JP6160950B2 - Thin-film sulfur-coated conductive carbon, positive electrode mixture, and all-solid-state lithium-sulfur battery - Google Patents

Description

The present invention relates to a thin film sulfur-coated conductive carbon, a positive electrode mixture, and an all solid-state lithium-sulfur battery.

Sulfur is known to have a very high theoretical capacity of about 1672 mAh / g, and lithium sulfur batteries using sulfur as a positive electrode active material have been actively studied.
Lithium-sulfur batteries are roughly classified into liquid lithium-sulfur batteries that use liquid electrolytes as electrolytes and all-solid-state lithium-sulfur batteries that use solid electrolytes.

In the liquid type lithium-sulfur battery, lithium polysulfide produced by the reaction between lithium ions and sulfur is dissolved in the electrolyte solution, which adversely affects the charge / discharge capacity and life of the battery.
In order to improve this problem, a liquid lithium sulfur battery using a cathode electrode including a porous conductive material coated with sulfa is disclosed (Patent Document 1).

On the other hand, the all-solid-state lithium-sulfur battery is suitable for maintaining the charge / discharge capacity of the battery and extending its life because there is no problem that lithium polysulfide dissolves into the electrolyte solution. In addition, because it does not contain a flammable organic solvent, there is no risk of liquid leakage or ignition, and safety can be ensured. In addition, an all-solid-state lithium-sulfur battery is better than a liquid-type lithium-sulfur battery because it does not require a separator. preferable.

However, in the conventional all-solid-state lithium-sulfur battery, since the positive electrode active material sulfur is electrically insulating, the inside of the sulfur particles or the sulfur film has poor lithium ion conductivity and electronic conductivity, and the battery is sufficiently charged. There was a problem that no reaction (redox reaction) occurred.
Patent Document 2 proposes a positive electrode mixture in which metallic copper, metallic iron, copper sulfide, iron sulfide, or cerium sulfide is added as an electrode catalyst to sulfur and a carbon-based conductive agent in view of the above problems.
Patent Document 3 discloses a mesoporous carbon composite material having mesoporous carbon in which sulfur is arranged in mesopores in order to utilize sulfur as an insulator as a positive electrode active material of an all-solid battery.

JP 2003-197196 A JP 2004-95243 A JP 2010-95390 A

However, in the all solid-state lithium-sulfur battery provided with the positive electrode mixture layer using the materials disclosed in Patent Documents 2 and 3, the discharge capacity per positive electrode mixture layer is insufficient, and the excellent physical properties of sulfur There was a problem that it was not fully utilized.

The present invention provides a thin-film sulfur-coated conductive carbon that can be suitably used for a positive electrode mixture of an all-solid-state lithium-sulfur battery having excellent discharge capacity and rate characteristics by making the best use of the excellent physical properties of sulfur. The purpose is to do. Moreover, it aims at providing the positive electrode compound material containing the said thin film sulfur covering conductive carbon, and the all-solid-state lithium-sulfur battery containing the said positive electrode compound material.

As a result of intensive studies, the inventors of the present invention have a conductive carbon whose surface is coated with a sulfur film, and the conductive carbon has a BET specific surface area of 500 m ² / g or more, and the sulfur film has a film thickness. The present invention was completed by finding that a thin film sulfur-coated conductive carbon having a thickness of 0.4 to 5.0 nm is surprisingly suitable for use in an all-solid-state lithium-sulfur battery having excellent discharge capacity and rate characteristics. It came to do.

Patent Document 2 discloses a positive electrode mixture obtained by ball milling sulfur, metallic copper and acetylene black. The specific surface area of acetylene black, covering acetylene black with a sulfur film, and The film thickness of the sulfur film is not disclosed. In addition, as described above, since Patent Document 3 arranges sulfur in a mesoporous for the purpose of utilizing sulfur, which is an insulator, as a main positive electrode active material, it is technical that the mesoporous carbon is covered with a sulfur film. The idea is not disclosed, and naturally the film thickness of the sulfur film is not disclosed.

The thin film sulfur-coated conductive carbon of the present invention is a conductive carbon whose surface is coated with a sulfur film, and the conductive carbon has a BET specific surface area of 500 m ² / g or more, and the sulfur film has a film thickness. It is a thin film sulfur-coated conductive carbon used for a positive electrode mixture of an all solid-state lithium-sulfur battery having a thickness of 0.4 to 5.0 nm.

In the thin film sulfur-coated conductive carbon of the present invention, the film thickness is preferably 1.0 to 2.5 nm.

In the thin film sulfur-coated conductive carbon of the present invention, the conductive carbon is preferably at least one selected from the group consisting of furnace black, activated carbon, and acetylene black, is furnace black, and has a hollow shell structure. It is more preferable to have.

The thin film sulfur-coated conductive carbon of the present invention is preferably heat-treated at 60 ° C. or higher, and more preferably heat-treated at 100 ° C. or higher.

The positive electrode mixture of the present invention is a positive electrode mixture used for an all solid-state lithium-sulfur battery including the thin film sulfur-coated conductive carbon of the present invention and a solid electrolyte.

The all-solid-state lithium-sulfur battery of the present invention is an all-solid-state lithium-sulfur battery including a positive electrode mixture layer including the positive electrode mixture of the present invention, a solid electrolyte layer, a negative electrode, and a current collector.

The thin film sulfur-coated conductive carbon of the present invention has a sulfur film coated with a conductive film having a BET specific surface area of 500 m ² / g or more with a thin film thickness of 0.4 to 5.0 nm. The diffusion of electrons and lithium ions easily occurs. Therefore, by using the thin film sulfur-coated conductive carbon for the positive electrode mixture of an all-solid-state lithium-sulfur battery, an all-solid-state lithium-sulfur battery having a large discharge capacity per cathode mixture layer and excellent in rate characteristics is provided. Can do.
Moreover, since the positive electrode mixture of the present invention uses the above-described thin film sulfur-coated conductive carbon, it is suitable for forming a positive electrode mixture layer having a large discharge capacity.
Furthermore, since the all-solid-state lithium-sulfur battery of the present invention includes the positive electrode mixture layer using the positive electrode mixture of the present invention, the discharge capacity is excellent.

It is sectional drawing which represented typically an example of embodiment of the all-solid-state lithium sulfur battery of this invention.

<< Thin Sulfur Coated Conductive Carbon >>
First, the thin film sulfur-coated conductive carbon of the present invention will be described.
The thin film sulfur-coated conductive carbon is a conductive carbon whose surface is coated with a sulfur film, and the conductive carbon has a BET specific surface area of 500 m ² / g or more, and the sulfur film has a film thickness of 0.00. It is a thin film sulfur-coated conductive carbon having a thickness of 4 to 5.0 nm used for a positive electrode mixture of an all-solid-state lithium-sulfur battery.

<Conductive carbon>
The conductive carbon is used as an electron conductor.
Although it does not specifically limit as said conductive carbon, For example, acetylene black, activated carbon, furnace black, a carbon nanotube, graphene etc. can be used.
The conductive carbon is preferably at least one selected from the group consisting of furnace black, activated carbon, and acetylene black. This is because the BET specific surface area is large and it is advantageous for securing a conductive path in the positive electrode mixture layer.
The conductive carbon is more preferably furnace black having a hollow shell structure. The reason is that the BET specific surface area is very large because of the hollow shell structure, and the furnace black is advantageous in forming a conductive path in the positive electrode mixture layer because the structure is developed.

The furnace black having a hollow shell structure is a kind of conductive furnace black and means a hollow shell structure having a porosity of about 60 to 80%. Here, the “hollow shell structure” refers to a structure in which graphite crystals are thinly gathered to form an outer shell in the form of particles and have voids inside the outer shell. As furnace black which has the said hollow shell structure, ketjen black (made by Lion Corporation) etc. are mentioned, for example.

The conductive carbon has a BET specific surface area of 500 m ² / g or more.
This is because when the BET specific surface area is less than 500 m ² / g, the amount of sulfur covering the conductive carbon decreases, and the sulfur content in the positive electrode mixture decreases.
The BET specific surface area is preferably 750 m ² / g or more, and more preferably 1,000 m ² / g or more.

In this specification, the BET specific surface area refers to the specific surface area determined by the Brenauer-Emmet-Telle (BET) method. Specifically, a conductive carbon sample is subjected to nitrogen gas at a liquid nitrogen temperature. The specific surface area determined using a nitrogen adsorption isotherm obtained by adsorption.
As a measuring apparatus for obtaining the BET specific surface area, for example, an automatic specific surface area / pore distribution measuring apparatus (BELSORP-miniII, manufactured by Nippon Bell Co., Ltd.) can be used.

Although content of the said conductive carbon is not specifically limited, It is preferable to contain 5 to 80 weight% in thin film sulfur covering conductive carbon, and it is more preferable to contain 10 to 50 weight%.
When the content of the conductive carbon is less than 5% by weight, the sulfur film may be thick, the diffusion resistance inside the sulfur film may be increased, and the discharge capacity may be reduced. This is because if the amount exceeds 80% by weight, the content of sulfur in the thin film sulfur-coated conductive carbon decreases, and the content of sulfur in the positive electrode mixture may decrease.

<Sulfur membrane>
The sulfur film is a film made of sulfur used as a positive electrode active material and covering the conductive carbon.

The sulfur is not limited to single sulfur, and a sulfur-containing compound can be used.
Examples of the sulfur-containing compound is not particularly limited, for _example, can be used _{Li 2 S 8, Li 2 S} 4, Li 2 S 2 polysulphide or lithium sulfide such as _(Li 2 S) and the like. These compounds may be used alone or in combination of two or more, and may be used in combination with single sulfur.

