JP7257520B2 - Inorganic solid electrolyte-containing composition, all-solid secondary battery sheet and all-solid secondary battery, and method for producing all-solid secondary battery sheet and all-solid secondary battery - Google Patents

Description

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

An all-solid secondary battery consists of a negative electrode, an electrolyte, and a positive electrode, all of which are solid, and can greatly improve safety and reliability, which are problems of batteries using an organic electrolyte. In addition, it is said that it will be possible to extend the service life. Furthermore, the all-solid secondary battery can have a structure in which the electrodes and the electrolyte are directly arranged in series. Therefore, it is possible to achieve a higher energy density than a secondary battery using an organic electrolyte, and it is expected to be applied to electric vehicles, large storage batteries, and the like.

In such an all-solid secondary battery, one of the constituent layers (inorganic solid electrolyte layer, negative electrode active material layer, positive electrode active material layer, etc.) is combined with an inorganic solid electrolyte or active material and a binder (binder). Various techniques for forming with a material (constituent layer forming material) containing are proposed.
For example, Patent Document 1 discloses (A) an inorganic solid electrolyte having ion conductivity of a metal belonging to Group 1 or Group 2 of the periodic table, (B) a polymer, and (C) a dispersion medium. (B) polymer has a hydrocarbon polymer segment in the main chain, and the main chain has a bond group (I): an ester bond, an amide bond, a urethane bond, a urea bond, an imide bond, A solid electrolyte composition is described comprising at least one bond selected from an ether bond and a carbonate bond. Further, Patent Document 2 discloses a solid electrolyte composition containing non-spherical polymer particles, a dispersion medium, and an inorganic solid electrolyte, wherein the non-spherical polymer particles contain functional groups selected from the specific functional group group a. , an acidic group with an acid dissociation constant pKa of 14 or less, or a basic group with a conjugate acid pKa of 14 or less.

International Publication No. 2018/020827A1 JP 2015-167126 A

From the viewpoint of productivity, the constituent layers of the all-solid-state secondary battery are preferably continuously produced in a sheet form, and are practically wound around a roll or the like and stored. When or after forming the constituent layers into a sheet, it is inevitable that the constituent layers will be subjected to stress such as bending, bending, and restoration (stretching). In addition, the sheet-like constituent layers are usually stored by being wound around a core or the like, and are sent out from the core when used.
However, since the constituent layers of an all-solid secondary battery are usually formed of solid particles such as an inorganic solid electrolyte, a binder, and an active material, interfacial contact between solid particles is generally insufficient. Therefore, the bending and restoring described above causes a problem that interfacial contact between solid particles in the constituent layers is gradually impaired (poor bending durability). From the standpoint of industrial production of all-solid-state secondary batteries, when the sheet-shaped constituent layers are produced by the roll-to-roll method, this problem is caused by many bends and restorations following the surface of the carrier roll or support roll during production. repeated several times and become particularly pronounced.
However, even if a conventional binder is used in combination with the solid particles, it is not possible to sufficiently suppress the decrease in interfacial contact between the solid particles due to bending and restoring, and there is room for improvement.

An object of the present invention is to provide an inorganic solid electrolyte-containing composition that can be used as a material for constituting a constituent layer of an all-solid secondary battery, thereby realizing a constituent layer having excellent bending durability. The present invention also provides a sheet for an all-solid secondary battery and an all-solid secondary battery, and a method for producing an all-solid secondary battery sheet and an all-solid secondary battery using this inorganic solid electrolyte-containing composition. The task is to provide

As a result of various investigations, the present inventors have found that a binder containing a polymer having a tensile hysteresis loss of less than 40% in a stress-strain curve obtained by repeating tension and restoration 10 times for a material constituting a constituent layer is an inorganic binder. It was found that a constituent layer having excellent bending durability can be realized by using it in combination with a solid electrolyte. The present invention has been completed through further studies based on these findings.

That is, the above problems have been solved by the following means.
<1> An inorganic solid electrolyte-containing composition containing an inorganic solid electrolyte having ion conductivity of a metal belonging to Group 1 or Group 2 of the periodic table and a binder,
A composition containing an inorganic solid electrolyte, wherein the binder comprises a polymer having a tensile hysteresis loss of less than 40% in a stress-strain curve obtained by repeating stretching and restoring 10 times.
<2> The inorganic solid electrolyte-containing composition according to <1>, wherein the polymer has a tensile hysteresis loss of less than 35% in a stress-strain curve obtained by repeating stretching and restoring 30 times.
<3> The inorganic solid electrolyte-containing composition according to <1> or <2>, wherein the polymer has a tensile modulus of 400 MPa or more.
<4> The inorganic solid electrolyte-containing composition according to any one of <1> to <3>, wherein the polymer has an elongation at break of 300% or more.
<5> The inorganic according to any one of <1> to <4>, wherein the polymer has at least one bond selected from a urethane bond, a urea bond, an amide bond, an imide bond and an ester bond in the main chain. A composition containing a solid electrolyte.
<6> The polymer according to any one of <1> to <5>, wherein the main chain has at least two polyether structures selected from a polyethyleneoxy chain, a polypropyleneoxy chain and a polytetramethyleneoxy chain. A composition containing an inorganic solid electrolyte.
<7> The inorganic solid electrolyte-containing composition according to <6>, wherein the at least two polyether structures have a number average molecular weight of 400 or less.
<8> The inorganic solid electrolyte-containing composition according to any one of <1> to <7>, which contains an active material.
<9> The inorganic solid electrolyte-containing composition according to <8>, wherein the active material is an active material containing elemental silicon or elemental tin.
<10> The inorganic solid electrolyte-containing composition according to any one of <1> to <9>, which contains a conductive aid.
<11> The inorganic solid electrolyte-containing composition according to any one of <1> to <10>, wherein the inorganic solid electrolyte is a sulfide-based inorganic solid electrolyte.
<12> A sheet for an all-solid secondary battery, having a layer composed of the inorganic solid electrolyte-containing composition according to any one of <1> to <11> above.
<13> An all-solid secondary battery comprising a positive electrode active material layer, a solid electrolyte layer and a negative electrode active material layer in this order,
At least one 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 inorganic solid electrolyte-containing composition according to any one of <1> to <11> above. Solid secondary battery.
<14> A method for producing a sheet for an all-solid secondary battery, comprising forming a film from the inorganic solid electrolyte-containing composition according to any one of <1> to <11> above.
<15> A method for manufacturing an all-solid secondary battery, comprising manufacturing an all-solid secondary battery through the manufacturing method according to <14> above.

INDUSTRIAL APPLICABILITY The present invention can provide an inorganic solid electrolyte-containing composition that can form a constituent layer having excellent bending durability and is suitably used as a constituent layer constituent material of an all-solid secondary battery. Moreover, the present invention can provide a sheet for an all-solid secondary battery and an all-solid secondary battery having a layer composed of this inorganic solid electrolyte-containing composition. Furthermore, the present invention can provide a sheet for an all-solid secondary battery and a method for producing an all-solid secondary battery using this inorganic solid electrolyte-containing composition.
The above and other features and advantages of the present invention will become more apparent from the following description, with appropriate reference to the accompanying drawings.

1 is a vertical cross-sectional view schematically showing an all-solid secondary battery according to a preferred embodiment of the present invention; FIG. FIG. 2 is a vertical cross-sectional view schematically showing a coin-type all-solid-state secondary battery produced in Examples.

In this specification, a numerical range represented by "to" means a range including the numerical values before and after "to" as lower and upper limits.
In the present specification, the expression of a compound (for example, when it is called with a compound at the end) is used to mean the compound itself, its salts, and its ions. In addition, it is meant to include derivatives in which a part is changed, such as by introducing a substituent, within a range that does not impair the effects of the present invention.
In the present invention, (meth)acryl means one or both of acryl and methacryl. The same is true for (meth)acrylates.
In the present specification, substituents, linking groups, etc. (hereinafter referred to as substituents, etc.) for which substitution or unsubstitution is not specified are intended to mean that the group may have an appropriate substituent. Therefore, even if the YYY group is simply referred to in this specification, the YYY group includes not only the embodiment having no substituent but also the embodiment having a substituent. This also applies to compounds that are not specified as substituted or unsubstituted. Preferred substituents include, for example, substituent Z described later.
In this specification, when there are a plurality of substituents or the like indicated by a specific symbol, or when a plurality of substituents or the like are defined simultaneously or alternatively, the respective substituents or the like may be the same or different from each other. means good. Further, even if not otherwise specified, when a plurality of substituents and the like are adjacent to each other, they may be connected to each other or condensed to form a ring.

[Inorganic solid electrolyte-containing composition]
The inorganic solid electrolyte-containing composition of the present invention contains an inorganic solid electrolyte having ion conductivity of a metal belonging to Group 1 or Group 2 of the periodic table, and a binder.
The binder contained in the inorganic solid electrolyte-containing composition of the present invention is a solid such as an inorganic solid electrolyte (and further, an active material and a conductive aid that can coexist) in at least the layer formed from the inorganic solid electrolyte-containing composition. It functions as a binder that binds particles together (for example, inorganic solid electrolytes together, inorganic solid electrolytes and active materials, active materials together). Furthermore, it may function as a binder that binds the current collector and the solid particles together. The binder contained in the composition containing an inorganic solid electrolyte of the present invention may or may not have the function of binding solid particles together in the composition containing an inorganic solid electrolyte.
The inorganic solid electrolyte-containing composition of the present invention is preferably slurry in which the inorganic solid electrolyte is dispersed in a dispersion medium. In this case, the binder may or may not have the function of dispersing the solid particles in the dispersion medium. In addition, the binder may be dissolved in the dispersion medium (also referred to as a dissolved binder). Binders that do so are also referred to as particulate binders.) is preferred. The inorganic solid electrolyte-containing composition of this aspect usually becomes a slurry.

By using the inorganic solid electrolyte-containing composition of the present invention as a constituent layer constituent material of an all-solid secondary battery, a constituent layer having excellent bending durability can be realized (produced).
Although the details of the reason are not clear yet, it is considered as follows. That is, a binder containing a polymer having a tensile hysteresis loss of less than 40% in a stress-strain curve obtained by repeating tension and restoration 10 times is solid particles in the constituent layers that follow the bending and restoration of the constituent layers well. (Initial) interfacial contact (bonding) between them can be maintained. As a result, it is possible to suppress the deterioration or breakage (generation of voids) of interfacial contact between solid particles in the constituent layers, which can be gradually weakened by repeated bending and restoration during production or storage, and excellent initial interfacial contact. can be maintained (suppressing the decrease in bending durability). Due to the action and function of the binder, the all-solid secondary battery comprising the constituent layers formed using the inorganic solid electrolyte-containing composition of the present invention is one in which the constituent layers are (repeatedly) bent and restored. However, excellent bending durability can be achieved.
Since the binder used in the present invention exhibits the above function, it not only bends and restores the above-mentioned constituent layers, but also follows the expansion and contraction due to charging and discharging of the all-solid secondary battery well, and expands and contracts due to charging and discharging. Even when used in combination with a large negative electrode active material, the interfacial contact state between the solid particles due to repeated expansion and contraction can be maintained, and deterioration of battery performance (eg, battery resistance and cycle characteristics) due to expansion and contraction can be suppressed.

The inorganic solid electrolyte-containing composition of the present invention is a material for forming a solid electrolyte layer, an active material layer, etc. of an all-solid secondary battery sheet (including an all-solid secondary battery electrode sheet) or an all-solid secondary battery. It can be preferably used as a (constituent layer forming material). In particular, from the viewpoint of productivity, it can be preferably used as a material for forming constituent layers produced by the roll-to-roll method, and excellent bending durability can be achieved in this embodiment as well. Furthermore, it can be preferably used as a material for forming a negative electrode sheet or a negative electrode active material layer for an all-solid secondary battery containing a negative electrode active material that expands and contracts greatly due to charging and discharging, and deterioration of battery performance can be suppressed in this aspect as well.

The inorganic solid electrolyte-containing composition of the present invention is preferably a non-aqueous composition. In the present invention, the non-aqueous composition includes not only a form containing no water but also a form having a water content (also referred to as water content) of preferably 500 ppm or less. In the non-aqueous composition, the water content is more preferably 200 ppm or less, still more preferably 100 ppm or less, and particularly preferably 50 ppm or less. When the inorganic solid electrolyte-containing composition is a non-aqueous composition, deterioration of the inorganic solid electrolyte can be suppressed. The water content indicates the amount of water contained in the inorganic solid electrolyte-containing composition (mass ratio to the inorganic solid electrolyte-containing composition). It is the value measured using titration.

The composition containing an inorganic solid electrolyte of the present invention also includes an embodiment containing an active material, a conductive aid, etc. in addition to an inorganic solid electrolyte (a composition of this embodiment is referred to as an electrode composition).
Components contained and components that can be contained in the composition containing an inorganic solid electrolyte of the present invention are described below.

<Inorganic solid electrolyte>
The inorganic solid electrolyte-containing composition of the present invention contains an inorganic solid electrolyte.
In the present invention, an inorganic solid electrolyte means an inorganic solid electrolyte, and a solid electrolyte means a solid electrolyte in which ions can move. Since the main ion-conducting materials do not contain organic substances, organic solid electrolytes (polymer electrolytes typified by polyethylene oxide (PEO), etc., organic electrolytes typified by lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), etc.) electrolyte salt). Further, since the inorganic solid electrolyte is solid in a steady state, it is not usually dissociated or released into cations and anions. In this respect, it is clearly distinguished from electrolytes or inorganic electrolyte salts that are dissociated or released into cations and anions in polymers (LiPF ₆ , LiBF ₄ , lithium bis(fluorosulfonyl)imide (LiFSI), LiCl, etc.). be done. The inorganic solid electrolyte is not particularly limited as long as it has ion conductivity of a metal belonging to Group 1 or Group 2 of the periodic table, and generally does not have electronic conductivity. When the all-solid secondary battery of the present invention is a lithium ion battery, the inorganic solid electrolyte preferably has ion conductivity of lithium ions.
As the inorganic solid electrolyte, a solid electrolyte material normally used in all-solid secondary batteries can be appropriately selected and used. Examples of inorganic solid electrolytes include (i) sulfide-based inorganic solid electrolytes, (ii) oxide-based inorganic solid electrolytes, (iii) halide-based inorganic solid electrolytes, and (iv) hydride-based solid electrolytes. A sulfide-based inorganic solid electrolyte is preferable from the viewpoint that a better interface can be formed between the active material and the inorganic solid electrolyte.

(i) Sulfide-based inorganic solid electrolyte The sulfide-based inorganic solid electrolyte contains sulfur atoms, has the ion conductivity of a metal belonging to Group 1 or Group 2 of the periodic table, and is electronically insulating. It is preferable to use a material having properties. The sulfide-based inorganic solid electrolyte preferably contains at least Li, S and P as elements and has lithium ion conductivity. element may be included.

