Inorganic solid electrolyte-containing composition, sheet for all-solid-state secondary battery, all-solid-state secondary battery, and method for manufacturing sheet for all-solid-state secondary battery and all-solid-state secondary battery

Abstract

Provided is an inorganic solid electrolyte-containing composition containing an inorganic solid electrolyte, a polymer binder, and a dispersion medium, wherein the polymer binder: has a constituent component (X) derived from a polycondensable compound having a polycondensable group and a polymerized chain, and a constituent component (A) derived from a polycondensable compound having a specific functional group; includes a polymer having a constituent component (N) comprising a nitrogen atom and being contained in an amount of less than 10 mol% with respect to the total constituent components; and is dissolved in a dispersion medium. Also provided are an all-solid secondary battery sheet and an all-solid secondary battery using the inorganic solid electrolyte-containing composition, and methods for producing an all-solid secondary battery sheet and an all-solid secondary battery.

Description

[Technical Field]

[0001] The present invention relates to an inorganic solid electrolyte-containing composition, a sheet for an all-solid-state secondary battery, an all-solid-state secondary battery, and a method for producing the sheet for an all-solid-state secondary battery and the all-solid-state secondary battery. [Background technology]

[0002] All-solid-state secondary batteries are made of solid-state materials, including the negative electrode, electrolyte, and positive electrode, which significantly improves the safety and reliability issues associated with batteries that use organic electrolytes. They are also expected to achieve longer battery life. Furthermore, all-solid-state secondary batteries can be constructed with electrodes and electrolytes directly arranged in series. This allows for higher energy density than secondary batteries that use organic electrolytes, and they are expected to be used in electric vehicles, large-scale storage batteries, and other applications.

[0003] In such all-solid-state secondary batteries, inorganic solid electrolytes, active materials, etc. are used as materials for forming constituent layers (such as a solid electrolyte layer, a negative electrode active material layer, and a positive electrode active material layer). These inorganic solid electrolytes, particularly oxide-based inorganic solid electrolytes and sulfide-based inorganic solid electrolytes, have recently been expected as electrolyte materials with high ionic conductivity approaching that of organic electrolyte solutions. In consideration of improving productivity, constituent layers using such inorganic solid electrolytes are typically formed using a material (constituent layer-forming material) containing an inorganic solid electrolyte and a binder. Patent Document 1, for example, describes a solid electrolyte layer slurry containing a solid electrolyte material and a graft polymer as an example of such a constituent layer-forming material. The graft polymer described in Patent Document 1 is a branched polymer consisting of two or more segments, one of which constitutes the main chain and the other of which constitutes the graft portion (side chain), and is a polymer that does not have polar functional groups such as carboxy groups. Furthermore, Patent Document 2 describes a solid electrolyte composition containing a nitrogen-containing polymer having a repeating unit with a specific substituent, such as a substituent X having a pKa of 14 or less or a substituent Y having a polymer chain containing a heteroatom, and an inorganic solid electrolyte having ionic conductivity of a metal belonging to Group 1 or 2 of the periodic table. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 2011-014387 [Patent Document 2] Japanese Patent Application Laid-Open No. 2015-191865 Summary of the Invention [Problem to be solved by the invention]

[0005] In layers made up of solid particles such as inorganic solid electrolytes, active materials, and conductive additives, the interfacial contact between the solid particles is restricted, which tends to increase interfacial resistance (reduce conductivity). Moreover, all-solid-state secondary batteries equipped with such layers gradually lose battery performance (resulting in a deterioration of cycle characteristics) when repeatedly charged and discharged. Furthermore, from the viewpoint of improving battery performance (for example, resistance and cycle characteristics), the constituent layer forming materials used in the production of all-solid-state secondary batteries are required to have solid particles highly dispersed in the dispersion medium. Moreover, in recent years, development toward the practical application of all-solid-state secondary batteries has progressed rapidly, and corresponding measures are also required. For example, from the viewpoint of improving productivity and reducing manufacturing costs, practical application of inorganic solid electrolyte-containing compositions (thickened slurries) with increased solid content concentrations of solid particles, etc. is desired. However, when the solid content concentration of solid particles, etc. is increased, even inorganic solid electrolyte-containing compositions that exhibit excellent dispersibility inevitably experience some degree of aggregation or precipitation of solid particles over time. Therefore, for practical application, constituent layer-forming materials are required to have the property (redispersibility) of being able to redisperse solid particles that have aggregated or precipitated over time to the excellent dispersion state they had immediately after preparation (initial state), even when the solid content concentration is increased. However, Patent Documents 1 and 2 do not mention this point of view.

[0006] An object of the present invention is to provide an inorganic solid electrolyte-containing composition that exhibits excellent dispersion characteristics (initial dispersibility and redispersibility) even when the solid content concentration of solid particles is increased, and that enables the realization of an all-solid-state secondary battery that has low resistance and excellent cycle characteristics. Another object of the present invention is to provide a sheet for an all-solid-state secondary battery, an all-solid-state secondary battery, and a method for manufacturing the sheet for an all-solid-state secondary battery and the all-solid-state secondary battery, using this inorganic solid electrolyte-containing composition. [Means for solving the problem]

[0007] From the above perspective, the present inventors have conducted extensive research into polymer binders used in combination with inorganic solid electrolytes and dispersion media. As a result, they have discovered that by forming a polymer binder from a polymer containing a component (X) having a polymer chain and a component (A) having a specific functional group, and a low content of a component (N) containing a nitrogen atom, and by imparting to this polymer binder the property of dissolving rather than dispersing in a particulate form in the dispersion media, it is possible to reproduce excellent dispersibility (initial dispersibility) after preparation, even if the solid content of the solid particles is increased or the solid particles aggregate. Furthermore, they have discovered that by using an inorganic solid electrolyte-containing composition containing this specific polymer binder, an inorganic solid electrolyte, and a dispersion media as a component layer-forming material, it is possible to realize an all-solid-state secondary battery sheet having a low-resistance component layer, and further an all-solid-state secondary battery with low resistance and excellent cycle characteristics. Based on these findings, further research has led to the completion of the present invention.

[0008] That is, the above problems were solved by the following means. <1> An inorganic solid electrolyte-containing composition comprising an inorganic solid electrolyte having ionic conductivity of a metal belonging to Group 1 or 2 of the periodic table, a polymer binder, and a dispersion medium, The inorganic solid electrolyte-containing composition comprises a polymer binder having a constituent component (X) having a polymer chain and a constituent component (A) having at least one functional group selected from the following functional group group (a), and containing a nitrogen atom-containing constituent component (N) in an amount of less than 10 mol% based on all constituent components, and is soluble in the dispersion medium. <Functional group group (a)> Sulfonic acid group, phosphoric acid group, phosphonic acid group, carboxy group, hydroxy group, oxetane group, epoxy group, dicarboxylic acid anhydride group, thiol group, ether group, thioether group, thioester group, fluoroalkyl group, and salts thereof

[0009] <2> The component (X) is represented by the following formula (X1) or (X2): <1> The inorganic solid electrolyte-containing composition according to claim 1. [ka] In formula (X1) and formula (X2), R X1 ~R X3 and R X6 ~R X8 represents a hydrogen atom or a substituent. X4 R represents a hydrocarbon group or an alkylsilyl group. X5 R indicates a substituent. X9 represents a hydrogen atom or a substituent. L X1 ~L X3 represents a linking group. X4 represents a single bond or a linking group. n X and m X indicates the average degree of polymerization and is a number of 2 or more.

[0010] <3> The constituent (N) is a constituent containing a nitrogen atom that forms an amino group in a partial structure that is incorporated into the main chain of the polymer or in a partial structure that becomes a side chain other than the polymer chain. <1> or <2> The inorganic solid electrolyte-containing composition according to claim 1. <4> The polymer is a hyperbranched polymer having a core and three or more arms bonded to the core, and the arms contain the component (X). <1> ~ <3> 10. The inorganic solid electrolyte-containing composition according to claim 9, wherein the inorganic solid electrolyte-containing composition is a hydroxybenzoate. <5> The glass transition temperature of the polymer is -30°C or lower. <1> ~ <4> 10. The inorganic solid electrolyte-containing composition according to claim 9, wherein the inorganic solid electrolyte-containing composition is a hydroxybenzoate. <6> containing an active material, <1> ~ <5> 10. The inorganic solid electrolyte-containing composition according to claim 9, wherein the inorganic solid electrolyte-containing composition is a hydroxybenzoate. <7> Contains a conductive additive, <1> ~ <6> 10. The inorganic solid electrolyte-containing composition according to claim 9, wherein the inorganic solid electrolyte-containing composition is a hydroxybenzoate. <8> the above <1> ~ <7> 1. A sheet for an all-solid-state secondary battery, comprising a layer made of the inorganic solid electrolyte-containing composition according to any one of 1 to 8. <9> An all-solid-state secondary battery comprising a positive electrode active material layer, a solid electrolyte layer, and a negative electrode active material layer in this order, At least one of the positive electrode active material layer, the solid electrolyte layer, and the negative electrode active material layer is <1> ~ <7> 10. An all-solid-state secondary battery, wherein the layer is made of the inorganic solid electrolyte-containing composition according to any one of 1 to 8. <10> the above <1> ~ <7> 10. A method for producing a sheet for an all-solid-state secondary battery, comprising forming a film from the inorganic solid electrolyte-containing composition according to any one of the above items. <11> the above <10> 2. A method for producing an all-solid-state secondary battery, comprising the steps of: producing an all-solid-state secondary battery through the method for producing an all-solid-state secondary battery according to claim 1 ; [Effects of the Invention]

[0011] The present invention can provide an inorganic solid electrolyte-containing composition that exhibits excellent dispersion characteristics even when the solid content concentration of solid particles is increased, enabling the realization of an all-solid-state secondary battery that has low resistance and excellent cycle characteristics. The present invention can also provide a sheet for an all-solid-state secondary battery and an all-solid-state secondary battery that have a layer composed of this excellent inorganic solid electrolyte-containing composition. Furthermore, the present invention can provide a method for producing a sheet for an all-solid-state secondary battery and an all-solid-state secondary battery using this inorganic solid electrolyte-containing composition. The above and other features and advantages of the present invention will become more apparent from the following description, taken in conjunction with the accompanying drawings where appropriate. [Brief explanation of the drawings]

[0012] [Figure 1] 1 is a longitudinal sectional view schematically showing an all-solid-state secondary battery according to a preferred embodiment of the present invention. [Figure 2] FIG. 2 is a longitudinal sectional view schematically showing a coin-type all-solid-state secondary battery produced in the example. DETAILED DESCRIPTION OF THE INVENTION

[0013] In the present invention, a numerical range expressed using "to" means a range that includes the numerical values ​​written before and after "to" as the lower and upper limits. In the present invention, when multiple numerical ranges are set for the content of a component, physical properties, etc., the upper and lower limits forming the numerical range are not limited to a specific combination of upper and lower limits, and any numerical range can be formed by appropriately combining the upper and lower limits of each numerical range. In the present invention, the expression of a compound (for example, when it is referred to by adding "compound" to the end) is used to mean not only the compound itself, but also its salts and ions. It also means to include derivatives that have been partially modified, such as by introducing a substituent, within the scope that does not impair the effects of the present invention. In the present invention, (meth)acrylic means one or both of acrylic and methacrylic. The same applies to (meth)acrylate. In the present invention, substituents, linking groups, etc. (hereinafter referred to as substituents, etc.) that are not specified as substituted or unsubstituted mean that the group may have an appropriate substituent. Therefore, even when simply described as a YYY group in the present invention, this YYY group includes not only an embodiment in which it has no substituent, but also an embodiment in which it further has a substituent. This also applies to compounds in which it is not specified as substituted or unsubstituted. Preferred substituents include, for example, the substituent Z described below. In the present invention, when there are multiple substituents, etc., designated by a specific symbol, or when multiple substituents, etc., are simultaneously or alternatively specified, it means that the respective substituents, etc., may be the same or different from each other. Furthermore, even if not otherwise specified, when multiple substituents, etc., are adjacent, they may be linked to each other or condensed to form a ring. In the present invention, the term "polymer" refers to a polymer, and is synonymous with the term "polymer compound." The term "polymer binder" (also simply referred to as "binder") refers to a binder made of a polymer, and includes both the polymer itself and a binder formed containing a polymer.

[0014] [Inorganic solid electrolyte-containing composition] The inorganic solid electrolyte-containing composition of the present invention contains an inorganic solid electrolyte having ionic conductivity of a metal belonging to Group 1 or 2 of the periodic table, a polymer binder containing a polymer having the components described below, and a dispersion medium. This polymer binder has the property of dissolving in the dispersion medium contained in the inorganic solid electrolyte-containing composition (solubility). The polymer binder in the inorganic solid electrolyte-containing composition typically exists in a dissolved state in the dispersion medium, depending on its content. This allows the polymer binder to stably perform its function of dispersing solid particles in the dispersion medium, thereby maintaining excellent (initial) dispersion of the solid particles in the inorganic solid electrolyte-containing composition. Even if the solid particles aggregate or precipitate over time, the excellent initial dispersion can be restored by re-dispersing (mixing) the solid particles. Furthermore, the adhesion between the solid particles and each other or with the current collector can be strengthened, thereby enhancing the effect of improving the cycle characteristics of the all-solid-state secondary battery. In the present invention, the polymer binder being dissolved in the dispersion medium in the inorganic solid electrolyte-containing composition is not limited to an embodiment in which all of the polymer binder is dissolved in the dispersion medium, and a part of the polymer binder may be insoluble in the inorganic solid electrolyte-containing composition as long as the solubility in the dispersion medium is, for example, 80% or more. The solubility is measured as follows. Specifically, a specified amount of the polymer binder to be measured is weighed into a glass bottle, and 100 g of the same type of dispersion medium as the dispersion medium contained in the inorganic solid electrolyte-containing composition is added thereto. The mixture is stirred for 24 hours at 80 rpm on a mix rotor at a temperature of 25°C. The transmittance of the mixture thus obtained after 24 hours of stirring is measured under the following conditions. This test (transmittance measurement) is performed by changing the amount of binder dissolved (the above-specified amount), and the upper limit concentration X (mass%) at which the transmittance becomes 99.8% is defined as the solubility of the polymer binder in the above-specified dispersion medium. <Transmittance measurement conditions> Dynamic light scattering (DLS) measurements Equipment: DLS measurement equipment DLS-8000 manufactured by Otsuka Electronics Laser wavelength, output: 488nm / 100mW Sample cell: NMR tube

[0015] The inorganic solid electrolyte-containing composition of the present invention is preferably a slurry in which the inorganic solid electrolyte is dispersed in a dispersion medium. In the inorganic solid electrolyte-containing composition, the polymer binder dissolves in the dispersion medium and interacts with, preferably adsorbs onto, solid particles such as the inorganic solid electrolyte, thereby enhancing the dispersion characteristics of the solid particles. In the present invention, the adsorption of the polymer binder to the solid particles includes not only physical adsorption but also chemical adsorption (adsorption through chemical bond formation, adsorption through electron transfer, etc.). The dispersion characteristics exhibited by the polymer binder can be maintained even when the solid content of the solid particles is increased. The solid content in this case is determined by the content of the dispersion medium described below. The inorganic solid electrolyte-containing composition of the present invention contains the above-mentioned polymer binder in combination with the inorganic solid electrolyte and dispersion medium, so the solid content can also be increased. The solid content concentration is not uniquely determined by changes in the composition temperature, the type of solid particles, etc., but can be, for example, 40% by mass or more at 25°C, and even 50% by mass or more. Furthermore, the polymer binder functions as a binder that binds together solid particles (e.g., between inorganic solid electrolytes, between inorganic solid electrolytes and active materials, between active materials) such as inorganic solid electrolytes (and further, between active materials and conductive additives that may coexist) in a constituent layer formed from the inorganic solid electrolyte-containing composition. It also functions as a binder that binds together solid particles and a substrate such as a current collector. In the inorganic solid electrolyte-containing composition, the polymer binder may or may not have the function of binding together solid particles.

[0016] The inorganic solid electrolyte-containing composition of the present invention exhibits excellent dispersion properties even at an increased solid content concentration, and when used as a constituent layer, the solid particles can be bound to other solid particles and even to a substrate. Therefore, by using this inorganic solid electrolyte-containing composition as a constituent layer-forming material, it is possible to realize a sheet for an all-solid-state secondary battery having a low-resistance constituent layer, and further, an all-solid-state secondary battery having high conductivity (low resistance) and excellent cycle characteristics.

[0017] While the details of the reason are not yet clear, it is thought to be as follows. Specifically, the polymer binder containing the components (X), (A), and (N) described below is dissolved in the dispersion medium in the inorganic solid electrolyte-containing composition, with the polymer molecular chains spread out. Furthermore, it is thought that the excluded volume effect between binders due to the component (X) present in the polymer increases, while the repulsive force between binders due to the osmotic pressure effect also increases. This makes it difficult for binders to aggregate and adhere to each other, improving dispersibility. Solid particles adsorbed to the binder can also be highly dispersed, suppressing aggregation and precipitation. Therefore, excellent (initial) dispersibility can be maintained even when the solid content is increased. Furthermore, even if solid particles have aggregated or precipitated, the excellent (initial) dispersibility immediately after preparation can be reproduced due to the above-mentioned action of the polymer binder. Furthermore, it is thought that the above-mentioned repulsive force makes it difficult for the surfaces of the solid particles to be entirely coated, and direct contact (contact without the intervention of the binder) between the solid particles can be maintained without significantly impairing the adhesion between the solid particles. Therefore, the inorganic solid electrolyte-containing composition of the present invention can form a constituent layer that reduces the interfacial resistance between the solid particles and suppresses the inhibition of ion or electron conduction while causing the solid particles to adhere or bond to each other. As described above, in the present invention, the interaction (association) between the inorganic solid electrolyte, the dispersion medium, and the polymer binder in the inorganic solid electrolyte-containing composition and in the constituent layer is improved, thereby achieving excellent dispersion characteristics of the inorganic solid electrolyte-containing composition and reduced resistance when used as a constituent layer. Therefore, an all-solid-state secondary battery that combines low resistance (high conductivity) and excellent cycle characteristics can be realized. Furthermore, industrial production, such as a highly productive roll-to-roll process, can be applied to the production method of the all-solid-state secondary battery sheet and all-solid-state secondary battery using the inorganic solid electrolyte-containing composition of the present invention.

[0018] The polymer binder contained in the constituent layer is susceptible to degradation (oxidation) by oxygen (atoms or molecules), etc., and as degradation progresses, the binding strength of the solid particles and the state of interfacial contact gradually decrease, causing a further deterioration in cycle characteristics. Furthermore, in industrial production, such as the highly productive roll-to-roll method, it is difficult to completely remove oxygen from the production environment, storage environment, etc., and oxidative degradation cannot be avoided. However, binders containing the above-mentioned polymers can favorably exhibit resistance to oxidative degradation due to oxygen, etc., and suppress oxidative degradation of the inorganic solid electrolyte-containing composition and the constituent layer, thereby realizing a constituent layer that can suppress further deterioration in cycle characteristics due to oxidative degradation, even in industrial production methods.

[0019] The inorganic solid electrolyte-containing composition of the present invention can be preferably used as a forming material (constituent layer forming material) for a solid electrolyte layer or an active material layer of an all-solid-state secondary battery sheet (including an electrode sheet for an all-solid-state secondary battery) or an all-solid-state secondary battery. In particular, it can be preferably used as a forming material for an electrode sheet or an active material layer for an all-solid-state secondary battery, and in this embodiment, high cycle characteristics and high conductivity can also be achieved.

[0020] The inorganic solid electrolyte-containing composition of the present invention is preferably a non-aqueous composition. In the present invention, the non-aqueous composition includes not only an embodiment that does not contain water, but also an embodiment in which the water content (also referred to as water content) is preferably 500 ppm or less. In a non-aqueous composition, the water content is more preferably 200 ppm or less, even more preferably 100 ppm or less, and particularly preferably 50 ppm or less. When the inorganic solid electrolyte-containing composition is a non-aqueous composition, deterioration of the inorganic solid electrolyte can be suppressed. The water content refers to the amount of water contained in the inorganic solid electrolyte-containing composition (mass ratio relative to the inorganic solid electrolyte-containing composition), and specifically refers to the value measured by Karl Fischer titration after filtering through a 0.02 μm membrane filter.

[0021] The inorganic solid electrolyte-containing composition of the present invention also includes an embodiment containing an active material and further a conductive additive in addition to the inorganic solid electrolyte (the composition in this embodiment is referred to as an electrode composition). Components contained in the inorganic solid electrolyte-containing composition of the present invention and components that can be contained therein will be described below.

[0022] <Inorganic solid electrolyte> The inorganic solid electrolyte-containing composition of the present invention contains an inorganic solid electrolyte. In the present invention, the term "inorganic solid electrolyte" refers to an inorganic solid electrolyte, and a solid electrolyte is a solid electrolyte capable of transferring ions therein. Because inorganic solid electrolytes do not contain organic substances as the main ion-conducting material, they are clearly distinguished from organic solid electrolytes (polymer electrolytes such as polyethylene oxide (PEO) and organic electrolyte salts such as lithium bis(trifluoromethanesulfonyl)imide (LiTFSI)). Furthermore, inorganic solid electrolytes are solid in a steady state and are not typically dissociated or liberated into cations and anions. In this respect, they are also clearly distinguished from electrolytic solutions or inorganic electrolyte salts (such as LiPF, LiBF, lithium bis(fluorosulfonyl)imide (LiFSI), and LiCl) that are dissociated or liberated into cations and anions in a polymer. The inorganic solid electrolyte is not particularly limited as long as it has ionic conductivity for metals belonging to Group 1 or Group 2 of the periodic table, but generally does not have electronic conductivity. When the all-solid-state secondary battery of the present invention is a lithium-ion battery, the inorganic solid electrolyte preferably has ionic conductivity for lithium ions. The inorganic solid electrolyte may be selected from solid electrolyte materials typically used in all-solid-state secondary batteries. Examples of inorganic solid electrolytes include (i) sulfide-based inorganic solid electrolytes, (ii) oxide-based inorganic solid electrolytes, (iii) halide-based inorganic solid electrolytes, and (iv) hydride-based inorganic solid electrolytes. Sulfide-based inorganic solid electrolytes are preferred because they can form a better interface between the active material and the inorganic solid electrolyte.

[0023] (i) Sulfide-based inorganic solid electrolyte The sulfide-based inorganic solid electrolyte preferably contains sulfur atoms, has the ionic conductivity of a metal belonging to Group 1 or 2 of the periodic table, and has electronic insulation. The sulfide-based inorganic solid electrolyte preferably contains at least Li, S, and P as elements and has lithium ion conductivity, but may contain elements other than Li, S, and P as appropriate.

[0024] An example of the sulfide-based inorganic solid electrolyte is a lithium ion conductive inorganic solid electrolyte that satisfies the composition represented by the following formula (S1). L a1 M b1 P c1 S d1 A e1 (S1) In the formula, L represents an element selected from Li, Na, and K, and Li is preferred. M represents an element selected from B, Zn, Sn, Si, Cu, Ga, Sb, Al, and Ge. A represents an element selected from I, Br, Cl, and F. a1 to e1 represent the composition ratio of each element, and a1:b1:c1:d1:e1 satisfies the ratio 1-12:0-5:1:2-12:0-10. a1 is preferably 1-9, and more preferably 1.5-7.5. b1 is preferably 0-3, and more preferably 0-1. d1 is preferably 2.5-10, and more preferably 3.0-8.5. e1 is preferably 0-5, and more preferably 0-3.

[0025] The composition ratio of each element can be controlled by adjusting the blending amounts of raw material compounds when producing the sulfide-based inorganic solid electrolyte, as described below.

[0026] The sulfide-based inorganic solid electrolyte may be amorphous (glass) or crystallized (glass-ceramic), or may be only partially crystallized. For example, a Li-PS-based glass containing Li, P, and S, or a Li-PS-based glass-ceramic containing Li, P, and S may be used. The sulfide-based inorganic solid electrolyte can be produced by reacting at least two or more raw materials selected from the group consisting of lithium sulfide (LiS), phosphorus sulfide (e.g., diphosphorus pentasulfide (PS)), elemental phosphorus, elemental sulfur, sodium sulfide, hydrogen sulfide, lithium halides (e.g., LiI, LiBr, LiCl), and sulfides of the elements represented by M above (e.g., SiS, SnS, GeS).

[0027] In the Li-PS glass and Li-PS glass ceramics, the ratio of Li2S to P2S5 is preferably 60:40 to 90:10, more preferably 68:32 to 78:22, in terms of the molar ratio of Li2S:P2S5. By setting the ratio of Li2S to P2S5 within this range, the lithium ion conductivity can be increased. Specifically, the lithium ion conductivity is preferably 1×10 -4 S / cm or more, preferably 1×10 -3 S / cm or more. There is no upper limit, but it is 1×10 -1 It is practical to have a value of S / cm or less.