The thickness of the sulfur film is 0.4 to 5.0 nm. When the film thickness is thinner than 0.4 nm, the sulfur content in the thin film sulfur-coated conductive carbon decreases, and the sulfur content in the positive electrode mixture may decrease. On the other hand, if the thickness exceeds 5.0 nm, the diffusion resistance inside the sulfur film increases, and the discharge capacity may decrease or the rate characteristics may deteriorate.
The thickness of the sulfur film is preferably 1.0 to 2.5 nm.
The film thickness of the sulfur film may be calculated based on the weight of each of the conductive carbon and sulfur in the thin film sulfur-coated conductive carbon, and the BET specific surface area of the conductive carbon and the specific gravity of sulfur. .

In the present invention, the “surface” of conductive carbon refers to a portion where nitrogen gas is adsorbed when the specific surface area is measured by the BET method, and “covering” refers to a portion where nitrogen gas is adsorbed. Means to adhere.

<Method for producing thin-film sulfur-coated conductive carbon>
The thin film sulfur-coated conductive carbon can be produced, for example, by the following method.
That is, the step (a) of immersing the conductive carbon in a sulfur solution and coating the surface of the conductive carbon with the sulfur, and the conductive carbon whose surface is coated with sulfur in the step (a) It can be produced by a method for producing a thin film sulfur-coated conductive carbon including the step (b) of separating from the sulfur solution.
According to this method, the thin film sulfur-coated conductive carbon can be easily produced.

As said sulfur solution, what melt | dissolved sulfur in the solvent can be used, As said solvent, if it melt | dissolves sulfur, it will not specifically limit, For example, cyclohexane, n-hexane, toluene, xylene Carbon disulfide or the like can be used. These solvents may be used alone or in combination of two or more.
Among these solvents, it is preferable to use a solvent having a sulfur solubility of 1 to 10% by weight at the operating temperature. This is because the use of a solvent having a sulfur solubility of less than 1% by weight at the use temperature may reduce the amount of sulfur covering the conductive carbon. In addition, when a solvent having a solubility of sulfur exceeding 10% by weight is used, sulfur is very easily dissolved in the solvent and relatively difficult to adsorb on the conductive carbon. This is because the amount may be reduced.
Considering these matters, the solubility of sulfur at the operating temperature varies depending on the type of the above-described sulfur (single sulfur or sulfur-containing compound), but it cannot be generally stated, but it is preferable to use cyclohexane as the solvent.
As the above-mentioned sulfur solution, a sulfur solution obtained by dissolving sulfur in a solvent heated to increase the solubility of sulfur may be used, or a sulfur solution obtained by dissolving sulfur in a solvent is heated. May be used.

In the step (a), treatments such as ultrasonic treatment and stirring treatment may be performed as necessary.
The ultrasonic treatment is performed for the purpose of dispersing secondary particles of conductive carbon, and the conditions are not particularly limited. For example, the ultrasonic treatment can be performed for 1 to 500 minutes under an oscillation frequency of 20 to 50 Hz. .
Although the said stirring process is not specifically limited, For example, using a magnetic stirrer, a mechanical stirrer, a shaker etc., it is carried out on the conditions for 10 minutes-500 hours in the temperature range higher than melting | fusing point of the solvent to be used, and below a boiling point. be able to.
By performing these treatments, the surface of the conductive carbon can be more uniformly coated with sulfur.

The method for separating the conductive carbon whose surface is coated with sulfur in the step (b) is not particularly limited, and a known method such as filtration, centrifugation, decantation, or the like can be used.
Although it does not specifically limit as said filtration, For example, natural filtration, suction filtration (vacuum filtration), pressure filtration, centrifugal filtration, etc. are employable.

In the said manufacturing method, in addition to the said process (a) and process (b), the process (c) which heat-processes the conductive carbon by which the said surface isolate | separated in the said process (b) was coat | covered with sulfur is performed. Also good.
By performing the step (c), the solvent remaining in the conductive carbon whose surface is coated with sulfur can be more reliably removed. In addition, the sulfur film covering the surface of the conductive carbon can be tightly adhered to the surface of the conductive carbon, and the resistance at the solid interface (resistance between the sulfur film and the conductive carbon) can be reduced. .
In the step (c), multiple heat treatments may be performed step by step while changing temperature conditions.

The heat treatment of the conductive carbon whose surface is coated with sulfur in the step (c) is not particularly limited, but can be performed in an atmosphere of argon, nitrogen, air, or the like for 1 second to 50 hours. Moreover, you may carry out under reduced pressure on the conditions which sulfur does not sublime.
The temperature of the heat treatment (in the above step (c), in the case where a plurality of heat treatments are performed step by step while changing the temperature conditions) is not particularly limited, but should be 60 ° C. or higher. Is preferable, and it is more preferable to set it as 100 degreeC or more. The reason is that the above-mentioned interface resistance reduction effect can be enjoyed more reliably.
On the other hand, the upper limit of the temperature of the heat treatment is not particularly limited, but is preferably 250 ° C. The reason is that, even if the temperature is higher than 250 ° C., the above-described interface resistance reduction effect is not further improved, so that the energy required for heating is wasted.
In addition, what is necessary is just to perform the said heat processing using a conventionally well-known drying apparatus, for example, using a constant temperature dryer, a ventilation dryer, a vacuum dryer, an infrared dryer etc., for example.

In the above manufacturing method, the film thickness of the sulfur film is adjusted by adjusting the type and amount of conductive carbon, the type and amount of solvent, the concentration and temperature of the sulfur solution, the immersion time of the conductive carbon in the sulfur solution, the stirring conditions, etc. Can be controlled.
For example, in order to increase the thickness of the sulfur film, the temperature is first increased to increase the concentration of the sulfur solution, and as the concentration of the sulfur solution decreases with the conductive carbon coating, the saturation concentration of sulfur is increased. It is recommended to gradually lower the temperature while taking care not to exceed the temperature.

The thin film sulfur-coated conductive carbon of the present invention has a sulfur film coated with a conductive film having a BET specific surface area of 500 m ² / g or more with a thin film thickness of 0.4 to 5.0 nm. The diffusion of electrons and lithium ions easily occurs. Therefore, by using the thin film sulfur-coated conductive carbon for the positive electrode mixture of an all-solid-state lithium-sulfur battery, an all-solid-state lithium-sulfur battery having a large discharge capacity per cathode mixture layer and excellent in rate characteristics is provided. Can do.

The thin film sulfur-coated conductive carbon of the present invention is preferably heat-treated at 60 ° C. or higher, and more preferably heat-treated at 100 ° C. or higher. The reason for this is that the sulfur film covering the surface of the conductive carbon adheres more firmly to the surface of the conductive carbon by heat treatment, and the resistance (interface resistance) at the solid interface is reduced. This is because the effect that the all-solid-state lithium-sulfur battery using the positive electrode composite material containing the material has excellent discharge capacity and rate characteristics per positive electrode composite material layer becomes more remarkable.

<< Positive electrode mixture >>
Next, the positive electrode mixture of the present invention will be described.
The positive electrode mixture is used for an all-solid-state lithium-sulfur battery including the thin film sulfur-coated conductive carbon of the present invention and a solid electrolyte, and is a material for forming a positive electrode mixture layer.

Although content of the said thin film sulfur covering conductive carbon in the said positive electrode compound material is not specifically limited, It is preferable that it is 40 to 70 weight%.
When the content of the thin film sulfur-coated conductive carbon is less than 40% by weight, the content of sulfur in the positive electrode mixture may be reduced, and the discharge capacity per positive electrode mixture layer may be reduced. When the content of the thin film sulfur-coated conductive carbon exceeds 70% by weight, the lithium ion conductivity in the positive electrode mixture layer decreases due to the decrease in the solid electrolyte content, and the discharge capacity per positive electrode mixture layer is small. There is a case.

<Solid electrolyte>
The solid electrolyte is not particularly limited, and for example, a polymer solid electrolyte such as a polyethylene oxide polymer compound, a polymer compound containing at least one of a polyorganosiloxane chain and a polyoxyalkylene chain can be used.
Moreover, inorganic solid electrolytes, such as a sulfide type solid electrolyte and / or an oxide type solid electrolyte, can be used.
As the sulfide-based solid electrolyte, for example, an inorganic solid electrolyte containing at least one of phosphorus and sulfur and lithium can be suitably used. More specifically, for _{example, Li 2 S-P 2 S} 5, Li 2 S-P 2 S 5 -P 2 O 5, Li 2 S-SiS 2 -LiI, Li 2 S-SiS 2 -LiBr, Li ₂ S—SiS ₂ —LiSiO ₄ or the like can be used.
As the oxide-based solid electrolyte, for example, an inorganic solid electrolyte containing at least one of phosphorus and oxygen and lithium can be suitably used. More specifically, for example, Li ₂ O—P ₂ O ₅ , Li ₂ O—SiO ₂ , Li ₂ O—Nb ₂ O ₅ , Li ₂ O—P ₂ O ₅ —SiO ₂ , Li ₂ O—SiO _{2 -B 2 O 3, Li 2} O-Al 2 O 3 -GeO 2 -P 2 O 5, Li 2 O-Al 2 O 3 -TiO 2 -P 2 O 5 or the like can be used.
These solid electrolytes may be used alone or in combination of two or more.

Although content of the said solid electrolyte is not specifically limited, It is preferable that 30-60 weight% is contained in the said positive electrode compound material.
When the content of the solid electrolyte is less than 30% by weight, the lithium ion conductivity in the positive electrode mixture layer is decreased, and the discharge capacity per positive electrode mixture layer is reduced or the rate characteristics are deteriorated. On the other hand, when the content of the solid electrolyte exceeds 60% by weight, the content of sulfur in the positive electrode mixture is decreased, and the discharge capacity per positive electrode mixture layer may be decreased.