Examples of sulfide-based inorganic solid electrolytes include lithium ion conductive inorganic solid electrolytes that satisfy 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, preferably Li. M represents an element selected from B, Zn, Sn, Si, Cu, Ga, Sb, Al and Ge. A represents an element selected from I, Br, Cl and F; a1 to e1 indicate the composition ratio of each element, and a1:b1:c1:d1:e1 satisfies 1-12:0-5:1:2-12:0-10. a1 is preferably 1 to 9, more preferably 1.5 to 7.5. b1 is preferably 0-3, more preferably 0-1. d1 is preferably 2.5 to 10, more preferably 3.0 to 8.5. e1 is preferably 0 to 5, more preferably 0 to 3.

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

The sulfide-based inorganic solid electrolyte may be amorphous (glass), crystallized (glass-ceramics), or only partially crystallized. For example, Li--P--S type glass containing Li, P and S, or Li--P--S type 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 (e.g., diphosphorus pentasulfide (P ₂ S ₅ )), elemental phosphorus, elemental sulfur, sodium sulfide, hydrogen sulfide, lithium halide (e.g., LiI, LiBr, LiCl) and sulfides of the element represented by M above (eg, SiS ₂ , SnS, GeS ₂ ) can be produced by reacting at least two raw materials.

The ratio of Li ₂ S and P ₂ S ₅ in the Li—P—S type glass and Li—P—S type glass ceramics is Li ₂ S:P ₂ S ₅ molar ratio, preferably 60:40 to 90:10, more preferably 68:32 to 78:22. By setting the ratio of Li ₂ S and P ₂ S ₅ within this range, the lithium ion conductivity can be increased. Specifically, the lithium ion conductivity can be preferably 1×10 ⁻⁴ S/cm or higher, more preferably 1×10 ⁻³ S/cm or higher. Although there is no particular upper limit, it is practical to be 1×10 ⁻¹ S/cm or less.

Examples of combinations of raw materials are shown below as specific examples of sulfide-based inorganic solid electrolytes. For example, Li ₂ SP ₂ S ₅ , Li ₂ SP ₂ S ₅ -LiCl, Li ₂ SP ₂ S ₅ -H ₂ S, Li ₂ SP ₂ S ₅ -H ₂ S-LiCl, Li ₂ S—LiI—P ₂ S ₅ , Li ₂ S—LiI—Li ₂ OP ₂ S ₅ , Li ₂ S—LiBr—P ₂ S ₅ , Li ₂ S—Li ₂ OP ₂ S ₅ , Li ₂ S—Li ₃ PO ₄ —P ₂ S ₅ , Li ₂ SP ₂ S ₅ —P ₂ O ₅ , Li ₂ SP ₂ S ₅ —SiS ₂ , Li ₂ SP ₂ S ₅ —SiS _{2- LiCl , Li2SP2S5 -} SnS _{, Li2SP2S5} - _Al2S3 , _Li2S - _GeS2 , _Li2S - _{GeS2 -} ZnS, _Li2S -Ga _{2S3 , Li2S} -- _GeS2 -- _{Ga2S3 , Li2S -- GeS2} -- _{P2S5 , Li2S} -- _GeS2 -- _Sb2S5 , _Li2S -- _{GeS2 --} Al2S 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 _{2S5 -} LiI, _Li2S - _SiS2 - _{LiI , Li2S - SiS2} - _Li4SiO4 , _Li2S - _SiS2 - _Li3PO4 , _Li10GeP2S12 and the _like . However, the mixing ratio of each raw material does not matter. An example of a method for synthesizing a sulfide-based inorganic solid electrolyte material using such a raw material composition is an amorphization method. Amorphization methods include, for example, a mechanical milling method, a solution method, and a melt quenching method. This is because the process can be performed at room temperature, and the manufacturing process can be simplified.

(ii) Oxide-Based Inorganic Solid Electrolyte The oxide-based inorganic solid electrolyte contains oxygen atoms, has the ion conductivity of a metal belonging to Group 1 or Group 2 of the periodic table, and is electronically insulating. It is preferable to use a material having properties.
The ion conductivity of the oxide-based inorganic solid electrolyte is preferably 1×10 ⁻⁶ S/cm or more, more preferably 5×10 ⁻⁶ S/cm or more, and 1×10 ⁻⁵ S/cm or more. /cm or more is particularly preferable. Although the upper limit is not particularly limited, it is practically 1×10 ⁻¹ S/cm or less.

A specific example of the compound is Li _xa La _ya TiO ₃ [xa satisfies 0.3≦xa≦0.7, and ya satisfies 0.3≦ya≦0.7. _{] ( LLT} ⁾ _{; _} ^_ xb satisfies 5≦xb≦10, yb satisfies 1≦yb≦4, zb satisfies 1≦zb≦4, mb satisfies 0≦mb≦2, and nb satisfies 5≦nb≦20. _{satisfy .} ⁾ _{; _} ^_ , yc satisfies 0<yc≦1, zc satisfies 0<zc≦1, and nc satisfies 0<nc≦6.); Li _xd (Al, Ga) _yd (Ti, Ge) _zd Si _ad P _md O _nd (xd satisfies 1 ≤ xd ≤ 3, yd satisfies 0 ≤ yd ≤ 1, zd satisfies 0 ≤ zd ≤ 2, ad satisfies 0 ≤ ad ≤ 1, md satisfies 1 ≤ ^satisfies md _≦ 7 and ^nd satisfies 3≦nd ^≦ 13.) _; Li _xf Si _yf O ^zf (where xf satisfies 1≦xf≦5 and yf satisfies 0 _< yf≦3 , _zf satisfies 1≦zf _≦ 10. ₎ ; _{Li3BO3 - Li2SO4 ; Li2O - B2O3 - P2O5 ; Li2O - SiO2 ; Li6BaLa2Ta2O12 ; Li3PO _ (4-3/2w)} N _w (w is w<1); Li _3.5 Zn _0.25 GeO ₄ having a LISICON (lithium superionic conductor) type crystal structure; La _0.55 having a perovskite type crystal structure LiTi ₂ P ₃ O ₁₂ having a NASICON (Natrium superionic conductor) type crystal structure; Li _{1+xh+yh (} Al, Ga) _xh (Ti, Ge) _2-xh Si _yh P _{3-yh O 12} (xh satisfies 0≦xh≦1, and yh satisfies 0≦yh≦1. ); and 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 obtained by substituting a part of oxygen of lithium phosphate with nitrogen; LiPOD ¹ (D ¹ is preferably Ti, V, Cr, Mn, Fe, Co, Ni, It is one or more elements selected from Cu, Zr, Nb, Mo, Ru, Ag, Ta, W, Pt and Au.) and the like.
Furthermore, 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 a halogen atom and has ion conductivity of a metal belonging to Group 1 or Group 2 of the periodic table, and electron Compounds having insulating properties are preferred.
Examples of the halide-based inorganic solid electrolyte include, but are not limited to, compounds such as LiCl, LiBr, LiI, and Li ₃ YBr ₆ and Li ₃ YCl ₆ described in ADVANCED MATERIALS, 2018, 30, 1803075. Among them, Li ₃ YBr ₆ and Li ₃ YCl ₆ are preferable.

(iv) Hydride-Based Inorganic Solid Electrolyte The hydride-based inorganic solid electrolyte contains hydrogen atoms, has the ion conductivity of a metal belonging to Group 1 or Group 2 of the periodic table, and is electronically insulating. A compound having a property is preferred.
The hydride-based inorganic solid electrolyte is not particularly limited, but examples thereof include LiBH ₄ , Li ₄ (BH ₄ ) ₃ I, 3LiBH ₄ --LiCl, and the like.

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, more preferably 0.1 μm or more. The upper limit is preferably 100 μm or less, more preferably 50 μm or less.
The particle size of the inorganic solid electrolyte is measured by the following procedure. A 1% by mass dispersion of inorganic solid electrolyte particles is prepared by diluting it in a 20 mL sample bottle with water (heptane for water-labile substances). The diluted dispersion sample is irradiated with ultrasonic waves of 1 kHz for 10 minutes and immediately used for the test. Using this dispersion liquid sample, using a laser diffraction/scattering particle size distribution analyzer LA-920 (trade name, manufactured by HORIBA), data was taken 50 times using a quartz cell for measurement at a temperature of 25 ° C. 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 type or two or more types.
When forming the solid electrolyte layer, the mass (mg) (basis weight) of the inorganic solid electrolyte per unit area (cm ² ) of the solid electrolyte layer is not particularly limited. It can be determined appropriately according to the designed battery capacity, and can be, for example, 1 to 100 mg/cm ² .
However, when the inorganic solid electrolyte-containing composition contains an active material, which will be described later, the weight per unit area of the inorganic solid electrolyte is preferably such that the total amount of the active material and the inorganic solid electrolyte is within the above range.

The content of the inorganic solid electrolyte in the inorganic solid electrolyte-containing composition is not particularly limited, but in terms of binding properties and dispersibility in the composition, it is 50% by mass at a solid content of 100% by mass. % or more, more preferably 70 mass % or more, and particularly preferably 90 mass % or more. From the same viewpoint, the upper limit is preferably 99.9% by mass or less, more preferably 99.5% by mass or less, and particularly preferably 99% by mass or less.
However, when the inorganic solid electrolyte-containing composition contains the active material described later, the content of the inorganic solid electrolyte in the inorganic solid electrolyte-containing composition is the total content of the active material and the inorganic solid electrolyte within the above range. is preferred.
As used herein, the solid content (solid component) refers to a component that does not disappear by volatilization or evaporation when the inorganic solid electrolyte-containing composition is dried at 150° C. for 6 hours under a pressure of 1 mmHg under a nitrogen atmosphere. say. Typically, it refers to components other than the dispersion medium described below.

<Binder>
The inorganic solid electrolyte-containing composition of the present invention contains a binder that binds solid particles in at least the constituent layers of an all-solid secondary battery.
The binder comprises a polymer having a tensile hysteresis loss of less than 40% in a stress-strain curve obtained by repeating stretching and restoring 10 times (sometimes conveniently referred to as a low-loss polymer). Moreover, the binder should just contain at least 1 type of low-loss polymer, and may contain 1 or more types of polymers other than a low-loss polymer. In the present invention, that the binder contains a polymer includes not only the embodiment in which the binder is formed by containing the polymer, but also the embodiment in which the binder is formed of the polymer. Examples of polymers other than low-loss polymers include polymers having a 10-times tensile hysteresis loss of 40% or more (for convenience, also referred to as high-loss polymers). Any commonly used one can be used without particular limitation.

The inorganic solid electrolyte-containing composition of the present invention may contain one type of binder or may contain a plurality of types.
The content of the binder in the inorganic solid electrolyte-containing composition is preferably 0.001% by mass or more, more preferably 0.05% by mass or more, more preferably 0.05% by mass or more, based on 100% by mass of the solid component, from the viewpoint of bending durability. 1% by mass or more is more preferable, 0.2% by mass or more is particularly preferable, and 2% by mass or more is most preferable. The upper limit is preferably 20% by mass or less, more preferably 10% by mass or less, and even more preferably 5% by mass or less in terms of battery capacity (ionic conductivity).
In the inorganic solid electrolyte-containing composition of 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 binder [(mass of inorganic solid electrolyte + mass of active material) / (mass of binder) ] is preferably in the range of 1,000 to 1. This ratio is more preferably 1000-2, more preferably 500-10.

The low-loss polymer has a tensile hysteresis loss (hereinafter sometimes referred to as 10-times tensile hysteresis loss) in a stress-strain curve obtained by repeating tension and restoration 10 times for a test piece made of the low-loss polymer.) is 40%. is less than With this 10-fold tensile hysteresis loss of less than 40%, the binder containing this low-loss polymer well follows the bending and restoration of the all-solid-state secondary battery in the constituent layers, and the (initial) interfacial contact between solid particles is achieved. It is possible to suppress the decrease or breakage of the strength and realize high bending durability. From the viewpoint of further improving bending durability, the 10-times tensile hysteresis loss is preferably less than 38%, more preferably less than 35%, and even more preferably less than 32%. Although the lower limit of the 10-times tensile hysteresis loss is not particularly limited, for example, 10% is practical, preferably 15% or more, and may be 25% or more.

In addition to the above 10 times tensile hysteresis loss, the low loss polymer has a stress-strain curve obtained by repeating tension and recovery 30 times for a test piece made of the low loss polymer - tensile hysteresis loss (hereinafter referred to as 30 times tensile hysteresis loss) is preferably less than 35%. A 30 times tensile hysteresis loss of less than 35% allows stable and effective maintenance of (initial) interfacial contact between solid particles. The 30-times tensile hysteresis loss is preferably less than 32%, more preferably less than 30%, and even more preferably less than 28%, in order to stably achieve high bending durability. Although the lower limit of the 30-times tensile hysteresis loss is not particularly limited, for example, 10% is practical, preferably 15% or more, and may be 20% or more.

In the present invention, the tensile hysteresis loss is the area ratio of the loss energy to the total strain energy (the sum of the elastic strain energy and the loss energy) in the stress-strain curve obtained for the test piece that was repeatedly stretched and restored a predetermined number of times ( %). Specifically, the 10-times tensile hysteresis loss and the 30-times tensile hysteresis loss are values calculated by the method described in Examples. The tensile hysteresis loss of the polymer contained in the constituent layers of the all-solid secondary battery is obtained by, for example, disassembling the battery and peeling off the constituent layer containing the binder, and then extracting the binder (polymer) from this constituent layer. Measured on the polymer. The same applies to the tensile modulus and elongation at break, which will be described later.
In the present invention, the tensile hysteresis loss can be appropriately set depending on the composition of the polymer forming the binder (kind or content of constituent components). For example, it can be adjusted by changing the type, number of combined use, molecular weight or content of the component having a polyether structure.

The low-loss polymer preferably has a tensile modulus of 400 MPa or more, more preferably 450 MPa or more, and even more preferably 500 MPa or more. It is considered that when the tensile modulus of the low-loss polymer is at least the above value, the solid particles that bind to the constituent layers during bending can be restored from the bent state to the restored state without impairing interfacial contact. As a result, the low-loss polymer exhibits a high elastic modulus in addition to well following bending and restoration (development of followability), and as a result, exhibits a further improvement in bending durability. Although the upper limit of the tensile modulus is not particularly limited, for example, it is preferably 1500 MPa or less, more preferably 1000 MPa % or less, and may be 650 MPa or less.

The low-loss polymer preferably has an elongation at break of 300% or more, more preferably 320% or more, even more preferably 350% or more. When the elongation at break of the low-loss polymer is at least the above value, the resistance of the low-loss polymer to bending and restoration of the constituent layers (particularly, breakage prevention properties during bending) is improved. As a result, the low-loss polymer exhibits excellent breakage prevention properties in addition to exhibiting the conformability described above, and as a result, exhibits the effect of further improving bending durability. Although the upper limit of the elongation at break is not particularly limited, for example, it is preferably 1500% or less, more preferably 1000% or less, and may be 550% or less.

