mixing (for example, ball mill).

(Metathesis reaction)
The compound (B) having a non-aromatic carbon-carbon unsaturated bond is polymerized by the progress of the metathesis reaction in the presence of the metathesis catalyst (C).
In particular, when the compound (B) has two or more non-aromatic unsaturated bonds in one molecule, the cross-metathesis reaction proceeds, so that the non-aromatic unsaturated bonds of the compound (B) are , A new non-aromatic unsaturated bond is formed. Therefore, the solid electrolyte composition of the present invention is presumed to cure when the cross-metathesis reaction (crosslinking) progresses to form a network polymer and gel, and the cross-metathesis reaction (crosslinking) is completed. ..

Specifically, the structure represented by the following general formula (3) is obtained by the progress of the cross metathesis reaction (hereinafter, simply referred to as metathesis reaction) of the compound (B) represented by the above formula (1a). It is considered that a compound (B2) having a unit is produced. The structural unit represented by the following general formula (3) has a non-aromatic carbon-carbon unsaturated bond.

In the above formula, Z ¹ represents the following general formula (3-1), and Z ² represents the following general formula (3-2). R ³ represents a hydrogen atom, an alkyl group or an aryl group. L ³ represents a single bond or a divalent linking group. n and m are integers of 1 to 20, and l is an integer of 0 to 20. X represents an organic group having a valence of n+m+1.

In the above formula, R ¹ and R ² represent a hydrogen atom, an alkyl group, an alkenyl group or an aryl group. L ¹ and L ² represent a single bond or a divalent linking group. * Indicates a binding site with X.

The alkyl group, alkenyl group and aryl group for R ¹ and R ² in the general formula (3) and the alkyl group and aryl group for R ³ are the alkyl group for R ¹³ and R ²³ in the above general formula (1a). , Alkenyl group and aryl group, and the same as the alkyl group and aryl group for R ³¹ .
In addition, L ¹ , L ² and L ³ , n, m and l in the general formula (3) and X are L ¹¹ , L ²¹ and L ³¹ , n, m and l in the above general formula (1a). 1 and synonymous with X.

The metathesis reaction may occur in any of a pulverizing step using a ball mill when preparing a composition, a heating step different from the composition preparation, and a step of heating a sheet coated with the composition. The reaction is preferably completed in the state of the solid electrolyte-containing sheet produced by coating.
Regarding the reaction conditions using the metathesis catalyst (C) of the compound (B), a conventional method in the metathesis reaction is used, but for example, from the viewpoint of completing the metathesis reaction, the reaction temperature is preferably 50°C to 180°C, C. to 120.degree. C. is more preferable, the reaction time is preferably 0.1 hour to 2 hours, and more preferably 0.5 hour to 1 hour.

In the all-solid secondary battery and the sheet for all-solid secondary battery, the unsaturated bond ratio of the compound (B2) calculated by the following formula (5) preferably satisfies the following formula (6).
The number of non-aromatic carbon-carbon unsaturated bonds in the compound (B2) is set to 1 in the case of double bond and 2 in the case of triple bond, and the unsaturated bond ratio is calculated by the following formula (5). R.

Unsaturated bond ratio=(sum of the number of non-aromatic carbon-carbon unsaturated bonds in compound (B2))/(sum of the number of all carbon-carbon bonds in compound (B2))×100 formula ( 5)
1% <unsaturated bond rate <90% Formula (6)

In the present invention, the unsaturated bond ratio of the compound (B2) is more preferably 2%<unsaturated bond ratio<50%, more preferably 3%<unsaturated bond ratio<20%.

Specific examples of the structural unit represented by the general formula (3) in the compound (B2) include the following structural units, but the present invention is not construed as being limited thereto. In addition, in the structural formulas below, the part marked with "**" corresponds to the terminal site in the structural unit represented by the general formula (3-1) or (3-2). Further, the number of subscripts in () or [] represents mol %. However, the number in parentheses () in [] indicates the number of repeating units.

[Solid electrolyte containing sheet]
The solid electrolyte-containing sheet (solid electrolyte sheet for an all-solid secondary battery) of the present invention comprises an inorganic solid electrolyte having ion conductivity of a metal belonging to Group 1 or 2 of the periodic table, and the above-mentioned general formula ( Compound (B2) having a structural unit having a non-aromatic carbon-carbon unsaturated bond represented by 3) and a metathesis catalyst (C) residue of Ru, Mo and/or W metal of 10 ppm or more ( Preferably 10,000 ppm or less).

As a method for detecting the amount of catalyst before metathesis crosslinking and the amount of catalyst residue after metathesis crosslinking, there is a method of determining from the amount of elements contained in Ru, Mo, and W metals. The content of elements contained in Ru, Mo, and W metals is, for example, X-ray photoelectron spectroscopy, Auger electron spectroscopy, ICP (Inductively Coupled Plasma)-mass spectrometry, ICP-emission spectrometry, atomic absorption spectrometry, fluorescent X-ray analysis. It can be measured by an analysis method, a neutron activation analysis method, or the like.

The metathesis catalyst (C) residue means a compound or partial structure containing a metal element derived from the metathesis catalyst (C). The metathesis catalyst (C) residue may be present in any structure as long as it contains a metal element (Ru, Mo and/or W metal). For example, it may be incorporated in the compound (B2). It is assumed that they exist as a carbene metal complex.

The compound (B2) may be contained in one kind or two or more kinds.

The content of the compound (B2) in the solid electrolyte-containing sheet is 0.05% by mass to 30% by mass at 100% by mass of all solid components in consideration of both battery performance and reduction in interfacial resistance and maintaining effect. %, preferably 0.1% by mass to 20% by mass, more preferably 1% by mass to 10% by mass.