The positive electrode mixture may contain optional components such as a binder and a solvent as necessary.

<Binder>
Although it does not specifically limit as said binder, A thermoplastic resin, a thermosetting resin, etc. can be used, for example, 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), polychlorotrifluoroethylene (PCTFE), vinylidene fluoride-pentaph Olefin copolymer, propylene-tetrafluoroethylene copolymer, ethylene-chlorotrifluoroethylene copolymer (ECTFE), vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene copolymer, vinylidene fluoride-perfluoromethyl Examples thereof include vinyl ether-tetrafluoroethylene copolymer and ethylene-acrylic acid copolymer.
These binders may be used alone or in combination of two or more.
Although content of the said binder is not specifically limited, It is preferable to contain 0.01 to 10weight% in the said positive electrode compound material.

<Solvent>
The solvent is not particularly limited. For example, amine solvents such as N, N-dimethylaminopropylamine and diethylenetriamine, ether solvents such as tetrahydrofuran, ketone solvents such as methyl ethyl ketone, ester solvents such as methyl acetate, Examples include amide solvents such as dimethylacetamide and 1-methyl-2-pyrrolidone, and hydrocarbon solvents such as toluene, xylene, n-hexane, and cyclohexane.
These solvents may be used alone or in combination of two or more.
Although content of the said solvent is not specifically limited, It is preferable that 10 to 99 weight% is contained in the said positive electrode compound material.
By using the positive electrode mixture containing the solvent, the positive electrode mixture layer can be easily produced. The solvent is removed by drying after the production of the positive electrode mixture layer.

<Method for producing positive electrode mixture>
The positive electrode mixture can be obtained by mixing a thin film sulfur-coated conductive carbon and a solid electrolyte and, further, optional components such as a binder and a solvent as necessary.
A method for mixing these is not particularly limited, and a conventionally known method can be used. For example, planetary ball mill (manufactured by Fritsch), hybridization system (manufactured by Nara Machinery Co., Ltd.), cosmos (manufactured by Kawasaki Heavy Industries, Ltd.) ), Mechano-fusion system (manufactured by Hosokawa Micron Co., Ltd.), mechano mill (manufactured by Okada Seiko Co., Ltd.), theta composer (manufactured by Tokusu Kosakusho Co., Ltd.), nanosonic mill (manufactured by Inoue Seisakusho Co., Ltd.), kneader (manufactured by Inoue Seisakusho Co., Ltd.), super mass collider (Masuyuki Industrial Co., Ltd.), Nanomec Reactor (Techno Eye Co., Ltd.), Cornell Despa (Asada Iron Works Co., Ltd.), Planetary Mixer (Asada Iron Works Co., Ltd.) and the like.
Moreover, in preparation of the said positive electrode compound material, you may heat-process, after mixing each component.
This is because the contact interface of sulfur, conductive carbon, and solid electrolyte contained in the positive electrode mixture can be strengthened, and the interface resistance can be reduced.
What is necessary is just to perform the said heat processing on the conditions similar to the heat processing conditions of the process (c) in the manufacturing method of the thin film sulfur covering conductive carbon of this invention.

Such a heat treatment is the thin film produced without performing the step (c) in the method for producing the thin film sulfur-coated conductive carbon as the thin film sulfur-coated conductive carbon used for the production of the positive electrode mixture. It is particularly preferred to use sulfur-coated conductive carbon.
This is because the effect of performing the heat treatment during the production of the positive electrode mixture, that is, the effect of reducing the interfacial resistance of sulfur, conductive carbon and solid electrolyte contained in the positive electrode mixture can be particularly remarkably enjoyed.

<< All solid-state lithium-sulfur battery >>
Next, the all solid-state lithium-sulfur battery of the present invention will be described with reference to the drawings.
The all-solid-state lithium-sulfur battery is an all-solid-state lithium-sulfur battery including a positive electrode mixture layer including the positive electrode mixture of the present invention, a solid electrolyte layer, a negative electrode, and a current collector.

In the present specification, the “all solid type” means a polymer solid electrolyte and / or an inorganic solid electrolyte as an electrolyte, and contains substantially no solvent in the negative electrode, the solid electrolyte layer, and the positive electrode mixture layer. Say things.
In the present specification, “substantially no solvent” means that a trace amount of the solvent may remain.

FIG. 1 is a cross-sectional view schematically showing an example of an embodiment of an all solid-state lithium-sulfur battery of the present invention.
As shown in FIG. 1, an all-solid-state lithium-sulfur battery 10 includes a negative electrode 2, a solid electrolyte layer 3, and a positive electrode mixture layer 4 that are stacked in order, and current collectors (negative electrode current collector 1 and positive electrode current collector) on both sides thereof. It has a structure in which the body 5) is arranged.
Hereinafter, each of the current collector (negative electrode current collector, positive electrode current collector), negative electrode, solid electrolyte layer, and positive electrode mixture layer will be described in order.

<Current collector>
Although it does not specifically limit as said electrical power collector, For example, Al, Cu, Ni, stainless steel etc. can be used.
As the negative electrode current collector, Cu is preferably used because it is difficult to make an alloy with lithium and it can be easily processed into a thin film.
As the positive electrode current collector, Al is preferably used because it is easy to process into a thin film and is inexpensive.

<Negative electrode>
The negative electrode is not particularly limited as long as it contains a material that absorbs and releases lithium ions as a negative electrode active material. Here, examples of the material that occludes and releases lithium ions include metallic lithium, lithium alloy, metal oxide, metal sulfide, and a carbonaceous substance that occludes and releases lithium ions.
Examples of the lithium alloy include alloys of lithium with aluminum, silicon, tin, magnesium, indium, calcium, and the like. Examples of the metal oxide include tin oxide, silicon oxide, lithium titanium oxide, niobium oxide, and tungsten oxide. Examples of the metal sulfide include tin sulfide and titanium sulfide. Examples of the carbonaceous material that absorbs and releases lithium ions include graphite, coke, mesophase pitch-based carbon fiber, spherical carbon, and resin-fired carbon.

The method of obtaining the negative electrode is not particularly limited, but a method of pressing the material that absorbs and releases lithium ions, and a negative electrode precursor dispersion containing the material that absorbs and releases lithium ions and a solvent are used as a negative electrode current collector. Examples thereof include a method of pressing after coating and drying.
As the solvent contained in the negative electrode precursor dispersion, the same solvents as those used for the positive electrode mixture can be used.
The solvent is used to assist the application of the negative electrode precursor dispersion and is removed by drying after the application.

<Solid electrolyte layer>
The solid electrolyte layer can be obtained by a method in which the solid electrolyte is pressure-molded, a method in which the solid electrolyte is dispersed in a solvent, and then applied and dried.
When a solid electrolyte layer is obtained by these methods, heat treatment may be performed at an arbitrary timing for the purpose of reducing the interface resistance of the solid electrolyte layer and improving the denseness.
The method for pressure-forming the solid electrolyte is not particularly limited. For example, a method of sandwiching and pressing the solid electrolyte between the negative electrode current collector and the positive electrode current collector, a method of pressing with a jig of a pressure molding machine Etc.
When a solid electrolyte layer is obtained by a method in which the solid electrolyte is dispersed in a solvent and then applied and dried, the dried solid electrolyte layer may be pressed by the same method as described above.

<Positive electrode mixture layer>
The positive electrode mixture layer can be obtained, for example, by a method of supporting the positive electrode mixture on a positive electrode current collector, a method of pressure forming the positive electrode mixture, or the like.
The method for supporting the positive electrode mixture on the positive electrode current collector is not particularly limited. For example, a method of pressure molding, a positive electrode mixture paste using an organic solvent, etc. is applied to the positive electrode current collector and dried. Examples thereof include a method of fixing by post-pressing.
The method for applying the positive electrode mixture to the positive electrode current collector is not particularly limited, and examples thereof include a slit die coating method, a screen coating method, a curtain coating method, a knife coating method, a gravure coating method, and an electrostatic spray method. It is done.
The method of pressure-forming the positive electrode mixture is not particularly limited. For example, a method of pressing the positive electrode mixture between the negative electrode current collector and the solid electrolyte layer and the positive electrode current collector, pressurization Examples include a method of pressing with a jig of a molding machine.
When the positive electrode mixture layer is obtained by these methods, heat treatment may be performed at an arbitrary timing for the purpose of reducing the interface resistance of the positive electrode mixture layer and improving the denseness.

The all solid-state lithium-sulfur battery may have a separator, in addition to the above-described negative electrode current collector, negative electrode, solid electrolyte layer, positive electrode mixture layer, and positive electrode current collector.
The shape of the all-solid-state lithium-sulfur battery is not particularly limited, and examples thereof include a coin type, a button type, a sheet type, a laminated type, a cylindrical type, a flat type, and a rectangular type.

<Method for producing all solid-state lithium-sulfur battery>
The method for producing the all solid-state lithium-sulfur battery is not particularly limited, and examples thereof include the following methods.
First, a solid electrolyte is sandwiched between a negative electrode current collector and a positive electrode current collector and pressed to produce a solid electrolyte layer. Next, the positive electrode current collector is once removed, the positive electrode mixture is deposited on one side of the solid electrolyte layer, and both ends of the positive electrode current collector (the negative electrode current collector on the solid electrolyte layer side and the positive electrode current collector on the positive electrode mixture side) The positive electrode mixture layer and the positive electrode current collector are laminated on one surface of the solid electrolyte layer, and the negative electrode current collector is laminated on the other surface of the solid electrolyte layer. Finally, once remove the negative electrode current collector, put the negative electrode on the side opposite to the positive electrode mixture layer side of the solid electrolyte layer, and further press the negative electrode current collector on the negative electrode side and press the other side of the solid electrolyte layer A negative electrode and a negative electrode current collector are stacked on the surface. Moreover, it may be pressed one layer at a time as described above, or two or more layers may be deposited, and a plurality of layers may be pressed together and laminated. By such a method, an all solid-state lithium-sulfur battery can be produced.