The low-loss polymer preferably has a tensile modulus and elongation at break in the above ranges in addition to the 10-fold tensile hysteresis loss or the 30-fold tensile hysteresis loss. When the low-loss polymer satisfies these three properties, the effect of improving bending durability can be increased to a higher level.

In the present invention, the tensile modulus and elongation at break are values calculated by the methods described in Examples.
In the present invention, the tensile modulus and elongation at break can be appropriately set depending on the type of polymer forming the binder (structure of polymer main chain), polymer composition (type or content of constituent components), and the like.

Properties of the binder and properties of the low-loss polymer other than those described above will be described later, and the low-loss polymer will be explained.

(Polymer contained in binder)
The binder comprises at least one low-loss polymer and optionally a high-loss polymer, as described above.

In the present invention, the main chain of a polymer refers to a linear molecular chain from which all other molecular chains constituting the polymer can be regarded as branches or pendants with respect to the main chain. Depending on the mass average molecular weight of the molecular chains regarded as branched chains or pendant chains, the longest chain among the molecular chains constituting the polymer is typically the main chain. However, the main chain does not include terminal groups possessed by polymer terminals. Moreover, the side chains of a polymer refer to molecular chains other than the main chain, and include short molecular chains and long molecular chains.

The low-loss polymer is not particularly limited as long as the 10-fold tensile hysteresis loss is within the above range, and various polymers can be applied. For example, successive polymerization (polycondensation, polyaddition or addition condensation) polymers such as polyurethane, polyurea, polyamide, polyimide, polyester, polyether, polycarbonate, etc., further fluorine-containing polymers, hydrocarbon polymers, vinyl polymers, ( Examples include chain polymerization type polymers such as meth)acrylic polymers. Examples of hydrocarbon-based polymers include natural rubber, polybutadiene, polyisoprene, polystyrene-butadiene, acrylonitrile-butadiene copolymers, and hydrogenated (hydrogenated) polymers thereof.
The lossy polymer preferably includes a polymer having at least one bond selected from a urethane bond, a urea bond, an amide bond, an imide bond and an ester bond in the main chain.
The bonds contained in the main chain form hydrogen bonds, thereby contributing to improving the binding properties of solid particles and the like in the constituent layers of the all-solid secondary battery and the like. When these bonds form hydrogen bonds in the polymer, the hydrogen bonds may be formed between the above bonds, or between the above bonds and other partial structures of the main chain. The above bonds preferably have hydrogen atoms that form hydrogen bonds (the nitrogen atoms in each bond are unsubstituted) because they can form hydrogen bonds with each other.
The above bond is not particularly limited as long as it is contained in the main chain of the polymer, and may be contained in a structural unit (repeating unit) and/or contained as a bond connecting different structural units. . Moreover, the number of the bonds contained in the main chain is not limited to 1, but may be 2 or more, preferably 1 to 6, more preferably 1 to 4. In this case, the binding mode of the main chain is not particularly limited, and may have two or more types of bonds at random. It can be a chain.

The polymer having the above bond in the main chain means a polymer (polycondensate, polyaddition product or addition condensate), and is synonymous with a so-called polymer compound. Specific examples include polyurethane, polyurea, polyamide, polyimide and polyester 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 two or more constituent components of each of the above polymers are randomly bonded.

The main chain having the above bond is not particularly limited, but is preferably a main chain having at least one segment of a urethane bond, a urea bond, an amide bond, an imide bond and an ester bond, and a main chain made of polyamide, polyurea or polyurethane. A chain is more preferred, and a backbone consisting of polyurethane is even more preferred.

The low-loss polymer used in the present invention preferably has at least two types of polyether structures in its main chain in that the tensile hysteresis loss can be set within a predetermined range.
In the present invention, the "polyether structure" refers to a structure in which two or more alkyleneoxy groups are linked (also referred to as a polyalkyleneoxy chain or an alkyleneoxide chain), for example, -(O-alkylene group) n- Structure (n indicates the degree of polymerization and is a number of 2 or more).
This "polyether structure" may be a single polyalkyleneoxy chain or a structure derived from a copolymer of at least two polyalkyleneoxy chains (having different chemical structures). In the present invention, a single polyalkyleneoxy chain is preferred.
The "polyether structure" is incorporated into the backbone of the polymer via atoms or linking groups, as appropriate. The atoms and linking groups at this time are the same as those mentioned for X in formula (I-7) described later.
The component containing a polyether structure is not particularly limited, and components derived from polyether polyols such as polyalkylene glycol (components M2 and M3 of the low-loss polymers B-1 to B-6 synthesized in Examples ), polyether polyamine, and the like. Examples of the polyether structure in the component derived from polyether polyamine or the like include a component composed of a copolymer of a polyethyleneoxy chain and a polypropyleneoxy chain possessed by a polyimide polymer as a specific example of a low-loss polymer described later. .

In the present invention, "at least two types" of the polyether structure means polyethers having different chemical structures (wherein the alkylene groups), regardless of the differences in the constituent components forming the main chain and the position of incorporation in the main chain. It means that the number of types of structures is at least two, and polyether structures having the same chemical structure may be incorporated in different constituent components, or may be incorporated in a single constituent component. Seed.
When the low-loss polymer has a main chain having at least two types of polyether structures with different chemical structures, the predetermined tensile hysteresis loss can be exhibited and bending durability can be achieved. Although the details of the reason are not clear yet, it is considered as follows. That is, having two or more types of polyether structures can reduce the crystallinity of the low-loss polymer, and can achieve a high elongation at break of, for example, 300% or more. Furthermore, by having at least two types of the above-mentioned polyether structure and setting the (number average) molecular weight within the range described later, a low-loss polymer having low tensile hysteresis loss, high elastic modulus and high elongation at break It is possible to impart high bending durability to the all-solid secondary battery.
The number of types of polyether structures possessed by the low-loss polymer may be two or more, preferably two or three, more preferably two.

The alkyleneoxy group forming the polyether structure is not particularly limited, but preferably has 1 to 6 carbon atoms, more preferably 2 to 4 carbon atoms.
Although the combination of polyether structures is not particularly limited, at least two polyether structures selected from polyethyleneoxy chains, polypropyleneoxy chains and polytetramethyleneoxy chains are preferred. A combination containing a polyethyleneoxy chain and a polypropyleneoxy chain or a polytetramethyleneoxy chain is more preferred, and a combination containing a polyethyleneoxy chain and a polypropyleneoxy chain is even more preferred.

The (number average) molecular weight of at least two polyether structures in the low-loss polymer is not particularly limited, but is preferably 400 or less, more preferably 350 or less, and even more preferably 300 or less. , 250 or less. When the molecular weight is 400 or less, the viscosity can be suppressed and the tensile hysteresis loss can be set within the predetermined range. Furthermore, the relative content of such bonds in the low-loss polymer is increased to exhibit a large tensile modulus, eg, 400 MPa or more. When it is 300 or less, the tensile hysteresis loss can be reduced and the tensile elastic modulus can be increased without reducing the elongation at break, and the effect of improving the bending durability can be further enhanced. The lower limit of the (number average) molecular weight is not particularly limited, but in practice it is preferably 100 or more, and the elongation at break can be increased without causing an increase in tensile hysteresis loss and a decrease in tensile elastic modulus. It is more preferably 150 or more in that the effect of improving bending durability can be further enhanced.
In the present invention, the (number-average) molecular weight of at least two polyether structures means the sum of the products of the (number-average) molecular weight and the mole fraction of each polyether structure.
The (number-average) molecular weight of each polyether structure is determined by the methods described below in compounds (usually with hydrogen atoms attached at each end) leading to constituents containing the polyether structure (rather than being incorporated into the main chain). A value measured for a compound (for example, a polyether polyol to be described later).

The (number average) molecular weight of each polyether structure is not particularly limited, but is appropriately set within a range that satisfies the above-mentioned "number average molecular weight of at least two types of polyether structures".
Moreover, the degree of polymerization of each polyether structure is not particularly limited as long as it is 2 or more, and is appropriately set within a range that satisfies the above-mentioned "number average molecular weight of at least two types of polyether structures". Although the degree of polymerization depends on the number of carbon atoms in the alkyleneoxy group, it is preferably, for example, 2 to 10, more preferably 3 to 8, even more preferably 2 to 5.

The main chain forming the low-loss polymer has two or more (preferably 2 to 8, more preferably 2 to 4) components represented by any of the following formulas (I-1) to (I-4). Species) Main chain formed by combining, or sequential polymerization of a carboxylic acid dianhydride represented by the following formula (I-5) and a diamine compound leading to a constituent component represented by the following formula (I-6) A backbone is preferred. The combination of each constituent component is appropriately selected according to the polymer species. One type of component in the combination of components means the number of types of components represented by any one of the following formulas, and two types of components represented by one formula below. is not to be construed as two components.

In the formula, R ^P1 and R ^P2 each represent a molecular chain having a molecular weight or a weight average molecular weight of 20 or more and 200,000 or less. The molecular weight of this molecular chain depends on its type and cannot be unambiguously determined. The upper limit is preferably 100,000 or less, more preferably 10,000 or less. The molecular weight of the molecular chain is measured on the starting compound prior to incorporation into the backbone of the polymer.
The molecular chains that can be used as R ^P1 and R ^P2 are not particularly limited, but are preferably hydrocarbon chains, polyalkylene oxide chains (excluding the polyether structure described above), polycarbonate chains or polyester chains, and hydrocarbon chains. or more preferably a polyalkylene oxide chain, more preferably a hydrocarbon chain, a polyethylene oxide chain or a polypropylene oxide chain.

Hydrocarbon chains that can be used as R ^P1 and R ^P2 refer to hydrocarbon chains composed of carbon and hydrogen atoms, more particularly of at least two compounds composed of carbon and hydrogen atoms. It means a structure in which an atom (eg, hydrogen atom) or group (eg, methyl group) is eliminated. However, in the present invention, the hydrocarbon chain also includes a chain having a group containing an oxygen atom, a sulfur atom or a nitrogen atom, such as a hydrocarbon group represented by the following formula (M2). Any terminal group that may be present at the end of the hydrocarbon chain shall not be included in the hydrocarbon chain. The hydrocarbon chain may have carbon-carbon unsaturated bonds and may have an aliphatic and/or aromatic ring structure. That is, the hydrocarbon chain may be a hydrocarbon chain composed of hydrocarbons selected from aliphatic hydrocarbons and aromatic hydrocarbons.

Such a hydrocarbon chain may be one that satisfies the above molecular weight. Contains hydrocarbon chains.
A low-molecular-weight hydrocarbon chain is a chain composed of ordinary (non-polymeric) hydrocarbon groups, such as aliphatic or aromatic hydrocarbon groups, specifically is an alkylene group (preferably 1 to 12 carbon atoms, more preferably 1 to 6, more preferably 1 to 3), an arylene group (preferably 6 to 22 carbon atoms, preferably 6 to 14, 6 to 10 is more preferred), or a group consisting of a combination thereof. The hydrocarbon group forming a low-molecular-weight hydrocarbon chain that can be used as R ^P2 is more preferably an alkylene group, more preferably an alkylene group having 2 to 6 carbon atoms, and particularly preferably an alkylene group having 2 or 3 carbon atoms. This hydrocarbon chain may have a polymer chain (for example, (meth)acrylic polymer) as a substituent.

The aliphatic hydrocarbon group is not particularly limited. group) and the like. Also included are hydrocarbon groups possessed by constituent components exemplified below.
The aromatic hydrocarbon group includes, for example, hydrocarbon groups possessed by constituent components illustrated below, and is preferably a phenylene group or a hydrocarbon group represented by the following formula (M2).

In formula (M2), X represents a single bond, —CH ₂ —, —C(CH ₃ ) ₂ —, —SO ₂ —, —S—, —CO— or —O—, from the viewpoint of binding and -CH ₂ - or -O- is preferred, and -CH ₂ - is more preferred. The alkylene group exemplified here may be substituted with a substituent Z, preferably a halogen atom (more preferably a fluorine atom).
R ^M2 to R ^M5 each represent a hydrogen atom or a substituent, preferably a hydrogen atom. Substituents that can be taken as R ^M2 to R ^M5 are not particularly limited, and include substituents Z described later, such as an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, and —OR ^M6 . , —N(R ^M6 ) ₂ , —SR ^M6 (R ^M6 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, fluorine atom, chlorine atom, bromine atom) are preferred. —N(R ^M6 ) ₂ is an alkylamino group (having preferably 1 to 20 carbon atoms, more preferably 1 to 6 carbon atoms) or an arylamino group (having preferably 6 to 40 carbon atoms, more preferably 6 to 20 carbon atoms). more preferable).

A hydrocarbon polymer chain is a polymer chain formed by polymerizing (at least two) polymerizable hydrocarbons, provided that the chain comprises a hydrocarbon polymer having a higher number of carbon atoms than the low molecular weight hydrocarbon chains described above. Although not particularly limited, it is preferably a chain composed of a hydrocarbon polymer composed of 30 or more carbon atoms, more preferably 50 or more carbon atoms. The upper limit of the number of carbon atoms constituting the hydrocarbon polymer is not particularly limited, and can be, for example, 3,000. This hydrocarbon polymer chain is preferably a chain composed of a hydrocarbon polymer composed of an aliphatic hydrocarbon having a main chain satisfying the above number of carbon atoms, and composed of an aliphatic saturated hydrocarbon or an aliphatic unsaturated hydrocarbon. It is more preferred that the chain consists of a polymer (preferably an elastomer) that Specific examples of the polymer include a diene polymer having a double bond in its main chain and a non-diene polymer having no double bond in its main chain. Examples of diene polymers include styrene-butadiene copolymers, styrene-ethylene-butadiene copolymers, copolymers of isobutylene and isoprene (preferably butyl rubber (IIR)), butadiene polymers, isoprene polymers and ethylene. - propylene-diene copolymers and the like. Examples of non-diene polymers include olefin polymers such as ethylene-propylene copolymers and styrene-ethylene-butylene copolymers, and hydrogen reduction products of the above diene polymers.

The hydrocarbon that forms the hydrocarbon chain preferably has a reactive group at its terminal, and more preferably has a reactive terminal group capable of polycondensation. A terminal reactive group capable of condensation polymerization or polyaddition forms a group attached to R ^P1 or R ^P2 in each of the above formulas by condensation polymerization or polyaddition. Examples of such terminal reactive groups include an isocyanate group, a hydroxy group, a carboxy group, an amino group, an acid anhydride, etc. Among them, a hydroxy group is preferred.
Hydrocarbon polymers having terminal reactive groups include, for example, the NISSO-PB series (manufactured by Nippon Soda Co., Ltd.), the Claysole series (manufactured by Tomoe Kogyo Co., Ltd.), and the PolyVEST-HT series (manufactured by Evonik), all of which are trade names. , poly-bd series (manufactured by Idemitsu Kosan Co., Ltd.), poly-ip series (manufactured by Idemitsu Kosan Co., Ltd.), EPOL (manufactured by Idemitsu Kosan Co., Ltd.), Polytail series (manufactured by Mitsubishi Chemical Co., Ltd.), and the like are preferably used.

