JP6040000B2 - Electrode for all-solid-state lithium ion battery, all-solid-state lithium-ion battery, and method for producing electrode for all-solid-state lithium-ion battery - Google Patents

Description

  The present invention relates to an electrode for an all solid state lithium ion battery, an all solid state lithium ion battery, and a method for producing an electrode for an all solid state lithium ion battery.

  Lithium ion batteries are generally used as a power source for small portable devices such as mobile phones and notebook computers. Recently, in addition to small portable devices, lithium ion batteries have begun to be used as power sources for electric vehicles and power storage.

  An electrolyte solution containing a flammable organic solvent is used in a lithium ion battery currently on the market. On the other hand, a lithium ion battery (hereinafter also referred to as an all-solid-state lithium ion battery) in which the electrolyte is changed to a solid electrolyte to make the battery completely solid does not use a flammable organic solvent in the battery. It is considered that the manufacturing cost and productivity are excellent (for example, Patent Documents 1 and 2).

JP 2011-175904 A JP 2011-175905 A

  However, the all-solid-state lithium ion battery, for example, is inferior in charge / discharge characteristics such as discharge capacity density and cycle characteristics compared to conventional lithium ion batteries using an electrolytic solution, and is not yet satisfactory as a lithium ion battery. It was.

  Accordingly, an object of the present invention is to provide an electrode for an all solid-state lithium ion battery capable of obtaining an all solid state lithium ion battery having improved charge / discharge characteristics such as discharge capacity density and cycle characteristics.

  In order to provide an all-solid-state lithium ion battery with improved charge / discharge characteristics, the present inventors have intensively studied the structure of an electrode that is a constituent member of the all-solid-state lithium ion battery. As a result, it has been found that an all-solid-state lithium ion battery with improved charge / discharge characteristics can be obtained by using an electrode in which an electrode active material layer is formed by attaching a particulate electrode active material to a conductive resin layer. The present invention has been reached.

That is, according to the present invention,
A sheet-like electrode used for a positive electrode layer or a negative electrode layer of an all-solid-state lithium ion battery,
An electrode active material layer containing a particulate electrode active material;
A conductive resin layer;
A current collector layer;
Is an electrode for an all solid-state lithium ion battery laminated in this order ,
The electrode active material layer is substantially free of pressure-sensitive adhesive and binder,
An electrode for an all solid-state lithium ion battery is provided in which the electrode active material layer has a thickness of 2 μm or more and 60 μm or less .

Furthermore, according to the present invention,
An all solid-state lithium ion battery in which a positive electrode layer, a solid electrolyte layer, and a negative electrode layer are laminated in this order,
There is provided an all solid state lithium ion battery in which at least one of the positive electrode layer and the negative electrode layer is the electrode for the all solid state lithium ion battery.

Furthermore, according to the present invention,
A manufacturing method for manufacturing the electrode for an all solid-state lithium ion battery,
There is provided a method for producing an electrode for an all-solid-state lithium ion battery, including a step of forming the electrode active material layer by attaching the electrode active material in the form of fine particles to the conductive resin layer.

  ADVANTAGE OF THE INVENTION According to this invention, the electrode for all-solid-state type lithium ion batteries which can obtain the all-solid-state type lithium ion battery by which charge / discharge characteristics, such as discharge capacity density and cycling characteristics, were improved can be provided.

It is sectional drawing which shows an example of the structure of the electrode for all-solid-state type lithium ion batteries of embodiment which concerns on this invention. It is sectional drawing which shows an example of the structure of the all-solid-state lithium ion battery of embodiment which concerns on this invention.

  Embodiments of the present invention will be described below with reference to the drawings. In all the drawings, similar constituent elements are denoted by common reference numerals, and description thereof is omitted as appropriate. Moreover, the figure is a schematic diagram and does not necessarily match the actual dimensional ratio. In addition, unless otherwise indicated, "to" represents the following from the above.

[All-solid-state lithium-ion battery electrode]
First, the all-solid-state lithium ion battery electrode 100 according to the present embodiment will be described. FIG. 1 is a cross-sectional view showing an example of the structure of an electrode 100 for an all solid-state lithium ion battery according to an embodiment of the present invention.
The electrode 100 for an all solid-state lithium ion battery according to this embodiment is a sheet-like electrode used for a positive electrode layer or a negative electrode layer of an all solid state lithium ion battery.

  An electrode 100 for an all solid-state lithium ion battery according to this embodiment includes an electrode active material layer 101 containing a particulate electrode active material, a conductive resin layer 102, and a current collector layer 103, which are stacked in this order. Being done.

  The electrode 100 for an all solid-state lithium ion battery according to this embodiment includes an electroconductive resin layer 102 between the electrode active material layer 101 and the current collector layer 103, thereby obtaining an all solid-state lithium ion battery obtained. Charge / discharge characteristics such as discharge capacity density and cycle characteristics can be improved. Although the reason for this is not necessarily clear, the electrode 100 for an all solid-state lithium ion battery according to the present embodiment includes the conductive resin layer 102 between the electrode active material layer 101 and the current collector layer 103. It is presumed that this is because of its excellent ability to relieve stress against the volume change of the electrode active material accompanying charge / discharge.

  A conventional electrode for an all-solid-state lithium ion battery is formed by press-molding an electrode active material layer containing an electrode active material and a conductive additive at high pressure, and then pressing the press-molded body and the current collector layer at high pressure. It was produced by. However, according to the study by the present inventors, an electrode produced by such a method is used between the electrode active material and the electrode active material, or between the electrode active material and the electrode active material due to the volume change of the electrode active material accompanying charge / discharge. It becomes clear that particles such as between conductive aids, or the electrode active material layer and the current collector layer are separated from each other, resulting in a decrease in the electron conductivity and ion conductivity of the entire electrode. It was. Naturally, when the electronic conductivity and ionic conductivity of the entire electrode are lowered, the charge / discharge characteristics of the all-solid-state lithium ion battery are lowered. That is, the conventional electrodes are difficult to contact again once the particles or layers are separated.

On the other hand, in the all solid-state lithium ion battery electrode 100 according to this embodiment, the electrode active material layer 101 is fixed on the current collector layer 103 via the conductive resin layer 102. Therefore, even if the volume change of the electrode active material due to charging / discharging occurs, the interlayer between the electrode active material layer 101 and the current collector layer 103 is bonded via the conductive resin layer 102. It seems difficult to leave. Furthermore, since particles such as an electrode active material and a conductive auxiliary agent contained in the electrode active material layer 101 are fixed to the conductive resin layer 102, even if the volume change of the electrode active material due to charging / discharging occurs. It is thought that it is difficult to leave.
As described above, since the electrode 100 for an all solid-state lithium ion battery according to the present embodiment is excellent in the ability to relax stress against the volume change of the electrode active material accompanying charge / discharge, the discharge capacity density of the obtained all solid-state lithium ion battery It is considered that charge and discharge characteristics such as cycle characteristics can be improved.

  Hereinafter, each component of the electrode 100 for an all solid-state lithium ion battery according to the present embodiment will be described.

<Conductive resin layer>
The conductive resin layer 102 according to the present embodiment is not particularly limited. For example, a structure including a resin and conductive fine particles, and the conductive fine particles dispersed in the conductive resin layer 102 is preferable.

The thickness of the conductive resin layer 102 according to the present embodiment is appropriately determined in consideration of characteristics such as the average particle diameter of the conductive fine particles and the pressure-sensitive adhesive, but is usually 5 μm or more and 60 μm or less, preferably 10 μm or more. 40 μm or less.
When the thickness of the conductive resin layer 102 is within the above range, the balance between the adhesion between the electrode active material layer 101 and the current collector layer 103 and the conductivity of the conductive resin layer 102 is excellent.