<Applications of all-solid-state lithium-sulfur batteries>
The use of the all-solid-state lithium-sulfur battery is not particularly limited, but can be suitably used for electrical products that require high energy density, such as hybrid vehicles and electric vehicles.

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples.

1. Raw materials used In the following examples and comparative examples, the following materials were used.
1-1. Positive electrode active material sulfur (manufactured by Aldrich, specific gravity 2 g / cm ³ )
1-2. Conductive carbon activated carbon (manufactured by Kuraray Chemical Co., Ltd., YP-80F (BET specific surface area: 1,933 m ² / g))
Furnace Black having a hollow shell structure (Leon Corporation, Ketjen Black EC-600JD (BET specific surface area: 1,156 m ² / g))
Acetylene black (manufactured by Denki Kagaku Kogyo Co., Ltd., OSAB (BET specific surface area: 850 m ² / g))
Acetylene black (manufactured by Strem Chemicals, acetylene carbon black (BET specific surface area: 75 m ² / g))
1-3. Anode material lithium sheet (Furuuchi Chemical Co., Ltd., thickness 0.25 mm)
Indium sheet (Furuuchi Chemical Co., Ltd., thickness 0.30mm)
1-4. Organic solvent cyclohexane (made by Wako Pure Chemical Industries, special reagent grade) for the production of thin film sulfur-coated conductive carbon
1-5. Raw material lithium sulfide for production of solid electrolyte (manufactured by Furuuchi Chemical Co., Ltd., Li ₂ S)
Phosphorus pentasulfide (manufactured by Aldrich, P ₂ S ₅ )

2. Solid electrolyte production method In a glove box (MDB-1KP type, manufactured by Miwa Seisakusho Co., Ltd.) in an argon atmosphere with a dew point temperature of −70 ° C. or less, 0.453 g of lithium sulfide and 0.547 g of diphosphorus pentasulfide were mixed in a mortar. A 180 mm zirconia ball and a 180 mm zirconia ball were placed in a zirconia container (Fritch Inc., Premium line P-7) with a capacity of 80 ml, and a planetary ball mill (Fritch Inc., Premium line P-7) was rotated at a rotational speed of 250 rpm. After treatment at a speed of 500 rpm (autorotation and reverse rotation) for 10 hours, the solid electrolyte was produced by heating at 220 ° C. for 2 hours in an argon atmosphere.

3. Production Method of All Solid Type Lithium Sulfur Battery The battery production described below was performed in a glove box in an argon atmosphere with a dew point temperature of −70 ° C. or lower.
A cylindrical jig made of SUS304 (10 mmφ, height 10 mm) is inserted as a negative electrode current collector from the lower side of a cylindrical tube jig made of polycarbonate (inner diameter 10 mmΦ, outer diameter 23 mmΦ, height 20 mm). 70.0 mg of a solid electrolyte is added from the upper side of the tool, and a cylindrical jig made of SUS304 (10 mmΦ, height 15 mm) is further inserted as a positive electrode current collector from the upper side of the cylindrical tube jig made of polycarbonate, and the solid electrolyte is sandwiched between them. A solid electrolyte layer having a diameter of 10 mmΦ and a thickness of about 0.6 mm was produced by pressing at a pressure of 200 MPa for 1 minute.
Next, the cylindrical jig made of SUS304 (positive electrode current collector) inserted from the upper side is temporarily extracted, 15.0 mg of the positive electrode mixture is put on the solid electrolyte layer in the polycarbonate cylindrical tube, and again made of SUS304 from the upper side. A cylindrical jig (positive electrode current collector) was inserted and pressed at 200 MPa for 3 minutes to form a positive electrode mixture layer having a diameter of 10 mmΦ and a thickness of about 0.1 mm.
Next, a cylindrical jig (negative electrode current collector) made of SUS304 inserted from the lower side is extracted, and a lithium sheet as a negative electrode is punched into a diameter of 8 mmΦ, and an indium sheet is punched into a diameter of 9 mmΦ with a punch. Are inserted from the lower side of the cylindrical tube jig made of polycarbonate, and the cylindrical jig made of SUS304 (negative electrode current collector) is inserted again from the lower side, and pressed at a pressure of 80 MPa for 3 minutes to form a lithium-indium alloy. A negative electrode was formed.
As described above, an all-solid-state lithium-sulfur battery in which the negative electrode current collector, the lithium-indium alloy negative electrode, the solid electrolyte layer, the positive electrode mixture layer, and the positive electrode current collector were stacked in this order from the bottom was produced.

4). Evaluation Method In the following examples and comparative examples, the following evaluations were performed.
(A) It measured using the BET specific surface area automatic specific surface area / pore distribution measuring apparatus (Nippon Bell Co., Ltd. make, BELSORP-mini II), and measured by BET method.
(B) Discharge capacity Charge / discharge is repeated at a current value of 0.20 mA (0.25 mA / cm ² ) using a charge / discharge test apparatus (ACD-M01A, manufactured by Asuka Electronics Co., Ltd.). It was measured.
Obtained by dividing the measured discharge capacity by the weight (g) of sulfur contained in the thin-film sulfur-coated conductive carbon (in the case of Comparative Examples 3 and 4, a mixture of sulfur and conductive carbon) in the positive electrode mixture. The numerical value obtained by dividing the numerical value by the discharge capacity per sulfur and dividing by the weight of the positive electrode mixture layer (0.015 g) was taken as the discharge capacity per positive electrode mixture layer.
In Table 1 below, there are several examples in which the discharge capacity per sulfur is higher than the theoretical capacity of about 1672 mAh / g, which remains in the solid electrolyte in the positive electrode mixture. This is probably because part of lithium sulfide (Li ₂ S) also works as the positive electrode active material.

(Comparative Example 1)
200 mg of sulfur and 20 g of cyclohexane were placed in a 50 ml screw tube and stirred with a magnetic stirrer to dissolve the sulfur. Next, 100 mg of activated carbon was immersed in this sulfur cyclohexane solution and subjected to ultrasonic treatment (output 100 W, oscillation frequency 28 Hz, 40 minutes) to disperse the activated carbon. Subsequently, the activated carbon was coated with sulfur by stirring with a magnetic stirrer at 25 ° C. for 48 hours to adsorb the sulfur to the activated carbon.
About 2 g of the dispersion after the sulfur coating was extracted, and the activated carbon whose surface was coated with sulfur was sedimented by centrifugation, and the solid content of the supernatant sulfur solution was measured and found to be 0.63 wt%. Since the concentration of the original sulfur solution is 0.99 wt%, 73.0 mg of sulfur coats 100 mg of activated carbon. Therefore, sulfur in the activated carbon whose surface is coated with sulfur is 42.2 wt% (Table 1). Since the activated carbon used has a BET specific surface area of 1,933 m ² / g, sulfur having a specific gravity of 2 g / cm ³ is coated with a thickness of 0.19 nm.
Separate the activated carbon with the surface covered with sulfur from the sulfur solution by suction filtration of the remaining amount other than about 2 g extracted for the calculation of the amount of sulfur coating and film thickness, and heat-treat at 70 ° C. for 1 hour. As a result, 160.9 mg (yield 93%) of thin film sulfur-coated activated carbon was obtained.
Next, in a glove box in an argon atmosphere with a dew point temperature of −70 ° C. or less, 40 g of 5 mmφ zirconia balls, 100 mg of thin-film sulfur-coated activated carbon, and 100 mg of a solid electrolyte were placed in a zirconia container having a capacity of 45 ml (Premium line P-, manufactured by Fritsch). 7) and a planetary ball mill (Premium line P-7, manufactured by Fritsch) for 2 hours at a rotation speed of 185 rpm and a rotation speed of 370 rpm (rotation and reverse rotation), 140 mg (yield 70%) A positive electrode mixture was obtained.
Using this positive electrode mixture, a battery was prepared according to the battery preparation method described above, and the discharge capacity was measured.

Example 1
500 mg of sulfur and 20 g of cyclohexane were put in a 50 ml screw tube and stirred with a magnetic stirrer while heating to 50 ° C. to dissolve the sulfur. Next, 100 mg of activated carbon was immersed in this sulfur cyclohexane solution and subjected to ultrasonic treatment (output 100 W, oscillation frequency 28 Hz, 40 minutes) to disperse the activated carbon. Subsequently, after stirring with a magnetic stirrer at 50 ° C. for 1 hour, the temperature was lowered to 25 ° C. over 3 hours, and then stirred at 25 ° C. for 48 hours to adsorb sulfur to the activated carbon. Covered.
About 2 g of the dispersion liquid after the sulfur coating was extracted, and the activated carbon whose surface was coated with sulfur was sedimented by centrifugation, and the solid content of the supernatant sulfur solution was measured and found to be 0.78 wt%. Since the concentration of the original sulfur solution is 2.44 wt%, 343.5 mg of sulfur coats 100 mg of activated carbon. Therefore, the sulfur in the activated carbon whose surface is coated with sulfur is 77.5 wt% (Table 1). Since the activated carbon used has a BET specific surface area of 1,933 m ² / g, sulfur having a specific gravity of 2 g / cm ³ is coated with a thickness of 0.89 nm.
Separate the activated carbon with the surface covered with sulfur from the sulfur solution by suction filtration of the remaining amount other than about 2 g extracted for the calculation of the amount of sulfur coating and film thickness, and heat-treat at 70 ° C. for 1 hour. As a result, 418.8 mg (yield 94%) of thin film sulfur-coated activated carbon was obtained.
Next, in a glove box in an argon atmosphere with a dew point temperature of −70 ° C. or less, 40 g of 5 mmφ zirconia balls, 100 mg of thin-film sulfur-coated activated carbon, and 100 mg of a solid electrolyte were placed in a zirconia container having a capacity of 45 ml (Premium line P-, manufactured by Fritsch). 7) and a planetary ball mill (Premium line P-7, manufactured by Fritsch) for 2 hours at a rotation speed of 185 rpm and a rotation speed of 370 rpm (rotation and reverse rotation), 140 mg (yield 70%) A positive electrode mixture was obtained.
Using this positive electrode mixture, a battery was prepared according to the battery preparation method described above, and the discharge capacity was measured.