[Sheet for all solid state secondary battery]
The solid electrolyte-containing sheet of the present invention can be suitably used for an all-solid-state secondary battery, and includes various aspects depending on its application. For example, a sheet preferably used for a solid electrolyte layer (also referred to as a solid electrolyte sheet for all solid state secondary battery), a sheet preferably used for an electrode or a laminate of an electrode and a solid electrolyte layer (electrode sheet for all solid state secondary battery) Etc. In the present invention, these various sheets may be collectively referred to as an all-solid-state secondary battery sheet.

The sheet for all-solid secondary batteries is a sheet having a solid electrolyte layer or an active material layer (electrode layer) on a base material. The sheet for an all-solid secondary battery may have other layers as long as it has a base material and a solid electrolyte layer or an active material layer, but one having an active material layer is an all-solid secondary battery described later. Classify as electrode sheet for secondary battery. Examples of the other layer include a protective layer, a current collector, a coat layer (current collector, solid electrolyte layer, active material), and the like.
As a solid electrolyte sheet for all-solid secondary battery, for example, for forming a solid electrolyte layer of the all-solid secondary battery of the present invention, on the substrate, a solid electrolyte layer, and optionally a protective layer in this order. The sheet which has is mentioned.
The base material is not particularly limited as long as it can support the solid electrolyte layer, and examples thereof include sheet materials (plate-like materials) such as the materials, organic materials, and inorganic materials described for the current collector. Examples of the organic material include various polymers, and specific examples thereof include polyethylene terephthalate, polypropylene, polyethylene, and cellulose. Examples of the inorganic material include glass and ceramics.

The structure and layer thickness of the solid electrolyte layer of the sheet for all-solid-state secondary battery are the same as the structure and layer thickness of the solid electrolyte layer described later in the all-solid-state secondary battery of the present invention.
This sheet is obtained by forming (coating and drying) the solid electrolyte composition of the present invention on a substrate (which may be through another layer) to form a solid electrolyte layer on the substrate. To be
Here, the solid electrolyte composition of the present invention can be prepared by the above method.

The electrode sheet for an all-solid secondary battery of the present invention (also simply referred to as “the electrode sheet of the present invention”) is a metal as a current collector for forming an active material layer of the all-solid secondary battery of the present invention. It is an electrode sheet having an active material layer on a foil. This electrode sheet is usually a sheet having a current collector and an active material layer, but an embodiment having a current collector, an active material layer and a solid electrolyte layer in this order, as well as a current collector, an active material layer and a solid electrolyte. A mode having a layer and an active material layer in this order is also included.
The constitution and layer thickness of each layer constituting the electrode sheet are the same as the constitution and layer thickness of each layer described later in the all solid state secondary battery of the present invention.
The electrode sheet is obtained by forming (coating and drying) the solid electrolyte composition of the present invention containing an active material on a metal foil to form an active material layer on the metal foil. The method for preparing the solid electrolyte composition containing the active material is the same as the method for preparing the solid electrolyte composition, except that the active material is used.
The active material layer and/or the solid electrolyte layer formed of the solid electrolyte composition of the present invention preferably has the same component species and content ratio as described above, except that the compound (B) is replaced with the compound (B2). The same as in the solid content of the solid electrolyte composition.

[All solid state secondary battery]
The all-solid secondary battery of the present invention has a positive electrode, a negative electrode facing the positive electrode, and a solid electrolyte layer between the positive electrode and the negative electrode. The positive electrode has a positive electrode active material layer on the positive electrode current collector. The negative electrode has a negative electrode active material layer on the negative electrode current collector.
At least one layer of the negative electrode active material layer, the positive electrode active material layer, and the solid electrolyte layer is preferably formed of the solid electrolyte composition of the present invention, and above all, all layers are formed of the solid electrolyte composition of the present invention. More preferably.
The active material layer or the solid electrolyte layer formed of the solid electrolyte composition is preferably the same as that in the above-mentioned sheet for all-solid-state secondary batteries with respect to the component species contained and the content ratio thereof.
Hereinafter, preferred embodiments of the present invention will be described, but the present invention is not limited thereto.

FIG. 1 is a schematic cross-sectional view showing an all-solid-state secondary battery (lithium ion secondary battery) according to a preferred embodiment of the present invention. The all-solid-state secondary battery 10 of the present embodiment includes a negative electrode current collector 1, a negative electrode active material layer 2, a solid electrolyte layer 3, a positive electrode active material layer 4, and a positive electrode current collector 5 stacked in this order when viewed from the negative electrode side. The adjacent layers are in direct contact with each other. By adopting such a structure, during charging, electrons (e ⁻ ) are supplied to the negative electrode side, and lithium ions (Li ⁺ ) are accumulated there. On the other hand, during discharge, lithium ions (Li ⁺ ) accumulated in the negative electrode are returned to the positive electrode side, and electrons can be supplied to the operating portion 6. In the example of the all-solid-state secondary battery shown in the figure, a light bulb is adopted as a model in the operating portion 6, and the light bulb is adapted to be lit by discharging.

[Positive electrode active material layer, solid electrolyte layer, negative electrode active material layer]
In the all-solid secondary battery 10, any of the positive electrode active material layer, the solid electrolyte layer, and the negative electrode active material layer is formed of the solid electrolyte composition of the present invention.
That is, when the solid electrolyte layer 3 is formed of the solid electrolyte composition of the present invention, the solid electrolyte layer 3 contains an inorganic solid electrolyte, a compound (B2), and a metathesis catalyst residue. The solid electrolyte layer usually does not contain a positive electrode active material and/or a negative electrode active material. In the solid electrolyte layer 3, the compound (B2) is present between the inorganic solid electrolyte and the solid particles such as the active material contained in the adjacent active material layer, whereby the interfacial resistance between the solid particles is reduced. , The binding is high.
When the positive electrode active material layer 4 and/or the negative electrode active material layer 2 is formed of the solid electrolyte composition of the present invention, the positive electrode active material layer 4 and the negative electrode active material layer 2 are respectively the positive electrode active material and the negative electrode active material. And further contains an inorganic solid electrolyte, a compound (B2), and a metathesis catalyst residue. When the active material layer contains an inorganic solid electrolyte, ionic conductivity can be improved. In the active material layer, the compound (B2) is present between the solid particles and the like, whereby the interfacial resistance between them is reduced and the binding property is enhanced.
The inorganic solid electrolyte contained in the positive electrode active material layer 4, the solid electrolyte layer 3, and the negative electrode active material layer 2, the compound (B2) which may be contained, and the metathesis catalyst residue are the same or different from each other. May be.
In the present invention, either or both of the positive electrode active material layer and the negative electrode active material layer may be simply referred to as an active material layer or an electrode active material layer. Further, either or both of the positive electrode active material and the negative electrode active material may be simply referred to as an active material or an electrode active material.

