JP7616715B2 - Manufacturing method for electrode composite for all-solid-state lithium-ion battery - Google Patents

Description

The present invention relates to a method for producing an electrode composite for an all-solid-state lithium ion battery.
This application claims priority based on Japanese Patent Application No. 2021-081219, filed in Japan on May 12, 2021, the contents of which are incorporated herein by reference.

Lithium-ion secondary batteries have a high energy density and are used in information-related devices such as personal computers and mobile phones. In recent years, development of high-output, high-capacity lithium-ion secondary batteries for electric or hybrid vehicles has been progressing.

However, current lithium-ion secondary batteries use flammable organic electrolytes, which means that they are prone to catching fire when they generate abnormal heat. In fact, there have been fires caused by lithium-ion secondary batteries in portable devices, and there is a strong demand for safety improvements.

By replacing the organic electrolyte in lithium-ion secondary batteries with an inorganic solid electrolyte, the risk of fire can be reduced. For this reason, all-solid-state lithium-ion batteries are attracting attention.

Patent Document 1 discloses an all-solid-state battery comprising a positive electrode layer containing a positive electrode active material and a first solid electrolyte, a negative electrode layer containing a negative electrode active material and lithium hydride, and a solid electrolyte layer provided between the positive electrode layer and the negative electrode layer and containing a second solid electrolyte, wherein the first solid electrolyte and the second solid electrolyte are glasses containing an oxide represented by the general formula LixAyOz (A is at least one of S, B, C, P, Al, and Ti).

Patent Document 2 discloses an all-solid-state lithium secondary battery comprising a counter electrode layer, a negative electrode layer, and a sulfide glass-based electrolyte disposed between the counter electrode layer and the negative electrode layer, the negative electrode layer being made of a mixture containing at least one high-capacity negative electrode material selected from Sn, Si, and Ge, and the sulfide glass-based electrolyte, a predetermined restraining force acts on both ends of the all-solid-state lithium secondary battery, and when observing the surface structure of the negative electrode layer, no voids are observed in comparison with a 25 μm scale, and the surface structure is densified.

Patent Document 3 discloses a negative electrode mixture for an all-solid-state lithium ion secondary battery, the negative electrode mixture containing a negative electrode active material, a solid electrolyte, and a conductive material, the negative electrode active material containing at least one active material selected from the group consisting of metals capable of forming an alloy with Li and oxides of the metals, the solid electrolyte being a LiX-Li ₂ S-P ₂ S ₅ -based solid electrolyte (X is at least one halogen selected from the group consisting of F, Cl, Br, and I), and a value obtained by multiplying the volume ratio (%) of the conductive material when the volume of the negative electrode mixture is taken as 100 volume % by the bulk density of the solid electrolyte is 0.53 to 3.0.

Patent Document 4 discloses a positive electrode for an all-solid-state secondary battery that includes a positive electrode active material represented by _A2S.AX , where A is an alkali metal and X is selected from _I , Br, Cl, F, _BF4 , _BH4 , _SO4 , BO3, _PO4 , O, Se, N, P, As, Sb, _PF6 , _AsF6 , _{ClO4 , NO3} , _CO3 , _CF3SO3 , _CF3COO , N( _SO2F ) _{2 ,} and N( _CF3SO2 ) ₂ .

Japanese Patent Application Publication No. 2020-64701 Japanese Patent Application Publication No. 2020-161309 Japanese Patent No. 6593381 Japanese Patent No. 6529508

However, in the manufacturing methods of the positive electrode composite and the negative electrode composite disclosed in Patent Documents 1 to 4, a solid electrolyte is first synthesized, and then the positive electrode composite or the negative electrode composite is manufactured. In particular, since the synthesis of the solid electrolyte takes a long time, the manufacturing methods of the positive electrode composite and the negative electrode composite disclosed in Patent Documents 1 to 4 have a problem of poor mass productivity.

The present invention has been developed in consideration of the above circumstances, and aims to provide a method for manufacturing an electrode composite for all-solid-state lithium-ion batteries that is easy to mass-produce.

In order to solve the above problems, the present invention proposes the following means.
(1) A method for producing an electrode composite for an all-solid-state lithium-ion battery according to one aspect of the present invention comprises combining an electrode composite raw material, which includes an electrode active material, a solid electrolyte raw material, and a carbon material as a conductive material, with mechanical energy.

(2) In the method for producing an electrode composite for an all-solid-state lithium ion battery according to (1) above, the carbon material may have a specific surface area of 10 m ² /g or more.

(3) In the method for producing an electrode composite for an all-solid-state lithium ion battery according to (1) or (2) above, the carbon material may have a specific surface area of 1000 m ² /g or more.

(4) In the method for manufacturing an electrode composite for an all-solid-state lithium ion battery described in any one of (1) to (3) above, the electrode active material may be a positive electrode active material.

(5) In the method for producing an electrode composite for an all-solid-state lithium-ion battery according to (4) above, the positive electrode active material may be a first Li ₂ S.

(6) In the method for producing an electrode composite for an all-solid-state lithium ion battery according to (5) above, the solid electrolyte raw material may be a sulfide solid electrolyte raw material containing a second Li ₂ S and P _{2 S5} .

(7) In the method for producing an electrode composite for an all-solid-state lithium-ion battery described in (6) above, in the electrode composite raw material, a weight ratio of the sum of the first Li ₂ S and the second Li ₂ S, P ₂ S ₅ , and the carbon material may be 30-80:10-50:3-20.

(8) In the method for producing an electrode composite for an all-solid-state lithium ion battery described in (6) or (7) above, the electrode composite raw material may further contain a lithium salt.

(9) In the method for manufacturing an electrode composite for an all-solid-state lithium ion battery described in (8) above, the lithium salt may be one or more selected from the group consisting of lithium oxide, lithium nitride, lithium fluoride, lithium chloride, lithium bromide, lithium iodide, lithium sulfate, lithium carbonate, lithium borate, lithium phosphate, lithium nitrate, lithium silicate, and lithium aluminate.

(10) In the method for producing an electrode composite for an all-solid-state lithium ion battery according to (8) or (9) above, in the electrode composite raw material, a weight ratio of the sum of the first Li ₂ S and the second Li ₂ S, the P ₂ S ₅ , the carbon material, and the lithium salt may be 30-80:10-40:3-20:5-30.

(11) The method for manufacturing an electrode composite for an all-solid-state lithium ion battery described in (5) above may include, as the solid electrolyte raw material, two or more selected from the group consisting of lithium oxide, lithium nitride, lithium fluoride, lithium chloride, lithium bromide, lithium iodide, lithium sulfate, lithium carbonate, lithium borate, lithium phosphate, lithium nitrate, lithium silicate, and lithium aluminate.

(12) In the method for producing an electrode composite for an all-solid-state lithium ion battery described in (11) above, in the electrode composite raw material, a weight ratio of the first Li ₂ S, the solid electrolyte raw material, and the carbon material may be 20-60:20-70:3-20.

(13) In the method for manufacturing an electrode composite for an all-solid-state lithium ion battery described in any one of (1) to (3) above, the electrode active material may be a negative electrode active material.

(14) In the method for manufacturing an electrode composite for an all-solid-state lithium ion battery described in (13) above, the negative electrode active material may be a Si-based active material consisting of one or more types of Si and Si compounds.

(15) In the method for manufacturing an electrode composite for an all-solid-state lithium ion battery described in (14) above, the Si-based active material may be Si.

(16) In the method for producing an electrode composite for an all-solid-state lithium ion battery according to (14) or (15) above, the solid electrolyte raw material may be a sulfide solid electrolyte raw material containing Li ₂ S and P _{2 S5} .

(17) In the method for producing an electrode composite for an all-solid-state lithium ion battery described in (16) above, in the electrode composite raw material, a weight ratio of the Si-based active material, Li ₂ S, P ₂ S ₅ , and the carbon material may be 20-70:10-30:10-40:3-20.

(18) In the method for producing an electrode composite for an all-solid-state lithium ion battery described in (16) or (17) above, the electrode composite raw material may further contain a lithium salt.

(19) In the method for producing an electrode composite for an all-solid-state lithium ion battery described in (18) above, the lithium salt may be one or more selected from the group consisting of lithium oxide, lithium nitride, lithium fluoride, lithium chloride, lithium bromide, lithium iodide, lithium sulfate, lithium carbonate, lithium borate, lithium phosphate, lithium nitrate, lithium silicate, and lithium aluminate.

(20) In the method for producing an electrode composite for an all-solid-state lithium ion battery according to (18) or (19) above, in the electrode composite raw material, a weight ratio of the Si-based active material, Li ₂ S, P ₂ S ₅ , the carbon material, and the lithium salt may be 20 to 70: 10 to 30: 10 to 40: 3 to 20: 5 to 30.

(21) The method for manufacturing an electrode composite for an all-solid-state lithium ion battery described in (14) or (15) above may include at least two of lithium oxide, lithium nitride, lithium fluoride, lithium chloride, lithium bromide, lithium iodide, lithium sulfate, lithium carbonate, lithium borate, lithium phosphate, lithium nitrate, lithium silicate, and lithium aluminate as the solid electrolyte raw material.

(22) In the method for manufacturing an electrode composite for an all-solid-state lithium ion battery described in (21) above, the weight ratio of the Si-based active material, the solid electrolyte raw material, and the carbon material in the electrode composite raw material may be 10-60:20-80:3-20.

According to the above aspect of the present invention, a method for manufacturing an electrode composite for an all-solid-state lithium ion battery that is excellent in mass productivity can be provided.

The inventors have found that an electrode composite for an all-solid-state lithium-ion battery can be manufactured in one step by compounding an electrode composite raw material containing an electrode active material, a solid electrolyte raw material, and a carbon material as a conductive material with mechanical energy, and have completed the present invention. In this specification, "compounding with mechanical energy" means "synthesizing a solid electrolyte from a solid electrolyte raw material with mechanical energy, and dispersing an electrode active material and a carbon material in the synthesized solid electrolyte." Whether or not a solid electrolyte has been synthesized can be determined by the disappearance of the solid electrolyte raw material peak by XPS or the appearance of an exothermic peak other than the solid electrolyte raw material by DSC. It is preferable that the synthesized solid electrolyte is amorphous. Whether or not the solid electrolyte is amorphous can be confirmed by the disappearance of the diffraction peak of raw materials other than the active material by XRD. Each embodiment of the present invention will be described below.

