WO2020196041A1

WO2020196041A1 - Solid electrolyte 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: WO2020196041A1
Application number: PCT/JP2020/011506
Authority: WO
Inventors: 安田　浩司
Original assignee: 富士フイルム株式会社
Priority date: 2019-03-28
Filing date: 2020-03-16
Publication date: 2020-10-01
Also published as: CN113614960A; KR20210134748A; JP7096426B2; JPWO2020196041A1

Abstract

The present invention provides: a solid electrolyte composition which contains an inorganic solid electrolyte, a polymer and a dispersion medium, and which is configured such that the polymer has a specific bond in the main chain, while having a polymer segment in the main chain, said polymer segment having a constituent which is derived from a hydrocarbon polymer that has at least two hydroxyl groups or amino groups, while having a number average molecular weight of 500 or more, and a constituent which is derived from a cyclic ester compound or a carboxylic acid compound; a sheet for all-solid-state secondary batteries, which uses this solid electrolyte composition; an all-solid-state secondary battery which uses this solid electrolyte composition; a method for producing a sheet for all-solid-state secondary batteries; and a method for producing an all-solid-state secondary battery.

Description

A method for producing a solid electrolyte composition, a sheet for an all-solid secondary battery and an all-solid secondary battery, and a sheet for an all-solid secondary battery and an all-solid secondary battery.

The present invention relates to a solid electrolyte 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 made of solid, and the safety and reliability, which are the problems of the battery using the organic electrolytic solution, 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 electrolytic solution, and it is expected to be applied to an electric vehicle, a large storage battery, or the like.

In such an all-solid-state secondary battery, any of the constituent layers (inorganic solid electrolyte layer, negative electrode active material layer, positive electrode active material layer, etc.) is a binder composed of the inorganic solid electrolyte or active material and a specific polymer. It has been proposed to form with a material containing particles (binders). For example, Patent Document 1 describes (A) an inorganic solid electrolyte, (B) a polymer having a hydrocarbon polymer segment in the main chain, and the main chain containing at least one specific bond, and (C) a dispersion medium. A solid electrolyte composition containing and is described.

International Publication No. 2018/20827

When forming a constituent layer of an all-solid secondary battery with solid particles (inorganic solid electrolyte, solid particles, conductive auxiliary agent, etc.), the material forming the constituent layer is excellent by dispersing the solid particles in a dispersion medium or the like. It is desirable to show good dispersibility. However, even if a material having good dispersibility is used, in general, in the constituent layer formed of solid particles, the interfacial contact state between the solid particles is insufficient and the interfacial resistance tends to be high. Further, if the binding property between the solid particles by the binder is weak, poor contact between the solid particles occurs. Moreover, the active material expands and contracts due to charging and discharging, which causes poor contact between the active material layer and the solid electrolyte layer. Further, if the binding property between the solid particles and the current collector is weak, poor contact between the active material layer and the current collector is also caused. When these poor contacts occur, the resistance of the all-solid-state secondary battery increases (battery performance deteriorates).

The inorganic solid electrolyte composition described in Patent Document 1 enhances the binding property between solid particles and the binding property between a current collector and solid particles (in addition, the binding property of solid particles may be referred to). , It is possible to impart excellent cycle characteristics to an all-solid secondary battery.
However, in recent years, research and development for improving the performance and practical application of electric vehicles have progressed rapidly, and the battery performance required for all-solid-state secondary batteries has also increased. Therefore, there is a demand for the development of an all-solid-state secondary battery that exhibits more excellent battery performance by further improving the binding property of solid particles.

The present invention is a solid electrolyte composition exhibiting excellent dispersibility, and by using it as a material constituting a constituent layer of an all-solid secondary battery, the binding property of solid particles is enhanced to form an all-solid secondary battery. An object of the present invention is to provide a solid electrolyte composition capable of imparting excellent battery performance. The present invention also provides a sheet for an all-solid-state secondary battery and an all-solid-state secondary battery, and a sheet for an all-solid-state secondary battery and a method for producing the all-solid-state secondary battery using this solid electrolyte composition. That is the issue.

As a result of various studies, the present inventors have derived from a cyclic compound having an ester bond with a constituent component derived from a hydrocarbon polymer having at least two hydroxy groups or amino groups, or a compound having at least two carboxy groups. By using a polymer segment having a constituent component and a polymer having a specific bond introduced into the main chain in combination with an inorganic solid electrolyte and a dispersion medium, the polymer itself is highly dispersed in the dispersion medium, which is excellent. It has been found that a solid electrolyte composition showing dispersibility can be prepared. Further, this solid electrolyte composition is a constituent layer in which other solid particles including an inorganic solid electrolyte are firmly bonded to each other, and when an active material layer is formed on the surface of the current collector, the solid particles and the current collector are firmly bonded to each other. Was found to be able to form. Furthermore, it has been found that excellent battery performance can be imparted to an all-solid-state secondary battery by using this solid electrolyte composition as a constituent material of a sheet for an all-solid-state secondary battery and a constituent layer of the all-solid-state secondary battery. 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> A solid electrolyte composition containing an inorganic solid electrolyte having conductivity of an ion of a metal belonging to Group 1 or Group 2 of the Periodic Table, a polymer, and a dispersion medium.
A polymer having a component derived from a hydrocarbon polymer having at least two hydroxy groups or amino groups and having a number average molecular weight of 500 or more, and a cyclic compound having an ester bond or a compound having at least two carboxy groups. A solid electrolyte having a polymer segment having an oxygen or nitrogen atom as a bond having a constituent component derived from the main chain, and having at least one bond selected from the following bond group (I) in the main chain. Composition.
<Binding group (I)>
Ester bond, amide bond, urethane bond, urea bond, imide bond, ether bond and carbonate bond

<2> The solid electrolyte composition according to <1>, wherein the polymer segment contains at least one of a polymer segment represented by the following formula (1) and a polymer segment represented by the formula (2).

In the formula, Ra represents ^a hydrocarbon polymer chain in the above hydrocarbon polymer.
X ^a is an oxygen atom or -NH-.
R ¹ represents an aliphatic hydrocarbon group having 3 to 15 carbon atoms.
R ² represents an aromatic hydrocarbon group having 6 to 20 carbon atoms or an aliphatic hydrocarbon group having 1 to 20 carbon atoms.
n1 is 1 to 100 and n2 is 1 to 10.

<3> The solid electrolyte composition according to <1> or <2>, wherein the cyclic compound having an ester bond or the compound having at least two carboxy groups contains a lactone compound.
<4> The solid electrolyte composition according to any one of <1> to <3>, wherein the polymer is a particulate polymer having an average particle size of 10 to 1000 nm.
<5> The solid electrolyte composition according to any one of <1> to <4>, wherein the content of the polymer segment in the polymer is 5 to 80% by mass.

<6> The solid electrolyte composition according to any one of <1> to <5>, wherein the polymer comprises at least one of the polymer represented by the following formula (3) and the polymer represented by the formula (4). object.

In the formula, Ra represents ^a hydrocarbon polymer chain in the above hydrocarbon polymer.
X ^a is an oxygen atom or -NH-.
R ¹ represents an aliphatic hydrocarbon group having 3 to 15 carbon atoms.
R ² represents an aromatic hydrocarbon group having 6 to 20 carbon atoms or an aliphatic hydrocarbon group having 1 to 20 carbon atoms.
n1 is 1 to 100 and n2 is 1 to 10.
R ^b1 represents an aromatic hydrocarbon group having 6 to 22 carbon atoms, an aliphatic hydrocarbon group having 1 to 15 carbon atoms, or a group formed by combining two or more of these groups.
R ^b2 represents an alkylene group having 2 to 12 carbon atoms.
R ^b3 represents an alkylene group having at least one functional group selected from the following functional group group (II).
R ^b4 represents an alkylene group having at least one functional group selected from the following functional group group (III).
R ^b5 is a divalent chain having a number average molecular weight of 100 or more, and represents a polyalkylene oxide chain, a polycarbonate chain, a polyester chain or a silicone chain, or a chain formed by combining two or more of these chains.
X ^b2 , X ^b3 , X ^b4 and X ^b5 represent an oxygen atom or -NH-.
a, b, c, d, e and f are the molar ratios of each structural component, a is 0.1 to 30 mol%, b is 40 to 60 mol%, and c and e are 0 to 30 mol%, respectively. d and f are 0 to 49 mol%, respectively, and a + b + c + d + e + f = 100 mol%.
<Functional group group (II)>
A carboxy group, a sulfonic acid group, a phosphoric acid group, an amino group, a hydroxy group, a sulfanyl group, an isocyanato group, an alkoxysilyl group and a group in which three or more rings are fused <functional group group (III)>
Group with carbon-carbon unsaturated bond, epoxy group and oxetanyl group

<7> The solid electrolyte composition according to any one of <1> to <6>, wherein the content of the polymer is 0.001 to 10% by mass in the solid content of the solid electrolyte composition.
<8> The solid electrolyte composition according to any one of <1> to <7>, wherein the inorganic solid electrolyte is 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. 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.
<9> The solid electrolyte composition according to any one of <1> to <8>, wherein the dispersion medium is selected from a ketone compound, an aliphatic compound, or an ester compound.
<10> The solid electrolyte composition according to any one of <1> to <9>, which contains an active material.
<11> An all-solid-state secondary battery sheet having a layer composed of the solid electrolyte composition according to any one of <1> to <10> above.
<12> 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 all-solid secondary layer in which at least one layer of the positive electrode active material layer, the solid electrolyte layer, and the negative electrode active material layer is a layer composed of the solid electrolyte composition according to any one of <1> to <10> above. battery.
<13> A method for producing a sheet for an all-solid secondary battery, which forms a film of the solid electrolyte composition according to any one of <1> to <10> above.
<14> 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 <13> above.

The solid electrolyte composition of the present invention has excellent dispersibility and can form a sheet or a constituent layer having strong binding properties of solid particles. The sheet for an all-solid-state secondary battery of the present invention exhibits strong binding properties of solid particles, and the all-solid-state secondary battery of the present invention exhibits excellent battery performance. Further, the method for manufacturing the all-solid-state secondary battery sheet and the all-solid-state secondary battery of the present invention can produce the all-solid-state secondary battery sheet and the all-solid-state secondary battery of the present invention exhibiting the above-mentioned excellent characteristics. it can.
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 cross-sectional view which shows typically the all-solid-state secondary battery which concerns on a preferable embodiment of this invention. It is a vertical cross-sectional view which shows typically the all-solid-state secondary battery (coin battery) produced in an Example.

In the present specification, 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 specification, the indication of a compound (for example, when referred to as a compound at the end) is used to mean that the compound itself, its salt, and its ion are included. Further, it is meant to include a derivative in which a part is changed such as introducing a substituent within a range that does not impair the effect of the present invention.
In the present specification, a substituent, a linking group, etc. (hereinafter, referred to as a substituent, etc.) for which substitution or non-substitution is not specified may mean that the group may have an appropriate substituent. Therefore, even if it is simply described as a YYY group in the present specification, 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 no substitution. Preferred substituents include, for example, the substituent T described later.
In the present specification, 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. It means good. 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.

[Solid electrolyte composition]
The solid electrolyte composition of the present invention (also referred to as an inorganic solid electrolyte-containing composition) is an inorganic solid electrolyte having conductivity of ions of a metal belonging to Group 1 or Group 2 of the periodic table, a polymer, and a dispersion medium. And contains. The solid electrolyte composition of the present invention is preferably a slurry in which the inorganic solid electrolyte and the polymer are dispersed in a dispersion medium. The polymer contained in the solid electrolyte layer (hereinafter, may be referred to as a specific polymer) contains a specific polymer segment described later in the main chain and has a specific bond. This polymer has excellent dispersibility in itself in the solid electrolyte composition (dispersion medium), and functions as a dispersant for dispersing solid particles with high dispersibility. Further, this polymer binds solid particles (for example, inorganic solid electrolytes to each other, inorganic solid electrolytes to active substances, active substances to each other) in a sheet or a constituent layer formed of a solid electrolyte composition, and further. It also functions as a binder that binds the current collector and solid particles.

The solid electrolyte composition of the present invention is capable of highly dispersing solid particles and exhibits excellent dispersibility. The specific polymer contained in the solid electrolyte composition exhibits high dispersibility with respect to the dispersion medium. In particular, when the dispersion medium is a hydrophobic dispersion medium described later, a plurality of molecules of a specific polymer are aggregated into particles. At this time, it is considered that the dispersion stability of the particles is enhanced by the polymer segments incorporated in the main chain of each polymer located outside the particles and sterically repelling each other. In particular, as will be described later, the polymer segment is a high molecular weight segment containing a specific hydrocarbon polymer, a cyclic compound, or the like as a constituent component, and the steric repulsion effect in the dispersion medium is further improved. Conceivable. Therefore, the solid particles adsorbed on the surface of the specific polymer can be dispersed highly and stably with respect to the dispersion medium, and the solid electrolyte composition of the present invention exhibits excellent dispersibility.
In addition, the solid electrolyte composition of the present invention can firmly bind solid particles when formed into a sheet or a constituent layer. Moreover, when the active material layer is formed on the surface of the current collector with this solid electrolyte composition, the solid particles and the current collector can be firmly bound in addition to the binding between the solid particles. As a result, the all-solid-state secondary battery provided with the sheet or constituent layer formed by using the solid electrolyte composition of the present invention exhibits excellent battery performance. The details of the reason are not yet clear, but it can be considered as follows. That is, the solid electrolyte composition of the present invention can bind solid particles while suppressing the formation of aggregates of the specific polymer, which has high dispersibility of the specific polymer and can be a resistance component. Further, since the specific polymer exhibits high dispersibility, it is possible to maintain high dispersibility of solid particles and the like with respect to the dispersion medium when forming the sheet or the constituent layer (excellent dispersion stability of the solid electrolyte composition). .. Therefore, it is considered that the solid particles are excellently bound to the sheet or the constituent layer and contribute to high battery performance.