In the present invention, a positive electrode active material layer, a solid electrolyte layer, a negative electrode active material prepared by using a solid electrolyte composition containing the compound (B), a metathesis catalyst, and an inorganic solid electrolyte and solid particles such as an active material. Each layer of the layers can improve the binding property between solid particles, and as a result, can also achieve good cycle characteristics in an all-solid secondary battery.
Although its action and mechanism are not clear, it can be considered as follows.
That is, a polymer of the compound (B) three-dimensionally crosslinked by heating and curing (metathesis reaction) the compound (B) and the metathesis catalyst in a state where solid particles such as an inorganic solid electrolyte are dispersed, that is, the compound (B2) is formed. When the solid particles are entangled in the three-dimensional network structure of the compound (B2), the three-dimensionally crosslinked polymer and the solid particles are dispersed, or a linear polymer is formed. It is considered that the binding property between the solid particles is improved as compared with.
Further, even when the charge and discharge are repeated, the solid particles are present in the three-dimensionally cross-linked compound (B2), so that the contact between the solid particles is maintained and the increase in the interfacial resistance between the solid particles is suppressed. It is thought to be. Therefore, it is considered that the all solid state secondary battery exhibits excellent cycle characteristics. In particular, when particles of an active material that expands and contracts due to charge and discharge are included, it is considered that the increase in interfacial resistance between solid particles is more effectively suppressed, and the all solid state secondary battery exhibits more excellent cycle characteristics.

The thicknesses of the positive electrode active material layer 4, the solid electrolyte layer 3, and the negative electrode active material layer 2 are not particularly limited. Considering the dimensions of a general battery, the thickness of each layer is preferably 10 to 1,000 μm, more preferably 20 μm or more and less than 500 μm. In the all solid state secondary battery of the present invention, the thickness of at least one of the positive electrode active material layer 4, the solid electrolyte layer 3, and the negative electrode active material layer 2 is more preferably 50 μm or more and less than 500 μm.

[Current collector (metal foil)]
The positive electrode current collector 5 and the negative electrode current collector 1 are preferably electron conductors.
In the present invention, either or both of the positive electrode current collector and the negative electrode current collector may be simply referred to as a current collector.
As a material for forming the positive electrode current collector, in addition to aluminum, aluminum alloy, stainless steel (SUS), nickel, titanium, etc., aluminum, stainless steel surface treated with carbon, nickel, titanium or silver ( (Thin film formed) is preferable, and among them, aluminum and aluminum alloys are more preferable.
As a material for forming the negative electrode current collector, in addition to aluminum, copper, copper alloy, stainless steel (SUS), nickel, titanium, etc., carbon, nickel, titanium or aluminum, copper, copper alloy, stainless steel surface or Those treated with silver are preferable, and aluminum, copper, copper alloy, and stainless steel are more preferable.

The shape of the current collector is usually a film sheet shape, but a net, a punched shape, a lath body, a porous body, a foamed body, a molded body of fibers, and the like can also be used.
The thickness of the current collector is not particularly limited, but is preferably 1 to 500 μm. Further, it is also preferable that the surface of the current collector is made uneven by surface treatment.

In the present invention, a functional layer or member is appropriately interposed or disposed between or outside each layer of the negative electrode current collector, the negative electrode active material layer, the solid electrolyte layer, the positive electrode active material layer and the positive electrode current collector. You may. Each layer may be composed of a single layer or multiple layers.

(Case)
By arranging the above layers, the basic structure of the all-solid-state secondary battery can be manufactured. Depending on the application, it may be used as it is as an all-solid-state secondary battery, but it is further enclosed in a suitable casing for use as a dry battery. The housing may be made of metal or resin (plastic). When using a metallic thing, an aluminum alloy and a thing made from stainless steel can be mentioned, for example. The metallic casing is preferably divided into a casing on the positive electrode side and a casing on the negative electrode side and electrically connected to the positive electrode current collector and the negative electrode current collector, respectively. It is preferable that the housing on the positive electrode side and the housing on the negative electrode side are joined and integrated via a gasket for preventing a short circuit.

[Production of solid electrolyte-containing sheet]
In the present invention, the sheet coated with the solid electrolyte composition containing the compound (B) having a non-aromatic carbon-carbon unsaturated bond and the metathesis catalyst (C) is heated to be non-aromatic. The compound having a carbon-carbon unsaturated bond undergoes a metathesis reaction to form a solid electrolyte-containing sheet containing the compound (B2) having a non-aromatic carbon-carbon unsaturated bond and the metathesis catalyst residue. It is preferable to form a structure in which solid particles such as a solid electrolyte and an active material are entangled in a network crosslinked body formed by the compound (B2), and finally cured.

From the above viewpoint, as the method for producing the solid electrolyte-containing sheet of the present invention, the following first and second aspects are preferably mentioned.
i) First aspect: a step (1a) of applying a solid electrolyte composition of the present invention onto a substrate to obtain a coated sheet,
A method for producing a solid electrolyte-containing sheet, which comprises a step (2a) of heating the coated sheet to 50° C. or higher to crosslink and cure the compound (B) having a non-aromatic carbon-carbon unsaturated bond by a metathesis reaction.
ii) Second aspect: a step (1b) of heating the solid electrolyte composition of the present invention to 50° C. or higher to bring the compound having a non-aromatic carbon-carbon unsaturated bond into the metathesis reaction initiation condition.
A method for producing a solid electrolyte-containing sheet, which comprises a step (2b) of applying the composition obtained in the step (1b) onto a substrate to crosslink and cure the composition.