Examples of the polyalkylene oxide chain (polyalkyleneoxy chain) include chains composed of known polyalkyleneoxy groups other than the polyether structure described above. Examples of the polyalkylene oxide chain other than the above polyether structure include those in which the number of carbon atoms in the alkyleneoxy group, the degree of polymerization (molecular weight), etc. do not satisfy the above polyether structure.
The number of carbon atoms in the alkyleneoxy group in the polyalkyleneoxy chain is preferably 1 to 10, more preferably 1 to 6, and more preferably 2 or 3 (polyethyleneoxy chain or polypropyleneoxy chain). preferable. The polyalkyleneoxy chain may be a chain consisting of one type of alkyleneoxy group, or a chain consisting of two or more types of alkyleneoxy groups (for example, a chain consisting of an ethyleneoxy group and a propyleneoxy group).
Polycarbonate or polyester chains include known polycarbonate or polyester chains.
The polyalkyleneoxy chain, polycarbonate chain or polyester chain each preferably has an alkyl group (having preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms) at its terminal.
The ends of the polyalkyleneoxy chains, polycarbonate chains and polyester chains that can be used as R ^P1 and R ^P2 are appropriately changed to ordinary chemical structures that can be incorporated into the constituents represented by the above formulas as R ^P1 and R ^P2 . be able to. For example, a polyalkyleneoxy chain may be stripped of the terminal oxygen atoms and incorporated as R ^P1 or R ^P2 in the above components.

An ether group (-O-), a thioether group (-S-), a carbonyl group (>C=O), an imino group (>NR ^N : ^RN is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 10 carbon atoms).
In each of the above formulas, R ^P1 and R ^P2 are divalent molecular chains, but at least one hydrogen atom is substituted with -NH-CO-, -CO-, -O-, -NH- or -N<. , it may be a trivalent or higher molecular chain.

Among the above molecular chains, R ^P1 is preferably a hydrocarbon chain, more preferably a low-molecular-weight hydrocarbon chain, more preferably a hydrocarbon chain composed of an aliphatic or aromatic hydrocarbon group, Hydrocarbon chains consisting of aromatic hydrocarbon groups are particularly preferred.
Among the above-described molecular chains, R ^P2 is preferably a low-molecular-weight hydrocarbon chain (more preferably an aliphatic hydrocarbon group) or a molecular chain other than a low-molecular-weight hydrocarbon chain. A more preferable embodiment is one in which each of them contains a molecular chain other than a hydrocarbon chain of molecular weight. In this aspect, the component represented by any one of formula (I-3), formula (I-4) and formula (I-6) is a component in which R ^P2 is a low-molecular-weight hydrocarbon group chain. and at least two of the constituents where R ^P2 is a molecular chain other than a low molecular weight hydrocarbon chain.

Specific examples of the constituent represented by formula (I-1) are shown below and in specific examples of the low-loss polymer. Further, as the raw material compound (diisocyanate compound) leading to the constituent represented by the formula (I-1), for example, a diisocyanate compound represented by the formula (M1) described in WO 2018/020827 and Specific examples thereof include polymeric 4,4′-diphenylmethane diisocyanate and the like. In the present invention, the constituent represented by the formula (I-1) and the raw material compounds leading to it are not limited to the following specific examples, specific examples of the low-loss polymer, and those described in the above literature.

The raw material compound (carboxylic acid or acid chloride thereof, etc.) leading to the constituent represented by the above formula (I-2) is not particularly limited, and is described in, for example, paragraph [0074] of WO 2018/020827. , carboxylic acid or acid chloride compounds and specific examples thereof.

Specific examples of the component represented by formula (I-3) or formula (I-4) are shown below and in specific examples of the low-loss polymer. Further, the raw material compound (diol compound or diamine compound) leading to the component represented by the above formula (I-3) or formula (I-4) is not particularly limited. 020827 and specific examples thereof, and also dihydroxyoxamide. In the present invention, the constituents represented by formula (I-3) or formula (I-4) and the raw material compounds leading to them are those described in the following specific examples, specific examples of low-loss polymers, and the above-mentioned documents. is not limited to
In the specific examples below, when a constituent component has a repeating structure, the number of repetitions is an integer of 1 or more, and is appropriately set within a range that satisfies the molecular weight or the number of carbon atoms of the molecular chain.

In formula (I-5), R ^{3 P3} represents an aromatic or aliphatic linking group (tetravalent), preferably a linking group represented by any one of the following formulas (i) to (iix).

In formulas (i) to (iix), X ¹ represents a single bond or a divalent linking group. As the divalent linking group, an alkylene group having 1 to 6 carbon atoms (eg, methylene, ethylene, propylene) is preferred. Propylene is preferably 1,3-hexafluoro-2,2-propanediyl. L represents -CH ₂ =CH ₂ - or -CH ₂ -. R ^X and R ^Y each represent a hydrogen atom or a substituent. In each formula, * indicates the bonding site with the carbonyl group in formula (1-5). Substituents that can be taken as R ^X and R ^Y are not particularly limited, and include the substituent Z described later, and an alkyl group (having preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms, more preferred) or an aryl group (having preferably 6 to 22 carbon atoms, more preferably 6 to 14 carbon atoms, and still more preferably 6 to 10 carbon atoms).

The carboxylic acid dianhydride represented by the above formula (I-5) and the raw material compound (diamine compound) leading to the constituent component represented by the above formula (I-6) are not particularly limited, for example, Each compound described in International Publication No. 2018/020827 and International Publication No. 2015/046313 and specific examples thereof can be mentioned.

R ^P1 , R ^P2 and R ^P3 may each have a substituent. The substituent is not particularly limited, and examples thereof include the substituent Z described later, and the above-mentioned substituents that can be taken as ^RM2 are preferably exemplified.

A low-loss polymer, particularly a polymer having a urethane bond in its main chain, is, as shown below, in addition to the constituent represented by formula (I-1), the above formula (I-3) or formula (I-4) ), preferably as a constituent represented by formula (I-3), R ² is a chain composed of a low-molecular-weight hydrocarbon group (as a functional group, preferably a group having an ether group or a carbonyl group, or both, or a component (preferably a component represented by the following formula (I-3A)), and a component in which R ^P2 is the above-mentioned hydrocarbon polymer chain as a molecular chain ( (preferably a component represented by the following formula (I-3C)) ^, and furthermore, a component (preferably may have a component represented by the following formula (I-3B)).

In formula (I-1), R ^P1 is as described above. In formula (I-3A), R ^P2A represents a chain of low molecular weight hydrocarbon groups (preferably aliphatic hydrocarbon groups), and the functional group is preferably selected from functional group group (I) described later. more preferably a group containing an ether group or a carbonyl group or both, more preferably a carboxy group. Examples thereof include bis(hydroxymethyl)acetic acid compounds such as 2,2-bis(hydroxymethyl)butyric acid. In formula (I-3B), R ^P2B represents a polyalkyleneoxy chain (excluding the polyether structure described above). In formula (I-3C), R ^P2C represents a hydrocarbon polymer chain. A chain composed of a low-molecular-weight hydrocarbon group that can be taken as R ^P2A , a polyalkyleneoxy chain that can be taken as R ^P2B , and a hydrocarbon polymer chain that can be taken as R ^P2C are each taken as R ^P2 in the above formula (I-3). are synonymous with an aliphatic hydrocarbon group, a polyalkyleneoxy chain, and a hydrocarbon polymer chain, and preferred ones are also the same.
The contents of the components represented by the above formulas in the low-loss polymer will be described later.

The low-loss polymer has, as described above, a component containing a polyether structure in its backbone.
Examples of the component containing a polyether structure include a component represented by the following formula (I-7), which corresponds to the "at least two types of polyether structures" described above.

In the formula, X represents a single bond, an oxygen atom or a nitrogen atom, or a group containing a linking group, and R ^P4A and R ^P4B represent different alkylene groups. n1 and n2 indicate the degree of polymerization.
X is appropriately selected according to the terminal group of the alkyleneoxy chain in the above formula. For example, when the terminal of the alkyleneoxy group is an oxygen atom, it is a group containing a single bond or a linking group, and when the terminal of the alkyleneoxy group is an alkylene group, it is a group containing an oxygen atom, a nitrogen atom, or a linking group. Groups containing a linking group that can be taken as X include a group consisting of a linking group and a group in which a linking group and an oxygen atom or a nitrogen atom are combined. The linking group is not particularly limited, but includes, for example, a group obtained by removing one hydrogen atom from each of the groups listed for the substituent Z, preferably an alkylene group that can be used as R ^P4A or R ^P4B . . Two X's in the constituent represented by the above formula (I-7) may be the same or different.

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

n1 and n2 each indicate the degree of polymerization, n1 is a number of 2 or more, n2 is 0 or a number exceeding 1, and may be a number of 2 or more.
When n2 is 0, the component represented by formula (I-7) is a component containing a single polyalkyleneoxy chain. In this embodiment, the main chain of the low-loss polymer has at least two, preferably two or three, more preferably two, different constituents represented by the above formula (I-7). . In this form, the component represented by formula (I-7) is preferably a component derived from at least two selected from polyethylene glycol, polypropylene glycol and polytetramethylene ether glycol. In addition, it may have a component represented by formula (I-7) in which n2 is a number greater than 1.
In this aspect, the (number average) molecular weight of the two or more different constituents represented by formula (I-7), the (number average) molecular weight of each is synonymous with the (number average) molecular weight of, and the preferred range is also the same. In addition, n1 in two or more different constituent components represented by formula (I-7) is appropriately set within a range satisfying the (number average) molecular weight, and is synonymous with the degree of polymerization of the polyether structure described above. and the preferred range is also the same.

When n2 is a number greater than 1, the component represented by formula (I-7) is a component containing a copolymer of two polyalkyleneoxy chains. The bonding mode of two polyalkyleneoxy chains in the copolymer is not particularly limited, and may be random bonding, block bonding, or alternating bonding. In this embodiment, the main chain of the low-loss polymer should have at least one component represented by formula (I-7) above, and preferably has one component. In this embodiment, the component represented by formula (I-7) is, for example, a component composed of a copolymer of polyethyleneoxy chains and polypropyleneoxy chains, which is contained in a polyimide polymer as a specific example of the low-loss polymer described later. are mentioned.
The (number average) molecular weight of the constituent represented by formula (I-7) is synonymous with the (number average) molecular weight of the at least two polyether structures described above, and the preferred ranges are also the same. The (number average) molecular weights of the two polyalkyleneoxy chains are synonymous with the (number average) molecular weights of the respective polyether structures described above, and the preferred ranges are also the same. When there are multiple identical polyalkyleneoxy chains, the (number average) molecular weight of the polyalkyleneoxy chains is taken as the total molecular weight. Furthermore, each of n1 and n2 is appropriately set within a range that satisfies the (number average) molecular weight, has the same meaning as the above-mentioned degree of polymerization of the polyether structure, and has the same preferred range.

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

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

The low-loss polymer may have constituents other than the constituents represented by the above formulas. Such constituents are not particularly limited as long as they are sequentially polymerizable with the raw material compound leading to the constituents represented by the above formulas.

The (total) content of the components represented by the above formulas (1-1) to (I-7) in the low-loss polymer is not particularly limited, but is preferably 5 to 100% by mass, It is more preferably 10 to 100% by mass, even more preferably 50 to 100% by mass, even more preferably 80 to 100% by mass. The upper limit of this content can be, for example, 90% by mass or less, regardless of the above 100% by mass.
The content of constituents other than the constituents represented by the above formulas in the low-loss polymer is not particularly limited, but is preferably 50% by mass or less.

When the low-loss polymer has a component represented by any one of formulas (I-1) to (I-6) above, the content is not particularly limited and can be set within the following range.
That is, the low-loss polymer contains a component represented by formula (I-1) or formula (I-2), or a component derived from the carboxylic acid dianhydride represented by formula (I-5). The amount is not particularly limited, and is preferably 10 to 50 mol%, more preferably 20 to 50 mol%, even more preferably 30 to 50 mol%.
The content of the component represented by Formula (I-3), Formula (I-4) or Formula (I-6) in the low-loss polymer is not particularly limited, and is 0 to 50 mol%. preferably 5 to 40 mol %, and even more preferably 10 to 30 mol %.

Among the constituents represented by formula (I-3) or formula (I-4), R ^P2 is a chain composed of a low-molecular-weight hydrocarbon group (for example, the constituent represented by formula (I-3A) above). The content of the low-loss polymer) is not particularly limited, but for example, it is preferably 0 to 50 mol%, more preferably 1 to 30 mol%, and 2 to 20 mol% and more preferably 4 to 10 mol %.
Among the constituents represented by the formula (I-3) or the formula (I-4), R ^P2 is the polyalkyleneoxy chain as the molecular chain (for example, the constituent represented by the above formula (I-3B) The content of the component) in the low-loss polymer is not particularly limited, but is, for example, preferably 0 to 50 mol%, more preferably 0 to 45 mol%, and 0 to 43 mol%. It is even more preferable to have
Among the constituents represented by the formula (I-3) or the formula (I-4), R ^P2 is the hydrocarbon polymer chain as the molecular chain (for example, the constituent represented by the above formula (I-3C) The content of the component) in the low-loss polymer is not particularly limited, but is, for example, preferably 0 to 50 mol%, more preferably 1 to 45 mol%, and 3 to 40 mol%. 3 to 30 mol % is even more preferable, 3 to 20 mol % is particularly preferable, and 3 to 10 mol % is most preferable.

The (total) content of the constituents represented by formula (I-7) in the low-loss polymer is not particularly limited, but is, for example, preferably 10 to 60 mol%, preferably 20 to 55 mol%. more preferably 30 to 50 mol %, particularly preferably 35 to 45 mol %.
When the low-loss polymer has a plurality of different constituents represented by formula (I-7), the content of each constituent is appropriately determined within a range that satisfies the above (total) content. For example, when there are two different constituents represented by formula (I-7), one constituent (preferably, a constituent having a polyether structure formed of an alkyleneoxy group with a large molecular weight) content is, for example, preferably 5 to 30 mol %, more preferably 10 to 25 mol %, even more preferably 15 to 20 mol %. The content of the other component (preferably, a component having a polyether structure formed of alkyleneoxy groups with a small molecular weight) is, for example, preferably 10 to 50 mol%, preferably 15 to 40 mol%. more preferably 20 to 30 mol %. In addition, the ratio of the contents of one constituent component to the other constituent component [one constituent component: the other constituent component] is not particularly limited, but for example, it is preferably 10: 90 to 80: 20, It is more preferably 20:80 to 70:30.
On the other hand, when the low-loss polymer has three or more different constituents represented by the formula (I-7), the constituent having a polyether structure formed by an alkyleneoxy group having the smallest molecular weight is the other constituent. , and the other components are defined as the one component.

When the low-loss polymer has a plurality of constituent components represented by each formula, the content of each constituent component is the total content.

