WO2021166968A1

WO2021166968A1 - Inorganic solid electrolyte-containing composition, sheet for all-solid-state secondary batteries, all-solid-state secondary battery, method for producing sheet for all-solid-state secondary batteries, and method for producing all-solid-state secondary battery

Info

Publication number: WO2021166968A1
Application number: PCT/JP2021/005973
Authority: WO
Inventors: 陽串田; 安田　浩司; 宏顕望月
Original assignee: 富士フイルム株式会社
Priority date: 2020-02-20
Filing date: 2021-02-17
Publication date: 2021-08-26
Also published as: JPWO2021166968A1

Abstract

The present invention provides: an inorganic solid electrolyte-containing composition which contains an inorganic solid electrolyte, a polymer binder and a dispersion medium, wherein the polymer binder is composed of a polymer that is configured from atoms which are not substituted by fluorine atoms, while having a main chain containing a specific bond such as a urethane bond and containing a constituent that has at least one specific functional group such as a hydroxyl group; a sheet for all-solid-state secondary batteries, said sheet using this inorganic solid electrolyte-containing composition; an all-solid-state secondary battery; a method for producing a sheet for all-solid-state secondary batteries; and a method for producing an all-solid-state secondary battery.

Description

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

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

In the all-solid-state secondary battery, the negative electrode, the electrolyte, and the positive electrode are all solid, and the safety and reliability of the battery using the organic electrolyte can be greatly improved. It is also said that it will be possible to extend the service life. Further, the all-solid-state secondary battery can have a structure in which electrodes and electrolytes are directly arranged side by side and arranged in series. Therefore, it is possible to increase the energy density as compared with a secondary battery using an organic electrolyte, and it is expected to be applied to an electric vehicle, a large storage battery, or the like.

In such an all-solid secondary battery, examples of the substance forming the constituent layers such as the solid electrolyte layer, the negative electrode active material layer, and the positive electrode active material layer include an inorganic solid electrolyte, an active material, and a binder (binder). .. Among the inorganic solid electrolytes, oxide-based inorganic solid electrolytes and sulfide-based inorganic solid electrolytes are expected in recent years as electrolyte materials having high ionic conductivity approaching that of organic electrolytes.
As a material for forming a constituent layer of an all-solid secondary battery (constituent layer forming material), a material containing the above-mentioned inorganic solid electrolyte and the like has been proposed. For example, Patent Document 1 describes a polymer containing a structural unit represented by a specific formula (1) and a hetero atom in the main chain as a constituent layer forming material, and belongs to Group 1 or Group 2 of the Periodic Table. A solid electrolyte composition containing an inorganic solid electrolyte having the conductivity of metal ions is described. As the polymer described in Patent Document 1, for example, a polymer containing a segment in which a plurality of difluoromethylene groups are bonded is described as a structural unit represented by the specific formula (1). Further, in Patent Document 2,
A sulfide-based solid electrolyte containing at least lithium, sulfur and phosphorus as elements, and a carbamide group having a hard segment and a soft segment and represented by -C (O) NR- (R is a hydrogen atom or a monovalent organic). A sulfide-based solid electrolyte composition containing a polymer having a group) is described.

Japanese Unexamined Patent Publication No. 2016-139512 Japanese Unexamined Patent Publication No. 2016-181448

Since the constituent layer of the all-solid-state secondary battery is usually formed of solid particles such as an inorganic solid electrolyte, an active material, and a conductive auxiliary agent, the interfacial contact state and the binding property between the solid particles are inherently restricted. NS. When the interfacial contact state is restricted, an increase in interfacial resistance (decrease in ionic conductivity) is induced, which in turn leads to a decrease in the cycle characteristics of the all-solid-state secondary battery. On the other hand, if the binding property between solid particles is weak, the binding state between solid particles is gradually impaired due to the contraction and expansion of the active material (constituent layer) accompanying the charging / discharging (release and absorption of lithium ions) of the all-solid secondary battery. This (causes poor contact) increases battery resistance and reduces cycle characteristics. All-solid-state secondary batteries, especially all-solid-state secondary batteries for electric vehicles, are urgently required to realize high-power charge / discharge (high-speed charge / discharge) for practical use. High-speed charge / discharge is a battery with cycle characteristics, etc. It causes a significant decrease in performance at an early stage.

One of the factors for the increase in battery resistance is not only the interfacial contact state between solid particles and the decrease in binding property, but also the non-uniform presence (arrangement) of solid particles in the constituent layer. Therefore, when the constituent layer is formed of the constituent layer-forming material, the constituent layer-forming material has the property of stably maintaining not only the dispersibility of the solid particles immediately after preparation but also the excellent dispersibility of the solid particles immediately after preparation. (Dispersion stability) is also required.

Further, from the viewpoint of industrial production of all-solid-state secondary batteries, it is preferable that the constituent layers are made into a sheet and continuously produced by, for example, a roll-to-roll method, and it is practical that the constituent layers are wound around a roll or the like. Is. In such a continuous production method, it is inevitable that stress such as bending or bending, and further restoration (stretching) acts on the constituent layer, and the solid particles are simply bound to each other with a binder. By itself, defects (chips, cracks, cracks, peeling, etc.) occur. In order to prevent the occurrence of defects in the manufacturing process, the constituent layers are required to strengthen not only the mere binding properties of the solid particles but also the strength (also referred to as film strength) of the entire layer.

As described in

Patent Documents

1 and 2, a binder is used to improve the binding property between solid particles, and the polymer structure constituting the binder has also been studied, and some effect has been obtained. However, in the polymer having the structure specifically described in

Patent Documents

1 and 2, the dispersion stability of the constituent layer forming material, the reduction of battery resistance, and the cycle characteristics, particularly the cycle characteristics for high-speed charge / discharge, have been studied. There is room for further improvement of these characteristics. In the first place, as described above, it is not easy to sufficiently strengthen the film strength of the constituent layer because the interfacial contact state and the binding property between the solid particles are restricted in the constituent layer, and it is not easy to sufficiently strengthen the film strength of the constituent layer. There is an urgent need to realize application to manufacturing.

The present invention is an inorganic solid electrolyte-containing composition having excellent dispersion stability, and by using it as a material for forming a constituent layer of an all-solid secondary battery, a constituent layer having enhanced film strength can be produced, and battery resistance is increased. An object of the present invention is to provide an inorganic solid electrolyte-containing composition capable of suppressing (increasing ionic conductivity) and achieving excellent cycle characteristics even for high-speed charging / discharging. Further, the present invention provides a method for manufacturing an all-solid-state secondary battery sheet and an all-solid-state secondary battery, and an all-solid-state secondary battery sheet and an all-solid-state secondary battery using this inorganic solid electrolyte-containing composition. The challenge is to provide.

As a result of various studies, the present inventors have introduced a polymer in which a specific bond such as a urethane bond is introduced into a main chain composed of atoms not substituted with fluorine atoms as an inorganic solid electrolyte-containing composition, which is a hydroxyl group. By using a polymer binder composed of a polymer incorporating a component having a specific functional group such as, etc. together with an inorganic solid electrolyte and a dispersion medium, reaggregation or precipitation of solid particles such as the inorganic solid electrolyte over time is suppressed. It has been found that the dispersion stability of the solid electrolyte-containing composition can be enhanced. Further, by using this inorganic solid electrolyte-containing composition as a constituent layer forming material, it is possible to form a constituent layer in which the solid particles are firmly bonded to each other as a whole layer while suppressing an increase in the interfacial resistance of the solid particles. We have found that it is possible to manufacture an all-solid secondary battery that can suppress an increase in battery resistance and realize excellent cycle characteristics even for high-speed charging and discharging. The present invention has been further studied based on these findings and has been completed.

That is, the above problem was solved by the following means.
<1> An inorganic solid electrolyte-containing composition containing an inorganic solid electrolyte having conductivity of metal ions belonging to Group 1 or Group 2 of the Periodic Table, a polymer binder, and a dispersion medium.
An inorganic solid electrolyte-containing composition comprising a polymer binder in which the polymer binder is composed of a polymer satisfying the following (P1) and (P2).
(P1) It is composed of atoms not substituted with fluorine atoms, and has a main chain containing at least one of urethane bond, urea bond and ester bond.
(P2) Contains a component having at least one functional group selected from the following functional group group.
<Functional group group>
Hydroxyl group, primary amino group, secondary amino group, sulfanyl group <2> The solid electrolyte-containing composition according to <1>, wherein the polymer binder composed of the above polymer is dispersed in a dispersion medium.
<3> The inorganic solid electrolyte-containing composition according to <1> or <2>, wherein the polymer binder composed of the above polymer has an average particle size of 1 to 1000 nm.
<4> The inorganic solid electrolyte-containing composition according to any one of <1> to <3>, wherein the constituent component has two or more of the above functional groups.
<5> The inorganic solid electrolyte-containing composition according to any one of <1> to <4>, wherein the content of the constituent component in the polymer is 0.01 to 50 mol%.

<6> The inorganic solid electrolyte-containing composition according to any one of <1> to <5>, wherein the constituent component has a partial structure represented by the following formula (F1).

In formula (F1), L ¹ and L ² represent a linking group, R ¹ represents a hydroxyl group or a primary or secondary amino group, and R ² represents a substituent.

<7> The inorganic solid electrolyte-containing composition according to any one of <1> to <6>, wherein the constituent component has a partial structure represented by the following formula (F2).

In formula (F2), L ¹ represents a linking group and R ³ represents a substituent.

<8> The dispersion medium contains a polymer binder composed of a soluble polymer, and the soluble polymer is any one of a (meth) acrylic polymer, a hydrocarbon polymer, a vinyl polymer, and a fluorine polymer. <1> The composition containing an inorganic solid polymer according to any one of <7>.
<9> The inorganic solid electrolyte-containing composition according to any one of <1> to <8>, which contains an active material.
<10> The inorganic solid electrolyte-containing composition according to <9>, wherein the active material is a negative electrode active material containing a silicon element or a tin element.
<11> The inorganic solid electrolyte-containing composition according to any one of <1> to <10>, which contains a conductive auxiliary agent.
<12> An all-solid-state secondary battery sheet having a layer composed of the inorganic solid electrolyte-containing composition according to any one of <1> to <11> above.
<13> An all-solid-state secondary battery including a positive electrode active material layer, a solid electrolyte layer, and a negative electrode active material layer in this order.
An all-solid-state layer in which at least one of the positive electrode active material layer, the solid electrolyte layer, and the negative electrode active material layer is a layer composed of the inorganic solid electrolyte-containing composition according to any one of <1> to <11>. Secondary battery.
<14> A method for producing a sheet for an all-solid secondary battery, which forms a film of the inorganic solid electrolyte-containing composition according to any one of <1> to <11> above.
<15> A method for manufacturing an all-solid-state secondary battery, wherein the all-solid-state secondary battery is manufactured through the manufacturing method according to <14> above.

The composition containing an inorganic solid electrolyte of the present invention can suppress reaggregation or sedimentation of solid particles such as an inorganic solid electrolyte over time, and can realize excellent dispersion stability. By using this inorganic solid electrolyte-containing composition as a material for forming a constituent layer, solid particles are uniformly scattered in the constituent layer, and a good contact state between surfaces is maintained to suppress an increase in interfacial resistance. Moreover, it is considered that the polymer binder can firmly bind the solid particles to each other as a whole layer. As a result, this inorganic solid electrolyte-containing composition can realize a constituent layer exhibiting a strong film strength with low resistance, and the all-solid secondary battery having this constituent layer has low battery resistance (high ionic conductivity) and high speed. Excellent cycle characteristics can be realized even for charging and discharging.
That is, the present invention is an inorganic solid electrolyte-containing composition having excellent dispersion stability, and by using it as a material for forming a constituent layer of an all-solid secondary battery, a constituent layer having enhanced film strength can be produced, and battery resistance can be produced. It is possible to provide an inorganic solid electrolyte-containing composition capable of suppressing an increase in the amount of the battery and achieving excellent cycle characteristics even for high-speed charging / discharging. Further, the present invention provides a method for manufacturing an all-solid-state secondary battery sheet and an all-solid-state secondary battery, and an all-solid-state secondary battery sheet and an all-solid-state secondary battery using this inorganic solid electrolyte-containing composition. Can be provided.
The above and other features and advantages of the present invention will become more apparent from the description below, with reference to the accompanying drawings as appropriate.

It is a vertical sectional view which shows typically the all-solid-state secondary battery which concerns on a preferable embodiment of this invention. FIG. 2 is a vertical cross-sectional view schematically showing the coin-type all-solid-state secondary battery produced in the examples.

In the present invention, the numerical range represented by using "-" means a range including the numerical values before and after "-" as the lower limit value and the upper limit value.
In the present invention, the indication of a compound (for example, when it is referred to as a compound at the end) is used to mean that the compound itself, its salt, and its ions are included. In addition, it is meant to include a derivative which has been partially changed, such as by introducing a substituent, as long as the effect of the present invention is not impaired.
In the present invention, (meth) acrylic means one or both of acrylic and methacryl. The same applies to (meth) acrylate.
In the present invention, a substituent, a linking group, etc. (hereinafter referred to as a substituent, etc.) for which substitution or non-substitution is not specified may have an appropriate substituent in the group. Therefore, in the present invention, even if it is simply described as a YYY group, this YYY group includes a mode having a substituent in addition to a mode having no substituent. This is also synonymous with compounds that do not specify substitution or non-substitution. Preferred substituents include, for example, Substituent Z, which will be described later.
In the present invention, when there are a plurality of substituents or the like indicated by specific reference numerals, or when a plurality of substituents or the like are specified simultaneously or selectively, the substituents or the like may be the same or different from each other. Means that. Further, even if it is not particularly specified, it means that when a plurality of substituents or the like are adjacent to each other, they may be connected to each other or condensed to form a ring.
In the present invention, the polymer means a polymer, but is synonymous with a so-called polymer compound.

[Inorganic solid electrolyte-containing composition]
The inorganic solid electrolyte-containing composition of the present invention contains an inorganic solid electrolyte having conductivity of metal ions belonging to Group 1 or Group 2 of the periodic table, a polymer binder, and a dispersion medium.
Details of the polymer binder contained in this inorganic solid electrolyte-containing composition will be described later, but at least one of the polymer binders satisfies the following (P1) with respect to the main chain of the polymer, and the following (P2) with respect to the constituent components constituting the polymer. It is a polymer binder composed (including) of a polymer satisfying the above conditions.
(P1) It is composed of atoms not substituted with fluorine atoms, and has a main chain containing at least one of urethane bond, urea bond and ester bond.
(P2) Contains a component having at least one functional group selected from the functional group group described later.

In the inorganic solid electrolyte-containing composition of the present invention, the content state of the polymer binder and the like are not particularly limited. For example, in the composition containing an inorganic solid electrolyte, the polymer binder may or may not be adsorbed on solid particles such as an inorganic solid electrolyte, but the fact that it is adsorbed is the point of dispersibility of the solid particles with respect to the dispersion medium. It is preferable. Here, the adsorption of the polymer binder to solid particles includes not only physical adsorption but also chemical adsorption (adsorption by chemical bond formation, adsorption by electron transfer, etc.).
On the other hand, in the polymer binder, solid particles such as inorganic solid electrolytes (furthermore, coexisting active materials and conductive aids) in a layer formed of at least an inorganic solid electrolyte-containing composition (for example, inorganic solid electrolytes). , Inorganic solid electrolyte and active material, active material to each other) functions as a binder. Furthermore, it may function as a binder that binds the current collector and the solid particles.
The inorganic solid electrolyte-containing composition of the present invention is preferably a slurry in which solid particles are dispersed in a dispersion medium. In this case, the polymer binder serves to disperse the solid particles in the dispersion medium. Further, the polymer binder (polymer) may or may not be dispersed in the dispersion medium (in the solid state), but when it is dispersed, a part thereof is a dispersion medium as long as the effect of the present invention is not impaired. It may be dissolved in.

The composition containing an inorganic solid electrolyte of the present invention is excellent in dispersion stability. By using this inorganic solid electrolyte-containing composition as a constituent layer forming material, an all-solid secondary battery sheet having a constituent layer exhibiting a strong layer strength, and further, high-speed charging in addition to the cycle characteristics for normal charging and discharging. It is possible to realize an all-solid secondary battery that has excellent cycle characteristics against discharge and that suppresses an increase in battery resistance.
In the embodiment in which the active material layer formed on the current collector is formed by the inorganic solid electrolyte-containing composition of the present invention, strong adhesion between the current collector and the active material layer can also be realized, and a cycle can be realized. The characteristics can be further improved.

Although the details of the reason are not yet clear, the polymer binder formed of the polymer satisfying the above (P1) and (P2) has the interaction between the polymer binders by the polymer main chain and the interaction with the solid particles by the functional group. It is considered that this is due to the well-balanced expression of.
That is, the polymer binder formed of the polymer satisfying the above (P1) and (P2) exhibits an appropriate interaction with solid particles such as an inorganic solid electrolyte in the dispersion medium due to its functional group, and is a solid. It does not adsorb excessively enough to reaggregate and precipitate particles. Therefore, in the inorganic solid electrolyte-containing composition (dispersion medium), the solid particles can be uniformly dispersed while effectively suppressing the reaggregation and precipitation of the solid particles over time, and the inorganic solid electrolyte-containing composition can be prepared. It is considered that the excellent dispersibility of time (uniform dispersibility and dispersion stability) can be maintained for a long period of time.

When the constituent layer is formed using the above-mentioned inorganic solid electrolyte-containing composition of the present invention exhibiting excellent dispersion stability, when the constituent layer is formed (for example, when the inorganic solid electrolyte-containing composition is applied and when it is dried). ), It is considered that the uneven distribution (transition) of solid particles and the generation of reaggregates or sediments can be suppressed. As a result, it is possible to suppress variations in the contact state of the solid particles in the constituent layer, and the solid particles are uniformly arranged in the constituent layer. Further, since the polymer binder does not excessively adsorb to the solid particles as described above, it is considered that the contact between the surfaces of the solid particles is not significantly hindered. As a result, it is possible to suppress an increase in the interfacial resistance between the solid particles and the resistance of the constituent layers.
On the other hand, it is considered that the polymer constituting the polymer binder exhibits an interaction with the solid particles in the constituent layer due to its functional group and binds the solid particles to each other. Furthermore, since this polymer has a specific bond such as a urethane bond in the main chain (satisfying the above (P1)), the interaction between the polymers (polymer binders) (for example, due to hydrogen bond or intermolecular force). It is considered that the interaction) is enhanced and the polymer binders are firmly bonded to each other in a state where the solid particles are appropriately adsorbed to reinforce the bonding of the solid particles by the polymer binder. As a result, high film strength can be achieved by binding the solid particles to each other with a strong binding force as the entire layer. Moreover, the contact state between the solid particles can be maintained even when the constituent layers are produced. In this way, it is possible to realize an all-solid-state secondary battery sheet having a constituent layer that exhibits low resistance (high conductivity) and strong film strength.

In addition, an all-solid secondary battery having a constituent layer that suppresses an increase in resistance and exhibits strong film strength is less likely to generate overcurrent during charging and discharging, can prevent deterioration of solid particles, and expands and contracts solid particles. It is possible to effectively suppress the decrease in the interfacial contact state between solid particles (generation of voids) due to the above. Therefore, it has excellent cycle characteristics without causing a significant decrease even if high-speed charging and discharging are repeated as well as normal charging and discharging, and also has high conductivity (ion conductivity, electron conductivity) by suppressing an increase in battery resistance. It is considered that the all-solid-state secondary battery shown can be realized.

When the active material layer is formed of the inorganic solid electrolyte-containing composition of the present invention, it is considered that the constituent layer is formed while maintaining the highly (uniform) dispersed cathode active material immediately after preparation as described above. Therefore, the polymer binder can come into contact (adhesion) with the surface of the current collector without being hindered by the solid particles that have been preferentially settled. As a result, the electrode sheet for an all-solid-state secondary battery in which the active material layer is formed on the current collector with the inorganic solid electrolyte-containing composition of the present invention can realize strong adhesion between the current collector and the active material. Further, the all-solid-state secondary battery in which the active material layer is formed on the current collector with the inorganic solid electrolyte-containing composition of the present invention shows strong adhesion between the current collector and the active material, and further improves the cycle characteristics. Furthermore, in addition to excellent cycle characteristics, improvement in conductivity can be realized.

The inorganic solid electrolyte-containing composition of the present invention is a material for forming a solid electrolyte layer or an active material layer of an all-solid secondary battery sheet (including an electrode sheet for an all-solid secondary battery) or an all-solid secondary battery. It can be preferably used as a constituent layer forming material). In particular, since the constituent layer composed of the inorganic solid electrolyte-containing composition of the present invention exhibits strong film strength, the constituent layer to be produced continuously from the viewpoint of productivity, particularly continuously by the roll-to-roll method, is formed. It can be preferably used as a material. Even in such a continuous production method, it is possible to suppress the occurrence of defects in the constituent layers. Further, it can be preferably used as a material for forming a negative electrode sheet for an all-solid secondary battery or a negative electrode active material layer containing a negative electrode active material having a large expansion and contraction due to charging and discharging, and in this embodiment as well, the battery performance (cycle characteristics, etc.) is deteriorated. Can be suppressed.

The inorganic solid electrolyte-containing composition of the present invention is preferably a non-aqueous composition. In the present invention, the non-aqueous composition includes not only a water-free aspect but also a form in which the water content (also referred to as water content) is preferably 500 ppm or less. In the non-aqueous composition, the water content is more preferably 200 ppm or less, further preferably 100 ppm or less, and particularly preferably 50 ppm or less. When the composition containing the inorganic solid electrolyte is a non-aqueous composition, deterioration of the inorganic solid electrolyte can be suppressed. The water content indicates the amount of water contained in the inorganic solid electrolyte-containing composition (mass ratio to the inorganic solid electrolyte-containing composition). Specifically, the mixture is filtered through a 0.02 μm membrane filter and curled fisher. The value shall be the value measured using titration.

The composition containing an inorganic solid electrolyte of the present invention also includes an embodiment containing an active material, a conductive additive, and the like in addition to the inorganic solid electrolyte (the composition of this embodiment is referred to as an electrode composition).
Hereinafter, the components contained in the inorganic solid electrolyte-containing composition of the present invention and the components that can be contained will be described.

<Inorganic solid electrolyte>
The inorganic solid electrolyte-containing composition of the present invention contains an inorganic solid electrolyte.
In the present invention, the inorganic solid electrolyte is an inorganic solid electrolyte, and the solid electrolyte is a solid electrolyte capable of transferring ions inside the solid electrolyte. Since it does not contain organic substances as the main ionic conductive material, it is an organic solid electrolyte (polyelectrolyte represented by polyethylene oxide (PEO), organic such as lithium bis (trifluoromethanesulfonyl) imide (LiTFSI)). It is clearly distinguished from electrolyte salts). Further, since the inorganic solid electrolyte is a solid in a steady state, it is usually not dissociated or liberated into cations and anions. _{In this respect, it is clearly distinguished from the electrolyte or inorganic electrolyte salts (LiPF 6} , LiBF ₄ , Lithium bis (fluorosulfonyl) imide (LiFSI), LiCl, etc.) that are dissociated or liberated into cations and anions in the polymer. Will be done. The inorganic solid electrolyte is not particularly limited as long as it has the ionic conductivity of a metal belonging to Group 1 or Group 2 of the periodic table, and is generally one having no electron conductivity. When the all-solid-state secondary battery of the present invention is a lithium-ion battery, the inorganic solid electrolyte preferably has lithium ion ionic conductivity.

As the above-mentioned inorganic solid electrolyte, a solid electrolyte material usually used for an all-solid secondary battery can be appropriately selected and used. For example, examples of the inorganic solid electrolyte include (i) a sulfide-based inorganic solid electrolyte, (ii) an oxide-based inorganic solid electrolyte, (iii) a halide-based inorganic solid electrolyte, and (iv) a hydride-based inorganic solid electrolyte. The sulfide-based inorganic solid electrolyte is preferable from the viewpoint that a better interface can be formed between the active material and the inorganic solid electrolyte.

(I) Sulfide-based inorganic solid electrolyte The sulfide-based inorganic solid electrolyte contains sulfur atoms, has ionic conductivity of metals belonging to Group 1 or Group 2 of the Periodic Table, and is electronically insulated. Those having sex are preferable. The sulfide-based inorganic solid electrolyte preferably contains at least Li, S and P as elements and has lithium ion conductivity, but other than Li, S and P may be used depending on the purpose or case. It may contain elements.

Examples of the sulfide-based inorganic solid electrolyte include a lithium ion conductive inorganic solid electrolyte satisfying the composition represented by the following formula (S1).

L _a1 M _b1 P _c1 S _d1 A _e1 (S1)

In the formula, L represents an element selected from Li, Na and K, with Li being preferred. M represents an element selected from B, Zn, Sn, Si, Cu, Ga, Sb, Al and Ge. A represents an element selected from I, Br, Cl and F. a1 to e1 indicate the composition ratio of each element, and a1: b1: c1: d1: e1 satisfy 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.

