JP2014191899A - Liquid solution for formation of a solid electrolyte-containing layer of all-solid type lithium secondary battery, all-solid type lithium secondary battery, and method for manufacturing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a liquid solution for formation of a solid electrolyte-containing layer of an all-solid type lithium secondary battery which allows the solid electrolyte-containing layer to be formed by a simple and convenient method.SOLUTION: A liquid solution for formation of a solid electrolyte-containing layer of an all-solid type lithium secondary battery comprises: a solid electrolyte expressed by LiS-MS(where M is selected from P, Si, Ge, B, Al and Ga; and x and y are figures which present a stoichiometric ratio according to the kind of M); and an organic solvent which can dissolve the solid electrolyte.

Description

  The present invention relates to a solution for forming a layer containing a solid electrolyte of an all-solid lithium secondary battery, an all-solid lithium secondary battery, and a method for producing the same. More specifically, the present invention relates to a solid electrolyte layer constituting an all-solid lithium secondary battery, a forming solution for enabling any one of a positive electrode and a negative electrode to be formed by a coating method, an all-solid lithium secondary battery, and a production thereof. Regarding the method.

Lithium secondary batteries have high voltage and high capacity, and are therefore widely used as power sources for mobile phones, digital cameras, video cameras, notebook computers, electric vehicles and the like. Generally, lithium secondary batteries in circulation use a liquid electrolyte in which an electrolytic salt is dissolved in a non-aqueous solvent as an electrolyte. Since non-aqueous solvents contain a lot of flammable solvents, it is desired to ensure safety.
In order to ensure safety, an all-solid lithium secondary battery using a so-called solid electrolyte in which an electrolyte is formed from a solid material without using a non-aqueous solvent has been proposed. This all-solid lithium secondary battery has a configuration including a positive electrode and a negative electrode, and a solid electrolyte layer positioned between the positive electrode and the negative electrode. The solid electrolyte layer is composed of a solid electrolyte. In addition, the positive electrode and the negative electrode include a positive electrode active material and a negative electrode active material, and a solid electrolyte is usually included in order to improve conductivity.

A method in which the solid electrolyte layer, the positive electrode, and the negative electrode are integrally formed by pressing raw materials is known. However, in this method, since the adhesion between the raw materials is low, it is difficult to obtain sufficient conductivity.
Then, the method of coat | covering a positive electrode active material with a solid electrolyte using a pulse laser deposition technique is proposed (Electrochemical and Solid-State Letters, 13 (6) A73-A75 (2010): nonpatent literature 1, Journal of Power Sources 196 (2011) 6735-6741: Non-Patent Document 2). In this method, it is said that the adhesion between the positive electrode active material and the solid electrolyte is high, so that the conductivity can be increased.

Electrochemical and Solid-State Letters, 13 (6) A73-A75 (2010) Journal of Power Sources 196 (2011) 6735-6741

  Vapor phase methods such as pulsed laser deposition techniques not only require large equipment and are expensive to form, but are difficult to continuously produce, so include solid electrolytes in a simple manner. It was desired to form a layer.

  As a result of studying a method for easily forming a layer containing a solid electrolyte, the inventors of the present invention, as a result, a simple manufacturing apparatus, if a coating method using a solution obtained by dissolving a solid electrolyte in an organic solvent, It has been found that a layer containing a solid electrolyte can be formed continuously and inexpensively, and the present invention has been achieved.

Thus, according to the present invention, Li ₂ S-M _x S _y (M is selected from P, Si, Ge, B, Al and Ga, and x and y are the stoichiometric ratios depending on the type of M. A solution for forming a layer containing the solid electrolyte of the all-solid-state lithium secondary battery, comprising: a solid electrolyte represented by the formula (1): and an organic solvent capable of dissolving the solid electrolyte. .
In addition, according to the present invention, a positive electrode and a negative electrode, and a solid electrolyte layer positioned between the positive electrode and the negative electrode are provided, and any of the solid electrolyte layer, the positive electrode, and the negative electrode is formed by applying and drying the forming solution. An all-solid lithium secondary battery is provided.
Furthermore, according to the present invention, there is provided a method for producing an all-solid lithium secondary battery comprising a positive electrode and a negative electrode, and a solid electrolyte layer positioned between the positive electrode and the negative electrode, wherein any one of the solid electrolyte layer, the positive electrode, and the negative electrode A method for producing an all-solid lithium secondary battery is provided, which is formed by applying and drying the forming solution.