The solid electrolyte composition of the present invention can be preferably used as a molding material for a sheet for an all-solid secondary battery or a solid electrolyte layer or an active material layer for an all-solid secondary battery.

The solid electrolyte composition of the present invention is not particularly limited, but the water content (also referred to as water content) is preferably 500 ppm or less, more preferably 200 ppm or less, and further preferably 100 ppm or less. It is preferably 50 ppm or less, and particularly preferably 50 ppm or less. When the water content of the solid electrolyte composition is low, deterioration of the inorganic solid electrolyte can be suppressed. The water content indicates the amount of water contained in the solid electrolyte composition (mass ratio to the solid electrolyte composition). Specifically, the water content is filtered through a 0.02 μm membrane filter, and Karl Fischer titration is used. It shall be the measured value.

Hereinafter, the components contained in the solid electrolyte composition of the present invention and the components that can be contained will be described.

<Inorganic solid electrolyte>
The solid electrolyte 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 (polymer electrolyte typified by polyethylene oxide (PEO), organic typified by lithium bis (trifluoromethanesulfonyl) imide (LiTFSI), etc. 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 the 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 inorganic solid electrolyte, a solid electrolyte material usually used for an all-solid secondary battery can be appropriately selected and used. 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 solid electrolyte. A sulfide-based inorganic solid electrolyte is preferable from the viewpoint that a better interface can be formed between the 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. The 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 non-crystal (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, a combination example of 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 Examples thereof include ₂ S _5- LiI, Li ₂ S-SiS _2- LiI, Li ₂ S-SiS ₂ -Li ₄ SiO ₄ , Li ₂ S-SiS ₂ -Li ₃ PO ₄ , Li ₁₀ GeP ₂ S ₁₂ . 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. Satisfies.); 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, 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. ); Examples thereof include Li ₇ La ₃ Zr ₂ O ₁₂ (LLZ) having a garnet-type crystal structure.
Phosphorus compounds containing Li, P and O are also desirable. For example, lithium phosphate (Li ₃ PO ₄ ); LiPON in which a part of oxygen of lithium phosphate is replaced with nitrogen; LiPOD ¹ (D ¹ is preferably Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zr, Nb, Mo, Ru, Ag, Ta, W, Pt and one or more elements selected from 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 contains halogen atoms, has the conductivity of ions of metals belonging to Group 1 or Group 2 of the Periodic Table, and has electrons. Insulating compounds are preferred.
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 contains a hydrogen atom, has ionic conductivity of a metal belonging to Group 1 or Group 2 of the Periodic Table, and is electronically insulated. A compound having a 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 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 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 laser diffraction / scattering particle size distribution measuring device LA-920 (trade name, manufactured by HORIBA) at a temperature of 25 ° C. using a measuring quartz cell. Obtain the volume average particle size. For other detailed conditions, etc., refer to the description of JIS Z 8828: 2013 "Particle size analysis-Dynamic light scattering method" as necessary. Five samples are prepared for each level and the average value is 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 solid electrolyte composition 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 solid electrolyte composition is preferably 50% by mass or more, preferably 70% by mass or more, based on 100% by mass of the solid content, in terms of dispersibility, reduction of interfacial resistance, and binding property. The above 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 solid electrolyte composition contains an active material described later, the content of the inorganic solid electrolyte in the solid electrolyte composition is preferably in the above range of the total content of the active material and the inorganic solid electrolyte.
In the present specification, the solid content (solid component) refers to a component that does not volatilize or evaporate and disappear when the solid electrolyte composition is dried at 170 ° 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>
The specific polymer contained in the solid electrolyte composition of the present invention is a polymer having a polymer segment described later as a constituent component in the main chain and at least one bond selected from the following bond group (I). .. As mentioned above, this particular polymer functions as a binder, more preferably a dispersant.
In the solid electrolyte composition of the present invention, the specific polymer may be dissolved in a dispersion medium and contained, but is preferably contained as particles.
<Binding group (I)>
Ester bond, amide bond, urethane bond, urea bond, imide bond, ether bond and carbonate bond

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 chain 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 functional group of the polymer terminal is not included in the main chain.

The bond selected from the bond group (I) is not particularly limited in its introduction position as long as it is contained in the main chain of the polymer, and is included as a bond connecting different constituent components constituting the polymer. , Any of the embodiments contained in the constituents is acceptable, but the embodiment contained as a bond connecting different constituent units is preferable. In this preferred embodiment, the ester bond in the bond group (I) means a bond different from the ester bond present in the polymer segment.

The bond selected from the above bond group (I) of the specific polymer is preferably an ester bond, an amide bond, a urethane bond, or a urea bond, and more preferably a urethane bond.
Further, the imide bond, the ether bond and the carbonate bond are preferably incorporated into the main chain in combination with at least one of an ester bond, an amide bond, a urethane bond and a urea bond.
The number of types of the above-mentioned bonds contained in the main chain is not particularly limited, and is preferably 1 to 6 and more preferably 1 to 4. Further, the number of the bonds possessed by the main chain varies depending on the mass average molecular weight, properties, etc. of the polymer, and is not unique and is appropriately determined.

Specific polymers having a bond selected from the bond group (I) in the main chain include polyester, polyamide, polyurethane, polyurea, polyimide, polyether and polycarbonate polymers, 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.
Among them, the specific polymer is preferably polyurethane, polyester, polyamide, polyether or polyurea, or a copolymer of two or more of these (sequentially polymerized polymer), and has an ester bond, an imide bond, an ether bond and a carbonate bond in the main chain. Polyurethane, polyester, polyamide or polyurea or a copolymer of two or more of these is preferable.

The particular polymer has at least one polymer segment in the main chain as a constituent. Details of the polymer segment will be described later. The number of types of polymer segments contained in the main chain is not particularly limited, but 1 to 3 types are preferable, and 1 type is more preferable.
The content of the polymer segment in the specific polymer is not particularly limited, and is appropriately set in consideration of dispersibility and the like. For example, the content (mass%) of the polymer segment is preferably 5 to 80% by mass, preferably 8 to 60%, in terms of the dispersibility and binding property of the solid particles and the battery performance of the solid secondary battery. It is more preferably 10 to 40% by mass, more preferably 10 to 30% by mass, and particularly preferably 10 to 30% by mass. When the content of the polymer segment is defined by mol%, the value of "a (molar ratio)" in the formulas (3) and (4) described later can be applied regardless of the above content (mass%). ..

The particular polymer preferably has a functional group for enhancing the wettability or adsorptivity of the solid particles to the surface. Examples of the functional group include a functional group that exhibits an interaction such as a hydrogen bond on the surface of the solid particle and a functional group that can form a chemical bond with a group existing on the surface of the solid particle. Specifically, the following functional group is used. It is more preferable to have at least one functional group selected from group (II). However, from the viewpoint of more effectively exhibiting the wettability or adsorptivity of the solid particles to the surface, it is preferable not to have two or more kinds of functional groups capable of forming a bond between the functional groups.
<Functional group group (II)>
Carboxy group, a sulfonic acid group _(-SO 3 H), phosphoric acid group _(-PO _{4 H} 2), amino group _(-NH 2), hydroxy group, sulfanyl group, isocyanato group, an alkoxysilyl group and 3 or more rings condensed Group with ring structure

The sulfonic acid group and the phosphoric acid group may be salts thereof, and examples thereof include sodium salts and calcium salts.
The alkoxysilyl group may be a silyl group in which the Si atom is substituted with at least one alkoxy group (preferably having 1 to 12 carbon atoms), and other substituents on the Si atom include an alkyl group and an aryl. The group etc. can be mentioned. As the alkoxysilyl group, for example, the description of the alkoxysilyl group in the substituent T described later can be preferably applied.
The group having a condensed ring structure of 3 or more rings is preferably a group having a cholesterol ring structure or a group having a condensed ring structure of 3 or more aromatic rings, and a cholesterol residue or a pyrenyl group is more preferable.

It is preferable that the specific polymer has a functional group selected from the functional group group (II) in the constituent components other than the polymer segment.
The content of the functional group selected from the functional group group (II) in the specific polymer is not particularly limited, but the functional group selected from the functional group group (II) among all the constituent components constituting the specific polymer is not particularly limited. The proportion of the constituent components having a group is preferably 0 to 50 mol%, preferably 0 to 49 mol%, more preferably 0.1 to 40 mol%, further preferably 1 to 30 mol%, and 3 to 25 mol%. Is particularly preferable. The content on a mass basis includes the same range as the content of the component having the alkylene group R ^b3 described later.

<Crosslinkable functional group>
It is also preferable that the specific polymer has a functional group (hereinafter, also referred to as a crosslinkable functional group) capable of forming a crosslinked structure by a radical polymerization reaction, a cationic polymerization reaction or an anionic polymerization reaction. By reacting the crosslinkable functional groups with each other to form a bond, the specific polymer can form a crosslinked structure within the polymer particles or between the polymer particles, and the strength can be improved.
As the crosslinkable functional group, a group having a carbon-carbon unsaturated bond and / or a cyclic ether group is preferable. The group having a carbon-carbon unsaturated bond is a group capable of forming a crosslinked structure by a radical polymerization reaction (that is, a group having a polymerizable carbon-carbon unsaturated bond), and specifically, an alkenyl group. (The number of carbon atoms is preferably 2 to 12, more preferably 2 to 8), the alkynyl group (the number of carbon atoms is preferably 2 to 12, more preferably 2 to 8), the acryloyl group and the methacryloyl group are preferable. More preferably, a vinyl group, an ethynyl group, an acryloyl group, a methacryloyl group and a 2-trifluoromethylpropenoyl group are mentioned. The cyclic ether group is a group capable of forming a crosslinked structure by a cationic polymerization reaction, and specific examples thereof include an epoxy group and an oxetanyl group.
That is, it is preferable that the specific polymer has at least one functional group selected from the following functional group group (III).
<Functional group group (III)>
Groups having carbon-carbon unsaturated bonds, epoxy groups and oxetanyl groups The groups having carbon-carbon unsaturated bonds are as described above.

The specific polymer preferably has the crosslinkable functional group as a constituent component other than the polymer segment. When the hydrocarbon polymer has a carbon-carbon unsaturated bond (for example, a polybutadiene component and a polyisoprene component), a crosslinkable functional group composed of a carbon atom and a hydrogen atom (for example, a vinyl group and a propenyl group) Can be present in the hydrocarbon polymer segment.
The content of the crosslinkable functional group in the specific polymer is not particularly limited, but the ratio of the component having the crosslinkable functional group to all the constituent components constituting the specific polymer is 0 to 0 to. 30 mol% is preferable, 0 to 25 mol% is more preferable, 0 to 20 mol% is further preferable, and 0 to 10 mol% is particularly preferable. Examples of the content on a mass basis include the same range as the content of the constituent component having the alkylene group R ^b4, which will be described later.

The specific polymer having the crosslinkable functional group includes both a form in which the crosslinkable functional group is not crosslinked and a form in which these functional groups are already crosslinked.

In the reaction between the crosslinkable functional groups, a polymerization initiator (radical, cation or anionic polymerization initiator) corresponding to each crosslinkable functional group is contained in the solid electrolyte composition of the present invention, and these are polymerized. The reaction may be carried out by an initiator or by a redox reaction during battery operation. The radical polymerization initiator may be either a thermal radical polymerization initiator that is cleaved by heat to generate a starting radical, or a photoradical polymerization initiator that generates a starting radical by light, electron beam, or radiation.
As the polymerization initiator that may be contained in the solid electrolyte composition of the present invention, commonly used polymerization initiators can be used without particular limitation.

(Polymer segment)
This polymer segment condenses a hydrocarbon polymer having a number average molecular weight of 500 or more having at least two hydroxy groups or amino groups described later and a cyclic compound having an ester bond or a compound having at least two carboxy groups described later. It is a segment (component) derived from a polymer obtained by a reaction (polycondensation reaction).
This polymer is formed at both ends of the segment by a combination of a group of the hydrocarbon polymer and a cyclic compound having an ester bond (referred to as a cyclic ester compound) or a compound having at least two carboxy groups (carboxylic acid compound). It has a hydroxyl group or an amino group. For example, it contains polyester polyol, polyester polyamine, polyamide polyol and polyamide polyamine, and polyester polyol is preferable.
The polyester polyol has at least two or more ester bonds and two or more hydroxyl groups in the molecule, and preferably has hydroxyl groups at both ends of the main chain. Polyester polyamines have at least two or more ester bonds and two or more amino groups in the molecule, and preferably have amino groups at both ends of the main chain. The polyamide polyol has at least two or more amide bonds and two or more hydroxyl groups in its molecule, and preferably has hydroxyl groups at both ends of the main chain. Polyamide polyamines have at least two or more amide bonds and two or more amino groups in the molecule, and preferably have amino groups at both ends of the main chain.