(Comparative Example 2)
200 mg of sulfur and 20 g of cyclohexane were placed in a 50 ml screw tube and stirred with a magnetic stirrer to dissolve the sulfur. Next, 100 mg of acetylene black (BET specific surface area: 75 m ² / g) was immersed in this sulfur cyclohexane solution and subjected to ultrasonic treatment (output 100 W, oscillation frequency 28 Hz, 40 minutes) to disperse acetylene black. Subsequently, acetylene black was coated with sulfur by stirring with a magnetic stirrer at 25 ° C. for 48 hours to adsorb sulfur to acetylene black.
About 2 g of the dispersion liquid after the sulfur coating was extracted, and acetylene black whose surface was coated with sulfur was settled by centrifugation, and the solid content of the supernatant sulfur solution was measured and found to be 0.94 wt%. . Since the concentration of the original sulfur solution is 0.99 wt%, 11.2 mg of sulfur coats 100 mg of acetylene black. Therefore, sulfur in the acetylene black whose surface is coated with sulfur is 10.1 wt% (Table 1). Since the acetylene black used has a BET specific surface area of 75 m ² / g, sulfur having a specific gravity of 2 g / cm ³ is coated with a thickness of 0.75 nm.
The remaining amount other than about 2 g extracted for the calculation of the amount of coating of the sulfur and the film thickness is subjected to suction filtration to separate the acetylene black whose surface is coated with sulfur from the sulfur solution and heat-treated at 160 ° C. for 1 hour. As a result, 102.1 mg (yield 92%) of thin film sulfur-coated acetylene black was obtained.
Next, in a glove box having an argon atmosphere with a dew point temperature of −70 ° C. or less, 40 g of 5 mmφ zirconia balls, 100 mg of thin-film sulfur-coated acetylene black, and 100 mg of a solid electrolyte were placed in a zirconia container having a capacity of 45 ml (Premium line P, manufactured by Fritsch). -7 mg) and processing with a planetary ball mill (Premium line P-7, manufactured by Fritsch) at a rotation speed of 185 rpm and a revolution speed of 370 rpm (rotation and reverse rotation) for 2 hours, 143 mg (yield 72%) A positive electrode composite was obtained.
Using this positive electrode mixture, a battery was prepared according to the battery preparation method described above, and the discharge capacity was measured.

(Comparative Example 3)
In a glove box under an argon atmosphere with a dew point temperature of −70 ° C. or less, 40 g of 5 mmφ zirconia balls, 68.4 mg of sulfur, and 31.6 mg of acetylene black (BET specific surface area: 850 m ^{2 /} g) It is put in a French product, Premium line P-7, and is treated with a planetary ball mill (Fritsch product, Premium line P-7) at a rotation speed of 185 rpm and a revolution speed of 370 rpm (rotation and reverse rotation) for 1 hour, and then 25 Heat treatment at 1 ° C. for 1 hour, followed by addition of 100 mg of solid electrolyte and further treatment with a planetary ball mill at a rotation speed of 185 rpm and a revolution speed of 370 rpm (rotation and reverse rotation) for 2 hours, 142 mg (yield 71%) A positive electrode composite was obtained.
Using this positive electrode mixture, a battery was prepared according to the battery preparation method described above, and the discharge capacity was measured.

(Comparative Example 4)
In a glove box under an argon atmosphere with a dew point temperature of −70 ° C. or less, 40 g of 5 mmφ zirconia balls, 68.4 mg of sulfur, and 31.6 mg of acetylene black (BET specific surface area: 850 m ^{2 /} g) It is put in a French product, Premium line P-7, and is treated with a planetary ball mill (Fritsch product, Premium line P-7) at a rotation speed of 185 rpm and a revolution speed of 370 rpm (rotation and reverse rotation) for 1 hour, and then 160 Heat treatment at 1 ° C. for 1 hour, followed by addition of 100 mg of solid electrolyte and further treatment with a planetary ball mill at a rotation speed of 185 rpm and a revolution speed of 370 rpm (rotation and reverse rotation) for 2 hours, 142 mg (yield 71%) A positive electrode composite was obtained.
Using this positive electrode mixture, a battery was prepared according to the battery preparation method described above, and the discharge capacity was measured.

(Example 2)
400 mg of sulfur and 20 g of cyclohexane were put into a 50 ml screw tube and stirred with a magnetic stirrer while heating to 50 ° C. to dissolve the sulfur. Next, 100 mg of acetylene black (BET specific surface area: 850 m ² / g) was immersed in this sulfur cyclohexane solution and subjected to ultrasonic treatment (output 100 W, oscillation frequency 28 Hz, 40 minutes) to disperse acetylene black. Subsequently, the mixture was stirred with a magnetic stirrer at 50 ° C. for 1 hour, then lowered to 25 ° C. over 3 hours, and then stirred at 25 ° C. for 48 hours to adsorb sulfur to acetylene black, thereby acetylene with sulfur. Black was coated.
About 2 g of the dispersion liquid after the sulfur coating was extracted, and acetylene black whose surface was coated with sulfur was settled by centrifugation, and the solid content of the supernatant sulfur solution was measured and found to be 0.91 wt%. . Since the concentration of the original sulfur solution is 1.96 wt%, 216.8 mg of sulfur coats 100 mg of acetylene black. Therefore, sulfur in the acetylene black whose surface is coated with sulfur is 68.4 wt% (Table 1). Since the acetylene black used has a BET specific surface area of 850 m ² / g, sulfur having a specific gravity of 2 g / cm ³ is coated with a thickness of 1.28 nm.
The remaining amount other than about 2 g extracted for calculation of the amount of sulfur coating and film thickness is filtered by suction to separate the acetylene black whose surface is coated with sulfur from the sulfur solution and heat-treated at 25 ° C. for 1 hour. As a result, 298.2 mg (yield 94%) of a thin film sulfur-coated acetylene black was obtained.
Next, in a glove box having an argon atmosphere with a dew point temperature of −70 ° C. or less, 40 g of 5 mmφ zirconia balls, 100 mg of thin-film sulfur-coated acetylene black, and 100 mg of a solid electrolyte were placed in a zirconia container having a capacity of 45 ml (Premium line P, manufactured by Fritsch). -7), and a planetary ball mill (Premium line P-7, manufactured by Fritsch) for 2 hours at a rotation speed of 185 rpm and a revolution speed of 370 rpm (rotation and reverse rotation), 138 mg (yield 69%) A positive electrode composite was obtained.
Using this positive electrode mixture, a battery was prepared according to the battery preparation method described above, and the discharge capacity was measured.

(Example 3)
In the same manner as in Example 2, acetylene black was coated with sulfur.
About 2 g of the dispersion liquid after the sulfur coating was extracted, and acetylene black whose surface was coated with sulfur was settled by centrifugation, and the solid content of the supernatant sulfur solution was measured and found to be 0.91 wt%. . Since the concentration of the original sulfur solution is 1.96 wt%, 216.8 mg of sulfur coats 100 mg of acetylene black. Therefore, sulfur in the acetylene black whose surface is coated with sulfur is 68.4 wt% (Table 1). Since the acetylene black used has a BET specific surface area of 850 m ² / g, sulfur having a specific gravity of 2 g / cm ³ is coated with a thickness of 1.28 nm.
The remaining amount other than about 2 g extracted for the calculation of the amount of coating of the sulfur and the film thickness is subjected to suction filtration to separate the acetylene black whose surface is coated with sulfur from the sulfur solution and heat-treated at 160 ° C. for 1 hour. As a result, 295.2 mg (yield 93%) of a thin film sulfur-coated acetylene black was obtained.
Next, in a glove box having an argon atmosphere with a dew point temperature of −70 ° C. or less, 40 g of 5 mmφ zirconia balls, 100 mg of thin-film sulfur-coated acetylene black, and 100 mg of a solid electrolyte were placed in a zirconia container having a capacity of 45 ml (Premium line P, manufactured by Fritsch). 140 mg (yield 70%) by processing for 2 hours at a rotation speed of 185 rpm and a rotation speed of 370 rpm (rotation and reverse rotation) with a planetary ball mill (French, Premium line P-7). A positive electrode composite was obtained.
Using this positive electrode mixture, a battery was prepared according to the battery preparation method described above, and the discharge capacity was measured.