The composition ratio of each element can be controlled by adjusting the blending amount of the raw material compound when producing the sulfide-based inorganic solid electrolyte as described below.

The sulfide-based inorganic solid electrolyte may be amorphous (glass) or crystallized (glass-ceramic), or only a part thereof may be crystallized. For example, Li-PS-based glass containing Li, P and S, or Li-PS-based glass ceramics containing Li, P and S can be used.
Sulfide-based inorganic solid electrolytes include, for example, lithium sulfide (Li ₂ S), phosphorus sulfide (for example, diphosphorus pentasulfide (P ₂ S ₅ )), simple phosphorus, simple sulfur, sodium sulfide, hydrogen sulfide, and lithium halide (for example). It can be produced by the reaction of at least two or more raw materials in sulfides of LiI, LiBr, LiCl) and the element represented by M (for example, SiS ₂ , SnS, GeS _2).

In Li-P-S based glass and Li-P-S based glass ceramics, the ratio of Li ₂ S and _P 2 _{S 5} _is, Li 2 _S: at a molar ratio of P 2 _{S 5,} preferably 60: 40 ~ It is 90:10, more preferably 68:32 to 78:22. By _{setting the ratio of Li 2} S and P ₂ S ₅ in this range, the lithium ion conductivity can be made high. Specifically, the lithium ion conductivity can be preferably 1 × 10 ^-4 S / cm or more, and more preferably 1 × 10 ^-3 S / cm or more. There is no particular upper limit, but it is practical that it is ^{1 × 10 -1 S / cm or less.}

As an example of a specific sulfide-based inorganic solid electrolyte, an example of combining raw materials is shown below. For _{_{_{_{example, Li 2 S-P 2 S}}}} 5, Li 2 S-P 2 S 5 -LiCl, Li 2 S-P 2 S 5 -H 2 S, Li 2 S-P 2 S 5 -H 2 S-LiCl, Li ₂ S-LiI-P ₂ S ₅ , Li ₂ S-LiI-Li ₂ O-P ₂ S ₅ , Li ₂ S-LiBr-P ₂ S ₅ , Li ₂ S-Li ₂ O-P ₂ S ₅ , Li ₂ S-Li ₃ PO _4- P ₂ S ₅ , Li ₂ S-P ₂ S _5- P ₂ O ₅ , Li ₂ S-P ₂ S _5- SiS ₂ , Li ₂ S-P ₂ S _5- SiS _{_{_{_{2 -LiCl, Li 2 S-P}}}} 2 S 5 -SnS, Li 2 S-P 2 S 5 -Al 2 S 3, Li 2 S-GeS 2, Li 2 S-GeS 2 -ZnS, Li 2 S-Ga ₂ S ₃ , Li ₂ S-GeS _2- Ga ₂ S ₃ , Li ₂ S-GeS _2- P ₂ S ₅ , Li ₂ S-GeS _2- Sb ₂ S ₅ , Li ₂ S-GeS _2- Al ₂ S ₃ , Li ₂ S-SiS ₂ , Li ₂ S-Al ₂ S ₃ , Li ₂ S-SiS _2- Al ₂ S ₃ , Li ₂ S-SiS _2- P ₂ S ₅ , Li ₂ S-SiS _2- P _{_{_{_{2 S 5 -LiI, Li 2 S}}}} -SiS 2 -LiI, such as _{_{_{Li 2 S-SiS 2 -Li 4}}} SiO 4, Li 2 S-SiS 2 -Li 3 PO 4, Li 10 GeP 2 S 12 and the like. However, the mixing ratio of each raw material does not matter. As a method for synthesizing a sulfide-based inorganic solid electrolyte material using such a raw material composition, for example, an amorphization method can be mentioned. Examples of the amorphization method include a mechanical milling method, a solution method and a melt quenching method. This is because processing at room temperature is possible and the manufacturing process can be simplified.

(Ii) Oxide-based Inorganic Solid Electrolyte The oxide-based inorganic solid electrolyte contains an oxygen atom, has ionic conductivity of a metal belonging to Group 1 or Group 2 of the Periodic Table, and is electronically insulated. Those having sex are preferable.
The oxide-based inorganic solid electrolyte preferably has an ionic conductivity of 1 × 10 ^-6 S / cm or more, more preferably 5 × 10 ^-6 S / cm or more, and 1 × 10 ^-5 S / cm or more. It is particularly preferable that it is / cm or more. The upper limit is not particularly limited, but it is practical that it is ^{1 × 10 -1 S / cm or less.}

As a specific example of the compound, for example, Li _xa La _ya TiO ₃ [xa satisfies 0.3 ≦ xa ≦ 0.7, and ya satisfies 0.3 ≦ ya ≦ 0.7. (LLT); Li _xb _Layb Zr _zb M ^bb _mb _Onb (M ^bb is one or more elements selected from Al, Mg, Ca, Sr, V, Nb, Ta, Ti, Ge, In and Sn. Xb satisfies 5 ≦ xb ≦ 10, yb satisfies 1 ≦ yb ≦ 4, zb satisfies 1 ≦ zb ≦ 4, mb satisfies 0 ≦ mb ≦ 2, and nb satisfies 5 ≦ nb ≦ 20. Satisfy.); Li _xc _Byc M ^cc _zc _Onc (M ^cc is one or more elements selected from C, S, Al, Si, Ga, Ge, In and Sn. Xc is 0 <xc ≦ 5 , Yc satisfies 0 <yc ≦ 1, zc satisfies 0 <zc ≦ 1, 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 is 1 ≦ met md ≦ 7, nd satisfies _{3 ≦ nd ≦ 13);.} Li (3-2xe) M ee xe D ee O (xe represents a number of 0 to ^{0.1, M ee} divalent ^{.D ee} representing the metal atom represents a combination of halogen atom or 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, and zg satisfies 1 ≦ zg ≦ 10. ); Li ₃ BO ₃ ; Li ₃ BO _3- _{Li 2} SO ₄ ; Li ₂ O-B ₂ O _3- P ₂ O ₅ ; Li ₂ O-SiO ₂ ; Li ₆ BaLa ₂ Ta ₂ O ₁₂ ; Li ₃ PO _{(4-3 / 2w)} N _w _{(w is w <1); Li 3.5} Zn _0.25 GeO ₄ having a LISION (Lithium super ionic controller) type crystal structure _{; La 0.55} having a perovskite type crystal structure Li _0.35 TiO ₃ _{; LiTi 2} P ₃ O ₁₂ having a NASICON (Naturium super ionic controller) type crystal structure; Li _{1 + xh + yh} (Al, Ga) _xh (Ti, Ge) _2-xh _Sihy P _3-yh O ₁₂ (xh satisfies 0 ≦ xh ≦ 1, yh satisfies 0 ≦ yh ≦ 1. _{); Li 7} La ₃ Zr ₂ O ₁₂ (LLZ) having a garnet-type crystal structure and the like can be mentioned.
Phosphorus compounds containing Li, P and O are also desirable. For example, lithium phosphate (Li ₃ PO ₄ ); LiPON in which a part of the oxygen element of lithium phosphate is replaced with a nitrogen element; LiPOD ¹ (D ¹ is preferably Ti, V, Cr, Mn, Fe, Co, It is one or more elements selected from Ni, Cu, Zr, Nb, Mo, Ru, Ag, Ta, W, Pt and Au) and the like.
Further, LiA ¹ ON (A ¹ is one or more elements selected from Si, B, Ge, Al, C and Ga) and the like can also be preferably used.

(Iii) Halide-based Inorganic Solid Electrolyte The halide-based inorganic solid electrolyte is generally used, contains a halogen atom, and has the conductivity of ions of a metal belonging to Group 1 or Group 2 of the Periodic Table. A compound having an electron insulating property and having an electron insulating property is preferable.
The halide-based inorganic solid electrolyte is not particularly limited, and examples thereof include compounds such as Li 3 YBr ₆ and Li ₃ YCl ₆ described in LiCl, LiBr, LiI, ADVANCED MATERIALS, 2018, _{30, 1803075.} Of these, Li ₃ YBr ₆ and Li ₃ YCl ₆ are preferable.

(Iv) Hydride-based Inorganic Solid Electrolyte The hydride-based inorganic solid electrolyte is generally used, contains a hydrogen atom, and exhibits ionic conductivity of a metal belonging to Group 1 or Group 2 of the Periodic Table. A compound having and having an electron insulating property is preferable.
The hydride-based inorganic solid electrolyte is not particularly limited, and examples thereof include LiBH ₄ , Li ₄ (BH ₄ ) ₃ I, and _{3 LiBH 4-} LiCl.

The inorganic solid electrolyte is preferably particles. In this case, the average particle size (volume average particle size) of the inorganic solid electrolyte is not particularly limited, but is preferably 0.01 μm or more, and more preferably 0.1 μm or more. The upper limit is preferably 100 μm or less, and more preferably 50 μm or less.
The average particle size of the inorganic solid electrolyte is measured by the following procedure. Inorganic solid electrolyte particles are prepared by diluting 1% by mass of a dispersion in a 20 mL sample bottle with water (heptane in the case of a water-unstable substance). The diluted dispersion sample is irradiated with 1 kHz ultrasonic waves for 10 minutes, and immediately after that, it is used for the test. Using this dispersion sample, data was captured 50 times using a measurement quartz cell at a temperature of 25 ° C. using a laser diffraction / scattering particle size distribution measuring device LA-920 (trade name, manufactured by HORIBA). Obtain the volume average particle size. For other detailed conditions, etc., refer to the description of Japanese Industrial Standards (JIS) Z 8828: 2013 "Grain size analysis-Dynamic light scattering method" as necessary. Five samples are prepared for each level and the average value is adopted.

The inorganic solid electrolyte may contain one kind or two or more kinds.
When forming the solid electrolyte layer, the mass (mg) (grain amount) of the inorganic solid electrolyte per ^{unit area (cm 2) of the solid electrolyte layer is not particularly limited.} It can be appropriately determined according to the designed battery capacity, and can be, for example, 1 to 100 mg / cm ² .
However, when the composition containing the inorganic solid electrolyte contains an active material described later, the amount of the inorganic solid electrolyte is preferably such that the total amount of the active material and the inorganic solid electrolyte is in the above range.

The content of the inorganic solid electrolyte in the composition containing the inorganic solid electrolyte is not particularly limited, but is 50% by mass or more at 100% by mass of the solid content in terms of binding property and dispersibility. Is more preferable, 70% by mass or more is more preferable, and 90% by mass or more is particularly preferable. From the same viewpoint, the upper limit is preferably 99.9% by mass or less, more preferably 99.5% by mass or less, and particularly preferably 99% by mass or less.
However, when the inorganic solid electrolyte-containing composition contains an active material described later, the content of the inorganic solid electrolyte in the inorganic solid electrolyte-containing composition is such that the total content of the active material and the inorganic solid electrolyte is in the above range. Is preferable.
In the present invention, the solid content (solid component) refers to a component that does not disappear by volatilizing or evaporating when the inorganic solid electrolyte-containing composition is dried at 150 ° C. for 6 hours under an atmospheric pressure of 1 mmHg and a nitrogen atmosphere. .. Typically, it refers to a component other than the dispersion medium described later.

<Polymer binder>
The inorganic solid electrolyte-containing composition of the present invention contains a polymer binder. The polymer binder contained in the inorganic solid electrolyte-containing composition of the present invention contains at least one polymer binder (also referred to as a binder used in the present invention) composed of a polymer satisfying the following (P1) and (P2). It may contain one or more polymer binders (also referred to as other binders, the details of which will be described later) other than the binder used in the present invention.
In the inorganic solid electrolyte-containing composition of the present invention, one type of binder used in the present invention may be contained as the polymer binder, or a plurality of types may be contained. When a plurality of kinds are contained, there is no particular limitation, but 2 to 4 kinds are preferable.
In the present invention, the polymer binder means a binder composed of a polymer, and includes the polymer itself and a binder formed containing the polymer.

(Binder used in the present invention)
The binder used in the present invention contained in the inorganic solid electrolyte-containing composition of the present invention as a polymer binder will be described.
The binder used in the present invention is composed of a polymer that satisfies the following (P1) for the main chain of the polymer and the following (P2) for the constituent components constituting the polymer. Such a binder can improve the dispersion stability of the inorganic solid electrolyte-containing composition (slurry) by using it in combination with solid particles such as the inorganic solid electrolyte and a dispersion medium in the inorganic solid electrolyte-containing composition. Further, a constituent layer having a strong film strength can be formed, and it is possible to reduce the battery resistance and improve the cycle characteristics of the all-solid-state secondary battery.
(P1) It is composed of atoms not substituted with fluorine atoms, and has a main chain containing at least one of urethane bond, urea bond and ester bond.
(P2) Contains a component having at least one functional group selected from the following functional group group.
<Functional group group>
Hydroxy group, primary amino group, secondary amino group, sulfanilic group

-Polymer forming the binder used in the present invention-
The polymer forming the binder used in the present invention is not particularly limited as long as the above (P1) and (P2) are satisfied, and various polymers can be used.
The bonding mode (primary structure) of the polymer forming the binder used in the present invention is not particularly limited, and may have any primary structure such as a random structure, a block structure, an alternating structure, and a graft structure. The molecular structure of this polymer is also not particularly limited, and examples thereof include a linear structure and a branched shape (star structure, branched structure), but the molecular structure is preferably linear.
In the present invention, the main chain of a polymer means a linear molecular chain in which all other molecular chains constituting the polymer can be regarded as a branched chain or a pendant with respect to the main chain. Although it depends on the mass average molecular weight of the molecular chain regarded as a branched chain or a pendant chain, the longest chain among the molecular chains constituting the polymer is typically the main chain. However, the terminal group of the polymer terminal is not included in the main chain. In addition, the atoms constituting the main chain mean each atom forming the atomic chain that becomes the main chain of the polymer, and an atom or an atom group (hydrogen atom, a substituent, etc.) for adjusting the valence of this atom. Furthermore, it does not contain atoms forming a molecular chain that is regarded as a branched chain or a pendant chain. When a cyclic structure is included in the main chain, it means all atoms forming the atomic chain of the cyclic structure. For example, the only atom that constitutes the main chain of polyethylene is a carbon atom, and does not contain a hydrogen atom for adjusting the valence of the carbon atom.
In the present invention, the side chain of the polymer means a molecular chain other than the main chain, and includes a short molecular chain and a long molecular chain.

The polymer forming the binder used in the present invention (sometimes referred to as a binder-forming polymer) satisfies the following (P1) with respect to the main chain of the polymer.

(P1) A main chain composed of atoms not substituted with fluorine atoms, which has a main chain containing at least one of urethane bond, urea bond and ester bond.

In the binder-forming polymer, the atoms constituting the main chain are not substituted with fluorine atoms (P1-1). The main chain of a polymer usually consists of a molecular chain in which an atom such as a hydrogen atom or an atom having a valence adjusted by bonding an atom or a substituent is continuously bonded, but a binder-forming polymer forms the main chain. The hydrogen atom bonded to the atom is not replaced by a fluorine atom. In other words, the atom forming the main chain has an atom or a substituent other than the fluorine atom bonded to it. A fluorine atom may be bonded to an atom other than the atom forming the main chain.
When the main chain is formed of atoms not substituted with fluorine atoms, the interaction between the binder-forming polymers is enhanced in combination with the satisfaction of (P1-2) described later, and the dispersion of the inorganic solid electrolyte-containing composition is enhanced. Not only the stability can be improved, but also the film strength can be strengthened, and the battery resistance and cycle characteristics can be improved.
As a main chain formed of atoms not substituted with fluorine atoms, for example, a carbon atom in which one hydrogen atom is substituted with a fluorine atom (fluoromethylene group, fluoromethine group, etc.) and two hydrogen atoms are fluorine. Examples thereof include a main chain that does not contain a carbon atom (difluoromethylene group) substituted with an atom, and a main chain that does not contain a molecular chain in which these atoms are linked. More specifically, the main chain described in Patent Document 1 that does not include the structural unit represented by the formula (I) can be mentioned. That is, the main chain of the binder-forming polymer does not contain a specific CF bond.
In the present invention, the main chain composed of atoms not substituted with fluorine atoms is one of the atoms constituting the main chain in addition to the embodiment in which all the atoms constituting the main chain are not substituted with fluorine atoms. This includes an embodiment in which the portion is substituted with a fluorine atom as long as the effect of the present invention is not impaired. The range that does not impair the effects of the present invention is not particularly limited, but for example, the molar ratio [F / C] of fluorine atoms to the atoms (usually carbon atoms) forming the main chain of the polymer is less than 0.001. be able to. The molar ratio [F / C] can be specified by the method described in paragraph [0123] of Patent Document 1.

Binder-forming polymer, a urethane bond ^(-NR PN COO-), a urea bond ^(-NR ^PN CONR PN -) having a backbone comprising at least one binding of and ester bond (-COO-) (P1-2 ). R ^PN represents a substituent other than a hydrogen atom or a fluorine atom in each bond.
In the present invention, the main chain containing at least one of the above-mentioned bonds means that the main chain contains at least one of the above-mentioned bonds, and the number of bonds contained in the main chain is particularly limited. However, it is appropriately determined by the molecular weight of the raw material compound, the molecular weight of the polymer, and the like. When the main chain satisfies the above (P1-1) and contains the above bond, the interaction between the binder-forming polymers is strengthened, and only the improvement of the dispersion stability of the main chain inorganic solid electrolyte-containing composition is required. The film strength can be strengthened, and the battery resistance and cycle characteristics can be improved.
Of the atoms forming each of the above bonds, the atoms forming the main chain of the polymer are not substituted with fluorine atoms as described above. For example, the nitrogen atom of the urethane bond or the urea bond has a hydrogen atom or a substituent (excluding the fluorine atom) ^RPN bonded to it, and the hydrogen atom is bonded in that the interaction between the polymer binders is strengthened. That (-NH-group) is preferable.

The bond is not particularly limited as long as it is contained in the main chain of the polymer, and may be any of the modes contained in the structural unit (repeating unit) and / or the mode contained as a bond connecting different structural units. .. Further, the above-mentioned bond contained in the main chain is not limited to one type, and may be two or more types. In this case, the binding mode of the main chain is not particularly limited, and may have two or more kinds of bonds at random, and the segmented main chain of a segment having a specific bond and a segment having another bond. It may be a chain.

Examples of the polymer having the above bond in the main chain include polymers such as polyurethane, polyurea, and polyester, or copolymers thereof. The copolymer may be a block copolymer having each of the above polymers as a segment, or a random copolymer in which each component constituting two or more of the above polymers is randomly bonded.

The binder-forming polymer satisfies the following (P2) with respect to the constituent components constituting the polymer.
(P2) Contains a component having at least one functional group selected from the following functional group group.
<Functional group group>
Hydroxy group, primary amino group, secondary amino group, sulfanilic group (mercapto group: -SH)

Details of the constituents having at least one functional group selected from the above functional group group will be described later.

(Components represented by any of formulas (I-1) to (I-4))
The binder-forming polymer is not particularly limited as long as it satisfies the above (P1) and (P2), but in addition to the constituent components having a functional group selected from the functional group group described later, the following formula (I-1) A polymer having at least one kind (preferably 2 to 8 kinds, more preferably 2 to 4 kinds) of the constituent components represented by any of (I-4) is preferable. Polymers having such a main chain include, for example, polyurethane, polyurea and polyester. The combination of each component is appropriately selected according to the polymer species. In the present invention, one kind of constituent component in the combination of constituent components means the number of kinds of constituent components represented by any one of the following formulas, and two kinds of one kind of constituent component represented by the following formula are used. Even if it has, it is not interpreted as two kinds of constituents.
The binder-forming polymer further contains a component having a functional group selected from the functional group group and a component different from the components represented by any of the following formulas (I-1) to (I-4). You may have.

In the formula, ^RP1 and ^RP2 each represent a molecular chain having a molecular weight or mass average molecular weight of 20 or more and 200,000 or less, respectively. The molecular weight of this molecular chain cannot be uniquely determined because it depends on the type and the like, but for example, 30 or more is preferable, 50 or more is more preferable, 100 or more is further preferable, and 150 or more is particularly preferable. The upper limit is preferably 100,000 or less, more preferably 10,000 or less. The molecular weight of the molecular chain is measured for the starting compound before it is incorporated into the main chain of the polymer.
^{The molecular chains that can be taken as RP1} and ^RP2 are not particularly limited, but are preferably a hydrocarbon chain, a polyalkylene oxide chain, a polycarbonate chain or a polyester chain, more preferably a hydrocarbon chain or a polyalkylene oxide chain, and a hydrocarbon chain. , Polyethylene oxide chains or polytetramethylene oxide chains are more preferred.

The ^{hydrocarbon chain that can be taken as RP1} and ^RP2 means a chain of hydrocarbons composed of carbon atoms and hydrogen atoms, and more specifically, at least two compounds composed of carbon atoms and hydrogen atoms. It means a structure in which an atom (for example, a hydrogen atom) or a group (for example, a methyl group) is eliminated. However, in the present invention, the hydrocarbon chain also includes a chain having a group containing an oxygen atom, a sulfur atom or a nitrogen atom in the chain, for example, a hydrocarbon group represented by the following formula (M2). The terminal group that can be contained at the end of the hydrocarbon chain shall not be included in the hydrocarbon chain. This hydrocarbon chain may have a carbon-carbon unsaturated bond and may have a ring structure of an aliphatic ring and / or an aromatic ring. That is, the hydrocarbon chain may be any hydrocarbon chain composed of hydrocarbons selected from aliphatic hydrocarbons and aromatic hydrocarbons.

Such a hydrocarbon chain may be any one that satisfies the above molecular weight, and both a chain composed of a low molecular weight hydrocarbon group and a hydrocarbon chain composed of a hydrocarbon polymer (also referred to as a hydrocarbon polymer chain). Includes hydrocarbon chains.
A low molecular weight hydrocarbon chain is a chain composed of ordinary (non-polymerizable) hydrocarbon groups, and examples of the hydrocarbon groups include aliphatic or aromatic hydrocarbon groups, and specific examples thereof. Is an alkylene group (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, further preferably 1 to 3 carbon atoms), an arylene group (preferably 6 to 22 carbon atoms, preferably 6 to 14 carbon atoms, 6 to 10 carbon atoms). Is more preferable), or a group consisting of a combination thereof is preferable. The hydrocarbon group forming the hydrocarbon chain of the low molecular weight that can be taken as R ^P2, and more preferably an alkylene group, more preferably an alkylene group having 2 to 6 carbon atoms, particularly preferably an alkylene group having 2 or 3 carbon atoms. This hydrocarbon chain may have a polymerized chain (eg, (meth) acrylic polymer) as a substituent.

The aliphatic hydrocarbon group is not particularly limited, and for example, from a hydrogen-reduced product of an aromatic hydrocarbon group represented by the following formula (M2), or a partial structure of a known aliphatic diisosoane compound (for example, from isophorone). Narumoto) and the like. In addition, the hydrocarbon group contained in each of the constituent components of each of the examples described later can also be mentioned.
Examples of the aromatic hydrocarbon group include a hydrocarbon group contained in each of the constituent components described below, and an arylene group (for example, one or more hydrogen atoms from the aryl group mentioned in Substituent Z described later). The removed group, specifically a phenylene group, a trilene group or a xylylene group) or a hydrocarbon group represented by the following formula (M2) is preferable.

In formula (M2), X represents a single bond, -CH _2- , -C (CH ₃ ) _2- , -SO _2- , -S-, -CO- or -O-, and is a viewpoint of binding property. Therefore, -CH _2- or -O- is preferable, and -CH _2- is more preferable. The above-mentioned alkylene group and methyl group exemplified here may be substituted with a substituent Z, for example, a halogen atom (excluding a fluorine atom), respectively.
^RM2 to ^RM5 each represent a hydrogen atom or a substituent, and a hydrogen atom is preferable. The ^{substituents that can be taken as RM2} to ^RM5 are not particularly limited, and examples thereof include a substituent Z described later. For example, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, and -OR ^M6. , -N ( ^RM6 ) ₂ , -SR ^M6 ( ^RM6 represents a substituent, preferably an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 10 carbon atoms), a halogen excluding a fluorine atom. Atoms (eg, chlorine atoms, bromine atoms) are preferred. The −N ( ^RM6 ) ₂ is an alkylamino group (preferably 1 to 20 carbon atoms, more preferably 1 to 6 carbon atoms) or an arylamino group (preferably 6 to 40 carbon atoms, 6 to 20 carbon atoms). More preferred).

