JP2020024780A - All-solid battery and manufacturing method thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an all-solid-state battery having excellent output characteristics. A method for producing an all-solid battery according to the present invention includes a positive electrode layer, a negative electrode layer, and a solid electrolyte layer, and comprises a positive electrode active material, an oxide glass powder, and a decomposition temperature of oxide glass. The step of forming a positive electrode sheet by molding a positive electrode slurry containing a binder containing a binder and a solvent below the crystallization temperature into a sheet, and the oxide glass powder and the decomposition temperature of the oxide glass are lower than the crystallization temperature of the oxide glass. A step of forming a solid electrolyte sheet by molding a solid electrolyte slurry containing a binder and a solvent into a sheet, a laminating step of laminating a positive electrode sheet and a solid electrolyte sheet and then applying pressure, and a laminated positive electrode sheet and a solid. The electrolyte sheet is degreased at a temperature lower than the crystallization temperature of the oxide glass and then pressed, and the pressed laminate is heated at a temperature equal to or higher than the crystallization temperature of the oxide glass and lower than 300 ° C. [Selection diagram] Figure 1

Description

  The present invention relates to an all-solid-state battery using a solid electrolyte and a method for manufacturing the same.

  Lithium-ion batteries are used not only in various mobile terminals but also in a wide range of fields such as in-vehicle and infrastructure applications. Furthermore, in recent years, various sensors and cameras have been miniaturized due to the high performance of electronic devices, and application of lithium ion batteries to these terminals is expected. Electronic devices are sometimes used in harsh environments, and lithium-ion batteries also require high temperature durability.

  An all-solid-state battery using a lithium-ion conductive solid electrolyte instead of an electrolyte has been proposed in order to lower the characteristics of a lithium-ion battery at high temperatures and to ensure safety. In particular, application studies on all-solid-state batteries are being vigorously pursued because lithium ion conductive oxide-based solid electrolytes having a NASICON, perovskite, or garnet structure have extremely high thermal stability.

  For example, Patent Document 1 discloses a method for manufacturing an all-solid-state battery using a green sheet method. A slurry of an active material, an oxide-based solid electrolyte, and a current collector is prepared, and a green sheet obtained by applying and drying the slurry is laminated and sintered in an oxidizing atmosphere to form a multi-layer structure. A solid state battery can be manufactured.

Patent Document 2 discloses an oxide solid electrolyte that can provide sufficient conductivity even when heated at about 300 ° C. or less. The oxide solid electrolyte has a general formula (I): A _a (B _1-b S _b ) O _c (where A is selected from Na and Li, a is 2.75 <a <3, b Is 0 <b <0.25, and c is 3 <c <3.25).

JP 2007-227362 A JP 2015-176854 A

  In the method of sintering the positive electrode layer and the solid electrolyte layer integrally described in Patent Document 1, a different phase is formed by a chemical reaction between the solid electrolyte and the positive electrode active material depending on the type of the positive electrode active material. In order to suppress the formation of a different phase, it is necessary to limit the type of the positive electrode active material used.

  On the other hand, if a glass-ceramic solid electrolyte described in Patent Document 2 is used, any active material can be applied. However, in the method of pressing powder as described in Patent Literature 2, it is difficult to reduce the thickness of the solid electrolyte layer to the order of 100 μm or less, and high output power is a problem.

  Therefore, an object of the present invention is to provide an all-solid-state battery having excellent output characteristics and a method for manufacturing the same.

  The method for manufacturing an all-solid battery according to the present invention includes a positive electrode layer, a negative electrode layer, and a solid electrolyte layer disposed between the positive electrode layer and the negative electrode layer, a positive electrode active material, and an oxide glass powder. Forming a positive electrode sheet by forming a positive electrode slurry containing a binder having a decomposition temperature lower than the crystallization temperature of the oxide glass and a solvent into a sheet shape, an oxide glass powder, and a decomposition temperature of the oxide glass A step of forming a solid electrolyte sheet by molding a solid electrolyte slurry containing a binder having a crystallization temperature of less than a solvent and a solvent into a sheet shape, and laminating the positive electrode sheet and the solid electrolyte sheet, and then pressing a laminating step, After degreasing the laminated positive electrode sheet and solid electrolyte sheet at a temperature lower than the crystallization temperature of the oxide glass, a degreasing step of applying pressure and heating the pressed laminate at a temperature higher than the crystallization temperature of the oxide glass and lower than 300 ° C Crystallization and process that, characterized in that it comprises a.