(Comparative Example 5)
200 mg of sulfur and 20 g of cyclohexane were placed in a 50 ml screw tube and stirred with a magnetic stirrer to dissolve the sulfur. Next, 100 mg of furnace black (BET specific surface area: 1,156 m ² / g) having a hollow shell structure is immersed in this cyclohexane solution of sulfur, and subjected to ultrasonic treatment (output 100 W, oscillation frequency 28 Hz, 40 minutes), Furnace black was dispersed. Subsequently, the furnace black was covered with sulfur by stirring with a magnetic stirrer at 25 ° C. for 48 hours to adsorb sulfur to the furnace black.
About 2 g of the dispersion liquid after the sulfur coating was extracted, and the furnace black whose surface was coated with sulfur was settled by centrifugation, and the solid content of the supernatant sulfur solution was measured and found to be 0.78 wt%. . Since the concentration of the original sulfur solution was 0.99 wt%, 43.2 mg of sulfur covered 100 mg of furnace black. Therefore, sulfur in the furnace black whose surface is coated with sulfur is 30.2 wt% (Table 1). Since the furnace black used has a BET specific surface area of 1,156 m ² / g, sulfur having a specific gravity of 2 g / cm ³ is coated with a thickness of 0.19 nm.
The remaining amount other than about 2 g extracted for the calculation of the amount of coating of the sulfur and the film thickness is suction filtered to separate the furnace black whose surface is coated with sulfur from the sulfur solution and heat-treated at 160 ° C. for 1 hour. As a result, 132.1 mg (yield 92%) of a thin film sulfur-coated furnace black was obtained.
Next, in a glove box in an argon atmosphere with a dew point temperature of −70 ° C. or less, 40 g of 5 mmφ zirconia balls, 100 mg of thin film sulfur-coated furnace black, and 100 mg of a solid electrolyte were placed in a 45 ml zirconia container (Premium line P, manufactured by Fritsch). 140 mg (yield 70%) by processing for 2 hours at a rotation speed of 185 rpm and a rotation speed of 370 rpm (rotation and reverse rotation) with a planetary ball mill (French, Premium line P-7). A positive electrode composite was obtained.
Using this positive electrode mixture, a battery was prepared according to the battery preparation method described above, and the discharge capacity was measured.

Example 4
275 mg of sulfur and 20 g of cyclohexane were placed in a 50 ml screw tube and stirred with a magnetic stirrer while heating to 50 ° C. to dissolve the sulfur. Next, 100 mg of furnace black (BET specific surface area: 1,156 m ² / g) having a hollow shell structure is immersed in this cyclohexane solution of sulfur, and subjected to ultrasonic treatment (output 100 W, oscillation frequency 28 Hz, 40 minutes), Furnace black was dispersed. Subsequently, after stirring with a magnetic stirrer at 50 ° C. for 1 hour, the temperature was lowered to 25 ° C. over 3 hours, and then stirred at 25 ° C. for 48 hours to adsorb sulfur to the furnace black, thereby making the furnace black with sulfur. Black was coated.
About 2 g of the dispersion liquid after the sulfur coating was taken out and the furnace black whose surface was coated with sulfur was sedimented by centrifugation, and the solid content of the supernatant sulfur solution was measured, and found to be 0.84 wt%. . Since the concentration of the original sulfur solution is 1.36 wt%, 106.0 mg of sulfur coats 100 mg of furnace black. Therefore, sulfur in the furnace black whose surface is coated with sulfur is 51.5 wt% (Table 1). Since the furnace black used has a BET specific surface area of 1,156 m ² / g, sulfur having a specific gravity of 2 g / cm ³ is coated with a thickness of 0.46 nm.
The remaining amount other than about 2 g extracted for the calculation of the amount of coating of the sulfur and the film thickness is suction filtered to separate the furnace black whose surface is coated with sulfur from the sulfur solution and heat-treated at 160 ° C. for 1 hour. As a result, 193.5 mg (yield 94%) of a thin film sulfur-coated furnace black was obtained.
Next, in a glove box in an argon atmosphere with a dew point temperature of −70 ° C. or less, 40 g of 5 mmφ zirconia balls, 100 mg of thin film sulfur-coated furnace black, and 100 mg of a solid electrolyte were placed in a 45 ml zirconia container (Premium line P, manufactured by Fritsch). -7), and a planetary ball mill (Premium line P-7, manufactured by Fritsch) for 2 hours at a rotation speed of 185 rpm and a revolution speed of 370 rpm (rotation and reverse rotation), 139 mg (yield 70%) A positive electrode composite was obtained.
Using this positive electrode mixture, a battery was prepared according to the battery preparation method described above, and the discharge capacity was measured.

(Example 5)
500 mg of sulfur and 20 g of cyclohexane were put in a 50 ml screw tube and stirred with a magnetic stirrer while heating to 50 ° C. to dissolve the sulfur. Next, 100 mg of furnace black (BET specific surface area: 1,156 m ² / g) having a hollow shell structure is immersed in this cyclohexane solution of sulfur, and subjected to ultrasonic treatment (output 100 W, oscillation frequency 28 Hz, 40 minutes), Furnace black was dispersed. Subsequently, after stirring with a magnetic stirrer at 50 ° C. for 1 hour, the temperature was lowered to 25 ° C. over 3 hours, and then stirred at 25 ° C. for 48 hours to adsorb sulfur to the furnace black, thereby making the furnace black with sulfur. Black was coated.
About 2 g of the dispersion after the sulfur coating was extracted, and the furnace black whose surface was coated with sulfur was settled by centrifugation, and the solid content of the supernatant sulfur solution was measured and found to be 1.09 wt%. . Since the concentration of the original sulfur solution is 2.44 wt%, 280.1 mg of sulfur coats 100 mg of furnace black. Therefore, sulfur in the furnace black whose surface is covered with sulfur is 73.7 wt% (Table 1). Since the furnace black used has a BET specific surface area of 1,156 m ² / g, sulfur having a specific gravity of 2 g / cm ³ is coated with a thickness of 1.21 nm.
The remaining amount other than about 2 g extracted for the calculation of the amount of coating of the sulfur and the film thickness is suction filtered to separate the furnace black whose surface is coated with sulfur from the sulfur solution and heat-treated at 160 ° C. for 1 hour. As a result, 357.2 mg (yield 94%) of a thin film sulfur-coated furnace black was obtained.
Next, in a glove box in an argon atmosphere with a dew point temperature of −70 ° C. or less, 40 g of 5 mmφ zirconia balls, 100 mg of thin film sulfur-coated furnace black, and 100 mg of a solid electrolyte were placed in a 45 ml zirconia container (Premium line P, manufactured by Fritsch). -7), and a planetary ball mill (Premium line P-7, manufactured by Fritsch) for 2 hours at a rotation speed of 185 rpm and a revolution speed of 370 rpm (rotation and reverse rotation), 139 mg (yield 70%) A positive electrode composite was obtained.
Using this positive electrode mixture, a battery was prepared according to the battery preparation method described above, and the discharge capacity was measured.

(Example 6)
1,000 mg of sulfur and 20 g of cyclohexane were put in a 50 ml screw tube and stirred with a magnetic stirrer while heating to 50 ° C. to dissolve the sulfur. Next, 145 mg of furnace black (BET specific surface area: 1,156 m ² / g) having a hollow shell structure is immersed in this cyclohexane solution of sulfur, and subjected to ultrasonic treatment (output 100 W, oscillation frequency 28 Hz, 40 minutes), Furnace black was dispersed. Subsequently, after stirring with a magnetic stirrer at 50 ° C. for 1 hour, the temperature was lowered to 25 ° C. over 3 hours, then stirred at 25 ° C. for 48 hours, then lowered to 15 ° C. over 3 hours, and then The furnace black was coated with sulfur by adsorbing sulfur to the furnace black by stirring at 15 ° C. for 48 hours.
About 2 g of the dispersion liquid after the sulfur coating was taken out and the furnace black whose surface was coated with sulfur was sedimented by centrifugation, and the solid content of the supernatant sulfur solution was measured and found to be 0.92 wt%. . Since the concentration of the original sulfur solution is 4.76 wt%, 814.3 mg of sulfur coats 145 mg of furnace black. Therefore, sulfur in the furnace black whose surface is coated with sulfur is 84.9 wt% (Table 1). Since the furnace black used has a BET specific surface area of 1,156 m ² / g, sulfur having a specific gravity of 2 g / cm ³ is coated with a thickness of 2.43 nm.
The remaining amount other than about 2 g extracted for the calculation of the amount of coating of the sulfur and the film thickness is suction filtered to separate the furnace black whose surface is coated with sulfur from the sulfur solution and heat-treated at 160 ° C. for 1 hour. As a result, 911.9 mg (yield 95%) of thin film sulfur-coated furnace black was obtained.
Next, in a glove box in an argon atmosphere with a dew point temperature of −70 ° C. or less, 40 g of 5 mmφ zirconia balls, 100 mg of thin film sulfur-coated furnace black, and 100 mg of a solid electrolyte were placed in a 45 ml zirconia container (Premium line P, manufactured by Fritsch). -7 mg) and processing with a planetary ball mill (Premium line P-7, manufactured by Fritsch) at a rotation speed of 185 rpm and a revolution speed of 370 rpm (rotation and reverse rotation) for 2 hours, 143 mg (yield 72%) A positive electrode composite was obtained.
Using this positive electrode mixture, a battery was prepared according to the battery preparation method described above, and the discharge capacity was measured.