(Conductive fine particles)
The conductive fine particles contained in the conductive resin layer 102 according to this embodiment are not particularly limited as long as they are conductive fine particles. For example, gold, silver, platinum, nickel, copper, cobalt, molybdenum, antimony, Metal particles such as iron and chromium; alloy particles such as aluminum / magnesium alloy and aluminum / nickel alloy; metal oxide particles such as tin oxide and indium oxide; precious metals such as gold, silver and platinum on metal particles such as nickel Coated particles; particles obtained by coating non-conductive particles such as glass, ceramic, and plastic with noble metals such as gold, silver, and platinum; and carbon particles.

The average particle diameter d ₅₀ in the weight-based particle size distribution by the laser diffraction / scattering particle size distribution measurement method of the conductive fine particles according to this embodiment is preferably 0.5 μm or more and 50 μm or less, more preferably 5 μm or more and 30 μm or less. . By setting the average particle diameter d ₅₀ within the above range, it is possible to maintain good handling properties of the conductive fine particles and improve the conductivity of the conductive resin layer 102.

  The content of the conductive fine particles contained in the conductive resin layer 102 is preferably 0.05% by weight or more and 20% by weight or less, more preferably 0, when the entire conductive resin layer 102 is 100% by weight. .1% by weight or more and 10% by weight or less. When the content of the conductive fine particles is within the above range, the balance between the adhesion between the electrode active material layer 101 and the current collector layer 103 and the conductivity of the conductive resin layer 102 is excellent.

(resin)
As the resin contained in the conductive resin layer 102 according to this embodiment, a pressure-sensitive adhesive capable of dispersing conductive fine particles and exhibiting adhesiveness is preferable. Examples thereof include (meth) acrylic thermoplastic resins. Here, in this embodiment, “(meth) acryl” is used as a general term for acrylic and methacrylic.

  In this embodiment, the (meth) acrylic thermoplastic resin is a thermoplastic resin containing a (meth) acrylic acid ester unit. For example, a (meth) acrylic acid ester homopolymer, two or more ( Examples thereof include a copolymer of a (meth) acrylic acid ester, a (meth) acrylic acid ester, and a copolymer of a vinyl monomer having an unsaturated bond copolymerizable therewith.

  Examples of the (meth) acrylic acid ester include methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, and tert-butyl (meth) acrylate. Cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, stearyl (meth) acrylate, isobornyl (meth) acrylate, benzyl (meth) acrylate, (meth) Methoxyethyl acrylate, 2-butoxyethyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, glycidyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, hexanediol di (meth) acrylate, ethylene Glycol di (meth) acrylate, polyethylene Glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol di (meth) acrylate, Pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, urethane acrylate, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, (meth ) 2-hydroxypropyl acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 5-hydro (meth) acrylate Cypentyl, 6-hydroxyhexyl (meth) acrylate, 3-hydroxy-3-methylbutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, pentaerythritol tri (meth) acrylate, 2- [ (Meth) acryloyloxy] ethyl-2-hydroxyethylphthalic acid, 2-[(meth) acryloyloxy] ethyl-2-hydroxypropylphthalic acid, and the like.

  Examples of the vinyl monomer having an unsaturated bond copolymerizable with the (meth) acrylic acid ester include (meth) acrylic acid, maleic anhydride, maleimide derivatives, (meth) acrylonitrile, N-vinylpyrrolidone, N -Acryloylmorpholine, N-vinylcaprolactone, N-vinylpiperidine, N-vinylformamide, N-vinylacetamide, styrene, indene, α-methylstyrene, p-methylstyrene, p-chlorostyrene, p-chloromethylstyrene, Examples thereof include p-methoxystyrene, p-tert-butoxystyrene, divinylbenzene, butadiene, isoprene, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl caproate, vinyl benzoate, vinyl cinnamate and derivatives thereof. The above (meth) acrylic acid ester and the vinyl monomer having an unsaturated bond copolymerizable with the (meth) acrylic acid ester may be used alone or in combination of two or more.

  The content of the (meth) acrylic ester unit contained in the (meth) acrylic thermoplastic resin is such that the dispersibility of the conductive fine particles is improved, so that the entire (meth) acrylic thermoplastic resin is 100% by weight. When it is, it is 20 to 100 weight%, More preferably, it is 50 to 100 weight%, More preferably, it is 80 to 100 weight%.

  The content of the (meth) acrylic thermoplastic resin contained in the conductive resin layer 102 according to this embodiment is preferably 80% by weight or more and 99.5% when the entire conductive resin layer 102 is 100% by weight. % By weight or less, more preferably 90% by weight or more and 99.9% by weight or less. When the content of the (meth) acrylic thermoplastic resin is within the above range, the balance between the adhesion between the electrode active material layer 101 and the current collector layer 103 and the conductivity of the conductive resin layer 102 is excellent.

The conductive resin layer 102 according to the present embodiment includes, as necessary, a crosslinking agent such as an isocyanate compound, an acid anhydride, an amine compound, an epoxy compound, a metal chelate, an aziridine compound, and a melamine compound; a rosin resin and a terpene resin. It may further contain a resin, a petroleum resin, a coumarone-indene resin, a tackifier resin such as a phenol resin, a xylene resin, or a styrene resin; a silane coupling agent; a solid electrolyte described later.
When the tackifying resin is contained in the conductive resin layer 102 according to the present embodiment, the initial tack and the adhesive force can be easily adjusted.

(Method for producing conductive resin layer)
Although the manufacturing method of the conductive resin layer 102 which concerns on this embodiment is not specifically limited, For example, it can manufacture with the following methods.
First, an adhesive such as the (meth) acrylic thermoplastic resin and, if necessary, a mixture containing appropriate amounts of the crosslinking agent, the tackifier resin, the silane coupling agent, and the solid electrolyte are heated and melted. Next, the conductive fine particles are added to the hot melt and mixed and dispersed uniformly.
After the obtained resin composition is applied on a current collector layer 103 described later, the conductive resin layer 102 is formed on the current collector layer 103 by cooling to room temperature by cooling. Mixing by heating and melting can be carried out usually in a temperature range of 100 ° C. to 250 ° C., for example, using a kneader ruder, an extruder, a mixin gall, a Banbury mixer, or other known kneading apparatuses.

<Electrode active material layer>
The electrode active material layer 101 according to the present embodiment includes a particulate electrode active material as an essential component, and includes a conductive additive, a solid electrolyte, and the like as necessary.

  In addition, the electrode active material layer 101 according to this embodiment has a content of the pressure-sensitive adhesive and the binder (also referred to as a binder) of 5 wt% when the entire electrode active material layer 101 is 100 wt%. % Or less, preferably 3% by weight or less. It is particularly preferable that the electrode active material layer 101 according to this embodiment does not substantially contain an adhesive and a binder. Here, “substantially free of adhesive and binder” includes other than the adhesive derived from the conductive resin layer 102 existing in the vicinity of the interface between the electrode active material layer 101 and the conductive resin layer 102. It means no.

  In addition, the said binder means the binder normally used for a lithium ion battery, for example, polyvinyl alcohol, polyacrylic acid, carboxymethylcellulose, polytetrafluoroethylene microparticles | fine-particles, a styrene butadiene type rubber microparticle, etc. Water-based binders; solvent-based binders such as polytetrafluoroethylene, polyvinylidene fluoride, and polyimide.

The electrode active material layer 101 according to this embodiment is bonded to the current collector layer 103 via the conductive resin layer 102. Therefore, the electrode active material layer 101 according to the present embodiment can maintain adhesion with the current collector layer 103 even when the contents of the pressure-sensitive adhesive and the binder are not more than the above upper limit values.
In addition, the electrode active material layer 101 according to the present embodiment can reduce the internal resistance of the obtained all-solid-state lithium ion battery because the insulating adhesive and binder can be set to the upper limit or less. be able to. As a result, the charge / discharge characteristics such as the discharge capacity density and cycle characteristics of the obtained all-solid-state lithium ion battery can be further improved.