- Functional group -
The low-loss polymer preferably has a functional group for enhancing wettability or adsorption to the surface of solid particles such as inorganic solid electrolytes. Examples of such functional groups include groups that exhibit physical interaction such as hydrogen bonding on the surface of the solid particles and groups that can form chemical bonds with groups present on the surface of the solid particles. It is more preferable to have at least one group selected from the following functional group group (I). However, from the viewpoint of more effectively expressing the wettability or adsorptivity to the surface of the solid particles, it is preferable not to have two or more types of groups capable of forming a bond between the functional groups.
<Functional group group (I)>
Carboxy group, sulfonic acid group (--SO ₃ H), phosphoric acid group (--PO ₄ H ₂ ), amino group (--NH ₂ ), hydroxy group, sulfanyl group, isocyanato group, alkoxysilyl group and condensation of three or more rings group having a ring structure

A group capable of forming a salt such as a carboxyl group, a sulfonic acid group, a phosphate group, a hydroxy group and a sulfanyl group may form a salt, 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 group. and the like. As the alkoxysilyl group, for example, the description of the alkoxysilyl group in the substituent Z described later can be preferably applied.
The group having a condensed ring structure of three or more rings is preferably a group having a cholesterol ring structure or a group having a condensed structure of three or more aromatic rings, more preferably a cholesterol residue or a pyrenyl group.

A carboxy group, a sulfonic acid group (--SO ₃ H), a phosphoric acid group (--PO ₄ H ₂ ), a hydroxy group and an alkoxysilyl group have high adsorptivity with an inorganic solid electrolyte or a positive electrode active material, and have three or more fused rings. A group having a ring structure has high adsorptivity with a negative electrode active material or the like. An amino group (--NH ₂ ), a sulfanyl group and an isocyanato group have high adsorptivity with an inorganic solid electrolyte.

The low-loss polymer may have a functional group selected from the above functional group group (I) in any constituent component forming the polymer, and in either the main chain or the side chain of the polymer. may Examples of the component having the functional group include a component represented by formula (I-3A).
The content of the functional group selected from the functional group group (I) in the low-loss polymer is not particularly limited. The proportion of all constituent components constituting the polymer is preferably 0.01 to 50 mol%, preferably 0.02 to 49 mol%, more preferably 0.1 to 40 mol%, and further 1 to 30 mol%. 3 to 25 mol % is particularly preferred.

The low-loss polymer (each component and raw material compound) may have a substituent. The substituent is not particularly limited, but preferably includes a group selected from the following substituents Z.

A low-loss polymer can be synthesized by selecting raw material compounds according to a known method according to the type of bond possessed by the main chain, and subjecting the raw material compounds to polyaddition or polycondensation. As for the synthesis method, for example, International Publication No. 2018/151118 can be referred to.

Polyurethane, polyurea, polyamide, and polyimide polymers that can be taken as low-loss polymers include, in addition to those synthesized in Examples, for example, International Publication Nos. 2018/020827 and 2015/046313, and further Examples include those in which two types of polyether structures are incorporated in the main chain of each polymer described in JP-A-2015-088480.

- Substituent Z -
alkyl groups (preferably alkyl groups having 1 to 20 carbon atoms, such as methyl, ethyl, isopropyl, t-butyl, pentyl, heptyl, 1-ethylpentyl, benzyl, 2-ethoxyethyl, 1-carboxymethyl, etc.), alkenyl groups (preferably alkenyl groups having 2 to 20 carbon atoms, such as vinyl, allyl, oleyl, etc.), alkynyl groups (preferably alkynyl groups having 2 to 20 carbon atoms, such as ethynyl, butadiynyl, phenylethynyl, etc.), cycloalkyl groups (Preferably a cycloalkyl group having 3 to 20 carbon atoms, for example, cyclopropyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, etc. In the present specification, the term alkyl group usually means including a cycloalkyl group, but here it is described separately. ), an aryl group (preferably an aryl group having 6 to 26 carbon atoms, such as phenyl, 1-naphthyl, 4-methoxyphenyl, 2-chlorophenyl, 3-methylphenyl, etc.), an aralkyl group (preferably having 7 carbon atoms to 23 aralkyl groups such as benzyl, phenethyl, etc.), heterocyclic groups (preferably heterocyclic groups having 2 to 20 carbon atoms, more preferably 5 or 5 having at least one oxygen atom, sulfur atom or nitrogen atom) It is a 6-membered heterocyclic group, including aromatic heterocyclic groups and aliphatic heterocyclic groups, such as tetrahydropyran ring group, tetrahydrofuran ring group, 2-pyridyl, 4-pyridyl, 2- imidazolyl, 2-benzimidazolyl, 2-thiazolyl, 2-oxazolyl, pyrrolidone groups, etc.), alkoxy groups (preferably alkoxy groups having 1 to 20 carbon atoms, such as methoxy, ethoxy, isopropyloxy, benzyloxy, etc.), aryloxy groups (Preferably an aryloxy group having 6 to 26 carbon atoms, such as phenoxy, 1-naphthyloxy, 3-methylphenoxy, 4-methoxyphenoxy, etc. In the present specification, an aryloxy group means an aryloxy group. ), a heterocyclic oxy group (a group in which an —O— group is bonded to the above heterocyclic group), an alkoxycarbonyl group (preferably an alkoxycarbonyl group having 2 to 20 carbon atoms, such as ethoxycarbonyl, 2-ethylhexyloxycarbonyl , dodecyloxycarbonyl, etc.), aryloxycarbonyl groups (preferably aryloxycarbonyl groups having 6 to 26 carbon atoms, such as phenoxycarbonyl, 1-naphthyloxycarbonyl, 3-methylphenoxycarbonyl, 4-methoxyphenoxycarbonyl, etc.), amino groups (preferably amino groups having 0 to 20 carbon atoms, alkylamino groups and arylamino groups, such as amino (—NH ₂ ), N,N-dimethylamino, N,N-diethylamino, N-ethylamino , anilino, etc.), a sulfamoyl group (preferably a sulfamoyl group having 0 to 20 carbon atoms, such as N,N-dimethylsulfamoyl, N-phenylsulfamoyl, etc.), an acyl group (alkylcarbonyl group, alkenylcarbonyl group, Alkynylcarbonyl groups, arylcarbonyl groups, heterocyclic carbonyl groups, preferably acyl groups having 1 to 20 carbon atoms, such as acetyl, propionyl, butyryl, octanoyl, hexadecanoyl, acryloyl, methacryloyl, crotonoyl, benzoyl, naphthoyl, nicotinoyl, etc.), acyloxy groups (including alkylcarbonyloxy groups, alkenylcarbonyloxy groups, alkynylcarbonyloxy groups, arylcarbonyloxy groups, heterocyclic carbonyloxy groups, preferably acyloxy groups having 1 to 20 carbon atoms, such as acetyloxy , propionyloxy, butyryloxy, octanoyloxy, hexadecanoyloxy, acryloyloxy, methacryloyloxy, crotoyloxy, benzoyloxy, naphthoyloxy, nicotinoyloxy, etc.), aryloxy groups (preferably having 7 to 23 carbon atoms) An aryloyloxy group, such as benzoyloxy, etc.), a carbamoyl group (preferably a carbamoyl group having 1 to 20 carbon atoms, such as N,N-dimethylcarbamoyl, N-phenylcarbamoyl, etc.), an acylamino group (preferably a carbon number 1-20 acylamino groups, such as acetylamino and benzoylamino), alkylthio groups (preferably C1-20 alkylthio groups, such as methylthio, ethylthio, isopropylthio, benzylthio, etc.), arylthio groups (preferably carbon arylthio groups of numbers 6 to 26, such as phenylthio, 1-naphthylthio, 3-methylphenylthio, 4-methoxyphenylthio, etc.), heterocyclic thio groups (groups in which -S- groups are bonded to the above heterocyclic groups), alkylsulfonyl group (preferably alkylsulfonyl group having 1 to 20 carbon atoms, such as methylsulfonyl, ethylsulfonyl, etc.), arylsulfonyl group (preferably arylsulfonyl group having 6 to 22 carbon atoms, such as benzenesulfonyl etc.), alkyl A silyl group (preferably an alkylsilyl group having 1 to 20 carbon atoms, such as monomethylsilyl, dimethylsilyl, trimethylsilyl, triethylsilyl, etc.), an arylsilyl group (preferably an arylsilyl group having 6 to 42 carbon atoms, such as triphenyl silyl, etc.), alkoxysilyl groups (preferably alkoxysilyl groups having 1 to 20 carbon atoms, such as monomethoxysilyl, dimethoxysilyl, trimethoxysilyl, triethoxysilyl, etc.), aryloxysilyl groups (preferably having 6 to 42 aryloxysilyl groups, such as triphenyloxysilyl, etc.), phosphoryl groups (preferably phosphate groups having 0 to 20 carbon atoms, such as —OP(=O)(R ^P ) ₂ ), phosphonyl groups (preferably is a phosphonyl group having 0 to 20 carbon atoms, such as —P(=O)(R ^P ) ₂ ), a phosphinyl group (preferably a phosphinyl group having 0 to 20 carbon atoms, such as —P(R ^P ) ₂ ), sulfo group (sulfonic acid group), carboxy group, hydroxy group, sulfanyl group, cyano group, halogen atom (eg, fluorine atom, chlorine atom, bromine atom, iodine atom, etc.). R ^P is a hydrogen atom or a substituent (preferably a group selected from substituent Z).
Further, each of the groups exemplified for the substituent Z may be further substituted with the substituent Z described above.
The alkyl group, alkylene group, alkenyl group, alkenylene group, alkynyl group and/or alkynylene group, etc. may be cyclic or chain, and may be linear or branched.

(Physical properties or characteristics of the binder or the polymer forming the binder)
The polymer forming the binder may be a non-crosslinked polymer or a crosslinked polymer. Further, when the polymer is crosslinked by heating or voltage application, the molecular weight may be larger than the above molecular weight. Preferably, the weight-average molecular weight of the polymer is within the above range at the start of use of the all-solid secondary battery.

When the binder is a particulate binder, its shape is not particularly limited, and may be flat, amorphous, or the like, preferably spherical or granular. Although the particle size of the particulate binder is not particularly limited, it is preferably 1000 nm or less, more preferably 500 nm or less, and even more preferably 300 nm or less. The lower limit is 1 nm or more, preferably 5 nm or more, more preferably 10 nm or more, and even more preferably 50 nm or more. The average particle size of the particulate binder can be measured in the same manner as the average particle size of the inorganic solid electrolyte.
The particle diameter of the particulate binder in the constituent layers of the all-solid secondary battery is measured in advance by, for example, measuring the constituent layers after disassembling the battery and peeling off the constituent layers containing the particulate binder. It can be determined by excluding the measured particle size of particles other than the particulate binder that was previously used.
The particle size of the particulate binder can be adjusted by, for example, the type of dispersion medium, the content and content of constituent components in the polymer, and the like.

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

The weight average molecular weight of the polymer forming the binder is not particularly limited. For example, 15,000 or more is preferable, 30,000 or more is more preferable, and 50,000 or more is still more preferable. The upper limit is substantially 5,000,000 or less, preferably 4,000,000 or less, more preferably 3,000,000 or less, and may be 1,500,000 or less.

-Measurement of molecular weight-
In the present invention, unless otherwise specified, the molecular weights of polymers, polymer chains (polyether structures) and macromonomers refer to mass average molecular weights and number average molecular weights converted to standard polystyrene by gel permeation chromatography (GPC). As a method of measurement, the values are basically measured by the method of Condition 1 or Condition 2 (priority) below. However, depending on the type of polymer or macromonomer, an appropriate eluent may be selected and used.
(Condition 1)
Column: Two TOSOH TSKgel Super AWM-H (trade name, manufactured by Tosoh Corporation) are connected Carrier: 10 mM LiBr / N-methylpyrrolidone Measurement temperature: 40 ° C.
Carrier flow rate: 1.0 ml/min
Sample concentration: 0.1% by mass
Detector: RI (refractive index) detector (Condition 2)
Column: A column in which TOSOH TSKgel Super HZM-H, TOSOH TSKgel Super HZ4000, and TOSOH TSKgel Super HZ2000 (all trade names, manufactured by Tosoh Corporation) are used.
Carrier: Tetrahydrofuran Measurement temperature: 40°C
Carrier flow rate: 1.0 ml/min
Sample concentration: 0.1% by mass
Detector: RI (refractive index) detector

Specific examples of the low-loss polymer include those synthesized in Examples in addition to those shown below, but the present invention is not limited thereto.
In the specific examples shown below, the degree of polymerization of the polyether structure is specifically shown, but in the present invention, it can be changed as appropriate as long as the 10-fold tensile hysteresis loss is satisfied.

<Dispersion medium>
The inorganic solid electrolyte-containing composition of the present invention contains a dispersion medium as a dispersion medium for dispersing or dissolving each of the above components.
The dispersion medium may be any organic compound that exhibits a liquid state in the environment of use, and examples thereof include various solvents. Specific examples include alcohol compounds, ether compounds, amide compounds, amine compounds, ketone compounds, aromatic compounds, Examples include aliphatic compounds, nitrile compounds and ester compounds.
The dispersion medium may be either a non-polar dispersion medium (hydrophobic dispersion medium) or a polar dispersion medium (hydrophilic dispersion medium), but a non-polar dispersion medium is preferable in that excellent dispersibility can be exhibited. A non-polar dispersion medium generally has a low affinity for water. In the present invention, examples thereof include ester compounds, ketone compounds, ether compounds, aromatic compounds, and aliphatic compounds.

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

Ether compounds include alkylene glycol (diethylene glycol, triethylene glycol, polyethylene glycol, dipropylene glycol, etc.), alkylene glycol monoalkyl ether (ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether, etc.), alkylene glycol dialkyl ether (ethylene glycol dimethyl ether, etc.), dialkyl ether (dimethyl ether, diethyl ether, diisopropyl ether, dibutyl ether, etc.) ), cyclic ethers (tetrahydrofuran, dioxane (including 1,2-, 1,3- and 1,4-isomers), etc.).

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

In the present invention, among others, ether compounds, ketone compounds, aromatic compounds, aliphatic compounds, and ester compounds are preferred, and ester compounds, ketone compounds, and ether compounds are more preferred.

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

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

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

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

(Positive electrode active material)
The positive electrode active material is an active material capable of inserting and releasing metal ions belonging to Group 1 or Group 2 of the periodic table, and preferably 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 an element such as a transition metal oxide, an organic substance, sulfur, or the like that can be combined with Li by decomposing the battery.
Among them, it is preferable to use a transition metal oxide as ^the positive electrode active material. objects are more preferred. Further, the transition metal oxide may contain an element M ^b (an element of group 1 (Ia) of the periodic table of metals other than lithium, an element of group 2 (IIa) of the periodic table, Al, Ga, In, Ge, Sn, Pb, elements such as Sb, Bi, Si, P and B) may be mixed. The mixing amount is preferably 0 to 30 mol % with respect to the amount (100 mol %) of the transition metal element ^Ma . More preferred is one synthesized by mixing so that the Li/M ^a molar ratio is 0.3 to 2.2.
Specific examples of the transition metal oxide include (MA) a transition metal oxide having a layered rock salt structure, (MB) a transition metal oxide having a spinel structure, (MC) a lithium-containing transition metal phosphate compound, (MD ) lithium-containing transition metal halide phosphate compounds and (ME) lithium-containing transition metal silicate compounds.

