Binder for all-solid-state secondary battery, inorganic-containing solid electrolyte composition, sheet for all-solid-state secondary battery, and all-solid-state secondary battery

Abstract

Provided are: a binder for all-solid secondary batteries, which contains a polymer represented by formula (I) and having an acid value of 3 mgKOH / g or less; and an inorganic solid electrolyte-containing composition containing the binder, an inorganic solid electrolyte, and a dispersion medium. And a sheet for an all-solid-state secondary battery and an all-solid-state secondary battery, each of which uses the inorganic solid electrolyte-containing composition. In formula (I), R1 represents an (m + n)-valent linking group. A1 represents a hydrogen atom, a functional group containing at least one amide substituent, or a polymer chain. A2 represents a polymer chain or a functional group containing at least one of a fluorine atom and a polysiloxane structure; n is an integer from 1 to 8, and m is an integer from 1 to 9. (In the formula, m + n is an integer of 2-10.

Description

Technical Field

[0001] This invention relates to an adhesive for all-solid-state secondary batteries, a composition containing inorganic solid electrolyte, a sheet for all-solid-state secondary batteries, and an all-solid-state secondary battery. Background Technology

[0002] In all-solid-state secondary batteries, all the negative electrode, electrolyte, and positive electrode are made of solids, significantly improving the safety and reliability issues associated with secondary batteries using organic electrolytes. Furthermore, they are believed to offer extended lifespan. In addition, all-solid-state secondary batteries can be configured with electrodes and electrolytes arranged in parallel and series. Therefore, compared to secondary batteries using organic electrolytes, they can achieve higher energy density and hold promise for applications in electric vehicles and large-scale batteries.

[0003] In such all-solid-state secondary batteries, the structural layers (solid electrolyte layer, negative electrode active material layer, positive electrode active material layer, etc.) are composed of solid particles such as inorganic solid electrolyte, active material, and conductive additives. Typically, an adhesive is used simultaneously to bind these solid particles together within the structural layers. Considering factors such as increased productivity, structural layer forming materials containing solid particles and adhesives are generally used to form these structural layers. Therefore, research has been conducted on adhesives and structural layer forming materials. For example, Patent Document 1 describes a multi-branched polymer and a solid electrolyte composition comprising the multi-branched polymer and an inorganic solid electrolyte as the adhesive. The multi-branched polymer is an amorphous polymer and is formed having a core and at least three polymeric arms bonded to the core. Specifically, a solid electrolyte composition is described, comprising a particulate multi-branched polymer, wherein all arms having the same constituent components are polymer chains bonded to a core, and is a copolymer chain or homopolymer chain or copolymer chain of (meth)acrylic acid monomers and alkyl methacrylate monomers containing acidic groups; an inorganic solid electrolyte; and a dispersion medium. Furthermore, Patent Document 2 describes a polymer represented by Formula 1 as an adhesive, and a solid electrolyte composition comprising the polymer and the inorganic solid electrolyte. In Patent Document 2, as an example of a polymer represented by Formula 1, a polymer represented by "(A" in Formula 1) is described. 1 )pR 2 - "and polymer D-14 (acid value: approximately 4 mg KOH / g) has a polymer chain containing methacrylamide sulfonic acid groups."

[0004] [Chemical Formula 1]

[0005]

[0006] In the formula, R1 Indicates a (m+n) valence linker. A 1 This represents a hydrogen atom, an acidic group, a group with a basic nitrogen atom, a urea group, a carbamate group, an alkoxysilyl group, an epoxy group, an isocyanate group, or a hydroxyl group. p is an integer from 1 to 10. R 2 and R 3 Indicates a single bond or a linking group. P C This refers to a polymer chain having at least one constituent element selected from fluorinated alkyl and siloxane structures. m is an integer from 1 to 8, and n is an integer from 2 to 9. Wherein, m+n is an integer from 3 to 10.

[0007] Previous technical documents

[0008] Patent documents

[0009] Patent Document 1: Japanese Patent Application Publication No. 2015-164125

[0010] Patent Document 2: International Publication No. 2020 / 067106 Summary of the Invention

[0011] The technical problem to be solved by the invention

[0012] In all-solid-state secondary batteries with structural layers formed using structural layer-forming materials, from the viewpoint of improving battery performance (e.g., reducing battery resistance), the structural layer-forming materials require solid particles to be dispersed in the dispersion medium without deterioration or decomposition (the dispersion state of the solid particles). Furthermore, in recent years, with the rapid advancement of research into the high performance and practical application of electric vehicles, the performance requirements for all-solid-state secondary batteries have also increased, thus necessitating further improvements in the dispersion state of solid particles in the structural layer-forming materials.

[0013] To meet this need, the inventors conducted in-depth research on structural layer forming materials and polymers that function as binders therein. As a result, they came to the following conclusion: when preparing structural layer forming materials by mixing solid particles such as inorganic solid electrolytes and binders, the exothermic reaction, especially when mixing inorganic solid electrolytes and binders, may be one of the reasons for reducing the dispersion state of solid particles in the structural layer forming material.

[0014] However, previous studies on structural layer forming materials and adhesives have focused on the dispersibility of solid particles in the mixed structural layer forming materials, but have not included studies on the heat release during mixing.

[0015] The present invention aims to provide an all-solid-state secondary battery adhesive capable of preparing a structural layer forming material while suppressing heat release during mixing with an inorganic solid electrolyte, and an inorganic solid electrolyte composition containing the all-solid-state secondary battery adhesive and the inorganic solid electrolyte. Furthermore, the present invention aims to provide an all-solid-state secondary battery sheet and an all-solid-state secondary battery using the inorganic solid electrolyte composition.

[0016] means for solving technical problems

[0017] Based on the above-described concept, the inventors have continued their research and discovered that an adhesive comprising a multi-branched polymer having a specific chemical structure represented by formula (I) and an acid value of 3 mg KOH / g or less can suppress the exothermic reaction when mixed with the inorganic solid electrolyte. More preferably, it can suppress excessive interaction between the adhesives and excessive adsorption of solid particles by the adhesive, thus preparing an inorganic solid electrolyte-containing composition. Furthermore, it has been discovered that by using an inorganic solid electrolyte-containing composition containing this specific adhesive, inorganic solid electrolyte, and dispersion medium as a structural layer forming material, it is possible to realize a sheet for an all-solid-state secondary battery with a low-resistance structural layer, and also a low-resistance all-solid-state secondary battery. Based on these insights, the present invention has been completed through repeated research.

[0018] That is, the above-mentioned problems are solved by the following methods.

[0019] <1> An all-solid-state secondary battery adhesive comprising a polymer represented by the following formula (I) and having an acid value of less than 3 mg KOH / g.

[0020] [Chemical Formula 2]

[0021]

[0022] In equation (I), R 1 The linking group represents the (m+n) valence.

[0023] A 1 A functional group or polymer chain representing a hydrogen atom, or containing at least one of an amide group, a sulfonamide group, and an imide group.

[0024] A 2 It refers to a functional group or polymer chain containing at least one of fluorine atoms and a polysiloxane structure.

[0025] n is an integer from 1 to 8, m is an integer from 1 to 9, and m+n is an integer from 2 to 10.

[0026] <2> The adhesive for all-solid-state secondary batteries according to <1>, wherein,

[0027] A 1 It refers to a functional group or polymer chain containing at least one of amide, sulfonamide and imide groups.

[0028] <3> The all-solid-state secondary battery adhesive according to <1> or <2>, wherein,

[0029] A 2 It contains functional groups or polymer chains that include polysiloxane structures.

[0030] <4> The adhesive for all-solid-state secondary batteries according to any one of <1> to <3>, wherein,

[0031] The polymer has an acid value of less than 0.5 mg KOH / g and an alkalinity of less than 0.5 mg KOH / g.

[0032] <5> The adhesive for all-solid-state secondary batteries according to any one of <1> to <4>, wherein,

[0033] A 1 Polymer chains containing (meth)acrylamide compounds.

[0034] <6> The adhesive for all-solid-state secondary batteries according to any one of <1> to <5>, wherein,

[0035] A 1 A polymer chain containing hydrogen atoms and (meth)acrylamide compounds.

[0036] <7> The adhesive for all-solid-state secondary batteries according to any one of <1> to <6>, wherein,

[0037] A 1 It accounts for 1 to 30% of the content in the polymer.

[0038] <8> An adhesive for all-solid-state secondary batteries according to any one of <1> to <7>, wherein,

[0039] The weight-average molecular weight of the polymer is below 30,000.

[0040] <9> An inorganic solid electrolyte composition comprising an all-solid-state secondary battery binder as described in any one of <1> to <8> above, an inorganic solid electrolyte having conductivity of ions belonging to Group 1 or Group 2 of the periodic table, and a dispersion medium.

[0041] <10> The inorganic solid electrolyte composition according to <9> contains active substances.

[0042] <11> The inorganic solid electrolyte composition according to <9> or <10> contains a conductive additive.

[0043] <12> A sheet for an all-solid-state secondary battery, having a layer formed using any one of <9> to <11> above.

[0044] <13> An all-solid-state secondary battery, which sequentially comprises a positive electrode active material layer, a solid electrolyte layer, and a negative electrode active material layer, wherein,

[0045] At least one of the positive electrode active material layer, the solid electrolyte layer, and the negative electrode active material layer is a layer formed using any one of <9> to <11> containing an inorganic solid electrolyte composition.

[0046] Invention Effects

[0047] This invention provides an all-solid-state secondary battery adhesive capable of preparing a structural layer forming material while suppressing heat release during mixing with an inorganic solid electrolyte, and an inorganic solid electrolyte composition containing the all-solid-state secondary battery adhesive and the inorganic solid electrolyte. Furthermore, this invention provides an all-solid-state secondary battery sheet having a layer formed from the inorganic solid electrolyte composition, and an all-solid-state secondary battery.

[0048] The above-described features, other features, and advantages of the present invention will become clearer with appropriate reference to the accompanying drawings and the following description. Attached Figure Description

[0049] Figure 1 The diagram schematically shows a longitudinal sectional view of an all-solid-state secondary battery according to a preferred embodiment of the present invention.

[0050] Figure 2 This is a schematic longitudinal sectional view of the button-type all-solid-state secondary battery fabricated in the embodiment. Detailed Implementation

[0051] In this invention, when numerical ranges are shown and explained for the content, physical properties, etc. of a component, and when the upper and lower limits of the numerical range are explained separately, any one of the upper and lower limits can be appropriately combined to form a specific numerical range. On the other hand, when multiple numerical ranges represented by "~" are set and explained, the upper and lower limits forming the numerical range are not limited to a specific combination before and after "~" as a specific numerical range, and can be set as a numerical range obtained by appropriately combining the upper and lower limits of each numerical range. Furthermore, in this invention, the numerical range represented by "~" refers to a range that includes the values ​​before and after "~" as lower and upper limits.

[0052] In this invention, the designation of a compound (e.g., when referred to as a compound by appending "compound") means that, in addition to the compound itself, it also includes its salts and their ions. Furthermore, it means that, without impairing the effects of this invention, it includes derivatives obtained by modifying a portion by introducing substituents or the like.

[0053] In this invention, (meth)acrylic acid refers to one or both of acrylic acid and methacrylic acid. The same applies to (meth)acrylates.

[0054] In this invention, the term "substituent, linking group, etc., which are not explicitly described as substituted or unsubstituted" (hereinafter referred to as "substituent, etc.") means that the group may also have suitable substituents. Therefore, in this invention, even when simply described as a YYY group, the YYY group includes both a form without substituents and a form with substituents. This also applies to compounds where the substituted or unsubstituted nature is not explicitly stated. As a preferred substituent, for example, substituent Z, described later, can be cited.

[0055] In this invention, when multiple substituents, etc., are represented by specific symbols, or when multiple substituents, etc., are specified simultaneously, it means that each substituent, etc., may be the same as or different from each other. Furthermore, even without special explanation, when multiple substituents, etc., are adjacent, it means that they may connect or fused together to form a ring.

[0056] In this invention, polymer refers to aggregates, but has the same meaning as so-called high molecular weight compounds.

[0057] Adhesive for all-solid-state rechargeable batteries

[0058] The all-solid-state secondary battery adhesive of the present invention (hereinafter, sometimes simply referred to as "the adhesive of the present invention") comprises a polymer represented by formula (I) described below and having an acid value of 3 mg KOH / g or less.

[0059] In this invention, the adhesive for all-solid-state secondary batteries (hereinafter, sometimes simply referred to as "adhesive") includes polymers in two ways: an adhesive consisting of the polymer itself and an adhesive obtained by including the polymer and other components. Other components that may be included in the adhesive are not particularly limited, but examples include polymer synthesis byproducts, decomposition products (residues) of polymerization catalysts, and residual synthesis solvents. The content of other components in the adhesive of this invention can be appropriately set within a range that does not impair the effects of this invention; for example, it can be set to 10% by mass or less.

[0060] The adhesive of the present invention may contain one or more polymers represented by formula (I). Furthermore, the adhesive of the present invention is generally formed from the polymer represented by formula (I) as a polymer component, but may include other polymers, etc., to the extent that the function of the polymer represented by formula (I) is impaired. Examples of other polymers include polymers that do not have the chemical structure represented by formula (I), for example, polymers that can be used without particular limitation as adhesives for all-solid-state secondary batteries.

[0061] The adhesive of the present invention can suppress the exothermic reaction during mixing with solid particles, especially with inorganic solid electrolytes, when preparing compositions containing inorganic solid electrolytes. Therefore, even without setting specific preparation conditions (mixing conditions), for example, without excessive cooling, it is believed that the deterioration and decomposition of solid particles, especially inorganic solid electrolytes, can be suppressed, and the solid particles can be dispersed in the dispersion medium. Furthermore, since the adhesive of the present invention has an acid value of 3 mg KOH / g, it is believed that excessive interaction between adhesives and excessive adsorption of solid particles by the adhesives can be suppressed in the dispersion medium, and excessive aggregation and precipitation of adhesives and solid particles can be suppressed. As a result, the deterioration and decomposition of solid particles can be suppressed while they are dispersed in the dispersion medium, thereby improving the dispersion state of solid particles. By using the inorganic solid electrolyte composition of the present invention, which has excellent dispersion of solid particles, as a structural layer forming material for all-solid-state secondary batteries, it is possible to realize all-solid-state secondary battery sheets with low resistance (high conductivity) structural layers and all-solid-state secondary batteries with low resistance (high conductivity).

[0062] As described above, the adhesive of the present invention functions as a dispersant in the dispersion medium during the preparation of the inorganic solid electrolyte composition, suppressing the deterioration and decomposition of solid particles. Furthermore, in the structural layer formed from the inorganic solid electrolyte composition, the adhesive of the present invention also functions as a binder (adhesive) that adsorbs onto solid particles, causing them to bond, and also binds current collectors to solid particles. Additionally, in the inorganic solid electrolyte composition, the adhesive of the present invention may or may not have the function of bonding solid particles. The adsorption of solid particles by the adhesive of the present invention includes not only physical adsorption but also chemical adsorption (adsorption through the formation of chemical bonds, adsorption caused by electron transfer, etc.).

[0063] The adhesive of the present invention, which exhibits the above-described excellent effects, can preferably be used as a forming material for all-solid-state secondary battery sheets (including all-solid-state secondary battery electrode sheets) or for the formation of solid electrolyte layers or active material layers in all-solid-state secondary batteries.

[0064] <Polymer represented by formula (I)>

[0065] The polymer represented by the following formula (I) (hereinafter sometimes simply referred to as "polymer (I)") is a multi-branched polymer (also called a star polymer) having the chemical structure represented by the following formula (I).

[0066] [Chemical Formula 3]

[0067]

[0068] In equation (I), R 1 Indicates a (m+n) valence linker. A 1 A represents a hydrogen atom, or a functional group or polymer chain containing at least one of an amide group, a sulfonamide group, and an imide group. 2 This represents a functional group or polymer chain containing at least one of fluorine atoms and a polysiloxane structure. n is an integer from 1 to 8, and m is an integer from 1 to 9. Wherein, m+n is an integer from 2 to 10.

[0069] Furthermore, in the above equation (I), when there are multiple A's... 1 and A 2 In the case of multiple A's 1 and A 2 They can be the same or different.

[0070] (R in formula (I)) 1 )

[0071] In equation (I), R 1It is a (m+n) valence linking group, usually a linking group (organic linking group) consisting of an organic group containing a skeleton of carbon atoms linked together by covalent bonds, and preferably a linking group that also contains oxygen atoms. For example, the linking group R in Formula 1B described later can be cited as such a linking group. 1C The linking group described herein. Linking group R 1 The molecular weight is not particularly limited, but is preferably 100 or more, more preferably 200 or more, and even more preferably 300 or more. The upper limit of the molecular weight is preferably 5,000 or less, more preferably 4,000 or less, and particularly preferably 3,000 or less. The linking group preferably has more than one tetravalent carbon atom.

[0072] The valence of the linking group is 2 to 10, which has the same meaning as the sum of m and n (m+n) described later, and the preferred range is also the same.

[0073] The linking group is preferably a group represented by the following formula 1a. Linking group R 1 The number of groups represented by formula 1a is preferably the same as that of R. 1 The valences, i.e. (m+n), are the same. When the linking group has multiple of these groups, they can be the same or different.

[0074] -(CR f 2) n -O(C=O)-(CR) f 2) n -……(Equation 1a)

[0075] In Equation 1a, n is an integer from 0 to 10, preferably an integer from 1 to 6, and more preferably 1 or 2. The two n's can be the same or different.

[0076] R f This represents a hydrogen atom or a substituent, preferably a hydrogen atom. As a substance capable of acting as R... fThe substituents used are not particularly limited, but examples of substituents Z described later can be included, specifically halogen atoms (e.g., fluorine, chlorine, iodine, bromine), alkyl groups (preferably 1 to 12 carbon atoms, more preferably 1 to 6, and especially preferably 1 to 3), alkoxy groups (preferably 1 to 12 carbon atoms, more preferably 1 to 6, and especially preferably 1 to 3), acyl groups (preferably 2 to 12 carbon atoms, more preferably 2 to 6, and especially preferably 2 to 3), aryl groups (preferably 6 to 22 carbon atoms, more preferably 6 to 10), alkenyl groups (preferably 2 to 12 carbon atoms, more preferably 2 to 5), hydroxyl groups, nitro groups, cyano groups, mercapto groups, amino groups, amide groups, acidic groups (carboxyl groups, phosphate groups, sulfonic acid groups, etc.), etc. The acidic group can be a salt. Examples of counter ions for salt formation include alkali metal ions, alkaline earth metal ions, ammonium ions, and alkylammonium ions.

[0077] Linking group R 1 More preferably, it is a linking group represented by Formula 1A or Formula 1B below.

[0078] [Chemical Formula 4]

[0079]

[0080] In both equations, R f and n and R in equation 1a above f And n has the same meaning, and the preferred range is also the same. * indicates the bonding part with the sulfur atom in Formula 1.

[0081] In Equation 1A, R 1A This represents a hydrogen atom or a substituent. As it can act as R... 1A The substituents used are not particularly restricted; for example, examples of substituents that can act as R... f The substituents used include those described above, as well as groups represented by Formula 1a. Preferably, these are alkyl groups or groups represented by Formula 1a. The alkyl group preferably has 1 to 12 carbon atoms, more preferably 1 to 6, and particularly preferably 1 to 3. It can be used as R 1A The substituents used can have one or more substituents, and there are no particular restrictions on the substituents that can be included. For example, examples of substituents that can be used as R... f The substituents described above are used. Among them, hydroxyl is preferred. As a substituent that may have one or more substituents, hydroxyalkyl (with the number of carbon atoms as described above) can be mentioned. Specifically, hydroxymethyl is preferred.

[0082] In Equation 1B, R 1C Indicates a linking group. As it can act as R... 1CThe linking group used is not particularly limited. For example, it is preferably an alkylene group with 1 to 30 carbon atoms, a cycloalkylene group with 3 to 12 carbon atoms, an aryl group with 6 to 24 carbon atoms, a heteroaryl group with 3 to 12 carbon atoms, an ether group (-O-), a thioether group (-S-), a phosphine group (-PR-: R is a hydrogen atom or an alkyl group with 1 to 6 carbon atoms), or a silyl group (-SiR). S1 R S2 -:R S1 R S2 (Hydrogen atoms or alkyl groups having 1 to 6 carbon atoms), carbonyl groups, imino groups (-NR) N -:R N The linking group is a combination of two or more (preferably two to ten) of the following: a bonding site, a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 10 carbon atoms. Preferably, the linking group is an alkylene group, an ether group, a thioether group, or a carbonyl group, or a combination of two or more (preferably two to five), and more preferably an ether group. 1B This represents a hydrogen atom or a substituent, preferably a hydrogen atom. As a substance capable of acting as R... 1B The substituents used are not particularly restricted; for example, examples of substituents that can act as R... f The aforementioned substituents are used.

[0083] In Formula 1A and Formula 1B, the same symbols may represent the same or different groups.

[0084] Regarding the linking group R 1 In addition to the linking group mentioned above, for example, in Formula 1B above, one or more groups represented by Formula 1a above can be used as R. f The aforementioned substituents, especially the hydroxymethyl-substituted linking group, are preferred.

[0085] Linking group R 1 Preferably, it is a linking group represented by any one of the following formulas 1C to 1H. In each formula, * represents the bonding portion with S in formula 1.

[0086] [Chemical Formula 5]

[0087]

[0088] In formulas 1C to 1H, T is a linking group, preferably a group represented by any one of formulas T1 to T6 below, or a linking group obtained by combining two or more of them (preferably two or three). As a linking group obtained by combination, for example, a linking group (-OCO-alkylene) obtained by combining the linking group represented by formula T6 and the linking group represented by formula T1 can be given. In the groups represented by formulas T1 to T6, the bonding portion bonded to the sulfur atom in formula 1 above can be any kind, but when T is an oxidized alkenyl group (a group represented by formulas T2 to T5) or -OCO-alkylene, it is preferable that the terminal carbon atom (bonding portion) is bonded to the sulfur atom in formula 1 above.

[0089] In the above formulas, there are multiple T values ​​that can be the same or different.

[0090] In formulas 1C to 1H, n is an integer, preferably an integer from 0 to 14, more preferably an integer from 0 to 5, and especially preferably an integer from 1 to 3.

[0091] [Chemical Formula 6]

[0092]

[0093] Z D It is a linking group, preferably a group represented by Z1 or Z2 below.

[0094] In formulas T1 and Z1, m is an integer from 1 to 8, more preferably an integer from 1 to 5, and especially preferably an integer from 1 to 3.

[0095] In equation Z2, Z 3 It is a linking group, preferably an alkylene group with 1 to 12 carbon atoms, more preferably an alkylene group with 1 to 6 carbon atoms. Among them, 2,2-propanediol is particularly preferred.

[0096] The following are examples of linking groups R. 1 These are specific examples, but the invention is not limited to these. In each specific example, * denotes the bonding portion with the sulfur atom in Formula 1.

[0097] [Chemical Formula 7]

[0098]

[0099] (A in formula (I)) 1 )

[0100] In equation (I), A 1 It represents any one of (A-1) to (A-3) below.

[0101] (A-1) Hydrogen atom

[0102] (A-2) A functional group comprising at least one of an amide group, a sulfonamide group, and an imide group.

[0103] (A-3) A polymer chain containing at least one of an amide group, a sulfonamide group, and an imide group.

[0104] If polymer (I) has A 1 This can suppress the heat release when the adhesive and inorganic solid electrolyte of the present invention are mixed, and also promote the adsorption of solid particles such as active substances. As a result, the deterioration of solid particles can be suppressed.

[0105] A 1 It can be any of (A-1) to (A-3) above, but from the viewpoint of suppressing the deterioration of solid particles, it is preferable to contain a polymer chain (A-3) containing at least one of amide group, sulfonamide group and imide group, and more preferably a polymer chain containing amide group.

[0106] In A 1 When two or three of (A-1) to (A-3) are included, these combinations are not particularly limited, and (A-1) to (A-3) can be appropriately combined. For example, combinations of (A-1) and (A-2) and (A-1) and (A-3) can be cited. From the perspective of suppressing the degradation of solid particles, the combination of (A-1) and (A-3) is preferred. Among these combinations, the one that can be used as A 1 The polymer chain (A-3) used is preferably a polymer chain containing amide groups.