A hydrocarbon polymer chain may be a polymer chain in which (at least two) polymerizable hydrocarbons are polymerized, and may be a chain composed of a hydrocarbon polymer having a larger number of carbon atoms than the above-mentioned low molecular weight hydrocarbon chain. The chain is not particularly limited, but is preferably a chain composed of a hydrocarbon polymer composed of 30 or more, more preferably 50 or more carbon atoms. The upper limit of the number of carbon atoms constituting the hydrocarbon polymer is not particularly limited, and may be, for example, 3,000. The hydrocarbon polymer chain is preferably a chain composed of an aliphatic hydrocarbon having a main chain satisfying the above number of carbon atoms, and is composed of an aliphatic saturated hydrocarbon or an aliphatic unsaturated hydrocarbon. It is more preferable that the chain is made of a polymer (preferably an elastomer). Specific examples of the polymer include a diene polymer having a double bond in the main chain and a non-diene polymer having no double bond in the main chain. Examples of the diene polymer include a styrene-butadiene polymer, a styrene-ethylene-butadiene copolymer, a copolymer of isobutylene and isoprene (preferably butyl rubber (IIR)), a butadiene polymer, an isoprene polymer, and ethylene. -Propylene-diene copolymer and the like can be mentioned. Examples of the non-diene polymer include olefin polymers such as ethylene-propylene copolymer and styrene-ethylene-butylene copolymer, and hydrogen-reduced products of the above-mentioned diene polymer.

The hydrocarbon to be a hydrocarbon chain preferably has a reactive group at its terminal, and more preferably has a polycondensable terminal reactive group. The polycondensation or polyaddition-capable terminal reactive group forms a group bonded to ^RP1 or ^RP2 of each of the above formulas by polycondensation or polyaddition. Examples of such a terminal reactive group include an isocinate group, a hydroxy group, a carboxy group, an amino group and an acid anhydride, and a hydroxy group is preferable.
Examples of hydrocarbon polymers having terminal reactive groups include NISSO-PB series (manufactured by Nippon Soda Co., Ltd.), clay sole series (manufactured by Tomoe Kosan Co., Ltd.), and PolyVEST-HT series (manufactured by Ebonic) under the trade names. , Poly-bd series (manufactured by Idemitsu Kosan Co., Ltd.), poly-ip series (manufactured by Idemitsu Kosan Co., Ltd.), EPOL (manufactured by Idemitsu Kosan Co., Ltd.), Polytail series (manufactured by Mitsubishi Chemical Co., Ltd.) and the like are preferably used.

Examples of the polyalkylene oxide chain (polyalkyleneoxy chain) include chains composed of known polyalkyleneoxy groups. The number of carbon atoms of the alkyleneoxy group in the polyalkyleneoxy chain is preferably 1 to 10, more preferably 1 to 6, and 2 to 4 (polyethylene oxy chain, polypropylene oxy chain, polytetra). Methyleneoxy chain) is more preferred. The polyalkyleneoxy chain may be a chain composed of one type of alkyleneoxy group or a chain composed of two or more types of alkyleneoxy groups (for example, a chain composed of an ethyleneoxy group and a propyleneoxy group).
Examples of the polycarbonate chain or polyester chain include known chains made of polycarbonate or polyester.
The polyalkyleneoxy chain, the polycarbonate chain, or the polyester chain each preferably has an alkyl group (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms) at the terminal.
Polyalkyleneoxy chain can be taken as R ^P1 and R ^P2, end of the polycarbonate chain and a polyester chain, appropriately changing the constituents as R ^P1 and R ^P2 are represented by the formulas above the embeddable ordinary chemical structure be able to. For example, the polyalkylene oxy chain is incorporated as ^RP1 or ^RP2 of the above-mentioned constituents by removing the terminal oxygen atom.

An ether group (-O-), a thioether group (-S-), a carbonyl group (> C = O), an imino group (> NR ^N : ^RN is a hydrogen atom, and RN are hydrogen atoms, inside or at the end of the alkyl group contained in the molecular chain. It may have an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 10 carbon atoms).
In each of the above formulas, ^RP1 and ^RP2 are preferably divalent molecular chains, but at least one hydrogen atom is substituted with -NH-CO-, -CO-, -O-, -NH-, or the like. It may be a branched molecular chain having a valence of 3 or more.

R ^P1, among the molecular chain is preferably a hydrocarbon is a chain, more preferably a hydrocarbon chain of low molecular weight, more preferably a hydrocarbon chain comprised of hydrocarbon groups aliphatic or aromatic, Hydrocarbon chains consisting of aromatic hydrocarbon groups are particularly preferred.
^{Among the above molecular chains, RP2} is preferably a low molecular weight hydrocarbon chain (more preferably an aliphatic hydrocarbon group) or a molecular chain other than a low molecular weight hydrocarbon chain, and is other than a low molecular weight hydrocarbon chain. Molecular chains (more preferably polyalkylene oxide chains) are more preferred.

Specific examples of the constituent components represented by the above formula (I-1) are shown in the following and Examples. Further, as the raw material compound (diisocyanate compound) for deriving the constituent component represented by the above formula (I-1), for example, the diisocyanate compound represented by the formula (M1) described in International Publication No. 2018/20827 and the diisocyanate compound represented by the formula (M1). Specific examples thereof include polypeptide 4,4'-diphenylmethane diisocyanate and the like. In the present invention, the constituent component represented by the formula (I-1) and the raw material compound derived from the constituent component are not limited to those described in the following specific examples, examples and the above documents.

The raw material compound (carboxylic acid or acid chloride thereof, etc.) that derives the constituents represented by the above formula (I-2) is not particularly limited, and is described in, for example, paragraph [0074] of International Publication No. 2018/020827. , Carboxylic acid or acid chloride compounds and specific examples thereof (eg, adipic acid or an esterified product thereof).

Specific examples of the constituents represented by the above formula (I-3) or the formula (I-4) are shown below in the exemplary polymers and examples described later. Further, the raw material compound (diol compound or diamine compound) for deriving the constituent component represented by the above formula (I-3) or formula (I-4) is not particularly limited, and for example, International Publication No. 2018 / Examples of each compound described in No. 020827 and specific examples thereof are given, and dihydroxyoxamid is also mentioned. In the present invention, the constituent components represented by the formula (I-3) or the formula (I-4) and the raw material compounds derived thereto are not limited to those described in the following specific examples, examples and the above documents.
In the following specific example, when the constituent has a repeating structure, the number of repetitions is an integer of 1 or more, and is appropriately set within a range satisfying the molecular weight or the number of carbon atoms of the molecular chain.

^RP1 and ^RP2 may each have a substituent. Examples of the substituent group is not particularly limited, for example, include substituents Z to be described later, the substituents which can take as R ^M2 are preferably exemplified. Incidentally, atoms a atoms constituting R ^P1 and R ^P2 also constitute backbone no fluorine atom as a substituent.

As shown below, the binder-forming polymer is represented by the above formula (I-3) or formula (I-4) in addition to the constituent components represented by the formula (I-1) or the formula (I-2). It is preferable to have a constituent component represented by the formula (I-3), and more preferably to have a constituent component represented by the formula (I-3). The components represented by the formula (I-3) include a component in which ^RP2 is a chain composed of a low molecular weight hydrocarbon group (preferably a component represented by the following formula (I-3A)). A ^{component in which RP2} is the above-mentioned hydrocarbon polymer chain as a molecular chain (preferably a component represented by the following formula (I-3C)) and a component in which ^RP2 is the above-mentioned polyalkylene oxide chain as a molecular chain. It is preferable to have at least one of (preferably a constituent component represented by the following formula (I-3B)), and the constituent component in which ^RP2 is the above-mentioned hydrocarbon polymer chain as a molecular chain and R ^{It is more preferable that P2} has at least one of the constituent components which is the polyalkylene oxide chain as a molecular chain, and it is further preferable that P2 has both constituent components. The components represented by the formula (I-4) are the same as the components represented by the formula (I-3), but in each of the following formulas (I-3A) to (I-3C). Replace oxygen atom with nitrogen atom.

In formula (I-1), ^RP1 is as described above. In formula (I-3A), ^RP2A represents a chain of low molecular weight hydrocarbon groups (preferably an aliphatic hydrocarbon group). In formula (I-3B), ^RP2B represents a polyalkyleneoxy chain. In formula (I-3C), ^RP2C represents a hydrocarbon polymer chain. Chain composed of a hydrocarbon group of low molecular weight that can be taken as R ^{^P2A,} hydrocarbon polymer chain which can be taken as a polyalkyleneoxy chain and ^{R P2C} can take as ^{R P2B} are respectively taken as ^{R P2} in the above formula (I-3) It is synonymous with the aliphatic hydrocarbon groups, polyalkyleneoxy chains and hydrocarbon polymer chains, and the preferred ones are also the same.

The binder-forming polymer preferably has a component containing a polyether structure, for example, a component represented by the above formula (I-3B) in the main chain. Of these, those having at least two types of polyether structures in the main chain are more preferable. When the above-mentioned functional group-containing constituents are incorporated into a polymer having at least two types of polyether structures in the main chain, the action of the polyether structure and the functional group-containing constituents is synergistically expressed, resulting in dispersion stability and a film. Strength and battery performance (resistance and cycle characteristics) can be improved at a high level in a well-balanced manner.
In the present invention, the "polyether structure" refers to a structure in which two or more alkyleneoxy groups are linked (also referred to as a polyalkyleneoxy chain or an alkylene oxide chain), for example,-(O-alkylene group) n-. The structure (n indicates the degree of polymerization and is a number of 2 or more) is shown.
This "polyether structure" may be a single polyalkyleneoxy chain or a structure derived from a copolymer of at least two polyalkyleneoxy chains (having different chemical structures). In the present invention, it is preferably a single polyalkyleneoxy chain.
The "polyether structure" is optionally incorporated into the backbone of the polymer via atoms or linking groups. The atom and the linking group at this time have the same meaning as those listed with X in the formula (I-7) described later.
The constituent component containing the polyether structure is not particularly limited, and examples thereof include a constituent component derived from a polyether polyol such as polyalkylene glycol and a constituent component derived from a polyether polyamine or the like.

In the present invention, "at least two kinds" of the polyether structure means a polyether having a chemical structure (alkylene groups) different from each other regardless of the difference in the constituent components forming the main chain and the position incorporated in the main chain. It means that the number of types of structures is at least two, and even if a polyether structure having the same chemical structure is incorporated into different constituent components or a plurality of types are incorporated into one constituent component, 1 Seed.
The number of types of the polyether structure contained in the binder-forming polymer is preferably two or more, more preferably two or three, and even more preferably two.

Alkyleneoxy group forming a polyether structure is not particularly limited, and for example include polyalkylene oxide chain can take as the R ^P2, it is preferred that the number of carbon atoms in the alkylene group of the alkylene group is 1 to 6 It is more preferably 2 to 4.
The combination of the polyether structures is not particularly limited, but at least two types of polyether structures selected from the polyethylene oxy chain, the polypropylene oxy chain and the polytetramethylene oxy chain are preferable. A combination containing a polyethylene oxy chain and a polypropylene oxy chain or a polytetramethylene oxy chain is more preferable, and a combination containing a polyethylene oxy chain and a polytetramethylene oxy chain is further preferable.

The (number average) molecular weight of each of the at least two types of polyether structures is not particularly limited, but is preferably 400 or less, more preferably 350 or less, further preferably 300 or less, and more preferably 250 or less. It is particularly preferable to have. The lower limit of the (number average) molecular weight is not particularly limited, but is actually preferably 100 or more, and more preferably 150 or more. In the present invention, the (number average) molecular weight of at least two types of polyether structures means the sum of the products of the (number average) molecular weight of each polyether structure and the mole fraction. The (number average) molecular weight of each polyether structure is not particularly limited, but is preferably set appropriately within a range satisfying the above-mentioned "number average molecular weight of at least two types of polyether structures". The (number average) molecular weight of each polyether structure is determined by a compound (usually a hydrogen atom bonded to each end) that leads to a component containing the polyether structure (rather than being incorporated into the main chain) by the method described below. It is a value measured for a compound (for example, a polyether polyol described later).
Further, the degree of polymerization of each polyether structure is not particularly limited as long as it is 2 or more, and it is preferable that the degree of polymerization is appropriately set within a range satisfying the above-mentioned "number average molecular weight of each polyether structure". The degree of polymerization depends on the number of carbon atoms of the alkyleneoxy group and the like, but is preferably 2 to 10, more preferably 3 to 8, and even more preferably 2 to 5.

Examples of the constituent component containing the polyether structure include the constituent component represented by the following formula (I-7).

In the formula, X represents a group containing a single bond, an oxygen atom or a nitrogen atom, or a linking group, and ^RP4A ^{and RP4B} represent alkylene groups different from each other. n1 and n2 indicate the degree of polymerization.
X is appropriately selected according to the terminal group of the alkyleneoxy chain in the above formula. For example, when the end of the alkyleneoxy group is an oxygen atom, it becomes a group containing a single bond or a linking group, and when the end of the alkyleneoxy group is an alkylene group, it becomes a group containing an oxygen atom or a nitrogen atom or a linking group. Examples of the group containing a linking group that can be taken as X include a group consisting of a linking group and a group in which a linking group and an oxygen atom or a nitrogen atom are combined. The linking group is not particularly limited, and examples thereof include a group obtained by further removing one hydrogen atom from each group listed in the substituent Z, and preferably an alkylene group which can be taken as ^RP4A or ^RP4B. .. The two Xs in the constituents represented by the above formula (I-7) may be the same or different.

The ^{alkylene group that can be taken as RP4A} and ^RP4B is not particularly limited, but is synonymous with the above-mentioned alkylene group in the alkyleneoxy group forming the polyether structure, and the preferred one is also the same. The combination of R ^P4A and R ^P4B is synonymous with the combination described in the above-mentioned combination of polyether structures, and the preferred one is also the same.

n1 and n2 indicate the degree of polymerization, respectively, n1 is a number of 2 or more, n2 is a number of 0 or more than 1, and can be a number of 2 or more.
When n2 is 0, the component represented by the formula (I-7) is a component containing a single polyalkyleneoxy chain. In this form, the main chain of the binder-forming polymer has at least two different constituents represented by the above formula (I-7), preferably two or three types, and more preferably two types. .. In this form, the constituent component represented by the formula (I-7) is preferably a constituent component derived from at least two kinds selected from polyethylene glycol, polypropylene glycol and polytetramethylene ether glycol. Further, it may have a constituent component represented by the formula (I-7) in which n2 is a number exceeding 1.
In this embodiment, the (number average) molecular weight of two or more different constituents represented by the formula (I-7) and the (number average) molecular weight of each constituent are the above-mentioned at least two types of polyether structures, respectively. It is synonymous with the (number average) molecular weight of, and the preferred range is also the same. Further, n1 in two or more different constituents represented by the formula (I-7) is appropriately set within a range satisfying the (number average) molecular weight, and has the same meaning as the degree of polymerization of the above-mentioned polyether structure. And the preferred range is the same.

When n2 is a number exceeding 1, the constituent component represented by the formula (I-7) is a constituent component containing a copolymer of two types of polyalkyleneoxy chains. The bonding mode of the two polyalkyleneoxy chains in the copolymer is not particularly limited, and may be a random bond, a block bond, or an alternating bond. In this form, the main chain of the binder-forming polymer may have at least one kind of constituent components represented by the above formula (I-7), and preferably one kind. In this form, examples of the constituent component represented by the formula (I-7) include a constituent component composed of a polyethylene oxy chain and a copolymer of a polypropylene oxy chain.
The (number average) molecular weight of the constituents represented by the formula (I-7) is synonymous with the (number average) molecular weight of at least two of the above-mentioned polyether structures, and the preferable range is also the same. Further, the (number average) molecular weights of the two polyalkyleneoxy chains are synonymous with the (number average) molecular weights of the above-mentioned respective polyether structures, and the preferable ranges are also the same. When having a plurality of the same polyalkyleneoxy chains, the (number average) molecular weight of the polyalkyleneoxy chains shall be the total molecular weight. Further, n1 and n2 are appropriately set within a range satisfying the (number average) molecular weight, respectively, and have the same meaning as the degree of polymerization of the above-mentioned polyether structure, and the preferable range is also the same.

The above formula (I-7) defines a component containing two types of polyether structures (alkyleneoxy chains), but in the present invention, the component containing a polyether structure, the above formula (I-7), is used. The constituent component represented may contain three or more types of polyether structures.

Specific examples of the constituents represented by the above formula (I-7) are shown below, but the present invention is not limited thereto. In the following specific example, the degree of polymerization of the alkyleneoxy group is omitted, but it is set within the above range.

-Components having functional groups selected from the functional group group-
The binder-forming polymer contains a component having at least one functional group selected from the above-mentioned functional group group (sometimes referred to as a functional group-containing component). Since the binder-forming polymer used in the inorganic solid electrolyte-containing composition satisfies the above-mentioned (P1) and contains a functional group-containing component (P2), only the improvement of the dispersion stability of the inorganic solid electrolyte-containing composition is achieved. In addition, the film strength can be strengthened, and the battery resistance and cycle characteristics can also be improved. The number of functional group-containing constituent components contained in the binder-forming polymer is not particularly limited as long as it is one or more, and may be, for example, 1 to 4, preferably 1 to 2.

The functional group contained in the functional group-containing constituent component is a functional group selected from the following functional group group.

<Functional group group>
Hydroxy group, primary amino group, secondary amino group, sulfanilic group (mercapto group: -SH)

The hydroxyl group (−OH) includes an alcoholic hydroxyl group and a phenolic hydroxyl group, and an alcoholic hydroxyl group is preferable. The primary amino group means an unsubstituted amino group (-NH ₂ ), and the secondary amino group is a monosubstituted amino group (-NRH: R represents a substituent) or an unsubstituted imino group (-NH-, but wherever , = NH is excluded.), And an unsubstituted imino group is preferable. As the amino group, a primary amino group is preferable to a secondary amino group. The hydroxyl group, each amino group and the sulfanilic group may form a salt.
Each functional group means a group represented by the above chemical formula alone, and does not include an embodiment having a partial structure contained in a part of other functional groups. For example, a carboxy group (-CO-OH) is formed by containing a carbonyl group and a hydroxyl group, but the hydroxyl group forming the carboxy group is not interpreted as a hydroxyl group contained in the functional group group.

The functional groups selected from the above functional groups are all functional groups containing active hydrogen and exhibit a common action. That is, when these functional groups are present in the composition containing the inorganic solid electrolyte in a state of being incorporated in the binder used in the present invention, they are appropriate for solid particles such as the inorganic solid electrolyte (reaggregation with respect to the solid particles). (To the extent that it does not adsorb excessively enough to precipitate). In addition, in the constituent layers, the interaction is such that solid particles are bound to each other.
The functional group exhibiting the above-mentioned common action can be defined by, for example, the negative common logarithm of the acid dissociation constant (Ka): -logKa (pKa), and the pKa is preferably in the range of 1 to 20. The range of ~ 16 is more preferable. pKa can be calculated by dropping a 0.01 mL / L sodium hydroxide aqueous solution with respect to the polymer binder aqueous solution and reading the amount of the sodium hydroxide aqueous solution dropped up to the half equivalence point.

The functional group selected from the functional group group is preferably a hydroxyl group, a primary amino group or a secondary amino group, and more preferably a hydroxyl group or a primary amino group in terms of adsorptivity to solid particles, particularly an inorganic solid electrolyte or an active material. Preferably, hydroxyl groups are even more preferred.

The functional group means a group introduced into a constituent component of a binder-forming polymer, and specifically, a group incorporated between atoms forming a main chain, and further, an atom forming a main chain. Means a group attached directly to, preferably via a linking group. That is, the functional group does not include the group forming each bond specified in (P1-2) above (for example, the imino group in the urethane bond or the urea bond: -NH-), and the end of the main chain. Does not include the terminal functional groups present in.

The number of types of the functional groups contained in one functional group-containing component is not particularly limited, and is preferably one or two. Further, the number of the functional groups contained in one functional group-containing component may be at least one, and may be, for example, one to four. The number of functional groups in one functional group-containing component can be determined in consideration of the content of the functional group-containing component in the polymer, which will be described later, but the dispersion stability of the inorganic solid electrolyte-containing composition In this respect, it is preferably two or more, and more preferably two. When one functional group-containing constituent has two or more functional groups, it is preferable that at least one functional group is a hydroxyl group, one functional group is a hydroxyl group, and the other functional group is a primary amino group. Alternatively, it is more preferably a hydroxyl group, and it is further preferable that all functional groups are hydroxyl groups.
The average number of functional groups contained in the entire binder-forming polymer of one molecule is not particularly limited as long as the effects of the present invention are not impaired, and the number of functional groups in one functional group-containing constituent component and this functional group are not particularly limited. It is appropriately determined in consideration of the content of the group-containing constituent component in the polymer.

The functional group-containing constituent component is not particularly limited as long as it is a constituent component having the above functional group, and is coexisting with a compound that derives a constituent component represented by any of the above formulas (I-1) to (I-4). Examples thereof include constituent components derived from a compound in which the above functional group is introduced into a polymerizable compound.
The functional group-containing constituent component may be a high molecular weight component (for example, a component derived from a macromonomer), or may contain a polymerized chain in the chemical structure. In the present invention, the functional group-containing component is, for example, a component derived from a low molecular weight compound having a molecular weight of 400 or less (low molecular weight component), or a component that does not contain a polymer chain in its chemical structure (non-polymerizable component). ) Is preferable in terms of molecular compound, film strength and battery performance.
For example, a component in which the above functional group is introduced into a component represented by any of the above formulas (1-1) to (1-4) can be mentioned, and the components represented by the above formulas (1-1) to (1-4) can be mentioned. 4) In the constituent components in which the above functional group (preferably a hydroxyl group or a primary amino group) is introduced into ^RP1 and ^RP2 directly or via a linking group, and in the structure of ^RP1 and ^{RP2 of each formula.} A constituent component (for example, constituent component A-7 described later) incorporating the above functional group (preferably an unsubstituted imino group) and the like are preferably mentioned.

The linking group is not particularly limited, but is, for example, an alkylene group (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms), an alkenylene group (2 to 6 carbon atoms is preferable). and more preferably from 2-3), an arylene group (number of carbon atoms is preferably 6 to 24, more preferably 6 to 10), an oxygen atom, a sulfur atom, an imino group ^(-NR ^N -: ^R N is hydrogen, An alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 10 carbon atoms is shown), 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 a combination thereof and the like can be mentioned. A polyalkyleneoxy chain can also be formed by combining an alkylene group and an oxygen atom. As the linking group, an alkylene group or an arylene group, or a group consisting of a combination of an alkylene group, an arylene group, a carbonyl group, an oxygen atom, a sulfur atom and an imino group is preferable, and an alkylene group, an alkylene group, an arylene group, or a carbonyl group is preferable. group, more preferably comprising a combination of an oxygen atom and an imino group group, an alkylene group, or, ^{-CO-O-group, -CO-N (R N)} - based on ^{(R N} are as defined above.) more preferably a group containing, -CO-O-alkylene - or ^{-CO-N (R} N) - alkylene - group (. ^{R N} are as defined above) are particularly preferred.
In the present ^invention, the number of atoms constituting the linking group which links the closest functional group with respect to ^{R P1} and ^{R P2} constituting atom and ^{R P1} and ^{R P2} is preferably 1 to 36, 1 It is more preferably to 24, and even more preferably 1 to 12. The number of connecting atoms of the linking group is preferably 10 or less, more preferably 8 or less. The lower limit is 1 or more. The number of connected atoms is the minimum number of atoms connecting a predetermined structural part. For example, in the case of -C (= O) -O-CH _2- , the number of atoms constituting the linking group is 6, but the number of linking atoms is 3.
The linking group may or may not have a substituent. Examples of the substituent which may be possessed include a substituent Z, and a group other than the functional group selected from the above functional group group is preferable.

The constituent component into which the functional group is introduced is preferably the constituent component represented by the formula (I-3) or the formula (I-4) among the above-mentioned formulas (1-1) to (1-4). , Among the constituents represented by the formula (I-3), the constituents represented by the above formula (I-3A) are more preferable.

As the partial structure (side chain) of the functional group-containing constituent component composed of the linking group and the functional group, the partial structure represented by the following formula (F1) has the dispersion stability, film strength and battery performance. It is preferable in terms of balance. This partial structure may be a structure composed of a polymerized chain or a structure containing a polymerized chain, such as a graft polymerized chain for the main chain of a polymer, but a structure not containing the polymerized chain is preferable.

In the formula (F1), L ¹ and L ² each indicate a linking group and are synonymous with the above linking group. However, L ¹ is preferably a —CO— group, L ² is preferably an alkylene group, and for example, the partial structure represented by the formula (F1) is preferably an alkylosikicarbonyl group.
R ¹ represents a hydroxyl group or a primary or secondary amino group, which is synonymous with the corresponding group contained in the functional group group. As R ¹ , a hydroxyl group or a primary amino group is preferable, and a hydroxyl group is more preferable.
R ² indicates a substituent. The ^{substituent that can be taken as R 2} is not particularly limited, but preferably, each group selected from the following substituent Z, or a group combining a plurality of groups selected from the substituent Z can be mentioned. The group selected from the following substituent Z is not particularly limited, but an alkyl group, an aryl group, a heterocyclic group, or each functional group contained in the above functional group group is preferable. The combined group is not particularly limited, but at least one is preferably a functional group selected from the above functional group group, and an alkyl group, an aryl group or a heterocyclic group selected from the substituent Z and a functional group. A group in combination with (an alkyl group having a functional group, an aryl group having a functional group or a heterocyclic group having a functional group) is more preferable, and a group in which an alkyl group and a functional group are combined is further preferable.

