JP6030960B2 - Manufacturing method of all solid state battery - Google Patents

Description

  The present invention relates to an electrode active material for an all-solid battery and an all-solid battery using the same. In particular, the present invention relates to an electrode active material containing a lithium-containing compound having a NASICON structure.

  In recent years, batteries, particularly secondary batteries, have been used as main power sources, backup power sources, and hybrid vehicle (HEV) power sources for portable electronic devices such as cellular phones and portable personal computers. Among secondary batteries, a lithium ion secondary battery having a high energy density and capable of being charged and discharged is used.

  In such a lithium ion secondary battery, an organic electrolyte (electrolytic solution) in which a lithium salt is dissolved in a carbonate ester or an ether organic solvent is conventionally used as a medium for transferring ions.

  However, in the lithium ion secondary battery having the above configuration, there is a risk that the electrolyte solution leaks. Moreover, the organic solvent etc. which are used for electrolyte solution are combustible substances. For this reason, it is required to further increase the safety of the battery.

  Therefore, in order to enhance the safety of the lithium ion secondary battery, it has been proposed to use a solid electrolyte as the electrolyte instead of the organic solvent electrolyte. In particular, since a compound having a NASICON structure is an ionic conductor capable of conducting lithium ions at a high speed, development of an all-solid battery using such a compound as a solid electrolyte has been underway.

For example, Japanese Patent Application Laid-Open No. 2007-258148 (hereinafter referred to as Patent Document 1) proposes an all-solid battery including an electrode layer (positive electrode, negative electrode) and an internal electrode body having a solid electrolyte layer. In this all-solid-state battery, a positive electrode, a negative electrode, and a solid electrolyte are all phosphoric acid compounds, and an internal electrode body is integrated by firing a positive electrode, a negative electrode, and a solid electrolyte layer. As an example of this all solid state battery, Li _1.5 Al _0.5 Ge _1.5 (PO ₄ ) ₃ (hereinafter referred to as LAGP) is preliminarily sintered as a solid electrolyte to produce a sintered body, and both sides of this sintered body are prepared. By printing and baking an electrode paste containing Li ₃ V ₂ (PO ₄ ) ₃ (hereinafter referred to as LVP) as an electrode active material, an internal electrode body in which the electrode layer and the solid electrolyte layer are integrated is produced. .

JP 2007-258148 A

  In Patent Document 1, although an all-solid battery in which an electrode layer and a solid electrolyte layer are integrated is obtained, battery characteristics are not sufficient.

  When the inventors use a lithium-containing compound having a NASICON structure as an electrode active material of an all-solid battery, the electrode active material filled in the electrode layer is completely used depending on the particle size of the electrode active material. It has been found that when the amount of electricity obtained is 100%, the utilization ratio of the electrode active material, which is the ratio of the amount of electricity that can be taken out by actual discharge, varies greatly. That is, it has been found that the battery characteristics are improved by the particle diameter of the electrode active material used.

Accordingly, an object of the present invention is to provide a method for producing an all-solid battery using an electrode active material having a high electrode active material utilization rate.

The method for producing an all-solid battery of the present invention is a method for producing an all-solid battery comprising an electrode active material containing a lithium-containing compound having a NASICON structure and comprising an electrode layer made of an inorganic material and a solid electrolyte layer. Forming a lithium-containing compound having a NASICON structure in which the D ₅₀ is 1.1 μm or more and 20 μm or less and the D ₉₀ is 40 μm or less in the particle size distribution measured using a laser diffraction / scattering type particle size distribution analyzer , A green sheet of the electrode layer is prepared by forming an electrode slurry containing an electrode active material powder obtained by mixing and baking this lithium-containing compound having a NASICON structure with carbon powder, and forming a solid electrolyte slurry. The green sheet of the solid electrolyte layer is prepared, and the green sheet of the electrode layer and the green sheet of the solid electrolyte layer are stacked and stacked. Body is formed by firing the laminate, it is characterized by integrally sintering bonding the solid electrolyte layer and the electrode layer.

  In this case, the utilization rate of the electrode active material of the lithium-containing compound having a NASICON structure can be increased by reducing the average particle size and omitting coarse particles having a large particle size.

According to the present invention, it is possible to manufacture an all-solid battery having a high utilization rate of an electrode active material and good battery characteristics.

It is typical sectional drawing of the battery laminated body which concerns on embodiment of this invention.