[0107] In this invention, a functional group or polymer chain containing at least one of an amide group, a sulfonamide group, and an imide group (hereinafter sometimes referred to as an "amide substituent") includes two modes: the functional group or polymer chain is composed of an amide substituent, and the functional group or polymer chain is composed of an amide substituent and other partial structures.

[0108] In this invention, the amide group refers to a group having *-CONR NA1 The -** group represents the amide bond. The amide group will not form other functional groups containing amide bonds, such as urethane, urea, imide, or carbamate. The sulfonamide group refers to a group with *-SO2NR. NA1 The -** group represents the sulfonamide bond. The imide group refers to the group with *-CO-NR NA2 -CO-** represents the imide bond group. * and ** represent the bonding portion.

[0109] R NA1 R represents a hydrogen atom or substituent. NA2 This indicates the bonding portion, hydrogen atom, or substituent. As a component capable of functioning as R...NA1 and R NA2 The substituents used are not particularly limited; for example, substituent Z described later can be cited. Preferably, they are alkyl (including cycloalkyl), aryl, heterocyclic, or alkoxy groups, with alkyl or aryl being more preferred. The number of carbon atoms in the alkyl group is preferably 1 to 20, more preferably 1 to 12, and even more preferably 1 to 6. The number of carbon atoms in the aryl group is preferably 6 to 26, more preferably 6 to 20, and even more preferably 6 to 12. The R group in the amide and sulfonamide groups... NA1 Preferably, each is a hydrogen atom, R NA2 Preferably, it is a bonding portion or a hydrogen atom, more preferably a bonding portion.

[0110] Of the aforementioned groups, any one of the two bonding portions* and ** can be bonded to the R of polymer (I). 1 However, regarding the amide and sulfonamide groups, the preferred bonding portion is *bonded to the R of polymer (I). 1 On the side, regarding the imide group, R is preferred. NA2 R bonded to polymer (I) 1 side.

[0111] The amide, sulfonamide, and imide groups can each directly form a cyclic structure, or the two bonding portions* and ** can form a cyclic structure via connecting groups described later. For example, the imide group preferably forms a cyclic imide group, specifically a cyclic imide group derived from maleimide or phthalimide. On the other hand, the amide and sulfonamide groups are each preferably bonded to a terminal group described later via another bonding portion, and constitute an acyclic molecular structure.

[0112] The amide group, sulfonamide group, and imide group each have a terminal group bonded to the end (one bonding portion) of each group. The terminal group is not particularly limited and can include hydrogen atoms or substituents. The substituents that can be used as terminal groups are not particularly limited; for example, substituent Z described later can be included. Preferably, alkyl (including cycloalkyl), aryl, heterocyclic, or alkoxy groups are used, more preferably alkyl or aryl. The number of carbon atoms in the alkyl group is preferably 1 to 20, more preferably 2 to 8, and even more preferably 3 or 4. The number of carbon atoms in the aryl group is related to the number of atoms that can be used as R... NA1 The aryl groups used have the same number of carbon atoms.

[0113] In this invention, in the above-mentioned R NA1 In the case of any one of the terminal groups taking a hydrogen atom, the hydrogen atom is interpreted as the above R NA1 .

[0114] In polymer (I), A 1From the perspective of the dispersion state of solid particles and electrical resistance, the amide substituent is preferably an amide group.

[0115] A 1 The amide substituents contained therein can be at least one type, preferably one or two. In A 1 When multiple amide substituents are present, their combination is not particularly limited and can be appropriately determined. A 1 The number of amide substituents in the polymer (I) is not particularly limited and can be appropriately determined based on the functional groups or polymer chains.

[0116] (A functional group containing at least one of amide, sulfonamide and imide groups) 1G )

[0117] Functional group A containing at least one of amide, sulfonamide and imide groups 1G (A-2) above can be a functional group composed of at least one of amide, sulfonamide and imide groups, but preferably also includes a linking group L connected to "S" (sulfur atom) in formula (I). A1 The functional groups. That is, the groups in the amide group, sulfonamide group, and imide group can react directly (without via the linking group L) with the sulfur atom in formula (I). A1 Bonding, but preferably via a linking group L A1 Bonding.

[0118] L, as a linking group A1 The method is not particularly limited, but examples include alkylene groups (preferably 1 to 12 carbon atoms, more preferably 2 to 6, and even more preferably 2 or 3), alkenyl groups (preferably 2 to 6 carbon atoms, more preferably 2 to 3), aryl groups (preferably 6 to 24 carbon atoms, more preferably 6 to 10), oxygen atoms, sulfur atoms, and imino groups (-NR). N -:R N This refers to a hydrogen atom, an alkyl group with 1 to 6 carbon atoms or an aryl group with 6 to 10 carbon atoms, a carbonyl group, a phosphate linking group (-OP(OH)(O)-O-), a phosphonic acid linking group (-P(OH)(O)-O-), or a group related to combinations thereof. As a linking group, L... A1 Preferably, it is an alkylene, arylene, carbonyl, oxygen atom, sulfur atom, or imino group, or a combination thereof, more preferably an alkylene, arylene, or a combination thereof. As a linking group L... A1 Further preferably, it contains an alkylene group, especially alkylene or alkylene-arylene. The linking group L A1 It is a group that is different from amide, sulfonamide and imide groups, and is a preferred method.

[0119] The above-mentioned linking group L A1 The number of atoms is preferably 1 to 36, more preferably 1 to 24, and even more preferably 1 to 12. Linking group LA1 The number of connecting atoms is preferably 12 or less, more preferably 10 or less, and particularly preferably 8 or less. The lower limit is 1 or more. The above-mentioned number of connecting atoms refers to the minimum number of atoms connecting the predetermined structural parts. For example, in the case of -CH2-CH2-(p-C6H4-)- group, the number of atoms constituting the connecting group is 16, but the number of connecting atoms is 6.

[0120] Functional group A containing an amide substituent 1G Preferably, the group is derived from a low molecular weight compound, and more preferably, it does not have a group that can act as A. 1 The polymer chain A used (described later) 1P Furthermore, the functional group A... 1G Preferably, it does not have fluorine atoms or a polysiloxane structure.

[0121] Functional group A 1G Considering the dispersion state of solid particles and electrical resistance, functional groups containing amide groups are preferred.

[0122] As a means to introduce what can be used as A 1 The functional group A used 1G Compounds are not particularly limited; for example, compounds that are reactive to thioalkyl groups and at least one amide substituent can be mentioned directly or via a linking group L. A2 (Excluding the aforementioned reactive groups.) The reactive compound obtained by bonding is preferably a reactive compound obtained by directly bonding the reactive group with at least one amide substituent.

[0123] The reactive group can be appropriately selected based on the type of thioalkyl group it reacts with. Examples include olefinic unsaturated groups capable of undergoing olefin-thiol reactions or free radical polymerization, carboxyl groups capable of undergoing condensation reactions, and thioetherified alkyl groups. For example, vinyl groups can be used as olefinic unsaturated groups. It is sufficient for the reactive group to be present at the end of the molecular structure or on the side chain of the reactive compound, preferably 1 to 4, and more preferably 1.

[0124] L, as a linking group A2 It is not particularly restricted and can use the above-mentioned linking group L. A1 The groups described herein, but L as a linking group A2 More preferably, it is an arylene group. Additionally, the above-mentioned linking group L... A1The reactive groups and linking groups L formed after the reaction with thioalkyl groups. A2 The groups formed are the same.

[0125] As a means of introducing functional group A 1G The reactive compounds are not particularly limited, but reactive compounds having olefinic unsaturated bonds are preferably included. Examples include (meth)acrylic acid compounds, (meth)acrylate compounds, (meth)acrylamide compounds, (meth)acrylonitrile compounds, and other (meth)acrylic acid compounds (M1); vinyl aromatic compounds such as styrene compounds, vinylnaphthalene compounds, and vinyl carbazole compounds; allyl compounds; vinyl ether compounds; vinyl ester compounds; cyclic olefin compounds; diene compounds; and vinyl carboxylic acid ester compounds (M2). Furthermore, reactive compounds obtained by introducing at least one of the above-mentioned amide substituents into compounds such as itaconic acid dialkyl compounds and unsaturated carboxylic anhydrides are also possible. Besides these compounds, examples include (meth)acrylamide compounds, maleimide compounds, N-vinyl-substituted imide compounds, and vinylsuccinimide compounds. Among these, reactive compounds obtained by introducing at least one of the above-mentioned amide substituents into styrene compounds, vinylnaphthalene compounds, and (meth)acrylate compounds, as well as (meth)acrylamide compounds and N-vinyl-substituted imide compounds, are preferred.

[0126] Examples of (meth)acrylate compounds include alkyl (meth)acrylate compounds and aryl (meth)acrylate compounds, with alkyl (meth)acrylate compounds being preferred. The number of carbon atoms in the alkyl group constituting the alkyl (meth)acrylate compound is not particularly limited, but can be, for example, 1 to 24, preferably 1 to 12, more preferably 1 to 6, and even more preferably 1 to 4. 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.

[0127] Examples of reactive compounds used to introduce functional groups containing amide groups include, for example, N-unsubstituted (meth)acrylamide compounds, N-monosubstituted or disubstituted (meth)acrylamide compounds, ethylene compounds containing amide groups, (meth)acrylate compounds containing amide groups, and (meth)acrylamide compounds containing amide groups. Specifically, N-unsubstituted (meth)acrylamide compounds, N-alkyl (meth)acrylamide compounds, N,N-dialkyl (meth)acrylamide compounds, N-aryl (meth)acrylamide compounds, and N,N-diaryl (meth)acrylamide compounds are preferred.

[0128] As substituents that replace nitrogen atoms in acrylamide compounds, examples include those bonded to R. NA1 Or the terminal group at the end of the amide bond, preferably an alkyl group.

[0129] As a reactive compound for introducing a functional group containing an amide group, a compound for introducing a group having the chemical structure represented by formula (A1) described later is also preferred. In addition, the terminal group at the end of the chemical structure bonded to one side of the chemical structure represented by formula (A1) is the same as the terminal group of the amide substituent described above.

[0130] Examples of reactive compounds for introducing functional groups containing sulfonamide groups include vinyl aromatic sulfonamide compounds and (meth)acrylic acid compounds (M1) containing sulfonamide groups. Preferably, compounds obtained by introducing sulfonamide groups into vinyl aromatic compounds such as styrene compounds and vinyl naphthalene compounds are examples. More preferably, vinylbenzene sulfonamides are examples.

[0131] The reactive compound used to introduce a functional group containing a sulfonamide group can be an N-mono- or di-substituted sulfonamide compound. Examples of substituents for the nitrogen atom of the sulfonamide group include those bonded to R... NA1 Or the terminal group at the end of the amide bond, preferably an alkyl group.

[0132] Examples of reactive compounds for introducing functional groups containing imide groups include maleimide compounds, N-vinyl-substituted imide compounds, and preferably maleimide, vinyl phthalimide compounds, vinyl succinimide compounds, etc.

[0133] (A polymer chain containing at least one of amide, sulfonamide and imide groups) 1P )

[0134] The polymer chain A 1P(A-3) above can be a polymer chain composed of at least one of amide, sulfonamide, and imide groups, but preferably a polymer chain (polymer chain) obtained by reacting with a group (e.g., thioalkyl) used to introduce the sulfur atom in formula (I) into polymer (I). There are no particular limitations on such polymer chains, and chains composed of common polymers can be used. For example, chains composed of polymers with carbon-carbon double bonds as the main chain are preferred. In this invention, a carbon-carbon double bond polymer chain refers to a polymer chain formed by polymerizing carbon-carbon double bonds (olefinic unsaturated groups), specifically, a polymer chain formed by polymerizing (homogeneous polymerization or copolymerization) monomers with carbon-carbon unsaturated bonds. Examples of polymers with carbon-carbon double bond polymer chains as the main chain include chain polymers such as hydrocarbon polymers, vinyl polymers, and (meth)acrylic acid polymers, with vinyl polymers and (meth)acrylic acid polymers being preferred. Among them, as a (meth)acrylic acid polymer, a polymer composed of a (co)polymer containing 50% by mass or more of a component derived from the aforementioned (meth)acrylic acid compound (M1) can be cited. As a vinyl polymer, a polymer composed of a copolymer containing 50% by mass or more of a component derived from the aforementioned vinyl compound (M2) (wherein the content of the component derived from (meth)acrylic acid compound (M1) is less than 50% by mass) can be cited. As a polymer chain containing an imide group, in addition to the above, polymer chains formed by homopolymerization or copolymerization of maleimides such as polybismaleimide can also be cited. Among them, [the following can be used as A] 1 The polymer chain A used 1P Preferably, it does not have fluorine atoms or a polysiloxane structure.

[0135] In being able to serve as A 1 The polymer chain A used 1P In this process, the amide substituent may be present in the main chain of the polymer chain or at the end of the main chain, but preferably in the molecular chain that serves as its side chain, for example, more preferably embedded in the interior or end of the molecular chain that serves as the side chain of the polymer chain.

[0136] In this invention, the molecular chain that serves as a side chain of a polymer chain refers to the molecular chain that constitutes the side chain of the polymer chain, which is a molecular chain (atomic group) bonded to the molecular chain (atomic group) that constitutes the main chain of the polymer chain.

[0137] Furthermore, in this invention, the main chain of a polymer and polymer chain refers to all molecular chains constituting the polymer or polymer chain other than those that can be considered as linear molecular chains branching from the main chain or as side groups. Although the weight-average molecular weight depends on the branched chains or side groups, typically the longest chain constituting the polymer is considered the main chain. The terminal groups of the polymer are not included in the main chain. In contrast, the side chains of a polymer and polymer chain refer to branches other than the main chain, including short chains and long chains (grafted chains). The terminal groups of the polymer and polymer chain are not particularly limited, and appropriate groups can be used through polymerization methods, etc. Examples include hydrogen atoms, alkyl groups, aryl groups, hydroxyl groups, and residues such as polymerization initiators.

[0138] As polymer chain A 1P Examples of polymer chains include those having at least one amide substituent (hereinafter, sometimes referred to as amide-substituent components). Polymer chain A 1P Among the constituent components containing amide substituents, it is preferable to have a constituent component containing any one of amide group, sulfonamide group and imide group. From the perspective of the dispersion state of solid particles and electrical resistance, it is more preferable to have a constituent component containing amide group.

[0139] Examples of constituents containing amide substituents include those derived from those used to introduce the aforementioned functional group A. 1G The constituent components of reactive compounds.

[0140] As polymer chain A 1P For example, one could cite examples of the introduction of functional group A. 1G A chain composed of homopolymers or copolymers of reactive compounds. This polymer chain A... 1PAmong chains composed of homopolymers or copolymers of reactive compounds, polymer chains comprising constituent components derived from at least one reactive compound selected from (meth)acrylic acid, (meth)acrylate compounds, (meth)acrylamide compounds, and (meth)acrylonitrile compounds are preferred (referred to as chains composed of (meth)acrylic acid polymers). More preferably, polymer chains comprising constituent components derived from at least one reactive compound selected from (meth)acrylic acid, (meth)acrylate compounds, and (meth)acrylamide compounds are preferred. Even more preferably, polymer chains comprising constituent components derived from at least one reactive compound selected from (meth)acrylate compounds and (meth)acrylamide compounds are preferred. Further preferably, polymer chains comprising constituent components derived from (meth)acrylamide compounds are preferred (also referred to as polymer chains of (meth)acrylamide compounds). Particularly preferred are polymer chains composed of homopolymers of (meth)acrylamide compounds, and most preferably are polymer chains composed of homopolymers of N-unsubstituted (meth)acrylamide compounds. As constituent components derived from (meth)acrylamide compounds, constituent components represented by formula (A1) described later are preferably examples.

[0141] The polymer chain A 1P It may have constituent components other than those containing amide substituents (referred to as other constituent components). As other constituent components, there are no particular limitations as long as they do not have amide, sulfonamide, or imide groups. For example, constituent components derived from polymeric compounds capable of copolymerizing with reactive compounds used to introduce amide substituents can be cited. As other constituent components, for example, constituent components having olefinic unsaturated groups and derived from low-molecular-weight polymeric compounds can be cited. More specifically, constituent components derived from compounds mentioned above as reactive compounds (before the introduction of amide substituents), compounds obtained by introducing the functional group (a) described later into such compounds, etc., can be cited. Preferably, constituent components derived from reactive compounds selected from (meth)acrylic acid compounds, (meth)acrylate compounds, and (meth)acrylonitrile compounds, constituent components derived from compounds obtained by introducing the functional group (a) described later into (meth)acrylate compounds, etc., can be cited.

[0142] In this invention, polymer chain A 1P When the polymer chain contains components derived from (meth)acrylate compounds, particularly from unsubstituted alkyl esters of (meth)acrylate, the content of the components derived from (meth)acrylate compounds in the polymer chain is preferably 50% by mass or less, more preferably 25% by mass or less, and even more preferably 10% by mass or less. Polymer chain A 1PIt is also a preferred approach to not have components derived from (meth)acrylate compounds.

[0143] Examples of (meth)acrylate compounds used to introduce other constituent components include alkyl (meth)acrylate compounds and aryl (meth)acrylate compounds, with alkyl (meth)acrylate compounds being preferred. The number of carbon atoms in the alkyl group constituting the (meth)acrylate compound is not particularly limited, but can be, for example, 1 to 24. The number of carbon atoms in the alkyl group is generally preferred to be 1 to 12, more preferably 1 to 6, and from the viewpoint of solubility in the dispersion medium, preferably 3 to 16, 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, more preferably 6. The (meth)acrylate compound may have substituents. Substituents are not particularly limited; for example, substituent Z described later (excluding the groups included in functional group (a) described later) can be mentioned. Fluorine atoms are preferred substituents.

[0144] In polymer chain A 1P In the presence of other constituent components, polymer chain A 1P The primary structure (the bonding method of the constituent components) is not particularly restricted. Any bonding method can be adopted, such as random structure, block structure, alternating structure, graft structure, etc., but random structure and block structure are preferred.

[0145] Bonded to polymer chain A 1P The terminal group is not particularly restricted, and as mentioned above, appropriate groups can be used through polymerization methods, etc.

[0146] Polymer chain A 1P weight-average molecular weight Mw 1P Not particularly limited, the molecular weight can be appropriately set considering the weight-average molecular weight of polymer (I) described later, for example, preferably 200 to 10,000, more preferably 400 to 3,000. Polymer chain A 1P The degree of polymerization of all the constituent components is not particularly limited, but is preferably 2 to 100, more preferably 4 to 30.

[0147] Polymer chain A 1P The content of the amide-containing substituent is not particularly limited, but it is preferably 10% by mass or more. Considering the dispersion state of the solid particles and the electrical resistance, it is preferably 20% by mass or more, more preferably 30% by mass or more, and even more preferably 50% by mass or more. Setting it to 100% by mass is also a preferred method. In polymer chain A 1P When other constituent components are included, polymer chain A1P The upper limit of the content of the constituent components containing amide substituents can be appropriately determined, but for example, it can be set to 99% by mass or less.

[0148] Polymer chain A 1P The content of other constituent components is set within a range that does not impair the effects of the present invention, but from the perspective of the dispersibility and adhesion of solid particles, it is preferably 0 to 85% by mass, more preferably 0 to 80% by mass, further preferably 0 to 50% by mass, and especially preferably 0 to 40% by mass. Among the other constituent components, polymer chain A having the constituent component having the substituent (a) described later is preferred. 1P The content of the component can be appropriately determined by taking into account the total content of the other components mentioned above, for example, preferably 0 to 70% by mass, more preferably 0 to 50% by mass, and even more preferably 2 to 40% by mass.

[0149] -Functional Group A 1G Or polymer chain A 1P The preferred method -

[0150] Able to serve as A 1 The functional group A used 1G Or polymer chain A 1P Preferably, it is a polymer chain having a functional group having a chemical structure represented by the following formula (A1) or a constituent component having the following formula (A1).

[0151] In being able to serve as A 1 The functional group A used 1G When the functional group has the chemical structure represented by formula (A1), it is preferable that the group bonded to one of its bonding portions is the terminal group present in the aforementioned amide substituent. Furthermore, when it is possible to use A... 1 The polymer chain A used 1P In the case of a polymer chain having constituent components represented by formula (A1), the terminal groups of the polymer chain are as described above.

[0152] [Chemical Formula 8]

[0153]

[0154] In the above formula (A1), X 1 Represents a hydrogen atom or substituent. As it can act as X... 1 The substituents used are not particularly limited, and groups selected from substituent Z described later can be cited as examples, wherein alkyl groups are preferred. X 1 Preferably, it contains hydrogen atoms or methyl groups.

[0155] L 1This indicates a single bond or a linking group, preferably a single bond. As a group capable of acting as L... 1 The linking group used is not particularly restricted, and the aforementioned linking group L can be used without particular limitations. A2 Among them, those that can serve as L 1 The linking group used will not form a carbamate group, urea group or imide group together with the amide group in formula (A1).

[0156] Y 1 and Y 2 These represent hydrogen atoms or substituents, respectively. As a possible representation of Y... 1 and Y 2 The substituents used are not particularly restricted; one substituent can be combined with the aforementioned R. NA1 Having the same meaning, the other substituent has the same meaning as the terminal group of the aforementioned amide substituent, Y. 1 Preferably, hydrogen atoms, Y 2 Further preferably, it is an alkyl group. Wherein, as a component capable of serving as Y... 1 and Y 2 The substituents used will not form an imide group together with the amide group in formula (A1). 1 and Y 2 They can be the same or different.

[0157] In Y 1 and Y 2 When all are alkyl groups, as a form that can act as Y 1 and Y 2 The alkyl group used is preferably one that can be bonded to the aforementioned R. NA1 The alkyl group used as the terminal group of the aforementioned amide bond has the same meaning; for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, straight-chain or branched octyl, straight-chain or branched dodecyl, etc., can be used. As a group that can be used as Y 1 and Y 2 The combination of alkyl groups used is not particularly restricted, and the alkyl groups mentioned above can be appropriately combined with each other.

[0158] The functional group or constituent represented by formula (A1) may have substituents. For example, in formula (A1), the functional group or constituent is bonded to a group having X. 1 The carbon atom in the is represented as an unsubstituted carbon atom (methylene: -CH2-), but it can also have substituents. There are no particular restrictions on which substituents can be used, but examples can be given of substituents that can act as X. 1 The aforementioned substituents were used.

[0159] In this invention, it can be used as A 1 The functional group A used1G Or polymer chain A 1P Preferably, it does not contain fluorine atoms or a polysiloxane structure. Furthermore, it can serve as A. 1 The functional group A used 1G Or polymer chain A 1P For example, the terminal groups of amide substituents, Y 1 and Y 2 It may have substituents, but preferably does not have the functional group (a) described later, and more preferably is unsubstituted.

[0160] As can be A 1 The functional group A used 1G Or polymer chain A 1P Specific examples can be given by the constituent components of the polymer synthesized in the specific examples or embodiments of the polymers shown below, as well as constituent components derived from acrylamide compounds, etc., but the present invention is not limited to these.

[0161] (A in formula (I)) 2 )

[0162] In equation (I), A 2 Functional group A represents a structure containing at least one of fluorine atoms and polysiloxane. 2G Or polymer chain A 2P Preferably, it contains functional groups or polymer chains comprising a polysiloxane structure, and more preferably, it contains polymer chains comprising a polysiloxane structure. If polymer (I) has A 2 This process can suppress the heat release during the mixing of the adhesive and inorganic solid electrolyte of the present invention, and also promote the adsorption of solid particles such as active substances. As a result, the deterioration of solid particles can be suppressed. Furthermore, the reduction of the surface energy of polymer (I) can suppress excessive aggregation of solid particles and improve the dispersion state of solid particles.

[0163] In this invention, a functional group or polymer chain containing fluorine atoms and a polysiloxane structure refers to a configuration in which the functional group or polymer chain is composed of fluorine substituents or polysiloxane structures that are substituted with fluorine atoms, or a configuration in which the functional group or polymer chain is composed of fluorine substituents or polysiloxane structures and other partial structures.