(Positive electrode layer)
When the all-solid-state lithium ion battery electrode 100 according to this embodiment is used for a positive electrode layer, the electrode active material layer 101 according to this embodiment includes a positive electrode active material as a particulate electrode active material. In addition, it contains a conductive aid, a solid electrolyte, and the like.

  When the all-solid-state lithium ion battery electrode 100 according to this embodiment is used for a positive electrode layer, the thickness of the electrode active material layer 101 according to this embodiment is preferably 2 μm or more and 60 μm or less, more preferably 5 μm or more. 40 μm or less. When the thickness of the electrode active material layer 101 according to the present embodiment is in the above range, the stress relaxation ability with respect to the volume change of the positive electrode active material accompanying charge / discharge is particularly excellent, and thus the discharge capacity of the obtained all solid-state lithium ion battery Charge / discharge characteristics such as density and cycle characteristics can be further improved.

When the all-solid-state lithium ion battery electrode 100 according to this embodiment is used for a positive electrode layer, the weight per unit area of the positive electrode active material contained in the electrode active material layer 101 according to this embodiment is preferably 1. 5 g / ^{m 2} or more 65.0 g / ^{m 2} or less, more preferably 4.5 g / ^{m 2} or more 32.5 g / ^{m 2} or less. When the weight per unit area of the positive electrode active material is within the above range, the stress relaxation ability with respect to the volume change of the positive electrode active material accompanying charge / discharge is particularly excellent, so the discharge capacity density and cycle of the obtained all-solid-state lithium ion battery Charge / discharge characteristics such as characteristics can be further improved.

When the all-solid-state lithium ion battery electrode 100 according to the present embodiment is used for the positive electrode layer, the density of the electrode active material layer 101 according to the present embodiment is preferably 1.3 g / cm ³ or more and 3.3 g / cm. ³ or less, more preferably 2.5 g / cm ³ or more and 3.3 g / cm ³ or less. When the density of the electrode active material layer 101 according to the present embodiment is within the above range, the stress relaxation ability with respect to the volume change of the positive electrode active material accompanying charge / discharge is particularly excellent. Charge / discharge characteristics such as capacity density and cycle characteristics can be further improved.

"Positive electrode active material"
It does not specifically limit as a positive electrode active material which concerns on this embodiment, A generally well-known thing can be used. For example, composite oxides such as lithium cobalt oxide (LiCoO ₂ ), lithium nickel oxide (LiNiO ₂ ), and lithium manganese oxide (LiMn ₂ O ₄ ); conductive polymers such as polyaniline and polypyrrole; Li ₂ S, Lithium sulfide such as Li ₂ S ₂ , Li ₂ S ₄ , Li ₂ S ₈ , sulfides such as lithium copper sulfide; sulfur and the like can be used. These may be used individually by 1 type and may be used in combination of 2 or more type. In composite oxides such as lithium cobalt oxide (LiCoO ₂ ), lithium nickel oxide (LiNiO ₂ ), and lithium manganese oxide (LiMn ₂ O ₄ ), LiNbO ₃ and Li are used to reduce the interface resistance with the solid electrolyte. A coating with ₄ Ti ₅ O ₁₂ or the like, or a fine particle such as LiNbO ₃ or Li ₄ Ti ₅ O ₁₂ attached to the surface of the composite oxide can also be used.
Among these, sulfides such as lithium sulfide and lithium copper sulfide have a large volume change due to charge / discharge, and therefore the effects of the present invention can be obtained particularly when these positive electrode active materials are used.

Here, the lithium copper sulfide contains Li, S, and Cu as constituent elements, and heats a mixture containing Li ₂ S and CuS _1-X (0.0 ≦ X ≦ 0.5). Can be obtained. Here, as CuS _1-X (0.0 ≦ X ≦ 0.5), Cu ₂ S, Cu _1.97 S, Cu _1.96 S, Cu _1.95 S, Cu ₃₁ S are known substances. ₁₆ , Cu _1.81 S, Cu _1.8 S, Cu ₉ S ₅ , Cu _7.2 S ₄ , Cu _1.78 S, Cu _1.765 S, Cu ₇ S ₄ , CuS, etc. can do. Further, Li ₂ S and _{CuS 1-X (0.0 ≦ X} ≦ 0.5) and uniformly and Li ₂ S and _{CuS 1-X (0.0 ≦ X} ≦ 0.5) is a method of mixing Although it will not specifically limit if it is the mixing method which can be mixed in this, For example, it can carry out by stirring or a mechanochemical process in an inert atmosphere.

Further, in the lithium copper sulfide according to the present embodiment, the molar ratio (Li / Cu) of the content of Li to the content of Cu is preferably 2.1 or more and 6.0 or less, more preferably 2. 4 or more and 4.3 or less. The molar ratio (S / Cu) of the S content to the Cu content is preferably 1.5 or more and 3.5 or less, more preferably 1.6 or more and 2.7 or less. By setting the ratio of Li / Cu and the ratio of S / Cu within the above ranges, the initial discharge capacity can be further improved.
Here, the contents of Li, S, and Cu in the lithium copper sulfide according to the present embodiment can be determined by, for example, ICP emission spectroscopic analysis.

The positive electrode active material according to the present embodiment is not particularly limited, but the average particle diameter d ₅₀ in the weight-based particle size distribution by the laser diffraction / scattering particle size distribution measurement method is preferably 1 μm to 10 μm, more preferably 1 μm to 6 μm. It is as follows.
The average particle size d ₅₀ of the positive electrode active material to be in the above range, while maintaining good handling properties, it can be manufactured more density of the positive electrode.

The positive electrode active material according to the present embodiment is not particularly limited, but the specific surface area according to the BET three-point method in nitrogen adsorption is preferably 0.1 m ² / g or more and 3.0 m ² / g or less, more preferably 0.1 m. ^{It is 2} / g or more and 1.1 m ² / g or less.
When the specific surface area by the BET three-point method in nitrogen adsorption is not more than the above upper limit value, irreversible reaction between the positive electrode active material and the solid electrolyte can be suppressed.
Moreover, the permeability to the positive electrode active material of a solid electrolyte can be improved by making the specific surface area by BET 3 point method in nitrogen adsorption into more than the said lower limit.

"Conductive aid"
The electrode active material layer 101 according to this embodiment preferably contains a conductive additive from the viewpoint of improving the conductivity of the positive electrode layer. The conductive auxiliary agent according to the present embodiment is not particularly limited as long as it is a normal conductive auxiliary agent that can be used for a lithium ion battery. For example, carbon black such as acetylene black and ketjen black, vapor grown carbon fiber, etc. The carbon material is mentioned. These may be used individually by 1 type and may be used in combination of 2 or more type.

"Solid electrolyte"
The electrode active material layer 101 according to this embodiment preferably contains a solid electrolyte from the viewpoint of improving the ionic conductivity of the positive electrode layer. The solid electrolyte according to the present embodiment is not particularly limited as long as it has ion conductivity, but those generally used for all solid-state lithium ion batteries can be used. Examples thereof include a sulfide solid electrolyte material and an oxide solid electrolyte material. Among these, a sulfide solid electrolyte material is preferable. Thereby, the output characteristics of the obtained all solid-state lithium ion battery can be improved.

Examples of the sulfide solid electrolyte material according to the present embodiment include Li ₂ S—P ₂ S ₅ materials such as Li ₃ PS ₄ and Li ₇ P ₃ S ₁₁ ; Li ₂ S—SiS ₂ material; Li ₂ S— SiS ₂ —Li ₃ PO ₄ material; Li ₂ S—GeS ₂ material; Li ₂ S—Al ₂ S ₃ material; Li ₁₀ GeP ₂ S ₁₂ , Li _3.25 Ge _0.25 P _0.75 S ₄ etc. such as _{li 2 S-GeS 2 -P 2} S 5 material. These may be used individually by 1 type and may be used in combination of 2 or more type. Among these, Li ₂ S—P ₂ S ₅ material is preferable because it has excellent lithium ion conductivity and stability that does not cause decomposition in a wide voltage range.