The polymer segment has the above-mentioned structure in which the hydrogen atoms of the hydroxyl groups or amino groups at both ends of the polymer chain are removed (a structure in which an oxygen or nitrogen atom is a bond with the main chain), which will be described later. It is preferable to include at least one of the polymer segment represented by the formula (1) and the polymer segment represented by the formula (2), and it is more preferable to contain at least one segment represented by the formula (1) described later. ..

-Polymer segment consisting of a hydrocarbon polymer and a cyclic ester compound-
Examples of the polymer constituting the polymer segment composed of the hydrocarbon polymer and the cyclic ester compound include polyester polyol and polyamide polyol, and the number of ester bonds, amide bonds, hydroxyl groups and the like in the polymer is not particularly limited. However, 2 or more is preferable. Of these, polyester diol is preferable. The bonding mode between the hydrocarbon polymer and the cyclic ester compound is not particularly limited, but when the hydrocarbon polymer and the cyclic ester compound are bifunctional, they are preferably of the BAB type. Here, A is a constituent component derived from a hydrocarbon polymer, and B is a constituent component derived from a cyclic ester compound. More preferably, it is a polymer in which a ring-opened product of a cyclic ester compound is bonded to each of the two hydroxy groups or amino groups of a hydrocarbon polymer having two hydroxy groups or amino groups via an ester group. The ring-opening compound of the cyclic ester compound bonded to the hydroxy group or the amino group of the hydrocarbon polymer may be a single molecule ring-opening compound, but is usually a ring-opening polymer of this cyclic compound. The average degree of polymerization of the ring-opening polymer is not particularly limited and is appropriately determined according to the molecular weight and the like, and is synonymous with n1 of the following formula (1), for example.

The polymer segment composed of the hydrocarbon polymer and the cyclic ester compound is preferably a segment represented by the following formula (1).

In the formula (1), Ra represents ^a hydrocarbon polymer chain in a hydrocarbon polymer having at least two hydroxy groups or amino groups and having a number average molecular weight of 500 or more. The hydrocarbon polymer chain has the same meaning as the hydrocarbon polymer chain constituting the hydrocarbon polymer described later.
X ^a are each an atom derived from a hydroxy group or an amino group the hydrocarbon polymer has, an oxygen atom or -NH-. However, the two X ^a are the same. It is preferable that X ^a is an oxygen atom (the segment represented by the formula (1) is a polyester polyol segment).
Each of R ¹ represents an aliphatic hydrocarbon group having 3 to 15 carbon atoms, and an aliphatic hydrocarbon group having 4 to 10 carbon atoms is preferable. The aliphatic hydrocarbon group may be an unsaturated aliphatic hydrocarbon group, but a saturated aliphatic hydrocarbon group (alkylene group) is preferable. Two of R ¹ in the formula may be the same or different, but are preferably the same. The number of carbon atoms in R ¹ means the minimum number of carbon atoms connecting the oxygen atoms and the carbonyl carbon atom to which R ¹ is attached.
Each of ^Ra and R ¹ may have a substituent, and examples thereof include a substituent T described later. Preferred substituents of R ¹ include alkyl groups.
Each of n1 shows a number average degree of polymerization and can improve dispersibility, binding property and battery performance in a well-balanced manner, and is 1 to 100, preferably 1 to 50, and more preferably 1 to 25. In equation (1), the two n1s may be the same or different.

-Polymer segment consisting of hydrocarbon polymer and carboxylic acid compound-
The polymer constituting the polymer segment composed of the hydrocarbon polymer and the carboxylic acid compound is a polyester polyol and a polyamide polyamine, and the number of ester bonds, amide bonds, hydroxyl groups and amino groups in the polymer is not particularly limited. 2 or more is preferable. Among them, polyester diol and polyamide diamine are preferable, and diester diol and diamide diamine are preferable. The bonding mode between the hydrocarbon polymer and the carboxylic acid compound is not particularly limited, but when the hydrocarbon polymer and the carboxylic acid compound are bifunctional, the structure is usually (AB) xA type. Here, A is a constituent component derived from a hydrocarbon polymer, and B is a constituent component derived from a carboxylic acid compound. x is an integer of 1 or more, and the upper limit is appropriately set according to the molecular weight and the like. When x is 1, it is an ABA-type diesterdiol or polyamide diamine in which one molecule of a hydrocarbon polymer is bonded to each of the two carboxy groups of the carboxylic acid compound.

The polymer segment composed of the hydrocarbon polymer and the carboxylic acid compound is preferably a segment represented by the following formula (2).

In the formula (2), Ra represents ^a hydrocarbon polymer chain in a hydrocarbon polymer having at least two hydroxy groups or amino groups and having a number average molecular weight of 500 or more, and R in the formula (1). ^It is synonymous with a.
X ^a are each an atom derived from a hydroxy group or an amino group the hydrocarbon polymer has, an oxygen atom or -NH-. However, two ^{X a} binding to one ^{R a} are the same. It is preferable that X ^a is an oxygen atom (the segment represented by the formula (2) is a polyester polyol segment) or -NH- (the segment represented by the formula (2) is a polyamide polyamine segment). Is also more preferably an oxygen atom.

R ² represents an aromatic hydrocarbon group having 6 to 20 carbon atoms or an aliphatic hydrocarbon group having 1 to 20 carbon atoms, and an aliphatic hydrocarbon group having 1 to 20 carbon atoms is preferable. The aromatic hydrocarbon group having 6 to 20 carbon atoms is not particularly limited, and the carbon number thereof is as described in the aromatic dicarboxylic acid compound described later. Examples of the aromatic hydrocarbon group include an aromatic residue obtained by removing each hydroxy group from the two carboxy groups from the aromatic dicarboxylic acid compound described later in the aromatic dicarboxylic acid compound. The aliphatic hydrocarbon group having 1 to 20 carbon atoms may be an unsaturated aliphatic hydrocarbon group, but a saturated aliphatic hydrocarbon group (alkylene group) is preferable. The carbon number is as described in the carboxylic acid compound described later. Examples of the aliphatic hydrocarbon group include an aliphatic obtained by removing each hydroxy group from the two carboxy groups from the aliphatic dicarboxylic acid compound described in the carboxylic acid compound described later. The number of carbon atoms in R ² means the minimum number of carbon atoms connecting the two carbonyl carbon atoms to which R ² is attached.
Each of ^Ra and R ² may have a substituent, and examples thereof include a substituent T described later. Preferred substituents of R ² include a carbonyl group, a sulfonic acid group, a phosphoric acid group, an ether group (alkoxy group, aryloxy group, heterocyclic oxy group) and a halogen atom.
n2 indicates a number average degree of polymerization, which is 1 to 10, preferably 1 to 5, and more preferably 1 to 3.

The above-mentioned polymer segment may have a constituent component derived from a hydrocarbon polymer having at least two hydroxy groups or amino groups and a constituent component derived from a cyclic ester compound or a carboxylic acid compound, both of which are used. The constituents may be one type or two or more types, respectively.
In the present invention, the polymer segment may have components other than the above two components, but it is preferably a segment composed of both of the above components.

By appropriately selecting ^Ra and the chemical structure or carbon number of R ¹ or R ^{2 in} the polymer segment described above, the affinity for the dispersion medium described later, particularly the hydrophobic dispersion medium, is adjusted (enhanced). be able to. Further increasing the affinity for the dispersion medium can be expected to further improve the dispersibility of a specific polymer in the solid electrolyte composition, and realize the binding property of solid particles and the battery performance of an all-solid secondary battery at a higher level. it can.

The number average molecular weight of the polymer segment is not particularly limited, and is preferably more than 500, more preferably 1500 or more, and further preferably 3000 or more. The upper limit is not particularly limited, and is preferably 100,000 or less, more preferably 30,000 or less, and further preferably 10,000 or less. The number average molecular weight can be measured as a standard polystyrene-equivalent number average molecular weight in the same manner as the mass average molecular weight of a specific polymer.

(Components derived from hydrocarbon polymers having at least two hydroxy or amino groups and having a number average molecular weight of 500 or more)
A component derived from a hydrocarbon polymer having at least two hydroxy groups or amino groups and having a number average molecular weight of 500 or more (also referred to as a hydrocarbon polymer component) is a component constituting the polymer segment. A constituent component formed by a hydrocarbon polymer having at least two hydroxy groups or amino groups and having a number average molecular weight of 500 or more, which is formed by a condensation reaction with a cyclic ester compound or a carboxylic acid compound described later. is there. This constituent component is a residue obtained by removing a hydrogen atom from the hydroxy group or amino group of the above hydrocarbon polymer, and is "-X ^a- R ^a- X ^a- " in the above formulas (1) and (2). "(X ^a and ^Ra are as described above).
The hydrocarbon polymer forming this constituent has at least two hydroxy groups or at least two amino groups, and preferably has at least two hydroxy groups. The number of hydroxy groups or amino groups contained in the hydrocarbon polymer is not particularly limited, but is preferably 2 to 6, and more preferably 2. The hydrocarbon polymer may have a hydroxy group or an amino group at any position in the main chain, but it is preferable to have them at both ends.

-A hydrocarbon polymer having at least two hydroxy or amino groups and having a number average molecular weight of 500 or more-
This hydrocarbon polymer is a polymer having at least two hydroxy groups or amino groups in the polymer chain of a hydrocarbon polymer obtained by polymerizing (at least two) polymerizable hydrocarbons.
This hydrocarbon polymer is an oligomer or polymer composed of carbon atoms and hydrogen atoms, and the number of carbon atoms constituting the hydrocarbon polymer is preferably 30 or more, more preferably 50 or more. The upper limit of the number of carbon atoms constituting the hydrocarbon polymer is not particularly limited, and can be, for example, 3000. The hydrocarbon polymer is preferably a chain (hydrocarbon polymer chain) composed of an aliphatic hydrocarbon whose main chain satisfies the above-mentioned number of carbon atoms, and is preferably an aliphatic saturated hydrocarbon or an aliphatic unsaturated. More preferably, it is a chain made of a polymer (preferably an elastomer) composed of hydrocarbons. Specific examples of the hydrocarbon 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 copolymer, a styrene-ethylene-butadiene copolymer, a copolymer of isobutylene and isoprene (preferably butyl rubber (IIR)), a butadiene polymer, an isoprene polymer, and ethylene-. Examples include propylene-diene copolymers. 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 diene polymer.

The number average molecular weight of the hydrocarbon polymer having at least two hydroxy groups or amino groups is 500 or more. When the number average molecular weight of this polymer is 500 or more, it has an effect of being excellent in its own dispersibility and functioning as a dispersant for dispersing solid particles with high dispersibility. The number average molecular weight is preferably 1000 or more, and more preferably 1500 or more, in that this effect can be further enhanced. The upper limit is not particularly limited, but is preferably less than 100,000, more preferably less than 30,000, and even more preferably less than 10,000. The number average molecular weight can be measured as a standard polystyrene-equivalent number average molecular weight in the same manner as the mass average molecular weight of a specific polymer.

Examples of hydrocarbon polymers having a hydroxy group or an amino group include NISSO-PB series (manufactured by Nippon Soda Co., Ltd.), Claysol series (manufactured by Tomoe Kosan Co., Ltd.), and PolyVEST-HT series (manufactured by Idemitsu Kosan) 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 Corporation) and the like are preferably used.

(Constituents derived from cyclic ester compounds or carboxylic acid compounds)
This component (also referred to as an acid component) is a component that constitutes the polymer segment, and the cyclic ester compound or the carboxylic acid compound has at least two hydroxy groups or amino groups as described above, and is number average. It is a constituent component formed by a condensation reaction with a hydrocarbon polymer having a molecular weight of 500 or more. This acid component is a ring-opened body of the cyclic ester compound or a residue obtained by removing the hydroxy group from the carboxy group of the carboxylic acid compound, and is "-CO-R ^1- O-" in the above formula (1). (R ¹ is as described above.) Or corresponds to "-CO-R ^2- CO-" (R ² is as described above) in the above formula (2).
As the cyclic ester compound and the carboxylic acid compound forming the acid constituent, the cyclic ester compound is preferable, and the following lactone compound is more preferable.

-Cyclic ester compound-
The cyclic ester compound may be a compound having a cyclic structure containing at least one ester bond, and usually a compound having a cyclic structure containing one ester bond (lactone compound) is preferable.
The lactone compound is not particularly limited, and examples thereof include an aliphatic lactone compound and an aromatic lactone compound, and an aliphatic lactone compound is preferable. Examples of the aliphatic lactone compound include compounds having a cyclic structure consisting of an ester bond and an aliphatic group having 3 to 15 carbon atoms (preferably R ¹ of the above formula (1)). Specifically, ε-caprolactone, 4-methylcaprolactone, 3,5,5-trimethylcaprolactone, 3,3,5-trimethylcaprolactone, β-propiolactone, γ-butyrolactone, δ-valerolactone, γ-valero Examples thereof include lactone and enant lactone. Among them, ε-caprolactone, δ-valerolactone, and γ-valerolactone are preferable, and ε-caprolactone is more preferable because they are easily available and have high reactivity.
The lactone compound may have a substituent, such as γ-valerolactone, and examples thereof include a substituent T described later, and an alkyl group is preferable.
The lactone compound may be used alone or in combination of two or more.