[0164] In this invention, A 2 The polysiloxane structure contained therein refers to -(Si(R) S 2)-O) ns - The structure represented. R SThe substituent can be a hydrogen atom or a substituent. There are no particular limitations on the substituent, and examples include substituents selected from the substituent Z described later, such as hydroxyl, alkyl (preferably 1 to 12 carbon atoms, more preferably 1 to 6, and especially preferably 1 to 3), alkenyl (preferably 2 to 12 carbon atoms, more preferably 2 to 6, and especially preferably 2 or 3), alkoxy (preferably 1 to 24 carbon atoms, more preferably 1 to 12, further preferably 1 to 6, and especially preferably 1 to 3), aryl (preferably 6 to 22 carbon atoms, more preferably 6 to 14, and especially preferably 6 to 10), aryloxy (preferably 6 to 22 carbon atoms, more preferably 6 to 14, and especially preferably 6 to 10), aralkyl (preferably 7 to 23 carbon atoms, more preferably 7 to 15, and especially preferably 7 to 11), alkylsilyl, arylsilyl, alkoxysilyl, and groups represented by formula Z described later. The alkyl, phenyl, or group represented by formula Z (described later) having 1 to 3 carbon atoms is more preferably an alkyl group having 1 to 3 carbon atoms. ns represents the degree of polymerization (average repeat number) of the siloxane structure and can be appropriately determined by considering factors such as the number-average molecular weight of the polymer chain (described later), preferably as described later. The polysiloxane structure has a terminal group bonded to its end. This terminal group is not particularly limited and can include hydrogen atoms or substituents. Examples of substituents that can be used as terminal groups include those that can be used as R... S The substituents used.

[0165] The polysiloxane structure is preferably the polysiloxane structure represented by the following formula 4A.

[0166] [Chemical Formula 9]

[0167]

[0168] In Equation 4A, R 15 and R 16 R represents an alkyl or aryl group, and Z represents the group represented by the following formula (Z). In formula 4A, R... 15 R 16 and Z respectively with R in Equation 4 (described later) 15 R 16 And Z is the same.

[0169] In Equation 4A, x1, x2, and x3 are integers greater than or equal to 0, and y1 is an integer from 1 to 30. The x1, x2, x3, and y1 in Equation 4A are the same as the x1, x2, x3, and y1 in Equation 4, which will be described later.

[0170] A 2 The fluorine atoms and polysiloxane structures contained therein can be at least one type, preferably one or two. Furthermore, A 2The number of fluorine atoms and polysiloxane structures contained therein is not particularly limited and can be appropriately determined based on the functional groups or polymer chains.

[0171] Functional group A 2G Or polymer chain A 2P Preferably, it does not have amide substituents.

[0172] (Functional group A containing at least one of fluorine atoms and polysiloxane structure) 2G )

[0173] - Functional group A containing fluorine atoms 2GF -

[0174] As can be A 2 The functional group A containing fluorine atoms is used. 2GF It is not particularly limited, but preferably contains a group substituted with a fluorine atom (sometimes called a "fluorine substituent") and a linking group L connected to "S" (sulfur atom) in formula (I). A3 . group.

[0175] As a fluorine substituent, it is not particularly limited. For example, groups obtained by introducing a fluorine atom into the substituent Z described later can be cited. Groups obtained by introducing a fluorine atom into an alkyl, aryl, or heterocyclic group are preferred. Groups obtained by introducing a fluorine atom into an alkyl group are preferred. Fluoroalkyl groups are preferred.

[0176] A fluoroalkyl group is obtained by replacing at least one hydrogen atom in an alkyl group with a fluorine atom. Its molecular structure can be linear, branched, or cyclic, preferably linear or branched. The number of carbon atoms in the fluoroalkyl group is not particularly limited, but is preferably 1 to 20, more preferably 1 to 12, and even more preferably 2 to 8. A lower limit of 3 or more carbon atoms is also preferred, and when the fluoroalkyl group is linear, a lower limit of 4 or more is also preferred.

[0177] The fluoroalkyl group can be partially or completely replaced by fluorine atoms. In this invention, a fluoroalkyl group in which only a portion of the hydrogen atoms are replaced by fluorine atoms is preferred, and more preferably, it contains an L-type linkage bonded to the aforementioned linking group. A3 A fluoroalkyl group with a methylene (-CH2-) whose carbon atom is not replaced by a fluorine atom, more preferably containing an L-linked group bonded to the above-mentioned linking group. A3 A fluoroalkyl group consisting of ethylene (-CH2-CH2-) or propylene (-CH2-CH2-CH2-) carbon atoms, wherein two or three consecutive carbon atoms are not substituted with fluorine atoms. In such fluoroalkyl groups where some of the hydrogen atoms are substituted with fluorine atoms, the remaining alkyl group bonded to the unsubstituted carbon atoms is preferably a perfluoroalkyl group where all of the hydrogen atoms are substituted with fluorine atoms.

[0178] Fluoroalkyl groups may have substituents other than fluorine atoms; for example, they may have substituents that can act as the aforementioned R. f The substituents used do not include fluorine atoms.

[0179] L, as a linking group A3 It is not particularly limited; for example, the linking group L can be cited. A1 Among them, L serves as the linking group. A3 More preferably, it is an alkylene, alkenylene, arylene, carbonyl, oxygen atom, sulfur atom or imino group, or a combination thereof, and even more preferably, it is a group containing an alkylene group, especially preferably an alkylene-CO-O- group, or a group containing an alkylene group and a B group of Formula 4 described below. 2 The group obtained by combination. As a group consisting of an alkylene group and B of formula 4 (described later). 2 The resulting group, for example, is an alkylene group such as -CO-O-alkylene. Additionally, the linking group L... A3 Preferably, it does not have fluorine atoms or a polysiloxane structure.

[0180] Functional group A containing fluorine atoms 2GF Preferably, the group is derived from a low molecular weight compound, and more preferably, it does not have a group that can act as A. 2 The polymer chain A used (described later) 2P Furthermore, the functional group A... 2GF Preferably, it does not have amide substituents.

[0181] As a means to introduce what can be used as A 2 The functional group A containing fluorine atoms is used. 2GF Compounds are not particularly limited; for example, compounds having groups reactive to thioalkyl groups, the aforementioned fluorine substituents, and the linking group L connecting them can be cited. A4 (Excluding the aforementioned reactive groups.) Reactive compounds. As reactive groups, they are used to introduce compounds containing a group capable of acting as A. 1 The functional group A of the amide substituent used 1G The reactive groups in the compounds are the same. L acts as a linking group. A4 It is not particularly restricted and can use the above-mentioned linking group L. A3 The groups described herein, but more preferably groups containing a -CO-O- group, especially a -CO-O- group, or B of Formula 4 described later. 2 The linking groups described herein.

[0182] Functional group A used for introduction 2GFThe reactive compounds are not particularly limited, but preferably include reactive compounds having olefinic unsaturated bonds, such as (meth)acrylic acid compounds, (meth)acrylate compounds, (meth)acrylamide compounds, (meth)acrylonitrile compounds, etc. (M1); vinyl aromatic compounds such as styrene compounds, vinylnaphthalene compounds, vinyl carbazole compounds, allyl compounds, vinyl ether compounds, vinyl ester compounds, cyclic olefin compounds, diene compounds, vinyl carboxylic acid ester compounds, etc. (M2); in addition, reactive compounds obtained by introducing the above-mentioned fluorine substituents into itaconic acid dialkyl compounds, unsaturated carboxylic anhydrides, etc. are also possible. Among these, reactive compounds obtained by introducing the above-mentioned fluorine substituents into (meth)acrylic acid compounds, (meth)acrylate compounds, (meth)acrylamide compounds, etc. are preferred, reactive compounds for introducing the constituent elements represented by Formula 3 described later are more preferred, and fluorine-substituent (meth)acrylate compounds are even more preferred.

[0183] - Functional group A in the polysiloxane structure 2GS -

[0184] As can be A 2 The functional group A, which contains a polysiloxane structure, is used. 2GS It is not particularly limited, but preferably includes the above-described polysiloxane structure and the above-described linking group L connected to "S" (sulfur atom) in formula (I). A3 The group. Among them, the linking group L bonded to the polysiloxane structure. A3 Preferably, it does not have fluorine atoms or a polysiloxane structure.

[0185] Functional group A containing polysiloxane structure 2GS The functional group containing fluorine atoms is identical except that the fluorine substituent is replaced with a polysiloxane structure. This functional group A... 2GS Preferably, the group is derived from a low molecular weight compound, and more preferably, it does not have a group that can act as A. 2 The polymer chain A used (described later) 2P Furthermore, the functional group A... 2GS Preferably, it does not have an amide substituent. As for introducing a substance that can act as A... 2 The functional group A, which contains a polysiloxane structure, is used. 2GS The compounds, besides replacing the fluorine substituents with siloxane structures, are also used to introduce compounds that can act as A... 2 The functional group A containing fluorine atoms is used. 2GF The same compounds are mentioned, specifically, compounds used to introduce groups having the structure represented by Formula 4, which is described later.

[0186] (A polymer chain A containing at least one of fluorine atoms and siloxane structures) 2P )

[0187] The polymer chain can be a polymer chain composed of fluorinated substituents or a polysiloxane structure, but is preferably a polymer chain (polymer chain) that is introduced into polymer (I) by reacting with a group (e.g., a thioalkyl group) used to introduce the sulfur atom in the introduced formula (I). There are no particular limitations on such polymer chains; chains composed of common polymers can be used. For example, chains composed of polymers with a carbon-carbon double bond as the main chain, as described above, are preferred, and chains composed of vinyl polymers or (meth)acrylic acid polymers are more preferred. Among these, chains that can be used as A... 2 The polymer chain A used 2P Preferably, it does not have amide substituents.

[0188] In being able to serve as A 2 The polymer chain A used 2P In this process, fluorine atoms and polysiloxane structures can exist in polymer chain A. 2P It is located in or at the end of the main chain, but preferably exists in the molecular chain as its side chain, for example, more preferably embedded in or at the end of the molecular chain as a side chain of the polymer chain.

[0189] As polymer chain A 2P Examples of polymer chains include those comprising at least one of fluorine atoms and a polysiloxane structure. Polymer chain A 2P Preferably, it comprises a constituent having either a fluorine atom or a polysiloxane structure; more preferably, it comprises a constituent having a polysiloxane structure. As a constituent containing a fluorine atom, it is preferably a constituent containing the aforementioned fluorine substituent. As a constituent containing a polysiloxane structure, it is preferably a constituent containing the aforementioned siloxane structure.

[0190] As polymer chain A 2P For example, one could cite examples of the introduction of functional group A. 2G A chain composed of homopolymers or copolymers of reactive compounds. This polymer chain A... 2PIn chains composed of homopolymers or copolymers of reactive compounds, polymer chains comprising constituent components derived from at least one reactive compound selected from the above-described (meth)acrylic acid compound (M1) are preferred (referred to as chains composed of (meth)acrylic acid polymers), more preferably polymer chains comprising constituent components derived from at least one reactive compound selected from (meth)acrylic acid and (meth)acrylic acid ester compounds, and even more preferably polymer chains of (meth)acrylic acid ester compounds with fluorinated substituents or polysiloxane structures. As constituent components derived from (meth)acrylic acid ester compounds with fluorinated substituents or polysiloxane structures, constituent components represented by Formula 3 or Formula 4 described later are preferably examples.

[0191] The polymer chain may have constituent components other than those containing at least one of fluorine atoms and polysiloxane structures (referred to as other constituent components). As for other constituent components, there are no particular limitations as long as they do not contain fluorine atoms and polysiloxane structures. For example, there are no particular limitations as long as they are constituent components derived from polymerizable compounds that can copolymerize with reactive compounds used to introduce constituent components containing at least one of fluorine atoms and polysiloxane structures. Other constituent components include, for example, constituent components having olefinic unsaturated groups and originating from low-molecular-weight polymeric compounds. More specifically, constituent components can be derived from compounds mentioned above as reactive compounds (before the introduction of fluorine substituents and polysiloxane structures), compounds obtained by introducing the functional group (a) described later into such compounds, etc. Preferably, constituent components can be derived from reactive compounds selected from (meth)acrylic acid compounds, (meth)acrylate compounds, (meth)acrylamide compounds, and (meth)acrylonitrile compounds, etc., and constituent components derived from compounds obtained by introducing the functional group (a) described later into (meth)acrylate compounds, etc. As (meth)acrylate compounds, polymer chain A, for example... 1P As described in [the text].

[0192] In polymer chain A 2P In the presence of other constituent components, polymer chain A 2P The primary structure (the bonding method of the constituent components) is not particularly restricted. Any bonding method can be adopted, such as random structure, block structure, alternating structure, graft structure, etc., but random structure and block structure are preferred.

[0193] Bonded to polymer chain A 2P The terminal group is not particularly restricted, and as mentioned above, appropriate groups can be used through polymerization methods, etc.

[0194] Polymer chain A 2P weight-average molecular weight Mw 2PNot particularly limited, the molecular weight can be appropriately set considering the weight-average molecular weight of polymer (I) described later; for example, preferably 100 to 30,000, more preferably 400 to 10,000. Furthermore, polymer chain A... 2P The degree of polymerization of all the constituent components is not particularly limited, but is preferably 1 to 200, more preferably 1 to 50.

[0195] Among them, in polymer chain A 2P When the polymer chain comprises a polymer chain with a polysiloxane structure, the degree of polymerization of all structural units forming the polymer chain is not particularly limited, but is preferably 2 to 1000, more preferably 2 to 200, and even more preferably 6 to 80. The number-average molecular weight of the polymer chain is not particularly limited, but is preferably 400 or more, more preferably 800 or more, and even more preferably 2000 or more. As an upper limit, it is not particularly limited, but is preferably 500,000 or less, more preferably 100,000 or less, and particularly preferably 30,000 or less. The number-average molecular weight of the polymer chain, converted from standard polystyrene, can be measured in the same manner as the weight-average molecular weight of polymer (I).

[0196] Polymer chain A 2P The content of the constituent component containing at least one of fluorine atoms and polysiloxane structure is not particularly limited, but it is preferably 10% by mass or more. Considering the dispersion state of solid particles and electrical resistance, it is preferably 20% by mass or more, more preferably 30% by mass or more, and even more preferably 50% by mass or more. Setting it to 100% by mass is also a preferred method.

[0197] Polymer chain A 2P The total content of the other constituent components is set within a range that does not impair the effects of the present invention, but from the perspective of the dispersibility and adhesion of solid particles, it is preferably 0 to 90% by mass, more preferably 0 to 70% by mass, and even more preferably 0 to 50% by mass. Among the other constituent components, the polymer chain A having the constituent component having the substituent (a) described later is preferred. 2P The content of the component can be appropriately determined by taking into account the total content of the other components mentioned above, for example, preferably 0 to 70% by mass, more preferably 0 to 50% by mass, and even more preferably 0 to 30% by mass.

[0198] -Functional Group A 2G Or polymer chain A 2P The preferred method -

[0199] Able to serve as A 2 The functional group A containing fluorine atoms is used. 2GF Or polymer chain A 2PFPreferably, it is a polymer chain having a functional group having a chemical structure represented by Formula 3 below, or having a constituent component represented by Formula 3 below.

[0200] In being able to serve as A 2 The functional group A containing fluorine atoms is used. 2GF When the functional group has the chemical structure represented by Formula 3, it is preferable that the group bonded to one of its bonding portions is the terminal group of the aforementioned fluorine substituent. Furthermore, when it can be used as A... 2 The polymer chain A used 2PF In the case of a polymer chain having the constituent components represented by Formula 3, the terminal groups of the polymer chain are as described above.

[0201] [Chemical Formula 10]

[0202]

[0203] In Equation 3, R 11 It represents a hydrogen atom or a methyl group.

[0204] B 1 This indicates a single bond or a linking group, preferably a linking group. As a group capable of functioning as B... 1 The linking group used is not particularly limited, but examples of links that can be used as the aforementioned linking group L can be given. A4 The linking group used is one of the following groups. Preferably, it is an ether group, a thioether group, an imino group, or a carbonyl group, or a linking group obtained by combining two or more of them (preferably two to five), and more preferably a -CO-O- group.

[0205] R 12 and R 13 Each represents a hydrogen atom, a hydroxyl group, or an alkyl group having 1 to 4 carbon atoms (it may have a fluorine atom as a substituent, but is preferably not). The preferred substituents are hydrogen atoms or hydroxyl groups. R 12 and R 13 They can be the same or different.

[0206] R 14 It represents a hydrogen atom or a fluorine atom.

[0207] R F1 and R F2 These respectively represent fluorine atoms or fluoroalkyl groups having 1 to 4 carbon atoms. As a group capable of functioning as R... F1 and R F2 In the fluoroalkyl group used, some of the hydrogen atoms can be replaced by fluorine atoms, but perfluoroalkyl is preferred. The fluoroalkyl group preferably has 1 or 2 carbon atoms, more preferably 1. F1 and R F2 Preferably, it is a fluorine atom or a trifluoromethyl group, more preferably a fluorine atom. RF1 and R F2 They can be the same or different, but fluorine atoms are preferred.

[0208] a1 is not particularly restricted as long as it is an integer greater than or equal to 0. It is preferably an integer from 0 to 10, more preferably an integer from 1 to 5, and even more preferably an integer from 1 to 3.

[0209] b1 is not particularly restricted as long as it is an integer greater than or equal to 1. It is preferably an integer from 1 to 20, more preferably an integer from 1 to 10, and even more preferably an integer from 2 to 6.

[0210] In Formula 3, the sum of a1 and b1 is not particularly limited as long as a1 and b1 are within the above-mentioned ranges. For example, the preferred range is the same as the number of carbon atoms of the fluoroalkyl group that is the above-mentioned fluorine substituent.

[0211] When a1 and b1 are both integers greater than 2, there are multiple -C(R) in Equation 3. 12 (R) 13 -base, and -C(R) F1 (R) F2 The bases can be the same or different.

[0212] As specific examples of the functional groups or constituent components represented by Formula 3 above, examples can be given of the functional groups or constituent components shown in the specific examples of polymers shown later or in the embodiments described below, but the present invention is not limited to these.

[0213] Able to serve as A 2 The A-type structure used contains polysiloxane. 2GS Or polymer chain A 2PS Preferably, it is a functional group having the chemical structure represented by Formula 4 below, or a polymer chain having the constituent components represented by Formula 4 below.

[0214] In being able to serve as A 2 The functional group A, which contains a polysiloxane structure, is used. 2GS In the case of a group having the chemical structure represented by Formula 4, it is preferable that the group bonded to one of its bonding portions is the terminal group of the aforementioned fluorine substituent. Furthermore, when it can be used as A... 2 The polymer chain A used 2PS In the case of a polymer chain having the constituent components represented by Formula 4, the terminal groups of the polymer chain are as described above.

[0215] [Chemical Formula 11]

[0216]

[0217] In Equation 4, R 11 It represents a hydrogen atom or a methyl group.

[0218] B 2 Indicates a linking group. As a group capable of functioning as B... 2 The linking group used is not particularly limited, but examples of links that can be used as the aforementioned linking group L can be given. A1 Linking groups listed among the linking groups. Among them, B... 2 The linking group is preferably an alkylene group, an alkenylene group, an arylene group, an oxygen atom, a sulfur electron, a carbonyl group, or a group related to combinations thereof, more preferably a group containing a -CO-O- group, and even more preferably a -CO-O- group or a -CO-O-alkylene group.

[0219] R 15 Indicates alkyl or aryl, preferably alkyl. Capable of being R 15 The alkyl and aryl groups used are respectively related to the polysiloxane structure that can act as R... S The alkyl and aryl groups used have the same meaning and the preferred range is also the same. Among them, R... 15 Methyl groups are particularly preferred. Two R groups bonded to the same silicon atom 15 They can be the same or different, but methyl is preferred.

[0220] R 16 Indicates alkyl or aryl, preferably alkyl. Two R atoms bonded to the same silicon atom. 16 They can be the same or different. They can be used as R. 16 The alkyl and aryl groups used are respectively related to the polysiloxane structure that can act as R... S The alkyl and aryl groups used have the same meaning and the preferred range is also the same. Among them, R... 16 Methyl groups are particularly preferred.

[0221] R 16A This represents a hydrogen atom or a substituent. As it can act as R... 16A The substituents used are not particularly limited; for example, substituent Z described later is preferred. S The substituents used. Among them, [the substituent] is capable of acting as R. 16A The substituents used are more preferably alkyl, alkenyl, aralkyl, aryl, alkoxy, or aryloxy, and even more preferably alkyl.

[0222] Z represents the group represented by the following formula (Z).

[0223] [Chemical Formula 12]

[0224]

[0225] In formula (Z), R 17 and R 18 These represent alkyl or aryl groups, respectively. They can act as R... 17 and R 18 The alkyl and aryl groups used are respectively related to the polysiloxane structure that can act as R... S The alkyl and aryl groups used have the same meaning and the preferred range is also the same. 17 and R 18 They can be the same or different. R 19 It represents an unsubstituted alkyl group having 1 to 4 carbon atoms. y2 is an integer from 1 to 100, preferably an integer from 1 to 50, and more preferably an integer from 1 to 20.

[0226] In the constituent components represented by Equation 4, x1, x2, x3, y1 and y2 can be appropriately determined. The total (degree of polymerization) of x1, x2, x3, y1 and y2 is the same as the degree of polymerization in the polymer chain of the polysiloxane structure described above. In particular, it is preferred that the value of (x1+x2+x3)×y1 is the same as the degree of polymerization in the polymer chain of the polysiloxane structure described above.

[0227] In Equation 4, x1, x2, and x3 are all integers greater than or equal to 0.

[0228] x1 is preferably an integer from 0 to 50, and more preferably an integer from 0 to 20.

[0229] x2 is preferably an integer from 0 to 50, and more preferably an integer from 0 to 20.

[0230] x3 is preferably an integer from 1 to 100, and more preferably an integer from 1 to 30.

[0231] x1, x2 and x3 together are integers from 1 to 100, preferably integers from 2 to 70, and more preferably integers from 2 to 50.

[0232] When x1 and x3 are both integers greater than 2, in Equation 4, the two Z or R atoms bonded to the same silicon atom... 15 They can be the same or different.

[0233] y1 is an integer from 1 to 30, preferably an integer from 1 to 20, and more preferably an integer from 1 to 10.

[0234] In x1, x2, x3, y1 and y2, x1, x2 and y2 are 0, x3 is an integer from 1 to 100, and y1 is preferably an integer from 1 to 30.

[0235] Specific examples of the functional group or constituent component represented by Formula 4 above include, for example, terminal (meth)acrylic acid modified silicone compounds. More specifically, specific examples of the polymers shown later or the compounds shown in the polymers synthesized in the examples described below can be given, but the present invention is not limited to these.

[0236] In the polymer represented by formula (I), A 1 and A 2 The combinations are not particularly restricted; appropriate combinations can serve as A. 1 The functional group A used 1G Or polymer chain A 1P With the ability to be A 2 The functional group A used 2G Or polymer chain A 2P As A 1 and A 2 The combination of these is preferably one that can serve as A. 1 The preferred functional group A is adopted. 1P Or polymer chain A 1P With the ability to be A 2 The preferred functional group A is used. 2G Or polymer chain A 2P The combination of these is more preferably one that can serve as A. 1 The preferred polymer chain A is used. 1P With the ability to be A 2 The preferred polymer chain A is used. 2P Combinations, for example, can be exemplified in the polymers shown in the embodiments.

[0237] Polymer (I) may have substituents. There are no particular restrictions on the substituents that may be present, but substituent Z described later can be cited as an example. From the perspective of adsorption with solid particles, substituents (a) other than acidic groups are preferred.

[0238] In this invention, polymer (I) may have acidic groups in the following substituents (a) as long as the acid value is below 3 mg KOH / g. However, from the viewpoint of being able to suppress the acid value to a low level, and also from the perspective of the dispersion state of solid particles and electrical resistance, it is also a preferred mode not to have acidic groups in the following substituents (a). From the viewpoint of being able to suppress the acid value and base value to a low level, it is also a more preferred mode not to have any of the following substituents (a).

[0239] -Substituent(a)-

[0240] Acidic groups, groups with basic nitrogen atoms, urea groups, carbamate groups, alkoxysilyl groups, epoxy groups, isocyanate groups, and hydroxyl groups.