In steps (2a) and (1b), heating to 50° C. or higher provides the conditions for starting the metathesis reaction of compound (B). Then, the metathesis reaction (crosslinking) proceeds, so that the solid electrolyte composition of the present invention becomes a gel. Further, the reaction (crosslinking) proceeds to crosslink and cure.
Here, the condition for starting the metathesis reaction means a condition under which the metathesis reaction can be started. Further, the crosslinking and curing means that the metathesis reaction (crosslinking) is sufficiently advanced to cure the gelled product to a cured product.
In the second aspect, the solid electrolyte composition of the present invention is subjected to a metathesis reaction initiation condition in step (1b), and the composition is thickened by the progress of the metathesis reaction. Therefore, it is possible to facilitate the step of applying the composition onto the substrate by adjusting the time for applying the composition obtained in step (1b) to step (2b).

From the above points, the heating conditions in the step (2a) are preferably 50° C. to 180° C., more preferably 80° C. to 160° C., and heating time is preferably 0.1 hour to 2 hours, and 0.5 hour. ~1 hour is more preferred. The heating conditions in step (1b) are preferably 50° C. to 100° C., more preferably 50° C. to 80° C., and heating time is preferably 0.1 hour to 1 hour, and 0.1 hour to 0. More preferably 5 hours.
In addition, in the step (2b), it is also preferable that after the coating on the substrate, the reaction is promoted by heating to cure the substrate. The heating conditions in this case are preferably 50° C. to 180° C., more preferably 80° C. to 160° C., and heating time is preferably 0.1 hour to 2 hours, more preferably 0.5 hour to 1 hour. ..

According to the above aspect, a solid electrolyte sheet for an all solid state secondary battery, which is a sheet containing a substrate and a solid electrolyte layer, can be produced.

For other processes such as coating, the method described in the production of the all-solid-state secondary battery described below can be used.

[Manufacture of all-solid-state secondary battery and sheet for all-solid-state secondary battery]
The electrode sheet for an all-solid secondary battery can be manufactured by the method for manufacturing a solid electrolyte-containing sheet described above.
That is, when the solid electrolyte composition of the present invention contains an active material, it is preferable that the solid electrolyte composition is applied not on the base material but on the current collector in the steps (1a) and (2b). In this case, an electrode sheet for an all-solid secondary battery, which is a sheet containing a solid electrolyte layer and an active material layer, can be produced.
Further, the production of the all-solid secondary battery can be performed by a conventional method except that the method for producing the solid electrolyte-containing sheet is included. Specifically, an all-solid secondary battery and an electrode sheet for an all-solid secondary battery can be produced by forming the above layers using the solid electrolyte composition of the present invention. Incidentally, any one of the positive electrode active material layer, the solid electrolyte layer and the negative electrode active material layer may be produced by the method for producing the solid electrolyte-containing sheet, and the other layers are the solid electrolyte composition not of the present invention. It may be used and prepared by a conventional method. This will be described in detail below.

The all solid state secondary battery of the present invention is a solid electrolyte composition or the like of the present invention is applied on a metal foil to be a current collector by a method including (intermediate) a step of forming (forming) a coating film, Can be manufactured.
For example, a solid electrolyte composition containing a positive electrode active material is applied as a positive electrode material (composition for a positive electrode layer) on a metal foil that is a positive electrode current collector to form a positive electrode active material layer, and an all-solid electrolyte layer is formed. A positive electrode sheet for a secondary battery is produced. Then, a solid electrolyte composition for forming a solid electrolyte layer is applied onto the positive electrode active material layer to form a solid electrolyte layer. Further, on the solid electrolyte layer, a solid electrolyte composition containing a negative electrode active material is applied as a negative electrode material (negative electrode layer composition) to form a negative electrode active material layer. To obtain an all-solid secondary battery having a structure in which a solid electrolyte layer is sandwiched between a positive electrode active material layer and a negative electrode active material layer by stacking a negative electrode current collector (metal foil) on the negative electrode active material layer. You can If necessary, this can be enclosed in a housing to form a desired all solid state secondary battery.
Further, the formation method of each layer is reversed, and the negative electrode active material layer, the solid electrolyte layer and the positive electrode active material layer are formed on the negative electrode current collector, and the positive electrode current collector is overlaid to manufacture an all-solid secondary battery. You can also do it.

Another method is as follows. That is, the positive electrode sheet for all solid state secondary batteries is produced as described above. In addition, a solid electrolyte composition containing a negative electrode active material is applied as a negative electrode material (negative electrode layer composition) onto a metal foil that is a negative electrode current collector to form a negative electrode active material layer. A negative electrode sheet for a secondary battery is produced. Then, a solid electrolyte layer is formed on one of the active material layers of these sheets as described above. Further, the other of the positive electrode sheet for all-solid secondary battery and the negative electrode sheet for all-solid secondary battery is laminated on the solid electrolyte layer so that the solid electrolyte layer and the active material layer are in contact with each other. In this way, the all-solid-state secondary battery can be manufactured.
The following method can be given as another method. That is, the positive electrode sheet for all-solid-state secondary batteries and the negative electrode sheet for all-solid-state secondary batteries are produced as described above. Separately from this, the solid electrolyte composition is applied onto a substrate to prepare a solid electrolyte sheet for an all-solid secondary battery including a solid electrolyte layer. Further, the positive electrode sheet for all-solid secondary battery and the negative electrode sheet for all-solid secondary battery are laminated so as to sandwich the solid electrolyte layer peeled from the base material. In this way, the all-solid-state secondary battery can be manufactured.