-Carboxylic acid compound-
The carboxylic acid compound may be a compound having at least one carboxy group in the molecule, and a compound having at least two carboxy groups is preferable. The number of carboxylic acids contained in the carboxylic acid compound is not particularly limited, but is preferably 2 to 6, and more preferably 2 (dicarboxylic acid compound). The carboxylic acid compound may have a hydroxy group or an alkoxy group. In the present invention, the carboxylic acid compound is a compound capable of esterifying with the above hydrocarbon polymer, and includes a compound having an alkyl or aryl ester group (for example, a methoxycarbonyl group) instead of the carboxy group. To do.
The carboxylic acid compound may be an aliphatic carboxylic acid compound or an aromatic carboxylic acid compound, and an aliphatic carboxylic acid compound is preferable.

The dicarboxylic acid compound is not particularly limited, and examples thereof include an aliphatic dicarboxylic acid compound and an aromatic dicarboxylic acid compound.
The carbon number of the aliphatic dicarboxylic acid compound (excluding the carbon atom forming the carbonyl) is not particularly limited, but is 1 or more, preferably 2 or more, more preferably 3 or more, still more preferably 4 or more, and preferably 4. It is 20 or less, more preferably 16 or less, still more preferably 15 or less, and particularly preferably 14 or less. Specifically, malonic acid, succinic acid, maleic acid, fumaric acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, 1,9-nonamethylenedicarboxylic acid, 1,10-decamethylene. Examples thereof include dicarboxylic acid, 1,11-undecamethylene dicarboxylic acid and 1,12-dodecamethylene dicarboxylic acid.
The number of carbon atoms (excluding the carbon atom forming the carbonyl) of the aromatic dicarboxylic acid compound is not particularly limited, but is preferably 6 to 20, and the upper limit is more preferably 16 or less, still more preferably 14 or less. Specific examples thereof include orthophthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, anthracendicarboxylic acid, and phenanthrenedicarboxylic acid.
Among them, it is preferably an aliphatic dicarboxylic acid compound because it is easily available and has high thermal stability, and more preferably malonic acid, succinic acid, adipic acid, pimelic acid, suberic acid, azelaic acid, and sebacic acid. , More preferably, succinic acid and adipic acid.
The dicarboxylic acid compound can also be used as an anhydride, an ester of an alkyl or aryl, an unsaturated bond halogen substituent, or the like, but does not include use as an imide compound.
The carboxylic acid compound may have a substituent, and examples thereof include a substituent T described later.
The carboxylic acid compound may be used alone or in combination of two or more.

-Synthesis of polymer segments-
The method for synthesizing the polymer that leads to the polymer segment is not particularly limited, but for example, the above-mentioned hydrocarbon polymer having at least two hydroxy groups or amino groups is condensed (heavy) with a cyclic ester compound or a carboxylic acid compound and a condensation reaction. (Condensation) reaction method can be mentioned. As the condensation reaction, a known synthetic method (esterification method or amidation method) can be applied without particular limitation. For example, the polyester polyol composed of the above-mentioned hydrocarbon polymer and the cyclic ester compound is synthesized by a method of reacting the hydrocarbon polymer with the cyclic ester compound in the presence of a catalyst such as tetraisopropyl titanate or tetrabutyl titanate in the absence of a solvent. it can. Specific examples of the synthesis method include the synthesis method described in Examples.

Specific examples of the polymer segment include, for example, each segment shown in a specific example of the polymer described later, but the present invention is not limited thereto.

The polymer segment (each constituent and raw material compound) may have a substituent. The substituent is not particularly limited, but preferably, a group selected from the following substituent T can be mentioned.
-Substituent T-
Alkyl group (preferably an alkyl group having 1 to 20 carbon atoms, for example, methyl, ethyl, isopropyl, t-butyl, pentyl, heptyl, 1-ethylpentyl, benzyl, 2-ethoxyethyl, 1-carboxymethyl, etc.), alkenyl group. (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 used in the present specification to mean that an alkyl group usually includes 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). An aralkyl group of ~ 23 (eg, benzyl, phenethyl, etc.), a heterocyclic group (preferably a heterocyclic group having 2 to 20 carbon atoms, preferably 5 or 6 having at least one oxygen atom, sulfur atom, nitrogen atom). It is a member ring 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 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 mean an aryloxy group including an aryloxy group. ), Heterocyclic oxy group (group in which an —O— group is bonded to the heterocyclic group), alkoxycarbonyl group (preferably alkoxycarbonyl group having 2 to 20 carbon atoms, for example, ethoxycarbonyl, 2-ethylhexyloxycarbonyl, etc.) ), Aryloxycarbonyl group (preferably an aryloxycarbonyl group having 6 to 26 carbon atoms, such as phenoxycarbonyl, 1-naphthyloxycarbonyl, 3-methylphenoxycarbonyl, 4- Includes methoxyphenoxycarbonyl, etc.), amino groups (preferably amino groups with 0 to 20 carbon atoms, alkylamino groups, arylamino groups, etc., for example, amino (-NH ₂ ), N, N-dimethylamino, N, N- Diethylamino, N-ethylamino, anilino, etc.), sulfamoyl groups (preferably sulfamoyl groups having 0 to 20 carbon atoms, for example, N, N-dimethylsulfamoyl, N-phenylsulfamoyl, etc.), acyl groups (alkylcarbonyl). A group, an alkenylcarbonyl group, an alkynylcarbonyl group, an arylcarbonyl group, a heterocyclic carbonyl group, preferably an acyl group having 1 to 20 carbon atoms, for example, acetyl, propionyl, butyryl, octanoyl, hexadecanoyl, acryloyl, methacryloyl, Crotonoyl, benzoyl, naphthoyl, nicotineol, etc.), acyloxy groups (alkylcarbonyloxy groups, alkenylcarbonyloxy groups, alkynylcarbonyloxy groups, arylcarbonyloxy groups, heterocyclic carbonyloxy groups, etc., preferably acyloxy having 1 to 20 carbon atoms. Groups such as acetyloxy, propionyloxy, butyryloxy, octanoyloxy, hexadecanoyloxy, acryloyloxy, methacryloxy, crotonoyloxy, benzoyloxy, naphthoyloxy, nicotineoloxy, etc.), allyloyloxy groups (preferably). Is an allyloxy group having 7 to 23 carbon atoms, for example, benzoyloxy, a carbamoyl group (preferably a carbamoyl group having 1 to 20 carbon atoms, for example, N, N-dimethylcarbamoyl, N-phenylcarbamoyl, etc.), acylamino. Groups (preferably acylamino groups having 1 to 20 carbon atoms, such as acetylamino, benzoylamino, etc.), alkylsulfanyl groups (preferably alkylsulfanyl groups having 1 to 20 carbon atoms, such as methylsulfanyl, ethylsulfanyl, isopropyl. Sulfanyl, benzyl sulfanyl, etc.), aryl sulfanyl groups (preferably aryl sulfanyl groups having 6 to 26 carbon atoms, such as phenylsulfanyl, 1-naphthylsulfanyl, 3-methylphenylsulfanyl, 4-methoxyphenylsulfanyl, etc.), alkylthio groups. (Preferably an alkylthio group having 1 to 20 carbon atoms, for example, methylthio, ethylthio, isopropylthio, benzylthio, etc.), an arylthio group (preferably a carbonyl group). 6 to 26 arylthio groups such as phenylthio, 1-naphthylthio, 3-methylphenylthio, 4-methoxyphenylthio, etc., heterocyclic thiogroups (groups in which -S- group is bonded to the above heterocyclic group), alkyl Sulfonyl groups (preferably alkylsulfonyl groups having 1 to 20 carbon atoms, such as methylsulfonyl, ethylsulfonyl, etc.), arylsulfonyl groups (preferably arylsulfonyl groups having 6 to 22 carbon atoms, such as benzenesulfonyl, etc.), alkylsilyls. Groups (preferably alkylsilyl groups having 1 to 20 carbon atoms, such as monomethylsilyl, dimethylsilyl, trimethylsilyl, triethylsilyl, etc.), arylsilyl groups (preferably arylsilyl groups having 6 to 42 carbon atoms, such as triphenylsilyl). Etc.), alkoxysilyl group (preferably alkoxysilyl group having 1 to 20 carbon atoms, for example, monomethoxysilyl, dimethoxysilyl, trimethoxysilyl, triethoxysilyl, etc.), aryloxysilyl group (preferably 6 to 42 carbon atoms). aryloxy silyl group, for example, triphenyl oxysilyl etc.), a phosphoryl group (preferably a phosphate group having 0 to 20 carbon atoms, for ^{example, -OP (= O) (R} P) 2), a phosphonyl group (preferably phosphonyl group having 0 to 20 carbon atoms, for ^{example, -P (= O) (R} P) 2), a phosphinyl group (preferably a phosphinyl group having 0 to 20 carbon atoms, for ^{_{example, -P (R P) 2)}} , sulfo Examples thereof include a group (sulfonic acid group), a carboxy group, a hydroxy group, a sulfanyl group, a cyano group, and a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc.). ^RP is a hydrogen atom or a substituent (preferably a group selected from the substituent T).
Further, each group listed in these substituents T may be further substituted with the above-mentioned substituent T.
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.

(Other components)
In addition to the above-mentioned components and polymer segments, the specific polymer may have components that can be contained in the above-mentioned various polymers having a bond selected from the above-mentioned bond group (I). For example, a component derived from a low molecular weight polyol compound or a polyamine compound, a component derived from a polymer (for example, a polymer chain defined by R ^5b described later as a molecular chain), a polyol compound or a polyamine compound can be mentioned. Be done.

The specific polymer preferably contains at least one polymer represented by the following formula (3) and one polymer represented by the following formula (4), and preferably contains at least one polymer represented by the following formula (3). Is more preferable. Each component of the polymer represented by each of the following formulas may have one kind or two or more kinds.
The bonding mode of the constituent components of the polymer represented by each of the following formulas is not particularly limited, and examples thereof include random bonding, block bonding, and graft bonding.

^{^{^{Wherein, R a, X a, R}}} 1, R 2, n1 and n2, respectively, in the formula (1) and ^(2), R ^a, ^X a, and R ^1, R 2, n1 and n2 It is synonymous, and so is the preferred one.

R ^b1 represents an aromatic hydrocarbon group having 6 to 22 carbon atoms, an aliphatic hydrocarbon group having 1 to 15 carbon atoms, or a group formed by combining two or more of these groups.
The carbon number of the aliphatic hydrocarbon group that can be taken as R ^b1 means the minimum number of carbon atoms that connect two nitrogen atoms, and the carbon number of the aromatic hydrocarbon group that can be taken as R ^b1 is carbon when it is unsubstituted. Means a number.
The aliphatic hydrocarbon group having 1 to 15 carbon atoms (preferably 1 to 13 carbon atoms) may be saturated or unsaturated, may be chain-like or cyclic, and may have a branch. A hydrogen reduced product of an aromatic hydrocarbon group represented by the following formula (M2), a partial structure of a known aliphatic diisosoane compound (for example, a group consisting of isophorone), 1,1,3-trimethylcyclohexanediyl, methylenebis (). Cyclohexylene).
Examples of the aromatic hydrocarbon group having 6 to 22 carbon atoms (preferably 6 to 14, more preferably 6 to 10) include phenylene and naphthalene diyl.
Further, as the group composed of two or more of the aromatic hydrocarbon group and the aliphatic hydrocarbon group, a group composed of two or more of the phenylene group and the aliphatic hydrocarbon group is more preferable, and the total number of carbon atoms is 7. ~ 15 is preferable, and 8 to 15 is more preferable. The combined group may include a group containing an oxygen atom, a sulfur atom or a nitrogen atom in the molecular chain. For example, biphenylene, an aromatic hydrocarbon group represented by the following formula (M2) can be mentioned, and more specifically, methylenebis (phenylene), phenylenedimethylene and the like can be mentioned.

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 alkyl group and alkylene group exemplified here may be substituted with a substituent T, preferably a halogen atom (more preferably a fluorine atom).
^RM2 to ^RM5 each represent a hydrogen atom or a substituent, and a hydrogen atom is preferable. The substituent which can be taken as ^RM2 to ^RM5 is not particularly limited, but for example, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, -OR ^M6 , -N ( ^RM6 ) ₂ , and so on. -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 atom (for example, a fluorine atom, a chlorine atom, a bromine atom). Can be mentioned. -N ( ^RM6 ) ₂ includes 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).
R ^b1 may have a substituent, and examples thereof include a substituent T described later.

R ^b2 represents an alkylene group having 2 to 12 carbon atoms, and also includes a group formed by combining two or more kinds of alkylene groups.
The alkylene group that can be taken as R ^b2 may be chain-like, cyclic, or may have a branch, and the number of carbon atoms is more preferably 2 to 8 and even more preferably 2 to 6. The carbon number of each alkylene group that can be obtained from R ^b2 to R ^b4 means the minimum number of carbon atoms connecting two X ^bs .
Examples of the alkylene group include ethylene, 1,2-propylene, 1,3-propylene, 1,3-butylene, 1,4-butylene, hexylene, octylene, cyclohexylene and the like.
However, the alkylene group that can be taken as R ^b2 does not have a functional group selected from the functional group group (II) described later and a functional group selected from the functional group group (III) described later.