[0241] As an acidic group, there are no particular limitations; examples include carboxyl groups, sulfonic acid groups, phosphoric acid groups (also called phosphoryl groups), phosphonic acid groups, and hypophosphonic acid groups (phosphonyl groups). The sulfonic acid group, phosphoric acid group, and phosphonic acid group are not particularly limited individually, but they have the same meaning as the groups corresponding to substituent Z described later. Furthermore, acidic groups and other groups capable of forming salts can also form salts. Examples of salts include various metal salts, ammonium salts, and amine salts.

[0242] Examples of groups containing a basic nitrogen atom include amino, pyridyl, imino, and amidine. The amino group has the same meaning as the amino group of substituent Z, which will be discussed later.

[0243] As a urea group, for example, -NR can be cited. A1 CONR A2 R A3 (where R) A1 R A2 and R A3 (Referring to alkyl, aryl, or aralkyl groups having 1 to 20 hydrogen atoms or carbon atoms.) As a preferred example, the urea group is more preferably -NR. A1 CONHR A3 (where R) A1 and R A3 This refers to alkyl, aryl, or aralkyl groups having 1 to 10 hydrogen or carbon atoms. -NHCONHR is particularly preferred. A3 (where R) A3 This refers to alkyl, aryl, and aralkyl groups with 1 to 10 hydrogen or carbon atoms.

[0244] As a carbamate group, for example, -NHCOR can be cited. A4 -NR A5 COOR A6 -OCONHR A7 -OCONR A8 R A9 (where R) A4 R A5 R A6 R A7 R A8 and R A9 Examples of preferred groups include alkyl, aryl, and aralkyl groups having 1 to 20 carbon atoms, and containing at least an imino and a carbonyl group. As a carbamate group, -NHCOOR is more preferred. A4 -OCONHR A7 (where R) A4 R A7This refers to alkyl, aryl, and aralkyl groups having 1 to 20 carbon atoms, with -NHCOOR being particularly preferred. A4 -OCONHR A7 (where R) A4 R A7 This refers to alkyl, aryl, and aralkyl groups with 1 to 10 carbon atoms.

[0245] As can be R A1 ~R A8 The aryl group used preferably has 6 or more carbon atoms, and more preferably 24 or fewer. As a component capable of being used as R... A1 ~R A8 The aralkyl group used preferably has 7 or more carbon atoms, preferably 23 or less, and preferably 10 or less.

[0246] The alkoxysilyl group is not particularly limited, and examples include mono-, di-, or trialkoxysilyl groups. Preferably, alkoxysilyl groups with 1 to 20 carbon atoms are examples, and more preferably, alkoxysilyl groups with 1 to 6 carbon atoms are examples. For example, methoxysilyl, ethoxysilyl, tert-butoxysilyl, cyclohexylsilyl, dimethoxysilyl, trimethoxysilyl, and triethoxysilyl are examples.

[0247] -Substituent Z-

[0248] Examples of alkyl groups include alkyl groups (preferably alkyl groups with 1 to 20 carbon atoms, such as methyl, ethyl, isopropyl, tert-butyl, pentyl, heptyl, 1-ethylpentyl, benzyl, 2-ethoxyethyl, 1-carboxymethyl, etc.), alkenyl groups (preferably alkenyl groups with 2 to 20 carbon atoms, such as vinyl, allyl, oleyl, etc.), alkynyl groups (preferably alkynyl groups with 2 to 20 carbon atoms, such as ethynyl, butyrynyl, phenylethynyl, etc.), and cycloalkyl groups (preferably cycloalkyl groups with 3 to 20 carbon atoms, such as cyclopropyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, etc.). When referred to as alkyl groups in this invention... Typically, cycloalkyl groups are included, but are described separately here. These include aryl groups (preferably aryl groups with 6 to 26 carbon atoms, such as phenyl, 1-naphthyl, 4-methoxyphenyl, 2-chlorophenyl, 3-methylphenyl, etc.), aralkyl groups (preferably aralkyl groups with 7 to 23 carbon atoms, such as benzyl, phenethyl, etc.), and heterocyclic groups (preferably heterocyclic groups with 2 to 20 carbon atoms, more preferably heterocyclic groups with a 5 or 6-membered ring having at least one oxygen atom, sulfur atom, and nitrogen atom). Heterocyclic groups include aromatic heterocyclic groups and aliphatic heterocyclic groups. Examples include tetrahydropyranyl, tetrahydrofuranyl, 2-pyridyl, 4... -pyridyl, 2-imidazolyl, 2-benzimidazolyl, 2-thiazolyl, 2-oxazolyl, pyrrolidone, etc.), alkoxy groups (preferably alkoxy groups with 1 to 20 carbon atoms, such as methoxy, ethoxy, isopropoxy, benzyloxy, etc.), aryloxy groups (preferably aryloxy groups with 6 to 26 carbon atoms, such as phenoxy, 1-naphthoxy, 3-methylphenoxy, 4-methoxyphenoxy, etc.), heterocyclic oxy groups (groups with -O- groups bonded to the above heterocyclic groups), alkoxycarbonyl groups (preferably alkoxycarbonyl groups with 2 to 20 carbon atoms, such as ethoxycarbonyl, 2-ethylhexyloxycarbonyl, deca-hydroxycarbonyl, etc.). Dialkoxycarbonyl, etc.), aryloxycarbonyl (preferably an aryloxycarbonyl with 7 to 26 carbon atoms, such as phenoxycarbonyl, 1-naphthoxycarbonyl, 3-methylphenoxycarbonyl, 4-methoxyphenoxycarbonyl, etc.), heterocyclic oxycarbonyl (a group with a -O-CO- group bonded to the above heterocyclic group), amino (preferably an amino, alkylamino, or arylamino group containing 0 to 20 carbon atoms, such as amino(-NH2), N,N-dimethylamino, N,N-diethylamino, N-ethylamino, aniline, etc.), aminosulfonyl (preferably an aminosulfonyl group containing 0 to 20 carbon atoms, such as N,N-Dimethylaminosulfonyl, N-phenylaminosulfonyl, etc.), acyl groups (including alkyl carbonyl, alkenyl carbonyl, alkynyl carbonyl, aryl carbonyl, heterocyclic carbonyl, with the preferred number of carbon atoms being 1 to 20, such as acetyl, propionyl, butyryl, octanoyl, hexadecanoyl, acrylyl, methacrylyl, crotonyl, benzoyl, naphthoyl, nicotinyl, etc.), acyloxy groups (including alkyl carbonyloxy, alkenyl carbonyloxy, alkynyl carbonyloxy, heterocyclic carbonyloxy, with the preferred number of carbon atoms being 1 to 20, such as acetyloxy, propionyloxy, butyryloxy, octanoyloxy, hexadecanoyl... Oxyk-, acryloyloxy, methacryloyloxy, crotonyloxy, nicotinyloxy, etc.), aromatic acryloyloxy (preferably aromatic acryloyloxy with 7 to 23 carbon atoms, such as benzoyloxy, naphthyloxy, etc.), carbamoyl (preferably carbamoyl with 1 to 20 carbon atoms, such as N,N-dimethylcarbamoyl, N-phenylcarbamoyl, etc.), amide (preferably amide with 1 to 20 carbon atoms, such as acetamido, benzoylamino, etc.), alkylthio (preferably alkylthio with 1 to 20 carbon atoms, such as methylthio, ethylthio, isopropylthio, benzylthio, etc.), arylthio The following groups are used: alkyl sulfonyl (preferably an arylthio group with 6 to 26 carbon atoms, such as phenylthio, 1-naphthio, 3-methylphenylthio, 4-methoxyphenylthio, etc.), heterocyclic sulfonyl (a group having a -S- group bonded to the above heterocyclic group), alkylsulfonyl (preferably an alkylsulfonyl group with 1 to 20 carbon atoms, such as methylsulfonyl, ethylsulfonyl, etc.), arylsulfonyl (preferably an arylsulfonyl group with 6 to 22 carbon atoms, such as benzenesulfonyl, etc.), alkylsilyl (preferably an alkylsilyl group with 1 to 20 carbon atoms, such as monomethylsilyl, dimethylsilyl, trimethylsilyl, etc.). Silyl, triethylsilyl, etc.), arylsilyl (preferably arylsilyl with 6 to 42 carbon atoms, such as triphenylsilyl), alkoxysilyl (preferably alkoxysilyl with 1 to 20 carbon atoms, such as monomethoxysilyl, dimethoxysilyl, trimethoxysilyl, triethoxysilyl, etc.), aryloxysilyl (preferably aryloxysilyl with 6 to 42 carbon atoms, such as triphenoxysilyl), phosphoryl (preferably phosphate with 0 to 20 carbon atoms, such as -OP(=O)(R, P 2) Phosphonyl group (preferably phosphonyl group with 0 to 20 carbon atoms, for example, -P (=O) (R P 2) Oxyphosphin group (preferably an oxyphosphin group with 0 to 20 carbon atoms, for example, -P(R) P 2) Phosphonyl group (preferably a phosphonyl group with 0 to 20 carbon atoms, for example, -PO (OR) P 2) Sulfonate (sulfonic acid group), carboxyl group, hydroxyl group, thioalkyl group, cyano group, halogen atom (e.g., fluorine atom, chlorine atom, bromine atom, iodine atom, etc.). R PIt is a hydrogen atom or a substituent (preferably a group selected from substituent Z).

[0249] Furthermore, the groups listed in substituent Z can be further replaced by the aforementioned substituent Z.

[0250] The aforementioned alkyl, alkylene, alkenyl, alkenylene, alkynyl and / or alkynylene groups can be cyclic or chain-like, and can be straight-chain or branched.

[0251] (m and n in equation (I))

[0252] In the above equation (I), m represents A 2 The number of -S- bases is an integer from 1 to 9, preferably an integer from 2 to 5, and more preferably an integer from 3 to 5.

[0253] n represents A 1 The number of -S- bases is an integer from 1 to 8, preferably an integer from 1 to 4, more preferably an integer from 1 to 3, and even more preferably 1 or 2. Wherein, in A... 1 When two or three of the above (A-1) to (A-3) are present, the number of each of the (A-1)-S-based (HS-based), (A-2)-S-based, and (A-3)-S-based bases is not particularly restricted and can be appropriately determined as long as it satisfies the condition that it can be used as n. For example, the number of (A-1)-S-based bases and (A-3)-S-based bases are the same as n1 and n2 in equation (IA) described later.

[0254] Wherein, m+n is an integer from 2 to 10, preferably an integer from 3 to 8, more preferably an integer from 3 to 6, and even more preferably an integer from 4 to 6.

[0255] R 1 The content of "S" in polymer (I) is not particularly limited, but the total content of "S" in polymer (I) can be set to 1 to 90% by mass. Considering the dispersion state of solid particles and electrical resistance, it is preferably 2 to 60% by mass, more preferably 3 to 40% by mass, and even more preferably 5 to 30% by mass.

[0256] A 1 The total content of the polymer (I) is not particularly limited, but can be set to 1 to 90% by mass. The lower limit of the above total content, considering the dispersion state of the solid particles and electrical resistance, is preferably 3% by mass or more, more preferably 5% by mass or more, and even more preferably 8% by mass or more. The upper limit of the above total content, considering the dispersion state of the solid particles and electrical resistance, is preferably 50% by mass or less, more preferably 40% by mass or less, and even more preferably 30% by mass or less.

[0257] Among them, in A1 In the case of hydrogen atoms as described above (A-1), if the weight-average molecular weight of polymer (I) is taken into account, then A 1 The content of [A] decreases, therefore it is not included in the above-mentioned "A". 1 The total content is mentioned above. That is, the aforementioned "A" 1 "Total content" in A 1 In the case of (A-2) or (A-3) above, with A 1 The total content in polymer (I) has the same meaning. In this invention, in A 1 In the case of hydrogen atoms as described above (A-1), A 1 The total content in polymer (I) is not particularly limited, but is a small value, and is therefore determined, for example, by n in formula (I) or n2 in formula (IA).

[0258] A 2 The total content in polymer (I) is not particularly limited, but can be set to 1 to 98% by mass. From the perspective of the dispersion state of solid particles and electrical resistance, it is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, and even more preferably 30 to 70% by mass.

[0259] In polymer (I), A 2 The total content relative to A 1 The ratio of total content [A] 2 Total content / A 1 The total content is not particularly limited. For example, it can be set to 0.01 to 99. Considering the dispersion state of solid particles and resistance, it is preferably 0.1 to 80, more preferably 1 to 50, further preferably 2 to 30, and especially preferably 5 to 20.

[0260] The polymer represented by formula (I) is the polymer represented by the following formula (IA), which is also a preferred method.

[0261] [Chemical Formula 13]

[0262]

[0263] In equation (IA), R 1 It is a (m+n1+n2) valence linking group, and is related to the above R in formula (I). 1 same.

[0264] In formula (IA), A 11 This indicates a functional group or polymer chain containing at least one of amide, sulfonamide, and imide groups, and which can function as A in formula (I). 1 The above-mentioned (A-2) or (A-3) are the same. A11 From the perspective of suppressing the deterioration of solid particles, it is preferable to contain a polymer chain comprising at least one of amide, sulfonamide, and imide groups, and more preferably a polymer chain comprising an amide group. In formula (IA), A 12 It represents a hydrogen atom.

[0265] In formula (IA), A 2 It represents a functional group or polymer chain containing at least one of fluorine atoms and a polysiloxane structure, and is related to A in formula (I). 2 same.

[0266] In equation (IA), m represents A. 2 The number of -S- bases, and is the same as m in equation (I). n1 represents A 11 The number of S-radix bases is an integer from 0 to 8, with an upper bound of any integer from 2 to 4 and a lower bound of any integer from 0 to 2. n2 represents A. 12 The number of -S- bases is an integer from 0 to 8, with an upper limit of any integer from 2 to 4 and a lower limit of 1 or 2. The sum of n1 and n2 (n1+n2) is an integer from 1 to 8, and is the same as n in equation (I). Furthermore, the sum of m and n1 and n2 (m+n1+n2) is an integer from 2 to 10, and is the same as m+n in equation (I).

[0267] As specific examples of polymers represented by formula (I) or formula (IA), examples of polymers shown below or polymers synthesized in the embodiments described later can be cited, but the invention is not limited to these.

[0268] In the following polymers, TMS represents trimethylsilyl, and X represents... 1 It is a linking group, X 2 It is a substituent.

[0269] Additionally, in the following chemical formulas, determine A. 1 (Including SH) and A 2 The bonding positions are used to reveal the overall structure of each polymer, but only A 1 and A 2 If the quantities (n and m) are the same, then A 1 and A 2 The bonding positions are not limited to those determined by the following chemical formulas. For example, in polymer 1, A 1 This indicates a chemical structure in which two oxygen atoms are bonded to the left-hand structural portion relative to the central oxygen atom, but one of the A atoms... 1 The oxygen atom in the center can bond to the structure on the right.

[0270] [Chemical Formula 14]

[0271]

[0272] [Chemical Formula 15]

[0273]

[0274] [Chemical Formula 16]

[0275]

[0276] [Chemical Formula 17]

[0277]

[0278] [Chemical Formula 18]

[0279]

[0280] [Chemical Formula 19]

[0281]

[0282] [Chemical Formula 20]

[0283]

[0284] Polymer (I) (in this invention, includes polymers represented by formula (IA) as a preferred embodiment) can be commercially available or synthetic. Polymer (I) can be synthesized by selecting raw material compounds using known methods. For example, surfactants, emulsifiers, or dispersants can be used, and A-forming compounds can be formed. 1 (The reactive compounds of (A-2) or (A-3) above, and those capable of forming A) 2 Reactive compounds, as well as polymerizable compounds, etc., corresponding to R in formula (I). 1 Polymer (I) is synthesized by an addition reaction of a polythiol compound. Specifically, polymer (I) can be synthesized by the method described in Patent Document 2, or by the method illustrated in the examples described later. For example, polymers in which n2 is an integer greater than or equal to 1 can satisfy the proportion of m in formula (IA) such that R corresponds to the proportion in formula (IA). 1 Polythiols and compounds that can form A 2 The reactive compound undergoes an addition reaction, and furthermore, as needed, in a ratio satisfying n1 in formula (IA), it is reacted with A. 1The reactive compounds capable of forming (A-2) or (A-3) above undergo an addition reaction to be synthesized. In this synthesis, the polymer represented by formula (IA) in which n1 is 0 can, in the above synthesis method, satisfy the proportion of m in formula (IA) such that the corresponding R... 1 Polythiols and compounds that can form A 2 The reactive compound is subjected to an addition reaction to be synthesized, and can be synthesized as a synthetic intermediate in the synthesis method of the polymer (I) described in the examples described later.

[0285] Furthermore, the method of using the functional group as the intercalating substituent (a) is not particularly limited. Examples include copolymerization of compounds with functional groups, using polymerization initiators or chain transfer agents with (generating) functional groups, polymer reactions, reactions of alkenes with double bonds, ene-thiols reactions, or ATRP (Atom Transfer Radical Polymerization) polymerization using copper catalysts. In addition, functional groups can be introduced by using functional groups present in the polymer's main chain, side chains, or terminals as reaction sites. For example, compounds with functional groups can be used, and functional groups can be introduced through various reactions with dicarboxylic anhydride groups in the polymer chain.

[0286] -Physical properties or characteristics of the polymer (I) or the adhesive of the present invention-

[0287] The acid value of polymer (I) is below 3 mg KOH / g. Since the acid value is below 3 mg KOH / g, it is believed that, as described above, it can inhibit excessive aggregation and precipitation of binders and solid particles.

[0288] From the perspective of the dispersion state of solid particles, the acid value of polymer (I) is preferably 2 mg KOH / g or less, more preferably 1 mg KOH / g or less, and even more preferably 0.5 mg KOH / g or less. The lower limit of the acid value of polymer (I) is preferably 0 mg KOH / g.

[0289] The acid value of polymer (I) indicates the number of milligrams of potassium hydroxide required to neutralize the acidic groups present in 1g of polymer (I), and can be measured by the following method.

[0290] Furthermore, as an acidic group, it is not particularly limited as long as it is a group that is neutralized by potassium hydroxide. Examples include carboxylic acid group (carboxyl group), sulfonic acid group (sulfonyl group), phosphoric acid group (phosphoric group), phosphonic acid group, hypophosphonic acid group, or their salts.

[0291] (Measurement method)

[0292] The polymer (I) 1g can be dissolved in 25g of tetrahydrofuran and titrated with 0.01N-KOH solution using a potentiometric titration apparatus to determine its composition.

[0293] The polymer (I) or the adhesive of the present invention preferably has the following physical properties or characteristics.

[0294] Polymer (I) preferably has an alkalinity of 2 mg KOH / g or less. Since an alkalinity of 2 mg KOH / g or less is considered to suppress excessive aggregation and precipitation of the binder and solid particles. From the perspective of the dispersion state of the solid particles, the alkalinity of polymer (I) is more preferably 1 mg KOH / g or less, and even more preferably 0.5 mg KOH / g or less. The lower limit of the alkalinity of polymer (I) is preferably 0 mg KOH / g.

[0295] The base value of polymer (I) is expressed as the number of milligrams of potassium hydroxide equivalent to the number of moles of acid required to neutralize the basic groups present in 1g of polymer (I), and can be measured by the following method.

[0296] Furthermore, as a basic group, it is not particularly limited as long as it is a group that is neutralized by HCl. For example, groups having a basic nitrogen atom can be mentioned, preferably groups having a basic nitrogen atom bonded to a hydrogen atom. Specifically, amino, pyridyl, imino, amido, and urea or carbamate groups having a hydrogen atom bonded to a nitrogen atom can be mentioned.

[0297] (Measurement method)

[0298] 1g of polymer (I) can be dissolved in 25g of tetrahydrofuran, titrated with 1N-HCl solution using a potentiometric titration apparatus, and the number of moles of HCl required for neutralization can be converted into milligrams of potassium hydroxide.

[0299] The acid value and base value in polymer (I) can be within the above-mentioned ranges, but it is further preferred that the acid value is below 0.5 mg KOH / g and the base value is below 0.5 mg KOH / g.

[0300] The weight-average molecular weight of polymer (I) is not particularly limited. For example, it is preferably 3,000 or more, more preferably 5,000 or more, and even more preferably 7,000 or more. As an upper limit, it is actually 100,000 or less, but it is preferably 50,000 or less, and more preferably 30,000 or less from the perspective of the dispersion state of solid particles and electrical resistance.

[0301] The weight-average molecular weight of polymer (I) can be appropriately adjusted by changing the type and content of polymerization initiators, polymerization time, polymerization temperature, etc.

[0302] -Measurement of molecular weight-

[0303] In this invention, the molecular weight of polymers and polymer chains, unless otherwise specified, refers to the weight-average molecular weight or number-average molecular weight converted from standard polystyrene, as measured by gel permeation chromatography (GPC). The measurement method can be generally described by the method set in condition 1 or condition 2 (preferred) below. Depending on the type of polymer or polymer chain, a suitable eluent can be appropriately selected for use.

[0304] (Condition 1)

[0305] Tube string: Connects 2 TOSOH TSKgel Super AWM-H tubes (product name, manufactured by TOSOH CORPORATION)

[0306] Charge carriers: 10 mM LiBr / N-methylpyrrolidone

[0307] Temperature measured: 40℃

[0308] Carrier flow rate: 1.0 ml / min

[0309] Sample concentration: 0.1% by mass

[0310] Detector: RI (Refractive Index) Detector

[0311] (Condition 2)

[0312] Tube String: Use a tube string to connect TOSOH TSKgel Super HZM-H, TOSOH TSKgel Super HZ4000, and TOSOH TSKgel Super HZ2000 (all product names, manufactured by Tosoh Corporation).

[0313] Charge carrier: tetrahydrofuran

[0314] Temperature measured: 40℃

[0315] Carrier flow rate: 1.0 ml / min

[0316] Sample concentration: 0.1% by mass

[0317] Detector: RI (Refractive Index) Detector

[0318] Polymer (I) can be either a non-crosslinked polymer or a crosslinked polymer. Furthermore, when crosslinking polymer (I) is performed by heating or applying voltage, the molecular weight can be greater than the aforementioned molecular weight. Preferably, when using an all-solid-state secondary battery, the weight-average molecular weight of polymer (I) is within the aforementioned range.

[0319] The polymer (I) is preferably amorphous. In this invention, "amorphous" means that, typically, no endothermic peak due to crystal melting is observed when measurements are performed at the glass transition temperature.

[0320] The moisture concentration of polymer (I) is preferably below 100 ppm (by mass). Furthermore, polymer (I) can be crystallized and dried, or the polymer dispersion can be used directly.

[0321] [Inorganic solid electrolyte composition]

[0322] The inorganic solid electrolyte composition of the present invention comprises the polymer (I) of the present invention described above, an inorganic solid electrolyte having conductivity of ions belonging to Group 1 or Group 2 of the periodic table, and a dispersion medium.

[0323] In the inorganic solid electrolyte composition of the present invention, since the inorganic solid electrolyte has excellent dispersion state, it can be used as a structural layer forming material for all-solid-state secondary batteries to realize all-solid-state secondary battery sheets with low resistance structural layers and all-solid-state secondary batteries with low resistance (high conductivity).

[0324] Therefore, the inorganic solid electrolyte composition of the present invention can be preferably used as a sheet for all-solid-state secondary batteries (including electrode sheets for all-solid-state secondary batteries) or as a forming material for the solid electrolyte layer or active material layer of all-solid-state secondary batteries.

[0325] The adhesive of the present invention may not exhibit solubility (dissolution) relative to the dispersion medium contained in the inorganic solid electrolyte composition, but it is preferable to exhibit solubility. That is, although the adhesive of the present invention in the inorganic solid electrolyte composition depends on its content, it is preferably present in the inorganic solid electrolyte composition in a state of being dissolved in the dispersion medium. If the adhesive of the present invention dissolves, it can stably perform its function of dispersing solid particles in the dispersion medium, thereby further improving the dispersion state of solid particles in the inorganic solid electrolyte composition.

[0326] In this invention, the dissolution of the adhesive in the dispersion medium means that it is not limited to all ways in which the adhesive of this invention is dissolved in the dispersion medium. For example, as long as the solubility of the adhesive of this invention is 80% or more relative to the dispersion medium, a portion of the adhesive of this invention may also exist in the inorganic solid electrolyte composition without dissolving.