(MA) Specific examples of transition metal oxides having a layered rocksalt structure include LiCoO ₂ (lithium cobaltate [LCO]), LiNi ₂ O ₂ (lithium nickelate), LiNi _0.85 Co _0.10 Al _{0.85 . 05O2} (lithium nickel cobalt _aluminum oxide [NCA]), _{LiNi1 /3Co1/ 3Mn1} / _{3O2 (} lithium nickel manganese cobaltate [NMC]) and _{LiNi0.5Mn0.5O2 (} lithium manganese nickelate).
(MB) Specific examples of transition metal oxides having a spinel structure include 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 _{2NiMn3O8 . _}
Examples of (MC) lithium-containing transition metal phosphate compounds include olivine-type iron phosphates such as LiFePO ₄ and Li ₃ Fe ₂ (PO ₄ ) ₃ , iron pyrophosphates such as LiFeP ₂ O ₇ , and LiCoPO ₄ . and monoclinic Nasicon-type vanadium phosphates such as Li ₃ V ₂ (PO ₄ ) ₃ (lithium vanadium phosphate).
Examples of (MD) lithium-containing transition metal halogenated phosphate compounds include iron fluorophosphates such as Li ₂ FePO ₄ F, manganese fluorophosphates such as Li ₂ MnPO ₄ F, and Li ₂ CoPO ₄ F. and cobalt fluoride phosphates.
(ME) Lithium-containing transition metal silicate compounds include, for example, Li ₂ FeSiO ₄ , Li ₂ MnSiO ₄ , Li ₂ CoSiO ₄ and the like.
In the present invention, transition metal oxides having a (MA) layered rocksalt structure are preferred, and LCO or NMC is more preferred.

Although the shape of the positive electrode active material is not particularly limited, it is preferably particulate. The particle size (volume average particle size) of the positive electrode active material is not particularly limited. For example, it can be 0.1 to 50 μm. The particle size of the positive electrode active material particles can be measured in the same manner as the particle size of the inorganic solid electrolyte. A normal pulverizer or classifier is used to reduce 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 whirling jet mill, a sieve, or the like is preferably used. At the time of pulverization, wet pulverization can also be performed in which a dispersion medium such as water or methanol is allowed to coexist. Classification is preferably carried out in order to obtain a desired particle size. Classification is not particularly limited, and can be performed using a sieve, an air classifier, or the like. Both dry and wet classification can be used.
The positive electrode active material obtained by the calcination method may be washed with water, an acidic aqueous solution, an alkaline aqueous solution, or an organic solvent before use.

A positive electrode active material may be used individually by 1 type, or may be used in combination of 2 or more type.
When forming the positive electrode active material layer, the mass (mg) (basis weight) 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 determined appropriately according to the designed battery capacity, and can be, for example, 1 to 100 mg/cm ² .

The content of the positive electrode active material in the inorganic solid electrolyte-containing composition is not particularly limited. More preferably, 50 to 90% by mass is particularly preferable.

(Negative electrode active material)
The negative electrode active material is an active material capable of inserting and releasing metal ions belonging to Group 1 or Group 2 of the periodic table, and preferably capable of reversibly inserting and releasing lithium ions. The material is not particularly limited as long as it has the above properties, and carbonaceous materials, metal oxides, metal composite oxides, elemental lithium, lithium alloys, negative electrode active materials that can be alloyed with lithium (alloyable). substances and the like. Among them, carbonaceous materials, metal composite oxides, and lithium simple substance are preferably used from the viewpoint of reliability. An active material that can be alloyed with lithium is preferable from the viewpoint that the capacity of an all-solid secondary battery can be increased. Since solid particles are strongly bonded to each other in the constituent layer formed from 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 secondary battery and extend the life of the battery.

A carbonaceous material used as a negative electrode active material is a material substantially composed of carbon. For example, petroleum pitch, carbon black such as acetylene black (AB), graphite (natural graphite, artificial graphite such as vapor-grown graphite, etc.), and various synthetics such as PAN (polyacrylonitrile)-based resin or furfuryl alcohol resin A carbonaceous material obtained by baking a resin can be mentioned. Furthermore, various carbon fibers such as PAN-based carbon fiber, cellulose-based carbon fiber, pitch-based carbon fiber, vapor growth carbon fiber, dehydrated PVA (polyvinyl alcohol)-based carbon fiber, lignin carbon fiber, vitreous carbon fiber and activated carbon fiber. , mesophase microspheres, graphite whiskers and tabular graphite.
These carbonaceous materials can be classified into non-graphitizable carbonaceous materials (also referred to as hard carbon) and graphitic carbonaceous materials according to the degree of graphitization. The carbonaceous material preferably has the interplanar spacing or density and crystallite size 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, etc. can be used. can also
As the carbonaceous material, hard carbon or graphite is preferably used, and graphite is more preferably used.

The oxide of a metal or metalloid element that is applied as a negative electrode active material is not particularly limited as long as it is an oxide that can occlude and release lithium. Examples include oxides, composite oxides of metal elements and metalloid elements (collectively referred to as metal composite oxides), and oxides of metalloid elements (semimetal oxides). As these oxides, amorphous oxides are preferred, and chalcogenides, which are reaction products of metal elements and Group 16 elements of the periodic table, are also preferred. In the present invention, the metalloid element refers to an element that exhibits intermediate properties between metal elements and non-metalloid elements, and usually includes the six elements boron, silicon, germanium, arsenic, antimony and tellurium, and further selenium. , polonium and astatine. In addition, the term "amorphous" means a broad scattering band having an apex in the region of 20° to 40° in terms of 2θ value in an X-ray diffraction method using CuKα rays, and a crystalline diffraction line. may have. The strongest intensity among the crystalline diffraction lines seen at 2θ values of 40° to 70° is 100 times or less than the diffraction line intensity at the top of the broad scattering band seen at 2θ values of 20° to 40°. is preferable, more preferably 5 times or less, and it is particularly preferable not to have a crystalline diffraction line.

Among the compound group consisting of amorphous oxides and chalcogenides, amorphous oxides of metalloid elements or chalcogenides are more preferable, and elements of groups 13 (IIIB) to 15 (VB) of the periodic table (for example, , Al, Ga, Si, Sn, Ge, Pb, Sb and Bi) are particularly preferable. Specific examples of preferred amorphous oxides and chalcogenides include Ga ₂ O ₃ , GeO, PbO, PbO ₂ , Pb ₂ O ₃ , Pb ₂ O ₄ , Pb ₃ O ₄ , Sb ₂ O ₃ and Sb _{2 . O4 , Sb2O8Bi2O3 , Sb2O8Si2O3 , Sb2O5 , Bi2O3 , Bi2O4 , GeS , PbS , PbS2} , _Sb2S3 or _{Sb2 S5} is preferred.
Examples of negative electrode active materials that can be used together with amorphous oxides mainly composed of Sn, Si, and Ge include carbonaceous materials capable of absorbing and/or releasing lithium ions or lithium metal, elemental lithium, lithium alloys, and lithium. and a negative electrode active material that can be alloyed with.

From the viewpoint of high current density charge/discharge characteristics, the oxides of metals or semimetals, especially metal (composite) oxides and chalcogenides, preferably contain at least one of titanium and lithium as a constituent component. Examples of lithium-containing metal composite oxides (lithium composite metal oxides) include composite oxides of lithium oxide and the above metal (composite) oxides or chalcogenides, more specifically Li ₂ SnO ₂ . mentioned.
It is also preferable that the negative electrode active material, such as a metal oxide, contain a titanium element (titanium oxide). Specifically, Li ₄ Ti ₅ O ₁₂ (lithium titanate [LTO]) is excellent in rapid charge-discharge characteristics due to its small volume fluctuation during lithium ion absorption and release, suppressing deterioration of the electrode, and is a lithium ion secondary battery. It is preferable in that it is possible to improve the service life of

The lithium alloy as the negative electrode active material is not particularly limited as long as it is an alloy normally used as a negative electrode active material for secondary batteries, and examples thereof include lithium aluminum alloys.

The negative electrode active material capable of forming an alloy with lithium is not particularly limited as long as it is commonly used as a negative electrode active material for secondary batteries. Such an active material expands and contracts significantly during charging and discharging, and usually accelerates the deterioration of battery performance. However, in the present invention, the binder containing the low-loss polymer follows the expansion and contraction well and can suppress the deterioration of battery performance. Examples of such active materials include (negative electrode) active materials (alloys) containing silicon or tin, and metals such as Al and In. Silicon element-containing active material) is preferable, and a silicon element-containing active material having a silicon element content of 50 mol % or more of all constituent elements is more preferable.
In general, a negative electrode containing these negative electrode active materials (e.g., a Si negative electrode containing a silicon element-containing active material, a Sn negative electrode containing an active material containing a tin element) is a carbon negative electrode (graphite, acetylene black, etc.) can occlude more Li ions than That is, the amount of Li ions stored per unit mass increases. Therefore, the battery capacity (energy density) can be increased. As a result, there is an advantage that the battery driving time can be lengthened.
Silicon element-containing active materials include, for example, silicon materials such as Si and SiOx (0<x≦1), and silicon-containing alloys containing titanium, vanadium, chromium, manganese, nickel, copper, lanthanum, etc. (for example, LaSi ₂ , VSi ₂ , La—Si, Gd—Si, Ni—Si) or organized active materials (e.g. LaSi ₂ /Si), as well as elemental silicon and elemental tin such as SnSiO ₃ , SnSiS ₃ and active materials containing In addition, SiOx itself can be used as a negative electrode active material (semimetal oxide), and since Si is generated by the operation of the all-solid secondary battery, the negative electrode active material that can be alloyed with lithium (the can be used as a precursor substance).
Examples of negative electrode active materials containing tin include Sn, SnO, SnO ₂ , SnS, SnS ₂ , active materials containing silicon and tin, and the like. In addition, composite oxides with lithium oxide, such as Li ₂ SnO ₂ can also be mentioned.

In the present invention, the above-described negative electrode active material can be used without any particular limitation. , the above silicon materials or silicon-containing alloys (alloys containing elemental silicon) are more preferred, and silicon (Si) or silicon-containing alloys are even more preferred.

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

Although the shape of the negative electrode active material is not particularly limited, it is preferably particulate. 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, an ordinary pulverizer or classifier is used as in the case of the positive electrode active material.

The negative electrode active materials may be used singly or in combination of two or more.
When the negative electrode active material layer is formed, the mass (mg) (basis weight) 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 determined appropriately according to the designed battery capacity, and can be, for example, 1 to 100 mg/cm ² .

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

In the present invention, when the negative electrode active material layer is formed by charging the secondary battery, instead of the negative electrode active material, a metal belonging to Group 1 or Group 2 of the periodic table generated in the all-solid secondary battery Ions can be used. A negative electrode active material layer can be formed by combining this ion with an electron and depositing it 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 surface coating agents include metal oxides containing Ti, Nb, Ta, W, Zr, Al, Si or Li. Specific examples include spinel titanate, tantalum-based oxides _{, niobium} -based oxides, and lithium _niobate -based compounds. Specific examples include _Li4Ti5O12 , _Li2Ti2O5 , and _{LiTaO3 .} , _LiNbO3 , _{LiAlO2 , Li2ZrO3} , _{Li2WO4 , Li2TiO3 , Li2B4O7 , Li3PO4 , Li2MoO4 , Li3BO3 , LiBO2 , Li2CO 3} , Li ₂ SiO ₃ , SiO ₂ , TiO ₂ , ZrO ₂ , Al ₂ O ₃ , B ₂ O ₃ and the like.
Moreover, the surface of the electrode containing the positive electrode active material or the negative electrode active material may be surface-treated with sulfur or phosphorus.
Furthermore, the surface of the particles of the positive electrode active material or the negative electrode active material may be surface-treated with actinic rays or an active gas (such as plasma) before and after the surface coating.

<Conductivity aid>
The inorganic solid electrolyte-containing composition of the present invention may contain a conductive aid as appropriate, and it is particularly preferred that the silicon atom-containing active material as the negative electrode active material is used in combination with the conductive aid.
There is no particular limitation on the conductive aid, and any commonly known conductive aid can be used. For example, electronic conductive materials 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 fiber or carbon nanotube. carbon fibers such as carbon fibers such as graphene or fullerene, metal powders such as copper and nickel, metal fibers, and conductive polymers such as polyaniline, polypyrrole, polythiophene, polyacetylene, and polyphenylene derivatives. may be used.
In the present invention, when an active material and a conductive aid are used in combination, among the above conductive aids, when the battery is charged and discharged, ions of metals belonging to Group 1 or Group 2 of the periodic table (preferably Li A material that does not insert or release ions) and does not function as an active material is used as a conductive aid. Therefore, among the conductive aids, those that can function as an active material in the active material layer during charging and discharging of the battery are classified as active materials rather than conductive aids. Whether or not it functions as an active material when the battery is charged/discharged is not univocally determined by the combination with the active material.

The conductive aid may contain one type, or may contain two or more types.
The shape of the conductive aid is not particularly limited, but is preferably particulate.
When the inorganic solid electrolyte-containing composition of the present invention contains a conductive aid, the content of the conductive aid in the inorganic solid electrolyte-containing composition is preferably 0 to 10% by mass based on the solid content.

<Lithium salt>
The inorganic solid electrolyte-containing composition of the present invention also preferably contains a lithium salt (supporting electrolyte).
The lithium salt is preferably a lithium salt that is usually used in this type of product, and is not particularly limited.
When the inorganic solid electrolyte-containing composition of the present invention contains a lithium salt, the content of the lithium salt is preferably 0.1 parts by mass or more, more preferably 5 parts by mass or more, relative to 100 parts by mass of the solid electrolyte. The upper limit is preferably 50 parts by mass or less, more preferably 20 parts by mass or less.

<Dispersant>
The inorganic solid electrolyte-containing composition of the present invention may contain a dispersant. As the dispersing agent, those commonly used in all-solid secondary batteries can be appropriately selected and used. Generally compounds intended for particle adsorption and steric and/or electrostatic repulsion are preferably used.

<Other additives>
In the inorganic solid electrolyte-containing composition of the present invention, as other components other than the above components, an ionic liquid, a thickener, a cross-linking agent (such as those that undergo a cross-linking reaction by radical polymerization, condensation polymerization, or ring-opening polymerization). , a polymerization initiator (such as one that generates an acid or radical by heat or light), an antifoaming agent, a leveling agent, a dehydrating agent, an antioxidant, and the like. The ionic liquid is contained in order to further improve the ionic conductivity, and known liquids can be used without particular limitation. Further, it may contain a polymer other than the polymer contained in the binder, a commonly used binder, and the like.