  ADVANTAGE OF THE INVENTION According to this invention, the all-solid-state battery excellent in output characteristics and its manufacturing method can be provided.

It is a figure showing the manufacturing process of the all solid state battery concerning one embodiment of the present invention. It is a figure showing the manufacturing process of the cathode sheet concerning one embodiment of the present invention. It is a figure showing a manufacturing process of a solid electrolyte layer sheet concerning one embodiment of the present invention. It is a figure showing the manufacturing process of the all solid state battery concerning one embodiment of the present invention. 1 is a cross-sectional view of an all solid state battery according to the present invention.

  Hereinafter, an all-solid-state battery and a method for manufacturing the same according to an embodiment of the present invention will be described. The configuration of the all-solid-state battery and the method of manufacturing the same are not limited to those described below, and can be practiced with appropriate changes within a scope that does not change the gist thereof.

<Manufacturing method of all solid state battery>
FIG. 1 shows a manufacturing process of an all-solid-state battery according to one embodiment.

  The method for manufacturing an all-solid battery includes a positive electrode sheet preparation step, a solid electrolyte sheet preparation step, a lamination step, a degreasing step, and a crystallization step. Hereinafter, each step will be described.

(Positive electrode sheet manufacturing process)
In the positive electrode sheet preparation step, a positive electrode slurry containing a positive electrode active material, an oxide glass powder, a binder having a decomposition temperature lower than the crystallization temperature of the oxide temperature, and a solvent is formed into a sheet, thereby forming a positive electrode. Make a sheet. In the present specification, the decomposition temperature of the binder is defined as a temperature at which 90% of the binder is thermally decomposed.

  FIG. 2 is a diagram illustrating a positive electrode sheet manufacturing process according to one embodiment.

  First, a positive electrode slurry is prepared by mixing a positive electrode active material, an ion conductive oxide glass powder which is a main material of a lithium ion conductive solid electrolyte, and a binder solution.

  A conductive assistant may be added to the positive electrode slurry. Examples of the conductive additive include graphite such as natural graphite and artificial graphite, single- or multi-walled carbon nanotubes, graphene, fullerene, VGCF, acetylene black, Ketjen black (trade name), channel black 6, furnace black, and lamps. Carbon black such as black and thermal black, carbon fiber and the like can be used. These may be used alone or in combination of two or more. For example, in the case of particles, the particles are not limited to primary particles, and those having an aggregate form such as secondary particles or a chain structure can also be used. Since the DBP lubrication amount of carbon (value of how much oil is retained in the voids of the structure) is 100 (ml / 100 g) or more, it can be added in a small amount of 2.5 to 10 wt% of the solid content of the positive electrode slurry. It becomes possible to sufficiently secure electron conductivity after high-temperature storage.

  As the solvent of the binder solution, a solvent that does not chemically react with the oxide glass powder is used. Examples of the solvent that does not chemically react with the oxide glass powder include ethanol, butyl acetate, dibutyl ether and the like.

  The binder preferably has a decomposition temperature of less than 300 ° C. For example, methylcellulose and methylbutanetriol can be used. The binder is dissolved in the solvent at a weight ratio of 10% by mass to 20% by mass.

  The ion-conductive oxide glass powder is pulverized to a specific range of particle diameter by a method such as a bead mill or a ball mill. Oxide glass powder previously ground to a specific range of particle size may be used. The average particle size of the oxide glass powder is preferably 10 μm or less, more preferably 5 μm or less. The particle size distribution can be measured by a laser diffraction / scattering type particle size distribution measuring device. The average particle size is based on the median value (D50) of the particle size distribution. In the particle size distribution, the sum of volumes smaller than a certain particle size occupies 50% of the entire volume of the whole powder. is there.