[0327] The method for measuring solubility is as follows. Specifically, a predetermined amount of the polymer adhesive of the present invention, which is the object of measurement, is weighed and placed in a glass bottle. 100g of a dispersion medium of the same type as the dispersion medium contained in the inorganic solid electrolyte composition is added, and the mixture is stirred for 24 hours at 80 rpm on a mixing rotor at 25°C. The transmittance of the mixture obtained after 24 hours of stirring is measured under the following conditions: The amount of adhesive dissolved (the predetermined amount mentioned above) is varied to perform this test (transmittance measurement), and the upper limit concentration X (mass%) at which the transmittance becomes 99.8% is taken as the solubility of the adhesive of the present invention in the dispersion medium.

[0328] <Transmittance Measurement Conditions>

[0329] Dynamic light scattering (DLS) measurement

[0330] Device: DLS-8000 DLS measuring device manufactured by Otsuka Electronics Co., Ltd.

[0331] Laser wavelength and output: 488nm / 100mW

[0332] Sample cell: NMR tube

[0333] When the adhesive of the present invention is in particulate form (as opposed to the case where the dispersion medium contained in the inorganic solid electrolyte composition is insoluble), its shape is not particularly limited and can be flat, amorphous, etc., but is preferably spherical or granular. In this case, the average particle size of the particulate adhesive of the present invention in the inorganic solid electrolyte composition is not particularly limited, but is preferably 1 nm or more, more preferably 10 nm or more, and even more preferably 30 nm or more. As an upper limit, it is preferably 5 μm or less, more preferably 1 μm or less. The average particle size of the adhesive of the present invention can be measured in the same manner as the particle size of the inorganic solid electrolyte described above. The average particle size of the adhesive of the present invention can be adjusted, for example, by the type of dispersion medium, the composition of the polymer contained in the adhesive of the present invention, etc.

[0334] In this invention, the solubility of the adhesive in the dispersion medium can be appropriately imparted by the structure, composition (type and content of constituent components), weight-average molecular weight, and combination with the dispersion medium of the polymer (I) contained in the adhesive.

[0335] The inorganic solid electrolyte composition of the present invention is preferably a slurry in which the inorganic solid electrolyte is dispersed in a dispersion medium.

[0336] Furthermore, the inorganic solid electrolyte composition of the present invention is preferably a non-aqueous composition. In the present invention, a non-aqueous composition includes not only being free of water but also having a water content (also referred to as moisture content) preferably of 500 ppm or less. In a non-aqueous composition, a water content more preferably of 200 ppm or less, further preferably of 100 ppm or less, and particularly preferably of 50 ppm or less. If the inorganic solid electrolyte composition is a non-aqueous composition, the degradation of the inorganic solid electrolyte can be suppressed. Moisture content refers to the amount of water contained in the inorganic solid electrolyte composition (relative to the mass ratio of the inorganic solid electrolyte composition), specifically, it is defined as the value obtained by filtration using a 0.02 μm membrane filter and measurement using Karl Fischer titration.

[0337] The inorganic solid electrolyte composition of the present invention further includes the following: in addition to containing an inorganic solid electrolyte, it also contains an active substance and a conductive additive, etc. (the composition of this type is referred to as an electrode composition.)

[0338] The components contained in the inorganic solid electrolyte composition of the present invention and the components that may be contained therein will be described below.

[0339] <Adhesive>

[0340] The binder contained in the inorganic solid electrolyte composition of the present invention comprises the binder of the present invention described above. The binder of the present invention contained in the inorganic solid electrolyte composition of the present invention may be one type or two or more types.

[0341] The content (based on solids) of the adhesive in the inorganic solid electrolyte composition of the present invention is not particularly limited, but from the perspective of the dispersion state of the solid particles and the electrical resistance, it is preferably 0.1 to 5.0% by mass, more preferably 0.2 to 4.0% by mass, and even more preferably 0.3 to 2.0% by mass. Furthermore, for the same reason, the content (based on solids) of the adhesive in 100% by mass of the solids in the inorganic solid electrolyte composition of the present invention is preferably 0.1 to 6.0% by mass, more preferably 0.3 to 5.0% by mass, and even more preferably 0.4 to 2.5% by mass.

[0342] In this invention, the mass ratio of the total mass of the adhesive, inorganic solid electrolyte, and active material in 100% by mass of the solid component [(mass of inorganic solid electrolyte + mass of active material) / (total mass of adhesive)] to the total mass of the adhesive of this invention 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.

[0343] <Inorganic Solid Electrolytes>

[0344] The inorganic solid electrolyte composition of the present invention contains an inorganic solid electrolyte.

[0345] In this invention, inorganic solid electrolyte refers to an inorganic solid electrolyte, which is a solid electrolyte capable of ion movement within its interior. Because it does not contain organic matter as the primary ionic conductive material, it is significantly different from organic solid electrolytes (such as polymeric electrolytes represented by polyethylene oxide (PEO) and organic electrolyte salts represented by lithium bis(trifluoromethanesulfonyl)imide (LiTFSI)). Furthermore, since inorganic solid electrolytes are solid in their stable state, they generally do not dissociate or ionize into cations and anions. This is significantly different from inorganic electrolyte salts (LiPF6, LiBF4, lithium bis(fluorosulfonyl)imide (LiFSI), LiCl, etc.) that dissociate or ionize into cations and anions in electrolytes or polymers. While not particularly limited to inorganic solid electrolytes possessing ionic conductivity characteristic of metals belonging to Group 1 or Group 2 of the periodic table, they generally do not possess electronic conductivity. In the case that the all-solid-state secondary battery of the present invention is a lithium-ion battery, it is preferable that the inorganic solid electrolyte has the ionic conductivity of lithium ions.

[0346] The aforementioned inorganic solid electrolyte can be appropriately selected and used from solid electrolyte materials commonly 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. The binder of the present invention can suppress the degradation and decomposition of the inorganic solid electrolyte during the preparation of the inorganic solid electrolyte-containing composition. Therefore, it is possible to use sulfide-based inorganic solid electrolytes, which are generally prone to degradation and decomposition, and can effectively suppress the increase in interfacial resistance by forming a better interface between the active material and the inorganic solid electrolyte.

[0347] (i) Sulfide-based inorganic solid electrolytes

[0348] Sulfide-based inorganic solid electrolytes are preferably compounds containing sulfur atoms, possessing ionic conductivity of metals belonging to Group 1 or Group 2 of the periodic table, and exhibiting electronic insulation. Sulfide-based inorganic solid electrolytes preferably contain at least Li, S, and P as elements and possess lithium-ion conductivity, but may also appropriately contain other elements besides Li, S, and P.

[0349] As a sulfide-based inorganic solid electrolyte, for example, a lithium-ion conductive inorganic solid electrolyte that satisfies the composition represented by the following formula (S1) can be cited.

[0350] L a1 M b1 P c1 S d1 A e1 (S1)

[0351] In formula (S1), L represents an element selected from Li, Na, and K, preferably Li. 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 1 to 12:0 to 5:1:2 to 12:0 to 10. a1 is preferably 1 to 9, more preferably 1.5 to 7.5. b1 is preferably 0 to 3, more preferably 0 to 1. d1 is preferably 2.5 to 10, more preferably 3.0 to 8.5. e1 is preferably 0 to 5, more preferably 0 to 3.

[0352] As described below, the composition ratio of each element can be controlled by adjusting the amount of raw material compounds used in the manufacture of sulfide-based inorganic solid electrolytes.

[0353] Sulfide-based inorganic solid electrolytes can be in an amorphous state (glass), a crystalline state (glass-ceramic), or only partially crystalline. For example, Li-PS type glasses containing Li, P, and S, or Li-PS type glass-ceramics containing Li, P, and S can be used.

[0354] Sulfide-based inorganic solid electrolytes can be manufactured by reacting at least two of the following raw materials: lithium sulfide (Li2S), phosphorus sulfide (e.g., phosphorus pentasulfide (P2S5)), monomeric phosphorus, monomeric sulfur, sodium sulfide, hydrogen sulfide, lithium halides (e.g., LiI, LiBr, LiCl), and sulfides of the elements represented by M above (e.g., SiS2, SnS, GeS2).

[0355] In Li-PS glass and Li-PS glass-ceramics, the ratio of Li₂S to P₂S₅, expressed as a Li₂S:P₂S₅ molar ratio, is preferably 60:40 to 90:10, more preferably 68:32 to 78:22. Setting the Li₂S to P₂S₅ ratio within this range improves lithium-ion conductivity. Specifically, the lithium-ion conductivity is preferably set to 1 × 10⁻⁶. -4 S / cm or higher, more preferably 1×10 -3 S / cm or higher. There's no specific upper limit, but it's actually 1×10⁻⁶. -1 Below S / cm.

[0356] As specific examples of sulfide-based inorganic solid electrolytes, combinations of raw materials are shown below. Examples include 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-Al₂. S3, Li2S-GeS2, Li2S-GeS2-ZnS, Li2S-Ga2S3, Li2S-GeS2-Ga2S3, Li2S-GeS2-P2S5, Li2S-GeS2-Sb2S5, Li2S-GeS2-Al2S3, Li2S-SiS2, Li2S-Al2S3, Li2S-SiS2-Al2S3, Li2S-SiS2-P2S5, Li2S-SiS2-P2S5-LiI, Li2S-SiS2-LiI, Li2S-SiS2-Li4SiO4, Li2S-SiS2-Li3PO4, Li 10 GeP2S 12 And so on. The mixing ratio of each raw material is not limited. As a method for synthesizing sulfide-based inorganic solid electrolyte materials using this raw material composition, for example, an amorphization method can be mentioned. As an amorphization method, examples include mechanical polishing, solution processing, and melt quenching. Processing at room temperature is possible, thereby simplifying the manufacturing process.

[0357] (ii) Oxide-based inorganic solid electrolytes

[0358] Oxide-based inorganic solid electrolytes are preferably compounds containing oxygen atoms, possessing ionic conductivity of metals belonging to Group 1 or Group 2 of the periodic table, and having electronic insulation properties.

[0359] For oxide-based inorganic solid electrolytes, the preferred ionic conductivity is 1×10⁻⁶. -6 S / cm or higher, preferably 5×10 -6 S / cm or higher, especially preferably 1×10 -5 S / cm or higher. The upper limit is not specifically restricted, but it is actually 1×10⁻⁶. -1 Below S / cm.

[0360] As a specific example of a compound, Li can be cited. xa La yaTiO3 [xa satisfies 0.3≤xa≤0.7, ya satisfies 0.3≤ya≤0.7.] (LLT); Li xb La yb Zr zb M bb mb O nb (M) bb The elements are selected from one or more of 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 The elements are selected from one or more of 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, nd satisfies 3≤nd≤13.); Li （3-2xe） M ee xe D ee O(xe represents numbers greater than 0 and less than 0.1, M) ee This 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, zf satisfies 1 ≤ zf ≤ 10.); Li xg S yg O zg (xg satisfies 1≤xg≤3, yg satisfies 0<yg≤2, zg satisfies 1≤zg≤10.); Li3BO3; Li3BO3-Li2SO4; Li2O-B2O3-P2O5; Li2O-SiO2; Li6BaLa2Ta2O 12 Li3PO （4-3 / 2w） N w(w satisfies w < 1); Li has a LISICON (Lithium super ionic conductor) type crystal structure 3.5 Zn 0.25 GeO4; La with a perovskite-type crystal structure 0.55 Li 0.35 TiO3; LiTi2P3O with a NASICON (Natrium superionic conductor) type crystal structure 12 Li 1+xh+yh (Al, Ga) xh (Ti, Ge) 2-xh Si yh P 3-yh O 12 (xh satisfies 0 ≤ xh ≤ 1, yh satisfies 0 ≤ yh ≤ 1.); Li7La3Zr2O has a garnet-type crystal structure. 12 (LLZ) etc.

[0361] Furthermore, phosphorus compounds containing Li, P, and O are also preferred. Examples include lithium phosphate (Li3PO4); LiPON, obtained by replacing part of the oxygen element in lithium phosphate with nitrogen; and LiPOD. 1 (D) 1 Preferably, it contains one or more elements selected from Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zr, Nb, Mo, Ru, Ag, Ta, W, Pt, and Au.

[0362] Furthermore, LiA can also be preferably used. 1 ON(A) 1 It consists of one or more elements selected from Si, B, Ge, Al, C, and Ga.

[0363] (iii) Halogenated inorganic solid electrolytes

[0364] Halogen-based inorganic solid electrolytes are preferably compounds containing halogen atoms, possessing ionic conductivity of metals belonging to Group 1 or Group 2 of the periodic table, and having electronic insulation properties.

[0365] As a halide-based inorganic solid electrolyte, it is not particularly limited, but examples include LiCl, LiBr, LiI, and compounds such as Li3YBr6 and Li3YCl6 described in ADVANCED MATERIALS, 2018, 30, 1803075. Among them, Li3YBr6 and Li3YCl6 are preferred.

[0366] (iv) Hydride-based inorganic solid electrolytes

[0367] Hydride-based inorganic solid electrolytes are preferably compounds containing hydrogen atoms, possessing ionic conductivity of metals belonging to Group 1 or Group 2 of the periodic table, and having electronic insulation properties.

[0368] As hydride-based inorganic solid electrolytes, they are not particularly limited, but examples include LiBH4, Li4(BH4)3I, and 3LiBH4-LiCl.

[0369] The inorganic solid electrolyte is preferably in particles within the inorganic solid electrolyte composition. 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. As an upper limit, it is preferably 100 μm or less, more preferably 50 μm or less.

[0370] The particle size of the inorganic solid electrolyte was measured using the following steps. The inorganic solid electrolyte particles were diluted with water (or heptane if the substance is unstable in water) in a 20 mL sample vial to prepare a 1% (w / w) dispersion. The diluted dispersion sample was then irradiated with ultrasound at 1 kHz for 10 minutes and used immediately in the test. Using this dispersion sample, and employing a laser diffraction / scattering particle size distribution measuring device LA-920 (manufactured by HORIBA, Ltd.), data was collected 50 times at 25°C using a measuring quartz cuvette to obtain the volume average particle size. Other detailed conditions were referenced as needed in Japanese Industrial Standard (JIS) Z8828:2013 "Particle Size Analysis - Dynamic Light Scattering Method". Five samples were prepared for each grade, and their average value was used.

[0371] The method for adjusting particle size is not particularly limited, and well-known methods can be used, such as using a conventional pulverizer or classifier. As a pulverizer or classifier, a mortar, ball mill, sand mill, vibratory ball mill, satellite ball mill, planetary ball mill, and rotary airflow spray mill or sieve are preferred, for example. During pulverization, wet pulverization can be performed with a dispersion medium such as water or methanol. To obtain the desired particle size, classification is preferred. The classification method is not particularly limited, and sieves, air classifiers, etc., can be used. Both dry and wet classification methods can be used.

[0372] The inorganic solid electrolyte composition may contain one or more inorganic solid electrolytes.

[0373] The content of inorganic solid electrolyte in the composition containing inorganic solid electrolyte is not particularly limited. However, considering the dispersion state of the solid particles and the electrical resistance, it is preferable that the content of the solid component is 50% or more by mass, more preferably 70% or more by mass, and especially preferably 90% or more by mass, out of 100% by mass. As an upper limit, from the same viewpoint, it is preferable that the content is 99.9% or less by mass, more preferably 99.5% or less by mass, and especially preferably 99% or less by mass.

[0374] In the case where the inorganic solid electrolyte composition contains the active substance described later, the content of the inorganic solid electrolyte in the inorganic solid electrolyte composition is preferably within the above-mentioned range, where the total content of the active substance and the inorganic solid electrolyte is within the range described above.

[0375] In this invention, solid components refer to those components that do not volatilize or evaporate and disappear when the inorganic solid electrolyte composition is dried at 1 mmHg pressure under a nitrogen atmosphere and at 150°C for 6 hours. Typically, it refers to components other than the dispersion medium described later.

[0376] <Dispersion Medium>

[0377] As a dispersion medium contained in an inorganic solid electrolyte composition, any organic compound that appears liquid in the environment of use can be used. For example, various organic solvents can be cited, specifically alcohol compounds, ether compounds, amide compounds, amine compounds, ketone compounds, aromatic hydrocarbon compounds, aliphatic hydrocarbon compounds, nitrile compounds, ester compounds, etc.

[0378] The dispersion medium can be either a nonpolar (hydrophobic) or polar (hydrophilic) dispersion medium, but a nonpolar dispersion medium is preferred from the perspective of exhibiting excellent dispersibility. Nonpolar dispersion media generally refer to those with low affinity for water, but in this invention, examples include ester compounds, ketone compounds, ether compounds, aromatic hydrocarbon compounds, and aliphatic hydrocarbon compounds.

[0379] Examples of alcohol compounds include, for example, methanol, ethanol, 1-propanol, 2-propanol, 2-butanol, ethylene glycol, propylene glycol, glycerol, 1,6-hexanediol, cyclohexanediol, sorbitol, xylitol, 2-methyl-2,4-pentanediol, 1,3-butanediol, and 1,4-butanediol.

[0380] Examples of ether compounds include, for example, 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, dioxanes (including 1,2-, 1,3- and 1,4- isomers, etc.).

[0381] Examples of amide compounds include, for example, N,N-dimethylformamide, N-methyl-2-pyrrolidone, 2-pyrrolidone, 1,3-dimethyl-2-imidazolinone, ε-caprolactam, formamide, N-methylformamide, acetamide, N-methylacetamide, N,N-dimethylacetamide, N-methylpropaneamide, hexamethylphosphoric triamide, etc.

[0382] Examples of amine compounds include triethylamine, diisopropylethylamine, and tri-n-butylamine.

[0383] Examples of ketone compounds include, for example, acetone, methyl ethyl ketone, methyl isobutyl ketone (MIBK), cyclopentanone, cyclohexanone, cycloheptanone, dipropyl ketone, dibutyl ketone, diisopropyl ketone, diisobutyl ketone (DIBK), isobutylpropyl ketone, sec-butylpropyl ketone, pentylpropyl ketone, butylpropyl ketone, etc.

[0384] Examples of aromatic hydrocarbon compounds include, for example, benzene, toluene, xylene, and perfluorotoluene.

[0385] Examples of aliphatic hydrocarbon compounds include, for example, hexane, heptane, octane, nonane, decane, dodecane, cyclohexane, methylcyclohexane, ethylcyclohexane, cycloheptane, cyclooctane, decahydronaphthalene, paraffin wax, gasoline, naphtha, kerosene, and light oil.

[0386] Examples of nitrile compounds include acetonitrile, propionitrile, and isobutyronitrile.

[0387] Examples of ester compounds include, for example, ethyl acetate, propyl acetate, butyl acetate, ethyl butyrate, propyl butyrate, isopropyl butyrate, butyl butyrate, isobutyl butyrate, butyl valerate, pentyl valerate, ethyl isobutyrate, propyl isobutyrate, isopropyl isobutyrate, isobutyl isobutyrate, propyl neovalerate, isopropyl neovalerate, butyl neovalerate, isobutyl neovalerate, etc.

[0388] In this invention, the preferred compounds are ether compounds, ketone compounds, aromatic hydrocarbon compounds, aliphatic hydrocarbon compounds, and ester compounds, and more preferably ester compounds, ketone compounds, aromatic hydrocarbon compounds, or ether compounds.

[0389] The number of carbon atoms in the compound constituting the dispersion medium is not particularly limited, but is preferably 2 to 30, more preferably 4 to 20, even more preferably 6 to 15, and especially preferably 7 to 12.

[0390] The boiling point of the dispersion medium at atmospheric pressure (1 atmosphere: 101325 Pa) is preferably 50°C or higher, more preferably 70°C or higher. The upper limit is preferably 250°C or lower, and even more preferably 220°C or lower.

[0391] The dispersion medium contained in the inorganic solid electrolyte composition can be one or more. Examples of containing more than two dispersion media include xylene (a mixture of xylene isomers with a molar ratio of ortho-isomer: para-isomer: meta-isomer = 1:5:2) and mixed xylene (a mixture of ortho-xylene, para-xylene, meta-xylene, and ethylbenzene).

[0392] In this invention, the content of the dispersion medium in the inorganic solid electrolyte composition is not particularly limited and can be appropriately set. For example, the inorganic solid electrolyte composition is preferably 20-80% by mass, more preferably 30-70% by mass, and particularly preferably 40-60% by mass.

[0393] <Active Substances>

[0394] The inorganic solid electrolyte composition of the present invention contains an active material capable of intercalating and deintercalating ions belonging to Group 1 or Group 2 of the periodic table, which is also a preferred embodiment. Although described below, positive electrode active materials and negative electrode active materials can be cited as examples of active materials.

[0395] In this invention, the inorganic solid electrolyte composition containing active material (positive electrode active material or negative electrode active material) is sometimes referred to as an electrode composition (positive electrode composition or negative electrode composition).

[0396] (Positive electrode active material)

[0397] The positive electrode active material is an active material capable of intercalating and deintercalating ions of metals belonging to Group 1 or Group 2 of the periodic table, preferably capable of reversibly intercalating and deintercalating lithium ions. There are no particular limitations on the material as long as it possesses the aforementioned characteristics; it can be a transition metal oxide, an organic compound, or an element capable of complexing with Li, such as sulfur.

[0398] Among them, transition metal oxides are preferred as positive electrode active materials, and more preferably materials containing the transition metal element M. a A transition metal oxide (selected from one or more elements from Co, Ni, Fe, Mn, Cu, and V). Furthermore, element M may also be mixed into this transition metal oxide. b(Metals other than lithium, including elements in Group 1(Ia), Group 2(IIa), Al, Ga, In, Ge, Sn, Pb, Sb, Bi, Si, P, and B, etc.). As a mixture, relative to transition metal element M. a The amount (100 mol%) is preferably 0 to 30 mol%. More preferably, it is in the form of Li / M a The mixtures were synthesized by mixing in a molar ratio of 0.3 to 2.2.

[0399] Specific examples of transition metal oxides include (MA) transition metal oxides with a layered rock salt structure, (MB) transition metal oxides with a spinel structure, (MC) lithium-containing transition metal phosphate compounds, (MD) lithium-containing transition metal halophosphate compounds, and (ME) lithium-containing transition metal silicate compounds.

[0400] Specific examples of transition metal oxides (MA) with a layered rock salt-type structure include LiCoO2 (lithium cobalt oxide [LCO]), LiNi2O2 (lithium nickel oxide), and LiNi 0.85 Co 0.10 Al 0.05 O2 (lithium nickel cobalt aluminum oxide [NCA]), LiNi 1 / 3 Co 1 / 3 Mn 1 / 3O2 (lithium nickel manganese cobalt oxide [NMC]) and LiNi 0.5 Mn 0.5 O2 (lithium manganese nickel oxide).

[0401] Specific examples of transition metal oxides (MB) with spinel-type structures include LiMn2O4 (LMO), LiCoMnO4, Li2FeMn3O8, Li2CuMn3O8, Li2CrMn3O8, and Li2NiMn3O8.

[0402] Examples of lithium-containing transition metal phosphates (MC) 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).

[0403] Examples of lithium-containing transition metal halophosphates (MD) include, for example, iron fluorophosphates such as Li2FePO4F, manganese fluorophosphates such as Li2MnPO4F, and cobalt fluorophosphates such as Li2CoPO4F.

[0404] Examples of lithium-containing transition metal silicate compounds include, for example, Li2FeSiO4, Li2MnSiO4, and Li2CoSiO4.

[0405] In this invention, (MA) is preferably a transition metal oxide having a layered rock salt structure, and more preferably LCO or NMC.

[0406] The shape of the positive electrode active material is not particularly limited, but it is preferably particulate in the inorganic solid electrolyte composition. When the positive electrode active material is particulate, its particle size (volume average particle size) is not particularly limited. For example, it can be set to 0.1–50 μm. The particle size of the positive electrode active material can be measured in the same manner as the particle size of the inorganic solid electrolyte described above. To produce the predetermined particle size, a conventional pulverizer or classifier is used in the same manner as with the inorganic solid electrolyte.

[0407] Positive electrode active materials obtained by calcination can be used after being cleaned with water, acidic aqueous solutions, alkaline aqueous solutions, or organic solvents.

[0408] The positive electrode active material contained in the inorganic solid electrolyte composition can be one or more.

[0409] The content of the positive electrode active material in the inorganic solid electrolyte composition is not particularly limited, but is preferably 10-97% by mass, more preferably 30-95% by mass, even more preferably 40-93% by mass, and especially preferably 50-90% by mass in 100% by mass of solid components.