"Combination ratio of various materials"
When the all-solid-state lithium ion battery electrode 100 according to the present embodiment is used for the positive electrode layer, the blending ratio of various materials of the electrode active material layer 101 according to the present embodiment is appropriately determined according to the usage application of the battery. Since it is determined, it is not particularly limited and can be set according to generally known information.

"Method for manufacturing positive electrode layer"
Below, the manufacturing method of the positive electrode layer which concerns on this embodiment is demonstrated.
The positive electrode layer according to the present embodiment is not particularly limited. For example, the electrode active material layer 101 can be formed by attaching the fine particle positive electrode active material to the conductive resin layer 102. For example, it can be manufactured by the following method.

First, a positive electrode active material and, if necessary, a conductive additive, a solid electrolyte, and the like are mixed with a mixer. The mixing ratio of each material is appropriately determined according to the intended use of the battery.
A known mixer such as a ball mill or a planetary mixer can be used as the mixer, and is not particularly limited. The mixing method is not particularly limited, and can be performed according to a known method.

Subsequently, the electrode active material layer 101 is formed by adhering the obtained mixture containing the positive electrode active material to the conductive resin layer 102 formed on the current collector layer 103 so as to have a predetermined thickness. To do. By carrying out like this, the positive electrode layer concerning this embodiment can be obtained.
Further, a step of removing a positive electrode active material or the like that is not completely attached to the conductive resin layer 102 may be further performed. Further, by pressing the surface to which the positive electrode active material or the like is attached, the adhesion of the electrode active material layer 101 is increased, thereby suppressing the detachment of the positive electrode active material or the like, or the surface to which the positive electrode active material or the like is attached. The smoothness may be improved. Alternatively, the thickness and density of the electrode active material layer 101 may be adjusted by pressing the surface to which the positive electrode active material or the like is attached. As a pressing method, a generally known method can be used.

  A method for attaching the mixture containing the positive electrode active material on the conductive resin layer 102 is not particularly limited, but a method of directly supplying the mixture containing the positive electrode active material to the conductive resin layer 102 in air or in an inert atmosphere, There is a method in which a mixture containing a positive electrode active material is dispersed in a dispersion to form a slurry, and the slurry is supplied onto the conductive resin layer 102.

As a method of directly supplying the mixture containing the positive electrode active material to the conductive resin layer 102 in the air or in an inert atmosphere, a method of dropping the mixture containing the positive electrode active material on the conductive resin layer 102, The method of spraying the mixture containing on the conductive resin layer 102, etc. are mentioned.
In order to arrange the mixture containing the positive electrode active material on the conductive resin layer 102 to a uniform thickness, a guide having a predetermined height is placed, and the mixture containing the positive electrode active material is filled so as to fill the opening of the guide. Is also possible. The guide may be a structure made of metal or synthetic resin and having a large opening. For example, a metal or resin porous plate, a woven fabric, a non-woven fabric, etc. may be mentioned as an easily available guide.
The mixture containing the positive electrode active material is attached onto the conductive resin layer 102 due to the adhesiveness of the conductive resin layer 102.

(Negative electrode layer)
When the all-solid-state lithium ion battery electrode 100 according to this embodiment is used for a negative electrode layer, the electrode active material layer 101 according to this embodiment includes a negative electrode active material as a particulate electrode active material. In addition, it contains a conductive aid, a solid electrolyte, and the like.

  When the all-solid-state lithium ion battery electrode 100 according to this embodiment is used for the negative electrode layer, the thickness of the electrode active material layer 101 according to this embodiment is preferably 2 μm or more and 60 μm or less, more preferably 3 μm or more. 35 μm or less. When the thickness of the electrode active material layer 101 according to the present embodiment is within the above range, the stress relaxation ability with respect to the volume change of the negative electrode active material accompanying charge / discharge is particularly excellent, and thus the discharge capacity of the obtained all solid-state lithium ion battery Charge / discharge characteristics such as density and cycle characteristics can be further improved.

When the all-solid-state lithium ion battery electrode 100 according to this embodiment is used for a negative electrode layer, the weight per unit area of the negative electrode active material contained in the electrode active material layer 101 according to this embodiment is preferably 1. 5 g / ^{m 2} or more 65.0 g / ^{m 2} or less, more preferably 2.0 g / ^{m 2} or more 50.0 g / ^{m 2} or less. When the weight per unit area of the negative electrode active material is within the above range, the stress relaxation ability with respect to the volume change of the negative electrode active material accompanying charge / discharge is particularly excellent, so the discharge capacity density and cycle of the obtained all solid-state lithium ion battery Charge / discharge characteristics such as characteristics can be further improved.

When the all-solid-state lithium ion battery electrode 100 according to this embodiment is used for the negative electrode layer, the density of the electrode active material layer 101 according to this embodiment is preferably 0.065 g / cm ³ or more and 4.2 g / cm. ³ or less, more preferably 0.65 g / cm ³ or more and 4.0 g / cm ³ or less. When the density of the electrode active material layer 101 according to the present embodiment is within the above range, the stress relaxation ability with respect to the volume change of the negative electrode active material accompanying charge / discharge is particularly excellent. Charge / discharge characteristics such as capacity density and cycle characteristics can be further improved.

"Negative electrode active material"
The negative electrode active material according to the present embodiment is not particularly limited as long as it is a normal negative electrode active material that can be used for the negative electrode layer of a lithium ion battery. For example, natural graphite, artificial graphite, resin charcoal, carbon fiber, activated carbon, hard Carbonaceous materials such as carbon and soft carbon; alloy materials mainly composed of silicon, tin, gallium and indium; conductive polymers such as polyacene, polyacetylene and polypyrrole; lithium metal; lithium titanium composite oxide (for example, Li ₄ Ti ₅ O ₁₂ ). These may be used individually by 1 type and may be used in combination of 2 or more type.
Examples of the alloy-based material include tin, tin alloy, silicon, silicon alloy, gallium, gallium alloy, indium, and indium alloy.
Among these, fine particles of alloy materials such as tin, tin alloy, silicon, silicon alloy, and gallium alloy have a large volume change accompanying charge / discharge, and therefore when using these negative electrode active materials, An effect can be obtained.

The negative electrode active material according to the present embodiment is not particularly limited, but the average particle size d ₅₀ in the weight-based particle size distribution measured by the laser diffraction / scattering particle size distribution measurement method is preferably 1 μm or more and 50 μm or less, more preferably 5 μm or more and 30 μm. It is as follows.
The average particle size d ₅₀ of the negative electrode active material to be in the above range, while maintaining good handling properties, it can be manufactured more density of the negative electrode.

The negative electrode active material according to the present embodiment is not particularly limited, but the specific surface area by the BET three-point method in nitrogen adsorption is preferably 0.1 m ² / g or more and 15.0 m ² / g or less, more preferably 1.0 m. ^{It is 2} / g or more and 10.0 m ² / g or less.
When the specific surface area according to the BET three-point method in nitrogen adsorption is not more than the above upper limit, irreversible reaction between the negative electrode active material and the solid electrolyte can be suppressed.
Moreover, the permeability to the negative electrode active material of a solid electrolyte can be improved because the specific surface area by BET 3 point method in nitrogen adsorption is more than the said lower limit.

"Conductive aid"
The electrode active material layer 101 according to this embodiment preferably contains a conductive additive from the viewpoint of improving the conductivity of the negative electrode layer. Examples of the conductive auxiliary according to the present embodiment include the same ones as those used for the positive electrode layer described above.

"Solid electrolyte"
The electrode active material layer 101 according to this embodiment preferably contains a solid electrolyte from the viewpoint of improving the ionic conductivity of the negative electrode layer. Examples of the solid electrolyte according to the present embodiment include the same ones as those used for the positive electrode layer described above.