The ion-conductive oxide glass preferably contains at least one of lithium, boron, sulfur, and oxygen, and more preferably contains Li ₃ BO ₃ and Li ₂ SO ₄ .

The oxide glass containing Li ₃ BO ₃ and Li ₂ SO ₄ can be obtained by mixing Li ₃ BO ₃ and L ₂ ISO ₄ by mechanical milling in an inert atmosphere. Although a processing apparatus and processing conditions are not limited, a planetary ball mill is particularly preferable, and it is preferable that Li ₃ BO ₃ and L ₂ ISO ₄ are sufficiently mixed in a mortar or the like in an inert atmosphere before milling. The processing conditions need to be appropriately changed according to the processing apparatus used. However, when a planetary ball mill is used, the higher the rotation speed and / or the longer the processing time, the more uniformly the raw materials can be mixed and reacted. . Specifically, when a planetary ball mill is used, it is preferable that the force calculated from the acceleration of the sample and the ball weight is 0.02 N or more and the treatment is performed for 1 hour to 50 hours, and for 20 hours to 50 hours. It is more preferable that the treatment is performed within a period of time. The processing atmosphere is preferably an inert atmosphere such as argon, but the processing may be performed in a closed state using an overpot or the like. In addition, in order to avoid the hydrolysis reaction at the time of mechanical milling treatment, it is preferable that the salt is in an anhydrous state. When both salts contain water of crystallization, the temperature is 200 ° C. or more and 600 ° C. or less in air for 1 hour. It is preferable to dehydrate within 6 hours.

As the positive electrode active material, a known positive electrode active material capable of inserting and extracting lithium ions can be used. For example, it is represented by LiMO ₂ having a layered structure (M is at least one transition metal), and M is Ni, Co, Mn, Fe, Ti, Zr, Al, Mg, Cr, V, etc. Can be In addition, lithium manganate, lithium cobaltate, lithium nickelate, or those in which part of these manganese, cobert, and nickel are substituted with one or more transition metal elements may be used. In addition, an active material such as a spinel-based material represented by LiM ₂ O ₄ , an olivine-based material such as LiFePO ₄ , a layered solid solution in excess of Li, a silicate, and a vanadium oxide can be used.

  The solid content ratio of the positive electrode slurry is preferably at least 50%, more preferably at least 70%. Here, the solid content ratio is the total weight of the positive electrode active material, the oxide glass powder, and the binder with respect to the weight of the slurry. The solid content ratio of the slurry can be adjusted by the amount of the solvent added.

  The weight ratio of the positive electrode active material to the oxide glass powder is preferably 1 or more, and more preferably 4 or more. The weight ratio of the binder to the sum of the oxide glass powder and the positive electrode active material is preferably less than 0.6, and more preferably less than 0.3.

  Next, the positive electrode slurry is formed into a sheet. A green sheet having a thickness of 100 μm or less after drying can be obtained by a doctor blade method, a screen printing method, or the like. Specifically, the positive electrode slurry is formed on a carrier film such as PET which has been subjected to a release treatment, and dried. After drying, the film is punched to a predetermined size by a belt punch or the like, and the film is peeled off as necessary. After peeling, the positive electrode sheets may be laminated until a predetermined thickness is obtained. In addition, after laminating a plurality of positive electrode sheets until a predetermined thickness is obtained, the sheet may be punched to a predetermined size.

(Solid electrolyte sheet production process)
In the solid electrolyte sheet preparation step, a solid electrolyte slurry containing oxide glass powder, a binder having a decomposition temperature lower than the crystallization temperature of the oxide glass, and a solvent is formed into a sheet to form a solid electrolyte sheet. . FIG. 3 is a diagram showing a solid electrolyte sheet manufacturing process.

  First, a solid electrolyte slurry is prepared by mixing an ion-conductive oxide glass powder and a binder solution. A conductive additive may be added to the solid electrolyte slurry. As the conductive assistant, the same one as that used for the positive electrode slurry can be used. As the oxide glass powder, the binder, and the solvent of the binder solution, the same type and size as those used in the positive electrode slurry can be used.