As a partial structure composed of the linking group and the functional group contained in the functional group-containing constituent component, the partial structure represented by the following formula (F2) has a balance of dispersion stability, film strength and battery performance. , More preferred.

In the formula (F2), L ¹ represents a linking group, ^{which is synonymous with L 1 in the} above formula (F1), and the preferred one is also the same.
R ³ represents a substituent and is synonymous with ^{R 2 in the} formula (F1) except that it has a carbon atom (methylene group) between it and the carbon atom to which ^{R 1} in the above formula (F1) is bonded. Yes, and the preferred ones are the same.

The binder-forming polymer may contain only one type of functional group-containing constituent component, and may contain two or more types. When two or more kinds of functional group-containing constituents are contained, each functional group-containing constituent may have a different chemical structure. For example, a functional group-containing constituent having one functional group and two or more functionals It can include a functional group-containing constituent having a group.

Specific examples of the functional group-containing constituents include the constituents contained in the binder-forming polymer described later and the constituents A-1 to A-8 contained in the binder-forming polymer synthesized in the examples.

(Other components)
The polymer forming the binder used in the present invention may have a constituent component other than the constituent component represented by any of the above formulas (I-1) to (I-4) and the constituent component having a functional group. good. Such a constituent component is not particularly limited as long as it can be sequentially polymerized with the raw material compound that derives the constituent component represented by each of the above formulas.

The (total) content of the constituents represented by any of the above formulas (I-1) to (I-4) in the binder-forming polymer is not particularly limited, but may be 5 to 95 mol%. It is preferably 5 to 80 mol%, more preferably 10 to 60 mol%.
The content of the component having a functional group in the binder-forming polymer shall be 0.01 to 50 mol% in terms of improvement of dispersion stability, enhancement of film strength, improvement of battery resistance and cycle characteristics. Is preferable, 0.05 to 30 mol% is more preferable, and 0.1 to 20 mol% is further preferable.
The content of the other constituent components in the binder-forming polymer is not particularly limited, and can be, for example, 50% by mass or less.

The content of each component represented by any of the above formulas (I-1) to (I-4) in the binder-forming polymer is not particularly limited, but the binder-forming polymer must satisfy the above (total) content. Preferably, for example, it can be set in the following range.
That is, the content of each of the components represented by the formula (I-1) or the formula (I-2) in the binder-forming polymer is not particularly limited and is preferably 10 to 50 mol%, 20 It is more preferably to 50 mol%, further preferably 30 to 50 mol%.
The content of each component represented by the formula (I-3) or the formula (I-4) in the binder-forming polymer is not particularly limited and is preferably 0 to 50 mol%, preferably 5 to 45. It is more preferably mol%, and even more preferably 10 to 45 mol%.

Among the components represented by the formula (I-3) or the formula (I-4), the component in which ^RP2 is a chain composed of a low molecular weight hydrocarbon group (for example, represented by the above formula (I-3A)). The content of each of the constituent components in the binder-forming polymer is not particularly limited, and is, for example, preferably 0 to 50 mol%, more preferably 1 to 30 mol%, and 2 to 20 mol%. It is more preferably%, and even more preferably 4 to 25 mol%.
Among the components represented by the formula (I-3) or the formula (I-4), the component in which ^RP2 is the polyalkyleneoxy chain as a molecular chain (for example, represented by the above formula (I-3B)). The content of each of the constituents) in the binder-forming polymer is not particularly limited, and is, for example, preferably 0 to 50 mol%, more preferably 5 to 45 mol%, and 10 to 43 mol%. Is more preferable.
Among the components represented by the formula (I-3) or the formula (I-4), the component in which ^RP2 is the hydrocarbon polymer chain as a molecular chain (for example, represented by the above formula (I-3C)). The content of each of the constituents) in the binder-forming polymer is not particularly limited, but is preferably, for example, 0 to 50 mol%, more preferably 1 to 45 mol%, and 3 to 40 mol%. It is even more preferably 3 to 30 mol%, particularly preferably 3 to 20 mol%, and most preferably 3 to 10 mol%.

The (total) content of the component represented by the formula (I-7) in the binder-forming polymer is not particularly limited, but is set to the content of the component represented by the above formula (I-3B). NS.
When the binder-forming polymer has a plurality of different constituent components represented by the formula (I-7), the content of each constituent component is appropriately determined within a range satisfying the above (total) content. For example, when it has two different constituents represented by the formula (I-7), the content of one constituent (preferably a constituent having a polyether structure formed of an alkyleneoxy group having a large molecular weight). Is, for example, preferably 5 to 30 mol%, more preferably 10 to 25 mol%, and even more preferably 15 to 20 mol%. The content of the other component (preferably a component having a polyether structure formed of an alkyleneoxy group having a small molecular weight) is preferably, for example, 10 to 50 mol%, preferably 15 to 40 mol%. It is more preferably present, and further preferably 20 to 30 mol%. The ratio of the content of one component to the other component [one component: the other component] is not particularly limited, but is preferably, for example, 10:90 to 80:20. It is more preferably 20:80 to 70:30.
On the other hand, when polyurethane has three or more different constituents represented by the formula (I-7), a constituent having a polyether structure formed of an alkyleneoxy group having the smallest molecular weight is used as the other constituent. The other constituents are one of the above constituents.

When the binder-forming polymer has a plurality of constituent components represented by each formula, the above-mentioned content of each constituent component shall be the total content.

The binder-forming polymer (each constituent component and raw material compound) may have a substituent. The substituent is not particularly limited, but is preferably a group selected from the following substituent Z (however, each functional group included in the above-mentioned functional group group is excluded. The atom forming the main chain of the polymer is fluorine. Atoms are excluded.), Preferably, a carboxy group, a sulfo group, a phosphate group, a phosphonic acid group, a heterocyclic group, an aryl group, an alkoxysilyl group, a (meth) acryloyloxy group, and a condensed ring having three or more rings. Examples thereof include a group having a structure, or a functional group other than a group containing an ether bond, an ester bond, an amide bond, a urethane bond, and a urea bond.

-Substituent Z-
Alkyl groups (preferably alkyl groups having 1 to 20 carbon atoms, such as methyl, ethyl, isopropyl, t-butyl, pentyl, heptyl, 1-ethylpentyl, benzyl, 2-ethoxyethyl, 1-carboxymethyl, etc.), alkenyl groups. (Preferably an alkenyl group having 2 to 20 carbon atoms, for example, vinyl, allyl, oleyl, etc.), an alkynyl group (preferably an alkynyl group having 2 to 20 carbon atoms, for example, ethynyl, butadynyl, phenylethynyl, etc.), a cycloalkyl group. (Preferably, a cycloalkyl group having 3 to 20 carbon atoms, for example, cyclopropyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, etc., is usually used in the present specification to include a cycloalkyl group. An aryl group (preferably an aryl group having 6 to 26 carbon atoms, for example, phenyl, 1-naphthyl, 4-methoxyphenyl, 2-chlorophenyl, 3-methylphenyl, etc.), an aralkyl group (preferably having 7 carbon atoms). ~ 23 aralkyl groups (eg, benzyl, phenethyl, etc.), heterocyclic groups (preferably heterocyclic groups having 2 to 20 carbon atoms, more preferably 5 or 5 having at least one oxygen atom, sulfur atom, nitrogen atom. It is a 6-membered heterocyclic group. The heterocyclic group includes an aromatic heterocyclic group and an aliphatic heterocyclic group. For example, a tetrahydropyran ring group, a tetrahydrofuran ring group, 2-pyridyl, 4-pyridyl, 2-. Imidazolyl, 2-benzoimidazolyl, 2-thiazolyl, 2-oxazolyl, pyrrolidone group, etc.), alkoxy group (preferably alkoxy group having 1 to 20 carbon atoms, for example, methoxy, ethoxy, isopropyloxy, benzyloxy, etc.), aryloxy group (Preferably, an aryloxy group having 6 to 26 carbon atoms, for example, phenoxy, 1-naphthyloxy, 3-methylphenoxy, 4-methoxyphenoxy, etc., is used in the present specification to include an aryloxy group. There is), a heterocyclic oxy group (a group in which an —O— group is bonded to the heterocyclic group), an alkoxycarbonyl group (preferably an alkoxycarbonyl group having 2 to 20 carbon atoms, for example, ethoxycarbonyl, 2-ethylhexyloxycarbonyl). , Dodecyloxycarbonyl, etc.), aryloxycarbonyl groups (preferably aryloxycarbonyl groups with 6 to 26 carbon atoms, such as phenoxycarbonyl, 1-naphthyloxycarbonyl, 3-me Thiruphenoxycarbonyl, 4-methoxyphenoxycarbonyl, etc.), heterocyclic oxycarbonyl group (group in which -O-CO- group is bonded to the above heterocyclic group), amino group (preferably amino group having 0 to 20 carbon atoms, alkyl It contains an amino group and an arylamino group, for example, amino (-NH ₂ ), N, N-dimethylamino, N, N-diethylamino, N-ethylamino, anirino, etc.), sulfamoyl group (preferably 0 to 20 carbon atoms). Sulfamoyl group of, for example, N, N-dimethylsulfamoyl, N-phenylsulfamoyl, etc.), acyl group (alkylcarbonyl group, alkenylcarbonyl group, alkynylcarbonyl group, arylcarbonyl group, heterocyclic carbonyl group, etc. Preferably, an acyl group having 1 to 20 carbon atoms, for example, acetyl, propionyl, butyryl, octanoyl, hexadecanoyl, acryloyl, methacryloyl, crotonoyle, benzoyl, naphthoyl, nicotinoyle, etc., and an acyloxy group (alkylcarbonyloxy group, alkenylcarbonyloxy). A group, an alkynylcarbonyloxy group, an arylcarbonyloxy group, a heterocyclic carbonyloxy group, preferably an acyloxy group having 1 to 20 carbon atoms, for example, acetyloxy, propionyloxy, butyryloxy, octanoyloxy, hexadecanoyloxy, Acryloyloxy, methacryloyloxy, crotonoyloxy, benzoyloxy, naphthoyloxy, nicotinoyyloxy, etc.), allylloyloxy groups (preferably allylloyloxy groups having 7 to 23 carbon atoms, for example, benzoyloxy, etc.), carbamoyl groups (Preferably a carbamoyl group having 1 to 20 carbon atoms, for example, N, N-dimethylcarbamoyl, N-phenylcarbamoyl, etc.), an acylamino group (preferably an acylamino group having 1 to 20 carbon atoms, for example, acetylamino, benzoylamino, etc.) ), Alkylthio groups (preferably alkylthio groups having 1 to 20 carbon atoms, such as methylthio, ethylthio, isopropylthio, benzylthio, etc.), arylthio groups (preferably arylthio groups having 6 to 26 carbon atoms, such as phenylthio, 1-naphthylthio). , 3-Methylphenylthio, 4-methoxyphenylthio, etc.), heterocyclic thio group (group in which -S- group is bonded to the above heterocyclic group), alkylsulfonyl group (preferably alkylsulfonyl group having 1 to 20 carbon atoms). , For example, methylsulfonyl, ethyls Luhonyl, etc.), arylsulfonyl groups (preferably arylsulfonyl groups having 6 to 22 carbon atoms, such as benzenesulfonyl), alkylsilyl groups (preferably alkylsilyl groups having 1 to 20 carbon atoms, for example, monomethylsilyl, dimethylsilyl, etc.) , Trimethylsilyl, triethylsilyl, etc.), arylsilyl group (preferably arylsilyl group having 6 to 42 carbon atoms, for example, triphenylsilyl, etc.), alkoxysilyl group (preferably alkoxysilyl group having 1 to 20 carbon atoms, for example, Monomethoxysilyl, dimethoxysilyl, trimethoxysilyl, triethoxysilyl, etc.), aryloxysilyl group (preferably aryloxysilyl group having 6 to 42 carbon atoms, for example, triphenyloxysilyl group, etc.), phosphoryl group (preferably carbon) number 0-20 phosphate groups, for ^{example, -OP (= O) (R} P) 2), a phosphonyl group (preferably a phosphonyl group having 0-20 carbon atoms, for ^{example, -P (= O) (R} P) _2), a phosphinyl group (preferably a phosphinyl group having 0 to 20 carbon atoms, for example, ^-P (R _P) 2), phosphonic acid groups (preferably phosphonic acid groups having 0 to 20 carbon atoms, e.g., -PO (OR ^P ) ₂ ), sulfo group (sulfonic acid group), carboxy group, hydroxy group, sulfanyl group, cyano group, halogen atom (for example, fluorine atom, chlorine atom, bromine atom, iodine atom, etc.) can be mentioned. ^RP is a hydrogen atom or a substituent (preferably a group selected from the substituent Z).
Further, each group listed in these substituents Z may be further substituted with the above-mentioned substituent Z.
The alkyl group, alkylene group, alkenyl group, alkenylene group, alkynyl group and / or alkynylene group and the like may be cyclic or chain-like, or may be linear or branched.

The binder-forming polymer can be synthesized by selecting a raw material compound by a known method according to the type of bond possessed by the main chain and subjecting the raw material compound to polyaddition or polycondensation. As the synthesis method, for example, the above-mentioned

Patent Documents

1 and 2 can be referred to.
The method for incorporating the functional group is not particularly limited, and for example, a method for copolymerizing a compound having a functional group selected from the functional group group, a method using the above-mentioned (producing) polymerization initiator, and a polymer. Examples thereof include a method using a reaction. Specifically, the synthesis method and the like in the examples described later can be mentioned.

(Physical characteristics or properties of the binder used in the present invention or the polymer forming the binder used in the present invention)
The binder used in the present invention or the polymer forming the binder used in the present invention preferably has the following physical properties or properties.
The water concentration of the binder (polymer) used in the present invention is preferably 100 ppm (mass basis) or less. Further, as the binder used in the present invention, the polymer may be crystallized and dried, or the binder dispersion liquid used in the present invention may be used as it is.
The polymer forming the binder used in the present invention is preferably amorphous. In the present invention, the term "amorphous" as a polymer typically means that no endothermic peak due to crystal melting is observed when measured at the glass transition temperature.

The binder used in the present invention may be soluble (dissolved binder) or insoluble in the dispersion medium contained in the inorganic solid electrolyte-containing composition, but is preferably insoluble.
In the present invention, the fact that the polymer binder is soluble (dissolved) in the dispersion medium means that the polymer binder is dissolved in the dispersion medium of the inorganic solid electrolyte-containing composition, and for example, in the following solubility measurement. It means that the solubility is 10% or more. On the other hand, the fact that the polymer binder is insoluble in the dispersion medium means that the polymer binder is not dissolved in the dispersion medium of the composition containing an inorganic solid electrolyte and preferably exists in a solid state. For example, the following solubility measurement is performed. It means that the solubility is less than 10%.
In the present invention, the solubility in the dispersion medium can be appropriately set depending on the type of the polymer forming the polymer binder (structure and composition of the polymer chain), the type or content of the functional group of the polymer, the type of the dispersion medium, and the like.
(Measurement method of solubility)
A specified amount of the polymer binder to be measured is weighed in a glass bottle, 100 g of the dispersion medium contained in the composition containing an inorganic solid electrolyte is added thereto, and the mixture rotor is placed on a mix rotor at a rotation speed of 80 rpm for 24 hours at a temperature of 25 ° C. Stir. The transmittance of the mixed solution after stirring for 24 hours thus obtained is measured under the following conditions. This test (transmittance measurement) is performed by changing the amount of the binder dissolved (the above-specified amount), and the upper limit concentration X (mass%) at which the transmittance is 99.8% is defined as the solubility of the binder in the above dispersion medium.
<Transmittance measurement conditions>
Dynamic Light Scattering (DLS) Measuring Device: Otsuka Electronics DLS Measuring Device DLS-8000
Laser wavelength, output: 488 nm / 100 mW
Sample cell: NMR tube

When the binder used in the present invention is insoluble, it is preferably dispersed in the form of particles in the composition containing the inorganic solid electrolyte of the present invention (also referred to as a particulate binder).
The shape of the particles is not particularly limited and may be flat, amorphous or the like, but spherical or granular is preferable. The average particle size of the particulate binder is not particularly limited, but is preferably 1 nm or more, more preferably 5 nm or more, further preferably 10 nm or more, particularly preferably 50 nm or more, and particularly preferably 80 nm. The above is the most preferable. The upper limit is preferably 1700 nm or less, more preferably 1000 nm or less, further preferably 800 nm or less, particularly preferably 600 nm or less, and most preferably 500 nm or less.
The average particle size of the particulate binder can be measured in the same manner as the average particle size of the inorganic solid electrolyte.
The average particle size of the particulate binder in the constituent layers of the all-solid secondary battery is measured in advance by, for example, disassembling the battery and peeling off the constituent layer containing the particulate binder, and then measuring the constituent layers. The measurement can be performed by excluding the measured value of the particle size of the particles other than the particulate binder.
The average particle size of the particulate binder depends on, for example, the synthesis conditions of the polymer constituting the particulate binder, the dispersion method or dispersion conditions in the dispersion medium, the type of the dispersion medium, the content of the constituent components in the polymer, and the like. , Can be adjusted.

The polymer forming the binder used in the present invention may be a non-crosslinked polymer or a crosslinked polymer. Further, when the cross-linking of the polymer progresses by heating or application of a voltage, the molecular weight may be larger than the following molecular weight. Preferably, the polymer has a mass average molecular weight in the range described below at the start of use of the all-solid-state secondary battery.

The mass average molecular weight of the polymer forming the binder used in the present invention is not particularly limited. For example, 15,000 or more is preferable, 30,000 or more is more preferable, and 50,000 or more is further preferable. The upper limit is substantially 5,000,000 or less, preferably 4,000,000 or less, and more preferably 3,000,000 or less.

(Measurement of molecular weight)
In the present invention, the molecular weights of the polymer, the polymer chain (polyether structure) and the macromonomer refer to the mass average molecular weight or the number average molecular weight in terms of standard polystyrene by gel permeation chromatography (GPC) unless otherwise specified. As the measurement method, the following condition 1 or condition 2 (priority) method can be basically mentioned. However, an appropriate eluent may be appropriately selected and used depending on the type of polymer or macromonomer.
(Condition 1)
Column: Connect two TOSOH TSKgel Super AWM-H (trade name, manufactured by Tosoh Corporation) Carrier: 10 mM LiBr / N-methylpyrrolidone Measurement temperature: 40 ° C.
Carrier flow rate: 1.0 ml / min
Sample concentration: 0.1% by mass
Detector: RI (refractive index) detector (condition 2)
Column: A column connected with TOSOH TSKgel Super HZM-H, TOSOH TSKgel Super HZ4000, and TOSOH TSKgel Super HZ2000 (all trade names, manufactured by Tosoh Corporation) is used.
Carrier: tetrahydrofuran Measurement temperature: 40 ° C
Carrier flow rate: 1.0 ml / min
Sample concentration: 0.1% by mass
Detector: RI (refractive index) detector

Specific examples of the polymer contained in the binder used in the present invention include those shown below in addition to those synthesized in Examples, but the present invention is not limited thereto. In each specific example, the number attached to the lower right of the constituent component indicates the content in the polymer, and the unit thereof is mol%, but it can be appropriately changed within the above range.

The inorganic solid electrolyte-containing composition of the present invention may contain one or more of the above-mentioned binders used in the present invention as the polymer binder.

(Other binders)
The inorganic solid electrolyte-containing composition of the present invention may also contain a polymer binder other than the above-mentioned binder used in the present invention as the polymer binder. The polymer constituting the other binder may be a polymer other than the polymer constituting the binder used in the present invention, and examples thereof include various polymers usually used for the constituent layers of the all-solid-state secondary battery. For example, sequential polymerization (polycondensation, polyaddition or addition condensation) polymer such as polyurethane, polyurea, polyamide, polyimide, polyester, polyether, polycarbonate, etc., and further, fluoropolymer (fluorine-containing polymer), hydrocarbon polymer, etc. Examples thereof include chain polymerization polymers such as vinyl polymers and (meth) acrylic polymers. Among them, any of (meth) acrylic polymer, hydrocarbon polymer, vinyl polymer and fluorine polymer is preferable from the viewpoint of dispersion stability of the inorganic solid electrolyte-containing composition.
The polymer constituting the other binder may be soluble or insoluble with respect to the dispersion medium in the composition containing the inorganic solid electrolyte, but the solubility can further improve the dispersion stability of the solid particles. It is preferable.
The other binder is particularly preferably a polymer composed of a polymer soluble in a dispersion medium in the composition containing an inorganic solid electrolyte, which is any of a (meth) acrylic polymer, a hydrocarbon polymer, a vinyl polymer and a fluorine polymer. It is a binder.
The other binder may be one containing one kind or a kind containing a plurality of kinds as the polymer binder. When a plurality of kinds are contained, there is no particular limitation, but 2 to 4 kinds are preferable.

Examples of the polyurethane, polyurea, polyamide, and polyimide polymers that can be taken as sequential polymerization polymers include a polymer having a hard segment and a soft segment described in JP-A-2015-08480 (polymer binder (B)). , A polymer forming a binder having at least one component represented by a specific formula, which is described in WO2018 / 147051, and is described in WO2018 / 02827 and WO2015 / 046313. Each polymer and the like can be mentioned. Further, each polymer and the like described in Japanese Patent Application Laid-Open No. 2015-088486 can be mentioned. Further, the above-mentioned binder-forming polymer which does not contain a functional group-containing component can also be mentioned.

As the (meth) acrylic polymer, at least one (meth) acrylic compound (M1) selected from a (meth) acrylic acid compound, a (meth) acrylic acid ester compound, a (meth) acrylamide compound and a (meth) acrylonitrile compound. ) Is (co) polymerized to obtain a polymer. Further, a (meth) acrylic polymer composed of a copolymer of the (meth) acrylic compound (M1) and another polymerizable compound (M2) is also preferable. The other polymerizable compound (M2) is not particularly limited, and includes styrene compound, vinylnaphthalene compound, vinylcarbazole compound, allyl compound, vinyl ether compound, vinyl ester compound, dialkyl itaconate compound, maleic anhydride and the like. Examples thereof include vinyl compounds such as unsaturated carboxylic acid anhydride. Examples of the vinyl compound include "vinyl-based monomers" described in JP-A-2015-88486.
The content of the other polymerizable compound (M2) in the (meth) acrylic polymer is not particularly limited, but can be, for example, less than 50 mol%.
Examples of the (meth) acrylic polymer include the polymer described in International Publication No. 2016/132872, in which a macromonomer having a mass average molecular weight of 1,000 or more is incorporated as a side chain component.

Examples of the hydrocarbon polymer include polyethylene, polypropylene, natural rubber, polybutadiene, polyisoprene, polystyrene, polystyrene butadiene copolymer, styrene-based thermoplastic elastomer, polybutylene, acrylonitrile butadiene copolymer, or hydrogenation thereof (hydrogen). Chemistry) Polymers can be mentioned. The styrene-based thermoplastic elastomer or its hydride is not particularly limited, and for example, styrene-ethylene-butylene-styrene block copolymer (SEBS), styrene-isoprene-styrene block copolymer (SIS), hydride SIS. , Styrene-butadiene-styrene block copolymer (SBS), hydrogenated SBS, styrene-ethylene-ethylene-propylene-styrene block copolymer (SEEPS), styrene-ethylene-propylene-styrene block copolymer (SEPS), Examples thereof include styrene-butadiene rubber (SBR) and hydride styrene-butadiene rubber (HSBR). In the present invention, the hydrocarbon polymer having no unsaturated group (for example, 1,2-butadiene constituent) bonded to the main chain is preferable in that the formation of chemical crosslinks can be suppressed.
Hydrocarbon-based polymers include those modified with unsaturated carboxylic acid anhydrides and the like.

Examples of the vinyl-based polymer include polymers containing, for example, 50 mol% or more of vinyl-based monomers other than the (meth) acrylic compound (M1). Examples of the vinyl-based monomer include the above-mentioned vinyl compounds. Examples of the vinyl polymer include polyvinyl alcohol, polyvinyl acetal, polyvinyl acetate, and a copolymer containing these.
In addition to the constituent components derived from the vinyl-based monomer, this vinyl-based polymer preferably has a constituent component derived from the (meth) acrylic compound (M1) that forms the above-mentioned (meth) acrylic polymer, and further, the above-mentioned macromonomer. It may have a derived component (MM). The content of the constituent component derived from the vinyl-based monomer is preferably the same as the content of the constituent component derived from the (meth) acrylic compound (M1) in the (meth) acrylic polymer. The content of the constituent component derived from the (meth) acrylic compound (M1) is not particularly limited as long as it is less than 50% by mass in the polymer, but is preferably 0 to 30% by mass.

Examples of the fluorine-containing polymer include polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVdF), a copolymer of polyvinylidene fluoride and hexafluoropropylene (PVdF-HFP), polyvinylidene fluoride and hexafluoro. A copolymer of propylene and tetrafluoroethylene (PVdF-HFP-TFE) can be mentioned. In PVdF-HFP, the copolymerization ratio [PVdF: HFP] (mass ratio) of PVdF and HFP is not particularly limited, but is preferably 9: 1 to 5: 5, and 9: 1 to 7: 3 is adhesive. More preferable from the viewpoint. In PVdF-HFP-TFE, the copolymerization ratio [PVdF: HFP: TFE] (mass ratio) of PVdF, HFP, and TFE is not particularly limited, but may be 20 to 60:10 to 40: 5 to 30. preferable.