[0028] Specific examples of sulfide-based inorganic solid electrolytes, including combinations of raw materials, are shown below: Li2S-P2S5, Li2S-P2S5-LiCl, Li2S-P2S5-H2S, Li2S-P2S5-H2S-LiCl, Li2S-LiI-P2S5, Li2S-LiI-Li2O-P2S5, Li2S-LiBr-P2S5, Li2S-Li2O-P2S5, Li2S-Li3PO4-P2S5, Li2S-P2S5-P2O5, Li2S-P2S5-SiS2, Li2S-P2S5-SiS2-LiCl, Li2S-P2S5-SnS, and Li2S-P2S5-Al2S3 , Li2S-GeS2, Li2S-GeS2-ZnS, Li2S-Ga2S3, Li2S-GeS2-Ga2S3, Li2S-GeS2-P2S5, Li2S-GeS2-Sb2S5, Li2S-GeS2-Al2S3, Li2S-SiS2, L i2S-Al2S3, Li2S-SiS2-Al2S3, Li2S-SiS2-P2S5, Li2S-SiS2-P2S5-LiI, Li2S-SiS2-LiI, Li2S-SiS2-Li4SiO4, Li2S-SiS2-Li3PO4, Li 10 GeP2S 12 However, the mixing ratio of each raw material is not important. As a method for synthesizing a sulfide-based inorganic solid electrolyte material using such a raw material composition, for example, an amorphization method can be mentioned. Examples of the amorphization method include a mechanical milling method, a solution method, and a melt quenching method. This is because processing at room temperature becomes possible, and the manufacturing process can be simplified.

[0029] (ii) Oxide-based inorganic solid electrolyte The oxide-based inorganic solid electrolyte preferably contains oxygen atoms, has the ionic conductivity of a metal belonging to Group 1 or 2 of the periodic table, and has electronic insulation properties. Oxide-based inorganic solid electrolytes have an ionic conductivity of 1×10 -6 S / cm or more is preferable, and 5×10 -6 S / cm or more is more preferable, and 1×10 -5 It is particularly preferable that the viscosity is 1×10 S / cm or more. -1It is practical that it is below S / cm.

[0030] Specific compound examples include, for example, Li xa La ya TiO3 [xa satisfies 0.3 ≤ xa ≤ 0.7, and ya satisfies 0.3 ≤ ya ≤ 0.7.](LLT); Li xb La yb Zr zb M bb mb O nb (M bb is one or more elements selected from Al, Mg, Ca, Sr, V, Nb, Ta, Ti, Ge, In, and Sn. xb satisfies 5 ≤ xb ≤ 10, yb satisfies 1 ≤ yb ≤ 4, zb satisfies 1 ≤ zb ≤ 4, mb satisfies 0 ≤ mb ≤ 2, and nb satisfies 5 ≤ nb ≤ 20.); Li xc B yc M cc zc O nc (M cc is one or more elements selected from C, S, Al, Si, Ga, Ge, In, and Sn. xc satisfies 0 < xc ≤ 5, yc satisfies 0 < yc ≤ 1, zc satisfies 0 < zc ≤ 1, and nc satisfies 0 < nc ≤ 6.); Li xd (Al,Ga) yd (Ti,Ge) zd Si ad P md O nd (xd satisfies 1 ≤ xd ≤ 3, yd satisfies 0 ≤ yd ≤ 1, zd satisfies 0 ≤ zd ≤ 2, ad satisfies 0 ≤ ad ≤ 1, md satisfies 1 ≤ md ≤ 7, and nd satisfies 3 ≤ nd ≤ 13.); Li (3-2xe) M ee xe D ee O(xe represents a number from 0 or more to 0.1 or less, and M ee represents a divalent metal atom. D ee represents a halogen atom or a combination of two or more halogen atoms.); Li xf Si yf O zf (xf satisfies 1 ≤ xf ≤ 5, yf satisfies 0 < yf ≤ 3, and zf satisfies 1 ≤ zf ≤ 10.); Lixg S yg O zg (xg satisfies 1 ≤ xg ≤ 3, yg satisfies 0 < yg ≤ 2, and zg satisfies 1 ≤ zg ≤ 10); Li3BO3; Li3BO3-Li2SO4; Li2O-B2O3-P2O5; Li2O-SiO2; Li6BaLa2Ta2O 12 ; Li3PO (4-3 / 2w) N w (w is w < 1); Li having a LISICON (Lithium super ionic conductor) type crystal structure 3.5 Zn 0.25 GeO4; La having a perovskite type crystal structure 0.55 Li 0.35 TiO3; LiTi2P3O having a NASICON (Natrium super ionic conductor) type crystal structure 12 ; Li 1+xh+yh (Al,Ga) xh (Ti,Ge) 2-xh Si yh P 3-yh O[[ID=三十二]] 12 (xh satisfies 0 ≤ xh ≤ 1 and yh satisfies 0 ≤ yh ≤ 1); Li7La3Zr2O having a garnet type crystal structure 12 (LLZ), etc. can be mentioned. In addition, a phosphorus compound containing Li, P and O is also desirable. For example, lithium phosphate (Li3PO4); LiPON in which part of the oxygen element of lithium phosphate is substituted with a nitrogen element; LiPOD 1 (D 1 is preferably at least one element selected from Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zr, Nb, Mo, Ru, Ag, Ta, W, Pt and Au.) etc. can be mentioned. Furthermore, LiA 1 ON (A 1 is at least one element selected from Si, B, Ge, Al, C and Ga.) etc. can also be preferably used.

[0031] (iii) Halide-based inorganic solid electrolyte The halide-based inorganic solid electrolyte is preferably a compound that contains a halogen atom, has ionic conductivity of a metal belonging to Group 1 or 2 of the periodic table, and has electronic insulation properties. The halide-based inorganic solid electrolyte is not particularly limited, but examples thereof include LiCl, LiBr, LiI, and compounds such as Li3YBr6 and Li3YCl6 described in ADVANCED MATERIALS, 2018, 30, 1803075. Of these, Li3YBr6 and Li3YCl6 are preferred.

[0032] (iv) Hydride-based inorganic solid electrolytes The hydride-based inorganic solid electrolyte is preferably a compound that contains hydrogen atoms, has the ionic conductivity of a metal belonging to Group 1 or 2 of the periodic table, and has electronic insulation properties. The hydride-based inorganic solid electrolyte is not particularly limited, but examples thereof include LiBH4, Li4(BH4)3I, 3LiBH4-LiCl, and the like.

[0033] The inorganic solid electrolyte is preferably in the form of particles. In this case, the particle size (volume average particle size) of the inorganic solid electrolyte is not particularly limited, but is preferably 0.01 μm or more, more preferably 0.1 μm or more. The upper limit is preferably 100 μm or less, more preferably 50 μm or less. The particle size of inorganic solid electrolytes is measured using the following procedure. A 1% by mass dispersion of inorganic solid electrolyte particles is prepared by diluting them in water (or heptane if the substance is unstable in water) in a 20 mL sample bottle. The diluted dispersion sample is irradiated with 1 kHz ultrasound for 10 minutes and then immediately used for testing. Using this dispersion sample, a laser diffraction / scattering particle size analyzer LA-920 (product name, manufactured by HORIBA) is used to acquire data 50 times at 25°C using a quartz measurement cell to obtain the volume-average particle size. For other detailed conditions, refer to the description in Japanese Industrial Standards (JIS) Z 8828:2013, "Particle Size Analysis - Dynamic Light Scattering Method," as necessary. Five samples are prepared for each level, and the average value is used.

[0034] The inorganic solid electrolyte may be contained in one kind or in two or more kinds. The content of the inorganic solid electrolyte in the inorganic solid electrolyte-containing composition is not particularly limited, but from the viewpoints of binding property and further dispersibility, it is preferably 50% by mass or more, more preferably 70% by mass or more, and particularly preferably 90% by mass or more, based on 100% by mass of the solid content. From the same viewpoint, the upper limit is preferably 99.9% by mass or less, more preferably 99.5% by mass or less, and particularly preferably 99% by mass or less. However, when the inorganic solid electrolyte-containing composition contains an active material described below, the content of the inorganic solid electrolyte in the inorganic solid electrolyte-containing composition is preferably such that the total content of the active material and the inorganic solid electrolyte falls within the above range. In the present invention, the solid content (solid components) refers to components that do not volatilize or vaporize when the inorganic solid electrolyte-containing composition is dried at 150°C under a nitrogen atmosphere at an atmospheric pressure of 1 mmHg for 6 hours. Typically, this refers to components other than the dispersion medium described below.

[0035] <Polymer binder> The polymer binder contained in the inorganic solid electrolyte-containing composition of the present invention is formed by containing a polymer having each of the constituent components described below, and contains one or more polymer binders that are soluble in the dispersion medium contained in the inorganic solid electrolyte-containing composition. By using this polymer binder in combination with the inorganic solid electrolyte and the dispersion medium, the inorganic solid electrolyte-containing composition can exhibit excellent dispersion properties even when the solid content is increased, and when used as a constituent layer, it is possible to reduce an increase in interface resistance while maintaining the binding force of the solid particles.

[0036] In the present invention, the polymer contained in the polymer binder and forming the polymer binder (also referred to as a binder-forming polymer) dissolves the polymer binder in a dispersion medium and contains the components (X), (A), and (N) described below. The dissolution of the polymer binder in a dispersion medium is as described above.

[0037] - Component (X) - The binder-forming polymer contains the component (X), which has a polymer chain. The binder-forming polymer contains the component (X), which can enhance the excluded volume effect between polymer binders, thereby improving dispersion characteristics. This component (X) may have a polymer chain, and examples thereof include components derived from polycondensation compounds having a polycondensation group and a polymer chain. The polycondensation group is appropriately determined depending on the main chain structure of the binder-forming polymer. For example, in the case of a step-polymerization polymer described below, a condensation functional group is selected, and in the case of a chain-polymerization polymer, a polymerizable group (ethylenically unsaturated group) is selected.

[0038] This constituent (X) may contain a nitrogen atom; for example, a constituent that forms a polymer chain may contain a nitrogen atom, more specifically, it may be a constituent derived from acrylamide. In a preferred embodiment of the present invention, when constituent (X) has a nitrogen atom that forms an amino group in a partial structure incorporated into the main chain of the polymer or in a partial structure that becomes a side chain other than the polymer chain (which also corresponds to constituent (N)), it belongs to constituent (N) rather than constituent (X). On the other hand, in the present invention, constituent (X) may not contain a nitrogen atom. Although component (X) may have a functional group selected from functional group group (a) described below, it is preferable that it does not have one. In other words, component (X) preferably does not correspond to component (A). However, even if the polymer chain of component (X) contains the following functional group as a linking group described below, this functional group functions as a linking group and is not a functional group selected from functional group (a) described below. Furthermore, when component (X) is derived from a compound having a polycondensable group and a polymer chain described below, even if the linking group connecting the polycondensable group and the polymer chain has a functional group, this functional group does not sufficiently exhibit the function of adsorbing or adhering to solid particles, and therefore component (X) is considered to be included in the embodiment having no functional group (a component not corresponding to component (A)).

[0039] The polymer chain is a molecular chain constituting a side chain of the binder-forming polymer, and is a molecular chain in which two or more repeating units of one or more types are bonded. For example, a chain made of a normal polymer, specifically a step-polymerized polymer or a chain-polymerized polymer described later, can be applied without any particular limitation. This polymer chain does not have a nitrogen atom that forms an amino group in its main chain, for example, it is a molecular chain in which the main chain is formed of a polymer other than polyalkyleneimine and other than polyalkylamine. In the present invention, a polymer represented by the following formula (L P ), a polymer chain having a repeating unit represented by the formula (for example, a polymer chain made of polyether, a polymer chain made of polysiloxane), is preferred, and a polymer chain made of a (meth)acrylic polymer is more preferred.

[0040] [ka] The above formula (L P In the formula (I), X represents a divalent substituent, L represents a single bond or a linking group, and n represents the (average) degree of polymerization. The substituent that can be taken as X is not particularly limited, and examples thereof include a group in which one hydrogen atom has been further removed from a group appropriately selected from the substituent Z described below. In terms of dispersion properties, it is preferable to use a group selected from the group R described below. X4 X may have a substituent, and in particular, the group represented by the formula (L P ) is a chain formed from a chain-polymerized polymer, -L in formula (X2) described below X4 -R X9 It is preferable that the aryl group has a group represented by the following formula: L is selected depending on the type of polymer chain; for example, in the case of a chain consisting of a chain-polymerized polymer, it is a single bond, and in the case of a chain consisting of a step-polymerized polymer, it is a linking group. The linking group that can be taken as L is not particularly limited as long as it is a group that can bond to another repeating unit, and is appropriately selected depending on the type of polymer chain. This linking group is usually a linking group having a hetero atom, for example, an ester bond (-CO-O-), an ether bond (-O-), a carbonate bond (-O-CO-), an amide bond (-CO-N(R N)-), urethane bond (-N(R N )-CO-), urea bond (-N(R N )-CO-N(R N )-), imide bond (-CO-N(R N )-CO-). In each of the above bonds, R N represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 10 carbon atoms. Any bonding portion of the linking group may be bonded to the X. As the linking group, a group not containing a nitrogen atom is preferred, and an ester bond, an ether bond, a carbonate bond, etc. are more preferred. n represents the (average) degree of polymerization, and is not limited to a specific value, as long as it is 2 or more, and is appropriately determined in consideration of the number-average molecular weight of the polymer chains described below. For example, the degree of polymerization n is preferably 3 to 500, more preferably 4 to 300, and even more preferably 4 to 100. The upper limit of each numerical range may be set to 50, 40, or 15. In the polymer chain, two or more repeating units may be the same or different. When two or more repeating units are different, the bonding mode is not particularly limited and may be random, alternating, or block.

[0041] The above formula (L P ), examples of the polymer chain having a repeating unit represented by the formula (I) include a chain made of a chain-polymerized polymer and a polymer chain made of a step-polymerized polymer. More specifically, preferred examples include a polymer chain made of a (meth)acrylic polymer, a polymer chain made of polystyrene, a polymer chain made of polyether, a polymer chain made of polyester, a polymer chain made of polycarbonate, and a polymer chain made of polysiloxane.

[0042] Examples of the polymer chain made of polyether include a polyalkyleneoxy chain and a polyaryleneoxy chain. The alkylene group and the arylene group include a group in which one hydrogen atom has been further removed from an alkyl group or an aryl group appropriately selected from the substituent Z described below, and preferably, a group in which one hydrogen atom has been further removed from an alkyl group or an aryl group appropriately selected from the substituent Z described below. X4 Examples of the alkylene group include an alkylene group and an arylene group.

[0043] The polymer chain made of polysiloxane preferably has a structure represented by -(SiR2-O)n-. R represents a hydrogen atom or a substituent, and a substituent is preferred. The substituent is not particularly limited and may be selected from the substituent Z described below, and is preferably an alkyl group or an aryl group, more preferably an alkyl group having 1 to 6 carbon atoms. The (average) repeat number n is as described above. Examples of the constituent (X) having a polymer chain made of polysiloxane include a constituent derived from a terminal (meth)acrylic-modified silicone compound (e.g., product number X-22-174ASX manufactured by Shin-Etsu Silicones Co., Ltd.).

[0044] Examples of the polymer chain made of polyester include chains made of known polyesters, such as polyester polymer chains obtained by reacting a polyol such as alkylene glycol with a polybasic acid such as an aromatic dicarboxylic acid or an aliphatic dicarboxylic acid, and polyester polymer chains obtained by ring-opening polymerization of a cyclic ester compound such as a caprolactone monomer.

[0045] Preferred examples of the chain made of a chain-polymerized polymer include a polymer chain made of a (meth)acrylic polymer and a polymer chain made of polystyrene. The polymer chain made of a (meth)acrylic polymer preferably contains a component derived from a (meth)acrylic compound (M1) described below and a component derived from a vinyl compound (M2) described below. Among these, a polymer chain containing a component derived from one or more (meth)acrylic acid ester compounds is more preferred, and a polymer chain containing a component derived from a (meth)acrylic acid alkyl ester compound is even more preferred. The (meth)acrylic acid alkyl ester compound preferably contains an ester compound of a long-chain alkyl group having 4 or more carbon atoms (preferably 6 or more carbon atoms), and may further contain an ester compound of a short-chain alkyl group having 3 or less carbon atoms. The content of each component in the polymer chain is not particularly limited and may be appropriately set. For example, the content of the component derived from the (meth)acrylic compound (M1) in the polymer chain is preferably 30 to 100% by mass, and can also be 50 to 80% by mass. The content of the component derived from a (meth)acrylic acid alkyl ester compound is preferably 50 to 100% by mass, and can also be 60 to 80% by mass. Furthermore, when the composition contains a component derived from a (meth)acrylic acid long-chain alkyl ester compound and a component derived from a (meth)acrylic acid short-chain alkyl ester compound, the content of the component derived from the (meth)acrylic acid long-chain alkyl ester compound is preferably 20 to 100 mass%, more preferably 50 to 100 mass%, and the content of the component derived from the (meth)acrylic acid short-chain alkyl ester compound is preferably 5 to 80 mass%, more preferably 5 to 40 mass%.

[0046] The group bonded to the end of the polymer chain is not particularly limited and may be an appropriate group depending on the polymerization method, etc. Examples include a hydrogen atom, an alkyl group, an aryl group, and a hydroxy group, and from the viewpoint of dispersion characteristics, an alkyl group (preferably having 1 to 20 carbon atoms, more preferably 4 to 20 carbon atoms, and even more preferably 4 to 12 carbon atoms) is preferred. This group may further have a substituent, but is preferably unsubstituted.

[0047] The polymer chain is preferably bonded to the polycondensable group directly or via a linking group. Such a linking group is not particularly limited, but examples thereof include an alkylene group (preferably having 1 to 12 carbon atoms, more preferably having 1 to 6 carbon atoms, and even more preferably having 1 to 3 carbon atoms), an alkenylene group (preferably having 2 to 6 carbon atoms, and more preferably having 2 to 3 carbon atoms), an arylene group (preferably having 6 to 24 carbon atoms, and more preferably having 6 to 10 carbon atoms), an oxygen atom, a sulfur atom, an imino group (—NR N -:R N represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 10 carbon atoms. ), a carbonyl group, a phosphate linking group (-OP(OH)(O)-O-), a phosphonate linking group (-P(OH)(O)-O-), or a group relating to a combination thereof. The linking group is preferably a group formed by combining an alkylene group, an arylene group, a carbonyl group, an oxygen atom, a sulfur atom, and an imino group, and more preferably a group formed by combining an alkylene group, an arylene group, a carbonyl group, an oxygen atom, a sulfur atom, and an imino group. Preferred examples of the linking group include linking groups containing a structural moiety derived from a chain transfer agent (e.g., 3-mercaptopropionic acid) or a polymerization initiator used in the synthesis of the polymer chain, and further linking groups in which such a structural moiety is bonded to a structural moiety derived from the (meth)acrylic compound (M1) that reacts with the chain transfer agent. Specific examples of the linking group include the linking group in the constituent (X) contained in the polymer synthesized in the examples. The number of atoms constituting the linking group and the number of linking atoms are as follows: In the present invention, the number of atoms constituting the linking group is preferably 1 to 36, more preferably 1 to 24, and even more preferably 1 to 12. The number of linking atoms in the linking group is preferably 12 or less, more preferably 10 or less, and particularly preferably 8 or less. The lower limit is 1 or more. The number of linking atoms refers to the minimum number of atoms connecting predetermined structural moieties. For example, in the case of -OC(=O)-CH2-CH2-S-, the number of atoms constituting the linking group is 10, but the number of linking atoms is 5.

[0048] The constituent component (X) is preferably a constituent component represented by the following formula (X1) or (X2). [ka]

[0049] In the above formula (X1), R X1 ~R X3 represents a hydrogen atom or a substituent. X1 ~R X3 The substituent that can be adopted as R is not particularly limited, and examples thereof include groups selected from the substituent Z described below. Among these, an alkyl group or a halogen atom is preferred. X1 and R X3 are preferably hydrogen atoms, and R X2 is preferably a hydrogen atom or methyl.

[0050] L X1 represents a linking group. X1 As the linking group that can be used as L, the above-mentioned linking groups that link the above-mentioned polycondensable group and the above-mentioned polymer chain can be used without any particular limitation. X1 is more preferably a group containing a -CO-O- group or an oxygen atom, and particularly preferably a -CO-O- group. X1 The number of atoms constituting the group is particularly preferably 1 to 6, and the number of connecting atoms is more preferably 1 to 3.

[0051] R X4 represents a hydrocarbon group or an alkylsilylene group. R X4 The hydrocarbon group that can be R is not particularly limited, and examples thereof include an alkylene group, an alkenyl group, and an arylene group, with an alkylene group being preferred. X4 Examples of alkylene groups that can be used as -(R) include groups in which one hydrogen atom has been removed from each of the groups corresponding to the substituent Z described below. However, the number of carbon atoms in the alkylene group is more preferably 1 to 8. X4 -L X2 When )- is an alkyleneoxy group, the alkylene group more preferably has 1 to 6 carbon atoms. R X4The alkylsilylene group that can be taken as is not particularly limited, and a preferred example is the -SiR2- group in the polymer chain having the structure represented by -(SiR2-O)n-.

[0052] L X2 represents a linking group, and has the same meaning as the linking group that can be taken as L. R X5 represents a substituent, and P R X5 The substituents which may be present may further have a substituent, but are preferably unsubstituted. n X represents the average degree of polymerization, is a number of 2 or more, and is P ) is synonymous with the average degree of polymerization n of the polymer chain having the repeating unit represented by the formula (1).

[0053] Each of the substituents and linking groups in the above formula (X1) preferably does not contain a nitrogen atom. The constituent represented by the above formula (X1) contains a repeating unit -(R X4 -L X2 )- may be one kind or two or more kinds. When the binder-forming polymer has a plurality of constituent components represented by formula (X1), the constituent components represented by formula (X1) may be the same or different.

[0054] In the component represented by formula (X1), L X1 Polymer chains bonded to -(R X4 -L X2 )n X As the -, for example, the chain made of the step-growth polymer mentioned above is preferably mentioned, and particularly preferred examples include a polymer chain made of polyether, a polymer chain made of polysiloxane, a polymer chain made of polyester, and a polymer chain made of polycarbonate.

[0055] In the above formula (X2), R X1 ~R X3 represents a hydrogen atom or a substituent, and R in formula (X1)X1 ~R X3 is synonymous with.

[0056] L X3 represents a linking group. X3 The linking group that can be used as the linking group is not particularly limited and can be any of the above-mentioned linking groups that link the polycondensable group and the polymer chain. However, a linking group containing a structural part derived from a chain transfer agent or the like used in synthesizing the polymer chain is more preferred, and a linking group in which this structural part is bonded to a structural part derived from a (meth)acrylic compound (M1) that reacts with a chain transfer agent is particularly preferred. For example, a -COO-alkylene group-OCO-alkylene group-S- group (where the alkylene group is R X4 Specific examples include the linking group contained in the reaction product of 3-mercaptopropionic acid and glycidyl (meth)acrylate.

[0057] In the above formula (X2), R X6 ~R X8 represents a hydrogen atom or a substituent, and R in formula (X1) X1 ~R X3 is synonymous with. L X4 represents a single bond or a linking group. X4 As the linking group that can be used as L, the above-mentioned linking groups that link the above-mentioned polycondensable group and the above-mentioned polymer chain can be used without any particular limitation. X4 The linking group that can be used is a group containing a -CO-O- group or -CO-NR N -group(R N is as defined above.) is more preferred, and a group containing a -CO-O- group or a -CO-NR N The number of atoms constituting the linking group and the number of linking atoms are as described above. X4 The number of atoms constituting the group is particularly preferably 1 to 6, and the number of connecting atoms is more preferably 1 to 3. R X9 represents a hydrogen atom or a substituent, and is preferably a substituent. X9The substituents that can be taken as R are not particularly limited, and examples thereof include groups selected from the substituent Z described below. Among these, alkyl groups and aryl groups are preferred, and long-chain alkyl groups having 4 or more carbon atoms are more preferred. X9 The substituents that can be taken as may further have a substituent (for example, a halogen atom), but are preferably unsubstituted.

[0058] m X represents the average degree of polymerization, is a number of 2 or more, and is P ) is synonymous with the average degree of polymerization n of the polymer chain having the repeating unit represented by the formula (1).