First Embodiment
In the manufacturing method of the electrode composite for an all-solid-state lithium ion battery according to the first embodiment, an electrode composite raw material including a positive electrode active material which is an electrode active material, a sulfide solid electrolyte raw material which is a solid electrolyte raw material, and a carbon material is combined by mechanical energy. Each requirement will be described below.

[Electrode composite raw materials]
The electrode composite raw material used in the manufacturing method for an electrode composite for an all-solid-state lithium ion battery according to the first embodiment includes a positive electrode active material, a sulfide solid electrolyte raw material, and a carbon material. By using the sulfide solid electrolyte raw material, which is a solid electrolyte raw material, the electrical conductivity of the electrode composite can be improved.

(Positive Electrode Active Material)
The positive electrode active material is not particularly limited as long as it does not lose the function of the active material when it is combined with other materials by mechanical energy. For example, Li ₂ S can be mentioned as a positive electrode active material. Since L ₂ S has a large theoretical capacity compared to conventional lithium transition metal oxides, it is preferable because it dramatically improves the energy density. In addition, when the positive electrode active material is Li ₂ S, since Li ₂ S has a lithium source, it is not necessary for the negative electrode active material to have a lithium source. Therefore, by using Li _{2 S as the positive electrode active material, it is not necessary to use unstable lithium metal or lithium metal alloy during production, and the manufacturing aspect is improved. In addition, by using Li 2 S} , it is easy to uniformly disperse in the synthesized sulfide solid electrolyte while maintaining the characteristics of the active material. Therefore, Li ₂ S (sometimes referred to as first Li ₂ S) is preferable as the positive electrode active material.

(Sulfide solid electrolyte raw material)
The sulfide solid electrolyte raw material is not particularly limited as long as at least a part of the sulfide solid electrolyte raw material becomes an amorphous sulfide solid electrolyte by being composited with mechanical energy. , Li ₂ S, P ₂ S ₅ , SiS ₂ , GeS ₂ , Al ₂ S ₃ , ZnS, As ₂ S ₃ , Sb ₂ S ₃ , WS ₂ , CuS, etc. The sulfide solid electrolyte raw material is Li It is preferable that the sulfide solid electrolyte raw material contains _{Li 2} S (hereinafter, sometimes referred to as second Li ₂ S) and P ₂ S ₅ (hereinafter, sometimes referred to as first P ₂ S ₅ ). By containing Li ₂ S and P ₂ S ₅ , it is possible to obtain a good sulfide solid electrolyte that is amorphous and has excellent deformability by mechanical energy. When synthesizing a sulfide solid electrolyte from the second Li ₂ S and P ₂ S ₅ , the amount of the first Li _{2 S} functioning as an electrode active material and the amount of the solid electrolyte used in the synthesis of the solid electrolyte are ₅ . The ratio of the first Li ₂ S to the second Li 2 S to be added is determined.

(Carbon materials)
The carbon material supplements the electrical conductivity of the positive electrode active material. The carbon material is not particularly limited as long as it functions as a conductive material. The carbon material also has a function of promoting the synthesis of a solid electrolyte. Examples of the carbon material include acetylene black, carbon nanotubes, activated carbon, graphene, furnace black (for example, furnace black having a hollow shell structure), carbon fiber, and the like. The carbon material may contain one or more of these. The furnace black having a hollow shell structure is a type of conductive furnace black, and has a hollow shell-like structure with a porosity of about 60 to 80%. Here, the "hollow shell structure" refers to a structure in which graphite crystals are thinly gathered together to form a particle-shaped outer shell, and the inside of the outer shell has voids. Examples of the furnace black having a hollow shell structure include Ketjen Black (manufactured by Lion Corporation).

When a carbon material with low conductivity (low conductivity carbon material) is used, the electronic conductivity of the electrode composite can be improved by combining it with a carbon material with higher conductivity (high conductivity carbon material). This can further improve the charge/discharge capacity of the electrode composite. The low conductivity carbon material is activated carbon. The high conductivity carbon material is one or more selected from the group consisting of acetylene black, ketjen black, carbon nanotubes, and graphene. The weight ratio of the low conductivity carbon material to the high conductivity carbon material is preferably low conductivity carbon material:high conductivity carbon material = 10:0 to 5:5.

The specific surface area of the carbon material is preferably 10 m ² /g or more. The more preferred specific surface area of the carbon material is 100 m ² /g or more. The even more preferred specific surface area of the carbon material is 1000 m ² /g or more. The particularly preferred specific surface area of the carbon material is 1500 m ² /g or more. If the specific surface area is less than 10 m ² /g, the contact points between the positive electrode active material and the carbon material cannot be sufficiently increased, and therefore the effect of improving the charge/discharge capacity tends not to be fully enjoyed. The upper limit of the specific surface area is not particularly limited, but is usually 6000 m ² /g or less.

In this specification, the specific surface area of a carbon material refers to the BET specific surface area determined by the Brenauer-Emmet-Telle (BET) method, specifically, the specific surface area determined using a nitrogen adsorption isotherm obtained by adsorbing nitrogen gas to a carbon material at liquid nitrogen temperature. As a measuring device for determining the BET specific surface area, for example, an automatic specific surface area/pore distribution measuring device (BELSORP-mini II, manufactured by BEL Japan Co., Ltd.) can be used.

(Lithium salt)
The electrode composite raw material of the first embodiment may further contain a lithium salt in addition to the positive electrode active material, the sulfide solid electrolyte raw material, and the carbon material. The lithium salt has a function of improving the conductivity of the sulfide solid electrolyte and a function of improving the flexibility of the sulfide solid electrolyte. The lithium salt is not particularly limited as long as it has a function of improving the conductivity of the sulfide solid electrolyte or a function of improving the flexibility of the sulfide solid electrolyte. For example, the lithium salt is preferably one or more selected from the group consisting of lithium oxide, lithium nitride, lithium fluoride, lithium chloride, lithium bromide, lithium iodide, lithium sulfate, lithium carbonate, lithium borate, lithium phosphate, lithium nitrate, lithium silicate, and lithium aluminate.

(Other ingredients)
The electrode composite raw material of the first embodiment may further contain optional components such as a binder, a solvent, and an ion-conductive material.

"binder"
The binder is not particularly limited, and may be a thermoplastic resin, a thermosetting resin, etc. Examples of the binder include polyethylene, polypropylene, polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), styrene butadiene rubber, tetrafluoroethylene-hexafluoroethylene copolymer, tetrafluoroethylene-hexafluoropropylene copolymer (FEP), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), vinylidene fluoride-hexafluoropropylene copolymer, vinylidene fluoride-chlorotrifluoroethylene copolymer, ethylene-tetrafluoroethylene copolymer (ETFE resin), polychloro Examples of the binder include trifluoroethylene (PCTFE), vinylidene fluoride-pentafluoropropylene copolymer, propylene-tetrafluoroethylene copolymer, ethylene-chlorotrifluoroethylene copolymer (ECTFE), vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene copolymer, vinylidene fluoride-perfluoromethylvinyl ether-tetrafluoroethylene copolymer, ethylene-acrylic acid copolymer, polyacrylic acid, sodium polyacrylate, lithium polyacrylate, polymethacrylic acid, sodium polymethacrylate, lithium polymethacrylate, etc. These binders may be used alone or in combination of two or more.

When the electrode composite raw material contains a binder, its content is not particularly limited, but it is preferable that it be 0.01 to 10 weight % in the electrode composite raw material.

"solvent"
By using an electrode composite obtained by mixing a solvent, it becomes easier to prepare an electrode composite layer. The solvent is removed by drying when preparing an electrode composite layer. The solvent is not particularly limited, but examples thereof include amine-based solvents such as N,N-dimethylaminopropylamine and diethylenetriamine, ether-based solvents such as tetrahydrofuran, ketone-based solvents such as methyl ethyl ketone, ester-based solvents such as methyl acetate, amide-based solvents such as dimethylacetamide and 1-methyl-2-pyrrolidone, and hydrocarbon-based solvents such as toluene, xylene, n-hexane, and cyclohexane. These solvents may be used alone or in combination of two or more.

When the electrode composite raw material is obtained by mixing the above-mentioned solvent, the content is not particularly limited, but is preferably 10 to 10,000 parts by weight per 100 parts by weight of the solid content of the electrode composite raw material.

"Ion-conducting materials"
The electrode composite raw material may contain an ion conductive material. The ion conductive material is not particularly limited, but the lithium ion conductivity at room temperature is preferably 10 ⁻⁵ S/cm or more, more preferably 10 ⁻⁴ S/cm or more. Examples of crystalline oxide solid electrolytes having such characteristics include lithium aluminum titanium phosphate (LATP), lithium aluminum germanium phosphate (LAGP), lithium lanthanum zirconium oxide (LLZ), lithium lanthanum titanium oxide (LLT), lithium germanium phosphorus sulfide (LGPS), lithium silicon sulfide (LSS), lithium phosphorus halogen sulfide (LPSX), and lithium boron carbon hydride.

(Weight ratio)
In the first embodiment, when the positive electrode active material is the first Li ₂ S and the sulfide solid electrolyte raw material is the second Li ₂ S and P ₂ S ₅ , the weight ratio of the sum of the first Li ₂ S and the second Li ₂ S in the electrode composite raw material, the P ₂ S ₅ , and the carbon material (the sum of the first Li ₂ S and the second Li ₂ S: P ₂ S ₅ : the carbon material) is preferably 30 to 80: 10 to 50: 3 to 20. When the weight ratio of the sum of the first Li ₂ S and the second Li ₂ S in the electrode composite raw material, the P ₂ S ₅ , and the carbon material is 30 to 80: 10 to 50: 3 to 20, the ion conductivity in the electrode composite and the contact points between the electrode active material, the solid electrolyte, and the carbon material can be sufficiently obtained, so that the battery characteristics are improved, which is preferable.