"Combination ratio of various materials"
When the all-solid-state lithium ion battery electrode 100 according to the present embodiment is used for the negative electrode layer, the blending ratio of various materials of the electrode active material layer 101 according to the present embodiment is appropriately determined according to the usage application of the battery. Since it is determined, it is not particularly limited and can be set according to generally known information.

"Production method of negative electrode layer"
A method for manufacturing the negative electrode layer according to this embodiment will be described.
The negative electrode layer according to this embodiment is not particularly limited. For example, the negative electrode layer can be obtained by forming the electrode active material layer 101 by adhering the fine particle negative electrode active material to the conductive resin layer 102. For example, it can be manufactured by the following method.

First, the mixing ratio of each material for mixing the negative electrode active material and, if necessary, the conductive assistant, the solid electrolyte, etc. with a mixer is appropriately determined according to the intended use of the battery.
As a mixer, the thing similar to what is used for the manufacturing method of the positive electrode layer mentioned above can be mentioned.

Subsequently, the electrode active material layer 101 is formed by adhering the obtained mixture containing the negative electrode active material to the conductive resin layer 102 formed on the current collector layer 103 so as to have a predetermined thickness. To do. By carrying out like this, the negative electrode layer concerning this embodiment can be obtained.
Further, a step of removing a negative electrode active material or the like that is not completely attached to the conductive resin layer 102 may be further performed. Further, by pressing the surface to which the negative electrode active material or the like is adhered, the adhesion of the electrode active material layer 101 is increased, so that the detachment of the negative electrode active material is suppressed or the surface to which the negative electrode active material is adhered is smoothed. May be improved. Further, the thickness and density of the electrode active material layer 101 may be adjusted by pressing the surface to which the negative electrode active material or the like is attached. As a pressing method, a generally known method can be used.

  A method for attaching the mixture containing the negative electrode active material on the conductive resin layer 102 is not particularly limited, and a method of directly supplying the mixture containing the negative electrode active material to the conductive resin layer 102 in air or in an inert atmosphere, There is a method in which a mixture containing a negative electrode active material is dispersed in a dispersion to form a slurry, and the slurry is supplied onto the conductive resin layer 102.

As a method of directly supplying the mixture containing the negative electrode active material to the conductive resin layer 102 in the air or in an inert atmosphere, a method of dropping the mixture containing the negative electrode active material on the conductive resin layer 102, The method of spraying the mixture containing on the conductive resin layer 102, etc. are mentioned.
In order to arrange the mixture containing the negative electrode active material on the conductive resin layer 102 to have a uniform thickness, a guide having a predetermined height is placed, and the mixture containing the negative electrode active material is filled so as to fill the opening of the guide. Is also possible. The guide may be a structure made of metal or synthetic resin and having a large opening. For example, a metal or resin porous plate, a woven fabric, a non-woven fabric, etc. may be mentioned as an easily available guide.
The mixture containing the negative electrode active material is attached onto the conductive resin layer 102 due to the adhesiveness of the conductive resin layer 102.

<Current collector layer>
The current collector layer 103 according to the present embodiment is not particularly limited as long as it is made of metal such as iron, copper, aluminum, nickel, stainless steel, and titanium. From the viewpoints of price, availability and electrochemical stability, aluminum is preferable for the positive electrode and copper is preferable for the negative electrode. Further, the shape of the current collector layer 103 is not particularly limited, but it is preferable to use a sheet-like material having a thickness in the range of 0.001 to 0.5 mm. Examples of the sheet-like material include metal foil, non-woven fabric or woven fabric, and further, metal or carbon coated with a synthetic resin film, non-woven fabric or woven fabric, or paper.

[All-solid-state lithium-ion battery]
Next, the all solid-state lithium ion battery 200 according to the present embodiment will be described. FIG. 2 is a cross-sectional view showing an example of the structure of the all solid-state lithium ion battery according to the embodiment of the present invention.

The all solid-state lithium ion battery 200 according to the present embodiment includes a positive electrode layer 210, a solid electrolyte layer 220, and a negative electrode layer 230 that are stacked in this order. At least one of the positive electrode layer 210 and the negative electrode layer 230 is the all solid-state lithium ion battery electrode 100 according to this embodiment.
That is, when the positive electrode layer 210 includes the all-solid-state lithium ion battery electrode 100 according to this embodiment, the positive electrode layer 210 includes the positive electrode active material layer 203 (101), the conductive resin layer 202 (102), and the positive electrode collector. The electric conductor layer 201 (103) is laminated in this order. When the negative electrode layer 230 is made of the all solid-state lithium ion battery electrode 100 according to this embodiment, the negative electrode layer 230 includes the negative electrode active material layer 205 (101), the conductive resin layer 207 (102), and the negative electrode collector. The electric conductor layer 209 (103) is laminated in this order.

  The all-solid-state lithium ion battery 200 according to the present embodiment is generally manufactured according to a known method. For example, the positive electrode layer 210, the solid electrolyte layer 220, and the negative electrode layer 230 are stacked to form a cylindrical shape, a coin shape, a square shape, a film shape, or any other shape.

(Solid electrolyte layer)
The solid electrolyte layer 220 according to the present embodiment is a layer formed between the positive electrode layer 210 and the negative electrode layer 230, and is a layer formed of a solid electrolyte. The solid electrolyte contained in the solid electrolyte layer 220 is not particularly limited as long as it has lithium ion conductivity, and generally known ones can be used. For example, the same solid electrolyte as that contained in the electrode active material layer 101 described above can be used.

  The content of the solid electrolyte in the solid electrolyte layer 220 according to the present embodiment is not particularly limited as long as a desired insulating property is obtained. For example, the solid electrolyte content is within a range of 10% by volume to 100% by volume. Especially, it is preferable that it exists in the range of 50 to 100 volume%.

  Moreover, the solid electrolyte layer 220 according to the present embodiment may contain a binder. By containing the binder, the solid electrolyte layer 220 having flexibility can be obtained. Examples of the binder include fluorine-containing binders such as polytetrafluoroethylene and polyvinylidene fluoride. The thickness of the solid electrolyte layer 220 is, for example, in the range of 0.1 μm to 1000 μm, and preferably in the range of 0.1 μm to 300 μm.