R ^b3 represents an alkylene group having at least one functional group selected from the following functional group group (II).
The alkylene group that can be taken as R ^b3 may be chain-like, cyclic, or may have a branch, and the number of carbon atoms is preferably 1 to 15, more preferably 1 to 10, and even more preferably 1 to 8. For example, 2-ethylpropylene can be mentioned.
The functional group selected from the functional group group (II) below may be bonded to any carbon atom of the alkylene group, but is bonded to the carbon atom constituting the shortest carbon chain to be bonded to the two X ^b3s. Is preferable. The number of functional groups contained in the alkylene group is not particularly limited, but is preferably 1 to 5, and more preferably 1 or 2.
As the following functional group group (II) in R ^b3, the above functional group group (II) possessed by the above-mentioned specific polymer can be preferably applied.
Examples of R ^b3 include 2-ethyl-2-carboxypropylene.
<Functional group group (II)>
A carboxy group, a sulfonic acid group, a phosphoric acid group, an amino group, a hydroxy group, a sulfanyl group, an isocyanato group, an alkoxysilyl group and a group in which three or more rings are fused.

R ^b4 represents an alkylene group having at least one functional group selected from the following functional group group (III).
The alkylene group that can be taken as R ^b4 may be chain-like or cyclic, may have a branch, and has a carbon number of 1 to 15, more preferably 1 to 10, and even more preferably 1 to 8. For example, propylene can be mentioned.
The functional group selected from the following functional group group (III) may be bonded to any carbon atom of the alkylene group. The number of functional groups contained in the alkylene group is not particularly limited, but is preferably 1 to 5, and more preferably 1 or 2.
As the following functional group group (III) in R ^b4, the above functional group group (III) possessed by the above-mentioned specific polymer can be preferably applied.
<Functional group group (III)>
Group having carbon-carbon unsaturated bond, epoxy group and oxetanyl group The functional group selected from the above group includes a crosslinked form as described above.

R ^b5 is a divalent chain having a number average molecular weight of 100 or more, and represents a polyalkylene oxide chain, a polycarbonate chain, a polyester chain or a silicone chain, or a chain formed by combining two or more of these chains.
The number average molecular weight of each of the above chains that can be taken as R ^b5 is preferably 100 to 100,000, more preferably 100 to 10000, and even more preferably 150 to 5000. The number average molecular weight can be measured as a standard polystyrene-equivalent number average molecular weight in the same manner as the mass average molecular weight of a specific polymer.

The polyalkylene oxide chain that can be taken as R ^b5 is not particularly limited. The carbon number of the alkylene group constituting the alkylene oxide chain is preferably 1 to 10, more preferably 1 to 8, further preferably 1 to 6, and particularly preferably 2 or 3. The total number of repetitions of the alkyleneoxy groups constituting the alkylene oxide chain is preferably 1 to 100, more preferably 3 to 100, and even more preferably 4 to 50. The component having a polyalkylene oxide chain as R ^b5 may be one kind, but in terms of battery performance, it is preferably two or more kinds, and more preferably two kinds. In this case, the combination of the polyalkylene oxide chain is not particularly limited, and for example, it preferably contains an ethylene oxide chain, and examples thereof include a combination of an ethylene oxide chain or a propylene oxide chain and an alkylene oxide chain having 4 or more carbon atoms.
The polycarbonate chain that can be taken as R ^b5 is not particularly limited. The number of carbon atoms of the repeating unit constituting the carbonate chain is preferably 1 to 15, and more preferably 1 to 10. The number of repetitions of the repeating unit constituting the carbonate chain is preferably 4 to 40, more preferably 4 to 20.
The polyester chain that can be taken as R ^b5 means a poly (alkylene-ester) chain or a poly (arylene-ester) chain and does not include the above-mentioned polymer segment. The carbon number of the alkylene group constituting the polyester chain is preferably 1 to 10, more preferably 1 to 8, and the carbon number of the arylene group constituting the polyester chain is preferably 6 to 14, more preferably 6 to 10. The number of repetitions of the repeating unit constituting the polyester chain is preferably 2 to 40, more preferably 2 to 20.
The silicone chain that can be taken as R ^b5 means a chain having a siloxane bond (-Si—O—, Si atom has two organic groups such as an alkyl group and an aryl group), and the number of repetitions of the siloxane bond is 1 to 200 is preferable, and 1 to 100 is more preferable.

Each chain that can be taken as R ^b5 may have a group such as an alkylene group at the end thereof for the convenience of polymer synthesis based on the structure of a commercially available product to be used.
In each chain that can be taken as R ^b5 , when the chain has a structure different from the total number of repeating units constituting the chain (for example, polyethylene oxide chain and polypropylene oxide chain), the repeating unit constituting each chain Means the total number of repetitions of.
Further, examples of the chain formed by combining the above chains that can be taken as R ^b5 include a chain formed by combining a polyalkylene oxide chain and a polycarbonate chain or a polyester chain, and the polycarbonate chain or polyester is included in the polyalkylene oxide chain. A chain having a chain is preferable.

X ^b2 , X ^b3 , X ^b4 and X ^b5 each represent an oxygen atom or -NH-.
In each component, the two X ^b2 , X ^b3 , X ^b4 and X ^b5 may be the same or different, but are preferably the same.

a, b, c, d, e and f indicate the molar ratio of each structural component, and a + b + c + d + e + f = 100 mol%. The total of c + d + e + f may be 0 mol%, but is preferably not 0 mol%, and more preferably 40 mol% or more.
The a is not particularly limited, but is preferably 0.1 to 30 mol%, preferably 0.3 to 20 mol%, in terms of the dispersibility and binding property of the solid particles and the battery performance of the solid secondary battery. More preferably, 0.5 to 15 mol% is further preferable, and 1 to 10 mol% is particularly preferable.
b is preferably 40 to 60 mol%, more preferably 43 to 58 mol%, still more preferably 45 to 55 mol%.
c is preferably 0 to 30 mol%, more preferably 0 to 25 mol%, further preferably 0 to 20 mol%, and particularly preferably 0 to 15 mol%.
d is preferably 0 to 49 mol%, more preferably 0.1 to 40 mol%, further preferably 1 to 30 mol%, and particularly preferably 3 to 25 mol%.
e is preferably 0 to 30 mol%, more preferably 0 to 25 mol%, further preferably 0 to 20 mol%, and particularly preferably 0 to 10 mol%.
f is preferably 0 to 49 mol%, more preferably 5 to 49 mol%, further preferably 10 to 47 mol%, and particularly preferably 20 to 45 mol%.

When the molar ratios a to f are defined by the content (mass%), the following range is preferable, and the total is 100% by mass.
The content (mass%) of a is as described above.
The content (% by mass) of b is not particularly limited, and is preferably 20 to 60% by mass, more preferably 25 to 55% by mass, and even more preferably 30 to 50% by mass.
The content (% by mass) of c is not particularly limited, and is preferably 0 to 25% by mass, more preferably 0 to 15% by mass, and even more preferably 0 to 10% by mass.
The content (% by mass) of d is not particularly limited, and is preferably 0 to 40% by mass, more preferably 1 to 25% by mass, still more preferably 1 to 15% by mass.
The content (% by mass) of e is not particularly limited, and is preferably 0 to 20% by mass, more preferably 0 to 15% by mass, and even more preferably 0 to 10% by mass.
The content (% by mass) of f is not particularly limited, and is preferably 0 to 55% by mass, more preferably 10 to 50% by mass, and even more preferably 20 to 40% by mass.

The specific polymer 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 mass average molecular weight of a particular polymer is not particularly limited. For example, 5000 or more is preferable, 10,000 or more is more preferable, and 20,000 or more is further preferable. The upper limit is preferably 5,000,000 or less, more preferably 500,000 or less, still more preferably 200,000 or less.
-Measurement of molecular weight-
In the present invention, the mass average molecular weight is measured by gel permeation chromatography (GPC) in terms of standard polystyrene. As a measurement method, the value is basically measured by the method of condition 1 or condition 2 (priority) below. However, an appropriate eluent may be appropriately selected and used depending on the type of polymer (specific polymer, etc.) to be measured.
(Condition 1)
Column: Connect two TOSOH TSKgel Super AWM-H 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: Use a column connected with TOSOH TSKgel Super HZM-H, TOSOH TSKgel Super HZ4000, TOSOH TSKgel Super HZ2000 Carrier: tetrahydrofuran Measurement temperature: 40 ° C.
Carrier flow rate: 1.0 ml / min
Sample concentration: 0.1% by mass
Detector: RI (refractive index) detector

This specific polymer may be a non-crosslinked polymer or a crosslinked polymer. Further, when the cross-linking of a specific polymer proceeds by heating or application of a voltage, the molecular weight may be larger than the above molecular weight. Preferably, the particular polymer has a mass average molecular weight in the above range at the start of use of the all-solid-state secondary battery.

The shape of the specific polymer is not particularly limited, but is preferably particulate. The particles may be flat, amorphous, etc., but are preferably spherical or granular. The particle size of the particulate polymer is not particularly limited, but is preferably 10 to 1000 nm. Thereby, the dispersibility of the solid electrolyte composition and the binding property between the solid particles can be improved. The particle size is preferably 20 to 500 nm, more preferably 30 to 300 nm, and even more preferably 50 to 200 nm in that the dispersibility and binding property can be further improved. The particle size of the particulate polymer is the same as that of the inorganic solid electrolyte by appropriately changing the diluting solvent (for example, the same solvent as the polymer dispersion, more specifically, a hydrophobic solvent such as heptane, diisobutylketone, butyl butyrate, etc.). Can be measured.
The particle size of the particulate polymer 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 polymer, and then measuring the constituent layers. It can be measured by excluding the measured value of the particle size of the particles other than the particulate polymer.
The particle size of the particulate polymer can be adjusted, for example, by the type of dispersion medium, the content and content of constituents in the polymer, and the like.

The water concentration of the specific polymer is preferably 100 ppm (mass basis) or less. Further, this specific polymer may be crystallized and dried, or the polymer dispersion may be used as it is.

-Method of synthesizing a specific polymer-
As a method for synthesizing a specific polymer, a known polymerization method can be applied without particular limitation. For example, the polymerization method described in Examples can be mentioned.
Examples of the compound used for the synthesis include each compound described in Patent Document 1.

Specific examples of specific polymers are given below, but the present invention is not limited thereto.
In each specific example, the constituent components constituting a specific polymer are shown, and the molar ratio thereof is appropriately set.

The solid electrolyte composition of the present invention may contain a specific polymer alone or in combination of two or more.
The content of the specific polymer in the solid electrolyte composition is preferably 0.001% by mass or more, more preferably 0.01% by mass or more, further preferably 0.1% by mass or more, and 0. .3% by mass or more is particularly preferable. As the upper limit, 10% by mass or less is preferable, 5% by mass or less is more preferable, and 3% by mass or less is further preferable. By using a specific polymer in the above range, the binding property of solid particles can be enhanced more effectively, and the battery performance can be further improved.
In the present invention, the mass ratio of the total mass (total mass) of the inorganic solid electrolyte and the active material to the mass of the specific polymer [(mass of the inorganic solid electrolyte + mass of the active material) / mass of the specific polymer] is 1, The range of 000 to 1 is preferable. This ratio is more preferably 500 to 2, and even more preferably 100 to 10.

<Dispersion medium>
The dispersion medium (dispersion medium) contained in the solid electrolyte composition of the present invention may be any one that disperses or dissolves each of the above components, and preferably one that disperses polymer particles and solid particles. Examples of the dispersion medium include various organic solvents. Examples of the organic solvent include alcohol compounds, ether compounds, amide compounds, amine compounds, ketone compounds, aromatic compounds, aliphatic compounds, nitrile compounds, ester compounds and the like.
The dispersion medium may be either a hydrophobic dispersion medium or a hydrophilic dispersion medium, but a hydrophobic dispersion medium is preferable because it can exhibit excellent dispersibility of the polymer. In the present invention, hydrophobicity generally refers to a property having a low affinity for water, but in the present invention, it further refers to a property having a high affinity for a polymer segment, particularly a hydrocarbon polymer, possessed by the above-mentioned specific polymer. .. Specific examples thereof include dispersion media of aromatic compounds, aliphatic compounds, ketone compounds and ester compounds.

Specific examples of each of the above solvents are shown below.
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, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, etc.). Dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether, etc.), dialkyl ether (dimethyl ether, diethyl ether, diisopropyl ether, dibutyl ether, etc.), cyclic ether (tetrahydrofuran, dioxane (1,2-, 1,2-, etc.) (Including each isomer of 1,3- and 1,4-), etc.).

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, cyclohexanone, and diisobutyl ketone.
Examples of the aromatic compound include aromatic hydrocarbon compounds such as benzene, toluene and xylene.
Examples of the aliphatic compound include aliphatic hydrocarbon compounds such as hexane, heptane, octane, and decane.
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 carboxylic acid ester compounds such as propyl, isopropyl pivalate, butyl pivalate, and isobutyl pivalate.
Examples of the non-aqueous dispersion medium include the above aromatic compounds and aliphatic compounds.

In the present invention, among them, ether compounds, ketone compounds, aromatic compounds, aliphatic compounds or ester compounds are preferable, and ketone compounds, aliphatic compounds or ester compounds are more preferable. In the present invention, it is preferable to further select the above-mentioned specific organic solvent by using a sulfide-based inorganic solid electrolyte. By selecting this combination, the sulfide-based inorganic solid electrolyte can be handled stably because it does not contain a functional group that is active with respect to the sulfide-based inorganic solid electrolyte. In particular, a combination of a sulfide-based inorganic solid electrolyte and an aliphatic compound is preferable.