In the first embodiment, when the positive electrode active material is the first Li ₂ S, the sulfide solid electrolyte raw material is the second Li ₂ S and P ₂ S ₅ , and the electrode composite raw material further contains a lithium salt, the weight ratio of the total of the first Li ₂ S and the second Li ₂ S in the electrode composite raw material, the P ₂ S ₅ , the carbon material, and the lithium salt (the total of the first Li ₂ S and the second Li ₂ S: P ₂ S ₅ : the carbon material: the lithium salt) is preferably 30 to 80: 10 to 40: 3 to 20: 5 to 30. When the weight ratio of the total of the first Li ₂ S and the second Li ₂ S in the electrode composite raw material, the P ₂ S ₅ , the carbon material, and the lithium salt is 30 to 80: 10 to 40: 3 to 20: 5 to 30, the battery characteristics of the electrode composite are further improved, which is preferable.

[Combination through mechanical energy]
Examples of the method of compounding the electrode composite raw material with mechanical energy include a method of compounding the electrode composite raw material using a planetary ball mill, a kneader, a planetary mixer, a vibration mill, a magnetic stirrer, or the like. For example, when using a planetary ball mill, the electrode composite raw material of the present disclosure is obtained by mixing the electrode composite raw material with zirconia balls at 370 rpm for 2 hours. It can be confirmed that the electrode composite raw material is compounded and a solid electrolyte is synthesized by X-ray photoelectron spectroscopy (XPS) in which the S 2p1/2 peak observed at about 165 eV corresponding to the crosslinking S of P ₂ S ₅ used as the solid electrolyte raw material disappears. It can be confirmed that the solid electrolyte is amorphous in powder X-ray diffraction (XRD) of the obtained electrode composite by the disappearance of diffraction peaks other than the electrode active material. By using a confirmation method such as XRD or XPS, the conditions during compounding can be appropriately adjusted.

In the manufacturing method of the electrode composite for all-solid-state lithium-ion batteries according to the first embodiment, the electrode composite raw material may be composited by mechanical energy, and then a heat treatment may be performed. By performing the heat treatment, the contact interface between the electrode active material Li ₂ S and the solid electrolyte raw material, the carbon material and/or the first lithium salt can be strengthened, and the interface resistance can be reduced. The heat treatment after the composite can be performed, for example, in an atmosphere of argon, nitrogen, air, or the like, at 80 to 250°C, preferably 100 to 200°C, for 1 second to 10 hours, without particular limitation. The heat treatment after the composite can be performed using a known heating device, and specifically, for example, a constant temperature dryer, a blower dryer, a reduced pressure dryer, an infrared dryer, an electric furnace, a gas replacement furnace, a hot plate, or the like.

[Electrode composite]
The electrode composite manufactured by the manufacturing method of the electrode composite for all-solid-state lithium-ion batteries according to the first embodiment includes a positive electrode active material, a sulfide solid electrolyte, and a carbon material. The sulfide solid electrolyte is preferably amorphous. When the sulfide solid electrolyte is amorphous, it can be confirmed by the absence of diffraction peaks other than those of the electrode active material in powder X-ray diffraction (XRD) of the electrode composite. The generation of the sulfide solid electrolyte can be confirmed by the disappearance of the S 2p1/2 peak seen near 165 eV corresponding to the crosslinking S of P ₂ S ₅ used as the solid electrolyte raw material in X-ray photoelectron spectroscopy (XPS) of the electrode composite. The XRD spectrum can be obtained by, for example, measuring in the 2θ range of 10 to 60° using a SmartLab II manufactured by RIGAKU Corporation. The XPS spectrum can be measured, for example, using a KRATOS Nova manufactured by KRATOS ANALYTICAL.

Second Embodiment
In the manufacturing method of the electrode composite for an all-solid-state lithium ion battery according to the second embodiment, an electrode composite raw material including a positive electrode active material as an electrode active material, a solid electrolyte raw material, and a carbon material is composited by mechanical energy. Each requirement will be described below.

[Electrode composite raw materials]
The electrode composite raw material used in the manufacturing method of the electrode composite for an all-solid-state lithium ion battery according to the second embodiment includes a positive electrode active material, a solid electrolyte raw material, and a carbon material. By using the solid electrolyte raw material, the stability of the electrode composite can be improved.

(Positive Electrode Active Material)
The positive electrode active material is not particularly limited as long as it does not lose the function of the active material when it is combined with other materials by mechanical energy. For example, the positive electrode active material may be L ₂ S. L ₂ S has a large theoretical capacity compared to conventional lithium transition metal oxides, and is therefore preferable because it dramatically improves the energy density. In addition, when the positive electrode active material is Li ₂ S, since Li ₂ S has a lithium source, the negative electrode active material does not need to have a lithium source. Therefore, by using Li ₂ S as the positive electrode active material, it is not necessary to use unstable lithium metal or lithium metal alloy during production, and the manufacturing aspect is improved. In addition, by using Li ₂ S, it is easy to uniformly disperse in the synthesized solid electrolyte while maintaining the characteristics of the active material. Therefore, Li ₂ S (first Li ₂ S) is preferable as the positive electrode active material.

(Solid electrolyte raw material)
The solid electrolyte raw material is not particularly limited as long as it can synthesize a solid electrolyte from the solid electrolyte raw material by compounding with mechanical energy. The solid electrolyte raw material is preferably two or more selected from the group consisting of lithium oxide (Li ₂ O), lithium nitride, lithium fluoride, lithium chloride (LiCl), lithium bromide (LiBr), lithium iodide (LiI), lithium sulfate (Li ₂ SO ₄ ), lithium carbonate (Li ₂ CO ₃ ), lithium borate, lithium phosphate, lithium nitrate, lithium silicate (Li ₄ SiO ₄ ), and lithium aluminate. The solid electrolyte raw material is particularly preferably Li ₂ SO ₄ , Li ₂ CO ₃ , LiCl, LiBr, LiI, Li ₂ O, or Li ₄ SiO _4. By including these, a good solid electrolyte that is amorphous and has excellent deformability can be obtained by mechanical energy.

(Carbon materials)
The carbon material supplements the electrical conductivity of the positive electrode active material. The carbon material is not particularly limited as long as it functions as a conductive material. The carbon material also has a function of promoting the synthesis of a solid electrolyte. Examples of the carbon material include acetylene black, carbon nanotubes, activated carbon, graphene, furnace black (for example, furnace black having a hollow shell structure), carbon fiber, and the like. The carbon material may contain one or more of these. Examples of furnace black having a hollow shell structure include Ketjen Black (manufactured by Lion Corporation). When a low-conductivity carbon material is used, the electronic conductivity of the electrode composite can be improved by combining a low-conductivity carbon material with a high-conductivity carbon material. This further improves the charge/discharge capacity of the electrode composite. The low-conductivity carbon material is activated carbon. The high-conductivity carbon material is one or more selected from the group consisting of acetylene black, Ketjen black, carbon nanotubes, and graphene. The weight ratio of the low-conductivity carbon material to the high-conductivity carbon material is preferably low-conductivity carbon material:high-conductivity carbon material=10:0 to 5:5.

The specific surface area of the carbon material is preferably 10 m ² /g or more. The more preferred specific surface area of the carbon material is 100 m ² /g or more. The even more preferred specific surface area of the carbon material is 1000 m ² /g or more. The even more preferred specific surface area of the carbon material is 1500 m ² /g or more. If the specific surface area is less than 10 m ² /g, the contact points between the positive electrode active material and the carbon material cannot be sufficiently increased, and therefore the effect of improving the charge/discharge capacity tends not to be fully enjoyed. The upper limit of the specific surface area is not particularly limited, but is usually 6000 m ² /g or less.

(Other ingredients)
The electrode composite raw material of the second embodiment may further contain optional components such as a binder, a solvent, and an ion-conductive material.

(Weight ratio)
In the second embodiment, when the positive electrode active material is the first Li ₂ S and the solid electrolyte raw material is two or more selected from the group consisting of lithium oxide, lithium nitride, lithium fluoride, lithium chloride, lithium bromide, lithium iodide, lithium sulfate, lithium carbonate, lithium borate, lithium phosphate, lithium nitrate, lithium silicate, and lithium aluminate, the weight ratio of the first Li ₂ S, the solid electrolyte raw material, and the carbon material (first Li ₂ S: solid electrolyte raw material: carbon material) is preferably 20 to 60: 20 to 70: 3 to 20. When the weight ratio of the solid electrolyte raw material in the electrode composite raw material and the carbon material is 20 to 60: 20 to 70: 3 to 20, the ion conductivity in the electrode composite and the contact points between the active material, the solid electrolyte, and the carbon material can be sufficiently obtained, so that the battery characteristics are improved, which is preferable. By compounding two or more selected from the above group with mechanical energy, at least a part of the solid electrolyte raw material becomes a solid electrolyte.

[Combination through mechanical energy]
The method of compounding the electrode composite raw materials by mechanical energy may be the same as that of the first embodiment. The fact that the electrode composite raw materials are compounded and the solid electrolyte is synthesized can be confirmed, for example, by performing DSC measurement of the electrode composite and confirming the position of the exothermic peak. In addition, the fact that the solid electrolyte is amorphous can be confirmed by performing XRD measurement of the obtained electrode composite and the disappearance of the diffraction peaks of the solid electrolyte raw materials other than the electrode active material. The conditions during compounding can be appropriately adjusted using confirmation methods such as XRD and DSC.

In the manufacturing method of an electrode composite for an all-solid-state lithium-ion battery according to the second embodiment, the electrode composite raw material may be composited by mechanical energy and then subjected to a heat treatment. The heat treatment may be performed in the same manner as in the first embodiment.

[Electrode composite]
The electrode composite manufactured by the manufacturing method of the electrode composite for an all-solid-state lithium ion battery according to the second embodiment includes a positive electrode active material, a solid electrolyte, and a carbon material. It is preferable that the solid electrolyte is amorphous.