(Preparation of composition containing inorganic solid electrolyte)
The inorganic solid electrolyte-containing composition of the present invention can be prepared by mixing the inorganic solid electrolyte, the binder, the dispersion medium, and, optionally, a lithium salt and any other components, for example, with various commonly used mixers. , preferably as a slurry.
The mixing method is not particularly limited, and may be mixed all at once or sequentially. The mixing environment is not particularly limited, but examples include dry air, inert gas, and the like.

[Sheet for all-solid secondary battery]
The sheet for an all-solid secondary battery of the present invention is a sheet-shaped molded article that can form a constituent layer of an all-solid secondary battery, and includes various aspects according to 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 (electrode for an all-solid secondary battery sheet). In the present invention, these various sheets are collectively referred to as a sheet for an all-solid secondary battery.

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

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

The electrode sheet for an all-solid 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 substrate (current collector). The sheet may be a sheet having no base material and may be a sheet formed from an active material layer. This electrode sheet is usually a sheet having a current collector and an active material layer. A mode having a layer and an active material layer in this order is also included. The solid electrolyte layer and active material layer of the electrode sheet are preferably formed from the inorganic solid electrolyte-containing composition of the present invention. The content of each component in the solid electrolyte layer or active material layer is not particularly limited, but is preferably the content of each component in the solid content of the composition containing an inorganic solid electrolyte (composition for electrodes) of the present invention. is synonymous with The layer thickness of each layer constituting the electrode sheet of the present invention is the same as the layer thickness of each layer described in the all-solid secondary battery described later. The electroded sheet of the invention may have other layers as described above.

The sheet for an all-solid secondary battery of the present invention has at least one layer of the solid electrolyte layer and the active material layer formed of the inorganic solid electrolyte-containing composition of the present invention, is excellent in bending durability, and has a desired interface between solid particles. It has constituent layers that remain in contact. Furthermore, when used as a constituent layer of an all-solid secondary battery, it is possible to suppress deterioration of battery performance due to charging and discharging. Therefore, the sheet for an all-solid secondary battery of the present invention is suitably used as a sheet capable of forming a constituent layer of an all-solid secondary battery. In the all-solid secondary battery manufactured using the sheet for all-solid secondary battery of the present invention, the interfacial contact between the solid particles is maintained, and for example, the desired battery resistance is achieved (bending and restoring during sheet production). can suppress the decrease in battery resistance caused by Furthermore, the battery performance can be maintained even after repeated charging and discharging.

[Manufacturing method of sheet for all-solid secondary battery]
The method for producing the all-solid secondary battery sheet of the present invention is not particularly limited, and the sheet can be produced by forming each of the above layers using the inorganic solid electrolyte-containing composition of the present invention. For example, it is preferable to form a layer (coated and dried layer) composed of an inorganic solid electrolyte-containing composition (coated and dried) by forming a film (coating and drying) on a substrate or a current collector (may be via another layer). method. As a result, an all-solid secondary battery sheet having a base material or current collector and a coated dry layer can be produced. Here, the coated dry layer is a layer formed by applying the inorganic solid electrolyte-containing composition of the present invention and drying the dispersion medium (that is, using the inorganic solid electrolyte-containing composition of the present invention, Layer) composed of a composition obtained by removing the dispersion medium from the inorganic solid electrolyte-containing composition of the present invention. The dispersion medium may remain in the coated dry layer as long as it does not impair the effects of the present invention.
In the method for producing a sheet for an all-solid 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 secondary battery.

In the manufacturing method of the all-solid-state secondary battery sheet of the present invention, the applied dry layer obtained as described above can also be pressurized. Pressurization conditions and the like will be described later in the method for manufacturing an all-solid secondary battery.
Moreover, in the manufacturing method of the sheet for all-solid-state secondary batteries of this invention, a base material, a protective layer (especially a peeling sheet), etc. can also be peeled off.

The method for producing a sheet for an all-solid secondary battery of the present invention is a highly productive production method in which bending and restoring work by using the inorganic solid electrolyte-containing composition of the present invention, especially bending and restoring work repeatedly. Even if it is applied to an industrial manufacturing method (for example, a roll-to-roll method), a constituent layer in which solid particles are kept in contact with each other can be produced. That is, a sheet for an all-solid secondary battery having excellent bending durability can be produced with high productivity.

[All-solid secondary battery]
The all-solid secondary battery of the present invention comprises a positive electrode active material layer, a negative electrode active material layer facing the positive electrode active material layer, and a solid electrolyte layer disposed 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 constitute the negative electrode.
At least one of the negative electrode active material layer, the positive electrode active material layer and the solid electrolyte layer is preferably formed of the composition containing the inorganic solid electrolyte of the present invention, and at least the negative electrode active material layer contains the inorganic solid electrolyte of the present invention. It is more preferable that the negative electrode active material layer and the solid electrolyte layer are formed of the composition containing the inorganic solid electrolyte of the present invention. It is also one of preferred embodiments that all layers are formed of the inorganic solid electrolyte-containing composition of the present invention. In the active material layer or the solid electrolyte layer formed of the composition containing an inorganic solid electrolyte of the present invention, the types of components contained and their content ratios are preferably based on the solid content of the composition containing an inorganic solid electrolyte of the present invention. is the same as In addition, when the active material layer or the solid electrolyte layer is not formed of the inorganic solid electrolyte-containing composition of the present invention, known materials 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, considering the dimensions of a general all-solid secondary battery. In the all-solid 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.
Each of the positive electrode active material layer and the negative electrode active material layer may have a current collector on the side opposite to the solid electrolyte layer.

<Case>
Depending on the application, the all-solid secondary battery of the present invention may be used as an all-solid secondary battery with the above structure. is preferred. The housing may be made of metal or resin (plastic). When using a metallic one, for example, an aluminum alloy or a stainless steel one can be used. It is preferable that the metal casing be divided into a positive electrode side casing and a negative electrode side casing 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 short-circuit prevention.

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

FIG. 1 is a cross-sectional view schematically showing an all-solid secondary battery (lithium ion secondary battery) according to a preferred embodiment of the present invention. The all-solid 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, electrons (e ⁻ ) are supplied to the negative electrode during charging, and lithium ions (Li ⁺ ) are accumulated there. On the other hand, during 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 is lit by discharge.

When an all-solid secondary battery having the layer structure shown in FIG. A battery fabricated in a 2032-type coin case is sometimes called an all-solid secondary battery.

(Positive electrode active material layer, solid electrolyte layer, negative electrode active material layer)
In the all-solid secondary battery 10, all of the positive electrode active material layer, the solid electrolyte layer, and the negative electrode active material layer are formed from the inorganic solid electrolyte-containing composition of the present invention. This all-solid secondary battery 10 exhibits excellent battery performance. The inorganic solid electrolyte and binder contained in the positive electrode active material layer 4, the solid electrolyte layer 3, and the negative electrode active material layer 2 may be of the same type or different types.
In the present invention, either one of the positive electrode active material layer and the negative electrode active material layer, or both of them may be simply referred to as an active material layer or an electrode active material layer. Moreover, either or both of the positive electrode active material and the negative electrode active material may be simply referred to as an active material or an electrode active material.

In the present invention, when the binder is used in combination with solid particles such as an inorganic solid electrolyte or an active material for the constituent layers, interfacial contact between the solid particles can be maintained even when the sheet is flexed and restored as described above. can. Therefore, the all-solid secondary battery of the present invention can maintain high battery performance (for example, low battery resistance). Furthermore, battery performance such as low battery resistance and cycle characteristics can be maintained even after repeated charging and discharging.

In the all-solid secondary battery 10, the negative electrode active material layer can be a lithium metal layer. Examples of the lithium metal layer include a layer formed by depositing or molding lithium metal powder, a lithium foil, a lithium 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 electronic conductors.
In the present invention, either one of the positive electrode current collector and the negative electrode current collector, or both of them may simply be referred to as the current collector.
Examples of materials for forming the positive electrode current collector include aluminum, aluminum alloys, stainless steel, nickel and titanium, as well as materials obtained by treating the surface of aluminum or stainless steel with carbon, nickel, titanium or silver (thin films are formed). ) are preferred, and among them, aluminum and aluminum alloys are more preferred.
Materials for forming the negative electrode current collector include aluminum, copper, copper alloys, stainless steel, nickel and titanium, and the surface of aluminum, copper, copper alloys or stainless steel is treated with carbon, nickel, titanium or silver. and more preferably aluminum, copper, copper alloys and stainless steel.

As for the shape of the current collector, a film sheet is usually used, but a net, a punched one, a lath, a porous body, a foam, a molded body of fibers, and the like can also be used.
Although the thickness of the current collector is not particularly limited, it is preferably 1 to 500 μm. It is also preferable that the surface of the current collector is roughened by surface treatment.

In the all-solid-state secondary battery 10 described above, the positive electrode active material layer may be a layer formed of a known constituent layer-forming material.
In the present invention, functional layers, members, etc. are appropriately interposed or disposed between or outside the respective layers of the negative electrode current collector, the negative electrode active material layer, the solid electrolyte layer, the positive electrode active material layer, and the positive electrode current collector. You may Further, each layer may be composed of a single layer or may be composed of multiple layers.

[Manufacturing of all-solid secondary battery]
An all-solid secondary battery can be manufactured by a conventional method. Specifically, an all-solid secondary battery can be produced by forming each of the above layers using the inorganic solid electrolyte-containing composition of the present invention. Details will be described below.

The all-solid secondary battery of the present invention is obtained by applying the inorganic solid electrolyte-containing composition of the present invention onto a suitable substrate (for example, a metal foil that serves as a current collector) to form a coating film (film formation). ) can be produced by performing a method (method for producing a sheet for an all-solid secondary battery of the present invention) including (via) the step.
For example, an inorganic solid electrolyte-containing composition containing a positive electrode active material is applied as a positive electrode material (positive electrode composition) on a metal foil that is a positive electrode current collector to form a positive electrode active material layer, and an all-solid A positive electrode sheet for a secondary battery is produced. Next, an inorganic solid electrolyte-containing composition for forming a solid electrolyte layer is applied onto the positive electrode active material layer to form a solid electrolyte layer. Furthermore, an inorganic solid electrolyte-containing composition containing a negative electrode active material is applied as a negative electrode material (a negative electrode composition) on the solid electrolyte layer to form a negative electrode active material layer. To obtain an all-solid secondary battery having a structure in which a solid electrolyte layer is sandwiched between a positive electrode active material layer and a negative electrode active material layer by stacking a negative electrode current collector (metal foil) on a negative electrode active material layer. can be done. A desired all-solid secondary battery can also be obtained by enclosing this in a housing.
In addition, by reversing the formation 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 stacked to manufacture an all-solid secondary battery. You can also

Another method is the following method. That is, a positive electrode sheet for an all-solid secondary battery is produced as described above. In addition, an inorganic solid electrolyte-containing composition containing a negative electrode active material is applied as a negative electrode material (negative electrode composition) on a metal foil that is a negative electrode current collector to form a negative electrode active material layer. A negative electrode sheet for a secondary battery is produced. Next, a solid electrolyte layer is formed on the active material layer of one of these sheets as described above. Furthermore, the other of the all-solid secondary battery positive electrode sheet and the all-solid secondary battery negative electrode sheet is laminated on the solid electrolyte layer so that the solid electrolyte layer and the active material layer are in contact with each other. Thus, an all-solid secondary battery can be manufactured.
Another method is the following method. That is, as described above, a positive electrode sheet for an all-solid secondary battery and a negative electrode sheet for an all-solid secondary battery are produced. Separately from this, an inorganic solid electrolyte-containing composition is applied onto a substrate to prepare a solid electrolyte sheet for an all-solid secondary battery comprising a solid electrolyte layer. Further, the all-solid secondary battery positive electrode sheet and the all-solid secondary battery negative electrode sheet are laminated so as to sandwich the solid electrolyte layer peeled from the substrate. Thus, an all-solid secondary battery can be manufactured.
Furthermore, as described above, a positive electrode sheet for an all-solid secondary battery, a negative electrode sheet for an all-solid secondary battery, and a solid electrolyte sheet for an all-solid secondary battery are produced. Next, the all-solid secondary battery positive electrode sheet or the all-solid secondary battery negative electrode sheet and the all-solid secondary battery solid electrolyte sheet were brought into contact with the positive electrode active material layer or the negative electrode active material layer and the solid electrolyte layer. Apply pressure to the state. In this way, the solid electrolyte layer is transferred to the all-solid secondary battery positive electrode sheet or all-solid secondary battery negative electrode sheet. After that, the solid electrolyte layer obtained by peeling the base material of the solid electrolyte sheet for all-solid secondary batteries and the negative electrode sheet for all-solid secondary batteries or the positive electrode sheet for all-solid secondary batteries (the solid electrolyte layer and the negative electrode active material layer or (with the positive electrode active material layer in contact) and pressurized. Thus, an all-solid secondary battery can be manufactured. The pressurization method, pressurization conditions, and the like in this method are not particularly limited, and the method, pressurization conditions, and the like described later in the pressurization of the applied composition can be applied.

The solid electrolyte layer or the like can also be formed, for example, by pressure-molding a composition containing an inorganic solid electrolyte or the like on a substrate or an active material layer under pressure conditions described below.
In the above production method, the inorganic solid electrolyte-containing composition of the present invention may be used for any one of the positive electrode composition, the inorganic solid electrolyte-containing composition, and the negative electrode composition. It is preferable to use the inorganic solid electrolyte-containing composition of No., and the inorganic solid electrolyte-containing composition of the present invention can be used in any composition.
When forming the solid electrolyte layer or the active material layer with a composition other than the solid electrolyte composition of the present invention, examples of the material include commonly used compositions. In addition, without forming a negative electrode active material layer during the production of the all-solid secondary battery, it is accumulated in the negative electrode current collector during initialization or charging during use, which belongs to the first group or second group of the periodic table. The negative electrode active material layer can also be formed by combining metal ions with electrons and depositing the metal on the negative electrode current collector or the like.
The solid electrolyte layer or the like can be formed, for example, by pressure-molding a solid electrolyte composition or the like on a substrate or an active material layer under pressure conditions described later, or by forming a sheet compact of a solid electrolyte or an active material. can also be used.

<Formation of each layer (film formation)>
The method of applying the inorganic solid electrolyte-containing composition is not particularly limited and can be selected as appropriate. Examples thereof include coating (preferably wet coating), spray coating, spin coating, dip coating, slit coating, stripe coating, and bar coating.
At this time, the inorganic solid electrolyte-containing composition may be dried after each application, or may be dried 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 (coated dry layer) can be obtained. In addition, it is preferable because the temperature does not become too high and each member of the all-solid secondary battery is not damaged. As a result, the all-solid-state secondary battery exhibits excellent overall performance, good binding properties, and good ionic conductivity even without pressure.
When the inorganic solid electrolyte-containing composition of the present invention is applied and dried as described above, the solid particles are firmly bound, and the applied and dried layer has a small interfacial resistance between the solid particles. An electrolyte layer can be formed.