[0059] Each of the substituents and linking groups in the above formula (X2) preferably does not contain a nitrogen atom. The constituent component represented by the above formula (X2) may have one type of repeating unit or two or more types of repeating units in one component. When the binder-forming polymer has a plurality of constituent components represented by formula (X2), the constituent components represented by formula (X2) may be the same or different.

[0060] In the component represented by formula (X2), L X3 As the polymer chain bonded to the above, for example, the chain made of the chain-polymerized polymer mentioned above is preferably mentioned, and the polymer chain made of a (meth)acrylic polymer and the polymer chain made of polystyrene are particularly preferably mentioned.

[0061] The constituent (X) is preferably a constituent derived from a (meth)acrylic acid polymer chain ester compound having an ethylenically unsaturated group as a polycondensable group and containing -C(=O)-O- as a linking group.

[0062] The component (X) can further enhance the excluded volume effect between polymer binders to achieve excellent dispersion properties, for example, an SP value of 16.0 to 22.5 MPa. 1 / 2 Preferably, the pressure is 16.0 to 21.5 MPa. 1 / 2The SP value of the component (X) is a value calculated by the method described later. The difference (absolute value) in the SP value between the component (X) and the dispersion medium described later is not particularly limited, but from the viewpoint of improving the solubility of the polymer binder in the dispersion medium and dispersion characteristics, it is preferably 0.0 to 6.0 MPa. 1 / 2 is preferably 0.0 to 3.0 MPa 1 / 2 More preferably, 0.0 to 2.0 MPa 1 / 2 More preferably, 0.0 to 1.0 MPa 1 / 2 is particularly preferred. The component (X) may be any component whose repeating unit has a degree of polymerization of 2 or more, but is preferably a component derived from a macromonomer having a number average molecular weight of 200 or more as measured by the method described below. From the viewpoint of dispersion characteristics, the number average molecular weight of the macromonomer is preferably 1,000 to 100,000, more preferably 1,000 to 50,000, and even more preferably 2,000 to 20,000, and can also be 2,000 to 10,000.

[0063] The constituent component (X) is not particularly limited, but is preferably a constituent component derived from a (meth)acrylic compound (M1) described below, a constituent component derived from a vinyl compound (M2) described below, or a constituent component derived from a compound obtained by introducing (substituting) a polymer chain into these compounds (M1) or (M2).

[0064] Specific examples of the component (X) include those contained in the polymers synthesized in the examples and those shown below, but the present invention is not limited to these. Y and R Z represents a linking group or a substituent. In the following specific examples, the degree of polymerization of the repeating unit is specifically shown, but it can be changed appropriately in the present invention.

[0065] [ka]

[0066] - Component (A) - The binder-forming polymer has component (A) which has at least one (one type) of functional group selected from the following functional group group (a): When the binder-forming polymer has component (A), it can enhance the adsorptivity or adhesion to solid particles. The constituent component (A) may have at least one (one type) functional group, and usually preferably has 1 to 3 types of functional groups. This component (A) may have any of the above functional groups, and examples thereof include components derived from polycondensable compounds having at least one functional group selected from the functional group group (a) below. The polycondensable compound is not particularly limited as long as it has the above functional group, but is preferably a compound having a polycondensable group, a polar functional group or a substituent having the above functional group, and, optionally, a linking group connecting the polycondensable group and the substituent. The polycondensable group has the same meaning as the polycondensable group in the component (X). The substituent is not particularly limited, but examples include groups selected from the substituent Z described below, with alkyl groups being preferred. The linking group may be any of the above-mentioned linking groups connecting the polycondensable group and the polymer chain, without any particular limitation. However, a -CO-O- group or a -CO-NR N The - group is particularly preferred.

[0067] Component (A) preferably does not have a polymer chain; for example, the following substituent having the functional group is preferably a non-polymerizable substituent, and further preferably has a polymer chain without the functional group. In one embodiment of the present invention, when component (A) has a polymer chain, it is assigned to an appropriate component depending on the strength of the effects of the polymer chain and the functional group, but it is preferably assigned to component (A), for example. Furthermore, component (A) may contain a nitrogen atom, but preferably does not contain one (a component that does not correspond to component (N)). In a preferred embodiment of the present invention, when component (A) contains a nitrogen atom that forms an amino group (when it also corresponds to component (N)), it is assigned to component (N) rather than component (A).

[0068] <Functional group group (a)> Sulfonic acid group (sulfo group), phosphoric acid group, phosphonic acid group, carboxy group, hydroxy group, oxetane group, epoxy group, dicarboxylic acid anhydride group, thiol group (sulfanyl group), ether group, thioether group, thioester group, fluoroalkyl group, and salts thereof

[0069] The sulfonic acid group, phosphoric acid group (phosphoryl group), phosphonic acid group, and the like included in the functional group group (a) are not particularly limited, but each has the same meaning as the corresponding group of the substituent Z described below. The dicarboxylic acid anhydride group is not particularly limited, but includes groups formed by removing one or more hydrogen atoms from a dicarboxylic acid anhydride, as well as the constituent components themselves formed by copolymerization of polymerizable dicarboxylic acid anhydrides. As the group formed by removing one or more hydrogen atoms from a dicarboxylic acid anhydride, a group formed by removing one or more hydrogen atoms from a cyclic dicarboxylic acid anhydride is preferred. Examples include acyclic dicarboxylic acid anhydrides such as acetic anhydride, propionic anhydride, and benzoic anhydride, and cyclic dicarboxylic acid anhydrides such as maleic anhydride, phthalic anhydride, fumaric anhydride, succinic anhydride, and itaconic anhydride. The polymerizable dicarboxylic acid anhydride is not particularly limited, but includes dicarboxylic acid anhydrides having an unsaturated bond in the molecule, preferably polymerizable cyclic dicarboxylic acid anhydrides. Specific examples include maleic anhydride and itaconic anhydride.

[0070] The ether group (-O-), thioether group (-S-), and thioester group (-CO-S-, -CS-O-, -CS-S-) each refer to the bond shown in parentheses. The terminal group bonded to these groups is not particularly limited, and examples thereof include groups selected from the substituent Z described below, such as an alkyl group. Note that ether groups include carboxy groups, hydroxy groups, oxetane groups, epoxy groups, dicarboxylic anhydride groups, etc., but the -O- contained in these groups is not considered an ether group. The same applies to thioether groups. In one embodiment of the present invention, the ether group, thioether group, and thioester group are groups that do not constitute the above-mentioned polymer chain, and are, for example, groups represented by the above formula (L P ) is preferably not a group corresponding to L in The fluoroalkyl group is an alkyl group or a cycloalkyl group in which at least one hydrogen atom is substituted with a fluorine atom, and the number of carbon atoms therein is preferably 1 to 20, more preferably 2 to 15, and even more preferably 3 to 10. The number of fluorine atoms on the carbon atom may be such that some or all of the hydrogen atoms have been replaced (perfluoroalkyl group). Groups capable of forming salts, such as sulfonic acid groups (sulfo groups), phosphoric acid groups, phosphonic acid groups, and carboxy groups, may form salts, such as various metal salts, ammonium salts, and amine salts. The functional group contained in component (A) is preferably a carboxyl group or a hydroxyl group in terms of the adsorptivity (adhesion) to solid particles and further dispersion characteristics. When component (A) contains two or more types of functional groups, the combination thereof is not particularly limited and can be determined appropriately. For example, a combination of a carboxyl group and a hydroxyl group is preferred.

[0071] The polycondensable compound from which component (A) is derived is not particularly limited as long as it has the above-mentioned functional group, and examples thereof include compounds in which the above-mentioned functional group has been introduced into the raw material compound constituting the binder-forming polymer. Examples thereof include the (meth)acrylic compound (M1) or vinyl compound (M2) described below, or compounds in which the above-mentioned functional group has been introduced into these compounds (M1) or (M2).

[0072] - Component (N) - The constituent component (N) that forms the binder-forming polymer is a constituent component that contains a nitrogen atom. If the binder-forming polymer contains an excess of the constituent component (N), the polymer binder is prone to oxidative degradation, which reduces the cycle characteristics of the all-solid-state secondary battery. Therefore, in the present invention, in order to suppress the deterioration of the cycle characteristics, the constituent component (N) is contained in an amount of less than 10 mol % of all constituent components (that form the main chain) of the binder-forming polymer. This constituent component (N) may contain a nitrogen atom anywhere in the component, and has the nitrogen atom in a partial structure incorporated into the main chain of the binder-forming polymer or in a side chain.

[0073] In a preferred embodiment of the present invention, the constituent (N) is a constituent containing a nitrogen atom, and may be a constituent having a polymer chain or a constituent not having a polymer chain (a low-molecular-weight constituent). The nitrogen atom is preferably present in a partial structure other than the polymer chain in the side chain of the binder-forming polymer. In another preferred embodiment of the present invention, the constituent (N) is a constituent containing a nitrogen atom that forms an amino group in a partial structure incorporated into the main chain of the polymer or in a partial structure that becomes a side chain other than the polymer chain. In this embodiment, the amino group possessed by the constituent (N) is a monovalent amino group (—NR NN 2), a divalent amino group (also called an imino group) NN ), trivalent amino group (-N<), and further tetravalent amino group (ammonium salt). NN represents a hydrogen atom or a substituent (preferably the substituent Z described below), provided that the amino group present in the partial structure incorporated into the main chain of the polymer is a characteristic group that becomes an amino group by itself and does not form a functional group (bond) such as an amide bond, imide bond, urethane bond, or urea bond together with a characteristic group or functional group such as a carbonyl group or an ester bond in the main chain. In both of the above embodiments, the polymer chain may be a molecular chain in which two or more repeating units of one or more types are bonded together, and specific examples thereof include the polymer chains described above for the component (X). The component (A) may have a functional group selected from the functional group (a) above, but preferably does not have one. As described above, the components (X), (A), and (N) differ from one another in that they each essentially contain a polymer chain, a specific functional group, or the above-mentioned nitrogen atom. However, when a certain component corresponds to all of the components (X), (A), and (N), it is also a preferred embodiment to preferentially assign that certain component to the component (N).

[0074] Examples of such component (N) include components derived from polycondensation compounds having a polycondensable group, a non-polymeric substituent, and, optionally, a linking group connecting the polycondensable group and the substituent. The polycondensable group, non-polymeric substituent, and linking group are synonymous with the polycondensable group, substituent, and linking group in component (A), respectively. Examples of component (N) include components constituting polymers such as polyalkyleneimines, polyalkylamines, poly(meth)acrylalkylamines, poly(meth)acrylamides, poly(meth)acrylonitriles, polyamides, polyimides, polyureas, and polyurethanes, as well as components having amino groups as substituents. In one embodiment of the present invention, among the components constituting the above polymers, components constituting polyalkyleneimines, polyalkylamines, poly(meth)acrylalkylamines, poly(meth)acrylamides, and poly(meth)acrylonitriles are preferred. The binder-forming polymer may contain one or more of the above-mentioned constituent components. The binder-forming polymer may contain, in addition to the above-mentioned components, other components, for example, components derived from a (meth)acrylic compound (M1) or a vinyl compound (M2) described below. In the present invention, it is preferred that each of the constituent components, particularly the other constituent components, does not have a crosslinkable group, for example, an ethylenically unsaturated group such as a carbon-carbon double bond.

[0075] - Binder-forming polymer - The binder-forming polymer is not particularly limited as long as it is a polymer that has the above-mentioned components and dissolves in the dispersion medium, and various known polymers can be used. The primary structure of the binder-forming polymer (the bonding mode of the constituent components) is not particularly limited, and may be any bonding mode such as a random structure, a block structure, an alternating structure, or a graft structure. The molecular structure of the binder-forming polymer is also not particularly limited, and examples thereof include a branched structure and a multi-branched structure (graft structure, star structure, dendritic structure, etc.). Of these, a branched structure or a star structure is more preferred. In the present invention, a (multiple) branched structure refers to a polymer in which the polymer chain has a branched structure, such as a structure in which one or more separate polymer chains (side chains) are bonded to the main chain. A branched polymer refers to a structure in which one polymer chain is bonded to the main chain in a branched manner (as a side chain), such as a polymer structure containing a component (X) having a polymer chain. Among multi-branched structures, a star-structured polymer (also referred to as a star polymer) has a structure in which multiple (usually three or more) arm portions (polymer chains) are radially bonded to a central core portion (branching point), and one polymer molecule usually has one core portion. In contrast, a graft-structured polymer refers to a polymer in which multiple polymer chains (as side chains) are bonded to a single main chain in a branched manner, and a dendritic-structured polymer refers to a polymer having multiple core portions. In the star polymer, the core portion is an atom or linking group having a valence of three or more, and the valence is preferably three to eight, and more preferably three to six. The core portion can be appropriately selected from known core portions, and examples thereof include the core portions described below. In the star polymer, the number of arm portions bonded to one core portion is usually three or more, and is preferably the same as the valence of the core portion.

[0076] The binder-forming polymer will be described below, but the contents thereof can be applied to the polymer chains constituting the arm portions and each polymer chain (main chain and side chain) in binder-forming polymers having a linear structure and also in binder-forming polymers having a (multiple) branched structure. Preferred examples of binder-forming polymers (i.e., including the above-mentioned arm portions and each polymer chain in addition to a polymer having a linear structure) include polymers having at least one bond selected from a urethane bond, a urea bond, an amide bond, an imide bond, an ester bond, and a silyloxy bond, or a polymer chain of a carbon-carbon double bond in the main chain. In the present invention, the main chain of the binder-forming polymer is preferably a molecular chain formed by a polymer other than a polyalkyleneimine and a polymer other than a polyalkylamine.

[0077] In the present invention, the main chain of a polymer (including the above-mentioned arm portions and each polymer chain) refers to a linear molecular chain in which all other molecular chains constituting the polymer can be considered as branched chains or pendant groups relative to the main chain. Typically, the longest chain among the molecular chains constituting the polymer becomes the main chain, although this depends on the mass average molecular weight of the branched chains considered as branched chains or pendant groups. However, the terminal groups at the polymer ends are not included in the main chain. In contrast, the side chain of a polymer refers to a branched chain other than the main chain, and includes short and long chains. The terminal group of a polymer is not particularly limited and can be an appropriate group depending on the polymerization method, etc. Examples include a hydrogen atom, an alkyl group, an aryl group, a hydroxyl group, and even residues of a polymerization initiator.

[0078] The bond is not particularly limited as long as it is contained in the main chain of the polymer, and may be contained in a constituent component (repeating unit) and / or as a bond connecting different constituent components. Furthermore, the number of bonds contained in the main chain is not limited to one, but may be two or more, preferably one to six, and more preferably one to four. In this case, the bonding pattern of the main chain is not particularly limited, and may include two or more types of bonds randomly, or may be a segmented main chain consisting of segments having specific bonds and segments having other bonds. Examples of polymers having a urethane bond, urea bond, amide bond, imide bond, or ester bond in the main chain include sequential polymerization (polycondensation, polyaddition, or addition-condensation) polymers such as polyurethane, polyurea, polyamide, polyimide, polyester, and polysiloxane, or copolymers thereof. The copolymer may be a block copolymer having each of the above polymers as a segment, or a random copolymer in which the constituent components of two or more of the above polymers are randomly bonded.

[0079] Examples of polymers having a polymer chain of carbon-carbon double bonds in the main chain include chain-polymerized polymers such as fluorine-based polymers (fluorine-containing polymers), hydrocarbon-based polymers, vinyl polymers, (meth)acrylic polymers, etc. The polymerization mode of these chain-polymerized polymers is not particularly limited, and may be any of block copolymers, alternating copolymers, and random copolymers, with random copolymers being preferred. The binder-forming polymer can be appropriately selected from the above-mentioned polymers, but vinyl polymers or (meth)acrylic polymers are preferred.

[0080] Examples of (meth)acrylic polymers suitable as binder-forming polymers include copolymers of the above-mentioned components, and also copolymers with an appropriate (meth)acrylic compound (M1), which contain 50% by mass or more of components derived from (meth)acrylic compounds. When components (X), (A), and (N) are derived from (meth)acrylic compounds, the content of each component is included in the total content of the components derived from (meth)acrylic compounds. The content of the components derived from (meth)acrylic compounds is more preferably 60% by mass or more, and particularly preferably 70% by mass or more. The upper limit of the content can be 100% by mass, but can also be 97% by mass or less. Copolymers with a vinyl compound (M2) other than the (meth)acrylic compound (M1) are also preferred as (meth)acrylic polymers. In this case, the content of the components derived from the vinyl compound (M2) is 50% by mass or less, preferably 3 to 40% by mass, and more preferably 3 to 30% by mass. The (meth)acrylic polymer may contain a component derived from a (meth)acrylamide compound as one of its constituent components (excluding the components forming the polymer chain), but the content of the component derived from a (meth)acrylamide compound relative to the total components constituting the polymer is preferably less than 50 mol %, more preferably 40 mol % or less. Vinyl polymers suitable as binder-forming polymers include copolymers of the above-mentioned components, and also copolymers with an appropriate vinyl compound (M2), including copolymers containing 50% by mass or more of vinyl compound-derived components. When components (X), (A), and (N) are vinyl compound-derived components, the content of each component is included in the content of vinyl compound-derived components. The content of vinyl compound-derived components is preferably 60% by mass or more, and more preferably 65% ​​by mass or more. The upper limit of the content can be 100% by mass, but is preferably 95% by mass or less, and more preferably 90% by mass or less. Vinyl polymers are also preferably copolymers with a (meth)acrylic compound (M1). In this case, the content of the (meth)acrylic compound (M1)-derived component may be less than 50% by mass, and is preferably 0 to 40% by mass, and more preferably 0 to 30% by mass.

[0081] Examples of the (meth)acrylic compound (M1) include (meth)acrylic acid ester compounds, (meth)acrylamide compounds, and (meth)acrylonitrile compounds, except for compounds from which the above-mentioned components (X), (A), and (N) are derived. Among these, (meth)acrylic acid ester compounds are preferred. Examples of (meth)acrylic acid ester compounds include (meth)acrylic acid alkyl ester compounds and (meth)acrylic acid aryl ester compounds, with (meth)acrylic acid alkyl ester compounds being preferred. The number of carbon atoms in the alkyl group constituting the (meth)acrylic acid alkyl ester compound is not particularly limited, but can be, for example, 1 to 24. From the viewpoints of dispersion properties and adhesion, it is preferably 3 to 20, more preferably 4 to 16, and even more preferably 6 to 14. The number of carbon atoms in the aryl group constituting the aryl ester is not particularly limited, but can be, for example, 6 to 24, preferably 6 to 10, and more preferably 6. In the (meth)acrylamide compound, the nitrogen atom of the amide group may be substituted with an alkyl group or an aryl group.

[0082] The vinyl compound (M2) is not particularly limited, but among vinyl compounds copolymerizable with the (meth)acrylic compound (M1), vinyl compounds other than the vinyl compounds that derive the above-mentioned components (X), (A), and (N) are preferred, such as aromatic vinyl compounds such as styrene compounds, vinyl naphthalene compounds, vinyl carbazole compounds, vinyl imidazole compounds, and vinyl pyridine compounds, as well as allyl compounds, vinyl ether compounds, vinyl ester compounds (e.g., vinyl acetate compounds), and dialkyl itaconate compounds. Examples of vinyl compounds include the "vinyl monomers" described in JP 2015-88486 A. The (meth)acrylic compound (M1) and the vinyl compound (M2) may have a substituent, but in one preferred embodiment, they are unsubstituted. The substituent is not particularly limited and may be a group selected from the substituent Z described below, but is preferably a group other than the functional groups included in the functional group group (a) described above.

[0083] The (meth)acrylic compound (M1) and the vinyl compound (M2) are preferably compounds represented by the following formula (b-1), which are preferably different from the compounds from which the above-mentioned component (X) or component (A) is derived.

[0084] [ka]

[0085] In the formula, R 1 represents a hydrogen atom, a hydroxy group, a cyano group, a halogen atom, an alkyl group (preferably having 1 to 24 carbon atoms, more preferably having 1 to 12 carbon atoms, and particularly preferably having 1 to 6 carbon atoms), an alkenyl group (preferably having 2 to 24 carbon atoms, more preferably having 2 to 12 carbon atoms, and particularly preferably having 2 to 6 carbon atoms), an alkynyl group (preferably having 2 to 24 carbon atoms, more preferably having 2 to 12 carbon atoms, and particularly preferably having 2 to 6 carbon atoms), or an aryl group (preferably having 6 to 22 carbon atoms, and more preferably having 6 to 14 carbon atoms). Among these, a hydrogen atom or an alkyl group is preferred, and a hydrogen atom or a methyl group is more preferred.

[0086] R2 represents a hydrogen atom or a substituent. 2 The substituent that can be adopted as the alkyl group is not particularly limited, but examples thereof include an alkyl group (which may be branched but is preferably straight), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably 2 to 6, and particularly preferably 2 or 3), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 14), an aralkyl group (preferably having 7 to 23 carbon atoms, more preferably 7 to 15), and a cyano group. The number of carbon atoms in the alkyl group is the same as the number of carbon atoms in the alkyl group constituting the above-mentioned (meth)acrylic acid alkyl ester compound, and the preferred range is also the same.

[0087] L 1 is a linking group, and is not particularly limited, but the above-mentioned linking groups that link the above-mentioned polycondensable group and the above-mentioned polymer chain can be used without any particular limitation. 1 is particularly preferably a —CO—O— group. L 1 is a -CO-O- group or a -CO-N(R N )-group(R N is as described above.) is employed, the compound represented by the above formula (b-1) corresponds to the (meth)acrylic compound (M1), and the others correspond to the vinyl compound (M2).

[0088] n is 0 or 1, preferably 1, provided that -(L 1 ) n -R 2 When R represents one type of substituent (for example, an alkyl group), n is set to 0, and R 2 is the substituent (alkyl group).

[0089] Specific examples of the (meth)acrylic compound (M1) and the vinyl compound (M2) include compounds that lead to the constituent components of the polymers synthesized in the examples in addition to those mentioned above, but the present invention is not limited to these. The binder-forming polymer may contain one or more of the above (meth)acrylic compounds (M1) or vinyl compounds (M2).

[0090] The content of each component in the binder-forming polymer is not particularly limited and is determined taking into consideration the physical properties of the entire polymer, etc., and is set, for example, within the following ranges. The content of each component in the binder-forming polymer is set, for example, within the following range so that the total content of all components is 100% by mass. The content of component (X) is not particularly limited, but can be appropriately adjusted based on the total content of all components, taking into consideration, for example, dispersion characteristics, etc. The content of component (X) is preferably 20 to 100 mass%, more preferably 30 to 100 mass%, and even more preferably 40 to 97 mass%. The content of component (A) is not particularly limited, but is preferably 0.1 to 20 mass %, and more preferably 0.1 to 10 mass %, of the total content of all components, from the viewpoints of, for example, dispersion characteristics and further the binding property of solid particles. As described above, the content of component (N) may be less than 10 mol% relative to the total number of moles of all components. For example, from the viewpoint of resistance to oxidative degradation, it is preferably 5 mol% or less, and more preferably 3 mol% or less. The lower limit is preferably 0 mol% from the viewpoint of cycle characteristics, but in practice it can be set to 2 mol%. The content of component (N) is preferably 5 mass% or less, more preferably 0 to 3 mass%, and even more preferably 0 to 2 mass%, based on the total content of all components. The content of components other than component (X), component (A), and component (N) (also referred to as other components) is not particularly limited, but is preferably 10 to 80 mass %, more preferably 20 to 50 mass %, of the total content of all components.

[0091] The binder-forming polymer may have a substituent. The substituent is not particularly limited, but is preferably a group selected from the following substituent Z.

[0092] As described above, the hyperbranched polymer has a core portion and at least three polymeric arms bonded to the core portion. The core portion is preferably an atomic group having a molecular weight of 200 or more, more preferably an atomic group having a molecular weight of 300 or more. The upper limit is preferably 5,000 or less, more preferably 4,000 or less, and even more preferably 3,000 or less. The core portion preferably does not consist solely of tetravalent carbon atoms. The valence of the core portion is not particularly limited as long as it is trivalent or more, and is preferably, for example, trivalent to octavalent, and more preferably trivalent to hexavalent. The core portion can be, for example, L-(S-) of the following formula (1): n The arm portion is preferably a linking group represented by the following formula (1): 1 It is preferable that:

[0093] The hyperbranched polymer is preferably a polymer represented by the following formula (1).

[0094] [ka]

[0095] In the formula, L represents a trivalent or higher linking group. The valence of L is practically octavalent or less, and preferably 3 to 6. P 1 represents a polymer chain. n represents an integer of 3 or more, and is the same as the valence of L. n P 1 may be the same or different. 1 constitutes an arm portion. At least one, preferably two or more, and more preferably all n of the n polymer chains are polymer chains derived from the binder-forming polymer.