When the solid electrolyte of the electrode composite is amorphous, for example, in the XRD spectrum obtained by measurement in the 2θ range of 10 to 60° using a SmartLab II manufactured by RIGAKU Corporation, the diffraction peak of the solid electrolyte raw material disappears. In addition, in the curve (DSC curve) obtained by differential scanning calorimetry (DSC) measurement, the solid electrolyte has an exothermic peak at 400°C or less that is different from that of the solid electrolyte raw material. The DSC curve is obtained by installing a differential scanning calorimeter (for example, DSC6200 manufactured by Seiko Instruments Inc.) and performing measurements in the temperature range of 50°C to 500°C and at a heating rate of 5°C/min.

Third Embodiment
In the manufacturing method of the electrode composite for an all-solid-state lithium ion battery according to the third embodiment, an electrode composite raw material including a negative electrode active material as an electrode active material, a sulfide solid electrolyte raw material, and a carbon material is composited by mechanical energy. Each requirement will be described below.

[Electrode composite raw materials]
The electrode composite raw material used in the manufacturing method for an electrode composite for an all-solid-state lithium ion battery according to the third embodiment includes a negative electrode active material, a sulfide solid electrolyte raw material, and a carbon material. By using the sulfide solid electrolyte raw material, the electrical conductivity of the electrode composite can be improved.

(Negative Electrode Active Material)
The negative electrode active material is not particularly limited as long as it does not lose its function when it is combined with other materials by mechanical energy. The negative electrode active material is, for example, a Si-based active material consisting of one of Si and Si compounds. If the negative electrode active material is a Si-based active material, it can be uniformly dispersed in the sulfide solid electrolyte when the electrode composite raw material is combined by mechanical energy. Examples of the Si compound include SiO and LiSi. In particular, as the Si-based active material, Si is preferable because it has a very large theoretical capacity compared to conventional graphite.

(Sulfide solid electrolyte raw material)
The sulfide solid electrolyte raw material is not particularly limited as long as it can be compounded by mechanical energy to synthesize a sulfide solid electrolyte from the sulfide solid electrolyte raw material. Examples of the sulfide solid electrolyte raw material include Li ₂ S, Examples of sulfide solid electrolyte raw materials include _P2S5 , _SiS2 , _{GeS2 , Al2S3 ,} ZnS _{, As2S3 , Sb2S3} , _WS2 , and _{CuS .} It is preferable that the sulfide solid electrolyte raw material contains Li ₂ S and P _{2 S 5. When the sulfide solid electrolyte raw material contains Li 2 S and P 2 S 5} , it is possible to obtain an amorphous, highly deformable, and excellent sulfide solid electrolyte by mechanical energy. can be obtained.

(Carbon materials)
The carbon material supplements the electrical conductivity of the negative electrode active material. The carbon material is not particularly limited as long as it functions as a conductive material. The carbon material also has a function of promoting the synthesis of a solid electrolyte. Examples of the carbon material include acetylene black, carbon nanotubes, activated carbon, graphene, furnace black (for example, furnace black having a hollow shell structure), carbon fiber, and the like. The carbon material may contain one or more of these. Examples of furnace black having a hollow shell structure include Ketjen Black (manufactured by Lion Corporation). When a low-conductivity carbon material is used, the electronic conductivity of the electrode composite can be improved by combining a low-conductivity carbon material with a high-conductivity carbon material. This further improves the charge/discharge capacity of the electrode composite. The low-conductivity carbon material is activated carbon. The high-conductivity carbon material is one or more selected from the group consisting of acetylene black, Ketjen black, carbon nanotubes, and graphene. The weight ratio of the low-conductivity carbon material to the high-conductivity carbon material is preferably low-conductivity carbon material:high-conductivity carbon material=10:0 to 5:5.

The specific surface area of the carbon material is preferably 10 m ² /g or more. The more preferred specific surface area of the carbon material is 100 m ² /g or more. The even more preferred specific surface area of the carbon material is 1000 m ² /g or more. The particularly preferred specific surface area of the carbon material is 1500 m ² /g or more. If the specific surface area is less than 10 m ² /g, the contact points between the negative electrode active material and the carbon material cannot be sufficiently increased, and therefore the effect of improving the charge/discharge capacity tends not to be fully enjoyed. The upper limit of the specific surface area is not particularly limited, but is usually 6000 m ² /g or less.

(Lithium salt)
The electrode composite raw material of the third embodiment may further contain a lithium salt (lithium salt) in addition to the negative electrode active material, the sulfide solid electrolyte raw material, and the carbon material. The lithium salt has a function of improving the conductivity of the sulfide solid electrolyte and a function of improving the flexibility of the sulfide solid electrolyte. The lithium salt is not particularly limited as long as it has a function of improving the conductivity of the sulfide solid electrolyte or a function of improving the flexibility of the sulfide solid electrolyte. For example, the lithium salt is preferably one or more selected from the group consisting of lithium oxide, lithium nitride, lithium fluoride, lithium chloride, lithium bromide, lithium iodide, lithium sulfate, lithium carbonate, lithium borate, lithium phosphate, lithium nitrate, lithium silicate, and lithium aluminate.

(Other ingredients)
The electrode composite raw material of the third embodiment may further contain optional components such as a binder, a solvent, and an ion-conductive material.

(Weight ratio)
In the third embodiment, when the negative electrode active material is a Si-based active material and the sulfide solid electrolyte raw material is Li ₂ S and P ₂ S ₅ , the weight ratio of the Si-based active material, Li ₂ S, P ₂ S ₅ , and the carbon material in the electrode composite raw material (Si-based active material: Li ₂ S: P ₂ S ₅ : carbon material) is preferably 20 to 70: 10 to 30: 10 to 40: 3 to 20. When the weight ratio of the Si-based active material, Li ₂ S, P ₂ S ₅ , and the carbon material in the electrode composite raw material is 20 to 70: 10 to 30: 10 to 40: 3 to 20, the ion conductivity in the electrode composite and the contact points between the active material, the solid electrolyte, and the carbon material can be sufficiently obtained, which is preferable because the battery characteristics are improved.

In the third embodiment, when the negative electrode active material is a Si-based active material, the sulfide solid electrolyte raw material is Li ₂ S and P ₂ S ₅ , and the electrode composite raw material further contains a lithium salt, the weight ratio of the Si-based active material, Li ₂ S, P ₂ S ₅ , the carbon material, and the lithium salt in the electrode composite raw material (Si-based active material: Li ₂ S: P ₂ S ₅ : carbon material: lithium salt) is preferably 20 to 70: 10 to 30: 10 to 40: 3 to 20: 5 to 30. When the weight ratio of the Si-based active material, Li ₂ S, P ₂ S ₅ , the carbon material, and the lithium salt in the electrode composite raw material is 20 to 70: 10 to 30: 10 to 40: 3 to 20: 5 to 30, the battery characteristics of the electrode composite are further improved, which is preferable.

[Combination through mechanical energy]
The electrode composite raw material can be composited by mechanical energy in the same manner as in the first embodiment. The synthesis of the sulfide solid electrolyte can be confirmed in the same manner as in the first embodiment.

In the manufacturing method of an electrode composite for an all-solid-state lithium ion battery according to the third embodiment, the electrode composite raw material may be composited by mechanical energy and then subjected to a heat treatment. The heat treatment may be performed under the same conditions as those in the first embodiment.

[Electrode composite]
The electrode composite manufactured by the manufacturing method of the electrode composite for an all-solid-state lithium ion battery according to the third embodiment includes a negative electrode active material, a sulfide solid electrolyte, and a carbon material. It is preferable that at least a part of the sulfide solid electrolyte is amorphous.

Whether or not a sulfide solid electrolyte is produced can be confirmed by XPS, as in the first embodiment. Whether or not the sulfide solid electrolyte is amorphous can be confirmed by XRD, as in the first embodiment.

Fourth Embodiment
In the manufacturing method of the electrode composite for an all-solid-state lithium ion battery according to the fourth embodiment, an electrode composite raw material including a negative electrode active material as an electrode active material, a solid electrolyte raw material, and a carbon material is composited by mechanical energy. Each requirement will be described below.

[Electrode composite raw materials]
The electrode composite raw material used in the manufacturing method for an electrode composite for an all-solid-state lithium ion battery according to the fourth embodiment includes a negative electrode active material, a solid electrolyte raw material, and a carbon material. By using the solid electrolyte raw material, the stability of the electrode composite can be improved.

The negative electrode active material is not particularly limited as long as it does not lose its function as an active material when it is combined with other materials by mechanical energy. The negative electrode active material is, for example, a Si-based active material consisting of one type of Si and a Si compound. If the negative electrode active material is a Si-based active material, it can be uniformly dispersed in the solid electrolyte when the electrode composite raw material is combined by mechanical energy. Examples of Si compounds include SiO and LiSi. In particular, as a Si-based active material, Si is particularly preferred because it has a very large theoretical capacity compared to conventional graphite.

(Solid electrolyte raw material)
The solid electrolyte raw material is not particularly limited as long as it can synthesize a solid electrolyte from the solid electrolyte raw material by compounding with mechanical energy. The solid electrolyte raw material is preferably two or more selected from the group consisting of lithium oxide, lithium nitride, lithium fluoride, lithium chloride, lithium bromide, lithium iodide, lithium sulfate (Li ₂ SO ₄ ), lithium carbonate (Li ₂ CO ₃ ), lithium borate, lithium phosphate, lithium nitrate, lithium silicate, and lithium aluminate. The solid electrolyte raw material is particularly preferably Li ₂ SO ₄ , Li ₂ CO ₃ , LiCl, LiBr, LiI, Li ₂ O, or Li ₄ SiO _4. By including these, it is possible to obtain a good solid electrolyte that is amorphous and has excellent deformability by mechanical energy.

(Carbon materials)
The carbon material supplements the electrical conductivity of the negative electrode active material. The carbon material is not particularly limited as long as it functions as a conductive material. The carbon material also has a function of promoting the synthesis of a solid electrolyte. Examples of the carbon material include acetylene black, carbon nanotubes, activated carbon, graphene, furnace black (for example, furnace black having a hollow shell structure), carbon fiber, and the like. The carbon material may contain one or more of these. Examples of furnace black having a hollow shell structure include Ketjen Black (manufactured by Lion Corporation). When a low-conductivity carbon material is used, the electronic conductivity of the electrode composite can be improved by combining a low-conductivity carbon material with a high-conductivity carbon material. This further improves the charge/discharge capacity of the electrode composite. The low-conductivity carbon material is activated carbon. The high-conductivity carbon material is one or more selected from the group consisting of acetylene black, Ketjen black, carbon nanotubes, and graphene. The weight ratio of the low-conductivity carbon material to the high-conductivity carbon material is preferably low-conductivity carbon material:high-conductivity carbon material=10:0 to 5:5.