  Hereinafter, modes for carrying out the present invention will be described. The embodiment of the invention described here is an example for carrying out the present invention, and is not limited to the method and form described here.

The electrode active material for an all-solid-state battery of the present invention is characterized in that it contains a lithium-containing compound having a NASICON structure, the D ₅₀ of the lithium-containing compound is 20 μm or less, and D ₉₀ is 40 μm or less. Lithium-containing compound having a NASICON structure is not particularly limited, it preferably contains _{Li x M y (PO 4)} 3 (x = 1~2, y = 1~2). Note that M may be a metal, and particularly preferably contains at least one of Al, Ti, V, Cr, Fe, Co, Ni, Zr, and Nb. Specific examples include lithium-containing phosphate compounds such as Li ₃ V ₂ (PO ₄ ) ₃ and Li ₃ Fe ₂ (PO ₄ ) ₃ . In addition, the electrode active material of this invention should just be contained in at least any one of a positive electrode or a negative electrode.

Here, D ₅₀ is an integrated 50% particle size of the particle size distribution, and D ₉₀ is an integrated 90% particle size of the particle size distribution. The particle diameter of the electrode active material can be measured with a laser diffraction / scattering particle size distribution analyzer.

  FIG. 1 shows a schematic cross-sectional view of a battery stack according to an embodiment of the present invention. The battery stack 10 includes a solid electrolyte layer 12 including a solid electrolyte, a negative electrode layer 11, and a positive electrode layer 13. Note that at least one of the negative electrode layer 11 and the positive electrode layer 13 contains the electrode active material of the present invention. The negative electrode layer 11 and the positive electrode layer 13 are provided at positions facing each other with the solid electrolyte layer 12 interposed therebetween. And at least one of the negative electrode layer 11 or the positive electrode layer 13 and the solid electrolyte layer 12 are joined by baking. Although not shown, a current collector layer may be disposed on the surface of the positive electrode layer 13 not in contact with the solid electrolyte layer 12, and the current collector layer on the surface of the negative electrode layer 11 not in contact with the solid electrolyte layer 12. May be arranged.

For the solid electrolyte, for example, a material having ionic conductivity and small electronic conductivity can be used. Examples of the solid electrolyte include lithium halide, lithium nitride, lithium oxyacid salt, and derivatives thereof. Further, Li-PO compounds such as lithium phosphate (Li ₃ PO _4), LIPON mixed with nitrogen lithium phosphate _{(LiPO 4-x N x)} , Li-SiO , such as Li ₄ SiO ₄ Compounds, Li-P-Si-O compounds, Li-V-Si-O compounds, La _0.51 Li _0.35 TiO _2.94 having a perovskite structure, La _0.55 Li _0.35 TiO ₃ , Li _3x La _{2 / 3-x} TiO _{3 and the} like, and compounds having a garnet structure having Li, La, and Zr are mentioned, but it is particularly preferable that a compound having a NASICON structure is included. Table In composition Li _x M _y of the compound _{(PO 4) 3 (x =} 1~2, y = 1~2, including M = Ti, Ge, Al, Ga, at least one of Zr) having the NASICON structure In addition, a part of P may be substituted with B, Si or the like. Examples of the compound having a NASICON structure include Li _1.5 Al _0.5 Ge _1.5 (PO ₄ ) ₃ and Li _1.2 Al _0.2 Ti _1.8 (PO ₄ ) ₃ .

As the negative electrode active material contained in the negative electrode layer 11, in addition to the electrode active material of the present invention, graphite-lithium compounds, lithium alloys such as Li—Al, Li ₄ Ti ₅ O ₁₂ , Ti, Nb, W, Si, Sn, An oxide of at least one element selected from the group consisting of Cr, Fe, and Mo may be used. Specifically, it preferably contains at least one oxide selected from the group consisting of titanium oxide, silicon oxide, niobium oxide, tin oxide, chromium oxide, iron oxide, and molybdenum oxide. Such an oxide has a large capacity per weight and a low potential with respect to Li. Therefore, an all-solid battery having a large capacity density, a high battery voltage, and a high energy density can be obtained.

The positive electrode active material contained in the positive electrode layer 13 includes, in addition to the electrode active material of the present invention, a layered compound such as LiCoO ₂ , LiCo _1/3 Ni _1/3 Mn _1/3 O ₂ , LiMn ₂ O ₄ , LiNi _0.5 Mn Spinel materials such as _1.5 O ₄ and phosphorus-containing compounds such as LiFePO ₄ and LiMnPO ₄ may be used. If the electrode active material of the present invention is contained in at least one of the positive electrode active material and the negative electrode active material, the effects of the present invention are exhibited.