[0096] - Core part - The core of the hyperbranched polymer preferably has a sulfur atom, and more preferably has a sulfur atom at a linking position with the arm (a position directly linked to the arm). The core more preferably has a linking group of the following formula (1a): -(CR f 2)n -O(C=O)-(CR f 2) n -S- (1a) In formula (1a), n is an integer of 0 to 10, preferably an integer of 1 to 6, and more preferably 1 or 2. R f represents a hydrogen atom or a substituent, and a hydrogen atom is preferred. f The substituents that can be adopted as (I) are not particularly limited, and examples thereof include halogen atoms (e.g., fluorine, chlorine, iodine, and bromine atoms), alkyl groups (preferably having 1 to 12 carbon atoms, more preferably having 1 to 6 carbon atoms, and particularly preferably having 1 to 3 carbon atoms), alkoxy groups (preferably having 1 to 12 carbon atoms, more preferably having 1 to 6 carbon atoms, and particularly preferably having 1 to 3 carbon atoms), acyl groups (preferably having 2 to 12 carbon atoms, more preferably having 2 to 6 carbon atoms, and particularly preferably having 2 to 3 carbon atoms), aryl groups (preferably having 6 to 22 carbon atoms, more preferably having 6 to 10 carbon atoms), alkenyl groups (preferably having 2 to 12 carbon atoms, more preferably having 2 to 5 carbon atoms), hydroxy groups, nitro groups, cyano groups, mercapto groups, amino groups, amide groups, and acidic groups (e.g., carboxyl groups, phosphate groups, and sulfonic acid groups) (this group of substituents is referred to as "Substituent T"). The acidic groups may each be their salts. Examples of counter ions include alkali metal ions, alkaline earth metal ions, ammonium ions, and alkylammonium ions.

[0097] The hyperbranched polymer is more preferably represented by the following formula (2).

[0098] [ka]

[0099] In formula (2), R 5represents a hydrogen atom or a substituent (e.g., substituent T). Among these, a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6, and particularly preferably 1 to 3), a substituted or unsubstituted alkoxy group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6, and particularly preferably 1 to 3), and a substituted or unsubstituted aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 14 carbon atoms) are preferred. Examples of the substituent that the above alkyl group, alkoxy group, and aryl group may have include the substituent T, and among these, a hydroxy group is preferred. The above alkyl group may have an oxygen atom therebetween, and may be, for example, an oligooxyalkylene group. The oligoalkylene group is preferably one represented by the following formula (OA). Examples of the alkyl group having a halogen atom include a fluoroalkyl group. *-[L R -O] mR -L R -* (OA) In formula (OA), L R represents an alkylene group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and particularly preferably 1 to 3 carbon atoms). R may have an optional substituent T. mR is preferably an integer of 1 to 1000, more preferably an integer of 1 to 100, further preferably an integer of 1 to 30, and particularly preferably an integer of 1 to 10. * indicates a bonding position.

[0100] In formula (2), R f and P 1 are R in the above formula (1a), respectively. f and P in the above formula (1) 1 is synonymous with. Each n1 is independently an integer of 0 to 10, preferably 0 to 8, more preferably 0 to 6, and further preferably 1 to 3. k 1 is an integer of 0 to 3, preferably 0 to 2. l 1 is an integer of 0 to 4, preferably 1 to 4, more preferably 2 to 4, and even more preferably 2 to 3. m 1 is an integer of 0 to 3, preferably 0 to 2, and more preferably 0 to 1. k 2 is an integer of 0 to 3, preferably 0 to 2, and more preferably 0 to 1. l 2 is an integer of 0 to 3, preferably 1 to 3, and more preferably 2 to 3. m 2 is an integer of 0 to 3, preferably 0 to 2, and more preferably 0 to 1. However, k 1 and 1 and m 1 The sum of k and k is 4 or less, and preferably 3 or less. 2 and 2 and m 2 The sum of is 3 or less. 1 The number of groups having the formula is 3 or more, and more preferably 4 or more. 1 +[l 2 ×(4-k 1 -l 1 -m 1 )] is 3 or more, preferably 4 or more. The upper limit is preferably 8 or less, more preferably 6 or less. 1 It is preferable to form a connection part between the core part and the arm part P via -S-. 1 It is preferable that the and are linked together. In formula (2), groups represented by the same symbol may be the same or different.

[0101] Specific examples A-1 to A-9 of compounds (substrates) from which the core portion is derived are listed below, but those that can be used in the present invention are not limited to these specific examples. Note that, in these compounds, the hydrogen atom of the sulfanyl group (-SH group) is attached to the arm portion P 1 Alternatively, by being substituted with a group containing this, a hyperbranched polymer represented by the above formula (1) or formula (2) is obtained.

[0102] [ka]

[0103] The compound that leads to the core portion of the hyperbranched polymer is also preferably one represented by any one of the following formulas (3) to (8).

[0104] [ka]

[0105] In the formulas (3) to (8), R represents SH, a hydroxy group, or an alkyl group (preferably having 1 to 3 carbon atoms), provided that there are three or more SH groups in the molecule. T represents a linking group, and is preferably a group represented by any one of the following formulae (T1) to (T6), or a linking group formed by combining two or more (preferably two or three) of these groups. Examples of combined linking groups include a linking group (-OCO-alkylene group) formed by combining a linking group represented by formula (T6) with a linking group represented by formula (T1). In the groups represented by formulae (T1) to (T6), any of the bonding moieties bonded to R may be present, but when T is an oxyalkylene group (a group represented by formulae (T2) to (T5)) or an -OCO-alkylene group, it is preferred that the terminal carbon atom (bonding moiety) be bonded to R. Multiple Ts present in each of the above formulae may be the same or different. Z is preferably a linking group represented by the following formula (Z1) or (Z2).

[0106] [ka]

[0107] In the formulas (3) to (8), n is an integer, preferably an integer of 0 to 14, more preferably an integer of 0 to 5, and particularly preferably an integer of 1 to 3. In formula (T1) and formula (Z1), m is an integer of 1 to 8, preferably an integer of 1 to 5, and more preferably an integer of 1 to 3. Multiple R and T present in one molecule may be the same or different. When the terminal of T is an oxyalkylene group, it is preferable that the terminal on the carbon atom side is bonded to the above-mentioned R. Z 3 is a linking group, and is preferably an alkylene group having 1 to 12 carbon atoms, and more preferably an alkylene group having 1 to 6 carbon atoms. Of these, a 2,2-propanediyl group is particularly preferred.

[0108] - Arm section - At least one arm of the hyperbranched polymer preferably contains the above-mentioned component (X), more preferably the above-mentioned component (X) and component (A), with the component (N) being present in an amount of less than 10 mol % of all the components constituting the arm (i.e., containing a chain derived from the binder-forming polymer). For example, an arm containing component (X) having a polymer chain with a polyethylene chain as the main chain as a polymerizable group (e.g., a polymer chain composed of the above-mentioned chain-polymerized polymer) is preferred. In one preferred embodiment of the present invention, preferably two or more, more preferably all, of the arms of the hyperbranched polymer contain the above-mentioned component (X), preferably the components (X) and (A), with the component (N) being present in an amount of less than 10 mol % of all the components constituting the arm. The number-average molecular weight (measured by the method described below) of the arm is appropriately set depending on the molecular weight of the hyperbranched polymer, but is preferably 200 or more, more preferably 500 or more. The upper limit is preferably 1,000,000 or less, more preferably 500,000 or less, and even more preferably 5,000 or less.

[0109] The binder-forming polymer can be synthesized by selecting raw material compounds by a known method depending on the type of bond in the main chain, and subjecting the raw material compounds to polyaddition polymerization, condensation polymerization, chain polymerization, or the like.

[0110] - Substitution base Z - Alkyl groups (preferably alkyl groups having 1 to 20 carbon atoms, for example, methyl, ethyl, isopropyl, t-butyl, pentyl, heptyl, 1-ethylpentyl, benzyl, 2-ethoxyethyl, 1-carboxymethyl, etc.), alkenyl groups (preferably alkenyl groups having 2 to 20 carbon atoms, for example, vinyl, allyl, oleyl, etc.), alkynyl groups (preferably alkynyl groups having 2 to 20 carbon atoms, for example, ethynyl, butadiynyl, phenylethynyl, etc.), cycloalkyl groups (preferably cycloalkyl groups having 3 to 20 carbon atoms, for example, cyclopropyl, cyclopentyl, etc.), cyclohexyl, 4-methylcyclohexyl, etc. In the present invention, the term "alkyl group" generally includes a cycloalkyl group, but will be described separately here.), aryl groups (preferably aryl groups having 6 to 26 carbon atoms, for example, phenyl, 1-naphthyl, 4-methoxyphenyl, 2-chlorophenyl, 3-methylphenyl, etc.), aralkyl groups (preferably aralkyl groups having 7 to 23 carbon atoms, for example, benzyl, phenethyl, etc.), heterocyclic groups (preferably heterocyclic groups having 2 to 20 carbon atoms, more preferably at least one oxygen atom, sulfur atom, nitrogen atom, etc.), The heterocyclic group includes an aromatic heterocyclic group and an aliphatic heterocyclic group. Examples of the heterocyclic group include a tetrahydropyran ring group, a tetrahydrofuran ring group, 2-pyridyl, 4-pyridyl, 2-imidazolyl, 2-benzimidazolyl, 2-thiazolyl, 2-oxazolyl, a pyrrolidone group, etc.), an alkoxy group (preferably an alkoxy group having 1 to 20 carbon atoms, for example, methoxy, ethoxy, isopropyloxy, benzyloxy, etc.), an aryloxy group (preferably an aryloxy group having 6 to 26 carbon atoms, for example, phenoxy, 1-naphthyloxy, etc.), and the like. oxy, 3-methylphenoxy, 4-methoxyphenoxy, etc.), heterocyclic oxy groups (groups in which an -O- group is bonded to the above heterocyclic group), alkoxycarbonyl groups (preferably alkoxycarbonyl groups having 2 to 20 carbon atoms, for example, ethoxycarbonyl, 2-ethylhexyloxycarbonyl, dodecyloxycarbonyl, etc.), aryloxycarbonyl groups (preferably aryloxycarbonyl groups having 6 to 26 carbon atoms, for example, phenoxycarbonyl, 1-naphthyloxycarbonyl, 3-methylphenoxycarbonyl, 4-methoxyphenoxycarbonyl, etc.),Heterocyclic oxycarbonyl groups (groups in which an -O-CO- group is bonded to the above heterocyclic group), amino groups (preferably containing an amino group having 0 to 20 carbon atoms, an alkylamino group, or an arylamino group, for example, amino (-NH2), N,N-dimethylamino, N,N-diethylamino, N-ethylamino, anilino, etc.), sulfamoyl groups (preferably containing a sulfamoyl group having 0 to 20 carbon atoms, for example, N,N-dimethylsulfamoyl, N-phenylsulfamoyl, etc.), acyl groups (alkylcarbonyl groups, alkenylcarbonyl groups, alkynylcarbonyl groups, arylcarbonyl groups, etc.), and heterocyclic carbonyl groups, preferably acyl groups having 1 to 20 carbon atoms, such as acetyl, propionyl, butyryl, octanoyl, hexadecanoyl, acryloyl, methacryloyl, crotonoyl, benzoyl, naphthoyl, and nicotinoyl; acyloxy groups (including alkylcarbonyloxy groups, alkenylcarbonyloxy groups, alkynylcarbonyloxy groups, and heterocyclic carbonyloxy groups, preferably acyloxy groups having 1 to 20 carbon atoms, such as acetyloxy, propionyloxy, butyryloxy, octanoyloxy, and hexadecanoyl); Examples of such groups include aryloxy groups (preferably aryloxy groups having 7 to 23 carbon atoms, such as benzoyloxy and naphthoyloxy), aryloxy groups (preferably aryloxy groups having 7 to 23 carbon atoms, such as benzoyloxy and naphthoyloxy), carbamoyl groups (preferably carbamoyl groups having 1 to 20 carbon atoms, such as N,N-dimethylcarbamoyl and N-phenylcarbamoyl), acylamino groups (preferably acylamino groups having 1 to 20 carbon atoms, such as acetylamino and benzoylamino), alkylthio groups (preferably alkylthio groups having 1 to 20 carbon atoms, such as benzoyloxy and naphthoyloxy), and alkylthio groups (preferably alkylthio groups having 1 to 20 carbon atoms). an arylthio group (preferably an arylthio group having 6 to 26 carbon atoms, for example, phenylthio, 1-naphthylthio, 3-methylphenylthio, 4-methoxyphenylthio), a heterocyclic thio group (a group in which an -S- group is bonded to the above heterocyclic group), an alkylsulfonyl group (preferably an alkylsulfonyl group having 1 to 20 carbon atoms, for example, methylsulfonyl, ethylsulfonyl), an arylsulfonyl group (preferably an arylsulfonyl group having 6 to 22 carbon atoms, for example, benzenesulfonyl),Alkylsilyl groups (preferably alkylsilyl groups having 1 to 20 carbon atoms, for example, monomethylsilyl, dimethylsilyl, trimethylsilyl, triethylsilyl, etc.), arylsilyl groups (preferably arylsilyl groups having 6 to 42 carbon atoms, for example, triphenylsilyl, etc.), alkoxysilyl groups (preferably alkoxysilyl groups having 1 to 20 carbon atoms, for example, monomethoxysilyl, dimethoxysilyl, trimethoxysilyl, triethoxysilyl, etc.), aryloxysilyl groups (preferably aryloxysilyl groups having 6 to 42 carbon atoms, for example, triphenyloxysilyl, etc.), phosphoryl groups (preferably phosphate groups having 0 to 20 carbon atoms, for example, -OP(=O)(R, P )2), a phosphonyl group (preferably a phosphonyl group having 0 to 20 carbon atoms, for example, —P(═O)(R P )2), a phosphinyl group (preferably a phosphinyl group having 0 to 20 carbon atoms, for example, —P(R P )2), a phosphonic acid group (preferably a phosphonic acid group having 0 to 20 carbon atoms, for example, —PO(OR P ) 2), sulfo group (sulfonic acid group), carboxy group, hydroxy group, sulfanyl group, cyano group, halogen atom (e.g., fluorine atom, chlorine atom, bromine atom, iodine atom, etc.). P is a hydrogen atom or a substituent (preferably a group selected from the substituent Z). Furthermore, each of the groups listed as the substituent Z may be further substituted with the above-mentioned substituent Z. The alkyl group, alkylene group, alkenyl group, alkenylene group, alkynyl group and / or alkynylene group may be cyclic or chain-like, and may be straight-chain or branched.

[0111] - Physical properties or characteristics of binder-forming polymers or polymer binders - The polymer binder or binder-forming polymer used in the present invention preferably has the following physical properties or characteristics.

[0112] The glass transition temperature Tg of the binder-forming polymer is not particularly limited and can be set to 120°C or lower. In order to further improve dispersion characteristics and cycle characteristics, it is preferably 50°C or lower, more preferably -30°C or lower, and even more preferably -40°C or lower. The lower limit is not particularly limited and can be, for example, -160°C. The glass transition temperature Tg of the binder-forming polymer can be adjusted as appropriate depending on the polymer composition (type or content of constituent components), molecular structure, etc. The glass transition temperature Tg of the binder-forming polymer is the glass transition temperature measured by the following method. That is, the glass transition point is measured using a dry sample of the binder-forming polymer with a differential scanning calorimeter (DSC7000, manufactured by SII Technology Co., Ltd.) under the following conditions. The measurement is carried out twice on the same sample, and the result of the second measurement is used. Measurement chamber atmosphere: Nitrogen (50 mL / min) Heating rate: 5℃ / min ·Measurement start temperature: -100℃ Measurement end temperature: 200℃ Sample pan: Aluminum pan Measurement sample mass: 5 mg Calculation of Tg: Calculate Tg by rounding off the midpoint between the start and end points of the decline on the DSC chart. The glass transition temperature Tg can be adjusted by the type or composition (type and content of constituent components) of the binder-forming polymer.

[0113] The binder-forming polymer has, in terms of dispersibility, for example, an SP value of 17.0 to 25.0 MPa. 1 / 2 Preferably, the pressure is 17.0 to 23.0 MPa. 1 / 2 More preferably, the pressure is 17.0 to 21.0 MPa. 1 / 2 More preferably, the pressure is 18.0 to 20.5 MPa. 1 / 2 It is particularly preferred that: The method for calculating the SP value will be explained. First, the SP value (MPa) of each component that makes up the binder-forming polymer 1 / 2) is determined by the Hoy method (HL Hoy JOURNAL OF PAINT TECHNOLOGY Vol. 42, No. 541, 1970, 76-118, and POLYMER HANDBOOK 4 th , Chapter 59, VII, p. 686, Table 5, Table 6 and the following formula in Table 6). When the binder-forming polymer is a chain-polymerized polymer, the constituent components are the same units as the constituent components derived from the raw material compounds. On the other hand, when the binder-forming polymer is a step-polymerized polymer, the constituent components are different units from the constituent components derived from the raw material compounds. For example, in the case of polyurethane, the constituent components are determined as follows for convenience: A constituent component derived from a polyisocyanate compound is a unit in which an -O- group is bonded to two -NH-CO- groups in a constituent unit derived from a polyisocyanate compound. On the other hand, a constituent component derived from a polyol compound is a unit in which two -O- groups are removed from a constituent unit derived from a polyol compound.

[0114]

number

[0115] The SP value (MPa) of each component obtained as above 1 / 2 ) to calculate the SP value (MPa) of the binder-forming polymer. 1 / 2 ) is calculated from the following formula. The SP value of the constituent components obtained in accordance with the above literature is the SP value (MPa 1 / 2 ) (for example, 1 cal 1 / 2 cm -3 / 2 ≒2.05J 1 / 2 cm -3 / 2 ≒2.05 MPa 1 / 2 ) and use it. SP p 2 =(SP1 2 ×W1)+(SP2 2 ×W2)+··· In the above formula, SP1, SP2... represent the SP values ​​of the constituent components, and W1, W2... represent the mass fractions of the constituent components. In the present invention, the mass fraction of a constituent component is the mass fraction of the constituent component (the raw material compound from which this constituent component is derived) in the binder-forming polymer.

[0116] When the polymer is a hyperbranched polymer, the SP value of the entire hyperbranched polymer is calculated by calculating the SP value of each arm portion and the SP value of the core portion by the Hoy method, and then multiplying these values ​​by the mass fraction of each component using the above formula, and then calculating the sum of these values. When the arm portion is a copolymer made of multiple types of monomers, the SP value of this arm portion is calculated using the above formula.

[0117] The SP value of the polymer can be adjusted by the type or composition (type and content of constituent components) of the binder-forming polymer.

[0118] It is preferable that the SP value of the binder-forming polymer satisfy the difference (absolute value) in SP value between the SP value of the dispersion medium and the SP value within the range described below, in order to realize even higher level of dispersion characteristics.

[0119] The weight average molecular weight of the binder-forming polymer is not particularly limited. For example, it is preferably 2,000 or more, more preferably 4,000 or more, and even more preferably 6,000 or more. The upper limit is essentially 5,000,000 or less, but is preferably 100,000 or less, more preferably 50,000 or less, and even more preferably 30,000 or less.

[0120] - Molecular weight measurement - In the present invention, unless otherwise specified, the molecular weight of a polymer, polymer chain, or macromonomer refers to the mass average molecular weight or number average molecular weight measured by gel permeation chromatography (GPC) in terms of standard polystyrene. The measurement method can be basically the following Condition 1 or Condition 2 (preferred). However, depending on the type of polymer or macromonomer, an appropriate eluent may be selected and used. (Condition 1) Column: Two TOSOH TSKgel Super AWM-H (product name, manufactured by Tosoh Corporation) connected together Carrier: 10mM LiBr / N-methylpyrrolidone Measurement temperature: 40℃ Carrier flow rate: 1.0 ml / min Sample concentration: 0.1% by mass Detector: RI (refractive index) detector (Condition 2) Column: A column connected with TOSOH TSKgel Super HZM-H, TOSOH TSKgel Super HZ4000, or TOSOH TSKgel Super HZ2000 (all trade names, manufactured by Tosoh Corporation) is used. Carrier: Tetrahydrofuran Measurement temperature: 40℃ Carrier flow rate: 1.0 ml / min Sample concentration: 0.1% by mass Detector: RI (refractive index) detector

[0121] The water concentration of the binder (binder-forming polymer) is preferably 100 ppm (by mass) or less. The binder may be prepared by crystallizing the polymer and drying it, or the binder dispersion may be used as is. The binder-forming polymer is preferably amorphous. In the present invention, a polymer being "amorphous" typically means that no endothermic peak due to crystalline melting is observed when measured at the glass transition temperature.

[0122] The binder-forming polymer may be a non-crosslinked polymer or a crosslinked polymer. Furthermore, when crosslinking of the polymer progresses due to heating or application of voltage, the molecular weight may be larger than the above-mentioned molecular weight. Preferably, the binder-forming polymer has a mass average molecular weight within the above-mentioned range at the start of use of the all-solid-state secondary battery.

[0123] Specific examples of binder-forming polymers include the polymers synthesized in the examples, but the present invention is not limited to these.

[0124] The binder-forming polymer contained in the polymer binder may be one type or two or more types. The polymer binder may also contain other polymers, etc., as long as the action of the binder-forming polymer described above is not impaired. As the other polymer, polymers that are commonly used as binders for all-solid-state secondary batteries can be used without any particular limitation.

[0125] The inorganic solid electrolyte-containing composition may contain one or more types of polymer binders. The content of the polymer binder in the inorganic solid electrolyte-containing composition is not particularly limited, but is preferably 0.1 to 5.0 mass%, more preferably 0.2 to 4.0 mass%, and even more preferably 0.3 to 2.0 mass%, in terms of dispersion characteristics, ionic conductivity, and binding ability. For the same reasons, the content of the polymer binder in 100 mass% of the solid content of the inorganic solid electrolyte-containing composition is preferably 0.1 to 6.0 mass%, more preferably 0.3 to 5.0 mass%, and even more preferably 0.4 to 2.5 mass%. In the present invention, at 100% by mass of solid content, the mass ratio of the combined mass (total amount) of the inorganic solid electrolyte and the active material to the mass of the polymer binder [(mass of inorganic solid electrolyte + mass of active material) / (total mass of polymer binder)] is preferably in the range of 1,000 to 1. This ratio is more preferably 500 to 2, and even more preferably 100 to 10.

[0126] <Dispersion medium> The dispersion medium contained in the inorganic solid electrolyte-containing composition may be any organic compound that is liquid in the usage environment, and examples thereof include various organic solvents, and specific examples thereof include alcohol compounds, ether compounds, amide compounds, amine compounds, ketone compounds, aromatic compounds, aliphatic compounds, nitrile compounds, and ester compounds. The dispersion medium may be a non-polar dispersion medium (hydrophobic dispersion medium) or a polar dispersion medium (hydrophilic dispersion medium), but a non-polar dispersion medium is preferred in terms of exhibiting excellent dispersibility. A non-polar dispersion medium generally refers to a medium having low affinity for water, and in the present invention, examples thereof include ester compounds, ketone compounds, ether compounds, aromatic compounds, and aliphatic compounds.

[0127] Examples of alcohol compounds include methyl alcohol, ethyl alcohol, 1-propyl alcohol, 2-propyl alcohol, 2-butanol, ethylene glycol, propylene glycol, glycerin, 1,6-hexanediol, cyclohexanediol, sorbitol, xylitol, 2-methyl-2,4-pentanediol, 1,3-butanediol, and 1,4-butanediol.

[0128] Examples of the ether compound include alkylene glycols (diethylene glycol, triethylene glycol, polyethylene glycol, dipropylene glycol, etc.), alkylene glycol monoalkyl ethers (ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, diethylene glycol monobutyl ether, etc.), alkylene glycol dialkyl ethers (ethylene glycol dimethyl ether, etc.), dialkyl ethers (dimethyl ether, diethyl ether, diisopropyl ether, dibutyl ether, etc.), and cyclic ethers (tetrahydrofuran, dioxane (including 1,2-, 1,3-, and 1,4-isomers), etc.).

[0129] Examples of the amide compound include N,N-dimethylformamide, N-methyl-2-pyrrolidone, 2-pyrrolidinone, 1,3-dimethyl-2-imidazolidinone, ε-caprolactam, formamide, N-methylformamide, acetamide, N-methylacetamide, N,N-dimethylacetamide, N-methylpropanamide, and hexamethylphosphoric triamide.