As mentioned above, although embodiment of this invention was described, these are illustrations of this invention and various structures other than the above are also employable.
It should be noted that the present invention is not limited to the above-described embodiment, and modifications, improvements, and the like within the scope that can achieve the object of the present invention are included in the present invention.
Hereinafter, examples of the reference form will be added.
1.
A sheet-like electrode used for a positive electrode layer or a negative electrode layer of an all-solid-state lithium ion battery,
An electrode active material layer containing a particulate electrode active material;
A conductive resin layer;
A current collector layer;
Are stacked in this order, all-solid-state lithium-ion battery electrode.
2.
1. In the all-solid-state lithium ion battery electrode according to
The conductive resin layer includes a resin and conductive fine particles,
The electrode for an all solid-state lithium ion battery, wherein the conductive fine particles are dispersed in the conductive resin layer.
3.
2. In the all-solid-state lithium ion battery electrode according to
An electrode for an all-solid-state lithium ion battery, wherein an average particle diameter d ₅₀ in a weight-based particle size distribution measured by a laser diffraction / scattering particle size distribution measurement method of the conductive fine particles is 0.5 μm or more and 50 μm or less.
4).
1. To 3. In the electrode for an all solid-state lithium ion battery according to any one of the above:
An electrode for an all solid-state lithium ion battery, wherein the conductive resin layer has a thickness of 5 µm or more and 60 µm or less.
5.
1. To 4. In the electrode for an all solid-state lithium ion battery according to any one of the above:
An electrode for an all solid-state lithium ion battery, wherein the content of the pressure-sensitive adhesive and the binder contained in the electrode active material layer is 5% by weight or less when the entire electrode active material layer is 100% by weight.
6).
1. To 5. In the electrode for an all solid-state lithium ion battery according to any one of the above:
The conductive resin layer is an electrode for an all solid-state lithium ion battery, which is formed of a resin composition containing an adhesive and conductive fine particles.
7).
1. To 6. In the electrode for an all solid-state lithium ion battery according to any one of the above:
An electrode for an all-solid-state lithium ion battery, wherein at least one of the electrode active material layer and the conductive resin layer includes a solid electrolyte.
8).
1. To 7. In the electrode for an all solid-state lithium ion battery according to any one of the above:
The electrode active material layer is an electrode for an all solid-state lithium ion battery, further including a conductive additive.
9.
1. To 8. In the electrode for an all solid-state lithium ion battery according to any one of the above:
The all solid-state lithium ion battery electrode is used for the positive electrode layer,
The particulate electrode active material contained in the electrode active material layer is a positive electrode active material,
The positive electrode active material is an electrode for an all solid-state lithium ion battery, containing at least one selected from the group consisting of lithium sulfide and lithium copper sulfide.
10.
9. In the all-solid-state lithium ion battery electrode according to
The positive active mean particle size d ₅₀ is 1μm or more 10μm or less in weight particle size distribution by a laser diffraction scattering particle size distribution measurement method of material, all-solid-state lithium-ion cell electrodes.
11.
9. Or 10. In the all-solid-state lithium ion battery electrode according to
An electrode for an all solid-state lithium ion battery, wherein a thickness of the electrode active material layer containing the positive electrode active material is 2 μm or more and 60 μm or less.
12
9. To 11. In the electrode for an all solid-state lithium ion battery according to any one of the above:
The positive active weight per unit area of the material is 65.0 g / m ² or less 1.5 g / m ² or more, all-solid-state lithium ion battery electrode included in the electrode active material layer.
13.
1. To 8. In the electrode for an all solid-state lithium ion battery according to any one of the above:
The all solid-state lithium ion battery electrode is used for the negative electrode layer,
The particulate electrode active material contained in the electrode active material layer is a negative electrode active material,
The negative electrode active material is an electrode for an all-solid-state lithium ion battery, containing at least one selected from the group consisting of tin, tin alloy, silicon, silicon alloy, and gallium alloy.
14
13. In the all-solid-state lithium ion battery electrode according to
The negative active mean particle size d ₅₀ is 1μm or more 50μm or less in weight particle size distribution by a laser diffraction scattering particle size distribution measurement method of material, all-solid-state lithium-ion cell electrodes.
15.
13. Or 14. In the all-solid-state lithium ion battery electrode according to
An electrode for an all solid-state lithium ion battery, wherein a thickness of the electrode active material layer containing the negative electrode active material is 2 μm or more and 60 μm or less.
16.
13. To 15. In the electrode for an all solid-state lithium ion battery according to any one of the above:
The electrode active weight per unit area of the negative electrode active material contained in the material layer is 1.5 g / m ² or more 65.0 g / m ² or less, all-solid-state lithium-ion cell electrodes.
17.
An all solid-state lithium ion battery in which a positive electrode layer, a solid electrolyte layer, and a negative electrode layer are laminated in this order,
At least one of the positive electrode layer and the negative electrode layer is 1. To 8. An all-solid-state lithium ion battery, which is an electrode for an all-solid-state lithium ion battery according to any one of the above.
18.
An all solid-state lithium ion battery in which a positive electrode layer, a solid electrolyte layer, and a negative electrode layer are laminated in this order,
The positive electrode layer is 9. To 12. An all-solid-state lithium ion battery, which is an electrode for an all-solid-state lithium ion battery according to any one of the above.
19.
An all solid-state lithium ion battery in which a positive electrode layer, a solid electrolyte layer, and a negative electrode layer are laminated in this order,
The negative electrode layer is 13. To 16. An all-solid-state lithium ion battery, which is an electrode for an all-solid-state lithium ion battery according to any one of the above.
20.
1. To 16. A production method for producing an electrode for an all-solid-state lithium ion battery according to any one of the following:
The manufacturing method of the electrode for all-solid-state type lithium ion batteries including the process of forming the said electrode active material layer by adhering the said electrode active material of a particulate form to the said conductive resin layer.

  Hereinafter, although an example and a comparative example explain the present invention, the present invention is not limited to these. In Examples and Comparative Examples, “mAh / g” indicates the discharge capacity density per gram of electrode active material.

[1] Measuring method First, measuring methods in the following examples and comparative examples will be described.

(1) Particle size distribution The particle size distribution of the positive electrode active material and the negative electrode active material used in Examples and Comparative Examples was measured by laser diffraction method using a laser diffraction scattering type particle size distribution measuring device (manufactured by Malvern, Mastersizer 3000). It was measured. From the measurement results, for each positive electrode active material and negative electrode active material, the particle size (D ₅₀ , average particle size) at 50% accumulation in the weight-based cumulative distribution was determined.

[2] Production of positive electrode active material (step of mixing Li ₂ S and CuS)
Under an argon atmosphere, in a pot made of Al ₂ O ₃ , Li ₂ S (Aldrich, 500 mg, 10.9 mmol, average particle size: 7 μm) and CuS (Alfa Aesar, 500 mg, 5.2 mmol, average particle) (Diameter: 10 μm) was weighed and added, and ZrO ₂ balls were further added, and the Al ₂ O ₃ pot was sealed.
Next, the Al ₂ O ₃ pot was set on a planetary ball mill (Fritsch, P-7) and treated at 400 rpm for 1 hour to obtain a mixture.

(Step of heating the mixture)
Next, the obtained mixture was heated at 400 ° C. for 12 hours in an argon atmosphere using a tubular furnace. Then, it cooled to room temperature and obtained 800 mg of positive electrode active materials.
The obtained positive electrode active material was pulverized with a mortar and classified with a sieve having an opening of 45 μm to obtain a positive electrode active material 1 having an average particle diameter d ₅₀ of 3 μm.

(Physical properties)
ICP emission spectral analysis of the positive electrode active material 1 revealed that Li was 16.6% by weight, Cu was 35.9% by weight, and S was 47.5% by weight.

<Example 1>
100 mg of the positive electrode active material 1, 100 mg of acetylene black as a conductive additive, and 200 mg of Li ₃ PS ₄ as a solid electrolyte were mixed. Next, the mixture was attached to the adhesive surface of a conductive aluminum foil adhesive tape (Teraoka Seisakusho, No8303, φ14 mm, conductive resin layer thickness: 35 μm) to obtain a positive electrode layer 1 (diameter φ = 14 mm, positive electrode The thickness of the active material layer: 10 μm, the weight per unit area of the positive electrode active material 1: 6.5 g / m ² , and the density of the positive electrode active material layer: 2.6 g / cm ³ ). Here, the conductive aluminum foil pressure-sensitive adhesive tape is formed by applying a conductive acrylic pressure-sensitive adhesive on an aluminum foil having a thickness of 0.050 mm.

Subsequently, the solid electrolyte (Li ₃ PS ₄ , 120 mg) was pre-pressed at 83 MPa using a pressing jig. Thereafter, the solid electrolyte layer 1 was formed on the positive electrode layer 1 by being pressed on the positive electrode layer 1 and further press-molded at 250 MPa for 10 minutes.
Moreover, the positive electrode layer 1, the solid electrolyte layer 1, and the indium foil (φ = 14 mm, t = 0.5 mm) as the negative electrode obtained by the above method were laminated in this order to produce an all-solid-state lithium ion battery. Next, the all solid state lithium ion battery obtained was charged to a charge termination voltage 3.0V at a current density of 65μA / cm ^2, at a current density of 65μA / cm ^2, until the discharge cutoff potential 0.4V Charging / discharging was performed 3 times under the discharge conditions. Table 1 shows the results obtained for the discharge capacity density and the charge / discharge efficiency for the positive electrode active material.