  The solid content ratio of the solid electrolyte slurry is preferably 50% or more, more preferably 70% or more. By setting the solid content ratio to 50% or more, a sheet having a uniform thickness can be easily produced.

  The weight ratio of the binder to the oxide glass powder is preferably less than 0.6, and more preferably less than 0.3. By setting the ratio of the binder to less than 0.6, the density can be maintained even if the binder is removed after the degreasing step. As a result, the sheet becomes easy to stand on its own. Next, the solid electrolyte slurry is formed into a sheet. It can be formed into a sheet by the same method as the positive electrode sheet.

(Lamination process)
In the laminating step, after the positive electrode sheet and the solid electrolyte sheet are laminated, pressure is applied. By applying pressure before degreasing, the positive electrode sheet and the solid electrolyte sheet are densified, and the sheets are bonded to each other. Pressurization can be performed using a hydraulic press or a roll press. In order to obtain sufficient compactness, the pressure at the time of pressurization is preferably 100 MPa or more, and more preferably 350 MPa or more.

(Degreasing process)
In the degreasing step, the laminated positive electrode sheet and solid electrolyte sheet are degreased by heating to a temperature lower than the crystallization temperature of the oxide glass contained in the positive electrode sheet and solid electrolyte sheet, and then pressurized.

  The positive electrode and the solid electrolyte layer can be integrated by applying pressure after degreasing the stacked green sheets.

  The temperature at the time of degreasing may be lower than the crystallization temperature of the oxide glass contained in the positive electrode sheet and the solid electrolyte sheet, and is preferably 200 ° C. or higher and lower than 250 ° C., which is near the binder decomposition start temperature.

(Crystallization step)
In the crystallization step, the positive electrode layer and the solid electrolyte layer integrated in the degreasing step are heated at less than 300 ° C. By heating, a part of the oxide glass contained in the positive electrode layer and the solid electrolyte layer is crystallized. By crystallizing a part of the oxide glass, glass ceramics can be obtained, and ionic conductivity can be improved. By setting the heating temperature to less than 300 ° C., a crystal phase having high ionic conductivity can be grown. The crystallization temperature can be confirmed by suggestive scanning calorimetry.

  Since glass ceramics increases the Young's modulus, it becomes difficult to mold with a press after degreasing. Therefore, it is more preferable that the degreasing temperature in the degreasing step is 250 ° C. or less, and the heating temperature in the crystallization step is 250 ° C. or more and less than 300 ° C.

(Joining process)
In the joining step, the negative electrode layer is joined to the solid electrolyte layer after the crystallization step. Specifically, the negative electrode layer is joined by depositing metallic lithium, indium, or lithium aluminum alloy on the solid electrolyte layer, or by pressing and heating these foils. When the negative electrode layer is pressure-bonded, it may be formed on a current collector such as SUS, aluminum, or copper foil.

  The negative electrode layer may be joined by the following method. FIG. 5 is a diagram illustrating a manufacturing process of the all-solid-state battery. A negative electrode sheet is prepared in the same manner as the positive electrode sheet and the solid electrolyte sheet. The negative electrode sheet is prepared by molding a negative electrode slurry containing a negative electrode active material, an oxide glass powder, a binder having a decomposition temperature lower than the crystallization temperature of the oxide temperature, and a solvent into a sheet shape.

  In the laminating step, the all-solid-state battery may be manufactured by laminating and pressing the positive electrode sheet, the solid electrolyte sheet, and the negative electrode sheet in this order, and then performing a degreasing step and a crystallization step.

  By applying the green sheet method to a glassy oxide solid electrolyte, the solid electrolyte layer can be thinned. Since the thickness of the solid electrolyte layer can be reduced to 100 μm or less, the output of the all-solid-state battery can be increased. The all-solid-state battery manufactured in this manner exhibits excellent output characteristics in a high temperature environment of 80 ° C. or more from a low temperature of 0 ° C. or less for use in vehicles and infrastructure.