[0130] Examples of the amine compound include triethylamine, diisopropylethylamine, and tributylamine. Examples of ketone compounds include acetone, methyl ethyl ketone, methyl isobutyl ketone (MIBK), cyclopentanone, cyclohexanone, cycloheptanone, dipropyl ketone, dibutyl ketone, diisopropyl ketone, diisobutyl ketone (DIBK), isobutyl propyl ketone, sec-butyl propyl ketone, pentyl propyl ketone, and butyl propyl ketone. Examples of aromatic compounds include benzene, toluene, xylene, and perfluorotoluene. Examples of aliphatic compounds include hexane, heptane, octane, nonane, decane, dodecane, cyclohexane, methylcyclohexane, ethylcyclohexane, cycloheptane, cyclooctane, decalin, paraffin, gasoline, naphtha, kerosene, and diesel. Examples of the nitrile compound include acetonitrile, propionitrile, and isobutyronitrile. Examples of the ester compound include ethyl acetate, propyl acetate, butyl acetate, ethyl butyrate, propyl butyrate, isopropyl butyrate, butyl butyrate, isobutyl butyrate, butyl pentanoate, pentyl pentanoate, ethyl isobutyrate, propyl isobutyrate, isopropyl isobutyrate, isobutyl isobutyrate, propyl pivalate, isopropyl pivalate, butyl pivalate, and isobutyl pivalate.

[0131] In the present invention, among these, ether compounds, ketone compounds, aromatic compounds, aliphatic compounds, and ester compounds are preferred, and ester compounds, ketone compounds, aromatic compounds, and ether compounds are more preferred.

[0132] The number of carbon atoms in the compound constituting the dispersion medium is not particularly limited, and is preferably 2 to 30, more preferably 4 to 20, even more preferably 6 to 15, and particularly preferably 7 to 12.

[0133] The dispersion medium has the following characteristics in terms of the dispersion properties of solid particles: SP value (unit: MPa) 1 / 2 ) is preferably 14 to 24, more preferably 15 to 22, and even more preferably 16 to 20. The difference (absolute value) in the SP value between the dispersion medium and the binder-forming polymer is not particularly limited, but a value of 3 MPa is preferred in that the molecular chains of the binder-forming polymer spread in the dispersion medium, improving its own dispersibility, thereby further improving the dispersion characteristics of the solid particles. 1 / 2 Preferably, the pressure is 0 to 2 MPa or less. 1 / 2 More preferably, the pressure is 0 to 1 MPa. 1 / 2 It is more preferable that: The SP value of the dispersion medium is calculated by the Hoy method described above, and is expressed in units of MPa. 1 / 2 The SP value is a value converted into a mass fraction of the dispersion medium. When an inorganic solid electrolyte-containing composition contains two or more dispersion media, the SP value of the dispersion media means the SP value of the dispersion media as a whole, and is the sum of the products of the SP values ​​of the dispersion media and the mass fractions of the dispersion media. Specifically, the SP value is calculated in the same manner as the SP value of the polymer described above, except that the SP value of each dispersion media is used instead of the SP value of the constituent components. The SP values ​​(units omitted) of major dispersion media are shown below. MIBK (18.4), diisopropyl ether (16.8), dibutyl ether (17.9), diisopropyl ketone (17.9), DIBK (17.9), butyl butyrate (18.6), butyl acetate (18.9), toluene (18.5), ethylcyclohexane (17.1), cyclooctane (18.8), isobutyl ethyl ether (15.3), N-methylpyrrolidone (NMP, 25.4), perfluorotoluene (13.4)

[0134] The boiling point of the dispersion medium at normal pressure (1 atmosphere) is preferably 50° C. or higher, more preferably 70° C. or higher. The upper limit is preferably 250° C. or lower, more preferably 220° C. or lower.

[0135] The inorganic solid electrolyte-containing composition may contain one or more dispersion media. An example of a dispersion medium containing two or more dispersion media is a mixed xylene (a mixture of o-xylene, p-xylene, m-xylene, and ethylbenzene). In the present invention, the content of the dispersion medium in the inorganic solid electrolyte-containing composition is not particularly limited and can be set appropriately. For example, the content of the dispersion medium in the inorganic solid electrolyte-containing composition is preferably 20 to 80 mass %, more preferably 30 to 70 mass %, and particularly preferably 40 to 60 mass %. When setting a high solid content concentration, the content of the dispersion medium can be set to 60 mass % or less, 50 mass % or less, or even 40 mass % or less. The lower limit is not particularly limited, but can be, for example, 20 mass %.

[0136] <Active material> The inorganic solid electrolyte-containing composition of the present invention preferably contains an active material capable of inserting and releasing ions of a metal belonging to Group 1 or 2 of the periodic table. Examples of the active material include a positive electrode active material and a negative electrode active material, as described below. In the present invention, an inorganic solid electrolyte-containing composition containing an active material (positive electrode active material or negative electrode active material) may be referred to as an electrode composition (positive electrode composition or negative electrode composition).

[0137] (Cathode active material) The positive electrode active material is an active material capable of inserting and releasing ions of a metal belonging to Group 1 or 2 of the periodic table, and is preferably one that can insert and release lithium ions reversibly. The material is not particularly limited as long as it has the above-mentioned properties, and may be a transition metal oxide, an organic substance, sulfur, or other element that can be composited with Li when the battery is disassembled. Among these, it is preferable to use a transition metal oxide as the positive electrode active material, and a transition metal element M a A transition metal oxide containing at least one element selected from Co, Ni, Fe, Mn, Cu, and V is more preferred. b (Elements of Group 1 (Ia) of the periodic table other than lithium, elements of Group 2 (IIa), Al, Ga, In, Ge, Sn, Pb, Sb, Bi, Si, P, B, etc.) may be mixed. The amount of the mixed element is determined by the following formula: a The amount of Li / M is preferably 0 to 30 mol % relative to the amount of Li (100 mol %). a More preferably, the compounds are synthesized by mixing them so that the molar ratio is 0.3 to 2.2. Specific examples of transition metal oxides include (MA) transition metal oxides having a layered rock salt structure, (MB) transition metal oxides having a spinel structure, (MC) lithium-containing transition metal phosphate compounds, (MD) lithium-containing transition metal halide phosphate compounds, and (ME) lithium-containing transition metal silicate compounds.

[0138] (MA) Specific examples of transition metal oxides with a layered rock salt structure include LiCoO2 (lithium cobalt oxide [LCO]), LiNi2O2 (lithium nickel oxide), and LiNi 0.85 Co 0.10 Al 0.05 O2 (nickel cobalt lithium aluminate [NCA]), LiNi 1 / 3 Co 1 / 3 Mn 1 / 3 O2 (lithium nickel manganese cobalt oxide [NMC]) and LiNi 0.5 Mn 0.5 O2 (lithium manganese nickel oxide). (MB) Specific examples of transition metal oxides having a spinel structure include LiMn2O4 (LMO), LiCoMnO4, Li2FeMn3O8, Li2CuMn3O8, Li2CrMn3O8, and Li2NiMn3O8. (MC) Examples of lithium-containing transition metal phosphate compounds include olivine-type iron phosphates such as LiFePO4 and Li3Fe2(PO4)3, iron pyrophosphates such as LiFeP2O7, cobalt phosphates such as LiCoPO4, and monoclinic Nasicon-type vanadium phosphates such as Li3V2(PO4)3 (lithium vanadium phosphate). (MD) Examples of lithium-containing transition metal halide phosphate compounds include iron fluorophosphates such as Li2FePO4F, manganese fluorophosphates such as Li2MnPO4F, and cobalt fluorophosphates such as Li2CoPO4F. (ME) Examples of lithium-containing transition metal silicate compounds include Li2FeSiO4, Li2MnSiO4, and Li2CoSiO4. In the present invention, transition metal oxides having a layered rock salt structure (MA) are preferred, and LCO or NMC are more preferred.

[0139] The shape of the positive electrode active material is not particularly limited, but is preferably particulate. The particle size (volume average particle size) of the positive electrode active material is not particularly limited. For example, it can be 0.1 to 50 μm. The particle size of the positive electrode active material particles can be measured in the same manner as the particle size of the inorganic solid electrolyte. To adjust the positive electrode active material to a predetermined particle size, a conventional grinder or classifier is used. For example, a mortar, ball mill, sand mill, vibration ball mill, satellite ball mill, planetary ball mill, swirling airflow jet mill, or sieve is preferably used. Wet grinding in the presence of a dispersion medium such as water or methanol can also be performed during grinding. Classification is preferably performed to achieve the desired particle size. Classification is not particularly limited and can be performed using a sieve, air classifier, or the like. Classification can be performed using either a dry method or a wet method. The positive electrode active material obtained by the baking method may be used after being washed with water, an acidic aqueous solution, an alkaline aqueous solution, or an organic solvent.

[0140] The positive electrode active material may be used alone or in combination of two or more.

[0141] The content of the positive electrode active material in the inorganic solid electrolyte-containing composition is not particularly limited, and is preferably 10 to 97 mass %, more preferably 30 to 95 mass %, still more preferably 40 to 93 mass %, and particularly preferably 50 to 90 mass %, based on 100 mass % of the solid content.

[0142] (Negative electrode active material) The negative electrode active material is an active material capable of inserting and releasing ions of a metal belonging to Group 1 or 2 of the periodic table, and is preferably one that can insert and release lithium ions reversibly. The material is not particularly limited as long as it has the above-mentioned properties, and examples thereof include carbonaceous materials, metal oxides, metal composite oxides, lithium alone, lithium alloys, and negative electrode active materials that can form an alloy (can be alloyed) with lithium. Among these, carbonaceous materials, metal composite oxides, and lithium alone are preferably used from the viewpoint of reliability. Active materials that can be alloyed with lithium are preferred in that they enable the production of all-solid-state secondary batteries with a large capacity.

[0143] The carbonaceous material used as the negative electrode active material is a material essentially composed of carbon. Examples include carbon black such as petroleum pitch and acetylene black (AB), graphite (natural graphite, artificial graphite such as vapor-grown graphite, etc.), and carbonaceous materials obtained by calcining various synthetic resins such as PAN (polyacrylonitrile)-based resins and furfuryl alcohol resins. Further examples include various carbon fibers such as PAN-based carbon fiber, cellulose-based carbon fiber, pitch-based carbon fiber, vapor-grown carbon fiber, dehydrated PVA (polyvinyl alcohol)-based carbon fiber, lignin carbon fiber, glassy carbon fiber, and activated carbon fiber, as well as mesophase microspheres, graphite whiskers, and tabular graphite. These carbonaceous materials can be divided into non-graphitizable carbonaceous materials (also called hard carbon) and graphite-based carbonaceous materials depending on the degree of graphitization. Furthermore, the carbonaceous material preferably has the interplanar spacing, density, and crystallite size described in JP-A-62-22066, JP-A-2-6856, and JP-A-3-45473. The carbonaceous material does not need to be a single material, and a mixture of natural graphite and artificial graphite described in JP-A-5-90844, graphite with a coating layer described in JP-A-6-4516, and the like can also be used. As the carbonaceous material, hard carbon or graphite is preferably used, and graphite is more preferably used.

[0144] The oxide of a metal or metalloid element used as the negative electrode active material is not particularly limited as long as it is an oxide capable of absorbing and releasing lithium, and examples thereof include oxides of metal elements (metal oxides), composite oxides of metal elements, or composite oxides of metal elements and metalloid elements (collectively referred to as metal composite oxides), and oxides of metalloid elements (metalloid oxides). Amorphous oxides are preferred as these oxides, and chalcogenides, which are reaction products of metal elements and elements of Group 16 of the periodic table, are also preferred. In the present invention, the term "metalloid element" refers to an element exhibiting properties intermediate between metal elements and non-metalloid elements, and typically includes six elements: boron, silicon, germanium, arsenic, antimony, and tellurium, and three elements: selenium, polonium, and astatine. Furthermore, "amorphous" refers to an element that exhibits a broad scattering band with a peak in the 2θ range of 20° to 40° in an X-ray diffraction method using CuKα radiation, and may also have crystalline diffraction lines. The strongest intensity of the crystalline diffraction lines seen at 2θ values ​​of 40° to 70° is preferably 100 times or less, more preferably 5 times or less, the diffraction line intensity at the apex of the broad scattering band seen at 2θ values ​​of 20° to 40°, and it is particularly preferable that there are no crystalline diffraction lines.

[0145] Among the compounds consisting of the amorphous oxides and chalcogenides, amorphous oxides or chalcogenides of metalloid elements are more preferred, and (composite) oxides or chalcogenides consisting of one or a combination of two or more elements selected from the elements of Groups 13 (IIIB) to 15 (VB) of the Periodic Table (e.g., Al, Ga, Si, Sn, Ge, Pb, Sb, and Bi) are particularly preferred. Specific examples of preferred amorphous oxides and chalcogenides include Ga2O3, GeO, PbO, PbO2, Pb2O3, Pb2O4, Pb3O4, Sb2O3, Sb2O4, Sb2O8Bi2O3, Sb2O8Si2O3, Sb2O5, Bi2O3, Bi2O4, GeS, PbS, PbS2, Sb2S3, and Sb2S5. Suitable examples of negative electrode active materials that can be used in combination with amorphous oxides mainly containing Sn, Si, or Ge include carbonaceous materials that can occlude and / or release lithium ions or lithium metal, lithium alone, lithium alloys, and negative electrode active materials that can be alloyed with lithium.

[0146] From the viewpoint of high current density charge / discharge characteristics, it is preferable that the oxides of metal or semi-metal elements, particularly the metal (composite) oxides and the chalcogenides contain at least one of titanium and lithium as a constituent component. Examples of lithium-containing metal composite oxides (lithium composite metal oxides) include composite oxides of lithium oxide and the metal (composite) oxides or the chalcogenides, more specifically Li2SnO2. The negative electrode active material, for example, a metal oxide, preferably contains titanium (titanium oxide). Specifically, Li4Ti5O 12 Lithium titanate (LTO) is preferred because it has small volume fluctuations when absorbing and releasing lithium ions, has excellent rapid charge and discharge characteristics, suppresses electrode deterioration, and can improve the life of lithium ion secondary batteries.

[0147] The lithium alloy as the negative electrode active material is not particularly limited as long as it is an alloy commonly used as the negative electrode active material of a secondary battery. For example, a lithium aluminum alloy, specifically, a lithium aluminum alloy such as a lithium-based metal with 10% by mass of aluminum added, can be mentioned.

[0148] The negative electrode active material capable of forming an alloy with lithium is not particularly limited as long as it is commonly used as the negative electrode active material of a secondary battery. Such an active material has a large expansion and contraction due to charge and discharge of an all-solid-state secondary battery, accelerating the deterioration of cycle characteristics. However, since the inorganic solid electrolyte-containing composition of the present invention contains the above-mentioned polymer binder, the deterioration of cycle characteristics can be suppressed. Examples of such an active material include (negative electrode) active materials (alloys, etc.) having a silicon element or a tin element, and various metals such as Al and In. A negative electrode active material having a silicon element (silicon element-containing active material) that enables a higher battery capacity is preferable, and a silicon element-containing active material having a silicon element content of 50 mol% or more of all constituent elements is more preferable. Generally, negative electrodes containing these negative electrode active materials (for example, Si negative electrodes containing a silicon element-containing active material, Sn negative electrodes containing an active material having a tin element, etc.) can occlude more Li ions than carbon negative electrodes (graphite and acetylene black, etc.). That is, the amount of Li ions occluded per unit mass increases. Therefore, there is an advantage that the battery capacity (energy density) can be increased. As a result, the battery driving time can be lengthened. Examples of the silicon element-containing active material include silicon materials such as Si and SiOx (0 < x ≤ 1), and further silicon-containing alloys containing titanium, vanadium, chromium, manganese, nickel, copper, lanthanum, etc. (for example, LaSi2, VSi2, La-Si, Gd-Si, Ni-Si), or organized active materials (for example, LaSi2 / Si). In addition, active materials containing a silicon element and a tin element such as SnSiO3 and SnSiS3 can also be mentioned. Note that SiOx can be used as a negative electrode active material (semimetal oxide) itself, and can also be used as a negative electrode active material (its precursor material) capable of alloying with lithium because Si is generated by the operation of an all-solid-state secondary battery. Examples of negative electrode active materials containing tin include Sn, SnO, SnO2, SnS, SnS2, and the above-mentioned active materials containing silicon and tin. Also included are composite oxides with lithium oxide, such as Li2SnO2.

[0149] In the present invention, the above-mentioned negative electrode active material can be used without any particular limitation. However, in terms of battery capacity, a negative electrode active material that can be alloyed with lithium is a preferred embodiment. Among these, the above-mentioned silicon material or silicon-containing alloy (alloy containing silicon element) is more preferred, and it is even more preferred that the negative electrode active material contains silicon (Si) or a silicon-containing alloy.

[0150] The chemical formula of the compound obtained by the above calcination method can be measured by inductively coupled plasma (ICP) emission spectroscopy, or simply calculated from the difference in mass of the powder before and after calcination.

[0151] The shape of the negative electrode active material is not particularly limited, but is preferably particulate. The particle size of the negative electrode active material is not particularly limited, but is preferably 0.1 to 60 μm. The particle size of the negative electrode active material particles can be measured in the same manner as the particle size of the inorganic solid electrolyte. To achieve the desired particle size, a conventional grinder or classifier is used, as with the positive electrode active material.

[0152] The negative electrode active materials may be used singly or in combination of two or more. The content of the negative electrode active material in the inorganic solid electrolyte-containing composition is not particularly limited, and is preferably 10 to 90 mass %, more preferably 20 to 85 mass %, even more preferably 30 to 80 mass %, and still more preferably 40 to 75 mass %, based on 100 mass % of the solid content.

[0153] In the present invention, when the negative electrode active material layer is formed by charging the secondary battery, ions of a metal belonging to Group 1 or 2 of the periodic table that are generated in the all-solid-state secondary battery can be used instead of the above-mentioned negative electrode active material. The negative electrode active material layer can be formed by bonding these ions with electrons and depositing them as a metal.

[0154] (Coating of active material) The surfaces of the positive electrode active material and the negative electrode active material may be coated with another metal oxide. Examples of the surface coating agent include metal oxides containing Ti, Nb, Ta, W, Zr, Al, Si, or Li. Specific examples include titanate spinel, tantalum-based oxides, niobium-based oxides, and lithium niobate-based compounds, such as Li4Ti5O 12 , Li2Ti2O5, LiTaO3, LiNbO3, LiAlO2, Li2ZrO3, Li2WO4, Li2TiO3, Li2B4O7, Li3PO4, Li2MoO4, Li3BO3, LiBO2, Li2CO3, Li2SiO3, SiO2, TiO2, ZrO2, Al2O3, B2O3, etc. The surface of the electrode containing the positive electrode active material or the negative electrode active material may be surface-treated with sulfur or phosphorus. Furthermore, the particle surfaces of the positive electrode active material or negative electrode active material may be subjected to a surface treatment with active rays or active gas (plasma, etc.) before or after the above surface coating.

[0155] <Conductive additive> The inorganic solid electrolyte-containing composition of the present invention preferably contains a conductive aid, and for example, a silicon atom-containing active material as a negative electrode active material is preferably used in combination with a conductive aid. The conductive additive is not particularly limited, and may be any of those known as general conductive additives. For example, it may be an electron conductive material, such as graphites (e.g., natural graphite, artificial graphite), carbon blacks (e.g., acetylene black, ketjen black, furnace black), amorphous carbon (e.g., needle coke), carbon fibers (e.g., vapor-grown carbon fiber, carbon nanotube), carbonaceous materials (e.g., graphene, fullerene), metal powders (e.g., copper, nickel), metal fibers, or conductive polymers (e.g., polyaniline, polypyrrole, polythiophene, polyacetylene, polyphenylene derivatives). In the present invention, when an active material and a conductive additive are used in combination, the conductive additive is one among the above-mentioned conductive additives that does not insert or release ions of metals belonging to Group 1 or Group 2 of the periodic table (preferably Li ions) when the battery is charged and discharged, and does not function as an active material. Therefore, among conductive additives, one that can function as an active material in the active material layer when the battery is charged and discharged is classified as an active material rather than a conductive additive. Whether or not a conductive additive functions as an active material when the battery is charged and discharged is not uniquely determined, but is determined by the combination with the active material.

[0156] The conductive additive may contain one kind or two or more kinds. The shape of the conductive additive is not particularly limited, but a particulate shape is preferred. When the inorganic solid electrolyte-containing composition of the present invention contains a conductive aid, the content of the conductive aid in the inorganic solid electrolyte-containing composition is preferably 0 to 10 mass % relative to 100 mass % of the solid content.

[0157] <Lithium salt> The inorganic solid electrolyte-containing composition of the present invention also preferably contains a lithium salt (supporting electrolyte). The lithium salt is preferably a lithium salt that is usually used in this type of product, and is not particularly limited. For example, the lithium salts described in paragraphs 0082 to 0085 of JP-A No. 2015-088486 are preferred. When the inorganic solid electrolyte-containing composition of the present invention contains a lithium salt, the content of the lithium salt is preferably 0.1 parts by mass or more, more preferably 5 parts by mass or more, relative to 100 parts by mass of the solid electrolyte, and the upper limit is preferably 50 parts by mass or less, more preferably 20 parts by mass or less.

[0158] <Dispersant> The inorganic solid electrolyte-containing composition of the present invention may contain no dispersant other than the polymer binder because the polymer binder also functions as a dispersant. However, the dispersant may contain a dispersant. As the dispersant, a dispersant typically used in all-solid-state secondary batteries may be appropriately selected and used. In general, a compound intended for particle adsorption and steric and / or electrostatic repulsion is preferably used.

[0159] <Other additives> The inorganic solid electrolyte-containing composition of the present invention may contain, as appropriate, other components in addition to the above components, such as an ionic liquid, a thickener, a crosslinking agent (such as one that undergoes a crosslinking reaction by radical polymerization, condensation polymerization, or ring-opening polymerization), a polymerization initiator (such as one that generates an acid or radical by heat or light), an antifoaming agent, a leveling agent, a dehydrating agent, and an antioxidant. The ionic liquid is contained to further improve ionic conductivity, and any known ionic liquid can be used without particular limitation. Furthermore, the composition may contain a polymer other than the binder-forming polymer described above, a commonly used binder, and the like.

[0160] (Preparation of inorganic solid electrolyte-containing composition) The inorganic solid electrolyte-containing composition of the present invention can be prepared as a mixture, preferably as a slurry, by mixing an inorganic solid electrolyte, the above-mentioned polymer binder, a dispersion medium, preferably a conductive additive, and further optionally a lithium salt and other optional components, for example, in any of various commonly used mixers. In the case of an electrode composition, an active material is further mixed therein. The mixing method is not particularly limited, and can be carried out using a known mixer such as a ball mill, bead mill, planetary mixer, blade mixer, roll mill, kneader, disk mill, planetary mixer, or narrow-gap disperser. The components may be mixed all at once or sequentially. The mixing environment is not particularly limited, and examples include dry air or an inert gas. The mixing conditions are also not particularly limited and can be appropriately set; for example, the mixing temperature can be 15 to 40°C. The rotation speed of the planetary mixer can be 200 to 3,000 rpm. The inorganic solid electrolyte-containing composition of the present invention has excellent redispersibility of solid particles and is resistant to oxidation degradation, so it can be stored after preparation and does not need to be prepared every time it is used. Note that the conditions for redispersing the inorganic solid electrolyte-containing composition of the present invention after preparation are not particularly limited, and the above-mentioned preparation method and conditions can be appropriately adopted.

[0161] [Sheet for all-solid-state secondary batteries] The sheet for an all-solid-state secondary battery of the present invention is a sheet-like molded article capable of forming a constituent layer of an all-solid-state secondary battery, and includes various embodiments depending on its application. Examples include a sheet preferably used for a solid electrolyte layer (also referred to as a solid electrolyte sheet for an all-solid-state secondary battery), a sheet preferably used for an electrode, or a laminate of an electrode and a solid electrolyte layer (an electrode sheet for an all-solid-state secondary battery), etc. In the present invention, these various sheets are collectively referred to as a sheet for an all-solid-state secondary battery. In the present invention, each layer constituting the sheet for an all-solid-state secondary battery may have a single-layer structure or a multi-layer structure.

[0162] In the sheet for an all-solid-state secondary battery, the solid electrolyte layer or the active material layer on the substrate is formed from the inorganic solid electrolyte-containing composition of the present invention. Therefore, by appropriately peeling off the substrate from this sheet for an all-solid-state secondary battery and using it as the solid electrolyte layer of an all-solid-state secondary battery or as an electrode (a laminate of a current collector and an active material layer) as it is, the cycle characteristics and conductivity (lower resistance) of the all-solid-state secondary battery can be improved.