ADVANTAGE OF THE INVENTION According to this invention, the solution for formation of the layer containing the solid electrolyte of the all-solid-state lithium secondary battery which can form the layer containing a solid electrolyte simply can be provided.
In addition, the following configuration:
(1) The organic solvent is selected from lower aliphatic alcohol, lower aliphatic amine, formamide, and lower alkyl group-substituted formamide. (2) The lower aliphatic alcohol is methanol or ethanol, and the lower aliphatic amine is ethylenediamine. (3) M _x S _y is P ₂ S ₅ (4) Li ₂ S-M _x S _y is Li ₂ S and M _x S _y In a ratio of 50:50 to 90:10 (molar ratio) (5) When the layer containing a solid electrolyte has any one of a solid electrolyte layer, a positive electrode and a negative electrode, a layer containing a solid electrolyte It is possible to provide a solution for forming a layer containing a solid electrolyte of an all-solid lithium secondary battery that can be more easily formed.

2 is a Raman spectrum of the solid electrolyte of Example 1. FIG. 2 is an X-ray diffraction pattern of the solid electrolyte of Example 1. FIG. Is a SEM photograph and EDX mapping diagram of LiCoO ₂ coated with the solid electrolyte and the LiNbO ₃ of Example 2. It is a graph which shows the charging / discharging test result of the cell of Example 2. It is a graph which shows the charging / discharging test result of the cell of Example 2. 4 is an X-ray diffraction pattern of the solid electrolyte of Example 3. FIG.

(Solution for forming a layer containing a solid electrolyte of an all-solid lithium secondary battery)
The forming solution of the present invention can be used for forming any layer as long as it contains a solid electrolyte constituting an all-solid lithium secondary battery. Examples include a positive electrode including a positive electrode active material and a solid electrolyte, a negative electrode including a negative electrode active material and a solid electrolyte, and a solid electrolyte layer including a solid electrolyte.
The forming solution is Li ₂ S-M _x S _y (M is selected from P, Si, Ge, B, Al and Ga, where x and y are numbers giving a stoichiometric ratio depending on the type of M. And a solid electrolyte that can dissolve the solid electrolyte.

(1) Solid electrolyte (i) M _x S _y
In M _x S _y which is a sulfide, M is selected from P, Si, Ge, B, Al and Ga, and x and y are numbers giving a stoichiometric ratio depending on the type of M. The six elements that can be used as M can have various valences, and x and y can be set according to the valences. For example, P can be trivalent and pentavalent, Si can be tetravalent, Ge can be divalent and tetravalent, B can be trivalent, Al can be trivalent, and Ga can be trivalent. Specific examples of M _x S _y include P ₂ S ₅ , SiS ₂ , GeS ₂ , B ₂ S ₃ , Al ₂ S ₃ , Ga ₂ S _{3 and the} like. These specific M _x S _y may be used alone or in combination of two or more. For example, when two types are used together, it is represented by Li ₂ S-M _x1 S _y1 -M _x2 S _y2 (x1, x2, y1 and y2 are the same as x and y), for example, Li ₂ S-P ₂ S _5- GeS ₂ is exemplified. Of these, P ₂ S ₅ is particularly preferred.

(Ii) Mixing ratio of Li ₂ S—M _x S _y The mixing ratio of the two components is not particularly limited as long as it can be used as a solid electrolyte.
The ratio of Li ₂ S to M _x S _y is preferably a ratio of 50:50 to 90:10 (molar ratio). If the Li ₂ S ratio is less than 50 or greater than 90, the conductivity may be low. A preferred ratio is 60:40 to 80:20, and a more preferred ratio is 70:30 to 80:20.

(Iii) Other components The solid electrolyte may contain other components used in the all-solid lithium secondary battery in addition to Li ₂ S and M _x S _y . For example, electrolytes such as LiI and Li ₃ PO ₄ , binders such as oxides of Fe, Zn, and Bi, polyvinylidene fluoride, polytetrafluoroethylene, polyvinyl acetate, polymethyl methacrylate, and polyethylene can be used.