The physical characteristics or properties of the other binder and the polymer forming the other binder are basically the same as those of the binder used in the present invention or the polymer forming the binder used in the present invention described above.
However, from the viewpoint of further improving the dispersion stability of the solid particles, the polymer forming the other binder is soluble in the dispersion medium contained in the composition containing the inorganic solid electrolyte (the other binder is a soluble binder). There is) is preferable.

The inorganic solid electrolyte-containing composition of the present invention may contain one or more other binders as the polymer binder.

(Combination of polymer binder)
As described above, the polymer binder contained in the inorganic solid electrolyte-containing composition of the present invention may contain at least one binder used in the present invention, and may contain other binders.
Examples of the embodiment in which the polymer binder contains the binder used in the present invention include a mode containing the binder used in the present invention alone, a mode containing two or more kinds of binders used in the present invention, and one or more kinds of binders used in the present invention. Examples thereof include an aspect including one kind or two or more kinds of other binders.
In the embodiment including the binder used in the present invention and other binders, the combination of binders (polymers constituting the polymer binder) is not particularly limited, and preferred combinations of each binder can be mentioned, and urethane bonds are attached to the main chain. A combination of the binder used in the present invention composed of a polymer having the above and another soluble binder composed of any of a (meth) acrylic polymer, a hydrocarbon polymer, a vinyl-based polymer and a fluorine-containing polymer is particularly preferable.

(Content of polymer binder)
In the present invention, the total content of the polymer binder (the binder used in the present invention and other binders) in the inorganic solid electrolyte-containing composition is not particularly limited, but dispersion stability, film strength and battery performance (battery resistance, battery resistance, etc.) In terms of cycle characteristics), it is preferably 0.1 to 10.0% by mass, more preferably 0.2 to 5.0% by mass, and 0.3 to 4.0% by mass. Is more preferable. In the present invention, the (total) content of the polymer binder (the binder used in the present invention and other binders) in the inorganic solid electrolyte-containing composition is 0.1 at a solid content of 100% by mass for the same reason. It is preferably ~ 10.0% by mass, more preferably 0.3 to 8% by mass, and even more preferably 0.5 to 7% by mass.

The (total) content of the binder used in the present invention in the inorganic solid electrolyte-containing composition is appropriately set within a range that satisfies the total content of the polymer binder. For example, the (total) content is preferably 0.01 to 5% by mass, more preferably 0.05 to 4% by mass, and 0.1 to 3% by mass, based on 100% by mass of solid content. Is more preferable.
When the inorganic solid electrolyte-containing composition contains two or more kinds of binders used in the present invention, each content of the binder used in the present invention is appropriately set within a range satisfying the above (total) content of the binder used in the present invention. Is set to. For example, in terms of solid content of 100% by mass, it is preferably 0.01 to 5% by mass, more preferably 0.05 to 4% by mass, and even more preferably 0.1 to 3% by mass.

When the inorganic solid electrolyte-containing composition contains other binders, the (total) content of the binder used in the present invention may be lower than the content of the other binders, but is preferably the same or higher. .. Thereby, the film strength can be further strengthened without impairing the excellent dispersion stability. With respect to the solid content of 100% by mass, the difference (absolute value) between the (total) content of the binder used in the present invention and the content of other binders is not particularly limited, and may be, for example, 0 to 6% by mass. It is possible, 0 to 4% by mass is more preferable, and 0 to 2% by mass is further preferable. Further, the ratio of the (total) content of the binder used in the present invention to the content of other binders in 100% by mass of the solid content ((total) content of the binder used in the present invention / content of other binders). Is not particularly limited, but is preferably 1 to 4, more preferably 1 to 2, for example.

The content of the other binder in the composition containing the inorganic solid electrolyte is not particularly limited, and is appropriately set within a range that satisfies the total content of the above polymer binder. In terms of dispersion stability, the content thereof is preferably 0.01 to 4% by mass, more preferably 0.05 to 3% by mass, and 0. It is more preferably 1 to 2% by mass.

In the present invention, the mass ratio of the total mass (total mass) of the inorganic solid electrolyte and the active material to the total mass of the polymer binder in 100% by mass of the solid content [(mass of the inorganic solid electrolyte + mass of the active material) / (polymer binder). The total mass)] 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.

When the polymer binder is a particulate binder, its content is set to a content that does not dissolve in the inorganic solid electrolyte-containing composition in consideration of the solubility of the particulate binder within the range of each of the above contents. Is preferable.

<Dispersion medium>
The inorganic solid electrolyte-containing composition of the present invention preferably contains a dispersion medium for dispersing each of the above components.
The dispersion medium may be an organic compound that is liquid in the environment of use, and examples thereof include various organic solvents. Specifically, an alcohol compound, an ether compound, an amide compound, an amine compound, a ketone compound, and an aromatic compound. , Aliper compounds, nitrile compounds, ester compounds and the like.
The dispersion medium may be a non-polar dispersion medium (hydrophobic dispersion medium) or a polar dispersion medium (hydrophilic dispersion medium), but a non-polar dispersion medium is preferable because it can exhibit excellent dispersibility. The non-polar dispersion medium generally refers to a property having a low affinity for water, and in the present invention, for example, an ester compound, a ketone compound, an ether compound, an aromatic compound, an aliphatic compound and the like can be mentioned.

Examples of the alcohol compound include methyl alcohol, ethyl alcohol, 1-propyl alcohol, 2-propyl alcohol, 2-butanol, ethylene glycol, propylene glycol, glycerin, 1,6-hexanediol, cyclohexanediol, sorbitol, xylitol, and 2 -Methyl-2,4-pentanediol, 1,3-butanediol, 1,4-butanediol can be mentioned.

Examples of the ether compound include alkylene glycol (diethylene glycol, triethylene glycol, polyethylene glycol, dipropylene glycol, etc.), alkylene glycol monoalkyl ether (ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, diethylene glycol monomethyl ether, etc.). Dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, diethylene glycol monobutyl ether, etc.), alkylene glycol dialkyl ether (ethylene glycol dimethyl ether, etc.), dialkyl ether (dimethyl ether, diethyl ether, diisopropyl ether, dibutyl ether, etc.), cyclic ether (tetrahydrofuran, tetrahydrofuran, etc.) Dioxane (including 1,2-, 1,3- and 1,4-isomers) and the like) can be mentioned.

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

Examples of the amine compound include triethylamine, diisopropylethylamine, tributylamine and the like.
Examples of the ketone compound include acetone, methyl ethyl ketone, methyl isobutyl ketone (MIBK), cyclopentanone, cyclohexanone, cycloheptanone, dipropyl ketone, dibutyl ketone, diisopropyl ketone (DIPK), diisobutyl ketone (DIBK), and isobutyl propyl ketone. , Se-butyl propyl ketone, pentyl propyl ketone, butyl propyl ketone and the like.
Examples of the aromatic compound include benzene, toluene, xylene and the like.
Examples of the aliphatic compound include hexane, heptane, octane, nonane, decane, dodecane, cyclohexane, methylcyclohexane, ethylcyclohexane, cycloheptane, cyclooctane, decalin, paraffin, gasoline, naphtha, kerosene, and light oil.
Examples of the nitrile compound include acetonitrile, propionitrile, isobutyronitrile and the like.
Examples of the ester compound include ethyl acetate, butyl acetate, propyl acetate, propyl butyrate, isopropyl butyrate, butyl butyrate, isobutyl butyrate, butyl pentanate, ethyl isobutyrate, propyl isobutyrate, isopropyl isobutyrate, isobutyl isobutyrate, and pivalic acid. Examples thereof include propyl, isopropyl pivalate, butyl pivalate, and isobutyl pivalate.

In the present invention, the ether compound, the ketone compound, the aromatic compound, and the aliphatic compound are highly compatible with the binder used in the present invention and can enhance the dispersion stability of the inorganic solid electrolyte-containing composition. , Estelle compounds are preferred, and ester compounds, aliphatic compounds, ketone compounds or ether compounds are more preferred, for example, diisopropyl ether, dibutyl ether, isobutyl ethyl ether, MIBK, DIPK, DIBK, butyl butyrate, butyl acetate, ethylcyclohexane, cyclo. Examples thereof include octane, heptane, and toluene.

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

The dispersion medium preferably has a boiling point of 50 ° C. or higher at normal pressure (1 atm), and more preferably 70 ° C. or higher. The upper limit is preferably 250 ° C. or lower, and more preferably 220 ° C. or lower.

The inorganic solid electrolyte-containing composition of the present invention may contain at least one type of dispersion medium and may contain two or more types.
In the present invention, the content of the dispersion medium in the inorganic solid electrolyte-containing composition is not particularly limited and can be appropriately set. For example, in the composition containing an inorganic solid electrolyte, 20 to 80% by mass is preferable, 30 to 70% by mass is more preferable, and 40 to 60% by mass is particularly preferable.

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

(Positive electrode active material)
The positive electrode active material is an active material capable of inserting and releasing ions of a metal belonging to Group 1 or Group 2 of the periodic table, and is preferably one capable of reversibly inserting and releasing lithium ions. The material is not particularly limited as long as it has the above characteristics, and may be a transition metal oxide, an organic substance, an element that can be composited with Li such as sulfur, or the like by decomposing the battery.
Among them, as the positive electrode active material, a transition metal oxide having preferably used a transition metal oxide, a transition metal element ^{M a (Co, Ni, Fe} , Mn, 1 or more elements selected from Cu and V) the The thing is more preferable. Further, the 1 (Ia) group elements of the transition metal oxide to elemental ^{M b} (Table metal periodic other than lithium, the elements of the 2 (IIa) group, Al, Ga, In, Ge , Sn, Pb, Elements such as Sb, Bi, Si, P and B) may be mixed. The mixing amount is preferably 0 to 30 mol% relative to the amount of the transition metal element ^{M a} (100 mol%). That the molar ratio of li / ^{M a} was synthesized were mixed so that 0.3 to 2.2, more preferably.
Specific examples of the transition metal oxide include (MA) a transition metal oxide having a layered rock salt type structure, (MB) a transition metal oxide having a spinel type structure, (MC) a lithium-containing transition metal phosphoric acid compound, and (MD). ) Lithium-containing transition metal halide phosphoric acid compound, (ME) lithium-containing transition metal silicic acid compound and the like.

(MA) Specific examples of the transition metal oxide having a layered rock salt structure include LiCoO ₂ (lithium cobalt oxide [LCO]), LiNi ₂ O ₂ (lithium nickel oxide), LiNi _0.85 Co _0.10 Al _{0. 05} O ₂ (Lithium Nickel Cobalt Aluminate [NCA]), LiNi _1/3 Co _1/3 Mn _1/3 O ₂ (Lithium Nickel Manganese Cobalt Oxide [NMC]) and LiNi _0.5 Mn _0.5 O ₂ ( Manganese nickel oxide).
(MB) Specific examples of the transition metal oxide having a spinel _{_{_{structure, LiMn 2 O 4 (LMO)}}} , LiCoMnO 4, Li 2 FeMn 3 O 8, Li 2 CuMn 3 O 8, Li 2 CrMn 3 O 8 and Li ₂ Nimn ₃ O ₈ can be mentioned.
Examples of the (MC) lithium-containing transition metal phosphate compound include olivine-type iron phosphate salts such as _{LiFePO 4} and Li ₃ Fe ₂ (PO ₄ ) ₃ , iron pyrophosphates such as _{LiFeP 2} O ₇ _{, and LiCoPO 4.} Examples thereof include cobalt phosphates of Li ₃ V ₂ (PO ₄ ) ₃ (lithium vanadium phosphate) and other monoclinic panocycon-type vanadium phosphate salts.
(MD) as the lithium-containing transition metal halogenated phosphate compound, for _example, Li 2 FePO ₄ F such fluorinated phosphorus iron _salt, Li 2 MnPO ₄ hexafluorophosphate manganese salts such as F and _Li 2 CoPO ₄ F Fluorophosphate cobalts such as.
Examples of the (ME) lithium-containing transition metal silicic acid compound include Li ₂ FeSiO ₄ , Li ₂ MnSiO ₄ , and Li ₂ CoSiO ₄ .
In the present invention, a transition metal oxide having a (MA) layered rock salt type structure is preferable, and LCO or NMC is more preferable.

The shape of the positive electrode active material is not particularly limited, but is preferably in the form of particles. The average particle size (volume average particle size) of the positive electrode active material is not particularly limited. For example, it can be 0.1 to 50 μm. The average particle size of the positive electrode active material particles can be measured in the same manner as the average particle size of the above-mentioned inorganic solid electrolyte. A normal crusher or classifier is used to adjust the positive electrode active material to a predetermined particle size. For example, a mortar, a ball mill, a sand mill, a vibrating ball mill, a satellite ball mill, a planetary ball mill, a swirling airflow type jet mill, a sieve, or the like is preferably used. At the time of pulverization, wet pulverization in which a dispersion medium such as water or methanol coexists can also be performed. It is preferable to perform classification in order to obtain a desired particle size. The classification is not particularly limited, and can be performed using a sieve, a wind power classifier, or the like. Both dry and wet classifications can be used.
The positive electrode active material obtained by the firing method may be used after being washed with water, an acidic aqueous solution, an alkaline aqueous solution, or an organic solvent.

As the positive electrode active material, one type may be used alone, or two or more types may be used in combination.
When forming the positive electrode active material layer, the mass (mg) (grain amount) of the positive electrode active material per ^{unit area (cm 2) of the positive electrode active material layer is not particularly limited.} It can be appropriately determined according to the designed battery capacity, and can be, for example, 1 to 100 mg / cm ² .

The content of the positive electrode active material in the inorganic solid electrolyte-containing composition is not particularly limited, and is preferably 10 to 97% by mass, more preferably 30 to 95% by mass, and 40 to 93% by mass in terms of solid content of 100% by mass. Is more preferable, and 50 to 90% by mass is particularly preferable.

(Negative electrode active material)
The negative electrode active material is an active material capable of inserting and releasing ions of a metal belonging to Group 1 or Group 2 of the periodic table, and is preferably one capable of reversibly inserting and releasing lithium ions. The material is not particularly limited as long as it has the above characteristics, and is a negative electrode activity capable of forming an alloy with a carbonaceous material, a metal oxide, a metal composite oxide, a single lithium substance, a lithium alloy, or lithium. Examples include substances. Of these, carbonaceous materials, metal composite oxides, or elemental lithium are preferably used from the viewpoint of reliability. An active material that can be alloyed with lithium is preferable in that the capacity of the all-solid-state secondary battery can be increased. Since the constituent layer formed of the solid electrolyte composition of the present invention can maintain a strong bonded state between the solid particles, a negative electrode active material capable of forming an alloy with lithium can be used as the negative electrode active material. This makes it possible to increase the capacity of the all-solid-state secondary battery and extend the life of the battery.

The carbonaceous material used as the negative electrode active material is a material substantially composed of carbon. For example, various synthesis of petroleum pitch, carbon black such as acetylene black (AB), graphite (artificial graphite such as natural graphite and vapor-grown graphite), and PAN (polyacrylonitrile) -based resin or furfuryl alcohol resin. A carbonaceous material obtained by calcining a resin can be mentioned. Furthermore, various carbon fibers such as PAN-based carbon fibers, cellulose-based carbon fibers, pitch-based carbon fibers, vapor-grown carbon fibers, dehydrated PVA (polypoly alcohol) -based carbon fibers, lignin carbon fibers, graphitic carbon fibers, and activated carbon fibers. Kind, mesophase microspheres, graphite whisker, flat graphite and the like can also be mentioned.
These carbonaceous materials can also be divided into non-graphitizable carbonaceous materials (also referred to as hard carbon) and graphite-based carbonaceous materials depending on the degree of graphitization. Further, the carbonaceous material preferably has the plane spacing or density and the size of crystallites described in JP-A-62-22066, JP-A-2-6856, and JP-A-3-45473. The carbonaceous material does not have to be a single material, and a mixture of natural graphite and artificial graphite described in JP-A-5-90844, graphite having a coating layer described in JP-A-6-4516, and the like should be used. You can also.
As the carbonaceous material, hard carbon or graphite is preferably used, and graphite is more preferably used.

The metal or semi-metal element oxide applied as the negative electrode active material is not particularly limited as long as it is an oxide capable of storing and releasing lithium, and is a composite of the metal element oxide (metal oxide) and the metal element. Examples thereof include oxides or composite oxides of metal elements and semi-metal elements (collectively referred to as metal composite oxides) and oxides of semi-metal elements (semi-metal oxides). As these oxides, amorphous oxides are preferable, and chalcogenides, which are reaction products of metal elements and elements of Group 16 of the Periodic Table, are also preferable. In the present invention, the metalloid element means an element exhibiting properties intermediate between a metalloid element and a non-metalloid element, and usually contains six elements of boron, silicon, germanium, arsenic, antimony and tellurium, and further selenium. , Polonium and Astatine. Further, "amorphous" means an X-ray diffraction method using CuKα rays, which has a broad scattering band having an apex in a region of 20 ° to 40 ° in 2θ value, and a crystalline diffraction line is used. You may have. The strongest intensity of the crystalline diffraction lines seen at the 2θ value of 40 ° to 70 ° is 100 times or less of the diffraction line intensity at the apex of the broad scattering band seen at the 2θ value of 20 ° to 40 °. It is preferable that it is 5 times or less, and it is particularly preferable that it does not have a crystalline diffraction line.

Among the compound group consisting of the amorphous oxide and the chalcogenide, the amorphous oxide of the metalloid element or the chalcogenide is more preferable, and the elements of the Group 13 (IIIB) to 15 (VB) of the Periodic Table (for example). , Al, Ga, Si, Sn, Ge, Pb, Sb and Bi) alone or a combination of two or more of them (composite) oxide, or chalcogenide is particularly preferable. Specific examples of preferable amorphous oxides and chalcogenides include, for example, Ga ₂ O ₃ , GeO, PbO, PbO ₂ , Pb ₂ O ₃ , Pb ₂ O ₄ , Pb ₃ O ₄ , Sb ₂ O ₃ , Sb _2. O ₄ , Sb ₂ O ₈ Bi ₂ O ₃ , Sb ₂ O ₈ Si ₂ O ₃ , Sb ₂ O ₅ , Bi ₂ O ₃ , Bi ₂ O ₄ , GeS, PbS, PbS ₂ , Sb ₂ S ₃ or Sb ₂ S ₅ is preferably mentioned.
Negative electrode active materials that can be used in combination with amorphous oxides such as Sn, Si, and Ge include carbonaceous materials that can occlude and / or release lithium ions or lithium metals, lithium alone, lithium alloys, and lithium. A negative electrode active material that can be alloyed with is preferably mentioned.

It is preferable that the oxide of a metal or a metalloid element, particularly a metal (composite) oxide and the chalcogenide, contains at least one of titanium and lithium as a constituent component from the viewpoint of high current density charge / discharge characteristics. Examples of the lithium-containing metal composite oxide (lithium composite metal oxide) include a composite oxide of lithium oxide and the metal (composite) oxide or the chalcogenide, and more specifically, Li ₂ SnO _2. Can be mentioned.
It is also preferable that the negative electrode active material, for example, a metal oxide, contains a titanium element (titanium oxide). Specifically, Li ₄ Ti ₅ O ₁₂ (lithium titanate [LTO]) has excellent rapid charge / discharge characteristics because the volume fluctuation during storage and release of lithium ions is small, and deterioration of electrodes is suppressed and lithium ion secondary It is preferable in that the life of the battery can be improved.

The lithium alloy as the negative electrode active material is not particularly limited as long as it is an alloy usually used as the negative electrode active material of the secondary battery, and examples thereof include a lithium aluminum alloy.

The negative electrode active material that can be alloyed with lithium is not particularly limited as long as it is usually used as the negative electrode active material of the secondary battery. Such an active material has a large expansion and contraction due to charging and discharging of an all-solid secondary battery and accelerates a decrease in battery performance such as cycle characteristics. However, the inorganic solid electrolyte-containing composition of the present invention is used in the above-mentioned present invention. Since it contains a binder, deterioration of battery performance can be suppressed. Examples of such an active material include a (negative electrode) active material having a silicon element or a tin element (alloy, etc.), and metals such as Al and In, and a negative electrode active material having a silicon element that enables a higher battery capacity. (Silicon element-containing active material) is preferable, and a silicon element-containing active material having a silicon element content of 50 mol% or more of all the constituent elements is more preferable.
Generally, a negative electrode containing these negative electrode active materials (for example, a Si negative electrode containing a silicon element-containing active material, a Sn negative electrode containing a tin element active material, etc.) is a carbon negative electrode (graphite, acetylene black, etc.). ), More Li ions can be occluded. That is, the amount of Li ions occluded per unit mass increases. Therefore, the battery capacity (energy density) can be increased. As a result, there is an advantage that the battery drive time can be lengthened.
Examples of the silicon element-containing active material include silicon materials such as Si and SiOx (0 <x≤1), and silicon-containing alloys containing titanium, vanadium, chromium, manganese, nickel, copper, lanthanum, and the like (for example,). LaSi ₂ , VSi ₂ , La-Si, Gd-Si, Ni-Si) or organized active material (eg LaSi ₂ / Si), as well as other silicon and tin elements such as _{SnSiO 3} , SnSiS ₃ Examples include active materials containing. In addition, SiOx itself can be used as a negative electrode active material (metalloid oxide), and since Si is generated by the operation of an all-solid-state secondary battery, a negative electrode active material that can be alloyed with lithium (its). It can be used as a precursor substance).
Examples of the negative electrode active material having a tin element include Sn, SnO, SnO ₂ , SnS, SnS ₂ , and the active material containing the silicon element and the tin element. Further, a composite oxide with lithium oxide, for example, Li ₂ SnO ₂ can also be mentioned.

In the present invention, the above-mentioned negative electrode active material can be used without particular limitation, but in terms of battery capacity, a negative electrode active material that can be alloyed with lithium is a preferred embodiment as the negative electrode active material. , The above-mentioned silicon material or silicon-containing alloy (alloy containing a silicon element) is more preferable, and it is further preferable to contain silicon (Si) or a silicon-containing alloy.

The chemical formula of the compound obtained by the above firing method can be calculated from the inductively coupled plasma (ICP) emission spectroscopic analysis method as a measurement method and the mass difference of the powder before and after firing as a simple method.

The shape of the negative electrode active material is not particularly limited, but it is preferably in the form of particles. The average particle size (volume average particle size) of the negative electrode active material is not particularly limited, but is preferably 0.1 to 60 μm. The average particle size of the negative electrode active material particles can be measured in the same manner as the average particle size of the above-mentioned inorganic solid electrolyte. In order to obtain a predetermined particle size, a normal crusher or classifier is used as in the case of the positive electrode active material.

The negative electrode active material may be used alone or in combination of two or more.
When the negative electrode active material layer is formed, the mass (mg) (grain amount) of the negative electrode active material per ^{unit area (cm 2) of the negative electrode active material layer is not particularly limited.} It can be appropriately determined according to the designed battery capacity, and can be, for example, 1 to 100 mg / cm ² .

The content of the negative electrode active material in the inorganic solid electrolyte-containing composition is not particularly limited, and is preferably 10 to 90% by mass, more preferably 20 to 85% by mass, and 30 to 30% by mass, based on 100% by mass of the solid content. It is more preferably 80% by mass, and even more preferably 40 to 75% by mass.

In the present invention, when the negative electrode active material layer is formed by charging the secondary battery, instead of the negative electrode active material, a metal belonging to Group 1 or Group 2 of the periodic table generated in the all-solid secondary battery is used. Ions can be used. A negative electrode active material layer can be formed by combining these ions with electrons and precipitating them as a metal.

(Coating of active material)
The surfaces of the positive electrode active material and the negative electrode active material may be surface-coated with another metal oxide. Examples of the surface coating agent include metal oxides containing Ti, Nb, Ta, W, Zr, Al, Si or Li. Specific examples thereof include spinel titanate, tantalum oxide, niobate oxide, lithium niobate compound and the like. Specifically, Li ₄ Ti ₅ O ₁₂ , Li ₂ Ti ₂ O ₅ and LiTaO ₃ , LiNbO ₃ , LiAlO ₂ , Li ₂ ZrO ₃ , Li ₂ WO ₄ , Li ₂ TIO ₃ , Li ₂ B ₄ O ₇ , Li ₃ PO ₄ , Li ₂ MoO ₄ , Li ₃ BO ₃ , LiBO ₂ , Li ₂ CO ₃ , Li ₂ SiO ₃ , SiO ₂ , TiO ₂ , ZrO ₂ , Al ₂ O ₃ , B ₂ O _{3, and the} like.
Further, the surface of the electrode containing the positive electrode active material or the negative electrode active material may be surface-treated with sulfur or phosphorus.
Further, the surface of the positive electrode active material or the particle surface of the negative electrode active material may be surface-treated with active light rays or an active gas (plasma or the like) before and after the surface coating.