An all-solid-state secondary battery can also be manufactured by a combination of the above forming methods. For example, as described above, the positive electrode sheet for all-solid secondary batteries, the negative electrode sheet for all-solid secondary batteries, and the solid electrolyte sheet for all-solid secondary batteries are prepared. Then, after stacking the solid electrolyte layer peeled from the base material on the negative electrode sheet for all-solid-state secondary battery, it is possible to manufacture an all-solid secondary battery by laminating with the positive electrode sheet for all-solid secondary battery it can. In this method, the solid electrolyte layer may be laminated on the positive electrode sheet for an all-solid secondary battery and laminated with the negative electrode sheet for an all-solid secondary battery.

(Formation of each layer (deposition))
The method for applying the solid electrolyte composition is not particularly limited and can be appropriately selected. Examples thereof include coating (preferably wet coating), spray coating, spin coating, dip coating, slit coating, stripe coating, and bar coating.
At this time, the solid electrolyte composition may be subjected to a drying treatment after each coating, or may be subjected to a multilayer treatment and then a drying treatment. The drying temperature is not particularly limited. The lower limit is preferably 30° C. or higher, more preferably 60° C. or higher, even more preferably 80° C. or higher. The upper limit is preferably 300°C or lower, more preferably 250°C or lower, and further preferably 200°C or lower. By heating in such a temperature range, the dispersion medium can be removed and a solid state can be obtained. It is also preferable because the temperature is not raised too high and each member of the all solid state secondary battery is not damaged. As a result, in the all-solid-state secondary battery, excellent overall performance can be obtained, and good binding properties and good ionic conductivity can be obtained even without applying pressure.

It is preferable to pressurize each layer or the all-solid-state secondary battery after producing the applied solid electrolyte composition or the all-solid-state secondary battery. It is also preferable to apply pressure in a state where the layers are laminated. Examples of the pressurizing method include a hydraulic cylinder press machine. The pressing force is not particularly limited, and generally, it is preferably in the range of 50 to 1500 MPa.
Further, the applied solid electrolyte composition may be heated at the same time as pressurization. The heating temperature is not particularly limited and is generally in the range of 30 to 300°C. It is also possible to press at a temperature higher than the glass transition temperature of the inorganic solid electrolyte.
The pressurization may be performed in a state in which the coating solvent or dispersion medium is dried in advance, or may be performed in a state in which the solvent or dispersion medium remains.

The atmosphere during pressurization is not particularly limited, and may be under air, under dry air (dew point −20° C. or lower), in an inert gas (eg, argon gas, helium gas, nitrogen gas).
The pressing time may be short time (for example, within several hours) and high pressure may be applied, or long time (one day or more) and medium pressure may be applied. Other than the sheet for all-solid-state secondary batteries, for example, in the case of all-solid-state secondary batteries, a retainer (screw tightening pressure, etc.) for all-solid-state secondary batteries can be used to keep applying a moderate pressure.
The pressing pressure may be uniform or different with respect to the pressed portion such as the sheet surface.
The pressing pressure can be changed according to the area and film thickness of the pressed portion. It is also possible to change the same site stepwise with different pressures.
The pressed surface may be smooth or roughened.

(Initialization)
The all-solid-state secondary battery manufactured as described above is preferably initialized after manufacturing or before use. The initialization is not particularly limited, and can be performed, for example, by performing initial charge/discharge in a state where the press pressure is increased, and then releasing the pressure until it becomes a general working pressure of the all solid state secondary battery.

[Applications of all solid state secondary battery]
The all-solid secondary battery of the present invention can be applied to various uses. The application mode is not particularly limited. For example, when it is mounted on an electronic device, for example, a laptop computer, a pen input computer, a mobile computer, an electronic book player, a mobile phone, a cordless phone handset, a pager, a handy terminal, a mobile fax, a mobile phone. Copy, mobile printer, headphone stereo, video movie, LCD TV, handy cleaner, portable CD, mini disk, electric shaver, transceiver, electronic organizer, calculator, memory card, portable tape recorder, radio, backup power supply, memory card, etc. To be Other consumer products include automobiles, electric vehicles, motors, lighting equipment, toys, game machines, road conditioners, watches, strobes, cameras, medical equipment (pacemakers, hearing aids, shoulder massagers, etc.), and the like. Furthermore, it can be used for various military purposes and for space. It can also be combined with a solar cell.

Above all, it is preferably applied to applications requiring high capacity and high rate discharge characteristics. For example, in power storage equipment and the like, which is expected to have a large capacity in the future, high safety is essential, and it is also required to have compatible battery performance. In addition, an electric vehicle or the like is equipped with a high-capacity secondary battery, and is assumed to be used for daily charging at home, and further safety is required even when overcharged. According to the present invention, it is possible to suitably respond to such usage patterns and to exhibit the excellent effects.

The all-solid-state secondary battery refers to a secondary battery in which the positive electrode, the negative electrode, and the electrolyte are all solid. In other words, it is distinguished from an electrolytic solution type secondary battery in which a carbonate-based solvent is used as the electrolyte. Among these, the present invention is premised on an inorganic all solid state secondary battery. The all-solid-state secondary battery includes an organic (polymer) all-solid-state secondary battery that uses a polymer compound such as polyethylene oxide as an electrolyte, and an inorganic all-solid-state secondary battery that uses the above Li-PS, LLT, LLZ, or the like. It is classified as a battery. The application of the polymer compound to the inorganic all-solid secondary battery is not hindered, and the polymer compound can be applied as the binder particles of the positive electrode active material, the negative electrode active material, and the inorganic solid electrolyte particles.
The inorganic solid electrolyte is distinguished from the above-mentioned electrolyte (polymer electrolyte) using a polymer compound such as polyethylene oxide as an ion conductive medium, and the inorganic compound serves as an ion conductive medium. Specific examples thereof include Li-P-S, LLT, and LLZ described above. The inorganic solid electrolyte itself does not release cations (Li ions) but exhibits an ion transport function. On the other hand, a material that is added to the electrolytic solution or the solid electrolyte layer and serves as a supply source of ions that release cations (Li ions) is sometimes called an electrolyte. When it does, it is called an "electrolyte salt" or a "supporting electrolyte". Examples of the electrolyte salt include LiTFSI (lithium bistrifluoromethanesulfonyl imide).
In the present invention, the term “composition” means a mixture in which two or more components are uniformly mixed. However, it is sufficient that the uniformity is substantially maintained, and a part of the particles may be aggregated or unevenly distributed within a range in which a desired effect is obtained. Further, particularly when referring to a solid electrolyte composition, it basically refers to a composition (typically a paste) that is a material for forming a solid electrolyte layer, etc., and is an electrolyte layer formed by curing the above composition. Is not included in this.