<Example 2>
The mixture of positive electrode active material 1, acetylene black and Li ₃ PS ₄ of Example 1 was attached to the adhesive surface of a conductive aluminum foil adhesive tape (Teraoka Seisakusho, No8303, φ14 mm, conductive resin layer thickness: 35 μm). Thus, positive electrode layer 2 was obtained (diameter φ = 14 mm, positive electrode active material layer thickness: 50 μm, positive electrode active material 1 weight per unit area: 39.0 g / m ² , positive electrode active material layer density: 3.1 g. / Cm ³ ). Here, the conductive aluminum foil pressure-sensitive adhesive tape is formed by applying a conductive acrylic pressure-sensitive adhesive on an aluminum foil having a thickness of 0.050 mm.

Subsequently, after pre-pressing the solid electrolyte (Li ₃ PS ₄ , 120 mg) at 83 MPa using a pressing jig, the solid electrolyte (Li ₃ PS ₄ , 120 mg) was placed on the positive electrode layer 2 and further press molded at 250 MPa for 10 minutes. A solid electrolyte layer 2 was formed thereon.
Moreover, the positive electrode layer 2, the solid electrolyte layer 2, and the negative electrode indium foil (φ = 14 mm, t = 0.5 mm) obtained by the above method were laminated in this order to produce an all-solid-state lithium ion battery. Next, the all solid state lithium ion battery obtained was charged to a charge termination voltage 3.0V at a current density of 65μA / cm ^2, at a current density of 65μA / cm ^2, until the discharge cutoff potential 0.4V Charging / discharging was performed 3 times under the discharge conditions, and the discharge capacity density (mAh / g) and the charge / discharge efficiency (%) were calculated. The obtained results are shown in Table 1.

<Comparative Example 1>
A mixture of the positive electrode active material 1, the acetylene black and Li ₃ PS ₄ of Example 1 was press-molded at a pressure of 250 MPa on the surface of an aluminum foil (manufactured by Toyo Aluminum Co., Ltd., thickness 50 μm, φ14 mm) to obtain a positive electrode layer 3. (Diameter φ = 14 mm, thickness of positive electrode active material layer: 40 μm, weight per unit area of positive electrode active material 1: 32.5 g / m ² , density of positive electrode active material layer: 3.25 g / cm ³ ).

Subsequently, after pre-pressing the solid electrolyte (Li ₃ PS ₄ , 120 mg) at 83 MPa using a pressing jig, the solid electrolyte (Li ₃ PS ₄ , 120 mg) was placed on the positive electrode layer 3 and further press molded at 250 MPa for 10 minutes. A solid electrolyte layer 3 was formed thereon.
In addition, the positive electrode layer 3, the solid electrolyte layer 3, and the indium foil (φ = 14 mm, t = 0.5 mm) as the negative electrode obtained by the above method were laminated in this order to produce an all-solid-state lithium ion battery. Next, the all solid state lithium ion battery obtained was charged to a charge termination voltage 3.0V at a current density of 65μA / cm ^2, at a current density of 65μA / cm ^2, until the discharge cutoff potential 0.4V Charging / discharging was performed 3 times under the discharge conditions, and the discharge capacity density (mAh / g) and the charge / discharge efficiency (%) were calculated. The obtained results are shown in Table 1.

(Charge / discharge test results)
The charge / discharge test results of Examples 1 and 2 and Comparative Example 1 are shown in Table 1.

<Example 3>
150 mg of Li ₂ S (manufactured by Aldrich), 150 mg of acetylene black as a conductive auxiliary agent, and 300 mg of Li ₃ PS ₄ as a solid electrolyte were mixed. Next, the mixture was press-molded at a pressure of 250 MPa on the surface of an aluminum foil (manufactured by Toyo Aluminum Co., Ltd., thickness 50 μm, φ14 mm) to obtain a positive electrode layer 4 (diameter φ = 14 mm, positive electrode active material layer thickness: 200 μm). The weight per unit area of the positive electrode active material 1 is 65.0 g / m ² , and the density of the positive electrode active material layer is 1.30 g / cm ³ ).

Subsequently, a solid electrolyte (Li ₃ PS ₄ , 150 mg) was preliminarily pressed at 83 MPa using a pressing jig. Thereafter, the solid electrolyte layer 4 was formed on the positive electrode layer 4 by being pressed on the positive electrode layer 4 and further press-molded at 250 MPa for 10 minutes.

Next, 333 mg of negative electrode active material 1 (manufactured by Furukawa Denshi Co., Ltd., silicon, purity 99.999%, average particle size 2 μm), 333 mg of acetylene black as a conductive additive, and Li ₃ PS ₄ as a solid electrolyte 333 mg was mixed. Next, the mixture was adhered to the adhesive surface of a conductive aluminum foil adhesive tape (Teraoka Seisakusho Co., Ltd., No8303, φ14 mm, conductive resin layer thickness: 35 μm) to obtain negative electrode layer 1 (diameter φ = 14 mm, negative electrode Active material layer thickness: 3 μm, negative electrode active material 1 weight per unit area: 2.1 g / m ² , negative electrode active material layer density: 2.1 g / cm ³ ). Here, the conductive aluminum foil pressure-sensitive adhesive tape is formed by applying a conductive acrylic pressure-sensitive adhesive on an aluminum foil having a thickness of 0.050 mm.

Next, the positive electrode layer 4, the solid electrolyte layer 4, and the negative electrode layer 1 obtained by the above method were laminated in this order to produce an all solid-state lithium ion battery. Next, the all solid state lithium ion battery obtained was charged to a charge termination voltage 3.4V at a current density of 65μA / cm ^2, at a current density of 65μA / cm ^2, until the discharge cutoff potential 0.6V Charging / discharging was performed 3 times under the discharge conditions. Table 2 shows the results obtained for the discharge capacity density and the charge / discharge efficiency for the negative electrode active material.

<Example 4>
200 mg of negative electrode active material 2 (manufactured by Aldrich, tin, purity 99%, average particle size <10 μm), 200 mg of acetylene black as a conductive additive, and 200 mg of Li ₃ PS ₄ as a solid electrolyte were mixed. . Next, the mixture was adhered to the adhesive surface of a conductive aluminum foil adhesive tape (Teraoka Seisakusho, No8303, φ14 mm, conductive resin layer thickness: 35 μm) to obtain negative electrode layer 2 (diameter φ = 14 mm, negative electrode Active material layer thickness: 15 μm, negative electrode active material 1 weight per unit area: 10.8 g / m ² , negative electrode active material layer density: 0.72 g / cm ³ ). Here, the conductive aluminum foil pressure-sensitive adhesive tape is formed by applying a conductive acrylic pressure-sensitive adhesive on an aluminum foil having a thickness of 0.050 mm.

Next, the positive electrode layer 4, the solid electrolyte layer 4, and the negative electrode layer 2 obtained by the above method were laminated in this order to produce an all solid-state lithium ion battery. Next, the all solid state lithium ion battery obtained was charged to a charge termination voltage 3.4V at a current density of 65μA / cm ^2, at a current density of 65μA / cm ^2, until the discharge cutoff potential 0.6V Charging / discharging was performed 3 times under the discharge conditions. The obtained results are shown in Table 2.

<Example 5>
(Process for producing GaLi alloy)
In an argon atmosphere, gallium (made by DOWA Electronics, 99.9999%, 432 mg, 6.2 mmol) and Li foil (made by Honjo Metal Co., Ltd., thickness: 0.5 mm, 99.5% or more) in a carbon crucible , 43 mg, 6.2 mmol) was weighed in and heated in an electric furnace at 200 ° C. for 30 minutes. Put product made _{of Al} 2 _{O 3} pots, further put ZrO ₂ balls were sealed made _{of Al} 2 _{O 3} pots.
Next, the Al ₂ O ₃ pot was placed on a ball mill stand and treated at 95 rpm for 24 hours to obtain a homogenized alloy powder. As a result of powder X-ray diffraction, it was confirmed that the alloy powder was GaLi.