  The negative electrode layer 11 and the positive electrode layer 13 preferably include a solid electrolyte having a NASICON structure. This is because when the solid electrolyte layer 12 includes a solid electrolyte having a NASICON structure, the negative electrode layer 11, the positive electrode layer 13, and the solid electrolyte layer 12 are easily joined by firing.

  At least one of the negative electrode layer 11 or the positive electrode layer 13 and the solid electrolyte layer 12 are preferably joined by laminating a plurality of green sheets to form a laminate, and firing the laminate. In this case, since at least one of the negative electrode layer 11 or the positive electrode layer 13 and the solid electrolyte layer 12 can be integrally fired and bonded, it is possible to manufacture an all-solid battery at a lower cost. .

  The all solid state battery according to the present invention is manufactured as follows as an example.

First, an electrode active material and a solid electrolyte are prepared as inorganic materials. At this time, when the electrode active material includes oxides of two or more elements, a mixed material in which oxides of the respective elements are mixed may be prepared. When the solid electrolyte includes a NASICON-structured solid electrolyte, a NASICON-structured solid electrolyte is prepared. For example, a mixed material in which solid electrolytes having different composition of NASICON such as Li _1.5 Al _0.5 Ge _1.5 (PO ₄ ) ₃ and Li _1.2 Al _0.2 Ti _1.8 (PO ₄ ) ₃ may be used. Further, as the NASICON solid electrolyte, a material including a crystal phase of a solid electrolyte having a NASICON structure or glass precipitating a crystal phase of a NASICON solid electrolyte may be used.

Next, an electrode slurry and a solid electrolyte slurry are prepared. As a method for preparing the electrode slurry of the present invention, a lithium-containing compound having a NASICON structure in which the particle size is adjusted so that the D ₅₀ is 20 μm or less and the D ₉₀ is 40 μm or less is prepared in advance. The method for adjusting the particle diameter is not particularly limited, but a lithium-containing compound having a D ₅₀ of 20 μm or less and a D ₉₀ of 40 μm or less is synthesized, or a lithium-containing compound containing coarse particles is sieved and classified. The contained compound may be adjusted by grinding. In addition to the prepared lithium-containing compound, a solid electrolyte, a conductive agent and the like are mixed to prepare a mixture, and an organic vehicle prepared by mixing an organic material and a solvent is added to the mixture and mixed to prepare an electrode slurry.

  Examples of the solvent include water, cycloaliphatic hydrocarbons such as cyclopentane and cyclohexane; aromatic hydrocarbons such as toluene and xylene; ketones such as ethyl methyl ketone and cyclohexanone; ethyl acetate, butyl acetate, and γ-butyrolactone. Esters such as ε-caprolactone; Acylonitriles such as acetonitrile and propionitrile: Ethers such as tetrahydrofuran and ethylene glycol diethyl ether: Alcohols such as methanol, ethanol, isopropanol, ethylene glycol, and ethylene glycol monomethyl ether; N -Amides such as methylpyrrolidone and N, N-dimethylformamide. These solvents may be used alone or in admixture of two or more and appropriately selected from the viewpoint of drying speed and environment. In addition, although the solvent used when manufacturing the said organic vehicle may differ from the solvent used when manufacturing the said mixture, it is preferable to use the same solvent.

  Next, each of the solid electrolyte layer and the electrode layer slurry is molded to produce a green sheet. Although a shaping | molding method is not specifically limited, For example, the method using well-known coating machines, such as a die coater and a comma coater, a screen printing method, etc. are mentioned.

  Next, a green sheet of a solid electrolyte layer and an electrode layer is laminated to form a laminate. The lamination method is not particularly limited, and examples thereof include a hot isostatic press (HIP) method, a cold isostatic press (CIP) method, and a hydrostatic press (WIP) method.

  Next, the laminate is fired. The electrode layer and the solid electrolyte layer are joined by firing.

Finally, the fired laminate is sealed in, for example, a coin cell. The sealing method is not particularly limited. For example, you may seal the laminated body after baking with resin. Alternatively, an insulating paste having an insulating property such as Al ₂ O ₃ may be applied or dipped around the laminated body and sealed by heat treatment.