[0163] The solid electrolyte sheet for an all-solid-state secondary battery of the present invention may be any sheet having a solid electrolyte layer. It may be a sheet in which the solid electrolyte layer is formed on a substrate, or a sheet formed from the solid electrolyte layer without a substrate (a sheet from which the substrate has been peeled off). The solid electrolyte sheet for an all-solid-state secondary battery may have other layers in addition to the solid electrolyte layer. Examples of such other layers include a protective layer (release sheet), a current collector, and a coating layer. The solid electrolyte sheet for an all-solid-state secondary battery of the present invention may be, for example, a sheet having, on a substrate, a layer composed of the inorganic solid electrolyte-containing composition of the present invention, typically a solid electrolyte layer, and a protective layer, in this order. The solid electrolyte layer of the solid electrolyte sheet for an all-solid-state secondary battery is preferably formed from the inorganic solid electrolyte-containing composition of the present invention. The content of each component in this solid electrolyte layer is not particularly limited, but is preferably synonymous with the content of each component in the solid content of the inorganic solid electrolyte-containing composition of the present invention. The layer thickness of each layer constituting the solid electrolyte sheet for an all-solid-state secondary battery is the same as the layer thickness of each layer described in the all-solid-state secondary battery described below.

[0164] The substrate is not particularly limited as long as it can support the solid electrolyte layer, and examples thereof include sheets (plates) of materials described below for the current collector, organic materials, inorganic materials, etc. Examples of organic materials include various polymers, specifically polyethylene terephthalate, polypropylene, polyethylene, cellulose, etc. Examples of inorganic materials include glass, ceramics, etc.

[0165] The electrode sheet for an all-solid-state secondary battery of the present invention (also simply referred to as "electrode sheet") may be an electrode sheet having an active material layer. It may be a sheet in which the active material layer is formed on a substrate (current collector), or a sheet formed from the active material layer without a substrate (a sheet from which the substrate has been peeled off). This electrode sheet typically has a current collector and an active material layer, but it may also include an embodiment in which the current collector, active material layer, and solid electrolyte layer are formed in this order, as well as an embodiment in which the current collector, active material layer, solid electrolyte layer, and active material layer are formed in this order. The solid electrolyte layer and active material layer of the electrode sheet are preferably formed from the inorganic solid electrolyte-containing composition of the present invention. The content of each component in this solid electrolyte layer or active material layer is not particularly limited, but is preferably synonymous with the content of each component in the solid content of the inorganic solid electrolyte-containing composition (electrode composition) of the present invention. The layer thickness of each layer constituting the electrode sheet of the present invention is the same as the layer thickness of each layer described in the all-solid-state secondary battery described below. The electrode sheet may also have other layers as described above.

[0166] In the sheet for an all-solid-state secondary battery of the present invention, at least one of the solid electrolyte layer and the active material layer is formed from the inorganic solid electrolyte-containing composition of the present invention. Therefore, the sheet for an all-solid-state secondary battery of the present invention has a low-resistance constituent layer in which solid particles containing an inorganic solid electrolyte are bound together, and further has a constituent layer in which the polymer binder is resistant to oxidative degradation. By using this constituent layer as a constituent layer of an all-solid-state secondary battery, it is possible to achieve excellent cycle characteristics and low resistance (high conductivity) of the all-solid-state secondary battery. The sheet for an all-solid-state secondary battery of the present invention can also be produced industrially, for example, by a highly productive roll-to-roll method, using the inorganic solid electrolyte-containing composition of the present invention, which has excellent dispersion properties even when the solid content is increased.

[0167] [Method of manufacturing a sheet for all-solid-state secondary batteries] The method for producing the sheet for an all-solid-state secondary battery of the present invention is not particularly limited, and the sheet can be produced by forming each of the above layers using the inorganic solid electrolyte-containing composition of the present invention. A preferred method is to form a layer (coated and dried) of the inorganic solid electrolyte-containing composition on a substrate or a current collector (optionally via another layer) by film formation (coating and drying). This method allows for the production of a sheet for an all-solid-state secondary battery having a substrate or a current collector and a coated and dried layer. In particular, when the inorganic solid electrolyte-containing composition of the present invention is formed on a current collector to form a film, the adhesion between the current collector and the active material layer can be strengthened. Here, the coated and dried layer refers to a layer formed by coating the inorganic solid electrolyte-containing composition of the present invention and drying the dispersion medium (i.e., a layer formed using the inorganic solid electrolyte-containing composition of the present invention and having a composition obtained by removing the dispersion medium from the inorganic solid electrolyte-containing composition of the present invention). The active material layer and the coated and dried layer may contain residual dispersion medium as long as it does not impair the effects of the present invention. The residual amount can be, for example, 3 mass% or less in each layer. In the method for producing a sheet for an all-solid-state secondary battery of the present invention, each step such as coating and drying will be described in the method for producing an all-solid-state secondary battery below.

[0168] In the method for producing a sheet for an all-solid-state secondary battery of the present invention, the coated and dried layer obtained as described above can also be pressed. The pressing conditions and the like will be described later in the method for producing an all-solid-state secondary battery. In addition, in the method for producing a sheet for an all-solid-state secondary battery of the present invention, the substrate, protective layer (particularly the release sheet), etc. can also be peeled off.

[0169] [All-solid-state secondary battery] The all-solid-state secondary battery of the present invention has a positive electrode active material layer, a negative electrode active material layer facing the positive electrode active material layer, and a solid electrolyte layer disposed between the positive electrode active material layer and the negative electrode active material layer. The all-solid-state secondary battery of the present invention is not particularly limited in other configuration as long as it has a solid electrolyte layer between the positive electrode active material layer and the negative electrode active material layer, and for example, a known configuration related to all-solid-state secondary batteries can be adopted. The positive electrode active material layer is preferably formed on a positive electrode current collector and constitutes a positive electrode. The negative electrode active material layer is preferably formed on a negative electrode current collector and constitutes a negative electrode.

[0170] At least one of the negative electrode active material layer, positive electrode active material layer, and solid electrolyte layer is preferably formed from the inorganic solid electrolyte-containing composition of the present invention, and at least one of the negative electrode active material layer and the positive electrode active material layer is preferably formed from the inorganic solid electrolyte-containing composition of the present invention. The all-solid-state secondary battery of the present invention, in which at least one of the constituent layers is formed from the inorganic solid electrolyte-containing composition of the present invention, exhibits excellent cycle characteristics and low resistance (high conductivity) even when produced by the industrially advantageous roll-to-roll method. Furthermore, the all-solid-state secondary battery of the present invention exhibits low resistance and high ionic conductivity, allowing for the extraction of large currents. In the present invention, one of the preferred embodiments is that all layers are formed from the inorganic solid electrolyte-containing composition of the present invention. In the present invention, forming the constituent layers of an all-solid-state secondary battery from the inorganic solid electrolyte-containing composition of the present invention includes an embodiment in which the constituent layers are formed from the sheet for an all-solid-state secondary battery of the present invention (however, if a layer other than the layer formed from the inorganic solid electrolyte-containing composition of the present invention is present, this layer is removed from the sheet). When the active material layer or the solid electrolyte layer is not formed from the inorganic solid electrolyte-containing composition of the present invention, known materials can be used. In the present invention, each of the constituent layers (including the current collector, etc.) that constitute the all-solid-state secondary battery may have a single-layer structure or a multi-layer structure.

[0171] <Cathode active material layer, solid electrolyte layer, negative electrode active material layer> The active material layer or solid electrolyte layer formed from the inorganic solid electrolyte-containing composition of the present invention preferably has the same component types and contents as those in the solid content of the inorganic solid electrolyte-containing composition of the present invention. The thicknesses of the negative electrode active material layer, the solid electrolyte layer, and the positive electrode active material layer are not particularly limited. Taking into consideration the dimensions of a typical all-solid-state secondary battery, the thickness of each layer is preferably 10 to 1,000 μm, and more preferably 20 μm or more and less than 500 μm. In the all-solid-state secondary battery of the present invention, it is further preferable that the thickness of at least one of the positive electrode active material layer and the negative electrode active material layer is 50 μm or more and less than 500 μm. The positive electrode active material layer and the negative electrode active material layer may each have a current collector on the side opposite to the solid electrolyte layer.

[0172] <Current collector> The positive electrode current collector and the negative electrode current collector are preferably electronic conductors. In the present invention, either the positive electrode current collector or the negative electrode current collector, or both of them together, may be simply referred to as the current collector. As the material for forming the positive electrode current collector, aluminum, aluminum alloy, stainless steel, nickel, titanium, etc., as well as aluminum or stainless steel surface treated with carbon, nickel, titanium or silver (thin film formed), are preferred, and among these, aluminum and aluminum alloy are more preferred. As the material for forming the negative electrode current collector, aluminum, copper, a copper alloy, stainless steel, nickel, titanium, etc., as well as aluminum, copper, a copper alloy, or stainless steel whose surface is treated with carbon, nickel, titanium, or silver are preferred, and aluminum, copper, a copper alloy, and stainless steel are more preferred.

[0173] The collector is usually in the form of a film sheet, but it may also be in the form of a net, a punched material, a lath, a porous material, a foam, or a molded fiber material. The thickness of the current collector is not particularly limited, but is preferably 1 to 500 μm. It is also preferable to make the surface of the current collector uneven by surface treatment.

[0174] <Other configurations> In the present invention, a functional layer or member may be appropriately interposed or disposed between or on the outside of each of the negative electrode current collector, negative electrode active material layer, solid electrolyte layer, positive electrode active material layer, and positive electrode current collector.

[0175] <Case> Depending on the application, the all-solid-state secondary battery of the present invention may be used as an all-solid-state secondary battery with the above structure as it is, but it is preferable to further encapsulate it in an appropriate casing to make it into a dry battery. The casing may be made of metal or resin (plastic). When a metallic casing is used, for example, an aluminum alloy or stainless steel may be used. It is preferable that the metallic casing is divided into a positive electrode casing and a negative electrode casing, and that the positive electrode current collector and the negative electrode current collector are electrically connected, respectively. It is preferable that the positive electrode casing and the negative electrode casing are joined and integrated via a gasket to prevent short circuits.

[0176] An all-solid-state secondary battery according to a preferred embodiment of the present invention will be described below with reference to FIG. 1, but the present invention is not limited thereto.

[0177] FIG. 1 is a cross-sectional view showing a schematic diagram of an all-solid-state secondary battery (lithium ion secondary battery) according to a preferred embodiment of the present invention. The all-solid-state secondary battery 10 of this embodiment has, as viewed from the negative electrode side, a negative electrode current collector 1, a negative electrode active material layer 2, a solid electrolyte layer 3, a positive electrode active material layer 4, and a positive electrode current collector 5, in this order. Each layer is in contact with each other and has an adjacent structure. By adopting such a structure, electrons (e - ) is supplied to the battery, and lithium ions (Li + On the other hand, during discharge, the lithium ions (Li + ) is returned to the positive electrode side, and electrons are supplied to the operating part 6. In the illustrated example, a light bulb is used as a model for the operating part 6, and it is lit by the discharge.

[0178] When an all-solid-state secondary battery having the layer structure shown in FIG. 1 is placed in a 2032-type coin case, this all-solid-state secondary battery is referred to as a laminate 12 for an all-solid-state secondary battery, and a battery produced by placing this laminate 12 for an all-solid-state secondary battery in a 2032-type coin case 11 (for example, a coin-type all-solid-state secondary battery shown in FIG. 2) is sometimes referred to as an all-solid-state secondary battery 13.

[0179] (positive electrode active material layer, solid electrolyte layer, negative electrode active material layer) In the all-solid-state secondary battery 10, the positive electrode active material layer, the solid electrolyte layer, and the negative electrode active material layer are all formed from the inorganic solid electrolyte-containing composition of the present invention. This all-solid-state secondary battery 10 exhibits excellent battery performance. The inorganic solid electrolytes and polymer binders contained in the positive electrode active material layer 4, the solid electrolyte layer 3, and the negative electrode active material layer 2 may be the same or different from one another. In the present invention, either the positive electrode active material layer or the negative electrode active material layer, or both together, may be simply referred to as an active material layer or an electrode active material layer. Also, either the positive electrode active material or the negative electrode active material, or both together, may be simply referred to as an active material or an electrode active material.

[0180] The solid electrolyte layer contains an inorganic solid electrolyte having ionic conductivity of a metal belonging to Group 1 or 2 of the periodic table, a polymer binder, and the optional components described above within the scope of not impairing the effects of the present invention, and typically does not contain a positive electrode active material and / or a negative electrode active material. The positive electrode active material layer contains an inorganic solid electrolyte having ionic conductivity of a metal belonging to Group 1 or 2 of the periodic table, a positive electrode active material, a polymer binder, and the above-mentioned optional components and the like within the scope of not impairing the effects of the present invention. The negative electrode active material layer contains an inorganic solid electrolyte having ionic conductivity of a metal belonging to Group 1 or 2 of the periodic table, a negative electrode active material, a polymer binder, and the above-mentioned optional components and the like within the range not impairing the effects of the present invention. In the all-solid-state secondary battery 10, the negative electrode active material layer can be a lithium metal layer. Examples of the lithium metal layer include a layer formed by depositing or molding lithium metal powder, lithium foil, and a lithium vapor deposition film. The thickness of the lithium metal layer can be, for example, 1 to 500 μm, regardless of the thickness of the negative electrode active material layer.

[0181] In the present invention, when the constituent layers are formed from the inorganic solid electrolyte-containing composition of the present invention, an all-solid-state secondary battery having excellent cycle characteristics and low resistance can be realized even when produced by an industrially advantageous roll-to-roll method.

[0182] (current collector) The positive electrode current collector 5 and the negative electrode current collector 1 are as described above.

[0183] [Manufacturing all-solid-state secondary batteries] The all-solid-state secondary battery can be manufactured by a conventional method. Specifically, the all-solid-state secondary battery can be manufactured by forming each of the above-mentioned layers using the inorganic solid electrolyte-containing composition of the present invention, etc., as described in detail below.

[0184] The all-solid-state secondary battery of the present invention can be produced by a method (a method for producing a sheet for an all-solid-state secondary battery of the present invention) including (via) a step of applying the inorganic solid electrolyte-containing composition of the present invention to a suitable substrate (for example, a metal foil to be a current collector) and forming (forming) a coating film. For example, a cathode sheet for an all-solid-state secondary battery is produced by applying an inorganic solid electrolyte-containing composition containing a cathode active material as a cathode material (cathode composition) to a metal foil cathode current collector to form a cathode active material layer. Next, an inorganic solid electrolyte-containing composition for forming a solid electrolyte layer is applied to the cathode active material layer to form a solid electrolyte layer. Furthermore, an inorganic solid electrolyte-containing composition containing a negative electrode active material as a negative electrode material (negative electrode composition) is applied to the solid electrolyte layer to form a negative electrode active material layer. By overlaying a negative electrode current collector (metal foil) on the negative electrode active material layer, an all-solid-state secondary battery with a structure in which a solid electrolyte layer is sandwiched between a positive electrode active material layer and a negative electrode active material layer can be obtained. This can also be enclosed in a housing to form a desired all-solid-state secondary battery. Alternatively, the method for forming each layer may be reversed, and an all-solid-state secondary battery may be produced by forming an anode active material layer, a solid electrolyte layer, and a cathode active material layer on an anode current collector as a substrate, and then stacking the layers on top of the anode current collector.

[0185] Another method is as follows. That is, a positive electrode sheet for an all-solid-state secondary battery is produced as described above. Furthermore, an inorganic solid electrolyte-containing composition containing a negative electrode active material is applied as a negative electrode material (negative electrode composition) onto a metal foil serving as a negative electrode current collector to form a negative electrode active material layer, thereby producing a negative electrode sheet for an all-solid-state secondary battery. Next, a solid electrolyte layer is formed on the active material layer of either of these sheets as described above. Furthermore, the other of the positive electrode sheet for an all-solid-state secondary battery and the negative electrode sheet for an all-solid-state secondary battery is laminated on the solid electrolyte layer so that the solid electrolyte layer and the active material layer are in contact with each other. In this manner, an all-solid-state secondary battery can be produced. Another method is as follows. That is, a positive electrode sheet for an all-solid-state secondary battery and a negative electrode sheet for an all-solid-state secondary battery are prepared as described above. Separately, an inorganic solid electrolyte-containing composition is applied to a substrate to prepare a solid electrolyte sheet for an all-solid-state secondary battery comprising a solid electrolyte layer. Furthermore, the positive electrode sheet for an all-solid-state secondary battery and the negative electrode sheet for an all-solid-state secondary battery are laminated so as to sandwich the solid electrolyte layer peeled from the substrate. In this manner, an all-solid-state secondary battery can be manufactured.

[0186] Furthermore, a positive electrode sheet or a negative electrode sheet for an all-solid-state secondary battery, and a solid electrolyte sheet for an all-solid-state secondary battery are produced as described above. Next, the positive electrode sheet or the negative electrode sheet for an all-solid-state secondary battery and the solid electrolyte sheet for an all-solid-state secondary battery are superimposed on each other with the positive electrode active material layer or the negative electrode active material layer in contact with the solid electrolyte layer, and pressurized. In this way, the solid electrolyte layer is transferred to the positive electrode sheet or the negative electrode sheet for an all-solid-state secondary battery. Thereafter, the solid electrolyte layer from which the substrate of the solid electrolyte sheet for an all-solid-state secondary battery has been peeled is superimposed on the negative electrode sheet or the positive electrode sheet for an all-solid-state secondary battery (with the negative electrode active material layer or the positive electrode active material layer in contact with the solid electrolyte layer), and pressurized. In this way, an all-solid-state secondary battery can be produced. The pressurization method and pressurization conditions in this method are not particularly limited, and the method and pressurization conditions described in the pressurization step described below can be applied.

[0187] The solid electrolyte layer or the like can be formed, for example, by pressure molding an inorganic solid electrolyte-containing composition or the like on a substrate or an active material layer under pressure conditions described below, or a sheet molded product of the solid electrolyte or active material can also be used. In the above-described production method, the inorganic solid electrolyte-containing composition of the present invention may be used for any one of the positive electrode composition, the inorganic solid electrolyte-containing composition, and the negative electrode composition. It is preferable to use the inorganic solid electrolyte-containing composition of the present invention for the inorganic solid electrolyte-containing composition or at least one of the positive electrode composition and the negative electrode composition, and the inorganic solid electrolyte-containing composition of the present invention may be used for any of the compositions. When a solid electrolyte layer or an active material layer is formed using a composition other than the inorganic solid electrolyte-containing composition of the present invention, examples of the material include commonly used compositions, etc. Alternatively, instead of forming a negative electrode active material layer during the production of an all-solid-state secondary battery, the negative electrode active material layer can be formed by bonding ions of a metal belonging to Group 1 or Group 2 of the periodic table, which have accumulated in the negative electrode current collector during initialization or charging during use (described later), with electrons and depositing the metal on the negative electrode current collector, etc.

[0188] <Formation of each layer (film formation)> The method for applying the inorganic solid electrolyte-containing composition is not particularly limited and can be appropriately selected, for example, by coating (preferably wet coating), spray coating, spin coating, dip coating, slit coating, stripe coating, or bar coating. In this case, the inorganic solid electrolyte-containing composition may be dried after each coating, or may be dried after multiple coatings. The drying temperature is not particularly limited. The lower limit is preferably 30°C or higher, more preferably 60°C or higher, and even more preferably 80°C or higher. The upper limit is preferably 300°C or lower, more preferably 250°C or lower, and even more preferably 200°C or lower. Heating within this temperature range allows the dispersion medium to be removed and the resulting layer to be in a solid state (coated, dried layer). In addition, it is preferable not to raise the temperature too high, as this avoids damaging the components of the all-solid-state secondary battery. This allows the all-solid-state secondary battery to exhibit excellent overall performance, as well as to obtain good binding properties and good ionic conductivity.

[0189] After applying the inorganic solid electrolyte-containing composition, after stacking the constituent layers, or after fabricating the all-solid-state secondary battery, it is preferable to pressurize each layer or the all-solid-state secondary battery. Examples of a pressurizing method include a hydraulic cylinder press. The pressure is not particularly limited, and is generally preferably in the range of 5 to 1500 MPa. The applied inorganic solid electrolyte-containing composition may be heated simultaneously with pressing. The heating temperature is not particularly limited and is generally in the range of 30 to 300°C. Pressing may also be performed at a temperature higher than the glass transition temperature of the inorganic solid electrolyte. Note that pressing may also be performed at a temperature higher than the glass transition temperature of the polymer contained in the polymer binder. However, the temperature is generally not higher than the melting point of the polymer. The pressure may be applied after the application solvent or dispersion medium has been dried in advance, or may be applied while the solvent or dispersion medium remains. The compositions may be applied simultaneously, or coating, drying and pressing may be carried out simultaneously and / or sequentially. After being applied to separate substrates, the compositions may be laminated by transfer.

[0190] The atmosphere in the film-forming method (coating, drying, and pressurization (under heating)) is not particularly limited, and may be any of the atmosphere, dry air (dew point -20°C or lower), and inert gas (e.g., argon gas, helium gas, and nitrogen gas). The pressing time may be short (for example, within a few hours) and high pressure may be applied, or long (for example, one day or more) and moderate pressure may be applied. In the case of an all-solid-state secondary battery other than a sheet for an all-solid-state secondary battery, for example, a restraining device for the all-solid-state secondary battery (such as a screw tightening pressure) may be used to continuously apply moderate pressure. The pressing pressure may be uniform or may vary with respect to the pressed portion such as the sheet surface. The pressure can be varied depending on the area or thickness of the pressed portion, or the same portion can be subjected to different pressures in stages. The press surface may be smooth or roughened.

[0191] The inorganic solid electrolyte-containing composition of the present invention can maintain excellent dispersion properties even when the solid content is increased. Therefore, the inorganic solid electrolyte-containing composition can be applied at a high solid content. In addition, in the present invention, the formation (film formation) of each of the above-mentioned layers, particularly the application and drying of the inorganic solid electrolyte-containing composition of the present invention, can be performed using a sheet-like substrate in a so-called batch system, but can also be performed by a roll-to-roll method, which is one of the most productive industrial production methods.

[0192] <Initialization> The all-solid-state secondary battery produced as described above is preferably initialized after production or before use. The initialization is not particularly limited, and can be performed, for example, by carrying out initial charge and discharge under an elevated pressure, and then releasing the pressure until the pressure reaches the general operating pressure of an all-solid-state secondary battery.

[0193] [Applications of all-solid-state secondary batteries] The all-solid-state secondary battery of the present invention can be used in a variety of applications. While there are no particular limitations on the application, examples of applications include electronic devices such as notebook computers, pen-input PCs, mobile PCs, electronic book players, mobile phones, cordless phone handsets, pagers, handheld terminals, portable fax machines, portable copiers, portable printers, headphone stereos, video camcorders, LCD televisions, handheld vacuum cleaners, portable CD players, mini-discs, electric shavers, transceivers, electronic organizers, calculators, memory cards, portable tape recorders, radios, and backup power supplies. Other consumer applications include automobiles (e.g., electric vehicles), electric vehicles, motors, lighting fixtures, toys, game consoles, road conditioners, clocks, flash devices, cameras, and medical devices (e.g., pacemakers, hearing aids, and shoulder massagers). Furthermore, the battery can be used for various military and space applications. It can also be combined with solar cells. [Example]

[0194] The present invention will be described in more detail below based on examples, but the present invention should not be construed as being limited thereto. In the following examples, "parts" and "%" representing compositions are based on mass unless otherwise specified. In the present invention, "room temperature" means 25°C.

[0195] 1. Polymer synthesis and preparation of binder solution or dispersion The binder-forming polymers shown in Table 1 and with the chemical formulas given below were synthesized as follows. [Synthesis Example S-1: Synthesis of Polymer S-1 and Preparation of Binder Solution S-1] To a 100 mL measuring cylinder were added 17.3 g of dodecyl acrylate (Tokyo Chemical Industry Co., Ltd.), 18.0 g of polyethylene glycol monomethyl ether methacrylate (molecular weight 300, Aldrich Chemical Co., Ltd.), 0.72 g of acrylic acid, and 4.30 g of polymerization initiator V-601 (trade name, Fujifilm Wako Pure Chemical Industries, Ltd.), and the mixture was dissolved in 72.0 g of butyl butyrate to prepare a monomer solution. 72.0 g of butyl butyrate was added to a 300 mL three-neck flask and stirred at 80°C, to which the above monomer solution was added dropwise over 2 hours. After the dropwise addition was completed, the temperature was raised to 90°C and stirring was continued for 2 hours. The resulting polymerization solution was poured into 480 g of methanol, stirred for 10 minutes, and then allowed to stand for 10 minutes. The supernatant was removed, and the resulting precipitate was dissolved in 80 g of butyl butyrate. The methanol was distilled off by heating at 30 hPa and 60°C for 1 hour. In this way, polymer S-1 (a (meth)acrylic polymer of a random copolymer) was synthesized, and a binder solution S-1 (concentration: 37% by mass) consisting of this polymer was obtained.