(Iv) Manufacturing Method of Solid Electrolyte The manufacturing method of the solid electrolyte is not particularly limited as long as it is a method in which Li ₂ S, M _x S _y and other components can be mixed as necessary. In particular, it is preferable to manufacture by mechanical milling from the viewpoint of mixing the components more uniformly.
The mechanical milling process is not particularly limited to a processing apparatus and processing conditions as long as each component can be mixed uniformly.
As a processing apparatus, a ball mill can be used normally. A ball mill is preferable because large mechanical energy can be obtained. Among the ball mills, the planetary ball mill is preferable because the pot rotates and the platform rotates in the direction opposite to the direction of rotation, so that high impact energy can be efficiently generated.

The processing conditions can be appropriately set according to the processing apparatus to be used. For example, when using a ball mill, the higher the rotational speed and / or the longer the processing time, the more uniformly the raw material mixture can be mixed. Note that “and / or” means A, B, or A and B when expressed as A and / or B. Specifically, when a planetary ball mill is used, conditions of a rotation speed of 50 to 600 rotations / minute, a processing time of 0.1 to 20 hours, and 1 to 100 kWh / kg of a raw material mixture are exemplified. More preferable processing conditions include a rotational speed of 200 to 500 rotations / minute, a processing time of 1 to 10 hours, and 6 to 50 kWh / kg of a raw material mixture.
Further, the solid electrolyte can be obtained by dissolving the raw material for forming the solid electrolyte in an organic solvent and reacting the raw material in the process of drying the obtained solution.

(2) Organic solvent The organic solvent is not particularly limited as long as it can dissolve the solid electrolyte. It is preferable that the organic solvent dissolve 10 mg / 2 ml or more of the solid electrolyte by stirring at 500 rpm at room temperature (about 25 ° C.) for 6 to 12 hours. By dissolving 10 mg / 2 ml or more, a forming solution capable of more easily forming a layer containing a solid electrolyte can be provided. The preferred solubility is 100 mg / 2 ml or more, and the more preferred solubility is 300 mg / 2 ml or more. Since the higher the solubility, the easier the solution can be obtained, there is no particular upper limit to the solubility.
An organic solvent having a low boiling point can be selected to improve removability during drying, and a solvent having high solubility can be selected to form a thick layer with a small number of coatings.

The organic solvent can be selected from, for example, lower aliphatic alcohols, lower aliphatic amines, formamides and lower alkyl group-substituted formamides, hydrazine-related compounds, and lower aliphatic ethers. Here, “lower” preferably has 1 to 4 carbon atoms. Examples of the lower aliphatic alcohol include methanol, ethanol, propanol, butanol and the like. Examples of lower aliphatic amines include diamines such as ethylenediamine. Examples of the lower alkyl group-substituted formamide include N-methylformamide and N, N-dimethylformamide. Examples of the lower aliphatic ether include diethyl ether and tetrahydrofuran.
Of the organic solvents, N-methylformamide is particularly preferable from the viewpoint of solubility.
(3) Concentration of solid electrolyte in forming solution The concentration of the solid electrolyte is not particularly limited as long as the layer containing the solid electrolyte can be formed by a coating method using the forming solution. This concentration can be appropriately set according to the type of solid electrolyte and organic solvent and the type of coating method.

(All-solid lithium secondary battery)
The all solid lithium secondary battery includes a positive electrode and a negative electrode, and a solid electrolyte layer positioned between the positive electrode and the negative electrode. In the present invention, any of the solid electrolyte layer, the positive electrode, and the negative electrode is formed by applying and drying the forming solution.
(1) Negative electrode A negative electrode is not specifically limited, Any negative electrode normally used for an all-solid-state lithium secondary battery can be used.
When forming a negative electrode using the above forming solution, a forming solution containing a negative electrode active material can be used. The negative electrode active material may be dissolved in the forming solution or may be dispersed in the form of particles. Examples of the negative electrode active material include metals such as Li, In, and Sn, alloys thereof, various transition metal oxides such as graphite and SnO, and the like.
Furthermore, the forming solution may contain a binder, a conductive agent, and the like as necessary.
Examples of the binder include polyvinylidene fluoride, polytetrafluoroethylene, polyvinyl acetate, polymethyl methacrylate, and polyethylene.
Examples of the conductive agent include natural graphite, artificial graphite, acetylene black, and vapor grown carbon fiber (VGCF).
When the above forming solution is not used, a foil-like Li metal layer or Li alloy layer (eg, Li—In alloy, Li—Sn alloy, Li—Si alloy, Li—Al alloy, etc.) can be used as the negative electrode. .