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 dispersion medium may contain one kind alone or two or more kinds.

In the present invention, the content of the dispersion medium in the solid electrolyte composition is not particularly limited and can be appropriately set. For example, in the solid electrolyte composition, 20 to 99% by mass is preferable, 25 to 70% by mass is more preferable, and 30 to 60% by mass is particularly preferable.

<Active material>
The solid electrolyte 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, a solid electrolyte composition containing an active material (positive electrode active material or negative electrode active material) may be referred to as an electrode layer composition (positive electrode layer composition or negative electrode layer 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 element that can be composited with Li such as an organic substance or sulfur, or a composite of sulfur and a metal. Examples of the substance, it is preferable to use a transition metal oxide, a transition metal element M ^a transition metal oxide having ^{(Co, Ni, Fe, Mn} , 1 or more elements selected from Cu and V) a more preferred .. 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 ~ 30 mol% relative to the amount of the transition metal element ^{M a (100mol%).} 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 Oxide [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 ( Lithium 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 the above and monoclinic panocycon-type vanadium phosphate salts such as Li ₃ V ₂ (PO ₄ ) ₃ (lithium vanadium phosphate).
(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 Examples of cobalt fluoride phosphates 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 particle size (volume average particle size) of the positive electrode active material is not particularly limited. For example, it can be 0.1 to 50 μm. The particle size of the positive electrode active material particles can be measured in the same manner as the particle size of the 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 flow jet mill, a sieve, or the like is preferably used. At the time of pulverization, wet pulverization in which an organic solvent 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 the positive electrode active material layer is formed, 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 solid electrolyte composition is not particularly limited, and is preferably 10 to 97% by mass, more preferably 30 to 95% by mass, still more preferably 40 to 93% by mass, based on 100% by mass of the solid content. , 50-90% 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 solid particles are firmly bonded to each other in the constituent layer formed of the solid electrolyte composition of the present invention, 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. Examples thereof include carbonic materials obtained by firing a resin. 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 interplanar 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 a metal element oxide (metal oxide) and a 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. Amorphous means an X-ray diffraction method using CuKα rays, which has a broad scattering zone 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 groups 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 (composite) oxides, or chalcogenides are particularly preferred. 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 negative 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 lithium oxide and the metal (composite) oxide or a composite oxide of the chalcogenide, 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 due to small volume fluctuations during storage and release of lithium ions, and electrode deterioration is suppressed, resulting in a lithium ion secondary battery. 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 charge and discharge, and the binding property of solid particles is lowered as described above, but in the present invention, a high binding property can be achieved by a specific polymer. Examples of such an active material include a negative electrode active material (alloy) having a silicon element or a tin element, and each metal such as Al and In, and a negative negative active material (silicon element) having a silicon element that enables a higher battery capacity. (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 and a Sn negative electrode containing a tin element active material) is a carbon negative electrode (graphite, acetylene black, etc.). It can store more Li ions than the above. 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 (semi-metal 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 silicon is a preferable 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 measuring 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 volume average particle size of the negative electrode active material is not particularly limited, but is preferably 0.1 to 60 μm. The volume average particle size of the negative electrode active material particles can be measured in the same manner as the particle size of the inorganic solid electrolyte. 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 solid electrolyte composition is not particularly limited, and is preferably 10 to 90% by mass, more preferably 20 to 85% by mass, and 30 to 80% by mass based on 100% by mass of the solid content. It is more preferably%, and further 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. The 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 solid electrolyte composition of the present invention may appropriately contain a conductive auxiliary agent, and it is particularly preferable that the silicon atom-containing active material as the negative electrode active material is used in combination with the conductive auxiliary agent.
The conductive auxiliary agent is not particularly limited, and those known as general conductive auxiliary agents can be used. For example, 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, which are electron conductive materials. It may be a carbon fiber such as graphene or fullerene, a metal powder such as copper or nickel, or a metal fiber, or 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 Group 1 or Group 2 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 solid electrolyte composition of the present invention contains a conductive auxiliary agent, the content of the conductive auxiliary agent in the solid electrolyte composition is preferably 0 to 10% by mass in the solid content.

<Lithium salt>
The solid electrolyte 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 JP2015-088486 is preferable.
When the solid electrolyte 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, and more preferably 20 parts by mass or less.

<Dispersant>
Since the specific polymer also functions as a dispersant, the solid electrolyte composition of the present invention may not contain a dispersant other than this polymer, but may contain a dispersant. As the dispersant, those usually used for all-solid-state secondary batteries can be appropriately selected and used. In general, compounds intended for particle adsorption, steric repulsion and / or electrostatic repulsion are preferably used.

<Other additives>
The solid electrolyte composition of the present invention, as other components other than the above-mentioned components, appropriately includes an ionic liquid, a thickener, a cross-linking agent (such as one that undergoes a cross-linking reaction by radical polymerization, condensation polymerization, or ring-opening polymerization), and polymerization. It can contain initiators (such as those that generate acids or radicals by heat or light), defoaming agents, leveling agents, dehydrating agents, antioxidants and the like. 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 above polymer, a commonly used binder and the like may be contained.

(Preparation of solid electrolyte composition)
The solid electrolyte composition of the present invention is a mixture of an inorganic solid electrolyte, the above-mentioned specific polymer, a dispersion medium, and optionally a lithium salt, and any other components, for example, by mixing them in various commonly used mixers. As a slurry, preferably as a slurry.
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.
The composition for forming an active material layer (composition for an electrode layer) of the present invention can be a dispersion liquid containing highly dispersed solid particles by suppressing reaggregation of solid particles.

[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 may be 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 having a solid electrolyte layer 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.
Examples of the solid electrolyte sheet for an all-solid secondary battery of the present invention include a sheet having a layer composed of the solid electrolyte composition of the present invention, a normal solid electrolyte layer, and a protective layer on a substrate in this order. Be done.
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 and ceramics.

The composition and layer thickness of the solid electrolyte layer of the sheet for the all-solid-state secondary battery are the same as the composition and layer thickness of the solid electrolyte layer described in the all-solid-state secondary battery of the present invention.

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 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 electrode sheet of the present invention may have the other layers described above. The active material layer is preferably formed of the solid electrolyte composition (composition for electrode layer) of the present invention. The structure and thickness of each layer constituting the electrode sheet of the present invention are the same as the layer thickness of each layer described in the all-solid-state secondary battery described later.

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 solid electrolyte composition of the present invention, and the solid particles in this layer are firmly bonded to each other. Further, in the electrode sheet for an all-solid-state secondary battery, the active material layer formed of the solid electrolyte composition of the present invention is firmly bonded to the current collector. In the present invention, an increase in interfacial resistance between solid particles can be effectively suppressed. 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.
When an all-solid-state secondary battery is manufactured using the sheet for an all-solid-state secondary battery of the present invention, excellent battery performance is exhibited.

[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 can be produced by forming each of the above layers using the solid electrolyte composition of the present invention. For example, a method of forming a film (coating and drying) on a base material or a current collector (which may be via another layer) to form a layer (coating and drying layer) composed of a solid electrolyte composition is preferable. 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. Here, the coating dry layer is a layer formed by applying the solid electrolyte composition of the present invention and drying the dispersion medium (that is, the solid electrolyte composition of the present invention is used, and the solid of the present invention is used. A layer having a composition obtained by removing a dispersion medium from an electrolyte composition). In the active material layer and the coating dry layer, the dispersion medium may remain as long as the effect of the present invention is not impaired, and the residual amount may be, for example, 3% by mass or less in each layer.
In the method for producing a sheet for an all-solid-state secondary battery of the present invention, each step such as coating and drying will be described in the following method for producing 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.

[All-solid-state secondary battery]
The all-solid secondary battery of the present invention has a positive electrode active material layer, a negative electrode active material layer facing the positive electrode active material layer, and a solid electrolyte layer 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.
At least one layer of the negative electrode active material layer, the positive electrode active material layer and the solid electrolyte layer is preferably formed by the solid electrolyte composition of the present invention, and among them, all the layers are formed by the solid electrolyte composition of the present invention. It is more preferable to be done. The active material layer or the solid electrolyte layer formed of the solid electrolyte composition of the present invention preferably contains the same component species and their content ratios as those in the solid content of the solid electrolyte composition of the present invention. .. If the active material layer or the solid electrolyte layer is not formed by the solid electrolyte 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, the thickness of at least one of the positive electrode active material layer and the negative electrode active material layer is more preferably 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.

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

FIG. 1 is a 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. Batteries manufactured in a 2032 type coin case are sometimes referred to as all-solid secondary batteries.

(Positive electrode active material layer, solid electrolyte layer, negative electrode active material layer)
In the all-solid-state secondary battery 10, the positive electrode active material layer, the solid electrolyte layer, and the negative electrode active material layer are all formed of the solid electrolyte composition of the present invention. The all-solid-state secondary battery 10 exhibits excellent battery performance. The inorganic solid electrolyte and the specific polymer contained in the positive electrode active material layer 4, the solid electrolyte layer 3, and the negative electrode active material layer 2 may be the same 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 above-mentioned specific polymer is used in combination with solid particles such as an inorganic solid electrolyte or an active material, the binding property of the solid particles is enhanced, and poor contact between the solid particles and a current collector are obtained. It is possible to suppress the peeling of solid particles from the surface. Further, it is possible to suppress an increase in the interfacial resistance between the solid particles and an increase in the interfacial resistance between the solid particles and the current collector. Therefore, the all-solid-state secondary battery of the present invention exhibits excellent battery performance.

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 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 solid electrolyte composition of the present invention or the like. This makes it possible to manufacture an all-solid-state secondary battery that exhibits excellent battery performance and even smaller electrical resistance. The details will be described below.

In the all-solid secondary battery of the present invention, the solid electrolyte 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). It can be manufactured by performing a method including (via) (a method for manufacturing a sheet for an all-solid secondary battery of the present invention).
For example, a solid electrolyte composition containing a positive electrode active material is applied as a positive electrode material (composition for a positive electrode layer) on a metal foil which is a positive electrode current collector to form a positive electrode active material layer, and an all-solid rechargeable battery is formed. A positive electrode sheet for a next battery is produced. Next, a solid electrolyte composition for forming the solid electrolyte layer is applied onto the positive electrode active material layer to form the solid electrolyte layer. Further, a solid electrolyte composition containing a negative electrode active material is applied as a negative electrode material (composition for the negative electrode layer) on the solid electrolyte layer to form a negative electrode active material layer. By superimposing a negative electrode current collector (metal leaf) 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 collector is 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, a solid electrolyte composition containing a negative electrode active material is applied as a negative electrode material (composition for a negative electrode layer) on a metal foil which is a negative electrode current collector to form a negative electrode active material layer, and an all-solid rechargeable battery is formed. A negative electrode sheet for the next battery is produced. 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, the solid electrolyte composition is applied onto the 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.

In the above production method, the solid electrolyte composition of the present invention may be used as any one of the composition for the positive electrode layer, the solid electrolyte composition and the composition for the negative electrode layer, and all of them have the solid electrolyte composition of the present invention. It is preferable to use a thing.
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.
The solid electrolyte layer or the like can be formed, for example, by pressure-molding the solid electrolyte composition or the like on a substrate or the active material layer under the pressure conditions described later, or a sheet molded body of the solid electrolyte or the active material. It can also be used.

<Formation of each layer (deposition)>
The method for applying the solid electrolyte composition 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, bar coating coating can be mentioned.
At this time, the solid electrolyte 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 solid electrolyte composition of the present invention is applied and dried as described above, the solid particles are firmly bound to each other, and a coating dry layer having a small interfacial resistance between the solid particles can be formed.

It is preferable to pressurize each layer or the all-solid-state secondary battery after applying the solid electrolyte composition, superimposing the constituent layers, or preparing the all-solid-state secondary battery. It is also preferable to pressurize the layers in a laminated state. 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 solid electrolyte 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. On the other hand, when the inorganic solid electrolyte and the specific polymer coexist, it can be pressed at a temperature higher than the glass transition temperature of the specific polymer. However, in general, the temperature does not exceed the melting point of the above-mentioned specific 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 atmosphere during coating or pressurization is not particularly limited, and may be any of air, dry air (dew point -20 ° C or less), inert gas (for example, argon gas, helium gas, nitrogen gas), etc. It may be.
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.

[Applications for all-solid-state secondary batteries]
The all-solid-state 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, portable tape recorders, radios, backup power supplies, memory cards, etc. Other consumer products include automobiles (electric vehicles, etc.), 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.

The present invention will be described in more detail below 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 Polymers Used in Examples and Comparative Examples Polymers D-01 to D-12 are as described above. The polymers cD-01 and cD-02 used in Comparative Examples are shown below.

[Synthesis Example 1: Synthesis of Polymer PS1 (for Polymers D-01, D-06, D-07, D-08) that leads to a polymer segment]
In a 200 ml three-necked flask equipped with a stirrer, a thermometer, a reflux condenser and a nitrogen gas introduction tube, a hydrogenated polybutadiene polyol NISSO-PB GI-1000 (trade name, number average molecular weight 1500, manufactured by Nippon Soda Co., Ltd.) (30. 0 g), ε-caprolactone (50.2 g) and tetrabutyl orthotitanate (10 mg) were charged, the temperature was raised to 190 ° C. under a nitrogen stream, and the mixture was stirred for 7 hours. Then, the reaction solution was cooled to synthesize the polymer PS1 which leads to the segment represented by the formula (1).