250 mg of the obtained negative electrode active material 3 (GaLi, average particle diameter 2 μm), 250 mg of acetylene black as a conductive auxiliary agent, and 250 mg of Li ₃ PS ₄ as a solid electrolyte were mixed. Then, the mixture was attached to the adhesive surface of a conductive aluminum foil adhesive tape (Teraoka Seisakusho, No8303, φ14 mm, conductive resin layer thickness: 35 μm) to obtain negative electrode layer 3 (diameter φ = 14 mm, negative electrode The thickness of the active material layer: 35 μm, the weight per unit area of the negative electrode active material 1: 44.6 g / m ² , and the density of the negative electrode active material layer: 3.82 g / cm ³ ). Here, the conductive aluminum foil pressure-sensitive adhesive tape is formed by applying a conductive acrylic pressure-sensitive adhesive on an aluminum foil having a thickness of 0.050 mm.

Next, the positive electrode layer 4, the solid electrolyte layer 4, and the negative electrode layer 3 obtained by the above method were laminated in this order to produce an all solid-state lithium ion battery. Next, the all solid state lithium ion battery obtained was charged to a charge termination voltage 3.0V at a current density of 65μA / cm ^2, at a current density of 65μA / cm ^2, until the discharge cutoff potential 0.4V Charging / discharging was performed 3 times under the discharge conditions. The obtained results are shown in Table 2.

<Comparative example 2>
5 mg of negative electrode active material 1 (manufactured by Furukawa Electronics Co., Ltd., silicon, purity 99.999%, average particle diameter 2 μm), 5 mg of acetylene black as a conductive additive, and 5 mg of Li ₃ PS ₄ as a solid electrolyte Mixed. Subsequently, the mixture was press-molded on the surface of an aluminum foil (manufactured by Toyo Aluminum Co., Ltd., thickness 50 μm, φ14 mm) at a pressure of 250 MPa to obtain a negative electrode layer 4 (diameter φ = 14 mm, negative electrode active material layer thickness: 200 μm). The weight per unit area of the negative electrode active material 1: 260 g / m ² , and the density of the negative electrode active material layer: 1.3 g / cm ³ ).

Subsequently, the positive electrode layer 4, the solid electrolyte layer 4, and the negative electrode layer 4 obtained by the above method were laminated in this order to produce an all solid-state lithium ion battery. Next, the all solid state lithium ion battery obtained was charged to a charge termination voltage 3.0V at a current density of 65μA / cm ^2, at a current density of 65μA / cm ^2, until the discharge cutoff potential 0.4V Charging / discharging was performed 3 times under the discharge conditions. The obtained results are shown in Table 2.

(Charge / discharge test results)
The charge / discharge test results of Examples 3 to 5 and Comparative Example 2 are shown in Table 2.

DESCRIPTION OF SYMBOLS 100 Electrode for all solid-state lithium ion battery 101 Electrode active material layer 102 Conductive resin layer 103 Current collector layer 200 All solid state lithium ion battery 201 Positive electrode current collector layer 202 Conductive resin layer 203 Positive electrode active material layer 205 Negative electrode active Material layer 207 Conductive resin layer 209 Negative electrode current collector layer 210 Positive electrode layer 220 Solid electrolyte layer 230 Negative electrode layer

Claims (17)

A sheet-like electrode used for a positive electrode layer or a negative electrode layer of an all-solid-state lithium ion battery,
An electrode active material layer containing a particulate electrode active material;
A conductive resin layer;
A current collector layer;
Is an electrode for an all solid-state lithium ion battery laminated in this order ,
The electrode active material layer substantially does not contain an adhesive and a binder,
An electrode for an all solid-state lithium ion battery, wherein the electrode active material layer has a thickness of 2 μm or more and 60 μm or less . The all-solid-state lithium ion battery electrode according to claim 1,
The conductive resin layer includes a resin and conductive fine particles,
The electrode for an all solid-state lithium ion battery, wherein the conductive fine particles are dispersed in the conductive resin layer. The all-solid-state lithium ion battery electrode according to claim 2,
An electrode for an all-solid-state lithium ion battery, wherein an average particle diameter d ₅₀ in a weight-based particle size distribution measured by a laser diffraction / scattering particle size distribution measurement method of the conductive fine particles is 0.5 μm or more and 50 μm or less. The all-solid-state lithium ion battery electrode according to any one of claims 1 to 3,
An electrode for an all solid-state lithium ion battery, wherein the conductive resin layer has a thickness of 5 µm or more and 60 µm or less. In the all-solid-state lithium ion battery electrode according to any one of claims 1 to 4 ,
The conductive resin layer is an electrode for an all solid-state lithium ion battery, which is formed of a resin composition containing an adhesive and conductive fine particles. The all-solid-state lithium ion battery electrode according to any one of claims 1 to 5 ,
An electrode for an all-solid-state lithium ion battery, wherein at least one of the electrode active material layer and the conductive resin layer includes a solid electrolyte. The all-solid-state lithium ion battery electrode according to any one of claims 1 to 6 ,
The electrode active material layer is an electrode for an all solid-state lithium ion battery, further including a conductive additive. The all-solid-state lithium ion battery electrode according to any one of claims 1 to 7 ,
The all solid-state lithium ion battery electrode is used for the positive electrode layer,
The particulate electrode active material contained in the electrode active material layer is a positive electrode active material,
The positive electrode active material is an electrode for an all solid-state lithium ion battery, containing at least one selected from the group consisting of lithium sulfide and lithium copper sulfide. The all-solid-state lithium ion battery electrode according to claim 8 ,
The positive active mean particle size d ₅₀ is 1μm or more 10μm or less in weight particle size distribution by a laser diffraction scattering particle size distribution measurement method of material, all-solid-state lithium-ion cell electrodes. The all-solid-state lithium ion battery electrode according to claim 8 or 9 ,
The positive active weight per unit area of the material is 65.0 g / m ² or less 1.5 g / m ² or more, all-solid-state lithium ion battery electrode included in the electrode active material layer. The all-solid-state lithium ion battery electrode according to any one of claims 1 to 7 ,
The all solid-state lithium ion battery electrode is used for the negative electrode layer,
The particulate electrode active material contained in the electrode active material layer is a negative electrode active material,
The negative electrode active material is an electrode for an all-solid-state lithium ion battery, containing at least one selected from the group consisting of tin, tin alloy, silicon, silicon alloy, and gallium alloy. The all-solid-state lithium ion battery electrode according to claim 11 ,
The negative active mean particle size d ₅₀ is 1μm or more 50μm or less in weight particle size distribution by a laser diffraction scattering particle size distribution measurement method of material, all-solid-state lithium-ion cell electrodes. The all-solid-state lithium ion battery electrode according to claim 11 or 12 ,
The electrode active weight per unit area of the negative electrode active material contained in the material layer is 1.5 g / m ² or more 65.0 g / m ² or less, all-solid-state lithium-ion cell electrodes. An all solid-state lithium ion battery in which a positive electrode layer, a solid electrolyte layer, and a negative electrode layer are laminated in this order,
An all-solid-state lithium ion battery, wherein at least one of the positive electrode layer and the negative electrode layer is an electrode for an all-solid-state lithium ion battery according to any one of claims 1 to 7 . An all solid-state lithium ion battery in which a positive electrode layer, a solid electrolyte layer, and a negative electrode layer are laminated in this order,
An all-solid-state lithium ion battery, wherein the positive electrode layer is an electrode for an all-solid-state lithium ion battery according to any one of claims 8 to 10 . An all solid-state lithium ion battery in which a positive electrode layer, a solid electrolyte layer, and a negative electrode layer are laminated in this order,
An all-solid-state lithium ion battery, wherein the negative electrode layer is an electrode for an all-solid-state lithium ion battery according to any one of claims 11 to 13 . A manufacturing method for manufacturing an electrode for an all solid-state lithium ion battery according to any one of claims 1 to 13 ,
The manufacturing method of the electrode for all-solid-state type lithium ion batteries including the process of forming the said electrode active material layer by adhering the said electrode active material of a particulate form to the said conductive resin layer.

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