The specific surface area of the carbon material is preferably 10 m ² /g or more. The more preferred specific surface area of the carbon material is 100 m ² /g or more. The even more preferred specific surface area of the carbon material is 1000 m ² /g or more. The particularly preferred specific surface area of the carbon material is 1500 m ² /g or more. If the specific surface area is less than 10 m ² /g, the contact points between the negative electrode active material and the carbon material cannot be sufficiently increased, and therefore the effect of improving the charge/discharge capacity tends not to be fully enjoyed. The upper limit of the specific surface area is not particularly limited, but is usually 6000 m ² /g or less.

(Other ingredients)
The electrode composite raw material of the fourth embodiment may further contain optional components such as a binder, a solvent, and an ion-conductive material.

(Weight ratio)
In the fourth embodiment, when the negative electrode active material is a Si-based active material and the solid electrolyte raw material is two or more selected from the group consisting of lithium oxide, lithium nitride, lithium fluoride, lithium chloride, lithium bromide, lithium iodide, lithium sulfate, lithium carbonate, lithium borate, lithium phosphate, lithium nitrate, lithium silicate, and lithium aluminate, the weight ratio of the Si-based active material, the solid electrolyte raw material, and the carbon material (Si-based active material: solid electrolyte raw material: carbon material) is preferably 10 to 60: 20 to 80: 3 to 20. When the weight ratio of the Si-based active material, the solid electrolyte raw material, and the carbon material in the electrode composite raw material is 10 to 60: 20 to 80: 3 to 20, the ion conductivity in the electrode composite and the contact points between the active material, the solid electrolyte, and the carbon material can be sufficiently obtained, which is preferable because the battery characteristics are improved.

[Combination through mechanical energy]
The method of compounding the electrode composite raw materials by mechanical energy may be the same as that of the first embodiment. The fact that the electrode composite raw materials are compounded and the solid electrolyte is synthesized can be confirmed, for example, by performing DSC measurement of the electrode composite and confirming the position of the exothermic peak. In addition, the fact that the solid electrolyte is amorphous can be confirmed by performing XRD measurement of the obtained electrode composite and the disappearance of the diffraction peaks of the solid electrolyte raw materials other than the electrode active material. The conditions during compounding can be appropriately adjusted using confirmation methods such as XRD and DSC.

In the manufacturing method of an electrode composite for an all-solid-state lithium-ion battery according to the fourth embodiment, the electrode composite raw material may be composited by mechanical energy and then subjected to a heat treatment. The heat treatment may be performed in the same manner as in the first embodiment.

[Electrode composite]
The electrode composite manufactured by the manufacturing method of the electrode composite for an all-solid-state lithium ion battery according to the fourth embodiment includes a negative electrode active material, a solid electrolyte, and a carbon material. It is preferable that a part of the solid electrolyte is amorphous.

Whether the solid electrolyte is amorphous can be confirmed by XRD or DSC, as in the second embodiment.

The above describes in detail the manufacturing method of the electrode composite for all-solid-state lithium-ion batteries disclosed herein. In addition, it is possible to appropriately replace the components in the above embodiment with well-known components without departing from the spirit of the present invention.

Next, an embodiment of the present invention will be described. However, the conditions in the embodiment are merely an example of conditions adopted to confirm the feasibility and effects of the present invention, and the present invention is not limited to this example of conditions. Various conditions may be adopted in the present invention as long as they do not deviate from the gist of the present invention and achieve the object of the present invention.

(Positive electrode composite 1)
As electrode composite raw materials, Li ₂ S (manufactured by Mitsuwa Chemical Industry Co., Ltd.), P ₂ S ₅ (manufactured by Sigma-Aldrich Co., Ltd.), and activated carbon A (MSC30, manufactured by Kansai Thermochemical Co., Ltd., specific surface area 3000 m ² /g) were weighed out to a weight ratio of 57:33:10, with Li ₂ S: 114 mg, P ₂ S ₅ : 66 mg, and activated carbon: 20 mg. Using a planetary ball mill (Premium Line P-7 manufactured by Frilsch Co., Ltd.), the weighed electrode composite raw material was placed in a 45 ml pot together with about 40 g of 5 mm zirconia balls, and mixed at a revolution speed of 370 rpm for 2 hours to obtain a positive electrode composite 1.

(Positive electrode composite 2)
Positive electrode composite ₂ was obtained by _performing the same process _as positive electrode composite 1, except that 100 mg of Li _{2 S, 60 mg of P 2 S 5 , 20 mg of LiI, and 20 mg of activated carbon were used so that the weight ratio of Li 2 S:P 2 S 5} :LiI (manufactured by Sigma-Aldrich):activated carbon A was 50:30:10:10.

(Positive electrode composite 3)
Positive electrode composite ₃ was _{obtained by the same treatment as in the positive electrode composite 1, except that 130 mg of Li 2 S} , 50 mg of P ₂ S ₅ , and 20 mg of activated carbon were used so that the weight ratio of Li 2 S:P ₂ S 5 :activated carbon A was 65:25:10.

(Positive electrode composite 4)
Positive electrode composite 4 was _{obtained by the same treatment as in the positive electrode composite 1, except that 140 mg of Li 2 S} , 40 mg of P ₂ S ₅ , and 20 mg of activated carbon were used so that the weight ratio of Li 2 S:P ₂ S ₅ :activated carbon A was 70:20:10.

(Positive electrode composite 5)
Positive electrode _{composite 5} was obtained by performing the same process as positive electrode composite 1, except that 120 mg of Li ₂ S, 40 mg _of P ₂ S ₅ , 20 mg of LiI, and 20 mg of activated carbon were used so that the weight ratio of Li ₂ S:P 2 S 5 :LiI:activated carbon A was 60:20:10:10.

(Positive electrode composite 6)
Positive electrode composite ₆ was obtained by performing the same process as positive electrode composite 1, except that 130 mg of Li ₂ S, 40 mg _of P _{2 S 5 , 10 mg of LiI, and 20 mg of activated carbon were used so that the weight ratio of Li 2 S:P 2 S 5} :LiI:activated carbon A was 65:20:5:10.

(Positive electrode composite 7)
Positive electrode composite 7 was obtained by the same treatment as for positive electrode composite ₁ , except that 120 mg of Li ₂ S, 62 mg of P ₂ S _{5 , and 18 mg of activated carbon were used so that the weight ratio of Li 2 S:P 2 S 5 : activated} carbon A was 60:31:9.

(Positive electrode composite 8)
Positive electrode composite _{8 was obtained by the same treatment as in the positive electrode composite 1, except that 120 mg of Li 2 S} , 58 mg of P ₂ S ₅ , and 22 mg of activated carbon were used so that the weight ratio of Li 2 S:P ₂ S 5 :activated carbon A was 60:29:11.

(Positive electrode composite 9)
A positive electrode composite ₉ was obtained in the same manner as in the positive electrode composite 1, except that 120 mg of Li ₂ S, 66 mg of P ₂ S ₅ , and 14 mg of activated carbon were used so that the weight ratio of Li ₂ S:P ₂ S 5 :activated carbon A was 60:33:7.

(Positive electrode composite 10)
A positive electrode composite ₁₀ was obtained by performing the same process as for the positive electrode composite 1, except that 120 mg of Li ₂ S, 20 mg _of P ₂ S ₅ , 50 mg of LiI, and 10 mg of activated carbon were used so that the weight ratio of Li ₂ S:P 2 S 5 :LiI:activated carbon A was 60:10:25:5.

(Positive electrode composite 11)
A positive electrode composite ₁₁ was obtained by performing the same process as for the positive electrode composite 1, except that 120 mg of Li ₂ S, 20 mg _of P ₂ S ₅ , 40 mg of LiI, and 20 mg of activated carbon were used so that the weight ratio of Li ₂ S:P 2 S 5 :LiI:activated carbon A was 60:10:20:10.

(Positive electrode composite 12)
A positive electrode composite 12 was obtained by carrying out the same treatment as for the positive electrode composite 10, except that activated carbon B (MSA20, manufactured by Kansai Thermochemical Industry Co., Ltd., specific surface area 2500 m ² /g) was used instead of activated carbon A.

(Positive electrode composite 13)
A positive electrode composite 13 was obtained by carrying out the same treatment as for the positive electrode composite 10, except that Ketjen black (EC600JD, manufactured by Lion Corporation, specific surface area 1200 m ² /g) was used instead of the activated carbon A.

(Positive electrode composite 14)
A positive electrode composite 14 was obtained by carrying out the same treatment as the positive electrode composite 10, except that acetylene black (Li-100, manufactured by DENKA Corporation, specific surface area 100 m ² /g) was used instead of activated carbon A.

(Positive electrode composite 15)
A positive electrode composite 15 was obtained by _{carrying out the same process as in the positive electrode composite 1, except that 120 mg of Li 2 S} , 60 mg of P ₂ S ₅ , and 20 mg of activated carbon were used so that the weight ratio of Li 2 S:P ₂ S ₅ :activated carbon B was 60:30:10.

(Positive electrode composite 16)
Positive electrode composite 16 was obtained by carrying out the same treatment as for positive electrode composite 11, except that LiBr (manufactured by Sigma-Aldrich) was used instead of LiI.

(Positive electrode composite 17)
Positive electrode _{composite 17} was obtained by the same process as positive electrode composite 1, except that 100 mg of Li ₂ S, 20 mg _of P _{2 S 5 , 60 mg of LiI, and 20 mg of activated carbon were used so that the weight ratio of Li 2 S:P 2 S 5} :LiI:activated carbon A was 50:10:30:10.

(Positive electrode composite 18)
Positive electrode composite 18 was obtained by the same process as positive electrode composite 1, except that 60 mg of Li ₂ S, 63 mg of Li ₂ SO ₄ , 29 mg _of Li ₂ CO ₃ , 28 mg of LiBr, and 20 mg of activated carbon were used so that the weight ratio of Li ₂ S:Li ₂ SO 4:Li ₂ CO ₃ :LiBr:activated carbon A was 30:31.5:14.5:14:10.