Hereinafter, the present invention will be described in more detail with reference to Examples. The present invention is not limited to this. In the following examples, "parts" and "%" representing compositions are based on mass unless otherwise specified. Moreover, "room temperature" means 25 degreeC.

(Synthesis of sulfide-based inorganic solid electrolyte LPS)
2.42 g of lithium sulfide (Li ₂ S, manufactured by Aldrich, purity>99.98%) and diphosphorus pentasulfide (P ₂ S ₅ , manufactured by Aldrich) in a glove box under an argon atmosphere (dew point −70° C.). , Purity>99%) 3.90 g were weighed and put into an agate mortar and mixed for 5 minutes using an agate pestle. The mixing ratio of Li ₂ S and P ₂ S ₅ was set to Li ₂ S:P ₂ S ₅ =75:25 in terms of molar ratio.
Into a 45 mL zirconia container (manufactured by Fritsch), 66 g of zirconia beads having a diameter of 5 mm was charged, the entire amount of the mixture of lithium sulfide and diphosphorus pentasulfide was charged, and the container was completely sealed under an argon atmosphere. A sulfide-based inorganic solid electrolyte of yellow powder is obtained by setting the container in a planetary ball mill P-7 (trade name, manufactured by Fritsch) manufactured by Fritsch Co., and performing mechanical milling at a temperature of 25° C. and a rotation speed of 510 rpm for 20 hours. (Li/P/S glass, sometimes referred to as LPS.) 6.20 g was obtained.

[Example 1]
<Preparation example of solid electrolyte composition>
A zirconia 45 mL container (manufactured by Fritsch) was charged with 180 zirconia beads having a diameter of 5 mm, 9.0 g of an inorganic solid electrolyte, 0.9 g of a compound (B) and 18 g of a dispersion medium were charged, and then a planetary ball mill manufactured by Fritsch. The container was set on P-7 and mixed at a rotation speed of 300 rpm for 2 hours. 0.18 g of a catalyst was added thereto, and mixing was further continued at a rotation speed of 150 rpm for 5 minutes to prepare solid electrolyte compositions S-1 to S-10, T-1 and T-2.
When the solid electrolyte composition contains an active material, the active material was added and mixed at the same timing as the addition of the metathesis catalyst to prepare a solid electrolyte composition.

Table 1 below shows the components of each solid electrolyte composition and the blending mass ratio.

<Table notes>
LLT: Li _0.5 La _0.5 TiO ₃ (manufactured by Toshima Manufacturing Co., Ltd.)
LPS: above synthesized Li-P-S based glass _{LLZ: Li 7 La 3 Zr 2} O 12
B-1: Polyallyl methacrylate (Mw3200)
B-2: Sol gel of allyltriethoxysilane (containing 50% by mass of octaallylsilsesquioxane) (Mw2100)
B-3: Dipentaerythritol 3:3 modified product of succinic acid and linolenic acid (Mw3500)
B-4: 2:4 denatured product of dipentaerythritol deoxycholic acid and undecenoic acid (Mw2890)
B-5: Octamethacryloyl-substituted silsesquioxane (manufactured by Hybrid Plastics Co., Ltd., product number MA0735, Mw2560)
Cyclo-olefin polymer: Zeonex 330R (manufactured by Zeon Corporation, Mw 50,000, unsaturated bond ratio in the compound calculated by the following formula (5) is less than 1%)
C-1: Grubbs-2nd (manufactured by Aldrich, product number 569747)
C-2: Hoveyda-Grubbs-2nd (manufactured by Aldrich, product number 569755)
C-3: 1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidene-[2-(isopropoxy)-5-N,N-dimethylaminosulfonylphenyl] Methylene ruthenium (II) = dichloride (manufactured by Wako Pure Chemical Industries, product number 023-17481)
C-4: Dimethyl 2,2′-azobis(2-methylpropionate) (thermal radical polymerization initiator, Wako Pure Chemical Industries, Ltd., V-601)
LCO: LiCoO ₂ lithium cobalt oxide NCA: LiNi _0.85 Co _0.10 Al _0.05 O ₂ nickel cobalt aluminum lithium AB: acetylene black

In the above structural formula, * indicates a binding site.

<Preparation of solid electrolyte-containing sheet>
The solid electrolyte composition prepared above was applied onto a stainless steel (SUS) foil as a current collector.
The composition was cured by performing metathesis crosslinking (curing treatment) at the temperature and time shown in Table 2, the dispersion medium was dried, and each solid electrolyte-containing sheet No. 101-110, c11 and c12 were produced.

-Unsaturated bond rate-
The number of non-aromatic carbon-carbon unsaturated bonds in the compound after curing is 1 in the case of double bond and 2 in the case of triple bond, and the unsaturated bond ratio (%) is calculated by the following formula (5). Was calculated. The unsaturated bond rate is collectively shown in Table 2 below.