  In order to efficiently draw current from the electrode layer, a conductive layer such as a metal layer may be formed on the electrode layer as the current collector layer. Examples of the method for forming the conductive layer include a sputtering method. Alternatively, a metal paste may be applied or dipped and heat treated.

Hereinafter, examples and comparative examples of the all solid state battery of the present invention will be described. Hereinafter, the lithium-containing vanadium phosphate compound LVP was used as the electrode active material for an all-solid battery.
<Preparation of electrode active material>
Example 1
Lithium carbonate (Li ₂ CO ₃ ), vanadium pentoxide (V ₂ O ₅ ), and diammonium hydrogen phosphate ((NH ₄ ) ₂ HPO ₄ ) were used as starting materials. These raw materials are weighed so as to be 27.3% -LiCO ₃ , 18.2% -V ₂ O ₅ , 54.5%-(NH ₄ ) ₂ HPO ₄ in a molar ratio, and put in a 500 mL polyethylene pot. The mixed powder of the raw material was obtained by enclosing and rotating for 6 hours at 150 rpm on the pot rack. The mixed powder of the raw material obtained above was baked for 8 hours at a temperature of 600 ° C. in an air atmosphere to obtain a baked powder A.

  Water was added to the calcined powder A, enclosed in a 500 mL polyethylene pot together with a cobblestone having a diameter of 5 mm, and the calcined powder A was pulverized by rotating at a rotation speed of 150 rpm on the pot rack for 24 hours. Thereafter, the pulverized fired powder A was dried on a hot plate heated to a temperature of 120 ° C. to obtain pulverized powder A.

  By mixing ketjen black as a carbon powder with the pulverized powder A at a weight ratio of 90:10, enclosing it in a 500 mL polyethylene pot and rotating on the pot rack at 150 rpm for 6 hours, Carbon mixed powder A was obtained. Next, an electrode active material powder A was obtained by firing the carbon mixed powder A at a temperature of 900 ° C. for 20 hours in a nitrogen atmosphere.

(Comparative Example 1)
For comparison, an electrode active material powder B was prepared as follows. The calcined powder A and water were mixed and sealed in a 500 ml polyethylene pot together with a 5 mm cobblestone, and then spun at 150 rpm for 1 hour to crush the calcined powder A. Then, it dried on the hotplate heated at the temperature of 120 degreeC, and the pulverized powder B was obtained.

  By mixing Ketjen black as a carbon powder with the pulverized powder B at a weight ratio of 90:10, enclosing it in a 500 mL polyethylene pot and rotating on the pot rack at 150 rpm for 6 hours, Carbon mixed powder B was obtained. Next, an electrode active material powder B was obtained by firing the carbon mixed powder B at a temperature of 900 ° C. for 20 hours in a nitrogen atmosphere.

<Evaluation>
The electrode active material powder A and the electrode active material powder B were measured by XRD (X-ray diffractometer) at a scan rate of 1.0 ° / min and an angle measurement range of 10 ° to 60 °. Li ₃ Fe ₂ (PO ₄₎ substantially coincides with the pattern of the third JCPDS (Joint Committee on Powder Diffraction Standards ) card (card number 78-1106), the electrode active material powder A and the electrode active material powder B has a NASICON structure It was confirmed to be a lithium-containing compound.

Next, in order to investigate the particle size, the pulverized powder A and the pulverized powder B obtained in the pulverization step, the electrode active material powder A and the electrode active material powder B obtained in the firing step are dispersed in an aqueous solvent, respectively, and laser diffraction scattering is performed. The particle size distribution was measured using a mold particle size distribution measuring apparatus. As a result of the measurement, each of D ₅₀ and D ₉₀ is 1.1 μm and 2.0 μm for the pulverized powder A, 1.4 μm and 4.1 μm for the electrode active material powder A, respectively, D ₅₀ is 20 μm or less, D ₉₀ was found to be 40 μm or less. On the other hand, the pulverized powder B is 14.5 μm and 43.8 μm, respectively, and the electrode active material powder B is 15.6 μm and 46.3 μm, respectively, D ₅₀ is 20 μm or less, and D ₉₀ is 40 μm or more. all right.
<Preparation of all-solid battery>
In order to evaluate the electrode characteristics of the electrode active material powder A and the electrode active material powder B, an all-solid battery was produced. A coin cell using a mixture of each electrode active material powder, carbon powder, and PTFE as a positive electrode, a Li metal foil as a negative electrode, and an organic electrolyte as an electrolyte was produced. As a result of the cyclic voltammetry test at 3.0-4.5 V using a charge / discharge device, the coin cell using the electrode active material powder A has a theoretical capacity of two-electron reaction of Li ₃ V ₂ (PO ₄ ) ₃ ( The electrode active material utilization rate of about 100% was obtained for 120 mAh / g), but the electrode active material utilization rate of the coin cell using the electrode active material powder B was about 61%. Furthermore, the peak of the charge / discharge reaction of the coin cell using the electrode active material powder B was broader than that of the coin cell using the electrode active material powder A, indicating that the electrode activity was low.