[0410] (Negative electrode active material)

[0411] The negative electrode active material is an active material capable of intercalating and deintercalating ions of metals belonging to Group 1 or Group 2 of the periodic table, preferably capable of reversibly intercalating and deintercalating lithium ions. There are no particular limitations on the material as long as it possesses the aforementioned characteristics; examples include carbonaceous materials, metal oxides, metal composite oxides, lithium monomers, lithium alloys, and negative electrode active materials capable of forming alloys with lithium (capable of alloying). From a reliability perspective, carbonaceous materials, metal composite oxides, or lithium monomers are preferred. Considering the possibility of increasing the capacity of all-solid-state secondary batteries, active materials capable of alloying with lithium are preferred.

[0412] Carbonaceous materials used as negative electrode active materials refer to materials that are actually composed of carbon. Examples include carbon blacks such as calcined petroleum pitch and acetylene black (AB), graphite (natural graphite, vapor-grown graphite, and other artificial graphite), and various synthetic resins such as PAN (polyacrylonitrile) resins or furfuryl alcohol resins. Furthermore, examples include various types of carbon fibers such as PAN-based carbon fibers, cellulose-based carbon fibers, pitch-based carbon fibers, vapor-grown carbon fibers, dehydrated PVA (polyvinyl alcohol) carbon fibers, lignin carbon fibers, glassy carbon fibers, and activated carbon fibers, as well as mesophase microspheres, graphite whiskers, and planar graphite.

[0413] These carbonaceous materials can also be classified according to the degree of graphitization into non-graphitizable carbonaceous materials (also known as hard carbon) and graphitic carbonaceous materials. Furthermore, the carbonaceous material preferably has the facet spacing or density and crystallite size described in Japanese Patent Application Publication Nos. 62-22066, 2-6856, and 3-45473. The carbonaceous material does not have to be a single material; mixtures of natural and artificial graphite as described in Japanese Patent Application Publication No. 5-90844, or coated graphite as described in Japanese Patent Application Publication No. 6-4516, etc., can also be used.

[0414] As a carbonaceous material, hard carbon or graphite is preferred, and graphite is more preferred.

[0415] Oxides of metals or half-metals suitable for use as negative electrode active materials are not particularly limited as long as they can absorb and release lithium. Examples include oxides of metal elements (metal oxides), composite oxides of metal elements, or composite oxides of metal elements and half-metal elements (collectively referred to as metal composite oxides), and oxides of half-metal elements (half-metal oxides). Amorphous oxides are preferred among these oxides, and chalcogenides, the reaction products of metal elements with elements of Group 16 of the periodic table, are also preferred. In this invention, a half-metal element refers to an element exhibiting intermediate properties between a metal and a non-metal element. Typically, it includes six elements: boron, silicon, germanium, arsenic, antimony, and tellurium, and also includes three elements: selenium, polonium, and astatine. Furthermore, amorphous refers to a material that, by using CuKα X-ray diffraction, has a broad scattering band with vertices in the region of 2θ values ​​of 20° to 40°, and may also have crystalline diffraction lines. The strongest intensity of the crystal diffraction lines observed when the 2θ value is 40° to 70° is preferably less than 100 times the intensity of the diffraction line at the apex of the broad scattering band observed when the 2θ value is 20° to 40°, more preferably less than 5 times, and especially preferably does not have crystal diffraction lines.

[0416] Among the compounds composed of the aforementioned amorphous oxides and chalcogenides, amorphous oxides or chalcogenides composed of half-metallic elements are more preferred, and oxides or chalcogenides composed of a single element or a combination (composite) of two or more elements selected from 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, for example, Ga2O3, GeO, PbO, PbO2, Pb2O3, Pb2O4, Pb3O4, Sb2O3, Sb2O4, Sb2O8Bi2O3, Sb2O8Si2O3, Sb2O5, Bi2O3, Bi2O4, GeS, PbS, PbS2, Sb2S3, or Sb2S5.

[0417] As a negative electrode active material that can be used in conjunction with amorphous oxides centered on Sn, Si, and Ge, preferred examples include carbonaceous materials, lithium monomers, lithium alloys, and negative electrode active materials that can absorb and / or release lithium ions or lithium metal.

[0418] From the viewpoint of high current density charge and discharge characteristics, oxides of metal or half-metal elements, especially metal (composite) oxides and the aforementioned chalcogenides, are preferably composed of at least one of titanium and lithium. Examples of lithium-containing metal composite oxides (lithium composite metal oxides) include, for instance, composite oxides of lithium oxide with the aforementioned metal (composite) oxides or the aforementioned chalcogenides; more specifically, Li₂SnO₂ is an example.

[0419] The negative electrode active material, such as a metal oxide, is preferably also containing titanium (titanium oxide). Specifically, since Li4Ti5O 12 Lithium titanate (LTO) exhibits minimal volume change during lithium ion absorption and release, resulting in excellent rapid charge and discharge characteristics. It is also preferred in terms of suppressing electrode degradation and improving the lifespan of lithium-ion secondary batteries.

[0420] Regarding lithium alloys as negative electrode active materials, there are no particular restrictions as long as the alloy is commonly used as a negative electrode active material in secondary batteries. For example, lithium-aluminum alloys can be cited. Specifically, lithium-aluminum alloys can be cited, which are obtained by using lithium as the base metal and adding 10% by mass of aluminum.

[0421] Regarding the negative electrode active material capable of forming an alloy with lithium, there are no particular limitations as long as it is a material commonly used as a negative electrode active material in secondary batteries. Examples of such active materials include (negative electrode) active materials (alloys, etc.) containing silicon or tin, metals such as Al and In, with silicon-containing active materials being preferred to achieve higher battery capacity. More preferably, active materials containing silicon with a silicon content of 50 mol% or more of all constituent elements are also preferred.

[0422] Generally speaking, negative electrodes containing these active materials (e.g., Si negative electrodes containing silicon-containing active materials, Sn negative electrodes containing tin-containing active materials, etc.) can adsorb more Li ions compared to carbon negative electrodes (graphite and acetylene black, etc.). That is, the amount of Li ions adsorbed per unit mass increases. Therefore, the battery capacity (energy density) can be increased. As a result, it has the advantage of extending battery drive time.

[0423] Examples of silicon-containing active materials include, for example, Si and SiO. x Silicon materials such as (0 < x ≤ 1) and silicon-containing alloys (e.g., LaSi2, VSi2, La-Si, Gd-Si, Ni-Si) containing titanium, vanadium, chromium, manganese, nickel, copper, lanthanum, etc., or structured active materials (e.g., LaSi2 / Si), and active materials containing silicon and tin such as SnSiO3 and SnSiS3, etc. Additionally, SiO... x It can be used as a negative electrode active material (semi-metal oxide), and since Si is generated through the operation of an all-solid-state secondary battery, it can be used as a negative electrode active material (its precursor material) that can be alloyed with lithium.

[0424] Examples of tin-containing anode active materials include Sn, SnO, SnO2, SnS, and SnS2, as well as active materials containing both silicon and tin. Furthermore, composite oxides with lithium oxide, such as Li2SnO2, can also be cited.

[0425] In this invention, the above-mentioned negative electrode active material can be used without particular limitation. However, from the perspective of battery capacity, it is preferable to use a negative electrode active material that can be alloyed with lithium. More preferably, it is the above-mentioned silicon material or silicon-containing alloy (alloy containing silicon element). Even more preferably, it contains silicon (Si) or a silicon-containing alloy.

[0426] The chemical formula of the compound obtained by the above calcination method can be calculated as follows: Inductively coupled plasma (ICP) emission spectroscopy is used as the measurement method, and as a simplified method, it is calculated based on the mass difference of the powder before and after calcination.

[0427] The shape of the negative electrode active material is not particularly limited, but it is preferably particulate in the inorganic solid electrolyte composition. When the negative electrode active material is particulate, the particle size is not particularly limited, but is preferably 0.1–60 μm. The particle size of the negative electrode active material can be measured in the same manner as the particle size of the inorganic solid electrolyte described above. To produce the predetermined particle size, a conventional pulverizer or classifier is used in the same manner as with the inorganic solid electrolyte.

[0428] The negative electrode active material contained in the inorganic solid electrolyte composition can be one or more.

[0429] The content of the negative electrode active material in the inorganic solid electrolyte composition is not particularly limited, but is preferably 10-90% by mass, more preferably 20-85% by mass, more preferably 30-80% by mass, and even more preferably 40-75% by mass in 100% by mass of solid components.

[0430] In this invention, when the negative electrode active material layer is formed by charging a secondary battery, ions belonging to Group 1 or Group 2 of the periodic table, generated within an all-solid-state secondary battery, can be used instead of the aforementioned negative electrode active material. By causing these ions to combine with electron bonds and precipitate in metallic form, the negative electrode active material layer can be formed.

[0431] (Coating of active substances)

[0432] Different metal oxides can be used to coat the surfaces of positive and negative electrode active materials. Examples of surface coating agents include metal oxides containing Ti, Nb, Ta, W, Zr, Al, Si, or Li. Specifically, examples include spinel titanate, tantalum oxides, niobium oxides, and lithium niobate compounds; for instance, Li₄Ti₅O₅ can be used. 12 , Li2Ti2O5, LiTaO3, LiNbO3, LiAlO2, Li2ZrO3, Li2WO4, Li2TiO3, Li2B4O7, Li3PO4, Li2MoO4, Li3BO3, LiBO2, Li2CO3, Li2SiO3, SiO2, TiO2, ZrO2, Al2O3, B2O3, etc.

[0433] Furthermore, sulfur or phosphorus can be used to treat the surface of electrodes containing positive or negative active materials.

[0434] Furthermore, the particle surface of the positive or negative active material can be surface-treated by activating light or active gas (plasma, etc.) before or after the aforementioned surface coating.

[0435] <Conductive additives>

[0436] The inorganic solid electrolyte composition of the present invention contains a conductive additive, which is a preferred embodiment. It is preferable to use an active material and a conductive additive simultaneously. For example, it is preferable to use an active material containing silicon atoms as a negative electrode active material and a conductive additive simultaneously.

[0437] There are no particular restrictions on the conductive additives used; any commonly known conductive additives can be used. For example, these can be graphite materials such as natural graphite and artificial graphite, carbon black such as acetylene black, Ketjen black, and furnace black, amorphous carbon such as needle coke, carbon fiber materials such as vapor-grown carbon fibers or carbon nanotubes, carbonaceous materials such as graphene or fullerene, metal powders such as copper and nickel, metal fibers, or conductive polymers such as polyaniline, polypyrrole, polythiophene, polyacetylene, and polyphenylene derivatives.

[0438] In this invention, when both active materials and conductive additives are used simultaneously, the conductive additives described above are those that, during battery charging and discharging, do not involve the insertion and extraction of metal ions (preferably Li ions) belonging to Group 1 or Group 2 of the periodic table and do not function as active materials. Therefore, in the conductive additives, substances that function as active materials in the active material layer during battery charging and discharging are classified as active materials rather than conductive additives. Whether a substance functions as an active material during battery charging and discharging is not uniquely determined but rather by its combination with the active material.

[0439] The conductive additive is preferably in particulate form in the inorganic solid electrolyte composition. When the conductive additive is in particulate form, the particle size (volume average particle size) is not particularly limited, but is preferably, for example, 0.02 to 1.0 μm. The particle size of the conductive additive can be measured in the same manner as the particle size of the inorganic solid electrolyte.

[0440] The conductive additives contained in the inorganic solid electrolyte composition may be one or two.

[0441] In the case where the inorganic solid electrolyte composition of the present invention contains a conductive additive, the content of the conductive additive in the inorganic solid electrolyte composition is preferably 0 to 10% by mass in 100% by mass of the solid component.

[0442] <Lithium Salts>

[0443] The inorganic solid electrolyte composition of the present invention preferably contains a lithium salt (supporting electrolyte). As the lithium salt, a lithium salt commonly used in this type of product is preferred, and there are no particular limitations; for example, the lithium salt described in paragraphs 0082 to 0085 of Japanese Patent Application Publication No. 2015-088486 is preferred. When the inorganic solid electrolyte composition of the present invention contains a lithium salt, the content of the lithium salt relative to 100 parts by weight of the solid electrolyte is preferably 0.1 parts by weight or more, more preferably 5 parts by weight or more. As an upper limit, it is preferably 50 parts by weight or less, more preferably 20 parts by weight or less.

[0444] <Adhesives other than the adhesives of this invention>

[0445] In the inorganic solid electrolyte composition of the present invention, the binder of the present invention described above functions as a binder in the structural layer. Therefore, it may not contain any binders other than the binder of the present invention. However, to enhance the function of the binder of the present invention, it may also contain binders other than the binder of the present invention. As such a binder, binders commonly used in all-solid-state secondary batteries can be appropriately selected and used.

[0446] The inorganic solid electrolyte composition of the present invention may contain one or more adhesives other than the adhesive of the present invention.

[0447] In cases where the inorganic solid electrolyte composition of the present invention contains an adhesive other than the adhesive of the present invention, the content of the adhesive can be appropriately determined, for example, it can be set to 3% by mass or less in 100% by mass of the solid component of the inorganic solid electrolyte composition.

[0448] <Dispersant>

[0449] In the inorganic solid electrolyte composition of the present invention, the binder of the present invention also functions as a dispersant, therefore it may not contain any dispersant other than the binder of the present invention. However, to enhance the dispersing effect of the binder of the present invention, other dispersants (referred to as other dispersants) may be included. As a dispersant, dispersants commonly used in all-solid-state secondary batteries can be appropriately selected and used. Generally, compounds with particle adsorption and steric hindrance and / or electrostatic repulsion functions are preferably used.

[0450] The inorganic solid electrolyte composition of the present invention may contain one or more other dispersants.

[0451] In the case where the inorganic solid electrolyte composition of the present invention contains other dispersants, the content of the other dispersants can be appropriately determined, for example, it can be set to 3% by mass or less in 100% by mass of the solid component of the inorganic solid electrolyte composition.

[0452] <Other Additives>

[0453] Regarding the inorganic solid electrolyte composition of the present invention, in addition to the components described above, it is also possible to appropriately include ionic liquids, thickeners, crosslinking agents (such as crosslinking agents that undergo crosslinking reactions via free radical polymerization, condensation polymerization, or ring-opening polymerization), polymerization initiators (such as polymerization initiators that generate acids or free radicals through heat or light), defoamers, leveling agents, dehydrating agents, antioxidants, etc. The ionic liquid is a liquid included to further improve ionic conductivity, and known liquids can be used without particular limitation.

[0454] (Preparation of inorganic solid electrolyte compositions)

[0455] The inorganic solid electrolyte composition of the present invention can be prepared into a mixture, preferably a slurry, by mixing the inorganic solid electrolyte, the binder of the present invention, the dispersion medium, preferably a conductive additive, and also a suitable lithium salt and any other components, for example, using various commonly used mixers. In the case of the electrode composition, the active material is further mixed.

[0456] The mixing method is not particularly limited, and known mixers such as ball mills, bead mills, planetary mixers, scraper mixers, roller mills, kneaders, disc mills, rotary mixers, and narrow-gap dispersers can be used. The components can be mixed simultaneously or sequentially. The mixing environment is not particularly limited, but examples include dry air (dew point below -20°C) or an inert gas (e.g., argon, helium, nitrogen). Furthermore, the mixing conditions are not particularly limited and can be appropriately set; for example, the mixing temperature can be set to 15–40°C. The rotation speed of the rotary mixer or similar equipment can be set to 200–3,000 rpm.

[0457] The adhesive of the present invention can suppress exothermic reactions when mixed with solid particles such as inorganic solid electrolytes. Therefore, the inorganic solid electrolyte-containing composition of the present invention does not produce excessive exothermic reactions even without excessive cooling operations, and can be prepared while suppressing the increase in the internal temperature of the mixed system. The internal temperature of the mixed system is not unique due to variations in the temperature of the dispersion medium, the mixing amount, etc., but it can be suppressed to below 45°C, for example, when mixed at room temperature.

[0458] [Sheets for all-solid-state rechargeable batteries]

[0459] The sheet for all-solid-state secondary batteries of the present invention is a sheet-shaped molded body capable of forming structural layers of an all-solid-state secondary battery, and includes various forms depending on its application. For example, sheets preferably used for solid electrolyte layers (also called solid electrolyte sheets for all-solid-state secondary batteries) and sheets preferably used for electrodes, or laminates of electrodes and solid electrolyte layers (electrode sheets for all-solid-state secondary batteries) are examples. In the present invention, these various sheets are collectively referred to as sheets for all-solid-state secondary batteries.

[0460] In this invention, each layer constituting the sheet for all-solid-state secondary batteries can be a single-layer structure or a multi-layer structure.

[0461] In the sheet material for all-solid-state secondary batteries, the solid electrolyte layer or the active material layer on the substrate is formed by the inorganic solid electrolyte composition of the present invention. Therefore, the layer formed by the inorganic solid electrolyte composition of the present invention is formed from components derived from the inorganic solid electrolyte composition (excluding the dispersion medium), and is typically bonded together with each other in a state where solid particles (inorganic solid electrolyte and conductive additives, as well as active material) are mixed with the binder of the present invention.

[0462] By appropriately peeling the substrate or directly assembling the sheet for all-solid-state secondary batteries, the resistance of all-solid-state secondary batteries can be reduced (conductivity improved).

[0463] The solid electrolyte sheet for all-solid-state secondary batteries of the present invention can be any sheet having a solid electrolyte layer. It can be a sheet with the solid electrolyte layer formed on a substrate, or a sheet formed from the solid electrolyte layer without a substrate (a sheet with the substrate peeled off). The solid electrolyte sheet for all-solid-state secondary batteries may have other layers besides the solid electrolyte layer. Examples of other layers include, for example, a protective layer (release sheet), a current collector, and a coating. The solid electrolyte layer of the solid electrolyte sheet for all-solid-state secondary batteries is preferably formed from the inorganic solid electrolyte composition of the present invention. The content of each component in this solid electrolyte layer is not particularly limited, but it is preferably the same as the content of each component in the solid component of the inorganic solid electrolyte composition of the present invention. The layer thickness of each layer constituting the solid electrolyte sheet for all-solid-state secondary batteries is the same as the layer thickness described later in the section on all-solid-state secondary batteries.

[0464] As an example of the solid electrolyte sheet for all-solid-state secondary batteries of the present invention, a sheet having, in sequence, a layer composed of the inorganic solid electrolyte composition of the present invention, a conventional solid electrolyte layer, and a protective layer on a substrate can be described.

[0465] As a substrate, it is not particularly limited as long as it can support the solid electrolyte layer, and examples include sheet-like or plate-like materials such as those described in the current collector section later, organic materials, and inorganic materials. Examples of organic materials include various polymers, specifically polyethylene terephthalate, polypropylene, polyethylene, and cellulose. Examples of inorganic materials include, for example, glass and ceramics.

[0466] The electrode sheet for all-solid-state secondary batteries of the present invention (also simply referred to as "electrode sheet") can be any electrode sheet having an active material layer. It can be a sheet with the active material layer formed on a substrate (current collector), or a sheet formed from the active material layer without a substrate (a sheet with the substrate peeled off). The electrode sheet is typically a sheet having a current collector and an active material layer, but it also includes arrangements where the current collector, active material layer, and solid electrolyte layer are sequentially formed, as well as arrangements where the current collector, active material layer, solid electrolyte layer, and active material layer are sequentially formed. The solid electrolyte layer and active material layer of the electrode sheet are preferably formed from the inorganic solid electrolyte composition of the present invention. The content of each component in the solid electrolyte layer or active material layer is not particularly limited, but it is preferably the same as the content of each component in the solid component of the inorganic solid electrolyte 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 described later in the description of all-solid-state secondary batteries. The electrode sheet may have other layers as described above.

[0467] In addition, if the solid electrolyte layer or active material layer is not formed by the inorganic solid electrolyte composition of the present invention, it is formed by a conventional structural layer forming material.

[0468] In the all-solid-state secondary battery sheet of the present invention, at least one of the solid electrolyte layer and the active material layer is formed from the inorganic solid electrolyte composition of the present invention. Therefore, the all-solid-state secondary battery sheet of the present invention has a low-resistivity structural layer bonded with solid particles containing an inorganic solid electrolyte. By using this structural layer as the structural layer of the all-solid-state secondary battery, low resistance (high conductivity) of the all-solid-state secondary battery can be achieved.

[0469] [Manufacturing Method of Sheets for All-Solid-State Secondary Batteries]

[0470] The manufacturing method of the all-solid-state secondary battery sheet of the present invention is not particularly limited, and can be manufactured by forming the aforementioned layers using the inorganic solid electrolyte composition of the present invention. For example, a preferred method is to form a layer (coating-drying layer) composed of the inorganic solid electrolyte composition by performing a film-forming treatment (coating and drying) on ​​a substrate or current collector (or with other layers in between). This allows the production of an all-solid-state secondary battery sheet having a substrate or current collector and a coating-drying layer. In particular, if the all-solid-state secondary battery sheet is produced by performing a film-forming treatment on a current collector using the inorganic solid electrolyte composition of the present invention, the adhesion between the current collector and the active material layer can be enhanced. The coating-drying layer refers to a layer formed by coating the inorganic solid electrolyte composition of the present invention and drying the dispersion medium (i.e., a layer formed using the inorganic solid electrolyte composition of the present invention, and composed of a composition from which the dispersion medium has been removed from the inorganic solid electrolyte composition of the present invention). In the active material layer and the coating drying layer, a dispersion medium may remain within a range that does not impair the effect of the present invention. As a residual amount, for example, it can be set to 3% by mass or less in each layer.

[0471] In the manufacturing method of the all-solid-state secondary battery sheet of the present invention, the coating, drying and other processes will be described in the following manufacturing method of the all-solid-state secondary battery.

[0472] In the method for manufacturing the sheet material for all-solid-state secondary batteries of the present invention, the coated and dried layer obtained by the above method can also be pressurized. The pressurization conditions, etc., will be explained in the following description of the method for manufacturing all-solid-state secondary batteries.

[0473] Furthermore, in the manufacturing method of the all-solid-state secondary battery sheet of the present invention, it is also possible to peel off the substrate, protective layer (especially the release sheet), etc.

[0474] [All-solid-state rechargeable battery]

[0475] The all-solid-state secondary battery of the present invention comprises a positive electrode active material layer, a negative electrode active material layer opposite to 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 its structure as long as it has a solid electrolyte layer between the positive electrode active material layer and the negative electrode active material layer; for example, a known structure related to all-solid-state secondary batteries can be used. The positive electrode active material layer is preferably formed on a positive electrode current collector and constitutes the positive electrode. The negative electrode active material layer is preferably formed on a negative electrode current collector and constitutes the negative electrode. In the present invention, each structural layer constituting the all-solid-state secondary battery (including the current collector, etc.) can be a single-layer structure or a multi-layer structure.

[0476] Preferably, at least one of the negative electrode active material layer, positive electrode active material layer, and solid electrolyte layer is formed from the inorganic solid electrolyte composition of the present invention. Furthermore, it is also preferred that at least one of the negative electrode active material layer and positive electrode active material layer is formed from the inorganic solid electrolyte composition of the present invention. In the present invention, it is also preferred that all layers are formed from the inorganic solid electrolyte composition of the present invention. In the present invention, forming the structural layer of the all-solid-state secondary battery from the inorganic solid electrolyte composition of the present invention means forming the structural layer from a sheet of the all-solid-state secondary battery of the present invention (wherein, if there are layers other than those formed from the inorganic solid electrolyte composition of the present invention, the sheet is removed). The all-solid-state secondary battery of the present invention, with at least one layer of the structural layer formed from the inorganic solid electrolyte composition of the present invention, exhibits low resistance (high conductivity). Furthermore, the all-solid-state secondary battery of the present invention, due to its low resistance and high ionic conductivity, is also capable of outputting a large current.

[0477] Furthermore, if the active material layer or the solid electrolyte layer is not formed from the inorganic solid electrolyte composition of the present invention, known materials can be used.

[0478] In this invention, each structural layer (including current collectors, etc.) constituting the all-solid-state secondary battery can be a single-layer structure or a multi-layer structure.