Unsaturated bond ratio=(sum of the number of non-aromatic carbon-carbon unsaturated bonds in the compound after curing)/(sum of the number of all carbon-carbon bonds in the compound after curing)×100 formula ( 5)

[Test Example 1] Binding Test A 180° peel strength test (JIS Z0237-2009) was performed on the obtained solid electrolyte-containing sheet.
An adhesive tape (width 24 mm, length 300 mm) (trade name: Cellotape (registered trademark) CT-24, manufactured by Nichiban Co., Ltd.) was attached to the surface of the solid electrolyte-containing sheet on which the solid electrolyte composition was cured. After gripping the end of the tape and folding it back to 180° and peeling it from the solid electrolyte-containing sheet by 25 mm, one end of the solid electrolyte-containing sheet at the part where the adhesive tape was peeled off to the lower jig installed in the tester below. Was fixed, and the adhesive tape was fixed to the upper jig.
The test was carried out at a loading speed of 300 mm/min. After peeling off the 25 mm pressure-sensitive adhesive tape after the start of the measurement, for the 50 mm pressure-sensitive adhesive tape peeled from the solid electrolyte-containing sheet, the measured adhesive force values for every 0.05 mm in length were averaged, and the peeled adhesive force value ( The average peel strength (N) was used.
The average peel strength was evaluated according to the following evaluation criteria. The higher the average peel strength, the higher the binding strength. A rating of "B" or higher is the passing level of this test.
The peel strength was measured by combining a standard type digital force gauge ZTS-5N and a vertical electric measuring stand MX2 series (both are trade names, manufactured by Imada).

-Evaluation criteria-
A: 2.0 N or more B: 1.0 N or more and less than 2.0 N C: 0.5 N or more and less than 1.0 N D: less than 0.5 N

<Note to table>
*1: Since cycloolefin polymer is used, no curing treatment is applied.
*2: Temperature and time of curing treatment by radical polymerization *3: Unsaturated bond ratio is less than 1%.

From the results of Table 2, a solid produced using the solid electrolyte composition of the present invention containing the specific compound (B) having a non-aromatic unsaturated bond, the inorganic solid electrolyte (A), and the metathesis catalyst (C). The electrolyte-containing sheet had high adhesion and excellent binding property.
On the other hand, the solid electrolyte-containing sheet prepared by using the comparative solid electrolyte composition T-1 containing a cycloolefin polymer and the comparative solid electrolyte composition T-2 containing a radical polymerization initiator is In each case, the adhesion was low and the binding property was not sufficient.

<Manufacture of all solid state secondary battery>
Each of the solid electrolyte-containing sheets produced above was cut into a disk shape having a diameter of 14.5 mm to serve as an electrode, the Li—P—S-based glass synthesized above as a solid electrolyte, and the Li foil as a counter electrode were incorporated and pressed at 160 MPa. did. The obtained sheet for all-solid-state secondary batteries was put into a stainless steel 2032 type coin case in which a spacer and a washer were incorporated, and each all-solid-state secondary battery No. 201-206, c21 and c22 were produced.

[Test Example 2] Evaluation of cycle characteristics The cycle characteristics of the all-solid-state secondary battery produced above were measured by a charge/discharge evaluation device "TOSCAT-3000 (trade name)" manufactured by Toyo System Co., Ltd. Charging was performed at a current density of 0.1 mA/cm ² until the battery voltage reached 3.6V. The discharge was performed at a current density of 0.1 mA/cm ² until the battery voltage reached 2.5V. Initialization was performed by repeating charge and discharge for 3 cycles under the above conditions.
Each all-solid secondary battery after initialization was charged at a current density of 0.2 mA / cm ² until the battery voltage reached 4.2 V, then the battery voltage at a current density of 0.2 mA / cm ² 2.5V It was discharged until it reached. This charging/discharging was made into 1 cycle, and charging/discharging was repeated.
In this charge/discharge cycle, the number of cycles when the discharge capacity reached less than 80, where the discharge capacity in the first cycle after initialization was 100, was evaluated according to the following criteria. In addition, the evaluation "C" or higher is the pass level of this test.

-Evaluation criteria-
A: 30 times or more B: 20 times or more and less than 30 times C: 10 times or more and less than 20 times D: less than 10 times

From the results of Table 2, the electrode layer was formed using the solid electrolyte composition of the present invention containing the specific compound (B) having a non-aromatic unsaturated bond, the inorganic solid electrolyte (A) and the metathesis catalyst (C). The formed all-solid secondary battery had excellent cycle characteristics. As described above, the solid electrolyte composition of the present invention was able to produce an all-solid secondary battery having high binding properties and excellent cycle characteristics.
On the other hand, a solid electrolyte composition T-1 for comparison containing a cycloolefin polymer and a solid electrolyte composition T-2 for comparison containing a radical polymerization initiator None of the secondary batteries had sufficient cycle characteristics.

While this invention has been described in conjunction with its embodiments, we are not intended to limit our invention to any details of the description, unless otherwise indicated, contrary to the spirit and scope of the invention as set forth in the appended claims. I think it should be interpreted broadly without.

This application claims priority based on Japanese Patent Application No. 2016-014811 filed in Japan on January 28, 2016, which is hereby incorporated by reference in its entirety. Capture as a part.