From the above results, D ₅₀ is 20 μm or less, D ₉₀ is 40 μm or less, and D ₉₀ does not contain coarse particles of 40 μm or more, thereby increasing the electrode active material utilization rate of the lithium-containing compound having a NASICON structure. It was confirmed that it was possible.
(Example 2)
<Preparation of electrode active material>
Lithium carbonate (Li ₂ CO ₃ ), vanadium pentoxide (V ₂ O ₃ ), diammonium hydrogen phosphate ((NH ₄ ) ₂ HPO ₄ ) were used as raw materials, and these were in a molar ratio of 27.3% -LiCO _3. , 18.2% -V ₂ O ₃ , 54.5%-(NH ₄ ) ₂ HPO ₄ , weighed in a 500 ml polyethylene pot, rotated on the pot rack at 150 rpm for 6 hours, A mixed powder of raw materials was obtained. The mixed powder of raw materials was fired at 400 ° C. for 8 hours in an air atmosphere to obtain a fired powder C from which volatile components were removed.

  Water was added to the calcined powder C, sealed in a 500 ml polyethylene pot together with a 5 mm cobblestone, and rotated on a pot rack at 150 rpm for 24 hours to pulverize the calcined powder C. Then, it dried on a 120 degreeC hotplate and the pulverized powder C was obtained.

Add ketjen black as a carbon powder to the pulverized powder C in a weight ratio of 90:10, enclose it in a 500 ml polyethylene pot, rotate on the pot rack at 150 rpm for 6 hours, and mix the carbon mixed powder C. Obtained. The carbon mixed powder C was fired at 900 ° C. for 20 hours in a nitrogen atmosphere to obtain an electrode active material powder C.
(Comparative Example 2)
The pulverized powder C was classified through a sieve having an opening diameter of 32 μm to obtain a powder from which coarse particles had been removed and a powder having many coarse particles remaining on the sieve. Half of the powder from which coarse particles were classified and powder with many coarse particles were mixed, and pulverized powder D was obtained.

Add ketjen black as a carbon powder to the pulverized powder D in a weight ratio of 90:10, enclose it in a 500 ml polyethylene pot, rotate on the pot rack for 6 hours, and rotate the carbon mixed powder D Obtained. The carbon mixed powder D was fired at 900 ° C. for 20 hours in a nitrogen atmosphere to obtain an electrode active material powder D.
<Evaluation>
In the same manner as in Example 1, it was confirmed that the electrode active material powders C and D were lithium-containing compounds having a NASICON structure.

Next, the particle size distribution measurement of the electrode active material powders C and D was performed in the same manner as in Example 1. As a result of the measurement, D ₅₀ and D ₉₀ of the pulverized powder C are 7.0 μm and 23.9 μm, respectively, and the electrode active material powder C is 4.7 μm and 21.7 μm, respectively, D ₅₀ is 20 μm or less, and D ₉₀ is 40 μm. It turns out that it is the following. On the other hand, the pulverized powder D is 21.2 μm and 37.8 μm, the electrode active material powder D is 23.5 μm and 39.1 μm, respectively, D ₉₀ is 40 μm or less, and D ₅₀ is 20 μm or more. all right.

  In order to evaluate the electrode characteristics of the electrode active material powders C and D, an all-solid battery was prepared as described above, and the electrode active material utilization rate was measured.