(Positive electrode composite 19)
Positive electrode composite 19 was obtained by carrying out the same treatment as for positive electrode composite 18, except that the ball mill treatment time was changed from 2 hours to 8 hours.

(Positive electrode composite 20)
Positive electrode composite 20 was obtained by the same process as positive electrode composite 19, except that 60 mg of Li ₂ S, 52 mg _of Li ₂ SO ₄ , 23 mg of Li ₂ CO ₃ , 45 mg of LiI, and 20 mg of activated carbon were used so that the weight ratio of Li ₂ S:Li ₂ SO 4:Li ₂ CO ₃ :LiI:activated carbon A was 30:26:11.5:22.5:10.

(Positive electrode composite 21)
Positive electrode composite ₂₁ was obtained by the same process as positive electrode composite 19, except that 60 mg of Li ₂ S, 37 mg of Li ₂ O, 83 mg of LiI, and 20 mg of activated carbon were used so that the weight ratio of Li ₂ S:Li 2 O:LiI:activated carbon A was 30:18.5:41.5:10.

(Positive electrode composite 22)
Positive electrode composite ₂₂ was obtained by the same process as positive electrode composite 19, except that 60 mg of Li ₂ S, 58 mg of Li ₂ SO ₄ , 11 mg of Li ₂ O, 51 mg of LiI, and 20 mg of activated carbon were used so that the weight ratio of Li ₂ S:Li ₂ SO 4:Li ₂ O:LiI:activated carbon A was 30:29:5.5:25.5:10.

(Comparative Positive Electrode Composite 1)
A comparative positive electrode composite ₁ was obtained by treating 80Li ₂ S-20P ₂ S ₅ in a ball mill at 500 rpm for 10 hours using a solid electrolyte 1, and the same treatment as for the positive electrode composite 1 was performed except that 100 mg of Li ₂ S, 80 mg of solid electrolyte 1, and 20 mg of activated carbon were used so that the weight ratio of Li 2 S:solid electrolyte 1:activated carbon was 50:40:10.

(Comparative Positive Electrode Composite 2)
Comparative positive electrode composite 2 was obtained by carrying out the same process as comparative positive electrode composite 1, except that solid electrolyte 2 obtained by treating 60Li ₂ S-40P ₂ S ₅ in a ball mill at 500 rpm for 10 hours was used instead of solid electrolyte 1.

(Comparative Positive Electrode Composite 3)
A solid electrolyte 3 obtained by treating 45Li ₂ SO ₄ -30Li ₂ CO ₃ -25LiBr in a ball mill at 370 rpm for 60 hours was used, and a comparative positive electrode composite 3 was obtained by carrying out the same process as in the comparative positive electrode composite 1, except that 60 mg of Li ₂ S, 120 mg of solid electrolyte 3, and 20 mg of activated carbon were used so that the weight ratio of Li ₂ S:solid electrolyte 3:activated carbon was 30:60:10.

(Comparative Positive Electrode Composite 4)
Comparative positive electrode composite 4 was obtained by carrying out the same process as in comparative positive electrode composite 3, except that solid electrolyte 4 obtained by treating 45Li ₂ SO ₄ -30Li ₂ CO ₃ -30LiI in a ball mill at 370 rpm for 60 hours was used instead of solid electrolyte 3.

(Negative electrode composite 1)
A negative electrode composite 1 was obtained by carrying _out the same process as for positive electrode composite 1, except that 100 mg of Si, 18 mg of Li ₂ S, 28 mg of P ₂ S ₅ , 34 mg of LiI, and 20 mg of activated carbon were used so that the weight ratio of Si (manufactured by Nilaco Corporation, purity 99.999%):Li 2 S:P ₂ S ₅ :LiI:activated carbon A was 50:9:14:17:10.

(Negative electrode composite 2)
A negative electrode composite 2 was obtained by _carrying out the same process as for the positive electrode composite ₁ , except that 100 mg of Si, 17 mg of Li ₂ S, 28 mg of P ₂ S ₅ , 33 mg of LiI, and 22 mg of activated carbon were used so that the weight ratio of Si:Li 2 S:P ₂ S 5 :LiI:activated carbon A was 50:8.5:14:16.5:11.

(Negative electrode composite 3)
A negative electrode composite ₃ was obtained by performing the same process as for the positive electrode composite 1, except that 100 mg of Si, 18 mg of Li ₂ S, 29 mg of P ₂ S ₅ , 35 mg of LiI, and 18 mg of activated carbon were used so that the weight ratio of Si:Li 2 S:P ₂ S ₅ :LiI:activated carbon A was 50:9:14.5:17.5:9.

(Negative electrode composite 4)
A negative electrode composite 4 was obtained by carrying out the same treatment as in the positive electrode composite 1, except that the activated carbon B was used instead of the activated carbon A.

(Negative electrode composite 5)
A negative electrode composite 5 was obtained by carrying out the same treatment as in the positive electrode composite 1, except that Ketjen black was used instead of the activated carbon A.

(Negative electrode composite 6)
A negative electrode composite 6 was obtained by carrying out the same treatment as in the positive electrode composite 1, except that acetylene black was used instead of activated carbon A.

(Negative electrode composite 7)
Negative electrode composite 7 was _obtained by performing the same process as positive electrode composite 1, except that 100 mg of Si, 15 mg of Li ₂ S, 25 mg _of P ₂ S ₅ , 30 mg of LiI, and 30 mg of activated carbon were used so that the weight ratio of Si:Li 2 S:P ₂ S 5 :LiI:activated carbon B was 50:7.5:12.5:15:15.

(Negative electrode composite 8)
A negative electrode composite 8 was obtained by performing _the same process as for positive electrode _{composite 1} , except that 100 mg of Si, 13 mg of Li ₂ S, 21 mg of P ₂ S ₅ , 26 mg of LiI, and 40 mg of activated carbon B were used so that the weight ratio of Si:Li 2 S:P ₂ S 5 :LiI:activated carbon B was 50:6.5:10.5:13:20.

(Negative electrode composite 9)
A negative electrode composite 9 was obtained by performing the same process as for the positive electrode _{composite 1} , except that ₁₀₀ mg of Si _, 31 mg of Li ₂ S, 49 mg of P ₂ S ₅ , and 20 mg of activated carbon were used so that the weight ratio of Si:Li 2 S:P 2 S 5 :activated carbon A was 50:15.5:24.5:10.

(Negative electrode composite 10)
A _negative electrode _{composite 10 was obtained by performing the same process as for the positive electrode composite 19, except that 60 mg of Si, 52 mg of Li2SO4, 23 mg of Li2CO3, 45 mg of LiI, and 20 mg of activated carbon were used so that the weight ratio of Si:Li2SO4:Li2CO3 : LiI : activated carbon A} was 30:26:11.5:22.5:10.

(Negative electrode composite 11)
A negative _electrode composite 11 was obtained by the same process as for the positive electrode composite 19, except that 60 mg of Si, 37 mg of _Li2O , 83 mg of LiI, and 20 mg of activated carbon were used so that the weight ratio of Si:Li2O:LiI:activated carbon A was 30:18.5:41.5:10.

(Negative electrode composite 12)
A negative electrode _{composite 12} was obtained by _performing the same process as for the positive electrode composite 19, except that 60 mg of Si, 75 mg of _Li2SO4 , 45 mg of LiI, and 20 mg of activated carbon were used so that the weight ratio of Si: _Li2SO4 :LiI:activated carbon A was 30:37.5:22.5:10.

(Comparative Negative Electrode Composite 1)
A comparative negative electrode composite 1 was obtained by treating 3Li ₂ S-1P ₂ S ₅ -2LiI in a ball mill at 500 rpm for 10 hours with a solid electrolyte 5, and treating the same as in the positive electrode composite 1, except that 100 mg of Si, 80 mg of solid electrolyte 5, and 20 mg of activated carbon were used so that the weight ratio of Si:solid electrolyte 5:activated carbon A was 50:40:10.

(Comparative Negative Electrode Composite 2)
Comparative negative electrode composite 2 was obtained by carrying out the same process as in comparative negative electrode composite 1, except that solid electrolyte 6 obtained by treating 75Li ₂ S-25P ₂ S ₅ in a ball mill at 500 rpm for 10 hours was used instead of solid electrolyte 5.

(Comparative Negative Electrode Composite 3)
Comparative negative electrode composite 3 was obtained by carrying out the same process as in comparative negative electrode composite 1, except that solid electrolyte 7 obtained by treating 42Li ₂ SO ₄ -28Li ₂ CO ₃ -30LiI in a ball mill at 370 rpm for 60 hours was used instead of solid electrolyte 5.

( _Li2S Positive Electrode Half-Cell Preparation Condition 1: Positive Electrode Composites 1-17, Comparative Positive Electrode Composites 1-2)
In an argon gas atmosphere glove box, a cylindrical jig (10 mmΦ, height 10 mm) made of SUS304 was inserted as a negative electrode current collector from the bottom of a cylindrical tube jig made of polycarbonate (inner diameter 10 mmΦ, outer diameter 23 mmΦ, height 20 mm). Next, 80 mg of solid electrolyte (E-1) (composite 1 obtained by firing 5Li ₂ S-GeS ₂ -P ₂ S ₅ at 510 ° C. for 8 hours and composite 2 obtained by treating 80Li ₂ S-20P ₂ S ₅ with a ball mill at 500 rpm for 10 hours, mixed in a weight ratio of 90:10) was placed from the top of the cylindrical tube jig made of polycarbonate. Furthermore, a cylindrical jig (10 mmΦ, height 15 mm) made of SUS304 was inserted from the top of the cylindrical tube jig made of polycarbonate as a positive electrode current collector, and the solid electrolyte (E-1) was sandwiched between the cylindrical tube jig and pressed at a pressure of 80 MPa for 3 minutes to form a solid electrolyte layer having a diameter of 10 mmΦ and a thickness of about 0.6 mm. Next, the cylindrical jig (cathode current collector) made of SUS304 inserted from the top was once removed, and 7.5 mg of the positive electrode composite was placed on the solid electrolyte layer in the cylindrical tube made of polycarbonate. Then, a cylindrical jig (cathode current collector) made of SUS304 was inserted from the top again and pressed at a pressure of 200 MPa for 3 minutes to form a positive electrode composite layer having a diameter of 10 mmΦ and a thickness of about 0.1 mm. Next, the SUS304 cylindrical jig (negative electrode current collector) inserted from the bottom was removed, and a 0.20 mm thick lithium sheet (manufactured by Honjo Metals) punched to a diameter of 8 mmΦ with a hole punch and a 0.3 mm thick indium sheet (manufactured by Furuuchi Chemical Co., Ltd.) punched to a diameter of 9 mmΦ with a hole punch were stacked and inserted from the bottom of the polycarbonate cylindrical tube jig. A SUS304 cylindrical jig (negative electrode current collector) was inserted from the bottom again and pressed at a pressure of 80 MPa for 3 minutes to form a lithium-indium alloy negative electrode. In this way, an all-solid-state lithium ion battery was produced in which, from the bottom, a negative electrode current collector, a lithium-indium alloy negative electrode, a solid electrolyte layer, a positive electrode composite layer, and a positive electrode current collector were stacked. This was sealed to form a battery for evaluating the positive electrode composite.