(Example 7)
1,000 mg of sulfur and 20 g of cyclohexane were put in a 50 ml screw tube and stirred with a magnetic stirrer while heating to 50 ° C. to dissolve the sulfur. Next, furnace black (BET specific surface area: 1,156 m ² / g) 105 mg having a hollow shell structure is immersed in this sulfur cyclohexane solution, and subjected to ultrasonic treatment (output 100 W, oscillation frequency 28 Hz, 40 minutes), Furnace black was dispersed. Subsequently, after stirring with a magnetic stirrer at 50 ° C. for 1 hour, the temperature was lowered to 25 ° C. over 3 hours, then stirred at 25 ° C. for 48 hours, then lowered to 15 ° C. over 3 hours, and then The furnace black was coated with sulfur by adsorbing sulfur to the furnace black by stirring at 15 ° C. for 48 hours.
About 2 g of the dispersion after the sulfur coating was extracted, and the furnace black whose surface was coated with sulfur was precipitated by centrifugation, and the solid content of the supernatant sulfur solution was measured and found to be 1.02 wt%. . Since the concentration of the original sulfur solution was 4.76 wt%, 793.9 mg of sulfur covered 105 mg of furnace black. Accordingly, sulfur in the furnace black whose surface is coated with sulfur is 88.3 wt% (Table 1). Since the furnace black used has a BET specific surface area of 1,156 m ² / g, sulfur having a specific gravity of 2 g / cm ³ is coated with a thickness of 3.27 nm.
The remaining amount other than about 2 g extracted for the calculation of the amount of coating of the sulfur and the film thickness is suction filtered to separate the furnace black whose surface is coated with sulfur from the sulfur solution and heat-treated at 160 ° C. for 1 hour. As a result, 855.3 mg (yield 95%) of thin film sulfur-coated furnace black was obtained.
Next, in a glove box in an argon atmosphere with a dew point temperature of −70 ° C. or less, 40 g of 5 mmφ zirconia balls, 100 mg of thin film sulfur-coated furnace black, and 100 mg of a solid electrolyte were placed in a 45 ml zirconia container (Premium line P, manufactured by Fritsch). 142 mg (yield 71%) in a planetary ball mill (French Corp., Premium line P-7) at a rotation speed of 185 rpm and a revolution speed of 370 rpm (rotation and reverse rotation) for 2 hours. A positive electrode composite was obtained.
Using this positive electrode mixture, a battery was prepared according to the battery preparation method described above, and the discharge capacity was measured.

(Example 8)
1,000 mg of sulfur and 20 g of cyclohexane were put in a 50 ml screw tube and stirred with a magnetic stirrer while heating to 50 ° C. to dissolve the sulfur. Next, 70 mg of furnace black (BET specific surface area: 1,156 m ² / g) having a hollow shell structure is immersed in this cyclohexane solution of sulfur, and subjected to ultrasonic treatment (output 100 W, oscillation frequency 28 Hz, 40 minutes), Furnace black was dispersed. Subsequently, after stirring with a magnetic stirrer at 50 ° C. for 1 hour, the temperature was lowered to 25 ° C. over 3 hours, then stirred at 25 ° C. for 48 hours, then lowered to 15 ° C. over 3 hours, and then The furnace black was coated with sulfur by adsorbing sulfur to the furnace black by stirring at 15 ° C. for 48 hours.
About 2 g of the dispersion liquid after the sulfur coating was extracted, and the furnace black whose surface was coated with sulfur was sedimented by centrifugation, and the solid content of the supernatant sulfur solution was measured and found to be 1.05 wt%. . Since the concentration of the original sulfur solution was 4.76 wt%, 787.8 mg of sulfur covered 70 mg of furnace black. Accordingly, sulfur in the furnace black whose surface is coated with sulfur is 91.8 wt% (Table 1). Since the furnace black used has a BET specific surface area of 1,156 m ² / g, sulfur having a specific gravity of 2 g / cm ³ is coated with a thickness of 4.87 nm.
The remaining amount other than about 2 g extracted for the calculation of the amount of coating of the sulfur and the film thickness is suction filtered to separate the furnace black whose surface is coated with sulfur from the sulfur solution and heat-treated at 160 ° C. for 1 hour. As a result, 813.4 mg (yield 95%) of thin film sulfur-coated furnace black was obtained.
Next, in a glove box in an argon atmosphere with a dew point temperature of −70 ° C. or less, 40 g of 5 mmφ zirconia balls, 100 mg of thin film sulfur-coated furnace black, and 100 mg of a solid electrolyte were placed in a 45 ml zirconia container (Premium line P, manufactured by Fritsch). -7), and a planetary ball mill (Premium line P-7, manufactured by Fritsch) for 2 hours at a rotation speed of 185 rpm and a revolution speed of 370 rpm (rotation and reverse rotation), 139 mg (yield 70%) A positive electrode composite was obtained.
Using this positive electrode mixture, a battery was prepared according to the battery preparation method described above, and the discharge capacity was measured.

(Comparative Example 6)
1,000 mg of sulfur and 20 g of cyclohexane were put in a 50 ml screw tube and stirred with a magnetic stirrer while heating to 50 ° C. to dissolve the sulfur. Next, 60 mg of furnace black (BET specific surface area: 1,156 m ² / g) having a hollow shell structure is immersed in this sulfur cyclohexane solution, and subjected to ultrasonic treatment (output 100 W, oscillation frequency 28 Hz, 40 minutes), Furnace black was dispersed. Subsequently, after stirring with a magnetic stirrer at 50 ° C. for 1 hour, the temperature was lowered to 25 ° C. over 3 hours, then stirred at 25 ° C. for 48 hours, then lowered to 15 ° C. over 3 hours, and then The furnace black was coated with sulfur by adsorbing sulfur to the furnace black by stirring at 15 ° C. for 48 hours.
About 2 g of the dispersion after the sulfur coating was extracted, and the furnace black whose surface was coated with sulfur was precipitated by centrifugation, and the solid content of the supernatant sulfur solution was measured and found to be 1.10 wt%. . Since the concentration of the original sulfur solution is 4.76 wt%, 777.6 mg of sulfur covered 60 mg of furnace black. Accordingly, sulfur in the furnace black whose surface is coated with sulfur is 92.8 wt% (Table 1). Since the furnace black used has a BET specific surface area of 1,156 m ² / g, sulfur having a specific gravity of 2 g / cm ³ is coated with a thickness of 5.61 nm.
The remaining amount other than about 2 g extracted for the calculation of the amount of coating of the sulfur and the film thickness is suction filtered to separate the furnace black whose surface is coated with sulfur from the sulfur solution and heat-treated at 160 ° C. for 1 hour. As a result, 792.6 mg (yield 95%) of thin film sulfur-coated furnace black was obtained.
Next, in a glove box in an argon atmosphere with a dew point temperature of −70 ° C. or less, 40 g of 5 mmφ zirconia balls, 100 mg of thin film sulfur-coated furnace black, and 100 mg of a solid electrolyte were placed in a 45 ml zirconia container (Premium line P, manufactured by Fritsch). 142 mg (yield 71%) in a planetary ball mill (French Corp., Premium line P-7) at a rotation speed of 185 rpm and a revolution speed of 370 rpm (rotation and reverse rotation) for 2 hours. A positive electrode composite was obtained.
Using this positive electrode mixture, a battery was prepared according to the battery preparation method described above, and the discharge capacity was measured.

Example 9
900 mg of sulfur and 24 g of cyclohexane were put into a 50 ml screw tube and stirred with a magnetic stirrer while heating to 50 ° C. to dissolve the sulfur. Next, 174 mg of furnace black (BET specific surface area: 1,156 m ² / g) having a hollow shell structure is immersed in this cyclohexane solution of sulfur, and subjected to ultrasonic treatment (output 100 W, oscillation frequency 28 Hz, 40 minutes), Furnace black was dispersed. Subsequently, after stirring with a magnetic stirrer at 50 ° C. for 1 hour, the temperature was lowered to 25 ° C. over 3 hours, then stirred at 25 ° C. for 48 hours, then lowered to 15 ° C. over 3 hours, and then The furnace black was coated with sulfur by adsorbing sulfur to the furnace black by stirring at 15 ° C. for 48 hours.
About 2 g of the dispersion liquid after the sulfur coating was extracted, and the furnace black whose surface was coated with sulfur was sedimented by centrifugation, and the solid content of the supernatant sulfur solution was measured and found to be 0.97 wt%. . Since the concentration of the original sulfur solution was 3.61 wt%, 664.9 mg of sulfur covered 174 mg of furnace black. Accordingly, sulfur in the furnace black whose surface is coated with sulfur is 79.3 wt% (Table 1). Since the furnace black used has a BET specific surface area of 1,156 m ² / g, sulfur having a specific gravity of 2 g / cm ³ is coated with a thickness of 1.65 nm.
The remaining amount other than about 2 g extracted for calculation of the amount of sulfur coating and film thickness is filtered by suction to separate the furnace black whose surface is covered with sulfur from the sulfur solution and heat-treated at 25 ° C. for 1 hour. As a result, 792.2 mg (yield 94%) of thin film sulfur-coated furnace black was obtained.
Next, in a glove box in an argon atmosphere with a dew point temperature of −70 ° C. or less, 40 g of 5 mmφ zirconia balls, 100 mg of thin film sulfur-coated furnace black, and 100 mg of a solid electrolyte were placed in a 45 ml zirconia container (Premium line P, manufactured by Fritsch). -7 mg) and processing with a planetary ball mill (Premium line P-7, manufactured by Fritsch) at a rotation speed of 185 rpm and a revolution speed of 370 rpm (rotation and reverse rotation) for 2 hours, 143 mg (yield 72%) A positive electrode composite was obtained.
Using this positive electrode mixture, a battery was prepared according to the battery preparation method described above, and the discharge capacity was measured.