<All-solid-state battery>
The all solid state battery manufactured by the above manufacturing method will be described with reference to FIG.

  FIG. 4 is a cross-sectional view of the all-solid-state battery according to one embodiment. The all-solid-state battery includes a positive electrode layer 8, a negative electrode layer 6, and a solid electrolyte layer 7 (hereinafter, referred to as an electrode group) disposed between the positive electrode layer 8 and the negative electrode layer 6. The electrode group is housed in a battery case composed of a positive battery case 1 and a negative battery case 2. A gasket 4 is provided inside the battery case to maintain the airtightness inside the case and to prevent a short circuit between the positive terminal and the negative terminal. The all-solid-state battery further includes a wave washer 4 and a spacer 5 for fixing the electrode group.

  The solid electrolyte layer of the all-solid-state battery manufactured by the above manufacturing method includes a partially crystallized oxide glass and a binder having a decomposition temperature equal to or lower than the crystallization temperature of the oxide glass.

The oxide glass contains at least one of lithium, boron, sulfur, and oxygen, and preferably contains Li ₃ BO ₃ and Li ₂ SO ₄ .

  Most of the binder contained in the solid electrolyte sheet is decomposed in the degreasing step, but a part of the binder remains in the solid electrolyte layer without being decomposed. Therefore, the solid electrolyte layer of the all-solid-state battery manufactured by the above manufacturing method includes a binder whose decomposition temperature is equal to or lower than the crystallization temperature of the oxide glass. Specifically, the binder is preferably methylcellulose or methylbutanetriol.

  The thickness of the solid electrolyte layer is preferably 100 μm or less.

  Similarly to the solid electrolyte layer, binder residue remains in the positive electrode layer. Therefore, the positive electrode layer includes a positive electrode active material, a partially crystallized oxide glass, and a binder whose decomposition temperature is equal to or lower than the crystallization temperature of the oxide glass.

<Preparation of positive electrode active material>
Using Li ₂ CO ₃ as a compound serving as a Li source and Co ₃ O ₄ as a compound serving as a Co source, weighing them so that the molar ratio of Li to Co becomes 1.03, mixing them in a mortar, and using a hydraulic press machine To form a pellet.

The obtained pellets were heat-treated in an oxygen atmosphere at 1000 ° C. for 10 hours, and then pulverized in a mortar to synthesize a lithium-containing cobalt oxide represented by a general composition formula LiCoO ₂ having an average particle diameter of 15 μm. The composition ratio is measured by an ICP (Inductivity Coupled Plasma: Inductively Coupled Plasma Emission Spectroscopy) method, and the crystal structure is a layered structure belonging to the space group R-3m by XRD (X-ray Diffraction). It was confirmed.

The surface of the synthesized LiCoO ₂ particles was coated with LiNbO ₃ by the following method. First, ethanol was dissolved in ethanol so that ethoxylithium and pentaethoxyniobium were each contained at 0.6 mol / L to prepare a precursor solution for the LiNbO ₃ reaction suppression layer. The LiNbO ₃ precursor was coated on LiCoO ₂ using a tumbling fluidized coating apparatus (MP-01, manufactured by Powrex). LiCoO ₂ was placed in a tumbling fluidized coating apparatus, and dry air was introduced as a fluidized gas. The LiNbO ₃ precursor solution was sprayed for 1.5 hours while being coated with the positive electrode active material powder wound up by dry air and circulated inside the tumbling fluidized coating apparatus for coating. Next, a LiCoO ₂ cathode active material coated with LiNbO ₃ was obtained by performing a heat treatment at 400 ° C. for 30 minutes in an oxygen gas atmosphere using a tubular electric furnace.

  The surface of the obtained positive electrode active material was observed with a scanning electron microscope SEM (Scanning Electron Microscope, Hitachi S-4300), and Nb was present by EDS (Energy Dispersive X-ray Spectroscopy, manufactured by Horiba, Ltd.). It was confirmed.