[0479] <Positive electrode active material layer, solid electrolyte layer and negative electrode active material layer>

[0480] The active material layer or solid electrolyte layer formed by the inorganic solid electrolyte composition of the present invention is preferably the same as the content of the solid components in the inorganic solid electrolyte composition of the present invention in terms of the types and contents of the contained components.

[0481] The thicknesses of the negative electrode active material layer, the solid electrolyte layer, and the positive electrode active material layer are not particularly limited. Considering the typical dimensions of an all-solid-state secondary battery, the thickness of each layer is preferably 10 to 1,000 μm, more preferably 20 μm or more and less than 500 μm. In the all-solid-state secondary battery of the present invention, the thickness of at least one of the positive electrode active material layer and the negative electrode active material layer is further preferably 50 μm or more and less than 500 μm.

[0482] <Current Collector>

[0483] Both the positive and negative electrode active material layers may have current collectors on the side opposite to the solid electrolyte layer. The positive and negative electrode current collectors are preferably electronic conductors.

[0484] In this invention, either the positive current collector or the negative current collector, or both together, are sometimes referred to simply as a current collector.

[0485] In addition to aluminum, aluminum alloys, stainless steel, nickel, and titanium, the preferred material for forming the positive current collector is aluminum or stainless steel with a surface treated with carbon, nickel, titanium, or silver (material with a thin film), and aluminum and aluminum alloys are more preferred.

[0486] In addition to aluminum, copper, copper alloys, stainless steel, nickel, and titanium, the preferred materials for forming the negative current collector are those that have undergone carbon, nickel, titanium, or silver treatment on the surface of aluminum, copper, copper alloys, or stainless steel, and more preferably aluminum, copper, copper alloys, and stainless steel.

[0487] Current collectors are typically made of thin film sheets, but can also be made of mesh, perforated material, lath, porous material, foam, or molded material composed of fibers.

[0488] The thickness of the current collector is not particularly limited, but it is preferably 1 to 500 μm. Furthermore, it is also preferable to provide irregularities on the surface of the current collector through surface treatment.

[0489] <Other Structures>

[0490] In this invention, functional layers or components may be appropriately inserted or disposed between or on the outside of the layers of the negative electrode current collector, the negative electrode active material layer, the solid electrolyte layer, the positive electrode active material layer, and the positive electrode current collector.

[0491] <Frame>

[0492] The all-solid-state secondary battery of the present invention can be used directly as an all-solid-state secondary battery with the above structure, depending on the application. However, in order to make it into a dry cell form, it is preferable to encapsulate it in a more suitable frame. The frame can be a metal frame or a resin (plastic) frame. When using a metal frame, for example, aluminum alloy or stainless steel frames can be used. The metal frame is preferably divided into a positive electrode side frame and a negative electrode side frame, and is electrically connected to the positive electrode current collector and the negative electrode current collector, respectively. The positive electrode side frame and the negative electrode side frame are preferably joined together and integrated by a short-circuit prevention gasket.

[0493] The following is for reference. Figure 1 The preferred embodiments of the present invention will be described, but the present invention is not limited thereto.

[0494] Figure 1This diagram schematically illustrates a cross-sectional view of an all-solid-state secondary battery (lithium-ion secondary battery) according to a preferred embodiment of the present invention. When viewed from the negative electrode side, the all-solid-state secondary battery 10 of this embodiment sequentially comprises 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. Each layer is in contact with the others and is arranged adjacent to each other. By employing this structure, electrons (electrons) are supplied to the negative electrode side during charging. - ), and accumulate lithium ions (Li) here. + On the other hand, during discharge, lithium ions (Li) accumulated at the negative electrode... + The electrons return to the positive side and supply electrons to the working part 6. In the illustrated example, a light bulb is used as a model for the working part 6, and it is designed to be lit by discharging.

[0495] In having Figure 1 When the all-solid-state secondary battery with the layered structure shown is placed in the 2032-type button cell 11 (for example, see reference 11), Figure 2 Sometimes, this all-solid-state secondary battery is also called the all-solid-state secondary battery stack 12, and the battery (button type) made by placing the all-solid-state secondary battery stack 12 into the 2032 type button battery box 11 is called the all-solid-state secondary battery 13, in order to distinguish them.

[0496] (Positive electrode active material layer, solid electrolyte layer, and negative electrode active material layer)

[0497] In the all-solid-state secondary battery 10, the positive electrode active material layer 4, the solid electrolyte layer 3, and the negative electrode active material layer 2 are all formed from the inorganic solid electrolyte composition of the present invention. The inorganic solid electrolyte contained in the positive electrode active material layer 4, the solid electrolyte layer 3, and the negative electrode active material layer 2, as well as the binder of the present invention, can be of the same type or different types. Furthermore, the conductive additives contained in the positive electrode active material layer 4 and the negative electrode active material layer 2 can be of the same type or different types.

[0498] In this invention, either the positive electrode active material layer or the negative electrode active material layer, or both together, are simply referred to as the active material layer or the electrode active material layer. Furthermore, either the positive electrode active material or the negative electrode active material, or both together, are simply referred to as the active material or the electrode active material.

[0499] The solid electrolyte layer contains an inorganic solid electrolyte with conductivity of ions belonging to Group 1 or Group 2 of the periodic table, the binder of the present invention, and any of the above-mentioned components within the scope of not impairing the effects of the present invention, and generally does not contain positive electrode active material and / or negative electrode active material.

[0500] The positive electrode active material layer contains an inorganic solid electrolyte having conductive ions of metals belonging to Group 1 or Group 2 of the periodic table, a positive electrode active material, the binder of the present invention, and any of the above-mentioned components within the scope of not impairing the effects of the present invention.

[0501] The negative electrode active material layer contains an inorganic solid electrolyte having conductive ions of metals belonging to Group 1 or Group 2 of the periodic table, a negative electrode active material, the binder of the present invention, and any of the above-mentioned components within the scope of not impairing the effects of the present invention.

[0502] In the all-solid-state secondary battery 10, the negative electrode active material layer can be a lithium metal layer. Examples of lithium metal layers include layers formed by stacking or molding lithium metal powder, lithium foil, and lithium vapor-deposited films. The thickness of the lithium metal layer is independent of the thickness of the negative electrode active material layer, and for example, can be set to 1 to 500 μm.

[0503] In this invention, if the structural layer is formed by the inorganic solid electrolyte composition of this invention, a low-resistance all-solid-state secondary battery can be realized.

[0504] (Current collector)

[0505] The positive current collector 5 and the negative current collector 1 are as described above.

[0506] In the all-solid-state secondary battery 10, in the case of having structural layers other than the structural layer formed by the inorganic solid electrolyte composition of the present invention, a layer formed by a known structural layer forming material can also be applied.

[0507] Furthermore, each layer can be composed of a single layer or multiple layers.

[0508] [Manufacturing of all-solid-state rechargeable batteries]

[0509] All-solid-state secondary batteries can be manufactured using conventional methods. Specifically, all-solid-state secondary batteries can be manufactured by forming the aforementioned layers using the inorganic solid electrolyte composition of the present invention. Specifically, the all-solid-state secondary battery of the present invention can be manufactured by a method comprising (via) the following step (method for manufacturing sheet for all-solid-state secondary battery of the present invention): appropriately coating the inorganic solid electrolyte composition of the present invention onto a substrate (e.g., a metal foil as a current collector) to form a coating film (film formation treatment).

[0510] More specifically, a positive electrode active material layer is formed by coating and drying an inorganic solid electrolyte composition containing positive electrode active material onto a metal foil serving as the positive electrode current collector, thereby creating a positive electrode sheet for an all-solid-state secondary battery. Next, an inorganic solid electrolyte composition for forming the solid electrolyte layer is coated and dried onto this positive electrode active material layer, thereby forming a solid electrolyte layer. Furthermore, an inorganic solid electrolyte composition containing negative electrode active material is coated and dried onto the solid electrolyte layer as the negative electrode material, thereby forming a negative electrode active material layer. By stacking a negative electrode current collector (metal foil) onto the negative electrode active material layer, an all-solid-state secondary battery with a structure in which a solid electrolyte layer is sandwiched between the positive and negative electrode active material layers can be obtained. It can also be encapsulated in a frame to manufacture the desired all-solid-state secondary battery.

[0511] Furthermore, in a manner opposite to the formation of each layer, a negative electrode active material layer, a solid electrolyte layer, and a positive electrode active material layer can be formed on the negative electrode current collector, and a positive electrode current collector can be stacked to manufacture an all-solid-state secondary battery.

[0512] As another method, the following approach can be used: A positive electrode sheet for an all-solid-state secondary battery is manufactured using the method described above. Then, an inorganic solid electrolyte composition containing negative electrode active material is coated and dried onto a metal foil serving as the negative electrode current collector to form a negative electrode active material layer, thereby manufacturing an all-solid-state secondary battery negative electrode sheet. Next, a solid electrolyte layer is formed on the active material layer of any of these sheets using the method described above. Furthermore, another of the all-solid-state secondary battery positive electrode sheet and the all-solid-state secondary battery negative electrode sheet is stacked on the solid electrolyte layer in such a way that the solid electrolyte layer and the active material layer are in contact. All-solid-state secondary batteries can be manufactured using the above method.

[0513] Furthermore, as another method, the following approach can be used: A positive electrode sheet and a negative electrode sheet for an all-solid-state secondary battery are manufactured using the methods described above. Furthermore, a dried inorganic solid electrolyte composition is coated onto a substrate to create a solid electrolyte sheet for an all-solid-state secondary battery, consisting of a solid electrolyte layer. Then, the solid electrolyte layer, peeled from the substrate, is laminated between the positive and negative electrode sheets for the all-solid-state secondary battery. Using the above methods, an all-solid-state secondary battery can be manufactured.

[0514] Furthermore, using the above method, 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 manufactured. Next, the positive electrode sheet or a negative electrode sheet for an all-solid-state secondary battery and the solid electrolyte sheet for an all-solid-state secondary battery are laminated together with the positive or negative active material layer in contact with the solid electrolyte layer, and then pressurized. This transfers the solid electrolyte layer onto the positive or negative electrode sheet for an all-solid-state secondary battery. Then, the solid electrolyte layer obtained by peeling off the substrate of the solid electrolyte sheet for an all-solid-state secondary battery, and the negative or positive electrode sheet for an all-solid-state secondary battery (with the negative or positive active material layer in contact with the solid electrolyte layer) are laminated together and pressurized. This enables the manufacture of an all-solid-state secondary battery. The pressing method and conditions in this method are not particularly limited, and the methods and conditions described in the pressing process described later can be applied.

[0515] Regarding solid electrolyte layers, for example, on a substrate or active material layer, an inorganic solid electrolyte composition or the like is formed by pressure molding under pressure conditions described later.

[0516] In the above manufacturing method, the inorganic solid electrolyte composition of the present invention can be used for any one of the positive electrode composition, the inorganic solid electrolyte composition, and the negative electrode composition. Preferably, the inorganic solid electrolyte composition of the present invention is used for at least one of the inorganic solid electrolyte composition, the positive electrode composition, and the negative electrode composition. The inorganic solid electrolyte composition of the present invention can also be used for any composition.

[0517] When a solid electrolyte layer or active material layer is formed from a composition other than the inorganic solid electrolyte composition of the present invention, commonly used compositions can be cited as materials. Furthermore, in the manufacture of an all-solid-state secondary battery, instead of forming a negative electrode active material layer, ions and electrons of a metal belonging to Group 1 or Group 2 of the periodic table accumulated in the negative electrode current collector during initialization or charging (described later) are bonded together and deposited as metal on the negative electrode current collector, thereby also forming a negative electrode active material layer.

[0518] <Formation of each layer (film formation)>

[0519] The coating method for the inorganic solid electrolyte composition is not particularly limited and can be appropriately selected. Examples include coating (preferably wet coating), spraying, spin coating, dip coating, slot coating, strip coating, and bar coating. The coating temperature is not particularly limited; for example, a temperature range typically around room temperature (e.g., 15–30°C) in an unheated state can be cited.

[0520] The coated inorganic solid electrolyte composition is subjected to a drying treatment (heat treatment). The drying treatment can be performed after coating each composition or after multiple layers of the composition are coated. 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 removes the dispersion medium, making it solid (coating the dried layer). This is preferable because it avoids excessively high temperatures and damage to the components of the all-solid-state secondary battery. As a result, excellent overall performance is exhibited in the all-solid-state secondary battery, and good adhesion and good ionic conductivity are achieved.

[0521] After coating and drying the inorganic solid electrolyte composition, after laminating the structural layers, or after fabricating an all-solid-state secondary battery, it is preferable to pressurize each layer or the all-solid-state secondary battery. Furthermore, it is also preferable to pressurize while the layers are stacked. Examples of pressurization methods include hydraulic cylinder presses. The pressurization pressure is not particularly limited, but generally, a range of 5 to 1500 MPa is preferred.

[0522] Furthermore, the coated inorganic solid electrolyte composition can be heated while under pressure. The heating temperature is not particularly limited, but is generally in the range of 30 to 300°C. Pressing can also be performed at a temperature higher than the glass transition temperature of the inorganic solid electrolyte. Additionally, pressing can also be performed at a temperature higher than the glass transition temperature of the polymer (I) contained in the adhesive of this invention. Generally, this temperature does not exceed the melting point of the polymer (I).

[0523] Pressurization can be performed either with the solvent or dispersion medium pre-dried or with residual solvent or dispersion medium remaining.

[0524] Alternatively, the various compositions can be coated simultaneously, or coating, drying, and pressing can be performed simultaneously and / or sequentially. After coating onto the substrates, lamination can be achieved through transfer printing.

[0525] The atmosphere used in film-forming methods (coating, drying, pressurization (under heating)) is not particularly limited and can be any atmosphere, such as atmospheric pressure, dry air (dew point below -20°C), or inert gases (e.g., argon, helium, nitrogen).

[0526] The pressing time can be adjusted from applying high pressure for a short period (e.g., within a few hours) to applying medium pressure for a long period (more than one day). Except for sheets used in all-solid-state secondary batteries, for example, in the case of all-solid-state secondary batteries, a constraint device (such as screw tightening pressure) for all-solid-state secondary batteries can be used to continuously apply medium pressure. The pressing pressure on the pressed area, such as the sheet surface, can be uniform or varied. The pressing pressure can be varied according to the area or film thickness of the pressed area. Furthermore, different pressures can be applied to the same area in stages to vary the pressure. The pressed surface can be smooth or rough.

[0527] <Initialization>

[0528] The all-solid-state secondary battery manufactured in the above manner is preferably initialized after manufacturing or before use. Initialization is not particularly limited; for example, it can be performed by conducting an initial charge and discharge under increased pressure, and then releasing the pressure until the pressure for normal use of the all-solid-state secondary battery is reached.

[0529] Applications of all-solid-state rechargeable batteries

[0530] The all-solid-state secondary battery of this invention can be applied to a wide variety of uses. There are no particular limitations on its application; for example, when integrated into electronic devices, it can be used in laptops, pen-and-paper computers, mobile computers, e-book readers, mobile phones, cordless phones, pagers, handheld terminals, portable fax machines, portable copiers, portable printers, stereo headphones, camcorders, LCD TVs, handheld vacuum cleaners, portable CD players, mini disk drives, electric shavers, transceivers, electronic notebooks, calculators, memory cards, portable recorders, radios, backup power supplies, etc. As other civilian products, it can be used in automobiles (electric cars, etc.), electric vehicles, motors, lighting fixtures, toys, game consoles, load conditioners, clocks, flashlights, cameras, medical devices (pacemakers, hearing aids, shoulder massagers, etc.). Furthermore, it can be used in various military and aerospace applications. It can also be combined with solar cells.

[0531] Example

[0532] The present invention will now be described in further detail based on embodiments, but the invention should not be construed as being limited thereto. In the following embodiments, unless otherwise specified, "parts" and "%" of the composition refer to mass. In the present invention, "room temperature" refers to 25°C.

[0533] [Example 1] Synthesis of polymer and preparation of adhesive solution or dispersion

[0534] Adhesive solutions or dispersions were prepared by synthesizing the following chemical formulas and the polymers shown in Tables 1-1 and 1-2 (collectively referred to as Table 1) in the following manner.

[0535] [Synthetic Example S-1: Synthesis of Polymer S-1 and Preparation of Adhesive Solution S-1]

[0536] First, dipentaerythritol hexa(3-mercaptopropionate) (3.4 g), butyl butyrate (15.0 g), and nonafluorohexyl acrylate (5.6 g) were placed in a three-necked flask and heated to 80°C under a nitrogen atmosphere. Then, azo polymerization initiator V-601 (0.03 g, manufactured by Wako Pure Chemical, Ltd.) was added to the flask, and the mixture was stirred for 4 hours.

[0537] Next, acrylamide (1.0 g) was added to the three-necked flask and dissolved. Then, azo polymerization initiator V-601 (0.02 g) was added, and the mixture was stirred at 80°C for 2 hours.

[0538] Thus, polymer S-1 was synthesized, thereby obtaining an adhesive solution S-1 (concentration 67% by mass) composed of this polymer.

[0539] [Synthetic Examples S-2 to S-20: Synthesis of polymers S-2 to S-20 and preparation of adhesive solutions S-2 to S-20]

[0540] In Synthesis Example S-1, compounds of each constituent component were introduced in such a way that polymers S-2 to S-20 were the composition (types and amounts of constituent components) shown in Table 1, and the amount of polymerization initiator was adjusted in such a way that it was the weight-average molecular weight shown in Table 1. Otherwise, polymers S-2 to S-20 were synthesized in the same manner as in Synthesis Example S-1, thereby obtaining adhesive solutions S-2 to S-20 composed of each polymer.

[0541] [Synthetic Example S-21: Synthesis of Polymer S-21 and Preparation of Polymer Dispersion S-21]

[0542] In Synthesis Example S-1, compounds of each constituent component were introduced in a manner that made polymer S-21 have the composition (types and amounts of constituent components) shown in Table 1, and the amount of polymerization initiator was adjusted to have the weight-average molecular weight shown in Table 1. Otherwise, polymer S-21 was synthesized in the same manner as in Synthesis Example S-1, thereby obtaining an adhesive dispersion S-21 composed of this polymer. In this adhesive dispersion S-21, the particle size of polymer S-21 was measured using the aforementioned measurement method for inorganic solid electrolytes, and the result was 200 nm.

[0543] [Synthetic Example S-22: Synthesis of Polymer S-22 and Preparation of Polymer Solution S-22]

[0544] In Synthesis Example S-1, dipentaerythritol hexa(3-mercaptopropionate) and nonafluorohexyl acrylate were reacted in the proportions shown in Table 1 and the amount of polymerization initiator was adjusted to the weight-average molecular weight shown in Table 1. No reaction with acrylamide was carried out. Otherwise, polymer S-22 was synthesized in the same manner as in Synthesis Example S-1, thereby obtaining an adhesive solution S-22 composed of the polymer.

[0545] [Synthetic Example S-23: Synthesis of Polymer S-23 and Preparation of Polymer Solution S-23]

[0546] In Synthesis Example S-20, dipentaerythritol hexa(3-mercaptopropionate) and a compound having a polysiloxane structure (KF-2012: product number) were reacted in the proportions shown in Table 1 and the amount of polymerization initiator was adjusted to the weight-average molecular weight shown in Table 1. No reaction with acrylamide was carried out. Otherwise, polymer S-23 was synthesized in the same manner as in Synthesis Example S-20, thereby obtaining an adhesive solution S-23 composed of the polymer.

[0547] [Comparative Synthesis Example T-1: Synthesis of Polymer T-1 and Preparation of Adhesive Solution T-1]

[0548] In Synthesis Example S-1, compounds of each constituent component were introduced in a manner that made polymer T-1 the composition (type and content of constituent components) shown in Table 1. Otherwise, polymer T-1 was synthesized in the same manner as in Synthesis Example S-1, thereby obtaining a solution T-1 of adhesive composed of the polymer.

[0549] [Comparative Synthesis Example T-2: Synthesis of Polymer T-2 and Preparation of Adhesive Solution T-2]

[0550] Acrylamide (2.5 g), nonafluorohexyl acrylate (47.5 g), and butyl butyrate (50.0 g) were placed in a three-necked flask and heated to 80°C under a nitrogen atmosphere. Then, azo polymerization initiator V-601 (0.1 g, manufactured by Wako Pure Chemical, Ltd.) was added to the flask, and the mixture was stirred for 4 hours.

[0551] Thus, polymer T-2 was synthesized, thereby obtaining an adhesive solution T-2 (concentration 50% by mass) composed of this polymer.

[0552] [Comparative Synthesis Example T-3: Synthesis of Polymer T-3 and Preparation of Adhesive Dispersion T-3]

[0553] In Synthesis Example S-1, compounds of each constituent component were introduced in a manner that made polymer T-3 have the composition (types and amounts of constituent components) shown in Table 1. Otherwise, polymer T-3 was synthesized in the same manner as in Synthesis Example S-1, thereby obtaining a solution T-3 of the adhesive composed of this polymer. In this adhesive dispersion T-3, the particle size of polymer T-3 was measured by the above-described measurement method for inorganic solid electrolytes, and the result was 100 nm.

[0554] [Comparative Synthesis Examples T-4 to T-5: Synthesis of Polymers T-4 to T-5 and Preparation of Adhesive Solutions T-4 to T-5]

[0555] In Synthesis Example S-1, compounds of each constituent component were introduced in a manner that made polymers T-4 and T-5 the composition (type and content of constituent components) shown in Table 1. Otherwise, polymers T-4 and T-5 were synthesized in the same manner as in Synthesis Example S-1, thereby obtaining solutions T-4 and T-5 of adhesives composed of each polymer.

[0556] The chemical formulas of the synthesized polymers are shown below.

[0557] A in each polymer 1 (A) 11 ) and A 2 All are polymer chains. The polymers S-6 to S-12, S-21, T-4, and T-5 are equivalent to A. 1 The polymer chain is a polymer chain obtained by random bonding of two constituent components. In polymers S-16 to S-21 and S-23, X 1 It is a linking group, X 2 It is a substituent.

[0558] Additionally, in the following chemical formula, determine polymer chain A. 1 and A 2 The bonding positions are used to show the overall structure of each polymer, but only polymer chain A... 1 and A 2 If the quantities (n and m) are the same, then polymer chain A 1 and A 2 The bonding positions are not limited to those determined by the following chemical formula. For example, in polymer S-1, polymer chain A... 1 The diagram shows two chemical structures, both with oxygen atoms bonded to the left-hand structural portion relative to the central oxygen atom. However, a polymer chain A... 1 The oxygen atom in the center can bond to the structure on the right.

[0559] [Chemical Formula 21]

[0560]

[0561] [Chemical Formula 22]

[0562]

[0563] [Chemical Formula 23]

[0564]

[0565] [Chemical Formula 24]

[0566]

[0567] [Chemical Formula 25]

[0568]

[0569] [Chemical Formula 26]

[0570]

[0571] The acid value, base value, and weight-average molecular weight of each synthesized polymer are shown in Table 1. The acid value, base value, and weight-average molecular weight were measured using the methods described above. Furthermore, in the "State" column of Table 1, regarding the state of the binder in each composition described later, the solubility of the dispersion medium was measured using the methods described above, and the results were judged as either "dissolved" or "particulate" (undissolved and dispersed in particulate form) and shown. Additionally, in Table 1, "A"... 2 / A 1 "A is shown in the column" 2 The total content relative to A 1 The ratio of total content [A] 2 Total content / A 1 (Total content).

[0572] Furthermore, the "content" values ​​listed in Table 1 are calculated based on the addition ratio of each compound during preparation. In polymers S-22 and S-23, A 1 The total content is "2 / weight-average molecular weight", but because their values ​​are small, the content of "A" is not specified. 1 "Total content" and "A" 2 / A 1 The value of “” is not recorded in Table 1.

[0573] In Table 1, the units for acid value, base value, and content are “mgKOH / g”, “mgKOH / g”, and “mass%”, respectively, but are omitted.

[0574] [Table 1-1]

[0575]

[0576] [Table 1-2]

[0577]

[0578] <Abbreviation for table>

[0579] In the table, a "-" in the component column indicates that the corresponding component is not present.

[0580] The "R" in the table 1 " indicates the term used to introduce "-SR" in equation (I) above. 1 The following compounds are labeled "-S-".