Moreover, you may use the negative electrode obtained by pressing a granular negative electrode active material other than the said Li metal layer or Li alloy layer. The negative electrode obtained by this pressing may contain a binder, a conductive agent, a solid electrolyte, and the like as necessary. As the solid electrolyte, a solid electrolyte obtained by drying the forming solution may be used.
The negative electrode may include a current collector such as SUS (stainless steel), aluminum, or copper.

(2) Positive electrode A positive electrode is not specifically limited, Any positive electrode normally used for an all-solid-state lithium secondary battery can be used.
When forming a positive electrode using the said forming solution, the forming solution containing a positive electrode active material can be used. The positive electrode active material may be dissolved in the forming solution or may be dispersed in the form of particles. Examples of the positive electrode active material include Li ₄ Ti ₅ O ₁₂ , LiCoO ₂ , LiMnO ₂ , LiVO ₂ , LiCrO ₂ , LiNiO ₂ , Li ₂ NiMn ₃ O ₈ , LiNi _1/3 Co _1/3 Mn _1/3 O _2. , S, Li ₂ S and the like. Among these, the particulate positive electrode active material may be coated with a material such as LiNbO ₃ .
Furthermore, the forming solution may contain a binder, a conductive agent, and the like as necessary.
Examples of the binder include polyvinylidene fluoride, polytetrafluoroethylene, polyvinyl acetate, polymethyl methacrylate, and polyethylene.
Examples of the conductive agent include natural graphite, artificial graphite, acetylene black, and vapor grown carbon fiber (VGCF).
When the above forming solution is not used, the positive electrode is obtained as a pellet by, for example, mixing a positive electrode active material and, optionally, a binder, a conductive agent, a solid electrolyte, and the like, and pressing the obtained mixture. be able to. As the solid electrolyte, a solid electrolyte obtained by drying the forming solution may be used.
Moreover, when using the metal sheet (foil) which consists of a metal or its alloy as a positive electrode active material, it can be used as it is.
The positive electrode may be formed on a current collector such as SUS, aluminum, or copper.

(3) Solid electrolyte layer The above-mentioned forming solution can be used for forming a solid electrolyte layer.
The solid electrolyte layer may be obtained by pressing the solid electrolyte.
In addition to the glassy solid electrolyte obtained by the above method, a glass ceramic solid electrolyte can also be used for the solid electrolyte layer. The glass-ceramic solid electrolyte can be converted by subjecting the glass-like solid electrolyte to a heat treatment. This heat treatment can be performed at a temperature equal to or higher than the glass transition point of the glassy solid electrolyte. The glass transition point is usually in the range of 180 to 240 ° C., and the upper limit of the heat treatment temperature is not particularly limited, but is usually + 100 ° C. of the glass transition point.
The heat treatment time is a time that can be converted from glass to glass ceramics, and is short when the heat treatment temperature is high and long when the heat treatment temperature is low. The heat treatment time is usually in the range of 0.1 to 10 hours.

(4) Formation conditions of the layer containing a solid electrolyte The layer containing a solid electrolyte can be obtained by applying the above-mentioned forming solution and drying the resulting coating film. The application method is not particularly limited, and examples thereof include brush coating, a dropping method, a spin coating method, and a spray method. The drying conditions are not particularly limited as long as the organic solvent can be removed. Usually, it can carry out above the boiling point of an organic solvent. Moreover, if it dries under reduced pressure, a drying temperature can be lowered | hung.
(5) Manufacturing method of all solid state secondary battery All solid state secondary batteries are, for example,
(I) A method of forming a positive electrode, a solid electrolyte layer, and a negative electrode into pellets and laminating them,
(Ii) a method of laminating a positive electrode, a solid electrolyte layer and a negative electrode formed on a substrate by transfer from the substrate;
(Iii) A positive electrode, a solid electrolyte layer, and a negative electrode can be manufactured by a method of sequentially stacking by a coating method.