( _Li2S Positive Electrode Half-Cell Preparation Condition 2: Positive Electrode Composites 18-22, Comparative Positive Electrode Composites 3-4)
In an argon gas atmosphere glove box, a cylindrical jig made of SKD11 (10 mmΦ, height 10 mm) was inserted as a negative electrode current collector from the bottom of a ceramic cylindrical tube jig (inner diameter 10 mmΦ, outer diameter 23 mmΦ, height 20 mm). Next, 80 mg of solid electrolyte (E-1) (composite 1 obtained by firing 5Li ₂ S-GeS ₂ -P ₂ S ₅ at 510°C for 8 hours and composite 2 obtained by treating 80Li ₂ S-20P ₂ S ₅ in a ball mill at 500 rpm for 10 hours, mixed in a weight ratio of 90:10) was placed from the top of the ceramic cylindrical tube jig. Furthermore, a cylindrical jig (10 mmΦ, height 15 mm) made of SKD11 was inserted from the top of the ceramic cylindrical tube jig as a positive electrode current collector, and the solid electrolyte (E-1) was sandwiched between the cylindrical jig and pressed at a pressure of 80 MPa for 3 minutes to form a solid electrolyte layer with a diameter of 10 mmΦ and a thickness of about 0.6 mm. Next, the cylindrical jig (positive electrode current collector) made of SKD11 inserted from the top was once removed, and 10 mg of the prepared positive electrode composite was placed on the solid electrolyte layer in the ceramic cylindrical tube. After that, a cylindrical jig (positive electrode current collector) made of SKD11 was inserted from the top again and pressed at a pressure of 720 MPa for 3 minutes to form a positive electrode composite layer with a diameter of 10 mmΦ and a thickness of about 0.1 mm. Next, the cylindrical jig (negative electrode current collector) made of SKD11 inserted from the bottom was removed, and a lithium sheet (manufactured by Honjo Metals Co., Ltd.) with a thickness of 0.20 mm was punched out to a diameter of 8 mmΦ with a hole punch as a negative electrode, and an indium sheet (manufactured by Furuuchi Chemical Co., Ltd.) with a thickness of 0.3 mm was punched out to a diameter of 9 mmΦ with a hole punch and stacked and inserted from the bottom of the ceramic cylindrical tube jig. A cylindrical jig (negative electrode current collector) made of SKD11 was inserted again from the bottom and pressed at a pressure of 80 MPa for 3 minutes to form a lithium-indium alloy negative electrode. In this way, an all-solid-state lithium ion battery was produced in which the negative electrode current collector, lithium-indium alloy negative electrode, solid electrolyte layer, positive electrode composite layer, and positive electrode current collector were laminated in order from the bottom. This was sealed to form a battery for evaluating the positive electrode composite.

(Si negative electrode half-cell preparation condition 1: negative electrode composites 1-9, comparative negative electrode composites 1-2)
In an argon gas atmosphere glove box, a cylindrical jig made of SUS304 (10 mmΦ, height 10 mm) was inserted as a negative electrode current collector from the bottom of a cylindrical tube jig made of polycarbonate (inner diameter 10 mmΦ, outer diameter 23 mmΦ, height 20 mm). Next, 80 mg of solid electrolyte (E-2) (3Li ₂ S-P ₂ S ₅ -2LiI treated with a ball mill at 500 rpm for 10 hours) was placed from the top of the cylindrical tube jig made of polycarbonate. Furthermore, a cylindrical jig made of SUS304 (10 mmΦ, height 15 mm) was inserted as a positive electrode current collector from the top of the cylindrical tube jig made of polycarbonate to sandwich the solid electrolyte (E-2), and a solid electrolyte layer with a diameter of 10 mmΦ and a thickness of about 0.5 mm was formed by pressing at a pressure of 80 MPa for 3 minutes. Next, the SUS304 cylindrical jig (positive electrode current collector) inserted from above was temporarily removed, and 4.0 mg of the negative electrode composite was placed on the solid electrolyte layer in the polycarbonate cylindrical tube. The SUS304 cylindrical jig (positive electrode current collector) was inserted again from above, and pressed at a pressure of 200 MPa for 3 minutes to form a negative electrode composite layer with a diameter of 10 mmΦ and a thickness of about 0.05 mm. Next, the SUS304 cylindrical jig (negative electrode current collector) inserted from the bottom was removed, and a 0.20 mm thick lithium sheet (manufactured by Honjo Metals) punched out to a diameter of 8 mmΦ with a hole punch as the negative electrode and a 0.3 mm thick indium sheet (manufactured by Furuuchi Chemical Co., Ltd.) punched out to a diameter of 9 mmΦ with a hole punch were stacked and inserted from the bottom of a polycarbonate cylindrical tube jig, and a SUS304 cylindrical jig (negative electrode current collector) was inserted from the bottom again, and pressed at a pressure of 80 MPa for 3 minutes to form a lithium-indium alloy negative electrode. In this way, an all-solid-state lithium ion battery was produced in which, from the bottom, a negative electrode current collector, a lithium-indium alloy negative electrode, a solid electrolyte layer, a negative electrode composite layer, and a positive electrode current collector were stacked. This was sealed to form an evaluation battery.

(Si negative electrode half-cell preparation condition 2: negative electrode composites 10 to 12, comparative negative electrode composite 3)
In an argon gas atmosphere glove box, a cylindrical jig made of SKD11 (10 mmΦ, height 10 mm) was inserted as a negative electrode current collector from the bottom of a ceramic cylindrical tube jig (inner diameter 10 mmΦ, outer diameter 23 mmΦ, height 20 mm). Next, 80 mg of solid electrolyte (E-2) (3Li ₂ S-P ₂ S ₅ -2LiI treated with a ball mill at 500 rpm for 10 hours) was placed from the top of the ceramic cylindrical tube jig. Furthermore, a cylindrical jig made of SKD11 (10 mmΦ, height 15 mm) was inserted as a positive electrode current collector from the top of the ceramic cylindrical tube jig to sandwich the solid electrolyte (E-2), and pressed at a pressure of 80 MPa for 3 minutes to form a solid electrolyte layer with a diameter of 10 mmΦ and a thickness of about 0.5 mm. Next, the cylindrical jig made of SKD11 (cathode current collector) that had been inserted from above was temporarily removed, and 5.0 mg of the prepared anode composite was placed on the solid electrolyte layer in the ceramic cylindrical tube. The cylindrical jig made of SKD11 (cathode current collector) was again inserted from above, and pressed at a pressure of 720 MPa for 3 minutes to form a anode composite layer with a diameter of 10 mmΦ and a thickness of approximately 0.05 mm. Next, the cylindrical jig (negative electrode current collector) made of SKD11 inserted from the bottom was removed, and a 0.20 mm thick lithium sheet (manufactured by Honjo Metals) punched to a diameter of 8 mmΦ with a hole punch as a negative electrode and a 0.3 mm thick indium sheet (manufactured by Furuuchi Chemical Co., Ltd.) punched to a diameter of 9 mmΦ with a hole punch were stacked and inserted from the bottom of a ceramic cylindrical tube jig, and a cylindrical jig (negative electrode current collector) made of SKD11 was inserted from the bottom again, and pressed for 3 minutes at a pressure of 80 MPa to form a lithium-indium alloy negative electrode. In this way, an all-solid-state lithium ion battery was produced in which, from the bottom, a negative electrode current collector, a lithium-indium alloy negative electrode, a solid electrolyte layer, a negative electrode composite layer, and a positive electrode current collector were stacked. This was sealed to form an evaluation battery.

(Full cell 1)
In an argon gas atmosphere glove box, a cylindrical jig made of SUS304 (10 mmΦ, height 10 mm) was inserted as a negative electrode current collector from the bottom of a cylindrical tube jig made of polycarbonate (inner diameter 10 mmΦ, outer diameter 23 mmΦ, height 20 mm). Next, 80 mg of solid electrolyte (E-2) (3Li ₂ S-P ₂ S ₅ -2LiI treated with a ball mill at 500 rpm for 10 hours) was placed from the top of the cylindrical tube jig made of polycarbonate. Furthermore, a cylindrical jig made of SUS304 (10 mmΦ, height 15 mm) was inserted as a positive electrode current collector from the top of the cylindrical tube jig made of polycarbonate to sandwich the solid electrolyte (E-2), and a solid electrolyte layer with a diameter of 10 mmΦ and a thickness of about 0.5 mm was formed by pressing at a pressure of 80 MPa for 3 minutes. Next, the cylindrical jig (cathode current collector) made of SUS304 inserted from the top was removed once, and 7.5 mg of the prepared cathode composite was placed on the solid electrolyte layer in the cylindrical tube made of polycarbonate. A cylindrical jig (cathode current collector) made of SUS304 was inserted from the top again, and pressed at a pressure of 80 MPa for 3 minutes to form a cathode composite layer with a diameter of 10 mmΦ and a thickness of about 0.1 mm. Next, the cylindrical jig (negative electrode current collector) made of SUS304 inserted from the bottom was removed, and 4.0 mg of the anode composite was placed. Then, a cylindrical jig (negative electrode current collector) made of SUS304 was inserted from the bottom again, and pressed at a pressure of 200 MPa for 3 minutes to prepare an all-solid-state lithium ion battery in which the anode current collector, the anode composite layer, the solid electrolyte layer, the cathode composite layer, and the cathode current collector were stacked in order from the bottom. This was sealed to prepare an evaluation battery.