[Synthesis Examples 2 and 3: Synthesis of Polymers PS2 and PS3 (for Polymers D-02 and D-03) Leading Polymer Segments]
In the synthesis of Synthesis Example 1, ε-caprolactone was changed to a cyclic lactone compound corresponding to each of the polymers D-02 and D-03 shown in the above chemical formula, and the amounts used thereof and the amount of the catalyst used were appropriately changed. Except for this, the polymers PS2 and PS3, which lead to the segments represented by the formula (1), were synthesized in the same manner as in Synthesis Example 1.

[Synthesis Example 4: Synthesis of Polymer PS4 (for Polymer D-04) Leading Polymer Segment]
Hydrogenated polybutadiene polyol NISSO-PB GI-1000 (trade name) (30.0 g), adipate in a 200 ml three-necked flask equipped with a reflux condenser equipped with a stirrer, thermometer, Dean Stark and a nitrogen gas introduction tube. Dimethyl (1.7 g) and tetrabutyl orthotitanate (10 mg) were charged, the temperature was raised to 190 ° C. under a nitrogen stream, and the mixture was stirred for 7 hours. Then, the reaction solution was cooled to synthesize the polymer PS4 which leads to the segment represented by the formula (2).

[Synthesis Example 5: Synthesis of Polymer PS5 (for Polymer D-05) Leading Polymer Segment]
In the synthesis of Synthesis Example 4, dimethyl adipate was changed to a dicarboxylic acid diester compound corresponding to each polymer D-05 shown in the above chemical formula, and the amount used and the amount used of the catalyst were changed as appropriate. In the same manner as in Synthesis Example 4, the polymer PS5 leading to the segment represented by the formula (2) was synthesized.

[Synthesis Example 6: Synthesis of Polymer PS6 (for Polymer D-09) Leading Polymer Segment]
In the synthesis of Synthesis Example 1, the hydrogenated polybutadiene polyol was changed to the hydrogenated polybutadienediamine corresponding to each polymer D-09 shown in the above chemical formula, and the amount used and the amount of the catalyst used were changed as appropriate. , A polymer PS6 for deriving the segment represented by the formula (1) was synthesized in the same manner as in Synthesis Example 1. The hydrogenated polybutadienediamine was synthesized by reacting acrylonitrile with hydrogenated polybutadiene polyol NISSO-PB GI-1000 by adding a catalytic amount of t-butoxypotassium, and hydrogenating the obtained mixture with Raney nickel.

[Synthesis Examples 7, 8 and 9: Synthesis of Polymers PS7, PS8 and PS9 (for Polymers D-10, D-11, D-12) Leading Polymer Segments]
In the synthesis of Synthesis Example 1, the amount of ε-caprolactone used was changed to the amount corresponding to each polymer shown in the above chemical formula, and the amount of catalyst used was changed as appropriate, in the same manner as in Synthesis Example 1. , PS7, PS8 and PS9, which lead to the segment represented by the formula (1), were synthesized, respectively.

[Synthesis Example 10: Synthesis of Polymer D-01]
Polymer D-01 was synthesized as follows.
Synthesized with diphenylmethane diisocyanate (17.5 g), polyethylene glycol 200 (number average molecular weight 200, 13.2 g), in Synthesis Example 1 in a 500 ml three-necked flask equipped with a stirrer, thermometer, reflux condenser and nitrogen gas introduction tube. The polymer PS1 (7.7 g) and tetrahydrofuran (dehydrated product, 149.5 g) were charged and the temperature was raised to 60 ° C. under a nitrogen stream. Next, Neostan U-600 (manufactured by Nitto Kasei, 0.08 mg) and tetrahydrofuran (dehydrated product, 4.0 g) were added as bismuth-based catalysts, and the mixture was stirred at 60 ° C. for 5 hours. Then, methanol (1.2 g) was added, and the mixture was stirred at 60 ° C. for 30 minutes, and then the reaction solution was cooled to obtain a polymer D-01 solution.
Next, a dispersion of polymer D-01 was prepared as follows.
A 300 ml three-necked flask equipped with a stirrer, a thermometer and a nitrogen gas introduction tube was charged with a polymer D-01 solution (15.0 g) and tetrahydrofuran (dehydrated product, 15.0 g) under a nitrogen stream and at room temperature. Was stirred with. Butyl butyrate (90 g) was gradually added thereto, the obtained mixed solution was distilled off under reduced pressure, and butyl butyrate was added so as to have a solid content concentration of 5%, whereby a dispersion of polymer D-01 was added. Was prepared.

[Synthesis Examples 11-21: Synthesis of Polymers D-02 to D-12 and Preparation of Dispersion]
In Synthesis Example 1, polymers D-02 to D-12 were used in the same manner as in Synthesis Example 1, except that the compounds leading to the constituents shown in Table 1 were used in the amounts used to be the contents shown in Table 1. Each was synthesized.

[Comparative Synthesis Example 1: Synthesis of Polymer cD-01 and Preparation of Dispersion]
In Synthesis Example 1, the polymer cD-01 was synthesized in the same manner as in Synthesis Example 1 except that the compounds leading to the constituents shown in Table 1 were used in the amounts used to be the contents shown in Table 1.

[Comparative Synthesis Example 2: Synthesis of Polymer cD-02 and Preparation of Dispersion]
In Synthesis Example 1, the polymer cD-02 was synthesized in the same manner as in Synthesis Example 1 except that the compounds leading to the constituents shown in Table 1 were used in the amounts used to be the contents shown in Table 1.
Polymer cD-02 coagulated and settled in butyl butyrate, making it impossible to produce a dispersion of polymer cD-02.

The mass average molecular weight of each of the synthesized polymers and the number average molecular weight of the polymer segments (component a) were measured by the above method (condition 2). In addition, the particle size of each polymer was measured by the above method. The results are shown in Table 1.
Table 1 shows the bonds selected from the bond group (I) of each polymer (excluding the polymer segment).

In Table 1, the constituent components a to f correspond to the respective constituent components represented by the molar ratios a to f in the above formula (3) or the formula (4). Since the polymers D-01 to D-12 do not have the constituent component c and the constituent component e, the description in Table 1 is omitted. Although GI-1000 of the polymer cD01 does not correspond to the constituent component f, it is described in the constituent component f column for convenience. Further, 1,10-decanediol (DDO) of the polymer cD02 corresponds to the constituent component c, but is described in the constituent component d column for convenience.

<Table abbreviation>
In the table, "-" in the components and cross-linking agent column indicates that the components do not have the corresponding components.
In the table, the names of compounds leading to each constituent unit are indicated by the following abbreviations in the constituent components a to f columns.
-Component a-
PS1 to PS9: Polymers PS1 to PS9 synthesized in the above synthesis examples 1 to 9.
-Component b-
MDI: Diphenylmethane diisocyanate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)
-Component c-
DDO: 1,10-decanediol (manufactured by Tokyo Chemical Industry Co., Ltd.)
-Component d-
DMBA: 2,2-bis (hydroxymethyl) butyric acid (manufactured by Tokyo Chemical Industry Co., Ltd.)
-Component f-
PEG200: Polyethylene glycol 200 (number average molecular weight 200, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)
PTMG250: Polytetramethylene glycol (number average molecular weight 250, manufactured by Aldrich)
G3450J: Polycarbonate diol G3450J (trade name, number average molecular weight 800, manufactured by Asahi Kasei Corporation)
-Other components-
GI-1000: Hydrogenated polybutadiene polyol NISSO-PB GI-1000 (trade name, number average molecular weight 1500, manufactured by Nippon Soda Corporation)

In the "bond group (I)" column, U indicates a urethane bond, E indicates an ether bond, and C indicates a carbonate bond. When the polymer has multiple bonds, it is described together using "/". That is, U / E indicates that the polymer has a urethane bond and an ether bond.
In addition, in the "component f" column, when two or more types of components are contained, the abbreviations and contents of the components are described together using "/".

2. 2. Synthesis of sulfide-based inorganic solid electrolytes Sulfide-based inorganic solid electrolytes are described in T.I. Ohtomo, A. 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.M. Morimoto, M.D. Tassumisago, T. et al. Minami, Chem. Lett. , (2001), pp872-873, was synthesized with reference to the non-patent documents.
Specifically, in a glove box under an argon atmosphere (dew point -70 ° C.), lithium sulfide _(Li 2 S, Aldrich Corp., purity> 99.98%) 2.42 g and diphosphorus pentasulfide _(P 2 S _5. Aldrich, purity> 99%) 3.90 g 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.
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 / P / S glass, hereinafter may be referred to as LPS.) 6.20 g was obtained.

[Example 1]
In Example 1, an all-solid-state secondary battery sheet and an all-solid-state secondary battery having the layer structure shown in FIG. 1 were prepared using the solid electrolyte composition prepared using the polymer D-01 dispersion. , The performance was evaluated. The results are shown in Table 2.
<Preparation of solid electrolyte composition D-01>
180 zirconia beads having a diameter of 5 mm were put into a 45 mL container made of zirconia (manufactured by Fritsch), 9.5 g of LPS synthesized above, and 2.5 g of butyl butyrate as a dispersion medium were put. Then, 0.5 g of the polymer D-01 dispersion liquid equivalent to the solid content was added and set in a planetary ball mill P-7 (trade name, manufactured by Fritsch). Mixing was continued for 3 hours at a temperature of 25 ° C. and a rotation speed of 300 rpm to prepare a solid electrolyte composition D-01.

<Manufacture of positive electrode sheet D-01 for all-solid-state secondary battery>
180 zirconia beads having a diameter of 5 mm were placed in a 45 mL container made of zirconia (manufactured by Fritsch), and the solid electrolyte composition D-01 prepared above was 1.9 g in terms of solid content and butyl butyrate as the total amount of dispersion medium. 3 g was added. Further, 8.0 g of NCA (LiNi _0.85 Co _0.10 Al _0.05 O ₂ ) and 0.1 g of acetylene black were added thereto as the positive electrode active material, set in the planetary ball mill P-7, and the temperature was 25. Mixing was continued for 20 minutes at ° C. and a rotation speed of 200 rpm. In this way, the composition (slurry) D-01 for the positive electrode layer was prepared.
The positive electrode layer composition D-01 prepared above is applied to an aluminum foil having a thickness of 20 μm as a current collector with a baker-type applicator (trade name: SA-201, manufactured by Tester Sangyo Co., Ltd.) and at 80 ° C. for 1 hour. After heating, the composition D-01 for the positive electrode layer was dried by further heating at 110 ° C. for 1 hour. Then, using a heat press machine, the dried composition D-01 for the positive electrode layer is pressed while heating (120 ° C.) (20 MPa for 1 minute), and the positive electrode active material layer / aluminum foil having a layer thickness of 60 μm is laminated. A positive electrode sheet D-01 for an all-solid-state secondary battery having a structure was produced.

<Manufacture of negative electrode sheet D-01 for all-solid-state secondary battery>
Next, 180 zirconia beads having a diameter of 5 mm were placed in a 45 mL container made of zirconia (manufactured by Fritsch), and 5.0 g of the solid electrolyte composition D-01 prepared above was added as a dispersion medium, and butyl butyrate 12 as a dispersion medium. .3 g was added. Then, this container was set in a planetary ball mill P-7 (trade name, manufactured by Fritsch), and the mixture was stirred at a temperature of 25 ° C. and a rotation speed of 300 rpm for 3 hours. Then, 5.0 g of graphite was added as the negative electrode active material, and this container was set in the planetary ball mill P-7 again, and mixing was continued for 15 minutes at a temperature of 25 ° C. and a rotation speed of 100 rpm. In this way, the composition (slurry) D-01 for the negative electrode layer was obtained.
The negative electrode layer composition D-01 obtained above is applied onto a stainless foil having a thickness of 10 μm by the above baker type applicator, and heated at 80 ° C. for 2 hours to dry the negative electrode layer composition D-01. It was. Then, using a heat press machine, the dried composition D-01 for the negative electrode layer is pressurized (600 MPa for 1 minute) while heating (120 ° C.) to form a negative electrode active material layer / stainless foil having a layer thickness of 120 μm. A negative electrode sheet D-01 for an all-solid-state secondary battery having a laminated structure was produced.