<Conductive aid>
The inorganic solid electrolyte-containing composition of the present invention preferably contains a conductive auxiliary agent, and for example, a silicon atom-containing active material as a negative electrode active material is preferably used in combination with a conductive auxiliary agent.
The conductive auxiliary agent is not particularly limited, and those known as general conductive auxiliary agents can be used. For example, electron conductive materials such as graphites such as natural graphite and artificial graphite, carbon blacks such as acetylene black, ketjen black and furnace black, amorphous carbon such as needle coke, vapor-grown carbon fibers or carbon nanotubes. It may be a carbon fiber such as graphene or fullerene, a metal powder such as copper or nickel, or a metal fiber, and a conductive polymer such as polyaniline, polypyrrole, polythiophene, polyacetylene, or polyphenylene derivative. May be used.
In the present invention, when the active material and the conductive auxiliary agent are used in combination, among the above conductive auxiliary agents, metal ions (preferably Li) belonging to the first group or the second group of the periodic table when the battery is charged and discharged. A conductive auxiliary agent is one that does not insert and release ions) and does not function as an active material. Therefore, among the conductive auxiliary agents, those that can function as active materials in the active material layer when the battery is charged and discharged are classified as active materials instead of conductive auxiliary agents. Whether or not the battery functions as an active material when it is charged and discharged is not unique and is determined by the combination with the active material.

The conductive auxiliary agent may contain one kind or two or more kinds.
The shape of the conductive auxiliary agent is not particularly limited, but is preferably in the form of particles.
When the inorganic solid electrolyte-containing composition of the present invention contains a conductive auxiliary agent, the content of the conductive auxiliary agent in the inorganic solid electrolyte-containing composition is preferably 0 to 10% by mass with respect to 100% by mass of the solid content.

<Lithium salt>
The inorganic solid electrolyte-containing composition of the present invention preferably contains a lithium salt (supporting electrolyte).
As the lithium salt, the lithium salt usually used for this kind of product is preferable, and there is no particular limitation. For example, the lithium salt described in paragraphs 882 to 985 of JP-A-2015-084886 is preferable.
When the inorganic solid electrolyte-containing composition of the present invention contains a lithium salt, the content of the lithium salt is preferably 0.1 part by mass or more, more preferably 5 parts by mass or more, based on 100 parts by mass of the solid electrolyte. The upper limit is preferably 50 parts by mass or less, more preferably 20 parts by mass or less.

<Dispersant>
Since the binder used in the present invention described above functions as a dispersant, the inorganic solid electrolyte-containing composition of the present invention does not have to contain a dispersant other than the binder used in the present invention, but contains a dispersant. You may. As the dispersant, those usually used for all-solid-state secondary batteries can be appropriately selected and used. Generally, compounds intended for particle adsorption, steric repulsion and / or electrostatic repulsion are preferably used.

<Other additives>
The composition containing an inorganic solid electrolyte of the present invention contains, as other components other than the above components, an ionic liquid, a thickener, and a cross-linking agent (such as those that undergo a cross-linking reaction by radical polymerization, condensation polymerization, or ring-opening polymerization). , Polymerization initiators (such as those that generate acids or radicals by heat or light), defoaming agents, leveling agents, dehydrating agents, antioxidants and the like can be contained. The ionic liquid is contained in order to further improve the ionic conductivity, and known ones can be used without particular limitation. Further, a polymer other than the polymer forming the polymer binder described above, a commonly used binder and the like may be contained.

(Preparation of Inorganic Solid Electrolyte-Containing Composition)
The composition containing an inorganic solid electrolyte of the present invention is an inorganic solid electrolyte, a binder used in the present invention as a polymer binder, a dispersion medium, preferably a polymer binder other than the binder used in the present invention (for example, another binder), and a conductive auxiliary agent. Further, as appropriate, a lithium salt and any other component can be prepared as a mixture, preferably as a slurry, by mixing, for example, with various commonly used mixers. In the case of the electrode composition, the active material is further mixed.
The mixing method is not particularly limited, and the mixture may be mixed all at once or sequentially. The mixing environment is not particularly limited, and examples thereof include under dry air and under an inert gas.

[Sheet for all-solid-state secondary battery]
The sheet for an all-solid-state secondary battery of the present invention is a sheet-like molded body capable of forming a constituent layer of an all-solid-state secondary battery, and includes various aspects depending on its use. For example, a sheet preferably used for a solid electrolyte layer (also referred to as a solid electrolyte sheet for an all-solid secondary battery), an electrode, or a sheet preferably used for a laminate of an electrode and a solid electrolyte layer (an electrode for an all-solid secondary battery). Sheet) and the like. In the present invention, these various sheets are collectively referred to as an all-solid-state secondary battery sheet.

The solid electrolyte sheet for an all-solid secondary battery of the present invention may be a sheet having a solid electrolyte layer, and even a sheet in which the solid electrolyte layer is formed on a base material does not have a base material and is a solid electrolyte layer. It may be a sheet formed of. The solid electrolyte sheet for an all-solid secondary battery may have another layer in addition to the solid electrolyte layer. Examples of other layers include a protective layer (release sheet), a current collector, a coat layer, and the like.
As the solid electrolyte sheet for an all-solid secondary battery of the present invention, for example, a sheet having a layer composed of the inorganic solid electrolyte-containing composition of the present invention, a normal solid electrolyte layer, and a protective layer on a substrate in this order. Can be mentioned. The solid electrolyte layer contained in the solid electrolyte sheet for an all-solid secondary battery is preferably formed of the inorganic solid electrolyte-containing composition of the present invention. The content of each component in the solid electrolyte layer is not particularly limited, but is preferably synonymous with the content of each component in the solid content of the inorganic solid electrolyte-containing composition of the present invention. The layer thickness of each layer constituting the solid electrolyte sheet for an all-solid-state secondary battery is the same as the layer thickness of each layer described in the all-solid-state secondary battery described later.

The base material is not particularly limited as long as it can support the solid electrolyte layer, and examples thereof include a material described in the current collector described later, a sheet body (plate-shaped body) such as an organic material and an inorganic material. Examples of the organic material include various polymers, and specific examples thereof include polyethylene terephthalate, polypropylene, polyethylene, and cellulose. Examples of the inorganic material include glass, ceramic and the like.

The electrode sheet for an all-solid-state secondary battery of the present invention (also simply referred to as “electrode sheet”) may be an electrode sheet having an active material layer, and the active material layer is formed on a base material (current collector). The sheet may be a sheet that does not have a base material and is formed from an active material layer. This electrode sheet is usually a sheet having a current collector and an active material layer, but has an embodiment having a current collector, an active material layer and a solid electrolyte layer in this order, and a current collector, an active material layer and a solid electrolyte. An embodiment having a layer and an active material layer in this order is also included. The solid electrolyte layer and the active material layer of the electrode sheet are preferably formed of the inorganic solid electrolyte-containing composition of the present invention. The content of each component in the solid electrolyte layer or the active material layer is not particularly limited, but preferably, the content of each component in the solid content of the inorganic solid electrolyte-containing composition (electrode composition) of the present invention. Is synonymous with. The layer thickness of each layer constituting the electrode sheet of the present invention is the same as the layer thickness of each layer described in the all-solid-state secondary battery described later. The electrode sheet of the present invention may have the other layers described above.

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 of the inorganic solid electrolyte-containing composition of the present invention, and has a constituent layer having low resistance and high film strength. There is. Therefore, by using the sheet for the all-solid-state secondary battery of the present invention as a constituent layer of the all-solid-state secondary battery, excellent cycle characteristics of the all-solid-state secondary battery and low resistance (high conductivity) can be realized. .. Further, even if the sheet for an all-solid-state secondary battery is manufactured by the roll-to-roll method, defects are unlikely to occur in the constituent layers. Furthermore, the electrode sheet for an all-solid-state secondary battery and the all-solid-state secondary battery in which the active material layer is formed of the inorganic solid electrolyte-containing composition of the present invention show strong adhesion between the active material layer and the current collector. , Further improvement of cycle characteristics can be realized. Therefore, the sheet for an all-solid-state secondary battery of the present invention is suitably used as a sheet capable of forming a constituent layer of an all-solid-state secondary battery.

[Manufacturing method of all-solid-state secondary battery sheet]
The method for producing the sheet for an all-solid secondary battery of the present invention is not particularly limited, and the sheet can be produced by forming each of the above layers using the inorganic solid electrolyte-containing composition of the present invention. For example, a layer (coating and drying layer) composed of an inorganic solid electrolyte-containing composition is preferably formed on a base material or a current collector (which may be via another layer) by forming a film (coating and drying). The method can be mentioned. Thereby, an all-solid-state secondary battery sheet having a base material or a current collector and a coating dry layer can be produced. In particular, when the inorganic solid electrolyte-containing composition of the present invention is formed on a current collector to prepare a sheet for an all-solid secondary battery, the adhesion between the current collector and the active material layer can be strengthened. Here, the coating dry layer is a layer formed by applying the inorganic solid electrolyte-containing composition of the present invention and drying the dispersion medium (that is, the inorganic solid electrolyte-containing composition of the present invention is used. A layer having a composition obtained by removing a dispersion medium from the inorganic solid electrolyte-containing composition of the present invention). In the active material layer and the coating dry layer, the dispersion medium may remain as long as the effects of the present invention are not impaired, and the residual amount may be, for example, 3% by mass or less in each layer.
In the method for manufacturing an all-solid-state secondary battery sheet of the present invention, each step such as coating and drying will be described in the following method for manufacturing an all-solid-state secondary battery.

In the method for producing a sheet for an all-solid-state secondary battery of the present invention, the coating dry layer obtained as described above can also be pressurized. The pressurizing conditions and the like will be described later in the method for manufacturing an all-solid-state secondary battery.
Further, in the method for producing a sheet for an all-solid-state secondary battery of the present invention, the base material, the protective layer (particularly the release sheet) and the like can be peeled off.

The method for producing a sheet for an all-solid secondary battery of the present invention is a highly productive production method in which bending and restoration act by using the composition containing an inorganic solid electrolyte of the present invention, and in particular, bending and restoration act repeatedly. Even if it is applied to an industrial manufacturing method (for example, a roll-to-roll method), a constituent layer that maintains a contact state between solid particles can be produced. That is, it is possible to manufacture an all-solid-state secondary battery sheet having a constituent layer having a high film strength and suppressing the occurrence of defects with high productivity.

[All-solid-state secondary battery]
The all-solid secondary battery of the present invention comprises a positive electrode active material layer, a negative electrode active material layer facing the positive electrode active material layer, and a solid electrolyte layer arranged between the positive electrode active material layer and the negative electrode active material layer. Have. The positive electrode active material layer is preferably formed on the positive electrode current collector and constitutes the positive electrode. The negative electrode active material layer is preferably formed on the negative electrode current collector to form the negative electrode.
It is sufficient that at least one layer of the negative electrode active material layer, the positive electrode active material layer and the solid electrolyte layer is formed of the inorganic solid electrolyte-containing composition of the present invention, and the solid electrolyte layer, or the negative electrode active material layer and the positive electrode active material layer. It is preferable that at least one of the above is formed of the composition containing the inorganic solid electrolyte of the present invention. It is also one of the preferred embodiments that all layers are formed of the inorganic solid electrolyte-containing composition of the present invention. The active material layer or the solid electrolyte layer formed of the inorganic solid electrolyte-containing composition of the present invention is preferably one in the solid content of the inorganic solid electrolyte-containing composition of the present invention with respect to the component species contained therein and the content ratio thereof. Is the same as. When the active material layer or the solid electrolyte layer is not formed by the inorganic solid electrolyte-containing composition of the present invention, a known material can be used.
The thicknesses of the negative electrode active material layer, the solid electrolyte layer, and the positive electrode active material layer are not particularly limited. The thickness of each layer is preferably 10 to 1,000 μm, more preferably 20 μm or more and less than 500 μm, respectively, in consideration of the dimensions of a general all-solid-state secondary battery. In the all-solid-state secondary battery of the present invention, it is more preferable that the thickness of at least one of the positive electrode active material layer and the negative electrode active material layer is 50 μm or more and less than 500 μm.
The positive electrode active material layer and the negative electrode active material layer may each have a current collector on the opposite side of the solid electrolyte layer.

<Case>
Depending on the application, the all-solid-state secondary battery of the present invention may be used as an all-solid-state secondary battery with the above structure, but in order to form a dry battery, it should be further enclosed in a suitable housing. Is preferable. The housing may be made of metal or resin (plastic). When a metallic material is used, for example, one made of aluminum alloy or stainless steel can be mentioned. It is preferable that the metallic housing is divided into a positive electrode side housing and a negative electrode side housing, and electrically connected to the positive electrode current collector and the negative electrode current collector, respectively. It is preferable that the housing on the positive electrode side and the housing on the negative electrode side are joined and integrated via a gasket for preventing a short circuit.

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

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

When the all-solid secondary battery having the layer structure shown in FIG. 1 is placed in a 2032 type coin case, the all-solid secondary battery is referred to as an all-solid secondary battery laminate, and the all-solid secondary battery laminate is referred to as an all-solid secondary battery laminate. A battery manufactured in a 2032 type coin case (for example, a coin type all-solid secondary battery shown in FIG. 2) may be referred to as an all-solid secondary battery.

(Cathode active material layer, solid electrolyte layer, negative electrode active material layer)
In the all-solid-state secondary battery 10, all of the positive electrode active material layer, the solid electrolyte layer, and the negative electrode active material layer are formed of the inorganic solid electrolyte-containing composition of the present invention. The all-solid-state secondary battery 10 exhibits excellent battery performance. The inorganic solid electrolyte and the polymer binder (binder used in the present invention) contained in the positive electrode active material layer 4, the solid electrolyte layer 3, and the negative electrode active material layer 2 may be of the same type or different from each other.
In the present invention, either or both of the positive electrode active material layer and the negative electrode active material layer may be simply referred to as an active material layer or an electrode active material layer. Further, either or both of the positive electrode active material and the negative electrode active material may be collectively referred to as an active material or an electrode active material.

In the present invention, when the binder used in the present invention is used in combination with solid particles such as an inorganic solid electrolyte or an active material for the constituent layer, the interface between the solid particles is also caused by bending and restoration during sheet preparation as described above. Can maintain contact. Therefore, even if a sheet for an all-solid-state secondary battery continuously manufactured from an industrial point of view is used, the obtained all-solid-state secondary battery of the present invention can realize high battery performance with low battery resistance and excellent cycle characteristics. ..

In the all-solid-state secondary battery 10, the negative electrode active material layer can be a lithium metal layer. Examples of the lithium metal layer include a layer formed by depositing or molding a lithium metal powder, a lithium foil, a lithium vapor deposition film, and the like. The thickness of the lithium metal layer can be, for example, 1 to 500 μm regardless of the thickness of the negative electrode active material layer.

The positive electrode current collector 5 and the negative electrode current collector 1 are preferably electron conductors.
In the present invention, either or both of the positive electrode current collector and the negative electrode current collector may be collectively referred to as a current collector.
As a material for forming the positive electrode current collector, in addition to aluminum, aluminum alloy, stainless steel, nickel and titanium, the surface of aluminum or stainless steel is treated with carbon, nickel, titanium or silver (a thin film is formed). Of these, aluminum and aluminum alloys are more preferable.
As a material for forming the negative electrode current collector, in addition to aluminum, copper, copper alloy, stainless steel, nickel and titanium, carbon, nickel, titanium or silver is treated on the surface of aluminum, copper, copper alloy or stainless steel. Preferably, aluminum, copper, copper alloy and stainless steel are more preferable.

The shape of the current collector is usually a film sheet, but a net, a punched body, a lath body, a porous body, a foam body, a molded body of a fiber group, or the like can also be used.
The thickness of the current collector is not particularly limited, but is preferably 1 to 500 μm. Further, it is also preferable that the surface of the current collector is made uneven by surface treatment.

In the all-solid-state secondary battery 10, a layer formed of a known constituent layer-forming material can be applied to the positive electrode active material layer.
In the present invention, a functional layer, a member, or the like is appropriately interposed or arranged between or outside each 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. You may. Further, each layer may be composed of a single layer or a plurality of layers.

[Manufacturing of all-solid-state secondary batteries]
The all-solid-state secondary battery can be manufactured by a conventional method. Specifically, the all-solid-state secondary battery can be manufactured by forming each of the above layers using the inorganic solid electrolyte-containing composition or the like of the present invention. The details will be described below.

In the all-solid-state secondary battery of the present invention, the inorganic solid electrolyte-containing composition of the present invention is appropriately applied onto a base material (for example, a metal foil serving as a current collector) to form a coating film (film formation). ) A method including (via) a step (a method for producing a sheet for an all-solid-state secondary battery of the present invention) can be performed.
For example, an inorganic solid electrolyte-containing composition containing a positive electrode active material is applied as a positive electrode material (positive electrode composition) on a metal foil which is a positive electrode current collector to form a positive electrode active material layer, and the entire solid is formed. A positive electrode sheet for a secondary battery is produced. Next, an inorganic solid electrolyte-containing composition for forming the solid electrolyte layer is applied onto the positive electrode active material layer to form the solid electrolyte layer. Further, an inorganic solid electrolyte-containing composition containing a negative electrode active material is applied as a negative electrode material (negative electrode composition) on the solid electrolyte layer to form a negative electrode active material layer. By superimposing a negative electrode current collector (metal foil) on the negative electrode active material layer, an all-solid secondary battery having a structure in which a solid electrolyte layer is sandwiched between the positive electrode active material layer and the negative electrode active material layer can be obtained. Can be done. This can be enclosed in a housing to obtain a desired all-solid-state secondary battery.
Further, by reversing the forming method of each layer, a negative electrode active material layer, a solid electrolyte layer and a positive electrode active material layer are formed on the negative electrode current collector, and the positive electrode current collectors are superposed to manufacture an all-solid secondary battery. You can also do it.

As another method, the following method can be mentioned. That is, as described above, a positive electrode sheet for an all-solid-state secondary battery is produced. Further, an inorganic solid electrolyte-containing composition containing a negative electrode active material is applied as a negative electrode material (negative electrode composition) on a metal foil which is a negative electrode current collector to form a negative electrode active material layer, and the entire solid is formed. A negative electrode sheet for a secondary battery is manufactured. Next, a solid electrolyte layer is formed on the active material layer of any one of these sheets as described above. Further, the other of the positive electrode sheet for the all-solid secondary battery and the negative electrode sheet for the all-solid secondary battery is laminated on the solid electrolyte layer so that the solid electrolyte layer and the active material layer are in contact with each other. In this way, an all-solid-state secondary battery can be manufactured.
As another method, the following method can be mentioned. That is, as described above, a positive electrode sheet for an all-solid-state secondary battery and a negative electrode sheet for an all-solid-state secondary battery are produced. Separately from this, an inorganic solid electrolyte-containing composition is applied onto a base material to prepare a solid electrolyte sheet for an all-solid secondary battery composed of a solid electrolyte layer. Further, the positive electrode sheet for the all-solid-state secondary battery and the negative electrode sheet for the all-solid-state secondary battery are laminated so as to sandwich the solid electrolyte layer peeled off from the base material. In this way, an all-solid-state secondary battery can be manufactured.
Further, as described above, a positive electrode sheet for an all-solid-state secondary battery or a negative electrode sheet for an all-solid-state secondary battery, and a solid electrolyte sheet for an all-solid-state secondary battery are produced. Next, the positive electrode sheet for the all-solid secondary battery or the negative electrode sheet for the all-solid secondary battery and the solid electrolyte sheet for the all-solid secondary battery were brought into contact with the positive electrode active material layer or the negative electrode active material layer and the solid electrolyte layer. Overlay and pressurize in the state. In this way, the solid electrolyte layer is transferred to the positive electrode sheet for the all-solid-state secondary battery or the negative electrode sheet for the all-solid-state secondary battery. Then, the solid electrolyte layer from which the base material of the solid electrolyte sheet for the all-solid secondary battery is peeled off and the negative electrode sheet for the all-solid secondary battery or the positive electrode sheet for the all-solid secondary battery are separated (the negative electrode active material layer or the negative electrode active material layer on the solid electrolyte layer). Pressurize the positive electrode active material layer in contact with each other. In this way, an all-solid-state secondary battery can be manufactured. The pressurizing method and pressurizing conditions in this method are not particularly limited, and the methods and pressurizing conditions described later in the pressurization of the applied composition can be applied.

The solid electrolyte layer or the like can be formed, for example, by pressure-molding an inorganic solid electrolyte-containing composition or the like on a substrate or an active material layer under pressure conditions described later, or sheet molding of a solid electrolyte or an active material. You can also use the body.
In the above production method, the inorganic solid electrolyte-containing composition of the present invention may be used as any one of the positive electrode composition, the inorganic solid electrolyte-containing composition and the negative electrode composition, and the inorganic solid electrolyte-containing composition, Alternatively, it is preferable to use the inorganic solid electrolyte-containing composition of the present invention for at least one of the positive electrode composition and the negative electrode composition, and the inorganic solid electrolyte-containing composition of the present invention can be used for any of the compositions.
When the solid electrolyte layer or the active material layer is formed by a composition other than the solid electrolyte composition of the present invention, examples of the material include commonly used compositions and the like. In addition, it belongs to the first or second group of the periodic table, which is accumulated in the negative electrode current collector by initialization or charging during use, which will be described later, without forming the negative electrode active material layer during the manufacture of the all-solid secondary battery. A negative electrode active material layer can also be formed by combining metal ions with electrons and depositing them as a metal on a negative electrode current collector or the like.

<Formation of each layer (deposition)>
The method for applying the composition containing an inorganic solid electrolyte is not particularly limited and can be appropriately selected. For example, coating (preferably wet coating), spray coating, spin coating coating, dip coating coating, slit coating, stripe coating, and bar coating coating can be mentioned.
At this time, the inorganic solid electrolyte-containing composition may be subjected to a drying treatment after being applied to each of them, or may be subjected to a drying treatment after being applied in multiple layers. 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. By heating in such a temperature range, the dispersion medium can be removed and a solid state (coating dry layer) can be obtained. Further, it is preferable because the temperature is not raised too high and each member of the all-solid-state secondary battery is not damaged. As a result, in the all-solid-state secondary battery, it is possible to obtain excellent overall performance, good binding property, and good ionic conductivity even without pressurization.
When the composition containing the inorganic solid electrolyte of the present invention is applied and dried as described above, a coating and drying layer (inorganic solid electrolyte) exhibiting a strong film strength in which solid particles are firmly bonded to each other while suppressing an increase in interfacial resistance. Layer) can be formed.

It is preferable to pressurize each layer or the all-solid-state secondary battery after applying the inorganic solid electrolyte-containing composition, superimposing the constituent layers, or producing the all-solid-state secondary battery. Examples of the pressurizing method include a hydraulic cylinder press machine and the like. The pressing force is not particularly limited, and is generally preferably in the range of 5 to 1500 MPa.
Further, the applied inorganic solid electrolyte-containing composition may be heated at the same time as pressurization. The heating temperature is not particularly limited, and is generally in the range of 30 to 300 ° C. It can also be pressed at a temperature higher than the glass transition temperature of the inorganic solid electrolyte. It is also possible to press at a temperature higher than the glass transition temperature of the polymer contained in the polymer binder. However, in general, the temperature does not exceed the melting point of this polymer.
The pressurization may be carried out in a state where the coating solvent or the dispersion medium has been dried in advance, or may be carried out in a state where the solvent or the dispersion medium remains.
In addition, each composition may be applied at the same time, and the application drying press may be performed simultaneously and / or sequentially. After coating on separate substrates, they may be laminated by transfer.

The manufacturing process, for example, the atmosphere during coating, heating or pressurization, is not particularly limited, and is in air, dry air (dew point -20 ° C or lower), inert gas (for example, argon gas, helium gas, nitrogen). (In gas) or the like.
The pressing time may be short (for example, within several hours) and high pressure may be applied, or medium pressure may be applied for a long time (1 day or more). In the case of an all-solid-state secondary battery other than the all-solid-state secondary battery sheet, for example, in the case of an all-solid-state secondary battery, an all-solid-state secondary battery restraint (screw tightening pressure, etc.) can be used in order to continue applying a medium pressure.
The press pressure may be uniform or different with respect to the pressed portion such as the sheet surface.
The press pressure can be changed according to the area or film thickness of the pressed portion. It is also possible to change the same part step by step with different pressures.
The pressed surface may be smooth or roughened.

<Initialization>
The all-solid-state secondary battery manufactured as described above is preferably initialized after manufacturing or before use. The initialization is not particularly limited, and can be performed, for example, by performing initial charging / discharging with the press pressure increased, and then releasing the pressure until the pressure reaches the general working pressure of the all-solid-state secondary battery.

The method for producing an all-solid secondary battery of the present invention is a highly productive production method in which bending and restoration act by using the composition containing an inorganic solid electrolyte of the present invention, particularly an industry in which bending and restoration act repeatedly. Even if it is applied to a conventional manufacturing method (for example, a roll-to-roll method), an all-solid secondary battery that realizes the above-mentioned excellent battery performance can be manufactured. That is, the above-mentioned all-solid-state secondary battery having excellent battery performance can be manufactured with high productivity.