(XRD Measurement)
Positive electrode composites 1 to 22, comparative positive electrode composites 1 to 4, negative electrode composites 1 to 12, and comparative negative electrode composites 1 to 3 were measured in the 2θ range of 10 to 60° using a SmartLab II manufactured by RIGAKU Corporation to obtain XRD spectra. Cases in which there was a peak other than the active material were marked as "present," and cases in which there was no peak other than the active material were marked as "absent." The results are shown in Tables 1 and 2.

(XPS Measurement)
Positive electrode composites 1 to 17, comparative positive electrode composites 1 and 2, negative electrode composites 1 to 9, and comparative negative electrode composites 1 and 2 were measured using KRATOS Nova manufactured by KRATOS ANALYTICAL to obtain XPS spectra. A peak was recorded as present near 165 eV, and no peak was recorded as absent. The results are shown in Tables 1 and 2. The "-" in the column for the presence or absence of an XPS peak near 165 eV indicates that no measurement was performed.

(DSC Measurement)
Measurements were performed on positive electrode composites 18-22, comparative positive electrode composites 3 and 4, negative electrode composites 10-12, and comparative negative electrode composite 3 using a comparative differential scanning calorimeter (DSC6200 manufactured by Seiko Instruments Inc.). The measurements were performed in the temperature range of 50°C to 500°C, with a heating rate of 5°C/min. The exothermic peaks of each composite are shown in Tables 1 and 2. Note that none of the solid electrolyte raw materials used in the production of each composite exhibited an exothermic peak in the temperature range of 50°C to 500°C. A "-" in the DSC exothermic peak temperature column indicates that no measurement was performed.

(Charge/discharge characteristic evaluation)
The charging and discharging characteristics of the evaluation batteries prepared using the above positive electrode composites 1 to 22, comparative positive electrode composites 1 to 4, negative electrode composites 1 to 12, and comparative negative electrode composites 1 to 3 were evaluated using a charging and discharging device (ACD-M01A, manufactured by Aska Electronics Co., Ltd.). The positive electrode composites 1 to 17 and comparative positive electrode composites 1 to 2 were charged at a constant current-constant voltage of 0.2 mA at a voltage range of 0.5 V to 2.5 V and a current value of 0.2 mA at 25 ° C., and discharged at a constant current of 0.2 mA. The positive electrode composites 19 to 22 and comparative positive electrode composites 3 to 4 were charged at a constant current-constant voltage of 0.05 mA at a voltage range of 0.5 V to 2.5 V and a current value of 0.05 mA at 45 ° C. The discharge capacity per weight of the positive electrode composite at the second cycle of each positive electrode composite was examined, and the results obtained are shown in Table 1. Anode composites 1 to 9 and comparative anode composites 1 to 2 were discharged at a constant current of 0.2 mA and charged at a constant current of 0.2 mA at a voltage range of -0.6 V to 2.0 V at 25 ° C. Anode composites 10 to 12 and comparative anode composite 3 were discharged at a constant current of 0.05 mA and charged at a constant current of 0.05 mA at a voltage range of -0.6 V to 2.0 V at 45 ° C. The charge capacity per weight of the anode composite in the second cycle of each anode composite was examined, and the results are shown in Table 2. Furthermore, full cell 1 was charged at a constant current-constant voltage and discharged at a constant current of 0.2 mA at a voltage range of 0.0 V to 3.0 V at 25 ° C., and the discharge capacity per weight of the cathode composite in the second cycle of each full cell was examined, and the results are shown in Table 3. Here, for the half cells using the anode composite and comparative anode composite, the upper limit of the discharge capacity per active material was limited to 2500 mAh / g.

As shown in Tables 1 to 3, it was confirmed that the electrode composites (positive electrode composite and negative electrode composite) produced by the method for producing an electrode composite for an all-solid-state lithium-ion battery of the present invention had a solid electrolyte synthesized therein and were amorphous except for the positive electrode composite 21. Although the electrode composites (positive electrode composite and negative electrode composite) produced by the method for producing an electrode composite for an all-solid-state lithium-ion battery of the present invention were produced in a single step, they showed high battery performance similar to that of the conventional production method (comparative positive electrode composite and comparative negative electrode composite). Normally, the production of a positive electrode or negative electrode composite consists of two steps, a step of producing a solid electrolyte and a step of producing a positive electrode or negative electrode composite, but the present invention allows production in a single step, improving productivity.

By using the manufacturing method of the electrode composite for all-solid-state lithium-ion batteries disclosed herein, the electrode composite can be manufactured in fewer steps than conventional methods, making it highly applicable industrially.

Claims (20)

A method for producing an electrode composite for an all-solid-state lithium ion battery, comprising:
An electrode active material;
A solid electrolyte raw material;
A carbon material which is a conductive material;
The electrode composite material is compounded by mechanical energy to produce the electrode composite for an all-solid-state lithium ion battery,
The specific surface area of the carbon material is 1000 m ² /g or more.
A method for manufacturing an electrode composite for all-solid-state lithium-ion batteries. The method for producing an electrode composite for an all-solid-state lithium ion battery according to claim 1 , wherein the electrode active material is a positive electrode active material. The method for producing an electrode composite for an all-solid-state lithium ion battery according to claim 2 , wherein the positive electrode active material is a first Li ₂ S. The method for producing an electrode composite for an all-solid-state lithium ion battery according to claim 3 , wherein the solid electrolyte raw material is a sulfide solid electrolyte raw material containing a second Li ₂ S and P _{2 S5} . The method for producing an electrode composite for an all-solid-state lithium ion battery according to _{claim 4, wherein in the electrode composite raw material, a weight ratio of the total of the first Li 2 S and the second Li 2 S, P 2 S 5 , and the} carbon material is 30-80:10-50:3-20. The method for producing an electrode composite for an all-solid-state lithium ion battery according to claim 4 or 5 , wherein the electrode composite raw material further contains a lithium salt. 7. The method for producing an electrode composite for an all-solid-state lithium ion battery according to claim 6, wherein the lithium salt is at least one selected from the group consisting of lithium oxide, lithium nitride, lithium fluoride, lithium chloride, lithium bromide, lithium iodide, lithium sulfate, lithium carbonate, lithium borate , lithium phosphate, lithium nitrate, lithium silicate, and lithium aluminate. The method for producing an electrode composite for an all-solid-state lithium ion battery according to claim 6 or 7, wherein in the electrode composite raw material, a weight ratio of the total of the first Li ₂ S and the second Li ₂ S, the P ₂ S ₅ , the carbon material, and the lithium salt is 30 to 80: 10 to 40: 3 to 20: 5 to 30. 4. The method for producing an electrode composite for an all-solid-state lithium ion battery according to claim 3, wherein the solid electrolyte raw material contains two or more selected from the group consisting of lithium oxide, lithium nitride, lithium fluoride, lithium chloride, lithium bromide, lithium iodide, lithium sulfate, lithium carbonate, lithium borate, lithium phosphate, lithium nitrate, lithium silicate, and lithium aluminate. The method for producing an electrode composite for an all-solid-state lithium ion battery according to claim 9 , wherein in the electrode composite raw material, a weight ratio of the first Li ₂ S, the solid electrolyte raw material, and the carbon material is 20-60:20-70:3-20. The method for producing an electrode composite for an all-solid-state lithium ion battery according to claim 1 , wherein the electrode active material is a negative electrode active material. The method for producing an electrode composite for an all-solid-state lithium ion battery according to claim 11 , wherein the negative electrode active material is a Si-based active material comprising at least one of Si and a Si compound. The method for producing an electrode composite for an all-solid-state lithium ion battery according to claim 12 , wherein the Si-based active material is Si. The method for producing an electrode composite for an all-solid-state lithium ion battery according to claim 12 or ₁₃ , wherein the solid electrolyte raw material is a sulfide solid electrolyte raw material containing _Li2S and _P2S5 . The method for producing an electrode composite for an all-solid-state lithium ion battery according to claim 14, wherein in the electrode composite raw material, the weight ratio of the Si-based active material, Li ₂ S, P ₂ S _5, and the carbon material is 20-70:10-30:10-40:3-20. The method for producing an electrode composite for an all-solid-state lithium ion battery according to claim 14 or 15 , wherein the electrode composite raw material further contains a lithium salt. 17. The method for producing an electrode composite for an all-solid-state lithium ion battery according to claim 16, wherein the lithium salt is at least one selected from the group consisting of lithium oxide, lithium nitride, lithium fluoride, lithium chloride, lithium bromide, lithium iodide, lithium sulfate, lithium carbonate, lithium borate , lithium phosphate, lithium nitrate, lithium silicate, and lithium aluminate. The method for producing an electrode composite for an all-solid- _state lithium ion battery according to claim 16 or 17, wherein in the electrode composite raw material, the weight ratio of the Si-based active material, Li ₂ S, P ₂ S 5 , the carbon material, and the lithium salt is 20 to 70: 10 to 30: 10 to 40 : 3 to 20: 5 to 30. 14. The method for producing an electrode composite for an all-solid-state lithium ion battery according to claim 12 or 13 , wherein the solid electrolyte raw material contains at least two of lithium oxide, lithium nitride, lithium fluoride, lithium chloride, lithium bromide, lithium iodide, lithium sulfate, lithium carbonate, lithium borate, lithium phosphate, lithium nitrate , lithium silicate, and lithium aluminate. The method for producing an electrode composite for an all-solid-state lithium ion battery according to claim 19 , wherein in the electrode composite raw material, a weight ratio of the Si-based active material, the solid electrolyte raw material, and the carbon material is 10 to 60: 20 to 80: 3 to 20.