<Manufacturing of all-solid-state secondary battery D-01>
The prepared solid electrolyte composition D-01 is applied onto the negative electrode active material layer of the prepared negative electrode sheet D-01 for an all-solid secondary battery by the above-mentioned baker type applicator, heated at 80 ° C. for 1 hour, and then further. The solid electrolyte composition D-01 was dried by heating at 110 ° C. for 6 hours. The negative electrode sheet D-01 having the solid electrolyte layer (coating dry layer) formed on the negative electrode active material layer is pressurized (30 MPa, 1 minute) while heating (120 ° C.) using a heat press machine to achieve a layer thickness. A negative electrode sheet D-01 having a laminated structure of a 60 μm solid electrolyte layer / negative electrode active material layer / stainless foil was prepared.
This negative electrode sheet was cut out into a disk shape having a diameter of 15 mm. On the other hand, the positive electrode sheet D-01 for an all-solid-state secondary battery produced above was cut out into a disk shape having a diameter of 13 mm. After the positive electrode active material layer of the positive electrode sheet D-01 for the all-solid secondary battery and the solid electrolyte layer formed on the negative electrode sheet D-01 are arranged (laminated) so as to face each other, they are heated (laminated) using a heat press machine. Pressurization (40 MPa, 1 minute) while (120 ° C.) was performed to prepare a laminate for an all-solid secondary battery having a laminated structure of aluminum foil / positive electrode active material layer / solid electrolyte layer / negative electrode active material layer / stainless foil. ..
Next, the all-solid-state secondary battery laminate 12 thus produced is placed in a stainless steel 2032 type coin case 11 incorporating a spacer and a washer (not shown in FIG. 2), and the 2032 type coin case 11 is inserted. By tightening, the all-solid-state secondary battery D-01 shown by reference numeral 13 in FIG. 2 was manufactured.

[Examples 2 to 12 (No. D-02 to D-12), Comparative Example 1 (No. cD-01), and Comparative Example 2]
In the preparation of the solid electrolyte composition D-01, the production of the positive electrode sheet D-01 for the all-solid secondary battery, the production of the negative electrode sheet D-01 for the all-solid secondary battery, and the production of the all-solid secondary battery D-01. , All the positive electrode sheets for all-solid secondary batteries and all in the same manner as in Example 1 except that each composition prepared by using the polymer dispersion shown in Table 2 was used instead of the polymer D-01 dispersion. Negative electrode sheets for solid secondary batteries were prepared, and all-solid secondary battery No. D-02 to D-12 and cD-01 were produced, respectively.
Since the polymer dispersion liquid cD-02 could not be prepared, the sheet for the all-solid-state secondary battery and the all-solid-state secondary battery using the polymer cD-02 have not been prepared and evaluated.

<Dispersibility test of solid electrolyte composition>
Each solid electrolyte composition prepared as described above was separated from the planetary ball mill P-7 and filled in a transparent glass tube having a diameter of 10 mm to a height of 3 cm. This was allowed to stand in an environment of 25 ° C. for 48 hours. Then, the phase separation state of the composition and the degree of phase separation (dispersion stability) were judged by the following evaluation criteria. In this test, the evaluation standard "C" or higher is the passing level.
-Evaluation criteria-
A: When the location where layer separation (phase separation) occurs (interface with the supernatant layer) is less than 2 mm from the liquid surface B: When the location where layer separation occurs is 2 mm or more and less than 4 mm from the liquid surface C : When the part where the layer separation occurs is 4 mm or more and less than 7 mm from the liquid level D: When the part where the layer separation occurs is 7 mm or more and less than 10 mm from the liquid level

<Adhesion test of electrode sheet for all-solid-state secondary battery>
As a binding test of the positive electrode sheet for an all-solid-state secondary battery, it was evaluated by a bending resistance test (according to JIS K 5600-5-1) using a mandrel testing machine. Specifically, a strip-shaped test piece having a width of 50 mm and a length of 100 mm was cut out from each sheet. Set the active material layer surface of this test piece on the opposite side of the mandrel (the current collector is on the mandrel side) and so that the width direction of the test piece is parallel to the axis of the mandrel, and 180 along the outer peripheral surface of the mandrel. After bending (once), it was observed whether or not the active material layer had cracks and cracks. This bending test is first performed using a mandrel having a diameter of 32 mm, and if neither cracks nor cracks occur, the diameter (unit: mm) of the mandrel is set to 25, 20, 16, 12, 10, 8, 6 The diameter was gradually reduced to 5, 3 and 2, and the diameter of the mandrel where the crack and / or crack first occurred was recorded. The binding property was evaluated based on which of the following evaluation criteria included the diameter at which the cracks and cracks first occurred (defect generation diameter). In the present invention, the smaller the defect generation diameter, the stronger the binding property of the solid particles, and the evaluation standard "B" or higher is the pass level.

-Evaluation criteria-
AA: 2mm
A: 3 mm
B: 5 mm or 6 mm
C: 8 mm or more

(Measurement of battery performance (discharge capacity))
The discharge capacity was measured as the battery performance using the all-solid-state secondary battery manufactured in the same manner as the above <Manufacturing of the all-solid-state secondary battery D-01> except that the positive electrode sheet prepared as follows was used. ..
That is, 180 zirconia beads having a diameter of 5 mm were put into a 45 mL container made of zirconia (manufactured by Fritsch), and the solid electrolyte composition shown in Table 2 was 1.9 g in terms of solid content and 12.3 g of butyl butyrate as the total amount of dispersion medium. Was put in. Further, 8.0 g of NCA (LiNi _0.85 Co _0.10 Al _0.05 O ₂ ) and 0.1 g of acetylene black were added thereto as the positive electrode active material, set in the planetary ball mill P-7, and the temperature was 25. Mixing was continued for 20 minutes at ° C. and a rotation speed of 200 rpm. In this way, the composition (slurry) for the positive electrode layer for volume measurement was prepared respectively.
Next, the composition for the positive electrode layer prepared above was allowed to stand at 25 ° C. for 2 hours, and then applied to an aluminum foil having a thickness of 20 μm as a current collector by a baker type applicator (trade name: SA-201, manufactured by Tester Sangyo Co., Ltd.). The coating was applied, heated at 80 ° C. for 1 hour, and then further heated at 110 ° C. for 1 hour to dry the composition for the positive electrode layer. Then, using a heat press machine, the dried composition for the positive electrode layer is pressed while heating (120 ° C.) (20 MPa, 1 minute) to have a laminated structure of a positive electrode active material layer / aluminum foil having a layer thickness of 60 μm. , Positive electrode sheets for all-solid-state secondary batteries for capacity measurement were prepared.
The discharge capacity of each all-solid-state secondary battery manufactured using the positive electrode sheet for the all-solid-state secondary battery was measured by a charge / discharge evaluation device "TOSCAT-3000" (trade name, manufactured by Toyo System Co., Ltd.). The all-solid-state secondary battery was charged with a current value of 0.2 mA until the battery voltage reached 4.2 V, and then discharged at a current value of 0.2 mA until the battery voltage reached 3.0 V. This charging / discharging was set as one cycle, and charging / discharging was repeated. In this charge / discharge cycle, the discharge capacity of the third cycle was determined. This discharge capacity was converted into a surface area of the positive electrode active material layer per 100 cm ² , and the discharge capacity of the all-solid secondary battery was determined by the following evaluation criteria. In this test, the pass level is above the evaluation standard "B".
-Evaluation criteria-
AA: Discharge capacity is 200mAh or more A: Discharge capacity is 180mAh or more and less than 200mAh B: Discharge capacity is 150mAh or more and less than 180mAh C: Discharge capacity is 120mAh or more and less than 150mAh

The following can be seen from the results shown in Table 2.
That is, the solid electrolyte composition cD-01 in which the polymer cD-01 not containing the polymer segment specified in the present invention is used in combination with the inorganic solid electrolyte and the dispersion medium does not have sufficient dispersibility of the solid electrolyte composition. Further, the binding property of the positive electrode sheet cD-01 and the battery performance (discharge capacity) of the all-solid-state secondary battery cD-01 are not satisfactory.
The polymer cD-02 containing a component derived from an alkylene group having a molecular weight of less than 500 instead of a hydrocarbon polymer having a number average molecular weight of 500 or more has extremely poor dispersibility. Therefore, even if the positive electrode sheet and the all-solid-state secondary battery are manufactured using the polymer cD-02, the binding property of the positive electrode sheet cD-02 and the battery performance (discharge capacity) of the all-solid-state secondary battery cD-02 are sufficient. It turns out that it is not a good thing.

On the other hand, the solid electrolyte compositions D-01 to D-12 in which the polymers D-01 to D-12 having the polymer segment defined in the present invention in combination with the inorganic solid electrolyte and the dispersion medium are all used. , Solid particles are highly dispersed and show excellent dispersibility (dispersion stability). Further, in each of the positive electrode sheets D-01 to D-12 produced from these solid electrolyte compositions, solid particles are firmly bound (excellent in binding of solid particles), and these positive electrode sheets are excellent. It can be seen that all of the all-solid-state secondary batteries D-01 to D-12 provided with the above as a constituent layer exhibit high battery performance (discharge capacity).
From the above results, when the specific polymer contained in the solid electrolyte layer and the active material layer is different, and when the specific polymer is contained in at least one layer of the solid electrolyte layer and the active material layer, the above-mentioned effect can be exhibited. I understand.

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. 2019-062800, which was filed for patent in Japan on March 28, 2019, which is referred to herein and is described herein. Import 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 secondary battery 11 Coin case 12 All-solid secondary battery laminate 13 All-solid secondary Battery (coin battery)

Claims

A solid electrolyte composition containing an inorganic solid electrolyte having conductivity of metal ions belonging to Group 1 or Group 2 of the Periodic Table, a polymer, and a dispersion medium.
The polymer has at least two hydroxy or amino groups, a component derived from a hydrocarbon polymer having a number average molecular weight of 500 or more, and a cyclic compound having an ester bond or a compound having at least two carboxy groups. A solid having a polymer segment having an oxygen or nitrogen atom as a bond having a constituent component derived from the above, and having at least one bond selected from the following bond group (I) in the main chain. Polymer composition.
<Binding group (I)>
Ester bond, amide bond, urethane bond, urea bond, imide bond, ether bond and carbonate bond
The solid electrolyte composition according to claim 1, wherein the polymer segment contains at least one of a polymer segment represented by the following formula (1) and a polymer segment represented by the formula (2).

In the formula, Ra represents a hydrocarbon polymer chain in the hydrocarbon polymer.
X a is an oxygen atom or -NH-.
R 1 represents an aliphatic hydrocarbon group having 3 to 15 carbon atoms.
R 2 represents an aromatic hydrocarbon group having 6 to 20 carbon atoms or an aliphatic hydrocarbon group having 1 to 20 carbon atoms.
n1 is 1 to 100 and n2 is 1 to 10.
The solid electrolyte composition according to claim 1 or 2, wherein the cyclic compound having an ester bond or the compound having at least two carboxy groups contains a lactone compound.
The solid electrolyte composition according to any one of claims 1 to 3, wherein the polymer is a particulate polymer having an average particle size of 10 to 1000 nm.
The solid electrolyte composition according to any one of claims 1 to 4, wherein the content of the polymer segment in the polymer is 5 to 80% by mass.
The solid electrolyte composition according to any one of claims 1 to 5, wherein the polymer comprises at least one of a polymer represented by the following formula (3) and a polymer represented by the formula (4).

In the formula, Ra represents a hydrocarbon polymer chain in the hydrocarbon polymer.
X a is an oxygen atom or -NH-.
R 1 represents an aliphatic hydrocarbon group having 3 to 15 carbon atoms.
R 2 represents an aromatic hydrocarbon group having 6 to 20 carbon atoms or an aliphatic hydrocarbon group having 1 to 20 carbon atoms.
n1 is 1 to 100 and n2 is 1 to 10.
R b1 represents an aromatic hydrocarbon group having 6 to 22 carbon atoms, an aliphatic hydrocarbon group having 1 to 15 carbon atoms, or a group formed by combining two or more of these groups.
R b2 represents an alkylene group having 2 to 12 carbon atoms.
R b3 represents an alkylene group having at least one functional group selected from the following functional group group (II).
R b4 represents an alkylene group having at least one functional group selected from the following functional group group (III).
R b5 is a divalent chain having a number average molecular weight of 100 or more, and represents a polyalkylene oxide chain, a polycarbonate chain, a polyester chain or a silicone chain, or a chain formed by combining two or more of these chains.
X b2 , X b3 , X b4 and X b5 represent an oxygen atom or -NH-.
a, b, c, d, e and f are the molar ratios of each structural component, a is 0.1 to 30 mol%, b is 40 to 60 mol%, and c and e are 0 to 30 mol%, respectively. d and f are 0 to 49 mol%, respectively, and a + b + c + d + e + f = 100 mol%.
<Functional group group (II)>
A carboxy group, a sulfonic acid group, a phosphoric acid group, an amino group, a hydroxy group, a sulfanyl group, an isocyanato group, an alkoxysilyl group and a group in which three or more rings are fused <functional group group (III)>
Group with carbon-carbon unsaturated bond, epoxy group and oxetanyl group
The solid electrolyte composition according to any one of claims 1 to 6, wherein the content of the polymer is 0.001 to 10% by mass in the solid content of the solid electrolyte composition.
The solid electrolyte composition according to any one of claims 1 to 7, wherein the inorganic solid electrolyte is 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. 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.
The solid electrolyte composition according to any one of claims 1 to 8, wherein the dispersion medium is selected from a ketone compound, an aliphatic compound or an ester compound.
The solid electrolyte composition according to any one of claims 1 to 9, which contains an active material.
A sheet for an all-solid secondary battery having a layer composed of the solid electrolyte composition according to any one of claims 1 to 10.
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 all-solid secondary layer in which at least one layer of the positive electrode active material layer, the solid electrolyte layer, and the negative electrode active material layer is a layer composed of the solid electrolyte composition according to any one of claims 1 to 10. battery.
A method for producing a sheet for an all-solid secondary battery, which forms a film of the solid electrolyte composition according to any one of claims 1 to 10.
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 13.