[Applications for all-solid-state secondary batteries]
The all-solid secondary battery of the present invention can be applied to various applications. The application mode is not particularly limited, but for example, when mounted on an electronic device, a laptop computer, a pen input computer, a mobile computer, an electronic book player, a mobile phone, a cordless phone handset, a pager, a handy terminal, a mobile fax, or a mobile phone. Examples include copying, mobile printers, headphone stereos, video movies, LCD TVs, handy cleaners, portable CDs, mini discs, electric shavers, transceivers, electronic notebooks, calculators, memory cards, portable tape recorders, radios, backup power supplies, etc. Other consumer products include automobiles, electric vehicles, motors, lighting equipment, toys, game equipment, road conditioners, watches, strobes, cameras, medical equipment (pacemakers, hearing aids, shoulder massagers, etc.). Furthermore, it can be used for various munitions and space. It can also be combined with a solar cell.

Hereinafter, the present invention will be described in more detail based on Examples, but the present invention is not construed as being limited thereto. In the following examples, "parts" and "%" representing the composition are based on mass unless otherwise specified. In the present invention, "room temperature" means 25 ° C.

1. 1. Synthesis of polymer and preparation of binder solution or dispersion The polymer shown in Table 1 was synthesized as follows. In the synthesis of the polymer, commercially available compounds were used as the raw material compounds (other than those described in the synthesis examples) unless otherwise specified.
[Synthesis Example 1: Synthesis of Binder-Forming Polymer S-1 and Preparation of Binder Dispersion Liquid S-1]
A binder-forming polymer S-1 was synthesized to prepare a butyl butyrate dispersion S-1 of a binder composed of this polymer.
NISSO-PB GI1000 (trade name, manufactured by Nippon Soda Co., Ltd.) 8.10 g, polyethylene glycol (PEG200, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) 5.84 g, polytetramethylene glycol (PTMG250, manufactured by Aldrich) in a 500 mL three-necked flask. (Manufactured) 7.30 g and 1.47 g of the compound leading to the functional group-containing constituent component A-1 synthesized in Reference Synthesis Example 1 described later were added and dissolved in 103.2 g of tetrahydrofuran (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.). To this solution was added 18.52 g of diphenylmethane diisocyanate (MDI, manufactured by Tokyo Chemical Industry Co., Ltd.) and stirred at 60 ° C. to uniformly dissolve the solution. To the obtained solution, 100 mg of Neostan U-600 (trade name, manufactured by Nitto Kasei Co., Ltd.) was added and stirred at 60 ° C. for 6 hours.
The polymer solution thus obtained was cooled to 0 ° C., 15 g of tetrabutylammonium fluoride (1.0 M (mol / L) in tetrahydrofuran (THF) solution, manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and the temperature was maintained at 0 ° C. for 30 minutes. Stirred. A solution obtained by adding 20 g of a 1 M aqueous hydrochloric acid solution was poured into 600 g of acetonitrile, and the obtained polymer was redissolved in THF by removing the supernatant. ) Was obtained.
Next, 30 g of the above-mentioned polymer S-1 in THF was placed in a 300 mL three-necked flask and stirred at room temperature. 90 g of butyl butyrate was added dropwise thereto over 30 minutes, and then THF was distilled off under reduced pressure. In this way, a binder dispersion liquid S-1 (concentration: 4% by mass) made of the binder-forming polymer S-1 was obtained.

[Synthesis Example 2: Synthesis of Binder-Forming Polymer S-2 and Preparation of Binder Dispersion Liquid S-2]
A binder-forming polymer S-2 was synthesized to prepare a butyl butyrate dispersion S-2 of a binder composed of this polymer.
NISSO-PB GI1000 (trade name, manufactured by Nippon Soda Co., Ltd.) 11.10 g, polyethylene glycol (PEG200, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) 5.92 g, 1,4-butanediol (1,4-butanediol) in a 500 mL three-necked flask. 2.67 g of 4-BD) and 1.10 g of 2,2-bis (hydroxymethyl) butyric acid (DMBA, manufactured by Tokyo Chemical Industry Co., Ltd.) were added and dissolved in 101.6 g of tetrahydrofuran (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.). 18.52 g of diphenylmethane diisocyanate (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to this solution, and the mixture was stirred at 60 ° C. to uniformly dissolve it. To the obtained solution, 100 mg of Neostan U-600 (trade name, manufactured by Nitto Kasei Co., Ltd.) was added and stirred at 60 ° C. for 6 hours.
To the polymer solution thus obtained, 3.4 g of 1,2-epoxy heptane (manufactured by Tokyo Chemical Industry Co., Ltd.) and 1.2 g of tetrabutylammonium bromide (manufactured by Tokyo Chemical Industry Co., Ltd.) were added, and the mixture was stirred at 60 ° C. for 6 hours. .. The obtained solution was poured into 600 g of acetonitrile, the supernatant was removed, and the obtained polymer was redissolved in THF to cause a THF solution (concentration 10) of the polymer S-2 (polyurethane) having a functional group-containing component A-2. Mass%) was obtained.
Next, 30 g of the above-mentioned polymer S-2 in THF was placed in a 300 mL three-necked flask and stirred at room temperature. 90 g of butyl butyrate was added dropwise thereto over 30 minutes, and then THF was distilled off under reduced pressure. In this way, a binder dispersion liquid S-2 (concentration: 4% by mass) made of the binder-forming polymer S-2 was obtained.

[Synthesis Examples 3 to 5: Synthesis of Binder Forming Polymers S-3 to S-5 and Preparation of Binder Dispersion Liquids S-3 to S-5]
In Synthesis Example 2, instead of 1,2-epoxyheptane, 2-hydroxymethylaziridine, glycidylmethyl ether (manufactured by Tokyo Chemical Industry Co., Ltd.) and glycidol (manufactured by Tokyo Chemical Industry Co., Ltd.) synthesized in Reference Synthesis Example 2 were used, respectively. Binder-forming polymers S-3 to S- having functional group-containing constituents A-3, A-4 or A-5, as in Synthesis Example 2, except that they were used in the amounts shown in Table 1. Each of 5 (polyurethane) was synthesized to obtain binder dispersions S-3 to S-5 (concentration: 4% by mass) composed of each binder-forming polymer.

[Synthesis Example 6: Synthesis of Binder-Forming Polymer S-6 and Preparation of Binder Solution S-6]
In Synthesis Example 1, a binder is used in the same manner as in Synthesis Example 1, except that a compound that guides each component so that the polymer S-6 has the composition (type and content of components) shown in Table 1 is used. The forming polymer S-6 (polyurethane) was synthesized to obtain a binder solution S-6 (concentration: 4% by mass) composed of the binder forming polymer S-6.

[Synthesis Example 7: Synthesis of Binder-Forming Polymer S-7 and Preparation of Binder Solution S-7]
NISSO-PB GI1000 (trade name, manufactured by Nippon Soda Co., Ltd.) 11.10 g, polyethylene glycol (PEG200, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) 5.92 g, polytetramethylene glycol (PTMG250, manufactured by Aldrich) in a 500 mL three-necked flask. (Manufactured by) 7.40 g and 0.88 g of N-methyldiethanolamine were added and dissolved in 101.1 g of tetrahydrofuran (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.). 18.52 g of diphenylmethane diisocyanate (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to this solution, and the mixture was stirred at 60 ° C. to uniformly dissolve it. To the obtained solution, 100 mg of Neostan U-600 (trade name, manufactured by Nitto Kasei Co., Ltd.) was added and stirred at 60 ° C. for 6 hours.
30 g of a THF solution of the polymer S-7 (polyurethane) thus obtained was placed in a 300 mL three-necked flask and stirred at room temperature. 90 g of butyl butyrate was added dropwise thereto over 30 minutes, and then THF was distilled off under reduced pressure. In this way, a binder dispersion liquid S-7 (concentration: 4% by mass) made of the binder-forming polymer S-7 was obtained.

[Synthesis Example 8: Synthesis of Binder-Forming Polymer S-8 and Preparation of Binder Solution S-8]
In Synthesis Example 1, a binder is used in the same manner as in Synthesis Example 1, except that a compound that guides each component so that the polymer S-8 has the composition (type and content of components) shown in Table 1 is used. The forming polymer S-8 (polyurethane) was synthesized to obtain a binder solution S-8 (concentration: 4% by mass) composed of each binder forming polymer.

[Synthesis Example 9: Synthesis of Polymer S-9 and Preparation of Binder Dispersion Liquid S-9]
In a 500 mL three-necked flask, 7.78 g of dicyclohexylmethane-4,4'-diisocyanate, 183 g of THF, 55.50 g of the compound leading to the component B-1, and the functional group-containing component A synthesized in Reference Synthesis Example 4 described later. 14.95 g of the compound leading to -8 was added, and the mixture was stirred at 60 ° C. for 30 hours.
30 g of a THF solution of the polymer S-9 (polyurethane) thus obtained was placed in a 300 mL three-necked flask and stirred at room temperature. 90 g of butyl butyrate was added dropwise thereto over 30 minutes, and then THF was distilled off under reduced pressure. In this way, a binder dispersion liquid S-9 (concentration: 4% by mass) made of the binder-forming polymer S-9 was obtained.

[Synthesis Example 10: Synthesis of Polymer S-10 and Preparation of Binder Dispersion Liquid S-10]
In a 200 mL three-necked flask, 15.0 g of NISSO-PB GI1000 (trade name, manufactured by Nippon Soda Co., Ltd.), 14.0 g of a compound that derives a functional group-containing component A-1, and dimethyl adipate (manufactured by Tokyo Chemical Industry Co., Ltd.) 11. 0 g was added and the mixture was stirred at 150 ° C. To the obtained solution, 0.27 g of tetrabutyl orthotitanium was added and stirred at 180 ° C. for 8 hours to obtain a solution of polymer S-10 (polyester).
3 g of a solution of polymer S-10 and 27 g of THF were placed in a 300 mL three-necked flask and stirred at room temperature. 90 g of butyl butyrate was added dropwise thereto over 30 minutes, and then THF was distilled off under reduced pressure. In this way, a binder dispersion liquid S-10 (concentration: 4% by mass) made of the binder-forming polymer S-10 was obtained.

[Synthesis Example 11: Synthesis of Polymer S-11 and Preparation of Binder Dispersion Liquid S-11]
In Synthesis Example 2, a binder is used in the same manner as in Synthesis Example 2, except that a compound that guides each component so that the polymer S-11 has the composition (type and content of components) shown in Table 1 is used. The forming polymer S-11 (polyurethane) was synthesized to obtain a binder dispersion liquid S-11 (concentration: 4% by mass) composed of each binder forming polymer.

[Synthesis Example 12: Synthesis of Polymer S-12 and Preparation of Binder Dispersion Liquid S-12]
In Synthesis Example 1, the binder-forming polymer S-12 (polyurethane) was synthesized in the same manner as in Synthesis Example 1 except that PEG200 was replaced with 4.33 g of EDR-176 (manufactured by Huntsman) to form each binder. A binder dispersion S-12 (concentration: 4% by mass) made of a polymer was obtained.

[Synthesis Examples 13 to 16: Synthesis of Polymers T-1, T-3 to T-5, and Preparation of Binder Dispersions T-1, T-3 to T-5]
Synthesis example 1 except that a compound that guides each component so that the polymers T-1, T-3 to T-5 have the composition (type and content of the component) shown in Table 1 is used. Polymers T-1, T-3 to T-5 (polyurethane) are synthesized in the same manner as in Example 1, and binder dispersions T-1, T-3 to T-5 (concentration 4 mass) composed of the respective polymers are synthesized. %) Was obtained respectively.

[Synthesis Example 17: Synthesis of Polymer T-2 and Preparation of Binder Dispersion Liquid T-2]
Dodecyl acrylate (manufactured by Tokyo Kasei Kogyo Co., Ltd.) 13.7 g, mono oxalate (2-acryloyloxyethyl) (manufactured by Tokyo Kasei Kogyo Co., Ltd.) 7.20 g, 2-hydroxyethyl acrylate (manufactured by Tokyo Kasei Kogyo Co., Ltd.) in a 100 mL measuring flask. 15.2 g of the polymerization initiator V-601 (trade name, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was added and dissolved in 36 g of butyl butyrate to prepare a monomer solution.
Next, 18 g of butyl butyrate was added to a 300 mL three-necked flask, and the mixture was stirred at 80 ° C., and the above monomer solution was added dropwise over 2 hours. After completion of the dropping, the temperature is raised to 90 ° C. and stirred for 2 hours to synthesize a polymer T-2 ((meth) acrylic polymer), and a dispersion liquid T-2 (concentration 40% by mass) of a binder composed of the polymer T-2. Got

[Synthesis Example 18: Synthesis of Polymer T-6 and Preparation of Binder Dispersion Liquid T-6]
6FDA (manufactured by Tokyo Chemical Industry Co., Ltd.) 20.7 g, DAPE (manufactured by Tokyo Chemical Industry Co., Ltd.) 8.39 g, Amidol (manufactured by Tokyo Chemical Industry Co., Ltd.) 0.92 g and THF 120 g are added to a 300 mL three-necked flask, and the mixture is added at 40 ° C. for 8 hours. Stirring gave a THF solution.
Then, 30 g of the obtained THF solution and 30 g of THF were added to a 500 mL three-necked flask, and then 180 g of butyl butyrate was added dropwise at room temperature over 30 minutes. THF was distilled off from the obtained solution under reduced pressure to synthesize a polymer T-6 (polyimide) to obtain a binder dispersion T-6 (concentration: 4% by mass) composed of the polymer T-6.

[Measurement of average particle size and mass average molecular weight of polymers, etc.]
Table 1 shows the mass average molecular weight of each synthesized polymer and the average particle size of each binder (in Table 1, it is simply referred to as "particle size". If the binder is a soluble type, it is indicated as "dissolved" in the particle size column). show.
The mass average molecular weight of each polymer was measured by the above method (condition 2).
The pKa of the functional group in the polymers S-1 to S-12 is in the range of 1 to 20.

<Table abbreviation>
In the table, "-" in the component column indicates that the component does not have the corresponding component.
The components indicated by the abbreviations in the table are shown below. "PEG200" is polyethylene glycol (number average molecular weight 200, manufactured by Fujifilm Wako Junyaku Co., Ltd.), and "PPG400" is polypropylene glycol (number average molecular weight 400, manufactured by Fujifilm Wako Junyaku Co., Ltd.), and "PTMG250". Is polytetramethylene ether glycol (number average molecular weight 250, manufactured by SIGMA-Aldrich), and "GI1000" is hydride liquid polybutadiene diol: NISSO-PB GI1000 (trade name, number average molecular weight 1400, manufactured by Nippon Soda Co., Ltd.). Is. Further, "EDR-176" is a polyetheramine: Jeffamine EDR-176 (trade name, manufactured by Huntsman).
The component M1 represents a component represented by the above formula (I-1) or formula (I-2). However, with respect to the polymer T-6, the constituent components derived from the carboxylic acid anhydride are exceptionally described.
The component M2 represents a component represented by the above formula (I-3B). When the binder-forming polymer contains two or more kinds of polyether structures, the constituent components represented by the formula (I-7) having a polyether structure formed of an alkyleneoxy group having a small molecular weight are shown. However, with respect to the polymer T-6, the constituent components derived from diaminodiphenyl ether (DAPE) are described as an exception.
The component M3 represents a component represented by the above formula (I-3B). When the binder-forming polymer contains two or more kinds of polyether structures, the constituent components represented by the formula (I-7) having a polyether structure formed of an alkyleneoxy group having a large molecular weight are shown. However, for the polymer T-2, the constituent components derived from dodecyl methacrylate (LMA) are exceptionally described, and for the polymer T-3, the constituent components represented by the formula (I-3A) are exceptionally described. ..
The component M4 represents a component represented by the above formula (1-3C).
The component M5 represents a component containing the above-mentioned functional group. Exceptionally, the components derived from DMBA are described for the polymer T-5.

[Reference Synthesis Example 1: Synthesis of Compound Leading to Functional Group-Containing Component A-1]
30.0 g of thioglycerol (manufactured by Tokyo Chemical Industry Co., Ltd.), 42.4 g of 2,6-lutidine (manufactured by Tokyo Chemical Industry Co., Ltd.) and 150 g of tetrahydrofuran were added to a 500 mL three-necked flask, and the mixture was stirred at room temperature. To the obtained solution, 72.0 g of trimethylsilyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) and 42.4 g of 2,6-lutidine (manufactured by Tokyo Chemical Industry Co., Ltd.) were added, and the mixture was stirred at room temperature for 4 hours. 50 mL of a 1 M aqueous hydrochloric acid solution was added to the obtained solution, the mixture was extracted 3 times with 200 mL of ethyl acetate, and then dried over 30 g of sodium sulfate. By distilling off ethyl acetate under reduced pressure, a compound leading to the functional group-containing constituent component A-1 was synthesized.

[Reference Synthesis Example 2: Synthesis of 2-Hydroxymethyl Aziridine]
30.0 g of glycerol (manufactured by Tokyo Chemical Industry Co., Ltd.) and 100 g of acetonitrile were added to a 500 mL three-necked flask, and the mixture was stirred at room temperature. 56.5 g of sodium azide (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to the obtained solution, and the mixture was stirred at room temperature for 4 hours. A saturated aqueous sodium nitrite solution and 1M hydrochloric acid were added to the obtained solution, and the mixture was extracted 3 times with 300 g of ethyl acetate. After distilling off ethyl acetate under reduced pressure, the obtained compound was added to a 500 mL three-necked flask. 160 g of dichloromethane (manufactured by Tokyo Chemical Industry Co., Ltd.), 78.3 g of tributylchlorosilane (manufactured by Tokyo Chemical Industry Co., Ltd.) and 74.2 g of 2,6-lutidine (manufactured by Tokyo Chemical Industry Co., Ltd.) were added thereto, and the mixture was stirred at room temperature for 6 hours. 100 g of triphenylphosphine (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to the obtained solution, and the mixture was stirred at 50 ° C. for 8 hours. After adding 1M hydrochloric acid to the obtained solution, the mixture was extracted 3 times with 300 g of ethyl acetate. After distilling off ethyl acetate under reduced pressure, the obtained compound was added to a 500 mL three-necked flask. After adding 200 g of tetrahydrofuran to it, the mixture was stirred at 0 ° C. for 30 minutes, 60 g of tetrabutylammonium bromide fluoride (1M tetrahydrofuran solution, manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and the mixture was further stirred at room temperature for 1 hour. After adding 1M hydrochloric acid, the mixture was extracted 3 times with 300 g of ethyl acetate. 2-Hydroxymethylaziridine was synthesized by distilling off ethyl acetate under reduced pressure.

[Reference Synthesis Example 3: Synthesis of Compound Leading to Functional Group-Containing Component A-6]
Functional group-containing constituent A in the same manner as in Reference Synthesis Example 1, except that 3-amino-1,2-propanediol (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of thioglycerol in Reference Synthesis Example 1. A compound leading to -6 was synthesized.

[Reference Synthesis Example 4: Synthesis of Compound Leading to Functional Group-Containing Component A-8]
Add 50 g of N-methylpyrrolidone (NMP), 25 g of 1,5-hexadiendiepoxide (manufactured by Tokyo Chemical Industry Co., Ltd.) and 1.2 g of lithium chloride (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) to a 200 mL three-necked flask to create a carbon dioxide atmosphere. Underneath, it was stirred at 100 ° C. for 24 hours. 100 g of ethyl acetate was added to the obtained solution, the mixture was washed 3 times with 200 mL of water, and then dried over 30 g of sodium sulfate. By distilling off ethyl acetate under reduced pressure, a compound leading to the functional group-containing constituent component A-8 was synthesized.

[Reference Synthesis Example 5: Synthesis of Compound Leading to Component B-1]
To a 500 mL three-necked eggplant flask, 50 g of NISSO-PB GI1000, 100 g of dichloromethane (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), and 10 g of tosyl lolide (manufactured by Tokyo Chemical Industry Co., Ltd.) were added, and the mixture was stirred at 0 ° C. To the obtained solution, 24 g of triethylamine (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was added, and the mixture was further stirred at 0 ° C. for 4 hours. The obtained solution was poured into 500 g of acetonitrile and the supernatant was removed to obtain a solid substance.
To a 500 mL three-necked eggplant flask, 45 g of the above solid, 80 g of toluene (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) and 23 g of phthalimide (manufactured by Tokyo Chemical Industry Co., Ltd.) were added, and the mixture was stirred at room temperature for 12 hours. 100 g of ethanol was added to the obtained solution, and the mixture was further stirred at 80 ° C. for 12 hours. The resulting solution was poured into 500 g of acetonitrile and the supernatant was removed to give a solid. Acetonitrile was distilled off under reduced pressure to synthesize a compound leading to component B-1.

A binder solution was prepared using a soluble binder as another binder.
[Preparation Example 1: Synthesis of Vinyl Polymer D-1 and Preparation of Soluble Binder Solution D-1]
Dodecyl acrylate (manufactured by Tokyo Kasei Kogyo Co., Ltd.) 14.2 g, styrene (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) 21.6 g, maleic anhydride (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) 0.25 g and polymerization in a 100 mL measuring flask. 0.36 g of the initiator V-601 (trade name, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was added and dissolved in 36 g of butyl butyrate to prepare a monomer solution.
18 g of butyl butyrate was added to a 300 mL three-necked flask, and the mixture was stirred at 80 ° C., and the above monomer solution was added dropwise over 2 hours. After completion of the dropping, the temperature was raised to 90 ° C. and the mixture was stirred for 2 hours to synthesize polymer D-1 (vinyl-based polymer) to obtain a binder solution D-1 (concentration 40% by mass) composed of polymer D-1. ..

[Preparation Example 2: Synthesis of (meth) acrylic polymer D-2 and preparation of soluble binder solution D-2]
To a 100 mL volumetric flask, 36.0 g of hexyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) and 0.36 g of the polymerization initiator V-601 (trade name, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) were added and dissolved in 36 g of butyl butyrate. A monomer solution was prepared.
18 g of butyl butyrate was added to a 300 mL three-necked flask, and the mixture was stirred at 80 ° C., and the above monomer solution was added dropwise over 2 hours. After completion of the dropping, the temperature was raised to 90 ° C., and the mixture was further stirred for 2 hours to synthesize polymer D-2 (methacrylic polymer) to obtain a binder solution D-2 (concentration 40% by mass) composed of polymer D-2. ..

The synthesized vinyl polymer D-1 and (meth) acrylic polymer D-2 are shown below.
The number attached to the lower right of each component indicates the content in the polymer, and the unit is mol%.

[Preparation Example 3: Preparation of Soluble Binder Solution M1911 Consisting of Hydrocarbon Polymer]
Tough Tech (registered trademark) M1911: Maleic anhydride-modified hydrogenated styrene-based thermoplastic elastomer (trade name, SEBS, manufactured by Asahi Kasei Co., Ltd.) was dissolved in butyl butyrate to prepare a binder solution M1911 having a solid content concentration of 10% by mass.
Maleic anhydride-modified hydrogenated styrene-based thermoplastic elastomer has a mass average molecular weight of 120,000, a styrene / ethylene / butylene ratio of 30/70, and a maleic anhydride-modified amount (content of a component having a maleic anhydride group). ) Was 0.4 mol%.

[Preparation Example 4: Preparation of soluble binder solution UFB composed of fluoropolymer]
PVdF-HFP: Kynar Flex Ultraflex B (trade name, manufactured by Arkema Co., Ltd.) was dissolved in butyl butyrate to prepare a binder solution UFB having a solid content concentration of 3% by mass.
The mass average molecular weight of PVdF-HFP was 200,000, and the copolymerization ratio [PVdF: HFP] (mass ratio) was 58:42.

2. Synthesis of sulfide-based inorganic solid electrolyte [Synthesis Example A]
Sulfide-based inorganic solid electrolytes are described in T.I. Ohtomo, A.M. Hayashi, M. et al. Tassumisago, Y. et al. Tsuchida, S.A. Hama, K.K. Kawamoto, Journal of Power Sources, 233, (2013), pp231-235, and A.M. Hayashi, S.A. Hama, H. Morimoto, M.D. Tatsumi sago, T. et al. Minami, Chem. Lett. , (2001), pp872-873, was synthesized with reference to the non-patent documents.
_{Specifically, 2.42 g of lithium sulfide (Li 2} S, manufactured by Aldrich, purity> 99.98%) and diphosphorus pentasulfide (P ₂ S) in a glove box under an argon atmosphere (dew point -70 ° C). _5. Aldrich, purity> 99%) 3.90 g of each was weighed, placed in an agate mortar, and mixed for 5 minutes using an agate mortar. The mixing ratio of Li ₂ S and P ₂ S ₅ _{was Li 2} S: P ₂ S ₅ = 75: 25 in terms of molar ratio.
Next, 66 g of zirconia beads having a diameter of 5 mm was put into a 45 mL container made of zirconia (manufactured by Fritsch), and the entire amount of the above mixture of lithium sulfide and diphosphorus pentasulfide was put into the container, and the container was completely sealed under an argon atmosphere. A container is set in a planetary ball mill P-7 (trade name, manufactured by Fritsch) manufactured by Fritsch, and mechanical milling is performed at a temperature of 25 ° C. at a rotation speed of 510 rpm for 20 hours to produce a sulfide-based inorganic solid electrolyte of yellow powder. (Li-PS-based glass, hereinafter sometimes referred to as LPS.) 6.20 g was obtained. The average particle size of the Li-PS-based glass was 15 μm.