<Preparation of ion-conductive oxide glass>
Li ₂ SO ₄ · _{H 2} O (Wako Pure Chemical purity 98-102%) was heated for 2 hours at 300 ° C. vacuum oven to give the _Li 2 SO ₄ by dehydration. Similarly, Li ₃ BO ₃ (Toshima Seisakusho) was dried by heating in a vacuum oven at 300 ° C. for 2 hours. The dehydrated and dried Li ₃ BO ₃ and Li ₂ SO ₄ were mixed in an Ar atmosphere glove box having a dew point of −100 ° C. in a 9: 1 weight ratio using a mortar for 10 minutes.

The obtained mixed powder was charged into a zirconia ball mill pot together with 35 g of a ball having a diameter of 5 mm and sealed with an SUS overpot. Using a planetary ball mill (Pulverisette P-7, manufactured by Fritsch), a mechanical milling treatment was performed at 370 rpm for 20 hours to obtain i ₃ BO ₃ -Li ₂ SO ₄ glass powder having an average particle size of 5 μm.

  In addition, the said manufacturing method is based on Journal of Power Sources 270 (2014) 603-607.

<Preparation of positive electrode slurry>
Methylbutanetriol was dissolved in butyl acetate to a concentration of 15% by mass. LiNbO ₃ -coated LiCoO ₂ powder, Li ₃ BO ₃ -Li ₂ SO ₄ glass powder, and methylbutanetriol dissolved in butyl acetate were mixed in an environment having a dew point of −30 ° C. or less to prepare a positive electrode slurry.

The LiNbO ₃ -coated LiCoO ₂ powder and the Li ₃ BO ₃ -Li ₂ SO ₄ glass powder were set at a weight ratio of 1: 1. While mixing for 10 minutes, an appropriate amount of butyl acetate was added to obtain a positive electrode slurry.

<Preparation of solid electrolyte slurry>
Li ₃ BO ₃ -Li ₂ SO ₄ glass powder and a binder solution in which methylbutanetriol was dissolved in butyl acetate at a concentration of 15% by mass were mixed in an environment having a dew point of −30 ° C. or less to prepare a solid electrolyte slurry.

While mixing the Li ₃ BO ₃ -Li ₂ SO ₄ glass powder and the binder in a weight ratio of 7: 3 for 10 minutes, an appropriate amount of butyl acetate was added to obtain a solid electrolyte slurry.

<Preparation of positive electrode and solid electrolyte sheet>
Each of the positive electrode slurry and the solid electrolyte slurry was formed into a green sheet having a thickness of about 50 μm by a doctor blade method.

  First, the positive electrode slurry and the solid electrolyte slurry were applied on a release-treated carrier film such as PET with a doctor blade having a gap of 300 μm, dried at room temperature, and then dried in a vacuum oven at 100 ° C. for 2 hours.

  This was punched with a belt punch to obtain a positive electrode sheet and a solid electrolyte sheet, respectively.

  Next, the positive electrode sheet and the solid electrolyte sheet were laminated and pressed with a hydraulic press at a pressure of 350 MPa to be integrated.

<Preparation of all solid state battery>
The obtained green sheet was degreased at 250 ° C. and pressed again to integrate the positive electrode sheet and the solid electrolyte sheet.

Integral positive electrode sheet and solid electrolyte sheet, by heating for a further _{290 ℃, Li 3 BO 3 -Li} 2 SO 4 glass by partially crystallized, the high ionic conductivity _{Li 3} BO 3 -Li ₂ An electrode in which the positive electrode and the solid electrolyte layer were integrated as SO ₄ glass ceramics was obtained.

  The negative electrode layer was joined by vacuum-depositing metallic lithium on the solid electrolyte layer side after the crystallization step.

  The electrodes of the all-solid-state battery including the positive electrode layer 8, the solid electrolyte layer 7, and the negative electrode tank 8 are housed between the positive-side battery case 1 and the negative-side battery case 2 made of stainless steel. By stacking and caulking the periphery of both battery cases via a gasket 3, a coin-type all solid-state battery shown in FIG. 5 was manufactured. The coin battery had a diameter of 20 mm and a thickness of 3.2 mm.