(Example 10)
In a glove box in an argon atmosphere with a dew point temperature of −70 ° C. or less, 40 g of 5 mmφ zirconia balls and 100 mg of the thin film sulfur-coated furnace black obtained in Example 9 were further heat-treated at 40 ° C. for 1 hour, and a solid electrolyte 100 mg was put into a 45 ml zirconia container (Fritsch, Premium line P-7), and a planetary ball mill (Fritsch, Premium line P-7) was used to rotate at a rotation speed of 185 rpm and a revolution speed of 370 rpm (rotation and reverse rotation). ) To obtain 142 mg (yield 71%) of the positive electrode mixture.
Using this positive electrode mixture, a battery was prepared according to the battery preparation method described above, and the discharge capacity was measured.

(Example 11)
In a glove box in an argon atmosphere with a dew point temperature of −70 ° C. or less, 40 g of 5 mmφ zirconia balls and 100 mg of the thin film sulfur-coated furnace black obtained in Example 9 were further heat-treated at 60 ° C. for 1 hour, and a solid electrolyte 100 mg was put into a 45 ml zirconia container (Fritsch, Premium line P-7), and a planetary ball mill (Fritsch, Premium line P-7) was used to rotate at a rotation speed of 185 rpm and a revolution speed of 370 rpm (rotation and reverse rotation). ) To obtain 143 mg (yield 72%) of the positive electrode mixture.
Using this positive electrode mixture, a battery was prepared according to the battery preparation method described above, and the discharge capacity was measured.

(Example 12)
In a glove box in an argon atmosphere with a dew point temperature of −70 ° C. or lower, 40 g of 5 mmφ zirconia balls and 100 mg of the thin film sulfur-coated furnace black obtained in Example 9 were further heat-treated at 80 ° C. for 1 hour, and a solid electrolyte 100 mg was put into a 45 ml zirconia container (Fritsch, Premium line P-7), and a planetary ball mill (Fritsch, Premium line P-7) was used to rotate at a rotation speed of 185 rpm and a revolution speed of 370 rpm (rotation and reverse rotation). ) For 2 hours to obtain 140 mg (yield 70%) of the positive electrode mixture.
Using this positive electrode mixture, a battery was prepared according to the battery preparation method described above, and the discharge capacity was measured.

(Example 13)
In a glove box in an argon atmosphere with a dew point temperature of −70 ° C. or less, 40 g of 5 mmφ zirconia balls and 100 mg of the thin film sulfur-coated furnace black obtained in Example 9 were further heat-treated at 100 ° C. for 1 hour, and a solid electrolyte 100 mg was put into a 45 ml zirconia container (Fritsch, Premium line P-7), and a planetary ball mill (Fritsch, Premium line P-7) was used to rotate at a rotation speed of 185 rpm and a revolution speed of 370 rpm (rotation and reverse rotation). ) To obtain 141 mg (yield 71%) of the positive electrode mixture.
Using this positive electrode mixture, a battery was prepared according to the battery preparation method described above, and the discharge capacity was measured.

(Example 14)
In a glove box in an argon atmosphere with a dew point temperature of −70 ° C. or lower, 40 g of 5 mmφ zirconia balls and 100 mg of the thin film sulfur-coated furnace black obtained in Example 9 were further heat-treated at 160 ° C. for 1 hour, and a solid electrolyte 100 mg was put into a 45 ml zirconia container (Fritsch, Premium line P-7), and a planetary ball mill (Fritsch, Premium line P-7) was used to rotate at a rotation speed of 185 rpm and a revolution speed of 370 rpm (rotation and reverse rotation). ) To obtain 138 mg (yield 69%) of the positive electrode mixture.
Using this positive electrode mixture, a battery was prepared according to the battery preparation method described above, and the discharge capacity was measured.

(Example 15)
In a glove box in an argon atmosphere with a dew point temperature of −70 ° C. or less, 40 g of 5 mmφ zirconia balls and 100 mg of the thin film sulfur-coated furnace black obtained in Example 9 were further heat-treated at 250 ° C. for 1 hour, and a solid electrolyte 100 mg was put into a 45 ml zirconia container (Fritsch, Premium line P-7), and a planetary ball mill (Fritsch, Premium line P-7) was used to rotate at a rotation speed of 185 rpm and a revolution speed of 370 rpm (rotation and reverse rotation). ) For 2 hours to obtain 139 mg (yield 70%) of the positive electrode mixture.
Using this positive electrode mixture, a battery was prepared according to the battery preparation method described above, and the discharge capacity was measured.

In Comparative Examples 1 to 6 and Examples 1 to 15, the type of conductive carbon and the BET specific surface area, the presence or absence of sulfur coating, the film thickness, and the conductive carbon coated with sulfur (in Comparative Examples 3 and 4) Is the weight ratio of sulfur and conductive carbon in the mixture of sulfur and conductive carbon), heat treatment temperature (first and second times), discharge capacity per gram of sulfur, and discharge capacity per gram of positive electrode mixture layer Is shown in Table 1.
Table 2 shows the amounts of conductive carbon, sulfur, and solid electrolyte contained in the positive electrode composites produced in Comparative Examples 1 to 6 and Examples 1 to 15.

The discharge capacity per positive electrode mixture layer in Example 1 is 670 mAh / g, whereas the discharge capacity per positive electrode mixture layer in Comparative Example 1 is as small as 128 mAh / g. This is because the thickness is as thin as 0.19 nm.

The discharge capacity per positive electrode mixture layer of Example 2 is 496 mAh / g, whereas the discharge capacity per positive electrode mixture layer of Comparative Example 2 is as small as 83 mAh / g, which is used for thin film sulfur-coated acetylene black. This is because the BET specific surface area of the acetylene black was as small as 75 m ² / g, and the content of sulfur in the positive electrode mixture was reduced.

While the discharge capacity per positive electrode mixture layer in Comparative Example 3 is 451 mAh / g, the discharge capacity per positive electrode mixture layer in Example 2 is as large as 496 mAh / g. This is presumably because the diffusion distance inside the sulfur was shortened and the diffusion resistance was reduced by making the insulating sulfur thin.

In Comparative Example 3, a mixture of sulfur and acetylene black was heat-treated at 25 ° C, while in Comparative Example 4, heat-treated at 160 ° C. However, while the discharge capacity per positive electrode mixture layer of Comparative Example 3 was 451 mAh / g, the discharge capacity per positive electrode mixture layer of Comparative Example 4 was almost the same as 462 mAh / g.
On the other hand, in Example 2, acetylene black whose surface was coated with sulfur was heat-treated at 25 ° C., whereas in Example 3, when heat-treated at 160 ° C., the discharge capacity per positive electrode mixture layer was 496 mAh / g. Significantly increased from 568 mAh / g.
From the above, the mixture of sulfur and acetylene black treated with a planetary ball mill has almost no change in the discharge capacity per positive electrode mixture layer even when the temperature of the heat treatment is raised, whereas the surface is covered with sulfur. It can be seen that the discharge capacity per positive electrode mixture layer increases remarkably when the heat treatment temperature is increased.

In Comparative Examples 5 and 6 and Examples 4 to 8, the thickness of the sulfur film coated with the furnace black was changed, but the thickness of the sulfur film was as small as 0.19 nm per positive electrode mixture layer of Comparative Example 5. Has a small discharge capacity of 108 mAh / g, and the discharge capacity per positive electrode mixture layer of Comparative Example 6, which has a thick sulfur film of 5.61 nm, is as small as 255 mAh / g. On the other hand, in Examples 4 to 8 where the film thickness range of the sulfur film is 0.4 to 5.0 nm, the discharge capacity per positive electrode mixture layer is as large as 470 mAh / g or more. In particular, in Examples 5 and 6 in which the film thickness range of the sulfur film is 1.0 to 2.5 nm, the discharge capacity per positive electrode mixture layer is very large at 650 mAh / g or more.
From these facts, when the film thickness of the sulfur film is too thin, the content of sulfur in the positive electrode mixture decreases, and as a result, the discharge capacity per positive electrode mixture layer decreases, while the film thickness of the sulfur film is too thick. As the diffusion distance of lithium ions and electrons increases, the diffusion resistance increases, the resistance in the positive electrode mixture increases, and as a result, the discharge capacity per positive electrode mixture layer decreases.

In Example 9, furnace black whose surface was coated with sulfur was heated only once at 25 ° C., whereas in Examples 10 to 15, after the first heat treatment was performed at 25 ° C., A second heat treatment was performed at 40 to 250 ° C. As a result, the discharge capacity per positive electrode mixture layer was 404 mAh / g in Example 9, whereas 458 mAh / g in Example 10, 642 mAh / g in Example 11, 662 mAh / g in Example 12, In Example 13, it increased in steps to 710 mAh / g and in Example 14 to 751 mAh / g. In Example 15, the discharge capacity per positive electrode mixture layer was 753 mAh / g, almost the same as the discharge capacity per positive electrode mixture layer of Example 14.

DESCRIPTION OF SYMBOLS 1 Negative electrode collector 2 Negative electrode 3 Solid electrolyte layer 4 Positive electrode compound material layer 5 Positive electrode collector 10 All solid-state lithium-sulfur battery

Claims (4)

Conductive carbon whose surface is covered with a sulfur film made of simple sulfur ,
The conductive carbon has a BET specific surface area of 500 m ² / g or more,
The sulfur film has a thickness of 0.4 to 5.0 nm.
Thin-film sulfur-coated conductive carbon used for positive electrode composites for all-solid-state lithium-sulfur batteries. The thin film sulfur-coated conductive carbon according to claim 1, wherein the film thickness is 1.0 to 2.5 nm. The thin film sulfur-coated conductive carbon according to claim 1 or 2, wherein the conductive carbon is at least one selected from the group consisting of furnace black, activated carbon, and acetylene black. The thin film sulfur-coated conductive carbon according to claim 3, wherein the conductive carbon is furnace black and has a hollow shell structure .

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