[Example 1]
Each composition shown in Tables 2-1 to 2-3 (collectively referred to as Table 2) was prepared as follows.
<Preparation of composition containing inorganic solid electrolyte>
60 g of zirconia beads having a diameter of 5 mm was put into a zirconia 45 mL container (manufactured by Fritsch), 8.4 g of LPS synthesized in Synthesis Example A, 0.6 g or 0.4 g of the binder dispersion or solution shown in Table 2 (solid). When 0.4 g of the binder dispersion was used, 0.2 g (solid content mass) of the soluble binder solution shown in Table 2 and 11 g of butyl acetate as the dispersion medium were further added. After that, this container was set in a planetary ball mill P-7 (trade name) manufactured by Fritsch. Inorganic solid electrolyte-containing compositions (slurries) K-1 to K-16 and Kc-11 to Kc-16 were prepared by mixing at a temperature of 25 ° C. and a rotation speed of 150 rpm for 10 minutes, respectively.

<Preparation of composition for positive electrode>
60 g of zirconia beads having a diameter of 5 mm was put into a 45 mL container made of zirconia (manufactured by Fritsch), 8 g of LPS synthesized in Synthesis Example A, and 13 g (total amount) of the dispersion medium shown in Table 2 were put. This container was set on a planetary ball mill P-7 (trade name) manufactured by Fritsch, and stirred at 25 ° C. at a rotation speed of 200 pm for 30 minutes. Then, in this container, 27.5 g of NMC (manufactured by Aldrich) as the positive electrode active material, 1.0 g of acetylene black (AB) as the conductive auxiliary agent, and 0.5 g of the binder dispersion or solution shown in Table 2 (solid content). (Mass), when 12.5 g of butyl butyrate is used in PK-7 to PK-9, 0.5 g (solid content mass) of the soluble binder solution shown in Table 2 is further added, and the container is set in the planetary ball mill P-7. Mixing was continued for 30 minutes at a temperature of 25 ° C. and a rotation speed of 200 rpm to prepare positive electrode compositions (slurries) PK-1 to PK-9, respectively.

<Preparation of composition for negative electrode>
60 g of zirconia beads having a diameter of 5 mm was put into a 45 mL container made of zirconia (manufactured by Fritsch), 8.0 g or 7.6 g of LPS synthesized in Synthesis Example A, and 0.4 g of the binder dispersion or solution shown in Table 2 ( Solid content mass), when 7.6 g of LPS is used in NK-11 to NK-13, 0.4 g (solid content mass) of the soluble binder solution shown in Table 2 and 17.5 g (solid content mass) of the dispersion medium shown in Table 2 are further added. Total amount) was put in. This container was set on a planetary ball mill P-7 (trade name) manufactured by Fritsch, and mixed at a temperature of 25 ° C. and a rotation speed of 300 pm for 60 minutes. After that, 9.5 g of the negative electrode active material shown in Table 2 and 1.0 g of VGCF (manufactured by Showa Denko Co., Ltd.) were added as the conductive auxiliary agent, and similarly, the container was set on the planetary ball mill P-7 and the temperature was 25 ° C. , Negative electrode compositions (slurries) NK-1 to NK-13 and NKc21 to NKc26 were prepared by mixing at a rotation speed of 100 rpm for 10 minutes, respectively.

The particulate binders in the inorganic solid electrolyte-containing composition, the positive electrode composition, and the negative electrode composition maintained the average particle size in the binder dispersion.

<Table abbreviation>
LPS: LPS synthesized in Synthesis Example A
NMC: LiNi _1/3 Co _1/3 Mn _1/3 O ₂
Si: Silicon (Si, manufactured by Aldrich)
Graphite: CGB20 (trade name, manufactured by Nippon Graphite Co., Ltd.)
AB: Acetylene Black VGCF: Carbon Nanotube (manufactured by Showa Denko KK)

<Preparation of solid electrolyte sheet for all-solid secondary batteries>
Each of the inorganic solid electrolyte-containing compositions shown in Tables 3-1 and 3-2 (collectively referred to as Table 3) obtained above is placed on an aluminum foil having a thickness of 20 μm with a baker-type applicator (trade name:). The composition was applied using SA-201 (manufactured by Tester Sangyo Co., Ltd.) and heated at 80 ° C. for 2 hours to dry (remove the dispersion medium) the composition containing an inorganic solid electrolyte. Then, using a heat press machine, the inorganic solid electrolyte-containing composition dried at a temperature of 120 ° C. and a pressure of 40 MPa for 10 seconds is heated and pressurized to obtain a solid electrolyte sheet for an all-solid secondary battery (in Table 3). It is referred to as a solid electrolyte sheet.) 101 to 116 and c11 to c16 were prepared, respectively. The film thickness of the solid electrolyte layer was 50 μm.

<Manufacturing positive electrode sheets for all-solid-state secondary batteries>
As the electrode composition shown in Table 3, the positive electrode composition obtained above was applied onto an aluminum foil having a thickness of 20 μm using a baker-type applicator (trade name: SA-201), and heated at 80 ° C. for 1 hour. Further, the composition was heated at 110 ° C. for 1 hour to dry (remove the dispersion medium) the composition for the positive electrode. Then, using a heat press machine, the dried positive electrode composition is pressurized at 25 ° C. (10 MPa, 1 minute) to provide a positive electrode sheet for an all-solid secondary battery having a positive electrode active material layer having a thickness of 80 μm (10 MPa, 1 minute). In Table 3, it is referred to as a positive electrode sheet.) 117 to 125 were prepared respectively.

<Manufacturing of negative electrode sheet for all-solid-state secondary battery>
As the electrode composition shown in Table 3, the negative electrode composition obtained above was applied onto a copper foil having a thickness of 20 μm using a baker-type applicator (trade name: SA-201), and heated at 80 ° C. for 1 hour. Then, the composition was further heated at 110 ° C. for 1 hour to dry (remove the dispersion medium) the composition for the negative electrode. Then, using a heat press machine, the dried composition for the negative electrode is pressurized at 25 ° C. (10 MPa, 1 minute) to obtain a negative electrode sheet for an all-solid secondary battery having a negative electrode active material layer having a thickness of 70 μm (a negative electrode sheet for an all-solid secondary battery). In Table 3, it is referred to as a negative electrode sheet.) 126 to 138 and c21 to c26 were prepared, respectively.

<Evaluation 1: Dispersion stability>
Each of the prepared compositions (slurries) was placed in a glass test tube having a diameter of 10 mm and a height of 4 cm up to a height of 4 cm, and allowed to stand at 25 ° C. for 72 hours. The solid content ratio for 1 cm was calculated from the slurry liquid surface before and after standing. Specifically, before and after standing, liquids up to 1 cm below the slurry liquid surface were taken out and dried by heating in an aluminum cup at 120 ° C. for 2 hours. After that, the mass of the solid content in the cup was measured to determine the solid content before and after standing. The solid content ratio [WA / WB] of the solid content WA after standing to the solid content WB before standing was determined.
The ease of sedimentation (precipitation) of the inorganic solid electrolyte was evaluated as the dispersion stability of the composition containing the inorganic solid electrolyte depending on which of the following evaluation criteria the solid content ratio was included in. In this test, the closer the solid content ratio is to 1, the better the dispersion stability is, and the evaluation standard "D" or higher is the pass level. The results are shown in Table 3.

- Evaluation criteria -
A: 0.9 ≤ solid content ratio ≤ 1.0
B: 0.7 ≤ solid content ratio <0.9
C: 0.5 ≤ solid content ratio <0.7
D: 0.3 ≤ solid content ratio <0.5
E: 0.1 ≤ solid content ratio <0.3
F: Solid content ratio <0.1

<Evaluation 2: Membrane strength>
The solid electrolyte sheet for the all-solid-state secondary battery, the negative electrode sheet for each all-solid-state secondary battery, and the positive electrode sheet for each all-solid-state secondary battery produced as described above were cut out into a rectangle of 3 cm × 14 cm, respectively. The cut out sheet was cut out using a cylindrical mandrel testing machine "Product Code 056" (mandrel diameter 10 mm, manufactured by Allgood), Japanese Industrial Standards (JIS) K5600-5-1 (flexibility (cylindrical mandrel: type 2). (Test using the test equipment of the above), the same test as the international standard (ISO) 1519.). Then, the bent sheet was replaced. This bending and restoration was repeated 50 times as one time. The test piece was set with its solid electrolyte layer on the opposite side of the mandrel (base material on the mandrel side) and the width direction of the test piece substantially parallel to the central axis of the mandrel.
After the above bending test, a range of 3 cm × 8 cm including the bent portion of each sheet was visually observed to examine the state of occurrence of defects. The state of occurrence of defects was applied to the following evaluation criteria, and the film strength of the sheet (constructive layer) was applied. Was evaluated. In this test, the evaluation standard "C" or higher is passed. The results are shown in Table 3.

-Evaluation criteria-
A: No defects (chips, cracks, cracks, peeling) were found.
B: The area of the defective part is 0% or more and 10% or less of the total area to be observed C: The area of the defective part is 10% or more and 30% or less of the total area to be observed D: The area of the defective part However, 30% or more and 50% or less of the total area to be observed E: The area of the defective part is 50% or more and 70% or less of the total area to be observed F: The area of the defective part is the observation target More than 70% of the total area and 90% or less G: The area of the defective part exceeded 90% of the total area to be observed.

<Manufacturing of all-solid-state secondary batteries>
In the production of the all-solid-state secondary battery, a solid electrolyte layer was formed on each active material layer of the positive electrode sheet for the all-solid-state secondary battery and the negative electrode sheet for the all-solid-state secondary battery as follows.
(Preparation of positive electrode sheet for all-solid secondary battery with solid electrolyte layer)
Next, on the positive electrode active material layer of each positive electrode sheet for an all-solid secondary battery shown in the “electrode active material layer” column of Table 4, the solid electrolyte sheet shown in the “solid electrolyte layer” column of Table 4 prepared above was prepared. Is layered so that the solid electrolyte layer is in contact with the positive electrode active material layer, and is transferred (laminated) by pressurizing 50 MPa at 25 ° C. using a press machine, and then pressurizing 600 MPa at 25 ° C. to obtain a solid electrolyte layer having a thickness of 30 μm. The positive electrode sheets for all-solid secondary batteries (thickness of the positive electrode active material layer 60 μm) 117 to 125, respectively, were prepared.

(Preparation of negative electrode sheet for all-solid secondary battery with solid electrolyte layer)
First, on the negative electrode active material layer of each negative electrode sheet for an all-solid secondary battery shown in the "electrode active material layer" column of Table 4, the solid electrolyte sheet shown in the "solid electrolyte layer" column of Table 4 prepared above. The solid electrolyte layer is layered so that the negative electrode active material layer is in contact with the negative electrode active material layer, and is transferred (laminated) by pressurizing at 25 ° C. at 50 MPa using a press machine. The negative electrode sheets for all-solid secondary batteries (thickness of the negative electrode active material layer 50 μm) 126 to 138 and c21 to c26, respectively, were prepared.

(Manufacturing of all-solid-state secondary battery No. 101)
An all-solid-state secondary battery (No. 101) having the layer structure shown in FIG. 1 was produced as follows.
The positive electrode sheet No. 1 for an all-solid secondary battery having a solid electrolyte layer obtained above. 117 (the aluminum foil of the solid electrolyte-containing sheet has been peeled off) is cut out into a disk shape with a diameter of 14.5 mm, and as shown in FIG. 2, a stainless steel 2032 incorporating a spacer and a washer (not shown in FIG. 2). I put it in the mold coin case 11. Next, a lithium foil cut out in a disk shape having a diameter of 15 mm was overlaid on the solid electrolyte layer. After further stacking the stainless steel foil on it, the 2032 type coin case 11 was crimped to obtain the No. 2 shown in FIG. 101 all-solid-state secondary batteries 13 were manufactured.
The all-solid-state secondary battery manufactured in this manner has the layer structure shown in FIG. 1 (however, the lithium foil corresponds to the negative electrode active material layer 2 and the negative electrode current collector 1).

(Manufacturing of all-solid-state secondary batteries Nos. 102 to 109)
In the production of the all-solid-state secondary battery (No. 101), the positive electrode sheet No. 1 for an all-solid-state secondary battery provided with a solid electrolyte layer. Instead of 117, No. 1 shown in the “Electrode active material layer” column of Table 4. In the same manner as in the production of the all-solid-state secondary battery (No. 101), the all-solid-state secondary battery (No. 101) was used, except that the positive electrode sheet for the all-solid-state secondary battery provided with the solid-state electrolyte layer was used. 102 to 109) were produced respectively.

(Manufacturing of all-solid-state secondary battery No. 110)
An all-solid secondary battery (No. 110) having the layer structure shown in FIG. 1 was produced as follows.
Negative electrode sheet No. for each all-solid-state secondary battery having a solid electrolyte obtained above. 126 (the aluminum foil of the solid electrolyte-containing sheet has been peeled off) is cut out into a disk shape with a diameter of 14.5 mm, and as shown in FIG. 2, a stainless steel 2032 incorporating a spacer and a washer (not shown in FIG. 2). I put it in the mold coin case 11. Next, a disk-shaped positive electrode sheet (positive electrode active material layer) punched out from the positive electrode sheet for an all-solid secondary battery prepared below with a diameter of 14.0 mm was superposed on the solid electrolyte layer. From the all-solid secondary battery laminate 12 (stainless steel foil-aluminum foil-positive positive active material layer-solid electrolyte layer-negative negative active material layer-copper foil) by further stacking a stainless steel foil (positive electrode current collector) on it. Laminated body) was formed. After that, by crimping the 2032 type coin case 11, the all-solid-state secondary battery No. 2 shown in FIG. 110 was manufactured.

The positive electrode sheet for the solid-state secondary battery used in the production of the all-solid-state secondary battery (No. 110) was prepared as follows.
(Preparation of composition for positive electrode)
180 zirconia beads having a diameter of 5 mm were put into a 45 mL container made of zirconia (manufactured by Fritsch), 2.7 g of LPS synthesized in the above synthesis example A, KYNAR FLEX 2500-20 (trade name, PVdF-HFP: polyfluoridene fluoride). Vinylidene hexafluoropropylene copolymer (manufactured by Arkema) was added in an amount of 0.3 g as a solid content mass, and butyl butyrate was added in an amount of 22 g. This container was set on a planetary ball mill P-7 (trade name) manufactured by Fritsch, and stirred at 25 ° C. and a rotation speed of 300 rpm for 60 minutes. _{After that, 7.0 g of LiNi 1/3} Co _1/3 Mn _1/3 O ₂ (NMC) was added as the positive electrode active material, and in the same manner, the container was set in the planetary ball mill P-7, and the temperature was 25 ° C. Mixing was continued at 100 rpm for 5 minutes to prepare a positive electrode composition.
(Preparation of positive electrode sheet for solid secondary battery)
The positive electrode composition obtained above is applied onto an aluminum foil (positive electrode current collector) having a thickness of 20 μm with a baker-type applicator (trade name: SA-201, manufactured by Tester Sangyo Co., Ltd.) and heated at 100 ° C. for 2 hours. Then, the composition for the positive electrode was dried (the dispersion medium was removed). Then, using a heat press machine, the dried positive electrode composition is pressurized at 25 ° C. (10 MPa, 1 minute) to prepare a positive electrode sheet for an all-solid secondary battery having a positive electrode active material layer having a thickness of 80 μm. bottom.

(Manufacture of all-solid-state secondary batteries Nos. 111 to 122 and c101 to c106)
In the production of the all-solid-state secondary battery (No. 110), the negative electrode sheet No. 1 for an all-solid-state secondary battery provided with a solid electrolyte layer. Instead of 126, No. 1 shown in the “Electrode active material layer” column of Table 4. In the same manner as in the production of the all-solid-state secondary battery (No. 110), the all-solid-state secondary battery (No. 110) was used, except that the negative electrode sheet for the all-solid secondary battery provided with the solid-state electrolyte layer was used. 111 to 122 and c101 to c106) were produced, respectively.

<Evaluation 3: Ion conductivity measurement>
The ionic conductivity of each manufactured all-solid-state secondary battery was measured. Specifically, for each all-solid-state secondary battery, AC impedance was measured from a voltage amplitude of 5 mV and a frequency of 1 MHz to 1 Hz using 1255B FREQUENCY RESPONSE ANALYZER (trade name, manufactured by SOLARTRON) in a constant temperature bath at 30 ° C. As a result, the resistance of the sample for measuring ionic conductivity in the layer thickness direction was determined, and the ionic conductivity was determined by calculating with the following formula (1).

Equation (1): Ion conductivity σ (mS / cm) =
1000 x sample layer thickness (cm) / [resistance (Ω) x sample area (cm ² )]

In the formula (1), the sample layer thickness is a value obtained by measuring the laminate 12 before putting it in the 2032 type coin case 11 and subtracting the thickness of the current collector (total layer thickness of the solid electrolyte layer and the electrode active material layer). Is. The sample area is the area of the disk-shaped sheet.
It was determined which of the following evaluation criteria the obtained ionic conductivity σ was included in.
The ionic conductivity σ in this test passed the evaluation standard "D" or higher. The results are shown in Table 4.

- Evaluation criteria -
A: 0.90 ≤ σ
B: 0.80 ≤ σ <0.90
C: 0.70 ≤ σ <0.80
D: 0.60 ≤ σ <0.70
E: 0.50 ≤ σ <0.60
F: σ <0.50

<Evaluation 4: Cycle characteristics under high-speed charge / discharge conditions>
For each of the manufactured all-solid-state secondary batteries, the discharge capacity retention rate under high-speed charge / discharge conditions was measured by the charge / discharge evaluation device TOSCAT-3000 (trade name, manufactured by Toyo System Co., Ltd.).
Specifically, each all-solid-state secondary battery was charged in an environment of 25 ° C. at a current density of 0.1 mA / cm ² until the battery voltage reached 3.6 V. Then, the battery was discharged at a current density of 0.1 mA / cm ² until the battery voltage reached 2.5 V. This one charge and one discharge were set as one charge / discharge cycle, and charging / discharging was repeated for three cycles under the same conditions for initialization. Then, was charged at a current density of 1 mA / cm ² until the battery voltage reached 3.6V, as one cycle to discharge at a current density of 1 mA / cm ² until the battery voltage reached 2.5V, the charging and discharging cycle It was repeated, and the discharge capacity of each all-solid secondary battery was measured by a charge / discharge evaluation device: TOSCAT-3000 (trade name) every time the charge / discharge cycle was performed.
When the discharge capacity (initial discharge capacity) of the first charge / discharge cycle after initialization is 100%, the number of charge / discharge cycles when the discharge capacity retention rate (discharge capacity with respect to the initial discharge capacity) reaches 80% , Battery performance (cycle characteristics) was evaluated according to which of the following evaluation criteria was included. In this test, the higher the evaluation standard, the better the cycle characteristics for high-speed charging / discharging, and the initial battery performance can be maintained even if high-speed charging / discharging is repeated multiple times (even in long-term use). The cycle characteristics pass the evaluation standard "D" or higher. The results are shown in Table 4.
The all-solid-state secondary battery No. The initial discharge capacities of 101 to 122 all showed sufficient values to function as an all-solid-state secondary battery. Further, even if the normal charge / discharge cycle is repeated under the same conditions as the above initialization instead of the above-mentioned high-speed charge / discharge, the all-solid-state secondary battery No. 101-122 maintained excellent cycle characteristics.

- Evaluation criteria -
A: 500 cycles or more, B: 300 cycles or more, less than 500 cycles C: 200 cycles or more, less than 300 cycles D: 150 cycles or more, less than 200 cycles E: 80 cycles or more, less than 150 cycles F: 40 cycles or more, less than 80 cycles

The following can be seen from the results shown in Tables 3 and 4.
The inorganic solid electrolyte-containing compositions containing no polymer binder specified in the present invention shown in Comparative Examples Kc11 to Kc16 and NKc21 to NKc26 are all inferior in dispersion stability, and the constituent layer formed of these compositions is a film. The strength was insufficient. In addition, the all-solid-state secondary batteries of Comparative Examples c101 to c106 using these compositions do not show sufficient cycle characteristics or ionic conductivity (small battery resistance).
On the other hand, the inorganic solid electrolyte-containing composition having the polymer binder specified in the present invention shown in K-1 to K-16, PK-1 to PK-9 and NK-1 to NK-13 of the present invention. Shows high dispersion stability. The constituent layer formed of this inorganic solid electrolyte-containing composition exhibits strong film strength, and even when applied to an industrial manufacturing method (for example, a roll-to-roll method), the occurrence of defects is effectively suppressed. You can see that it is possible. Further, the all-solid-state secondary battery No. 1 having a layer composed of the above-mentioned inorganic solid electrolyte-containing composition. All of 101 to 122 can realize excellent cycle characteristics and high ionic conductivity (low battery resistance) at a high level even under high-speed charge / discharge conditions.

Although the present invention has been described with its embodiments, we do not intend to limit our invention in any detail of the description unless otherwise specified, and contrary to the spirit and scope of the invention set forth in the appended claims. I think that it should be widely interpreted without.

The present application claims priority based on Japanese Patent Application No. 2020-027911 filed in Japan on February 20, 2020, which is referred to herein and is described herein. Incorporate as a part.

1 Negative electrode current collector 2 Negative electrode active material layer 3 Solid electrolyte layer 4 Positive electrode active material layer 5 Positive electrode current collector 6 Operating part 10 All-solid-state secondary battery 11 2032 type Coin case 12 Laminate for all-solid-state secondary battery 13 Coin type All-solid-state secondary battery

Claims

An inorganic solid electrolyte-containing composition containing an inorganic solid electrolyte having conductivity of metal ions belonging to Group 1 or Group 2 of the Periodic Table, a polymer binder, and a dispersion medium.
An inorganic solid electrolyte-containing composition comprising a polymer binder in which the polymer binder is composed of a polymer satisfying the following (P1) and (P2).

(P1) It is composed of atoms not substituted with fluorine atoms, and has a main chain containing at least one of urethane bond, urea bond and ester bond.
(P2) Contains a component having at least one functional group selected from the following functional group group.
<Functional group group>
Hydroxy group, primary amino group, secondary amino group, sulfanilic group
The solid electrolyte-containing composition according to claim 1, wherein the polymer binder composed of the polymer is dispersed in the dispersion medium.
The inorganic solid electrolyte-containing composition according to claim 1 or 2, wherein the polymer binder composed of the polymer has an average particle size of 1 to 1000 nm.
The inorganic solid electrolyte-containing composition according to any one of claims 1 to 3, wherein the constituent component has two or more of the functional groups.
The inorganic solid electrolyte-containing composition according to any one of claims 1 to 4, wherein the content of the constituent component in the polymer is 0.01 to 50 mol%.
The inorganic solid electrolyte-containing composition according to any one of claims 1 to 5, wherein the constituent component has a partial structure represented by the following formula (F1).

In formula (F1), L 1 and L 2 represent a linking group, R 1 represents a hydroxyl group or a primary or secondary amino group, and R 2 represents a substituent.
The inorganic solid electrolyte-containing composition according to any one of claims 1 to 6, wherein the constituent component has a partial structure represented by the following formula (F2).

In formula (F2), L 1 represents a linking group and R 3 represents a substituent.
Claims 1 to 1, wherein the dispersion medium contains a polymer binder composed of a soluble polymer, and the soluble polymer is any one of a (meth) acrylic polymer, a hydrocarbon-based polymer, a vinyl-based polymer, and a fluorine-based polymer. 7. The composition containing an inorganic solid polymer according to any one of 7.
The inorganic solid electrolyte-containing composition according to any one of claims 1 to 8, which contains an active material.
The inorganic solid electrolyte-containing composition according to claim 9, wherein the active material is a negative electrode active material containing a silicon element or a tin element.
The inorganic solid electrolyte-containing composition according to any one of claims 1 to 10, which contains a conductive auxiliary agent.
A sheet for an all-solid secondary battery having a layer composed of the composition containing the inorganic solid electrolyte according to any one of claims 1 to 11.
An all-solid-state secondary battery including a positive electrode active material layer, a solid electrolyte layer, and a negative electrode active material layer in this order.
The positive electrode active material layer, the solid electrolyte layer, and at least one layer of the negative electrode active material layer are all layers composed of the inorganic solid electrolyte-containing composition according to any one of claims 1 to 11. Solid secondary battery.
A method for producing a sheet for an all-solid secondary battery, which forms a film of the inorganic solid electrolyte-containing composition according to any one of claims 1 to 11.
A method for manufacturing an all-solid-state secondary battery, which manufactures an all-solid-state secondary battery through the manufacturing method according to claim 14.