<Charging / discharging test>
The charge and discharge were performed at a constant current of 10 μA / cm ^{2 in} the range of 4.05 V to 3 V at a measurement temperature of 30 ° C. As a result, it was confirmed that the charge and discharge could be repeated.

  An all-solid-state battery was prepared in the same manner as in Example 1 except that a conductive additive was added to the positive electrode slurry, and a charge / discharge test was performed. Acetylene black was used as the conductive assistant. The amount of the conductive additive was 5% by weight based on the total weight of the solid electrolyte, the positive electrode active material, and the conductive additive contained in the positive electrode layer.

  As a result of the charge / discharge test, it was confirmed that the charge / discharge could be repeated.

  DESCRIPTION OF SYMBOLS 1 ... Positive electrode side battery case, 2 ... Negative electrode side battery case, 3 ... Gasket, 4 ... Wave washer, 5 ... Spacer, 6 ... Negative electrode layer, 7 ... Solid electrolyte layer, 8 ... Positive electrode layer

Claims (10)

A method for manufacturing an all-solid battery including a positive electrode layer, a negative electrode layer, and a solid electrolyte layer disposed between the positive electrode layer and the negative electrode layer,
Positive electrode active material, oxide glass powder, a binder whose decomposition temperature is lower than the crystallization temperature of the oxide glass, and a solvent, a step of forming a positive electrode slurry containing a positive electrode slurry into a sheet to form a positive electrode sheet,
Oxide glass powder, a binder having a decomposition temperature lower than the crystallization temperature of the oxide glass, and forming a solid electrolyte slurry containing a solvent into a sheet to form a solid electrolyte sheet,
After laminating the positive electrode sheet and the solid electrolyte sheet, a laminating step of applying pressure,
After degreasing the stacked positive electrode sheet and the solid electrolyte sheet at a temperature lower than the crystallization temperature of the oxide glass, a degreasing step of applying pressure,
A crystallization step of heating the laminate obtained by the degreasing step at a temperature higher than the crystallization temperature of the oxide glass and less than 300 ° C.
A method for manufacturing an all-solid-state battery, comprising: It is a manufacturing method of the all-solid-state battery of Claim 1, Comprising:
A method for manufacturing an all-solid battery, comprising a joining step of joining the negative electrode layer after the crystallization step. It is a manufacturing method of the all-solid-state battery of Claim 1 or 2, Comprising:
The method for manufacturing an all-solid battery, wherein the positive electrode slurry further includes a conductive additive. It is a manufacturing method of the all-solid-state battery of Claims 1-3, Comprising:
The method for manufacturing an all-solid battery, wherein the oxide glass includes at least one of lithium, boron, sulfur, and oxidation. It is a manufacturing method of the all-solid-state battery of any one of Claims 1-4, Comprising:
The degreasing temperature in the degreasing step is 250 ° C. or less,
A method for manufacturing an all-solid-state battery, wherein a heating temperature in the crystallization step is 250 ° C. or higher. A method for manufacturing an all-solid-state battery according to any one of claims 1 to 5,
The method for manufacturing an all-solid battery, wherein the binder is methylcellulose or methylbutanetriol. A positive electrode layer, a negative electrode layer, a solid electrolyte layer disposed between the positive electrode layer and the negative electrode layer, an all-solid battery,
The solid electrolyte layer includes a partially crystallized oxide glass, and a binder whose decomposition temperature is equal to or lower than the crystallization temperature of the oxide glass,
The all-solid-state battery, wherein the oxide glass includes at least one of lithium, boron, sulfur, and oxygen. The all-solid-state battery according to claim 7, wherein
An all-solid-state battery, wherein the thickness of the solid electrolyte layer is 100 μm or less. An all-solid-state battery according to claim 7 or 8, wherein
The oxide glass is, the all-solid-state battery, which comprises a _Li 3 BO ₃ and _Li 2 SO _4. An all solid state battery according to any one of claims 7 to 9, wherein
The all-solid-state battery, wherein the binder is methylcellulose or methylbutanetriol.

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