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.
Example 1
Li ₂ S (purity 99.9%, manufactured by Idemitsu Kosan Co., Ltd.) and P ₂ S ₅ (purity 99%, manufactured by Aldrich) were charged into a planetary ball mill at a molar ratio of 80:20. After the charging, a mechanical milling process was performed to obtain a glassy solid electrolyte (80Li ₂ S · 20P ₂ S ₅ ) having a particle size of 5 μm. As the planetary ball mill, Pulverisette P-7 manufactured by Fritsch was used, and the pot and balls were made of zirconium oxide, and a mill containing 500 balls having a diameter of 4 mm in a 45 ml pot was used. The mechanical milling process was performed for 20 hours in a dry nitrogen glove box at a rotation speed of 510 rpm, room temperature. This synthesis method is described in Akitoshi Hayashi et al. , Electrochemistry Communications 5 (2003) 111-114.

The obtained solid electrolyte was dissolved in N-methylformamide (NMF) under stirring at room temperature (about 25 ° C.) and 500 rpm. The resulting solution was yellow and the solid electrolyte concentration was 18.5% by weight.
The obtained solution was dried at 150 ° C. for 3 hours under vacuum to precipitate a yellow solid electrolyte.
FIG. 1 shows the Raman spectrum of the solid electrolyte before dissolution and the solid electrolyte after precipitation, and FIG. 2 shows the X-ray diffraction pattern. In the figure, (a) means before dissolution, (b) means the spectrum of the solution, and (c) means the spectrum and pattern after precipitation.
From FIG. 1, it can be seen that a Raman band belonging to the PS ₄ ^3- unit is obtained both before dissolution and after precipitation. That is, NMF does not react with the solid electrolyte, indicating that the solid electrolyte can be dissolved and deposited. From FIG. 2, it can be seen that the solid electrolyte after deposition shows peaks attributed to the Li ₂ S crystal and Li ₃ PS ₄ crystal.
Next, when the electrical conductivity of the solid electrolyte before dissolution was measured, the solid electrolyte before dissolution showed 2.3 × 10 ⁻⁴ Scm ⁻¹ . The solid electrolyte after deposition was subjected to mechanical milling treatment under the conditions for the production of the solid electrolyte, and then the conductivity was measured, indicating 5.1 × ⁻⁵ Scm ⁻¹ , substantially the same as before dissolution. It was about.
Furthermore, when Li / P of the solid electrolyte before and after dissolution was measured by ICP emission analysis, it was 3.87 before dissolution and 3.80 after precipitation (theoretical value is 4.00), and Li deficiency It turns out that there is almost no.

Example 2
LiNbO ₃ coated LiCoO ₂ was used as the positive electrode active material. This positive electrode active material was formed by the following procedure.
A solution containing a precursor of LiNbO ₃ was spray-coated on LiCoO ₂ and then heat-treated at 350 ° C.
The positive electrode active material was charged into an NMF solution of a solid electrolyte obtained in the same manner as in Example 1 so that the positive electrode active material: solid electrolyte = 92.5: 7.5 (weight ratio). After the addition, the mixture was mixed using a stir bar at room temperature (about 25 ° C.) for 15 minutes. The obtained dispersion was dried at 150 ° C. for 3 hours under vacuum to obtain LiCoO ₂ coated with a solid electrolyte and LiNbO ₃ .

Mapping of the obtained LiCoO ₂ by scanning electron microscope (SEM) with energy dispersive X-ray spectroscopy (EDX) of Co, O, S and P atoms corresponding to FIGS. 3 (a) and 3 (a) The figure is shown in FIGS. From these figures, S and P constituting the solid electrolyte are observed on Co and O constituting LiCoO ₂ . Therefore, it can be seen from these figures that LiCoO ₂ is coated with the solid electrolyte.
The obtained solid electrolyte-coated LiCoO ₂ and glass ceramic solid electrolyte (80Li ₂ S · 20P ₂ S ₅ ) were mixed so as to be 70:30 (weight ratio). The mixing was performed using an agate mortar and pestle at room temperature (about 25 ° C.) for 15 minutes.
The glass-ceramic solid electrolyte was obtained by heating the glass-like solid electrolyte from room temperature (25 ° C.) toward 220 ° C., which is equal to or higher than the crystallization temperature, to form glass ceramics.
A pellet-shaped positive electrode (thickness: about 1 mm) was obtained by pressing 10 mg of the obtained mixture using a pellet molding machine having a molding part with an area of 0.785 cm ² at a pressure of 370 MPa.