DESCRIPTION OF SYMBOLS 1 Negative electrode current collector 2 Negative electrode active material layer 3 Solid electrolyte layer 4 Positive electrode active material layer 5 Positive electrode current collector 6 Operating part 10 All solid state secondary battery 11 Coin case 12 Sheet for all solid state secondary battery 13 Cell for measuring cycle characteristics (Coin battery)

Claims (21)

An inorganic solid electrolyte having conductive metal ion belonging to Group 1 or Group 2 of the periodic table, a non-aromatic carbon - a compound having a carbon-carbon unsaturated bond, containing the metathesis catalyst, all-solid secondary Solid electrolyte composition for secondary battery . The solid electrolyte composition according to claim 1, wherein the non-aromatic carbon-carbon unsaturated bond is a terminal vinyl group or a terminal ethynyl group. The solid electrolyte composition according to claim 1 or 2, wherein the compound having a non-aromatic carbon-carbon unsaturated bond has at least one functional group selected from the following functional group group.
<Functional group>
Hydroxy group, mercapto group, carboxy group, sulfonic acid group, phosphoric acid group, amino group, cyano group, isocyanate group, acid anhydride group, epoxy group, oxetanyl group, alkoxy group, carbonyl group, three or more ring structure A group having, a group having an amide bond, a group having a urea bond, a group having a urethane bond, a group having an imide bond, a group having an isocyanurate bond. The solid electrolyte according to claim 1, wherein the compound having a non-aromatic carbon-carbon unsaturated bond has two or more non-aromatic carbon-carbon unsaturated bonds in one molecule. Composition. The solid electrolyte composition according to any one of claims 1 to 4, wherein the compound having a non-aromatic carbon-carbon unsaturated bond has a structure of any of a star type, a hyperbranched type and a dendrimer type. Stuff. The solid electrolyte composition according to claim 1, wherein the compound having a non-aromatic carbon-carbon unsaturated bond is represented by the following general formula (1a) or (2a).

In the above formula, R ^{11 to} R ¹³ , R ¹⁴ , R ^{21 to} R ²³ and R ²⁴ represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group or an aryl group, and R ³¹ and R ³⁴ represent a hydrogen atom or an alkyl group. Represents an alkenyl group, an alkynyl group or an aryl group. L ¹¹ , L ²¹ and L ³¹ represent a single bond or a divalent linking group. n and m are integers of 1 to 20, and l is an integer of 0 to 20. X represents an organic group having a valence of n+m+1. The solid electrolyte composition according to claim 6, wherein R ³¹ and R ³⁴ have at least one kind of functional group selected from the following functional group group.
<Functional group>
Hydroxy group, mercapto group, carboxy group, sulfonic acid group, phosphoric acid group, amino group, cyano group, isocyanate group, acid anhydride group, epoxy group, oxetanyl group, alkoxy group, carbonyl group, three or more ring structure A group having, a group having an amide bond, a group having a urea bond, a group having a urethane bond, a group having an imide bond, a group having an isocyanurate bond. The solid electrolyte composition according to claim 1, wherein the compound having a non-aromatic carbon-carbon unsaturated bond has a mass average molecular weight of less than 10,000. The solid electrolyte composition according to claim 1, wherein the metathesis catalyst is a ruthenium catalyst. The solid electrolyte composition according to any one of claims 1 to 9, wherein the metathesis catalyst is a catalyst in which an oxygen atom and/or a nitrogen atom is bonded and/or coordinated with a ruthenium atom. The solid electrolyte composition according to any one of claims 1 to 10, wherein a content of the metathesis catalyst in the total solid content in the solid electrolyte composition is 0.001% by mass to 5% by mass. The solid electrolyte composition according to any one of claims 1 to 11, which contains an active material. The solid electrolyte composition according to any one of claims 1 to 12, wherein the inorganic solid electrolyte is a sulfide-based inorganic solid electrolyte. The solid electrolyte composition according to any one of claims 1 to 13, which contains a dispersion medium. A step (1a) of applying the solid electrolyte composition according to any one of claims 1 to 14 onto a substrate to obtain a coated sheet;
A solid for an all-solid secondary battery, including a step (2a) of heating the coated sheet to 50° C. or higher to crosslink and cure the compound having a non-aromatic carbon-carbon unsaturated bond by a metathesis reaction. Method for manufacturing electrolyte-containing sheet. A step of heating the solid electrolyte composition according to any one of claims 1 to 14 to 50° C. or higher to bring it to a condition for initiating the metathesis reaction of the compound having the non-aromatic carbon-carbon unsaturated bond ( 1b),
A method for producing a solid electrolyte-containing sheet for an all-solid secondary battery, which comprises a step (2b) of applying the composition obtained in the step (1b) onto a base material and crosslinking-curing the composition. An inorganic solid electrolyte having ion conductivity of a metal belonging to Group 1 or Group 2 of the periodic table, and a structural unit having a non-aromatic carbon-carbon unsaturated bond represented by the following general formula (3): A solid electrolyte-containing sheet for an all-solid-state secondary battery, which comprises a compound having the following: and a metathesis catalyst residue containing Ru, Mo and/or W metal elements of 10 ppm or more.

In the above formula, Z ¹ represents the following general formula (3-1), and Z ² represents the following general formula (3-2). R ³ represents a hydrogen atom, an alkyl group or an aryl group. L ³ represents a single bond or a divalent linking group. n and m are integers of 1 to 20, and l is an integer of 0 to 20. X represents an organic group having a valence of n+m+1.

In the above formula, R ¹ and R ² represent a hydrogen atom, an alkyl group, an alkenyl group or an aryl group. L ¹ and L ² represent a single bond or a divalent linking group. * Indicates a binding site with X. The unsaturated bond ratio calculated by the following formula (5) of the compound having a structural unit having a non-aromatic carbon-carbon unsaturated bond represented by the general formula (3) is 1%. The solid electrolyte-containing sheet according to claim 17, which satisfies <unsaturated bond rate <90%.
Unsaturated bond ratio=(sum of the number of non-aromatic carbon-carbon unsaturated bonds in the compound)/
(Sum of the number of all carbon-carbon bonds in the compound)×100 Formula (5) The solid electrolyte-containing sheet according to claim 17, which contains an active material. An all-solid secondary battery comprising a positive electrode active material layer, a solid electrolyte layer, and a negative electrode active material layer in this order,
An all-solid secondary battery in which at least one layer of the positive electrode active material layer, the negative electrode active material layer, and the solid electrolyte layer comprises the solid electrolyte-containing sheet according to any one of claims 17 to 19. A method for manufacturing an all-solid secondary battery, which manufactures an all-solid secondary battery through the method for manufacturing a solid electrolyte-containing sheet according to claim 15.

Images