The coin cell using the electrode active material powder C has an electrode active material utilization rate of about 85% with respect to the theoretical capacity (120 mAh / g) of the two-electron reaction of Li ₃ V ₂ (PO ₄ ) ₃ . The utilization rate of the electrode active material of the coin cell using the electrode active material powder D was about 59%. Furthermore, the peak of the charge / discharge reaction of the coin cell using the electrode active material powder D was broader than that of the coin cell using the electrode active material powder C, indicating that the electrode activity was low.
Example 3
Lithium carbonate (Li ₂ CO ₃ ), vanadium pentoxide (V ₂ O ₃ ), and diammonium hydrogen phosphate ((NH ₄ ) ₂ HPO ₄ ) were used as raw materials, and these were in a molar ratio of 27.3% -Li _2. CO ₃ , 18.2%-V ₂ O ₃ , 54.5%-(NH ₄ ) ₂ HPO ₄ was weighed, sealed in a 500 ml polyethylene pot, and rotated on a pot rack at 150 rpm for 6 hours. Thus, a raw material mixed powder was obtained. The mixed powder of raw materials was fired at 400 ° C. for 8 hours in an air atmosphere to obtain a fired powder E from which volatile components were removed.

  Water was added to the calcined powder E, sealed in a 500 ml polyethylene pot together with a 5 mm cobblestone, and rotated on a pot rack at 150 rpm for 24 hours to pulverize the calcined powder E. Then, it dried on a 120 degreeC hotplate and the pulverized powder E was obtained.

The pulverized powder E was fired at 900 ° C. for 20 hours in a nitrogen atmosphere to obtain an electrode active material powder E.
(Comparative Example 3)
The pulverized powder E was classified through a sieve having an opening diameter of 32 μm to obtain a powder from which coarse particles had been removed and a powder having many coarse particles remaining on the sieve. Half of the powder that had been classified and from which coarse particles had been removed was mixed with powder having a large amount of coarse particles to obtain pulverized powder F. The pulverized powder F was fired at 900 ° C. for 20 hours in a nitrogen atmosphere to obtain an electrode active material powder F.
<Evaluation>
In the same manner as in Example 1, it was confirmed that the electrode active material powders E and F were lithium-containing compounds having a NASICON structure. Next, the particle size distribution measurement of the electrode active material powders E and F was performed in the same manner as in Example 1. As a result of the particle size distribution measurement, D ₅₀ and D ₉₀ of the pulverized powder E 1 are 9.1 μm and 16.1 μm, respectively, and the electrode active material powder E is 11.5 μm and 18.4 μm, respectively, and D ₅₀ and D ₉₀ are large. It turns out that it has not changed. On the other hand, D ₅₀ and D ₉₀ of the pulverized powder F are 9.1 μm and 37.8 μm, respectively, the electrode active material powder F is 25.4 μm and 39.1 μm, respectively, and D ₅₀ changes by 2.5 times or more. I found out.

  From the above results, it was confirmed that by mixing the carbon powder in the synthesis process, firing can be performed so that the adjusted particle diameter does not change significantly.

  In order to evaluate the electrode characteristics of the electrode active material powders E and F, an all-solid battery was prepared as described above, and the electrode active material utilization rate was measured.

In the coin cell using the electrode active material powder E, the electrode active material utilization rate of about 91% was obtained with respect to the theoretical capacity (120 mAh / g) of the two-electron reaction of Li ₃ V ₂ (PO ₄ ) ₃ . The utilization rate of the electrode active material of the coin cell using the electrode active material powder F was about 29%. Furthermore, the charge / discharge reaction peak of the coin cell using the electrode active material powder F was unclear, and it was found that the electrode activity was extremely low.

  The electrode active material for all solid state batteries of the present invention can increase the utilization rate of the electrode active material. Therefore, it is useful for an all solid state battery excellent in battery characteristics.

10: Laminate 11: Negative electrode layer 12: Solid electrolyte layer 13: Positive electrode layer

Claims (1)

A method for producing an all-solid battery comprising an electrode active material comprising a lithium-containing compound having a NASICON structure and comprising an electrode layer made of an inorganic material and a solid electrolyte layer,
Forming a lithium-containing compound having a NASICON structure having a D ₅₀ of 1.1 μm or more and 20 μm or less and a D ₉₀ of 40 μm or less in a particle size distribution measured using a laser diffraction / scattering type particle size distribution analyzer; Mixing a lithium-containing compound having a structure with carbon powder and forming an electrode slurry containing an electrode active material powder obtained by firing to produce a green sheet of the electrode layer,
Forming a solid electrolyte slurry to produce a green sheet of the solid electrolyte layer,
A laminate is formed by laminating the green sheet of the electrode layer and the green sheet of the solid electrolyte layer,
A method for manufacturing an all-solid battery, in which the electrode body and the solid electrolyte layer are integrally sintered and bonded by firing the laminate.

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