Next, the glass ceramic solid electrolyte was pressed in the same manner as the positive electrode to obtain a pellet-shaped solid electrolyte layer (thickness: about 1 mm).
A positive electrode, a solid electrolyte layer, and an indium foil as a counter electrode were laminated in this order, and the laminate was sandwiched between stainless steel current collectors to obtain a battery cell (all-solid lithium secondary battery). This cell was subjected to a charge / discharge test at 25 ° C. and a current density of 0.13 mAcm ⁻² . The test results are shown in FIG.
Moreover, the test result of the cell obtained by carrying out similarly to the above except having used the positive electrode active material which is not coat | covered with a solid electrolyte is shown in FIG.
4 and 5, it can be seen that the charge / discharge capacity is improved by about 10% by coating the positive electrode active material with the solid electrolyte.

Example 3
The solubility of the solid electrolyte in various organic solvents was confirmed.
The same solid electrolyte as in Example 1 was used. As the organic solvent, methanol, ethanol, dimethyl sulfoxide (DMSO), acetonitrile, ethylenediamine (EDA) and NMF were used.
In 2 ml of each organic solvent, the amount of solid electrolyte that could be dissolved after 10 hours was measured at room temperature (about 25 ° C.) at 500 rpm with stirring. The results are shown in Table 1.

From Table 1, it was confirmed that methanol, ethanol and NMF have sufficient solubility and are preferable as the organic solvent of the present invention.
About EDA, although the amount of dissolution was a little small, it was confirmed that it was sufficient for practical use. Furthermore, when the solid electrolyte was changed to 75Li ₂ S · 25P ₂ S ₅ and the amount of dissolution was measured in the same manner as described above, 300 mg could be dissolved.
FIG. 6 shows an X-ray diffraction pattern of the solid electrolyte obtained by drying the ethanol solution of Table 1 at 150 ° C. for 3 hours under vacuum. In FIG. 6, the five peaks shown on the horizontal axis mean the peaks of Li ₇ PS ₆ literature values. From FIG. 6, it can be seen that the solid electrolyte after drying has a crystal structure of Li ₇ PS ₆ .

Claims (8)

Li ₂ S-M _x S _y (M is selected from P, Si, Ge, B, Al and Ga, and x and y are numbers giving a stoichiometric ratio depending on the type of M). A solution for forming a layer containing a solid electrolyte of an all-solid lithium secondary battery, comprising: a solid electrolyte to be dissolved; and an organic solvent capable of dissolving the solid electrolyte.   The solution for forming a layer containing the solid electrolyte of the all-solid-state lithium secondary battery according to claim 1, wherein the organic solvent is selected from a lower aliphatic alcohol, a lower aliphatic amine, formamide, and a lower alkyl group-substituted formamide.   The solid electrolyte of an all-solid-state lithium secondary battery according to claim 2, wherein the lower aliphatic alcohol is methanol or ethanol, the lower aliphatic amine is ethylenediamine, and the lower alkyl group-substituted formamide is N-methylformamide. A solution for forming a layer containing. The solution for forming a layer containing a solid electrolyte of an all-solid lithium secondary battery according to any one of claims 1 to 3, wherein the M _x S _y is P ₂ S ₅ . The Li ₂ S-M _x S _y has a Li ₂ S and _{M x S y 50: 50~90:} 10 according to any one of claims 1 to 4 in a proportion (molar ratio) total A solution for forming a layer containing a solid electrolyte of a solid lithium secondary battery.   The solution for forming a layer containing a solid electrolyte of an all-solid lithium secondary battery according to any one of claims 1 to 5, wherein the layer containing the solid electrolyte is any one of a solid electrolyte layer, a positive electrode, and a negative electrode.   A positive electrode and a negative electrode, and a solid electrolyte layer located between the positive electrode and the negative electrode, and any one of the solid electrolyte layer, the positive electrode, and the negative electrode is applied with the forming solution according to claim 1 and An all solid lithium secondary battery formed by drying.   It is a manufacturing method of the all-solid-state lithium secondary battery provided with the positive electrode and the negative electrode, and the solid electrolyte layer located between a positive electrode and a negative electrode, and any one of a solid electrolyte layer, a positive electrode, and a negative electrode is any one of Claims 1-6 A method for producing an all-solid-state lithium secondary battery, which is formed by applying and drying the forming solution according to claim 1.