[0196] [Synthesis Example S-2: Synthesis of Polymer S-2 and Preparation of Binder Solution S-2] Polymer S-2 ((meth)acrylic polymer) was synthesized in the same manner as in Synthesis Example S-1, except that in Synthesis Example S-1, compounds were used that lead to each component so that polymer S-2 would have the following chemical formula and composition (types and contents of components) shown in Table 1, and a binder solution S-2 consisting of this polymer was obtained.

[0197] [Synthesis Example S-3: Synthesis of Polymer S-3 and Preparation of Binder Solution S-3] First, a macromonomer M-1 was synthesized as the constituent component (X) as follows. A monomer solution was prepared by adding 460 g of styrene (Tokyo Chemical Industry Co., Ltd.), 16.5 g of 3-mercaptopropionic acid, and 7.8 g of polymerization initiator V-601 (Fujifilm Wako Pure Chemical Industries, Ltd.) to a 1 L graduated cylinder and stirring to homogenize the mixture. A 2 L, three-neck flask was charged with 465.5 g of toluene (Fujifilm Wako Pure Chemical Industries, Ltd.) and stirred at 80°C. The monomer solution was then added dropwise over 2 hours. After the dropwise addition, the mixture was stirred at 80°C for 2 hours, then heated to 90°C and stirred for 2 hours. Next, 275 mg of 2,2,6,6-tetramethylpiperidine-1-oxyl (Fujifilm Wako Pure Chemical Industries, Ltd.), 27.5 g of glycidyl methacrylate (Tokyo Chemical Industry Co., Ltd.), and 5.5 g of tetrabutylammonium bromide (Fujifilm Wako Pure Chemical Industries, Ltd.) were added and stirred at 120°C for 3 hours. The solution was allowed to stand at room temperature, then poured into 1800 g of methanol, and the supernatant was removed. Butyl butyrate was added, and the methanol was distilled off under reduced pressure to obtain a butyl butyrate solution of macromonomer M-1. The solid content was 49% by mass. Next, polymer S-3 was synthesized using macromonomer M-1 as follows. To a 100 mL measuring cylinder, 10.8 g of dodecyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.), 47.8 g of macromonomer M-1 solution, 1.80 g of glycidyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.), and 2.10 g of polymerization initiator V-601 (trade name, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) were added and dissolved in 72.0 g of butyl butyrate to prepare a monomer solution. 72.0 g of butyl butyrate was added to a 300 mL three-neck flask and stirred at 80°C, to which the above monomer solution was added dropwise over 2 hours. After the dropwise addition was completed, the temperature was raised to 90°C and stirring was continued for 2 hours. The resulting polymerization solution was poured into 480 g of methanol, stirred for 10 minutes, and then allowed to stand for 10 minutes. The supernatant was removed, and the resulting precipitate was dissolved in 80 g of butyl butyrate. The methanol was distilled off by heating at 30 hPa and 60°C for 1 hour. In this way, polymer S-3 (a (meth)acrylic polymer of a random copolymer) was synthesized, and a binder solution S-3 (concentration: 32% by mass) consisting of this polymer was obtained.

[0198] [Synthesis Example S-4: Synthesis of Polymer S-4 and Preparation of Binder Solution S-4] First, macromonomer M-2 was synthesized as the constituent component (X) as follows. 156 g of ε-caprolactone and 44 g of 2-ethyl-1-hexanol were introduced into a 500 mL three-neck flask and dissolved by stirring while blowing in nitrogen. 0.1 g of monobutyltin oxide was added and the mixture was heated to 100°C. After 8 hours, the disappearance of the raw materials was confirmed by gas chromatography, and the mixture was cooled to 5°C. 233 g of butyl butyrate, 0.1 g of 2,6-di-t-butyl-4-methylphenol, and 38 g of triethylamine were added, followed by the addition of 32 g of acrylic acid chloride. After 1 hour, 1 After confirming the disappearance of the raw materials by H-NMR, 30 g of 1 M hydrochloric acid and 300 g of ethyl acetate were added, followed by extraction and washing with water. The resulting organic layer was dried over sodium sulfate and concentrated at 30 hPa and 70 °C to obtain macromonomer M-2. Next, polymer S-4 was synthesized using macromonomer M-2 as follows. A 100 mL measuring cylinder was charged with 34.6 g of macromonomer M-2, 1.08 g of 2-hydroxyethyl acrylate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), 0.36 g of maleic anhydride (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), and 4.20 g of polymerization initiator V-601 (trade name, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), and the resulting mixture was dissolved in 72.0 g of butyl butyrate to prepare a monomer solution. 72.0 g of butyl butyrate was added to a 300 mL three-neck flask and stirred at 80°C, to which the above monomer solution was added dropwise over 2 hours. After the dropwise addition was completed, the temperature was raised to 90°C and stirring was continued for 2 hours. The resulting polymerization solution was poured into 480 g of methanol, stirred for 10 minutes, and then allowed to stand for 10 minutes. The supernatant was removed, and the resulting precipitate was dissolved in 70 g of butyl butyrate. The methanol was distilled off by heating at 30 hPa and 60°C for 1 hour. In this way, polymer S-4 (a (meth)acrylic polymer of a random copolymer) was synthesized, and a binder solution S-4 (concentration: 36% by mass) consisting of this polymer was obtained.

[0199] [Synthesis Example S-5: Synthesis of Polymer S-5 and Preparation of Binder Solution S-5] First, macromonomer M-3 was synthesized as the constituent (X) in the following manner. A butyl butyrate solution of macromonomer M-3 (concentration 46% by mass) was obtained in the same manner as in Synthesis Example S-3 for synthesizing macromonomer M-1, except that dodecyl acrylate was used instead of styrene and the amount of 3-mercaptopropionic acid used was 25.4 g. Next, polymer S-5 ((meth)acrylic polymer) was synthesized in the same manner as in Synthesis Example S-4, except that in Synthesis Example S-4, compounds were used that lead to each component so that polymer S-5 had the composition (types and contents of components) shown in the following chemical formula and Table 1, and a binder solution S-5 consisting of this polymer was obtained.

[0200] [Synthesis Example S-6: Synthesis of Polymer S-6 and Preparation of Binder Solution S-6] First, macromonomer M-4 was synthesized as the constituent component (X) as follows. A butyl butyrate solution of macromonomer M-4 (solid concentration 46% by mass) was synthesized in the same manner as in Synthesis Example S-4, except that n-butyl acrylate was used instead of dodecyl acrylate in Synthesis Example S-5. Next, polymer S-6 ((meth)acrylic polymer) was synthesized in the same manner as in Synthesis Example S-4, except that in Synthesis Example S-4, compounds were used that would lead to each component so that polymer S-6 would have the composition (types and contents of components) shown in the following chemical formula and Table 1, and a binder solution S-6 consisting of this polymer was obtained.

[0201] [Synthesis Example S-7: Synthesis of Polymer S-7 and Preparation of Binder Solution S-7] Polymer S-7 ((meth)acrylic polymer) was synthesized in the same manner as in Synthesis Example S-4, except that in Synthesis Example S-4, compounds were used that lead to each component so that polymer S-7 would have the following chemical formula and composition (types and contents of components) shown in Table 1, and a binder solution S-7 consisting of this polymer was obtained.

[0202] [Synthesis Example S-8: Synthesis of Polymer S-8 and Preparation of Binder Solution S-8] Polymer S-8 ((meth)acrylic polymer) was synthesized using macromonomer M-7, which was synthesized in Synthesis Example S-5 by changing lauryl acrylate to dimethylacrylamide in the synthesis of macromonomer M-3, so that polymer S-8 had the following chemical formula and the composition (types and contents of constituent components) shown in Table 1, and binder solution S-8 consisting of this polymer was obtained. The content of constituent component (X) containing a polymer chain made of polydimethylacrylamide in polymer S-8 was 32.6 mol% based on the total number of moles.

[0203] [Synthesis Example S-9: Synthesis of Polymer S-9 and Preparation of Binder Solution S-9] In Synthesis Example S-5, macromonomer M-8 was synthesized by changing lauryl acrylate to trifluoroethyl methacrylate in the synthesis of macromonomer M-3, and polymer S-9 ((meth)acrylic polymer) was synthesized so that polymer S-9 had the following chemical formula and the composition (types and contents of constituent components) shown in Table 1, and binder solution S-9 consisting of this polymer was obtained.

[0204] [Synthesis Example S-10: Synthesis of Polymer S-10 and Preparation of Binder Solution S-10] In Synthesis Example S-1, lauryl acrylate was changed to isobutyl methacrylate and dimethylaminoethyl methacrylate to synthesize polymer S-10 ((meth)acrylic polymer) having the following chemical formula and composition (types and contents of constituent components) shown in Table 1, and a binder solution S-10 consisting of this polymer was obtained. In polymer S-10, the content of the component (N) derived from dimethylaminoethyl methacrylate was 6 mol % relative to the total number of moles.

[0205] [Synthesis Example S-11: Synthesis of Polymer S-11 and Preparation of Binder Solution S-11] In Synthesis Example S-1, lauryl acrylate was changed to methyl methacrylate, and polymer S-11 ((meth)acrylic polymer) was synthesized so that polymer S-11 had the following chemical formula and the composition (types and contents of constituent components) shown in Table 1, and binder solution S-11 consisting of this polymer was obtained.

[0206] [Synthesis Example S-12: Synthesis of Polymer S-12 and Preparation of Binder Solution S-12] In Synthesis Example S-11, polyethylene glycol monomethyl ether methacrylate (degree of polymerization 5, molecular weight 300) was changed to polyethylene glycol monomethyl ether methacrylate (degree of polymerization 19, molecular weight 950), and polymer S-12 ((meth)acrylic polymer) was synthesized so that polymer S-12 had the following chemical formula and composition (types and contents of constituent components) shown in Table 1, and binder solution S-12 consisting of this polymer was obtained.

[0207] [Synthesis Example S-13: Synthesis of Polymer S-13 and Preparation of Binder Solution S-13] In Synthesis Example S-1, lauryl acrylate was changed to benzyl methacrylate, and polymer S-13 ((meth)acrylic polymer) was synthesized so that polymer S-13 had the following chemical formula and the composition (types and contents of constituent components) shown in Table 1, and binder solution S-13 consisting of this polymer was obtained.

[0208] [Synthesis Example S-14: Synthesis of Polymer S-14 and Preparation of Binder Solution S-14] 25.0 g of diphenylmethane diisocyanate (manufactured by Tokyo Chemical Industry Co., Ltd.), 10.8 g of α-thioglycerol (manufactured by Tokyo Chemical Industry Co., Ltd.), and 200 g of butyl butyrate were charged and heated to 60°C under a nitrogen stream. Next, 0.05 g of Neostan U-600 (manufactured by Nitto Chemical Industry Co., Ltd.) was added, and the mixture was stirred at 60°C for 5 hours. Methanol was then added, and the mixture was stirred at 60°C for 30 minutes. After that, 27.6 g of polyethylene glycol monomethyl ether methacrylate (molecular weight 300, manufactured by Aldrich Chemicals), 0.58 g of acrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and 0.5 g of V-601 (trade name, manufactured by Fujifilm Wako Pure Chemical Industries Co., Ltd.) were added, and the mixture was stirred at 80°C for 2 hours. The reaction solution was then cooled to obtain a polymer S-14 solution (solids concentration 24% by mass).

[0209] [Synthesis Example S-15: Synthesis of Polymer S-15 and Preparation of Binder Solution S-15] 6.0 g of dipentaerythritol hexakis(3-mercaptopropionate) (Tokyo Chemical Industry Co., Ltd.), 18.0 g of polyethylene glycol monomethyl ether methacrylate (molecular weight 300, Aldrich Chemical Co., Ltd.), 72.0 g of butyl butyrate, and 1.0 g of polymerization initiator V-601 (trade name, Fujifilm Wako Pure Chemical Industries, Ltd.) were added and stirred at 80°C for 2 hours. Thereafter, 17.3 g of methyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.72 g of acrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and 1.0 g of a polymerization initiator V-601 (trade name, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) were added to the obtained solution, and the mixture was further stirred at 80°C for 2 hours to obtain binder solution S-15 (solid content concentration 38% by mass). Polymer S-15 is a (meth)acrylic polymer with a star structure in which six polymer chains made of a (meth)acrylic polymer having the composition shown in Table 1 are bonded as arms to one core derived from the above-mentioned compound A-5, and each arm has a mass-average molecular weight of 890.

[0210] [Synthesis Example T-1: Synthesis of Polymer T-1 and Preparation of Binder Solution T-1] Polymer T-1 ((meth)acrylic polymer) was synthesized in the same manner as in Synthesis Example S-4, except that in Synthesis Example S-4, compounds were used that lead to each component so that polymer T-1 had the following chemical formula and composition (types and contents of components) shown in Table 1, and a binder solution T-1 consisting of this polymer was obtained.

[0211] [Synthesis Example T-2: Synthesis of Polymer T-2 and Preparation of Binder Solution T-2] A 300 mL three-neck flask was charged with 20 g of polyethyleneimine (SP-200, number average molecular weight 10,000, manufactured by Nippon Shokubai Co., Ltd.), 0.19 g of p-methoxyphenol, 18.0 g of Blenmer PME-400 (manufactured by NOF Corporation), and 15.4 g of dodecyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.), and the mixture was heated at 80°C for 3 hours. Next, a solution of 5.0 g of succinic anhydride (Tokyo Chemical Industry Co., Ltd.) mixed with 100 g of propylene glycol 1-monomethyl ether 2-acetate was added dropwise over 20 minutes and stirred for 3 hours. The resulting polymer solution was poured into 800 g of hexane / isopropanol (mass ratio 8 / 2), the supernatant was removed, and the polymer was dissolved in 70 g of butyl butyrate. The mixture was heated at 60°C under 30 hPa for 1 hour to distill off the methanol. In this way, polymer T-2 was synthesized, and a binder solution T-2 (concentration: 30% by mass) made of this polymer was obtained.

[0212] [Synthesis Example T-3: Synthesis of Polymer T-3 and Preparation of Binder Dispersion T-3] 28.8 g of methoxyethyl acrylate (Tokyo Chemical Industry Co., Ltd.) and 1.40 g of polymerization initiator V-601 (trade name, Fujifilm Wako Pure Chemical Industries Co., Ltd.) were added to a 100 mL graduated cylinder and dissolved in 28.8 g of butyl butyrate to prepare a monomer solution. In a 300 mL three-necked flask, 15.7 g of the macromonomer M-4 solution and 36.0 g of butyl butyrate were added and stirred at 80° C., and the above monomer solution was added dropwise over 2 hours. After completion of the dropwise addition, the temperature was raised to 90° C. and the mixture was stirred for 2 hours. In this way, a binder dispersion T-3 (concentration: 40% by mass) was obtained by dispersing the polymer T-3 in butyl butyrate. The average particle size of the binder in this dispersion was 150 nm.

[0213] [Synthesis Example T-4: Synthesis of Polymer T-4 and Preparation of Binder Dispersion T-4] In Synthesis Example S-1, lauryl acrylate was changed to isobutyl methacrylate and dimethylaminoethyl methacrylate to synthesize polymer T-4 ((meth)acrylic polymer) having the following chemical formula and composition (types and contents of constituent components) shown in Table 1, and binder solution T-4 consisting of this polymer was obtained. In polymer T-4, the content of the component (N) derived from dimethylaminoethyl methacrylate was 18 mol % relative to the total number of moles.

[0214] [Synthesis Example T-5: Synthesis of Polymer T-5 and Preparation of Binder Solution T-5] In Synthesis Example S-1, polymer T-5 ((meth)acrylic polymer) was synthesized using dodecyl acrylate and acrylic acid instead of polyethylene glycol monomethyl ether methacrylate (degree of polymerization 5, molecular weight 300) so that polymer T-5 had the following chemical formula and the composition (types and contents of constituent components) shown in Table 1, and binder solution T-5 consisting of this polymer was obtained.

[0215] [Synthesis Example T-6: Synthesis of Polymer T-6 and Preparation of Binder Solution T-6] In Synthesis Example T-5, polymer T-6 ((meth)acrylic polymer) was synthesized without using acrylic acid so that polymer T-6 had the following chemical formula and the composition (types and contents of constituent components) shown in Table 1, and a binder solution T-6 consisting of this polymer was obtained.

[0216] The composition, glass transition temperature Tg (℃), and SP value (MPa) of each synthesized polymer 1 / 2 ) and mass average molecular weight, and further, the degree of polymerization, number average molecular weight and SP value (MPa 1 / 2) are shown in Table 1. The glass transition temperature Tg, SP value, mass average molecular weight, and number average molecular weight were measured by the above-mentioned methods. The "State" column in Table 1 shows the state of the binder in each composition (dissolved or dispersed in particulate form), which will be described later. In Table 1, when a polymer has two constituent components corresponding to each constituent component, they are both indicated with a " / " symbol.

[0217] The synthesized polymers are shown below. The numbers at the bottom right of each component indicate the content (mass%). Y and R Z indicates a linking group or a substituent. Polymer S-15 is shown separately as a core portion and an arm portion, and the wavy line portion of the core portion indicates the bonding position with the arm portion.

[0218] [ka]

[0219] [ka]

[0220] [Table 1]

[0221] In the table, "-" in the component column indicates that the corresponding component is not present. All of the components constituting polymer T-2 correspond to component (N), and are shown in the respective component columns. - Component (X) - PEGMEM: polyethylene glycol methyl ether methacrylate (degree of polymerization 5, manufactured by Aldrich) M-1 to M-4: Macromonomers synthesized in the above synthesis examples M-5: X-22-174ASX (product number, manufactured by Shin-Etsu Silicone Co., Ltd.) M-6: A component formed by adding Blenmar PME-400 to ethyleneimine M-7: Macromonomer synthesized in Synthesis Example S-8 above M-8: Macromonomer synthesized in Synthesis Example S-9 above

[0222] - Component (A) - AA: acrylic acid GMA: Glycidyl methacrylate MA: Maleic acid monomethyl ester HEA: 2-hydroxyethyl acrylate B-2: A component formed by the addition of succinic anhydride to ethyleneimine MEA: methoxyethyl acrylate The components (X) and (A) in polymer S-14 are components in which PEGMEM or AA is added to α-thioglycerol, respectively, but in Table 1 they are simply referred to as PEGMEM or AA.

[0223] -Other components- Other components refer to components that do not correspond to either component (X) or component (A). LA: Dodecyl acrylate St: styrene BA: n-butyl acrylate i-BuMA: Isobutyl methacrylate DMAEMA: Dimethylaminoethyl methacrylate MMA: Methyl methacrylate BnMA: benzyl methacrylate MDI: Diphenylmethane diisocyanate B-1: Component in which dodecyl methacrylate is added to ethyleneimine

[0224] 2. Synthesis of sulfide-based inorganic solid electrolytes [Synthesis example A] The sulfide-based inorganic solid electrolyte was synthesized with reference to the non-patent literature of T. Ohtomo, A. Hayashi, M. Tatsumisago, Y. Tsuchida, S. Hama, K. Kawamoto, Journal of Power Sources, 233, (2013), pp. 231-235, and A. Hayashi, S. Hama, H. Morimoto, M. Tatsumisago, T. Minami, Chem. Lett., (2001), pp. 872-873. Specifically, in a glove box under an argon atmosphere (dew point -70°C), 2.42 g of lithium sulfide (Li2S, Aldrich, purity >99.98%) and 3.90 g of diphosphorus pentasulfide (P2S5, Aldrich, purity >99%) were weighed out, placed in an agate mortar, and mixed for 5 minutes using an agate pestle. The molar ratio of Li2S to P2S5 was Li2S:P2S5 = 75:25. Next, 66 g of 5 mm diameter zirconia beads were placed in a 45 mL zirconia container (manufactured by Fritsch), and the entire lithium sulfide and diphosphorus pentasulfide mixture was added. The container was then completely sealed under an argon atmosphere. The container was then placed in a planetary ball mill (trade name, manufactured by Fritsch) and mechanically milled at 25°C and 510 rpm for 20 hours to obtain 6.20 g of a yellow sulfide-based inorganic solid electrolyte powder (Li-PS-based glass, hereafter sometimes referred to as LPS). The particle diameter of the Li-PS-based glass was 15 μm.

[0225] [Example 1] Each of the compositions shown in Tables 2-1 to 2-4 (collectively referred to as Table 2) was prepared as follows. <Preparation of Inorganic Solid Electrolyte-Containing Composition> 60 g of zirconia beads with a diameter of 5 mm were placed in a 45 mL zirconia container (manufactured by Fritsch), and 9.6 g of the LPS synthesized in Synthesis Example A above, 0.20 g (solid content by mass) of the binder solution or dispersion shown in Table 2-1, and 10.2 g of butyl butyrate as a dispersion medium were then placed in the container. The container was then set in a planetary ball mill P-7 (trade name). Mixing was carried out for 10 minutes at a temperature of 25°C and a rotation speed of 150 rpm to prepare inorganic solid electrolyte-containing compositions (slurries) K-1 to K-15, respectively. In addition, inorganic solid electrolyte-containing compositions (slurries) Kc11 to Kc16 were prepared in the same manner as in the preparation of inorganic solid electrolyte-containing composition K-1, except that the binder solution and the contents of each component were changed to the binder solutions or dispersions shown in Table 2-4 and the contents were set to those shown in the same table (the amount of butyl butyrate used was changed).

[0226] <Preparation of Positive Electrode Composition> 60 g of zirconia beads with a diameter of 5 mm were placed in a 45 mL zirconia container (manufactured by Fritsch), along with 3.8 g of the LPS synthesized in Synthesis Example A and 14.0 g (total amount) of butyl butyrate as a dispersion medium. The container was then placed in a planetary ball mill (product name) P-7 and stirred at 25°C and 200 rpm for 30 minutes. Next, 9.8 g of NMC (manufactured by Aldrich) as a positive electrode active material, 0.3 g of acetylene black (AB) as a conductive additive, and 0.14 g (solid content by mass) of the binder solution or dispersion shown in Table 2-2 were placed in the container. The container was then placed in a planetary ball mill (product name) P-7 and continued mixing at 25°C and 200 rpm for 30 minutes to prepare positive electrode compositions (slurries) PK-1 to PK-15, respectively. In addition, positive electrode compositions (slurries) PKc21 to PKc26 were prepared in the same manner as in the preparation of positive electrode composition PK-1, except that the binder solution or dispersion and the content of each component were changed to the binder solution shown in Table 2-4 and the contents were set to those shown in the same table (the amount of butyl butyrate used was changed).

[0227] <Preparation of negative electrode composition> A 45 mL zirconia container (manufactured by Fritsch) was charged with 60 g of zirconia beads with a diameter of 5 mm, 4.7 g of LPS synthesized in Synthesis Example A, 0.10 g (solid mass) of the binder solution or dispersion shown in Table 2-3, and 9.6 g (total amount) of butyl butyrate. The container was placed in a planetary ball mill P-7 (trade name) and mixed at 25°C and 300 rpm for 60 minutes. Subsequently, 5.2 g of silicon (Si) as the negative electrode active material and 0.4 g of VGCF (manufactured by Showa Denko K.K.) as the conductive additive were added. Similarly, the container was placed in a planetary ball mill P-7 (trade name) and mixed at 25°C and 100 rpm for 10 minutes to prepare negative electrode compositions (slurries) NK-1 to NK-15, respectively. In addition, negative electrode compositions (slurries) NKc21 to NKc26 were prepared in the same manner as negative electrode composition NK-1, except that the binder solution or dispersion and the content of each component were changed to the binder solution shown in Table 2-4 and the contents were set to those shown in the same table (the amount of butyl butyrate used was changed).

[0228] For each of the prepared compositions, the difference (absolute value) between the SP value of the polymers S-1 to S-15 and T-1 to T-6 that form the binder and the SP value of the dispersion medium, and the difference (absolute value) between the SP value of the constituent component (X) contained in the polymer and the SP value of the dispersion medium were calculated, and are shown in the "Polymer" and "Constituent component (X)" columns of the "Difference in SP value from dispersion medium" column in Table 2. The unit of the difference in SP value is MPa. 1 / 2 However, this is omitted in Table 2. In Table 2, the composition content is the content (mass%) relative to the total mass of the composition, and the solid content is the content (mass%) relative to 100% by mass of the solid content of the composition, and units are omitted in the table.