[0581] DPMP: Dipentaerythritol Hexa(3-mercaptopropionate), manufactured by FUJIFILM Wako Pure Chemical Corporation

[0582] PEMP: Pentaerythritol tetra(3-mercaptopropionate), manufactured by FUJIFILM Wako Pure Chemical Corporation

[0583] TMMP: Trimethylolpropane tris(3-mercaptopropionate), manufactured by FUJIFILM Wako Pure Chemical Corporation

[0584] "A" in the table 1 (A) 11 ")" indicates the term used to introduce "A" in the above formula (I). 1 "(A-3)" refers to the following compounds used to introduce constituents having amide, sulfonamide or imide groups, and "other components" refers to compounds used to introduce constituents not having amide, sulfonamide or imide groups.

[0585] "A" in the table 12 " is equivalent to "A" in the above formula (I). 1 (A-1) above, and corresponding to "A" in formula (IA). 12 ".

[0586] "A" in the table 2 “” indicates that “A” is used to introduce the above formula (I). 2 Compounds of the type "".

[0587] Nonafluorohexyl acrylate: 3,3,4,4,5,5,6,6,6-nonafluorohexyl acrylate, manufactured by Tokyo Chemical Industry Co., Ltd.

[0588] Heptafluorobutyl acrylate: 2,2,3,3,4,4,4-hexafluorobutyl acrylate, manufactured by Tokyo Chemical Industry Co., Ltd.

[0589] X-22-174ASX (Product No., manufactured by Shin-Etsu Chemical Co., Ltd.): A compound with a polysiloxane structure (molecular weight 900).

[0590] X-22-174BX: (Product number, manufactured by Shin-Etsu Chemical Co., Ltd.): A compound with a polysiloxane structure (molecular weight 2300).

[0591] KF-2012: (Product number, manufactured by Shin-Etsu Chemical Co., Ltd.): A compound with a polysiloxane structure (molecular weight 4600).

[0592] [[Example 2]]

[0593] 1. Synthesis of sulfide-based inorganic solid electrolytes

[0594] [Synthesis Example A]

[0595] The sulfide-based inorganic solid electrolyte was synthesized with reference to non-patent literature, T. Ohtomo, A. Hayashi, M. Tatsumisago, Y. Tsuchida, S. Hama, K. Kawamoto, Journal of Power Sources, 233, (2013), pp231-235, and A. Hayashi, S. Hama, H. Morimoto, M. Tatsumisago, T. Minami, Chem. Lett., (2001), pp872-873.

[0596] Specifically, in a glove box under an argon atmosphere (dew point -70°C), 2.42 g of lithium sulfide (Li2S, manufactured by Aldrich, Inc., purity >99.98%) and 3.90 g of phosphorus pentasulfide (P2S5, manufactured by Aldrich, Inc., purity >99%) were weighed out and placed into an agate mortar, and mixed with an agate pestle for 5 minutes. The mixing ratio of Li2S and P2S5, expressed as a molar ratio, was Li2S:P2S5 = 75:25.

[0597] Next, 66g of zirconia beads with a diameter of 5mm were added to a 45mL container (manufactured by Fritsch Co., Ltd.), along with the total amount of the aforementioned mixture of lithium sulfide and phosphorus pentasulfide. The container was then completely sealed under an argon atmosphere. The container was mounted on a planetary ball mill P-7 (product name, manufactured by Fritsch Co., Ltd.) and mechanically ground at 25°C and 510 rpm for 20 hours to obtain 6.20g of a yellow powder of sulfide-based inorganic solid electrolyte (Li-PS glass, hereinafter sometimes labeled LPS). The particle size of the Li-PS glass was 15μm.

[0598] 2. The compositions shown in Tables 2-1 to 2-4 (collectively referred to as Table 2) were prepared in the following manner.

[0599] <Preparation of Inorganic Solid Electrolyte Compositions>

[0600] 60 g of zirconia beads with a diameter of 5 mm were added to a 45 mL container (manufactured by Fritsch Co., Ltd.), along with 12.33 g of LPS synthesized in Synthesis Example A above, 0.2 g of the binder solution or dispersion shown in Table 2-1 or Table 2-4 (mass of solid components), and 12.5 g of butyl butyrate as the dispersion medium (total). The container was then mounted on a planetary ball mill P-7 (product name). Mixing was performed for 10 minutes at an initial temperature of 25°C and a rotation speed of 150 rpm (no temperature adjustment was performed during mixing) to prepare inorganic solid electrolyte compositions (slurries) K-1 to K-23 and Kc11 to Kc15, respectively.

[0601] <Preparation of the positive electrode composition>

[0602] 60 g of zirconia beads with a diameter of 5 mm were added to a 45 mL zirconium oxide container (manufactured by Fritsch Co., Ltd.), along with 4.8 g of LPS synthesized in Synthesis Example A and 7.5 g of butyl butyrate as a dispersion medium (total). The container was mounted on a planetary ball mill P-7 (product name), and the mixture was stirred at 200 rpm for 30 minutes at an initial temperature of 25°C (no temperature adjustment was performed during the mixing process). Then, 12.3g of NMC (manufactured by Sigma-Aldrich Co. LLC) as the positive electrode active material, 0.33g of acetylene black (AB) as the conductive additive, and 0.15g of the binder solution or dispersion shown in Table 2-2 or Table 2-4 (mass of solid components) were added to the container. The container was then mounted on a planetary ball mill P-7 (product name), and the mixture was continued to be mixed at an initial temperature of 25°C and a rotation speed of 200 rpm for 30 minutes (no temperature adjustment was performed during the mixing process), thereby preparing positive electrode compositions (slurries) PK-1 to PK-23 and PKc21 to PKc25, respectively.

[0603] <Preparation of the negative electrode composition>

[0604] To a 45 mL zirconium oxide container (manufactured by Fritsch Co., Ltd.), add 60 g of 5 mm diameter zirconium oxide beads, 4.58 g of LPS synthesized in Synthesis Example A, 0.1 g (solid mass) of the binder solution or dispersion shown in Table 2-3 or Table 2-4, and 12 g (total) of butyl butyrate. Mount the container on a planetary ball mill P-7 (product name) and mix for 60 minutes at an initial temperature of 25°C and a speed of 300 rpm (no temperature adjustment was performed during mixing). Then, 7.8g of silicon (Si) as the negative electrode active material and 0.53g of VGCF (manufactured by SHOWA DENKO KK) as the conductive additive were added. Similarly, the container was installed on a planetary ball mill P-7 (product name), and mixed for 10 minutes at an initial temperature of 25°C and a speed of 100 rpm (no temperature adjustment was performed during the mixing process), thereby preparing negative electrode compositions (slurries) NK-1 to NK-23 and NKc31 to NKc35 respectively.

[0605] In Table 2, the composition content is the content relative to the total mass of the composition (mass%), and the solid component content is the content relative to 100% mass of the solid component of the composition (mass%). Units are omitted in the table.

[0606] <Evaluation 1: Temperature measurement during composition preparation>

[0607] The internal temperature of the mixtures prepared according to the above method was measured, and the heat release during the mixing of the inorganic solid electrolyte and the binder was evaluated based on whether the highest internal temperature was included in any of the following evaluation criteria. In this test, an internal temperature of the mixture above the evaluation criterion "D" was considered acceptable. The results are shown in the "Heat Release Test During Dispersion" column of Table 2.

[0608] -Evaluation Criteria-

[0609] A: The highest internal temperature is <30℃

[0610] B: 30℃≤maximum internal temperature<35℃

[0611] C: 35℃ ≤ Maximum internal temperature < 40℃

[0612] D: 40℃≤maximum internal temperature<45℃

[0613] E: 45℃≤maximum internal temperature<50℃

[0614] F: Maximum internal temperature ≤ 50℃

[0615] [Table 2-1]

[0616]

[0617] [Table 2-2]

[0618]

[0619] [Table 2-3]

[0620]

[0621] [Table 2-4]

[0622]

[0623] <Abbreviation for table>

[0624] LPS: LPS synthesized in Synthesis Example A

[0625] NMC: LiNi 1 / 3 Co 1 / 3 Mn 1 / 3 O2

[0626] Si: Silicon (APS1~5μm, manufactured by Alfa Aesar)

[0627] AB: Acetylene Black

[0628] VGCF: Carbon nanofibers

[0629] 3. Fabrication of solid electrolyte sheets for all-solid-state secondary batteries

[0630] <Fabrication of Solid Electrolyte Sheets for All-Solid-State Secondary Batteries>

[0631] Using a Becker coating machine (product name: SA-201, manufactured by TESTER SANGYO CO,. LTD.), the inorganic solid electrolyte compositions shown in the "Solid Electrolyte Composition No." column of Table 3-1 or Table 3-4 obtained above were coated onto aluminum foil with a thickness of 20 μm. The mixtures were then heated at 80°C for 2 hours to dry the inorganic solid electrolyte compositions (removing the dispersion medium). Then, using a hot press, the dried inorganic solid electrolyte compositions were heated and pressurized for 10 seconds at a temperature of 120°C and a pressure of 40 MPa to produce solid electrolyte sheets (marked as solid electrolyte sheets in Tables 3-1 and 3-4) 101–123 and c11–c15 for all-solid-state secondary batteries. The film thickness of the solid electrolyte layer was 40 μm.

[0632] <Fabrication of Positive Electrode Sheets for All-Solid-State Secondary Batteries>

[0633] Using a Becker coating machine (product name: SA-201), the positive electrode compositions shown in the "Electrode Composition No." column of Table 3-2 or Table 3-4 obtained above were coated onto aluminum foil with a thickness of 20 μm. The coatings were then heated at 80°C for 1 hour, and further heated at 110°C for 1 hour to dry the positive electrode compositions (removing the dispersion medium). Then, using a hot press, the dried positive electrode compositions were pressurized at 25°C (10 MPa, 1 minute) to produce positive electrode sheets (labeled as positive electrode sheets in Tables 3-2 and 3-4) 201–223 and c21–c25 for all-solid-state secondary batteries, each with a positive electrode active material layer with a film thickness of 70 μm.

[0634] <Fabrication of negative electrode sheets for all-solid-state secondary batteries>

[0635] Using a Becker coating machine (product name: SA-201), the negative electrode compositions shown in the "Electrode Composition No." column of Table 3-3 or Table 3-4 obtained above were coated onto copper foil with a thickness of 20 μm. The coatings were then heated at 80°C for 1 hour, and further heated at 110°C for 1 hour to dry the negative electrode compositions (removing the dispersion medium). Then, using a hot press, the dried negative electrode compositions were pressurized at 25°C (10 MPa, 1 minute) to produce negative electrode sheets (labeled as negative electrode sheets in Tables 3-3 and 3-4) 301–323 and c31–c35 for all-solid-state secondary batteries, each with a negative electrode active material layer with a film thickness of 60 μm.

[0636] [Table 3-1]

[0637]

[0638] [Table 3-2]

[0639]

[0640] [Table 3-3]

[0641]

[0642] [Table 3-4]

[0643]

[0644] 4. Manufacturing of all-solid-state secondary batteries

[0645] First, positive electrode sheets for all-solid-state secondary batteries with solid electrolyte layers and negative electrode sheets for all-solid-state secondary batteries with solid electrolyte layers were manufactured.

[0646] - Fabrication of positive electrode sheets for all-solid-state secondary batteries with solid electrolyte layers-

[0647] On the positive electrode active material layer of each all-solid-state secondary battery positive electrode sheet shown in the "Electrode Active Material Layer (Sheet No.)" column of Tables 4-1 and 4-3, the solid electrolyte sheet shown in the "Solid Electrolyte Layer (Sheet No.)" column of Tables 4-1 and 4-3 was laminated in such a way that the solid electrolyte layer was in contact with the positive electrode active material layer. After transferring (lamination) by applying pressure at 50 MPa at 25°C using a press, the pressure was applied at 600 MPa at 25°C to produce all-solid-state secondary battery positive electrode sheets (positive electrode active material layer thickness 50 μm) with a solid electrolyte layer of 25 μm, No. 201 to 223 and c21 to c25 respectively.

[0648] - Fabrication of negative electrode sheets for all-solid-state secondary batteries with solid electrolyte layers-

[0649] On the negative electrode active material layer of each all-solid-state secondary battery negative electrode sheet shown in the "Electrode Active Material Layer (Sheet No.)" column of Tables 4-2 and 4-3, the solid electrolyte sheet shown in the "Solid Electrolyte Layer (Sheet No.)" column of Tables 4-2 and 4-3 was laminated in such a way that the solid electrolyte layer was in contact with the negative electrode active material layer. After transferring (lamination) by pressing at 50 MPa at 25°C using a press, the solid electrolyte layer was pressed at 600 MPa at 25°C to produce all-solid-state secondary battery negative electrode sheets (negative electrode active material layer thickness 40 μm) with a solid electrolyte layer of 25 μm thickness 301 to 323 and c31 to c35 respectively.

[0650] The following method was used to create a product with... Figure 1 The layered structure of the all-solid-state secondary battery No. 401 is shown in the figure.

[0651] The aforementioned all-solid-state secondary battery positive electrode sheet No. 201 (the aluminum foil containing the solid electrolyte sheet has been peeled off) with a solid electrolyte layer was cut into a circular plate with a diameter of 14.5 mm, and as follows... Figure 2 As shown, it is placed into an assembly containing spacers and gaskets (in Figure 2 The 2032-type button battery case 11 (not shown) is made of stainless steel. Next, lithium foil, cut into disc shapes with a diameter of 15 mm, is stacked and cut on a solid electrolyte layer. After further stacking stainless steel foil on top, the 2032-type button battery case 11 is riveted together, thus manufacturing the battery. Figure 2 The all-solid-state secondary battery 13 shown is No. 401.

[0652] The all-solid-state secondary battery manufactured in the above manner has the following characteristics: Figure 1 The layer structure shown in the figure (where the lithium foil corresponds to the negative electrode active material layer 2 and the negative electrode current collector 1).

[0653] All-solid-state secondary batteries No. 402~423 and C101~C105 were fabricated using the following method.

[0654] In the manufacture of the aforementioned all-solid-state secondary battery No. 401, instead of the all-solid-state secondary battery positive electrode sheet No. 201 with a solid electrolyte layer, the positive electrode sheet with a solid electrolyte layer indicated by the No. shown in the "Electrode Active Material Layer (Sheet No.)" column in Tables 4-1 and 4-3 was used. Otherwise, all-solid-state secondary batteries No. 402 to 423 and c101 to c105 were manufactured in the same manner as the manufacture of all-solid-state secondary battery No. 401.

[0655] The following method was used to create a product with... Figure 1The layered structure of the all-solid-state secondary battery No. 501 is shown in the figure.

[0656] The aforementioned negative electrode sheet No. 301 for all-solid-state secondary batteries with solid electrolyte (the aluminum foil containing the solid electrolyte has been peeled off) was cut into a circular plate with a diameter of 14.5 mm, and as follows... Figure 2 As shown, it is placed into an assembly containing spacers and gaskets (in Figure 2 The 2032-type button battery case 11 (not shown) is made of stainless steel. Next, a positive electrode sheet (positive active material layer) cut to a diameter of 14.0 mm from the positive electrode sheet for all-solid-state secondary batteries produced below is stacked on top of the solid electrolyte layer. A stainless steel foil (positive current collector) is then further stacked on top to form an all-solid-state secondary battery laminate 12 (a laminate composed of stainless steel foil, aluminum foil, positive active material layer, solid electrolyte layer, negative active material layer, and copper foil). The 2032-type button battery case 11 is then riveted together to manufacture the battery. Figure 2 The all-solid-state secondary battery shown is No. 501.

[0657] The positive electrode sheet for solid-state secondary batteries, used in the manufacture of all-solid-state secondary batteries No. 501, was prepared in the following manner.

[0658] -Preparation of the positive electrode composition-

[0659] 180 zirconia beads with a diameter of 5 mm were added to a 45 mL container (manufactured by Fritsch Co., Ltd.), along with 2.7 g of LPS synthesized in Synthesis Example A above, 0.3 g of KYNAR FLEX2500-20 (product name, PVdF-HFP: polyvinylidene fluoride hexafluoropropylene copolymer, manufactured by ARKEMA), and 22 g of butyl butyrate. The container was mounted on a planetary ball mill P-7 (product name) manufactured by Fritsch Co., Ltd., and stirred at 300 rpm for 60 minutes at 25°C. Then, LiNi was added as the positive electrode active material. 1 / 3 Co 1 / 3 Mn 1 / 3 7.0 g of O2 (NMC) was placed in a container on a planetary ball mill P-7 in the same manner and mixed for 5 minutes at 25°C and 100 rpm to prepare the positive electrode composition.

[0660] -Fabrication of positive electrode plates for solid-state secondary batteries-

[0661] Using a Becker coating machine (product name: SA-201, manufactured by TESTER SANGYO CO,. LTD.), the above-obtained positive electrode composition was coated onto an aluminum foil (positive electrode current collector) with a thickness of 20 μm, and heated at 100°C for 2 hours to dry the positive electrode composition (removing the dispersion medium). Then, using a hot press, the dried positive electrode composition was pressurized at 25°C (10 MPa, 1 minute) to produce a positive electrode sheet for all-solid-state secondary batteries with a positive electrode active material layer with a film thickness of 80 μm.

[0662] All-solid-state secondary batteries No. 502~523 and c201~c205 were manufactured using the following method.

[0663] In the manufacture of the aforementioned all-solid-state secondary battery No. 501, instead of the all-solid-state secondary battery negative electrode sheet No. 301 with a solid electrolyte layer, the all-solid-state secondary battery negative electrode sheet with a solid electrolyte layer indicated by the No. shown in the "Electrode Active Material Layer (Sheet No.)" column of Tables 4-2 and 4-3 was used. Otherwise, all-solid-state secondary batteries No. 502 to 523 and c201 to c205 were manufactured in the same manner as the manufacture of all-solid-state secondary battery No. 501.

[0664] <Evaluation 2: Measurement of Ionic Conductivity>

[0665] The ionic conductivity of each manufactured all-solid-state secondary battery was measured. Specifically, each all-solid-state secondary battery was used as a sample for ionic conductivity measurement. The AC impedance was measured in a constant temperature bath at 25°C using a 1255B Frequeny Response Analyzer (manufactured by SOLARTRON) at a voltage amplitude of 5 mV and a frequency of 1 MHz to 1 Hz. The resistance in the thickness direction of the sample for ionic conductivity measurement was then determined, and the ionic conductivity was calculated using the following formula (C1). The results are shown in Tables 4-1 to 4-3 (collectively referred to as Table 4).

[0666] Equation (C1): Ionic conductivity σ (mS / cm) =

[0667] 1000 × sample layer thickness (cm) / [resistance (Ω) × sample area (cm²)] 2 )]

[0668] In formula (C1), the sample layer thickness is the value obtained by measuring the laminate 12 before placing it into the 2032-type button battery case 11 and subtracting the thickness of the current collector (the total layer thickness of the solid electrolyte layer and the electrode active material layer). The sample area is the area of ​​a circular plate-shaped sheet with a diameter of 14.5 mm.

[0669] Determine whether the obtained ionic conductivity σ is included in any of the following evaluation criteria.

[0670] In the ionic conductivity σ in this test, those with an evaluation criterion of "D" or above are considered qualified.

[0671] - Evaluation Criteria -

[0672] A: 0.30 ≤ σ

[0673] B: 0.25 ≤ σ < 0.30

[0674] C: 0.20 ≤ σ < 0.25

[0675] D: 0.15 ≤ σ < 0.20

[0676] E: 0.10 ≤ σ < 0.15

[0677] F: σ < 0.10

[0678] [Table 4-1]

[0679]

[0680] [Table 4-2]

[0681]

[0682] [Table 4-3]

[0683]

[0684] From the results shown in Tables 1 to 4, the following can be known.

[0685] It can be seen that if a binder of a comparative example that does not contain a polymer represented by formula (I) and has an acid value of 3 mg KOH / g or less is used, heat generation during the preparation of the inorganic solid electrolyte composition cannot be suppressed, and the resistance of the all-solid-state secondary battery increases. Specifically, polymers T-1 and T-3 that do not have A in formula (I) 1 and linear polymer T-2, and furthermore, polymers T-4 and T-5 with an excessive acid value all generate heat when mixed with solid particles such as inorganic solid electrolytes. The inorganic solid electrolyte-containing compositions of the comparative examples prepared by mixing under such heat-generating conditions all exhibit a high resistance in the all-solid-state secondary battery.

[0686] In contrast, if the binder of the present invention that contains a polymer represented by formula (I) and has an acid value of 3 mg KOH / g or less is used, heat generation during the preparation of the inorganic solid electrolyte composition can be suppressed, and an increase in the resistance of the all-solid-state secondary battery can be suppressed.

[0687] The present invention has been described together with its embodiments, but we do not intend to limit the invention to any details described, and it is believed that it should be interpreted broadly without departing from the spirit and scope of the invention as shown in the technical solutions in the appendix.

[0688] This application claims priority based on Japanese Patent Application No. 2023-108489, filed on June 30, 2023, and Japanese Patent Application No. 2023-220463, filed on December 27, 2023, the contents of which are incorporated herein by reference and are included as a part of this specification.

[0689] Symbol Explanation

[0690] 1-Negative current collector, 2-Negative active material layer, 3-Solid electrolyte layer, 4-Positive active material layer, 5-Positive current collector, 6-Working part, 10-All-solid-state secondary battery, 11-Type 2032 button battery box, 12-Laminated body for all-solid-state secondary battery, 13-Button-type all-solid-state secondary battery.

Claims

1. An adhesive for all-solid-state secondary batteries, comprising a polymer represented by the following formula (I) and having an acid value of less than 3 mg KOH / g, [Chemical Formula 1] In equation (I), R 1 This represents a linking group with a valence of (m+n). A 1 A functional group or polymer chain representing a hydrogen atom, or containing at least one of an amide group, a sulfonamide group, and an imide group. A 2 This refers to a functional group or polymer chain containing at least one of fluorine atoms and a polysiloxane structure. n is an integer from 1 to 8, and m is an integer from 1 to 9, where... m+n is an integer from 2 to 10.

2. The adhesive for all-solid-state secondary batteries according to claim 1, wherein, The A 1 It refers to a functional group or polymer chain containing at least one of amide, sulfonamide and imide groups.

3. The adhesive for all-solid-state secondary batteries according to claim 1, wherein, The A 2 It contains functional groups or polymer chains that include polysiloxane structures.

4. The adhesive for all-solid-state secondary batteries according to claim 1, wherein, The polymer has an acid value of less than 0.5 mg KOH / g and an alkalinity of less than 0.5 mg KOH / g.

5. The adhesive for all-solid-state secondary batteries according to claim 1, wherein, The A 1 Polymer chains containing (meth)acrylamide compounds.

6. The adhesive for all-solid-state secondary batteries according to claim 1, wherein, The A 1 A polymer chain containing hydrogen atoms and (meth)acrylamide compounds.

7. The adhesive for all-solid-state secondary batteries according to claim 1, wherein, The A 1 The content of the polymer in the polymer is 1 to 30% by mass.

8. The adhesive for all-solid-state secondary batteries according to claim 1, wherein, The polymer has a weight-average molecular weight of less than 30,000.

9. A composition containing an inorganic solid electrolyte, comprising: an all-solid-state secondary battery binder according to any one of claims 1 to 8, an inorganic solid electrolyte having conductivity of ions belonging to Group 1 or Group 2 of the periodic table, and a dispersion medium.

10. The inorganic solid electrolyte composition according to claim 9, wherein it contains an active substance.

11. The inorganic solid electrolyte composition according to claim 9, wherein it contains a conductive additive.

12. A sheet for an all-solid-state secondary battery having a layer formed using the inorganic solid electrolyte composition of claim 9.

13. A sheet for an all-solid-state secondary battery, having an active material layer formed using the inorganic solid electrolyte composition of claim 10.

14. An all-solid-state secondary battery, comprising sequentially a positive electrode active material layer, a solid electrolyte layer, and a negative electrode active material layer, 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 formed using the inorganic solid electrolyte composition according to claim 9.

15. An all-solid-state secondary battery, comprising sequentially a positive electrode active material layer, a solid electrolyte layer, and a negative electrode active material layer, wherein, At least one of the positive electrode active material layer and the negative electrode active material layer is an active material layer formed using the inorganic solid electrolyte composition according to claim 10.

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