[0229] [Table 2-1]

[0230] [Table 2-2]

[0231] [Table 2-3]

[0232] [Table 2-4]

[0233] LPS: LPS synthesized in Synthesis Example A NMC:LiNi 1 / 3 Co 1 / 3 Mn 1 / 3 O2 Si: Silicon (APS 1-5 μm, manufactured by Alfa Aesar) AB: Acetylene black VGCF: Carbon nanotubes

[0234] <Preparation of solid electrolyte sheets for all-solid-state secondary batteries> Each of the inorganic solid electrolyte-containing compositions shown in the "Solid Electrolyte Composition No." column in Table 3-1 or Table 3-4 obtained above was applied to a 20 μm-thick aluminum foil using a Baker-type applicator (product name: SA-201, manufactured by Tester Sangyo Co., Ltd.) and heated at 80°C for 2 hours to dry the inorganic solid electrolyte-containing composition (removing the dispersion medium). The dried inorganic solid electrolyte-containing composition was then heated and pressed at 120°C and 40 MPa for 10 seconds using a heat press to produce solid electrolyte sheets for all-solid-state secondary batteries (referred to as solid electrolyte sheets in Tables 3-1 and 3-4) 101 to 107, 123 to 130, and c11 to c16, respectively. The solid electrolyte layer thickness was 40 μm. Sheet No. 122 will be omitted.

[0235] <Preparation of positive electrode sheet for all-solid-state secondary battery> Each of the positive electrode compositions shown in the "Electrode Composition No." column in Table 3-2 or Table 3-4 obtained above was applied to a 20 μm-thick aluminum foil using a Baker-type applicator (product name: SA-201), heated at 80°C for 1 hour, and then heated at 110°C for 1 hour to dry the positive electrode composition (removing the dispersion medium). Thereafter, using a heat press, the dried positive electrode composition was pressed (10 MPa, 1 minute) at 25°C to produce positive electrode sheets for all-solid-state secondary batteries (referred to as positive electrode sheets in Tables 3-2 and 3-4) 108 to 114, 131 to 138, and c21 to c26, respectively, each having a positive electrode active material layer with a thickness of 70 μm.

[0236] <Preparation of negative electrode sheet for all-solid-state secondary battery> Each negative electrode composition shown in the "Electrode Composition No." column in Table 3-3 or Table 3-4 obtained above was applied to a copper foil with a thickness of 20 μm using a Baker-type applicator (product name: SA-201), heated at 80°C for 1 hour, and then heated at 110°C for 1 hour to dry the negative electrode composition (removing the dispersion medium). Thereafter, using a heat press, the dried negative electrode composition was pressed (10 MPa, 1 minute) at 25°C to produce negative electrode sheets for all-solid-state secondary batteries (referred to as negative electrode sheets in Tables 3-3 and 3-4) 115 to 121, 139 to 146, and c31 to c36, respectively, each having a negative electrode active material layer with a thickness of 60 μm.

[0237] <Evaluation 1: Storage stability test (redispersibility)> For each composition prepared as described above, LPS, polymer binder, dispersion medium, active material, and conductive additive were mixed in the same proportions as the composition content and solid content ratios shown in Table 2 under the same conditions as for each composition to prepare a composition (slurry) for dispersibility evaluation. For each prepared composition, the occurrence (presence or absence) of solid particle aggregates was confirmed using a grind meter (manufactured by Asahi Research Institute Co., Ltd.). The size of the aggregates at this time was designated X (μm) and used as an index of initial dispersibility. Separately, each of the prepared compositions was left at 25°C for 24 hours and then remixed at 25°C using a planetary ball mill P-7 (trade name). The rotation speed and time during remixing were the same as those used for preparing the inorganic solid electrolyte composition, the positive electrode composition, and the negative electrode composition. The remixed compositions were examined for the presence or absence of solid particle aggregates using the grind meter. The size of the aggregates at this time was designated Y (μm) and used as an index of redispersibility after storage. The size of the aggregates was determined by the point at which noticeable spots appeared on the applied material on the grind meter (see JIS K-5600-2-5 6.6). The tendency for aggregates to form (aggregation tendency or sedimentation tendency) was evaluated as the storage stability (redispersibility of solid particles) of the solid electrolyte composition depending on which of the following evaluation criteria the aggregate sizes X and Y fell under. In this test, the smaller the aggregate size X, the better the initial dispersibility, and the smaller the aggregate size Y, the better the storage stability. In this test, an aggregate size Y of "D" or higher was considered acceptable, and when the size Y was 8 μm or less (evaluation criteria "C" or higher), the aggregate size X was also included in the evaluation. The results are shown in Tables 3-1 to 3-4 (collectively referred to as Table 3). - Evaluation Criteria - A: Y≦ 5μm and X≦ 5μm B: 5μm <Y≦ 8μm かつ 5μm<X≦ 8μm C: 5μm <Y≦ 8μm かつ 8μm<X≦12μm D: 8μm <Y≦10μm E: 10 μm <Y≦20μm F: 20 μm <Y

[0238] <Evaluation 2: Slurry thickening test (solids concentration test)> For each composition prepared as described above, LPS, polymer binder, dispersion medium, active material, and conductive additive were mixed in the same proportions as the composition content and solid content ratios shown in Table 2 under the same conditions as for each composition to prepare a composition (slurry) for dispersibility evaluation. Each prepared composition was checked for the presence of solid particle agglomerates using a grindmeter (manufactured by Asahi Research Institute Co., Ltd.). In this test, the particle size at which linear and granular marks were generated was observed using the grindmeter, and a particle size of 5 μm or less was defined as the absence of agglomerates. In addition, each composition was evaluated for uniformity (constant coating thickness without running out) using a Baker-type applicator (product name: SA-201) at 25°C. This evaluation (presence or absence of agglomerates and applicability) was repeated by gradually increasing the solids concentration in the composition until agglomerates formed or uniform application became impossible. The dispersibility at high solids concentrations was evaluated based on which of the following evaluation criteria the maximum solids concentration at which uniform application was possible without the formation of agglomerates fell under. The results are shown in Table 3. In this test, a higher maximum solid concentration indicates that excellent dispersibility of solid particles can be maintained even when the solid concentration of the composition is increased, and an evaluation standard of "D" or higher is a passing level. - Evaluation Criteria - A: 70% by mass or more B: Less than 70% by mass, 65% by mass or more C: Less than 65% by mass, 60% by mass or more D: Less than 60% by mass, 55% by mass or more E: Less than 55% by mass, 50% by mass or more F: Less than 50% by mass

[0239] <Evaluation 3: Oxidation resistance (resistance to oxidation degradation)> The prepared inorganic solid electrolyte-containing compositions (slurries) K-1 to K-15 and Kc11 to Kc16 were each placed in an aluminum cup and dried for 2 hours at 100° C. 30 mg of the obtained dried product and 9 mg of acetylene black were placed in a mortar and ground for 5 minutes to prepare test compositions. Next, 100 mg of LPS synthesized in Synthesis Example A was placed in a 10 mm inner diameter PET cylindrical container, and 10 mm stainless steel (SUS) rods were inserted into both openings of the cylindrical container and pressurized to 10 MPa. 30 mg of each test composition prepared above was then placed in the container and pressurized to 30 MPa. Indium foil and Lithium foil were then layered in this order and pressurized to 30 MPa. After releasing the pressure, cyclic voltammetry measurements were performed under the following conditions while applying a pressure of 8 MPa. - Cyclic voltammetry measurement conditions - Oxidation potential range: +1.8V to +5.0V (vs InLi) Sweep speed: 0.1mV / s The electrochemical oxidation resistance of the inorganic solid electrolyte-containing composition (polymer binder) was evaluated based on whether the minimum current value at 4.2 to 4.5 V in cyclic voltammetry fell within any of the following evaluation criteria. In this test, a smaller current value indicates better oxidation resistance and an effect of suppressing the deterioration of the cycle characteristics of the all-solid-state secondary battery. This test is a test for evaluating the cycle characteristics of the all-solid-state secondary battery from the perspective of the resistance of the polymer binder to oxidation degradation, and is used as a reference test in the present invention. In this test, the pass level is not limited as long as the cycle characteristics test is passed, but an evaluation criterion of "D" or higher is preferred. The results are shown in Tables 3-1 and 3-4. - Evaluation Criteria - A: Less than 0.030mA B: 0.030mA or more, less than 0.040mA C: 0.040mA or more, less than 0.050mA D: 0.050mA or more, less than 0.060mA E: 0.060mA or more, less than 0.070mA F: 0.070mA or more

[0240] [Table 3-1]

[0241] [Table 3-2]

[0242] [Table 3-3]

[0243] [Table 3-4]

[0244] <Manufacturing of all-solid-state secondary batteries> First, a positive electrode sheet for an all-solid-state secondary battery having a solid electrolyte layer and a negative electrode sheet for an all-solid-state secondary battery having a solid electrolyte layer were produced, both of which were to be used in the production of an all-solid-state secondary battery.

[0245] - Fabrication of a cathode sheet with a solid electrolyte layer for all-solid-state secondary batteries - On the positive electrode active material layer of each positive electrode sheet for an all-solid-state secondary battery shown in the "Electrode active material layer (sheet No.)" column of Table 4, the solid electrolyte sheet shown in the "Solid electrolyte layer (sheet No.)" column of Table 4 prepared above was superimposed so that the solid electrolyte layer was in contact with the positive electrode active material layer, and after transferring (laminating) by applying a pressure of 50 MPa at 25°C using a press, pressure was applied at 25°C and 600 MPa to prepare positive electrode sheets for an all-solid-state secondary battery Nos. 108 to 114, 131 to 138, and c21 to c26 (positive electrode active material layer thickness 50 μm), each having a solid electrolyte layer with a thickness of 25 μm. Two types of positive electrode sheets for all-solid-state secondary batteries No. 111 were produced: a sheet laminated with a solid electrolyte layer 104 for use in all-solid-state secondary battery No. 104, and a sheet laminated with a solid electrolyte layer c11 for use in all-solid-state secondary battery No. 108.

[0246] - Fabrication of a negative electrode sheet with a solid electrolyte layer for all-solid-state secondary batteries - On the negative electrode active material layer of each negative electrode sheet for all solid state secondary batteries shown in the "Electrode active material layer (sheet No.)" column of Table 4, the solid electrolyte sheet shown in the "Solid electrolyte layer (sheet No.)" column of Table 4 prepared above was superimposed so that the solid electrolyte layer was in contact with the negative electrode active material layer, and after transferring (laminating) by applying a pressure of 50 MPa at 25°C using a press, pressure was applied at 25°C and 600 MPa to prepare negative electrode sheets for all solid state secondary batteries 115 to 121, 139 to 146, and c31 to c36 each having a solid electrolyte layer with a thickness of 25 μm (negative electrode active material layer thickness: 40 μm). Two types of negative electrode sheets for all solid state secondary batteries No. 118 were produced: a sheet laminated with a solid electrolyte layer 104 for use in all solid state secondary battery No. 112, and a sheet laminated with a solid electrolyte layer c11 for use in all solid state secondary battery No. 116.

[0247] An all-solid-state secondary battery No. 101 having the layer structure shown in FIG. 1 was fabricated as follows. The positive electrode sheet for an all-solid-state secondary battery No. 108 provided with a solid electrolyte layer obtained above (the aluminum foil of the solid electrolyte-containing sheet had been peeled off) was cut into a disk shape with a diameter of 14.5 mm and placed in a stainless steel 2032-type coin case 11 incorporating a spacer and a washer (not shown in FIG. 2), as shown in FIG. 2. Next, a lithium foil cut into a disk shape with a diameter of 15 mm was placed on top of the solid electrolyte layer. After that, stainless steel foil was further placed on top of that, and the 2032-type coin case 11 was crimped to produce the all-solid-state secondary battery No. 101 shown in FIG. 2. The all-solid-state secondary battery produced in this manner has the layer structure shown in FIG. 1 (where the lithium foil corresponds to the negative electrode active material layer 2 and the negative electrode current collector 1).

[0248] All solid state secondary batteries Nos. 102 to 108, 117 to 124, c101 to c103, and c107 to c109 were produced in the same manner as in the production of all solid state secondary battery No. 101, except that in the production of the all solid state secondary battery No. 101, positive electrode sheets for all solid state secondary batteries having a solid electrolyte layer, represented by the numbers shown in the “Electrode active material layer (sheet No.)” column in Table 4, were used instead of positive electrode sheet No. 108 for all solid state secondary batteries having a solid electrolyte layer.

[0249] An all-solid-state secondary battery No. 109 having the layer structure shown in FIG. 1 was fabricated as follows. The solid electrolyte-containing negative electrode sheet No. 115 for an all-solid-state secondary battery obtained above (the aluminum foil of the solid electrolyte-containing sheet had been peeled off) was cut into a disk shape with a diameter of 14.5 mm and placed in a stainless steel 2032-type coin case 11 incorporating a spacer and a washer (not shown in FIG. 2 ) as shown in FIG. 2 . Next, a positive electrode sheet (positive electrode active material layer) punched out to a diameter of 14.0 mm from the positive electrode sheet for an all-solid-state secondary battery prepared below was placed on top of the solid electrolyte layer. A stainless steel foil (positive electrode current collector) was further placed on top of the positive electrode sheet to form an all-solid-state secondary battery laminate 12 (a laminate consisting of stainless steel foil-aluminum foil-positive electrode active material layer-solid electrolyte layer-negative electrode active material layer-copper foil). The 2032-type coin case 11 was then crimped to produce the all-solid-state secondary battery No. 109 shown in FIG. 2 .

[0250] A positive electrode sheet for a solid secondary battery used in the production of all solid secondary battery No. 109 was prepared as follows. - Preparation of positive electrode composition - A 45 mL zirconia container (manufactured by Fritsch) was charged with 180 zirconia beads with a diameter of 5 mm, and 2.7 g of the LPS synthesized in Synthesis Example A above, 0.3 g of KYNAR FLEX 2500-20 (trade name, PVdF-HFP: polyvinylidene fluoride hexafluoropropylene copolymer, manufactured by Arkema) as a solid content mass, and 22 g of butyl butyrate were added. The container was placed in a Fritsch planetary ball mill P-7 (trade name) and stirred at 25°C at 300 rpm for 60 minutes. LiNi was then added as a positive electrode active material.1 / 3 Co 1 / 3 Mn 1 / 3 7.0 g of O2 (NMC) was added, and the container was similarly set in the planetary ball mill P-7, and mixing was continued for 5 minutes at 25°C and 100 rpm to prepare a positive electrode composition. - Fabrication of positive electrode sheets for solid secondary batteries - The positive electrode composition obtained above was applied to a 20 μm-thick aluminum foil (positive electrode current collector) using a Baker-type applicator (product name: SA-201, manufactured by Tester Sangyo Co., Ltd.), and heated at 100° C. for 2 hours to dry the positive electrode composition (remove the dispersion medium). Thereafter, using a heat press, the dried positive electrode composition was pressed (10 MPa, 1 minute) at 25° C. to produce a positive electrode sheet for an all-solid-state secondary battery having a positive electrode active material layer with a thickness of 80 μm.

[0251] All solid state secondary batteries Nos. 110 to 116, 125 to 132, c104 to c106, and c110 to c112 were produced in the same manner as in the production of all solid state secondary battery No. 109, except that in the production of all solid state secondary battery No. 109, negative electrode sheets for all solid state secondary batteries having a solid electrolyte layer, represented by the numbers shown in the "Electrode active material layer (sheet No.)" column in Table 4, were used instead of negative electrode sheet No. 115 for all solid state secondary batteries having a solid electrolyte layer.

[0252] <Evaluation 4: Ionic conductivity measurement> The ionic conductivity of each of the manufactured all-solid-state secondary batteries was measured. Specifically, for each all-solid-state secondary battery, AC impedance was measured at a voltage amplitude of 5 mV and a frequency of 1 MHz to 1 Hz using a 1255B FREQUENCY RESPONSE ANALYZER (trade name, manufactured by SOLARTRON) in a thermostatic bath at 25°C. From this, the resistance in the layer thickness direction of the ionic conductivity measurement sample was determined, and the ionic conductivity was calculated using the following formula (C1). The results are shown in Table 4. Equation (C1): Ionic conductivity σ (mS / cm) = 1000 × sample layer thickness (cm) / [resistance (Ω) × sample area (cm 2 )] In formula (C1), the sample layer thickness is the value (total thickness of the solid electrolyte layer and the electrode active material layer) measured before placing the laminate 12 in the 2032-type coin case 11, and is the value obtained by subtracting the thickness of the current collector. The sample area is the area of ​​a disk-shaped sheet with a diameter of 14.5 mm. The obtained ionic conductivity σ was judged to fall within any of the following evaluation criteria. In this test, the ionic conductivity σ is evaluated as passing if it is "D" or higher. - Evaluation Criteria - A: 0.30≦σ B: 0.25≦σ<0.30 C: 0.20≦σ<0.25 D: 0.15≦σ<0.20 E:0.10≦σ<0.15 F: σ<0.10

[0253] <Evaluation 5: Cycle characteristics> The discharge capacity retention rate of each of the produced all-solid-state secondary batteries was measured using a charge / discharge evaluation device TOSCAT-3000 (trade name, manufactured by Toyo Systems Co., Ltd.). Specifically, each all-solid-state secondary battery was charged at a current density of 0.1 mA / cm in an environment of 25°C. 2 The battery was charged at a current density of 0.1 mA / cm until the battery voltage reached 4.3 V. 2 The battery was discharged at 1000 kJ / s until the battery voltage reached 2.5 V. This one charge and one discharge constituted one charge / discharge cycle, and three charge / discharge cycles were repeated under the same conditions to initialize the battery. Thereafter, the above charge / discharge cycle was repeated, and the discharge capacity of each all-solid-state secondary battery was measured after each charge / discharge cycle using a charge / discharge evaluation device: TOSCAT-3000 (product name). The discharge capacity of the first charge / discharge cycle after initialization (initial discharge capacity) was taken as 100%, and the number of charge / discharge cycles at which the discharge capacity retention rate (discharge capacity relative to the initial discharge capacity) reached 80% was evaluated based on which of the following evaluation criteria the battery performance (cycle characteristics) fell into. In this test, the higher the evaluation criterion, the better the battery performance (cycle characteristics), and the more likely the battery is to maintain its initial battery performance even after multiple charge / discharge cycles (even during long-term use). In this test, cycle characteristics that achieved an evaluation criterion of "D" or higher were considered acceptable. The results are shown in Table 4. All of the all solid state secondary batteries Nos. 101 to 132 exhibited initial discharge capacities sufficient to function as all solid state secondary batteries. - Evaluation Criteria - A: More than 600 cycles B: 450 cycles or more, less than 600 cycles C: 300 cycles or more, less than 450 cycles D: 150 cycles or more, less than 300 cycles E: 80 or more cycles, less than 150 cycles F: 40 cycles or more, less than 80 cycles

[0254] [Table 4]

[0255] The results shown in Tables 3 and 4 reveal the following. The comparative inorganic solid electrolyte-containing compositions shown in Nos. Kc11 and Kc13 to Kc16, which do not contain the polymer binder specified in the present invention, are inferior in dispersion characteristics (storage stability and slurry thickening) and cannot improve the cycle characteristics of all-solid-state secondary batteries. The ionic conductivity of Nos. Kc11 and Kc14 to Kc16 also cannot be improved. The comparative inorganic solid electrolyte-containing composition shown in No. Kc12, which does not contain the polymer binder specified in the present invention, meets the dispersion characteristics criteria, but also fails to improve the ionic conductivity and cycle characteristics. The polymer binder used in Kc12 and Kc14 also lacks sufficient resistance to oxidation degradation. It can be seen that the electrode compositions shown in PKc21 to PKc26 and NKc21 to NKc26 also show similar trends to the comparative inorganic solid electrolyte-containing compositions. In contrast, the inorganic solid electrolyte-containing compositions shown in Nos. K-1 to K-15, which contain the polymer binder defined in the present invention, have excellent dispersion properties and also excellent oxidation resistance. Furthermore, the electrode compositions shown in Nos. PK-1 to PK-15 and NK-1 to NK-15 also have excellent dispersion properties. Since the inorganic solid electrolyte-containing compositions of the present invention have excellent oxidation resistance, it is clear that electrode compositions using the same polymer binder as the inorganic solid electrolyte-containing compositions also exhibit excellent oxidation resistance. It is clear that by using these inorganic solid electrolyte-containing compositions to form the constituent layers of an all-solid-state secondary battery, the resulting all-solid-state secondary battery can achieve excellent cycle characteristics and high ionic conductivity (low resistance). The oxidation resistance test was performed on a sheet for an all-solid-state secondary battery, which is most likely to come into contact with oxygen in the actual manufacturing process. If a composition exhibits an oxidation-inhibiting effect in a sheet for an all-solid-state secondary battery, the same effect can be expected in an inorganic solid electrolyte-containing composition and further in a constituent layer incorporated in an all-solid-state secondary battery.

[0256] While the present invention has been described in connection with embodiments thereof, we do not intend to limit our invention to any of the details of the description unless otherwise specified, and believe that the claims should be construed broadly without departing from the spirit and scope of the invention as set forth in the appended claims.

[0257] This application claims priority based on Japanese Patent Application No. 2020-177999 filed on October 23, 2020, and Japanese Patent Application No. 2021-031967 filed on March 1, 2021, the contents of which are incorporated herein by reference. [Explanation of symbols]

[0258] 1 Negative electrode current collector 2 Negative electrode active material layer 3 Solid electrolyte layer 4 Cathode active material layer 5 Positive electrode current collector 6. Operating parts 10 All-solid-state secondary battery 11 2032 type coin case 12. Laminates for all-solid-state secondary batteries 13 Coin-type all-solid-state secondary battery

Claims

1. An inorganic solid electrolyte-containing composition comprising an inorganic solid electrolyte having ionic conductivity of a metal belonging to Group 1 or 2 of the periodic table, a polymer binder, and a dispersion medium, the polymer binder comprises a polymer having a constituent component (X) having a polymer chain and a constituent component (A) having at least one functional group selected from the following functional group group (a), and having a constituent component (N) containing a nitrogen atom in a content of less than 10 mol% based on all constituent components, and the inorganic solid electrolyte-containing composition is soluble in the dispersion medium: <Functional group group (a)> Sulfonic acid group, phosphoric acid group, phosphonic acid group, carboxy group, hydroxy group, oxetane group, epoxy group, dicarboxylic acid anhydride group, thiol group, ether group, thioether group, thioester group, fluoroalkyl group, and salts thereof

2. 2. The inorganic solid electrolyte-containing composition according to claim 1, wherein the constituent component (X) is represented by the following formula (X1) or (X2): 【Chemistry 1】 In formula (X1) and formula (X2), R Ｘ１ ~R Ｘ３ and R Ｘ６ ~R Ｘ８ represents a hydrogen atom or a substituent. Ｘ４ represents a hydrocarbon group or an alkylsilyl group. Ｘ５ represents a substituent. Ｘ９ represents a hydrogen atom or a substituent. L Ｘ１ ~L Ｘ３ represents a linking group. Ｘ４ represents a single bond or a linking group. n Ｘ and m Ｘ indicates the average degree of polymerization and is a number of 2 or more.

3. 3. The inorganic solid electrolyte-containing composition according to claim 1, wherein the constituent component (N) is a constituent component containing a nitrogen atom that forms an amino group in a partial structure incorporated into the main chain of the polymer or in a partial structure that becomes a side chain other than the polymer chain.

4. The inorganic solid electrolyte-containing composition according to any one of claims 1 to 3, wherein the polymer is a hyperbranched polymer having a core portion and three or more arm portions bonded to the core portion, and the arm portions contain the constituent component (X).

5. 5. The inorganic solid electrolyte-containing composition according to claim 1, wherein the polymer has a glass transition temperature of −30° C. or lower.

6. The inorganic solid electrolyte-containing composition according to any one of claims 1 to 5, which contains an active material.

7. The inorganic solid electrolyte-containing composition according to any one of claims 1 to 6, further comprising a conductive assistant.

8. A sheet for an all-solid-state secondary battery, comprising a layer made of the inorganic solid electrolyte-containing composition according to any one of claims 1 to 7.

9. An all-solid-state secondary battery comprising a positive electrode active material layer, a solid electrolyte layer, and a negative electrode active material layer in this order, An all-solid-state secondary battery, wherein at least one of the positive electrode active material layer, the solid electrolyte layer, and the negative electrode active material layer is a layer constituted by the inorganic solid electrolyte-containing composition according to any one of claims 1 to 7.

10. A method for producing a sheet for an all-solid-state secondary battery, comprising forming a film from the inorganic solid electrolyte-containing composition according to any one of claims 1 to 7.

11. A method for producing an all-solid-state secondary battery, comprising producing an all-solid-state secondary battery through the method according to claim 10.

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