After applying the inorganic solid electrolyte-containing composition, after laminating the constituent layers, or after producing the all-solid secondary battery, it is preferable to pressurize each layer or the all-solid secondary battery. A hydraulic cylinder press machine etc. are mentioned as a pressurization method. The applied pressure is not particularly limited, and is generally preferably in the range of 5 to 1500 MPa.
Moreover, the applied inorganic solid electrolyte-containing composition may be heated at the same time as being pressurized. The heating temperature is not particularly limited, and generally ranges from 30 to 300.degree. It is also possible to press at a temperature higher than the glass transition temperature of the inorganic solid electrolyte. On the other hand, when an inorganic solid electrolyte and a binder coexist, pressing can be performed at a temperature higher than the glass transition temperature of the binder. However, in general, the temperature does not exceed the melting point of the binder described above.
Pressurization may be performed after drying the coating solvent or dispersion medium in advance, or may be performed while the solvent or dispersion medium remains.
Each composition may be applied at the same time, or the application and drying presses may be performed simultaneously and/or sequentially. After coating on separate substrates, they may be laminated by transfer.

The atmosphere during the manufacturing process, such as heating or pressurization, is not particularly limited, and can be in air, in dry air (dew point of -20°C or less), or in inert gas (eg, in argon gas, helium gas, or nitrogen gas). and so on.
As for the pressing time, high pressure may be applied for a short period of time (for example, within several hours), or moderate pressure may be applied for a long period of time (one day or more). Other than the all-solid secondary battery sheet, for example, in the case of an all-solid secondary battery, a restraining tool (such as screw tightening pressure) for the all-solid secondary battery can be used to keep applying moderate pressure.
The press pressure may be uniform or different with respect to the pressed portion such as the seat surface.
The press pressure can be changed according to the area or film thickness of the portion to be pressed. Also, the same part can be changed step by step with different pressures.
The pressing surface may be smooth or roughened.

<Initialization>
The all-solid secondary battery manufactured as described above is preferably initialized after manufacturing or before use. Initialization is not particularly limited, and can be performed, for example, by performing initial charge/discharge while press pressure is increased, and then releasing the pressure to the general working pressure of all-solid secondary batteries.

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

[Applications of all-solid secondary batteries]
The all-solid secondary battery of the present invention can be applied to various uses. There are no particular restrictions on the mode of application, but for example, when installed in electronic equipment, notebook computers, pen-input computers, mobile computers, e-book players, mobile phones, cordless phone slaves, pagers, handy terminals, mobile faxes, mobile phones, etc. Copiers, portable printers, headphone stereos, video movies, liquid crystal televisions, handy cleaners, portable CDs, minidiscs, electric shavers, transceivers, electronic notebooks, calculators, memory cards, portable tape recorders, radios, backup power sources, etc. Other consumer products include automobiles, electric vehicles, motors, lighting equipment, toys, game equipment, road conditioners, clocks, strobes, cameras, and medical equipment (pacemakers, hearing aids, shoulder massagers, etc.). Furthermore, it can be used for various military applications and space applications. It can also be combined with a solar cell.

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

1. Synthesis of Low-Loss Polymer Used in Examples and Preparation of Binder Dispersion, etc. Polyurethanes B-1 to B-4 and B-6 synthesized as low-loss polymers are shown below. However, the content of each component is mol%. Polyurethane B-5 is a polyurethane having the same components as polyurethane B-3 but a different content, so description thereof is omitted.

[Synthesis Example 1: Synthesis of Polyurethane B-1 and Preparation of Binder Dispersion Liquid B-1 Comprising Polyurethane B-1]
(Synthesis of Polyurethane B-1)
2.92 g of polyethylene glycol (PEG200 (trade name), number average molecular weight 200, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) and polytetramethylene ether glycol (number average molecular weight 250, manufactured by SIGMA-Aldrich) were added to a 300 mL three-necked flask. 3.65 g, NISSO-PB G-1000 (trade name, manufactured by Nippon Soda Co., Ltd.) 3.78 g, and 2,2-bis(hydroxymethyl)butyric acid (manufactured by Tokyo Chemical Industry Co., Ltd.) 0.60 g were added, and THF ( Tetrahydrofuran) 80.85 g. 9.26 g of diphenylmethane diisocyanate (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) was added to this solution and stirred at 60° C. to dissolve uniformly.
65 mg of Neostan U-600 (trade name, manufactured by Nitto Kasei Co., Ltd.) was added to the obtained solution, and the mixture was stirred at 60° C. for 5 hours. 0.96 g of methanol was added to this solution to block the ends of the polymer to terminate the polymerization reaction to obtain a 20% by mass THF solution (polymer solution) of polymer B-1.

(Preparation of Binder Dispersion B-1)
15.00 g of the polymer solution obtained above was diluted with 15.00 g of THF, and 90.00 g of methyl isobutyl ketone was added dropwise with stirring over 1 hour to obtain an emulsion of polymer B-1. This emulsion was concentrated to about 70 g, and methyl isobutyl ketone was added to bring the total amount to 100.00 g, thereby obtaining a 3% by mass methyl isobutyl ketone dispersion of a binder composed of polymer B-1 (binder dispersion B-1). got

[Synthesis Examples 2 to 6: Synthesis of Polyurethanes B-2 to B-6, Preparation of Binder Dispersions B-2 to B-6 Consisting of Polyurethanes B-2 to B-6]
Polyurethane B-2 was prepared in the same manner as in Synthesis Example 1, except that in Synthesis Example 1, a compound was used that led to each constituent component so as to have the composition (type and content of constituent components) shown in Table 1-1. to B-6 were synthesized respectively.
Next, using the synthesized polyurethanes B-2 to B-6, binder dispersions B-2 to B-6 were prepared in the same manner as the binder dispersion B-1.

[Synthesis Examples 7 and 8: Synthesis of Polyurethanes BC-2 and BC-3, Preparation of Binder Dispersions BC-2 and BC-3 Consisting of Polyurethanes BC-2 and BC-3]
Polyurethane BC-2 was produced in the same manner as in Synthesis Example 1, except that in Synthesis Example 1, a compound was used that led to each constituent component so as to have the composition (type and content of constituent components) shown in Table 1-1. and BC-3 were synthesized respectively.
Then, using the synthesized polyurethanes BC-2 and BC-3, binder dispersions BC-2 and BC-3 were prepared in the same manner as binder dispersion B-1, respectively.

[Synthesis Example 9: Synthesis of Polyurethane BC-4, Preparation of Binder Dispersion Liquid BC-4 Consisting of Polyurethane BC-4]
As polyurethane BC-4, the following polyurethane BC- is prepared according to "(4) Synthesis of exemplary compound (B-4)" described in paragraph [0188] of Patent Document 1 (International Publication No. 2018/020827A1). 4 was synthesized to prepare a 10% by mass octane dispersion BC-4. Thus, a 10 mass % binder dispersion BC-4 of polyurethane BC-4 was obtained.

上記式において、各構成成分の右下に示す数値は含有量（モル％）を示し、ｉ１、ｉ２及びｎ１は構成成分中の構成単位の繰り返し単位数（平均単位数）を示し、具体的には使用した各化合物に特有の数値である。

In the above formula, the numerical value shown in the lower right of each component indicates the content (mol%), i1, i2 and n1 indicate the number of repeating units (average number of units) of the constituent units in the component, specifically is a numerical value specific to each compound used.

[Synthesis Example 10: Synthesis of Polyurethane BC-5, Preparation of Binder Dispersion Liquid BC-5 Consisting of Polyurethane BC-5]
As polyurethane BC-5, polyurethane BC-5 shown below was synthesized according to "(3) Synthesis of exemplary compound (B-3)" described in paragraph [0187] of Patent Document 1 above, and 10 masses A % octane dispersion BC-5 was prepared. Thus, a 10 mass % binder dispersion BC-5 of polyurethane BC-5 was obtained.

上記式において、各構成成分の右下に示す数値は含有量（モル％）を示し、ｈ１、ｈ２、ｐ、ｑ及びｒは構成成分中の構成単位の繰り返し単位数（平均単位数）を示し、具体的には使用した各化合物に特有の数値である。

In the above formula, the numerical value shown in the lower right of each component indicates the content (mol%), and h1, h2, p, q and r indicate the number of repeating units (average number of units) of the constituent units in the component. , specifically a numerical value specific to each compound used.

[Synthesis Example 11: Synthesis of Polyurethane BC-6, Preparation of Binder Dispersion Liquid BC-6 Consisting of Polyurethane BC-6]
Polyurethane shown below was prepared in the same manner as in Synthesis Example 1, except that in Synthesis Example 1, a compound was used that led to each constituent component so as to have the composition (type and content of constituent components) shown in Table 1-1. BC-6 was synthesized.
Next, using the synthesized polyurethane BC-6, binder dispersion BC-6 was prepared in the same manner as binder dispersion B-1.

[Preparation Example 1: Preparation of NBR solution BC-1]
Nipol 1041 (trade name, acrylonitrile-butadiene rubber (NBR), manufactured by Nippon Zeon Co., Ltd.) as NBR polymer BC-1 was dissolved in a solvent: isobutyronitrile at a solid content concentration of 3% by mass to obtain NBR solution BC-1. prepared.
[Preparation Example 2: Preparation of NBR solution B-7]
Perbutyl O (trade name, t-butyl peroxy-2-ethylhexanoate, manufactured by NOF Corporation) was added as a polymerization initiator to the NBR solution BC-1 so as to be 2% by mass based on Nipol 1041. The resulting solution was heated at 80° C. for 1 hour to crosslink the NBR, thereby preparing an NBR solution B-7 containing a crosslinked NBR polymer B-7.

[Measurement of molecular weight of polymer etc.]
Composition of each polymer synthesized or prepared, weight average molecular weight, number average molecular weight of two types of polyether structures (referred to as "number average molecular weight of polyether structure" in Table 1-2), and particle size of each binder (If the binder is a dissolution type, it is indicated by "-" in the particle size column.) are shown in Tables 1-1 and 1-2.
The mass average molecular weight of each polymer and the number average molecular weight of each polyether structure were measured by the above method (condition 2). The number average molecular weights of the two types of polyether structures were calculated from the number average molecular weights of each polyether structure by the method described above. Also, the particle size of each binder was measured by the above method. In addition, since the mass average molecular weights of NBR polymer BC-1 and NBR polymer B-7 were not measured, and because they are dissolved in the dispersion medium and the particle size cannot be measured, the "mass average molecular weight" column of Table 1-2 and "-" in the "particle size" column.

[Calculation of tensile hysteresis loss]
For each polymer synthesized or prepared in Synthesis Examples 1 to 11 and Preparation Examples 1 and 2, 10 times tensile hysteresis loss and 30 times tensile hysteresis loss were measured by the following method (according to JIS K7312-1996) to obtain a stress-strain curve. Calculated. The results are shown in Table 1-2.
(Preparation of test piece)
A dried film having a thickness of 80 μm was obtained by putting a binder dispersion or solution composed of each synthesized or prepared polymer in a glass petri dish and drying at 120° C. for 6 hours. Three strip-shaped test pieces each having a width of 5 mm and a length of 50 mm were cut out from each obtained dry film.
(Preparation of stress-strain curve and calculation of tensile hysteresis loss)
Each prepared test piece was set in a tensile tester (trade name: Autograph AG-X 5kN, manufactured by Shimadzu Corporation) so that the distance between chucks was 30 mm. It was pulled at a speed of 3 mm/min until it reached the target elongation (10%), and immediately after that, it was restored to the original chuck position at the same speed. This operation was repeated several times (10 times or 30 times), and the displacement and load were measured to create a stress-strain curve.
The hysteresis loss is the obtained stress-strain curve, the area surrounded by the curve during tension (integral value) (corresponding to the above-mentioned "total strain energy"), the area surrounded by the tension-restoration curve (above equivalent to “loss energy”).
The above measurements were performed on each of three specimens made from each dry film, resulting in three measurements for each dry film. Among them, the median value was adopted as the hysteresis loss of each polymer.
Polyurethanes BC-2 and BC-3 could not be measured because the test piece broke during the measurement. Both are indicated by "-" in the column.

[Calculation of tensile modulus and elongation at break]
For each polymer synthesized or prepared in Synthesis Examples 1 to 11 and Preparation Examples 1 and 2, tensile modulus and elongation at break were measured by the following methods. The results are shown in Table 1-2.
(Preparation of test piece)
Each synthesized or prepared polymer was placed in a glass petri dish and dried at 120° C. for 6 hours to obtain a dry film having a thickness of 80 μm. The obtained dried film was cut into strips of width 10 mm×length 40 mm to prepare test pieces.
(Measurement of tensile modulus and elongation at break)
Each prepared test piece was set in a force gauge (manufactured by IMADA) so that the distance between chucks was 30 mm. In this state, the test piece was pulled at a speed of 10 mm/min, the amount of displacement and stress were measured, the tensile modulus was calculated from the initial slope, and the elongation at break was calculated from the amount of displacement at break.

In Table 1-1 below, constituent components M1 to M6 are as follows.
Constituent component M1: Constituent component represented by formula (I-1) Constituent component M2: Constituent component represented by formula (I-7) (a component having a polyether structure formed of an alkyleneoxy group having a large molecular weight )
Component M3: a component represented by formula (I-7) (a component having a polyether structure formed of alkyleneoxy groups with a small molecular weight)
Constituent component M4: Constituent component represented by formula (I-3A) Constituent component M5: Constituent component represented by formula (I-3C) Constituent component M6: Other constituent components

<Table abbreviations>
In the table, "-" in the component column indicates that the corresponding component is not included.
In columns M1 to M6 of constituent components, the following abbreviations are used to indicate the names of compounds leading to the respective constituent components.
- Component M1 -
MDI: Diphenylmethane diisocyanate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)
IHDI: isophorone diisocyanate (manufactured by Tokyo Chemical Industry Co., Ltd.)
- Component M2 -
PTMG250: polytetramethylene ether glycol (number average molecular weight 250, manufactured by SIGMA-Aldrich)
PPG130: dipropylene glycol (number average molecular weight 130, manufactured by Tokyo Chemical Industry Co., Ltd.)
PEG200: polyethylene glycol (number average molecular weight 200, manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.)
PEG600: polyethylene glycol (number average molecular weight 600, manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.)
ED-600: Polyetheramine (trade name: Jeffamine ED-600, manufactured by Huntsman, number average molecular weight 600)
PPG3000: Polypropylene glycol (number average molecular weight 3000, manufactured by Tokyo Chemical Industry Co., Ltd.)
- Component M3 -
PEG200: polyethylene glycol (number average molecular weight 200, manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.)
PEG400: polyethylene glycol (number average molecular weight 400, manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.)
PEG150: 3,6-dioxa-1,8-octanediol (number average molecular weight 150, manufactured by Tokyo Chemical Industry Co., Ltd.)
PA150: 3,3'-diaminodipropylamine (number average molecular weight 130, manufactured by Tokyo Chemical Industry Co., Ltd.)
The component derived from PA150 is not the component represented by the above formula (I-7), but is listed in column M3 for convenience.
PEG2000: polyethylene glycol (number average molecular weight 2000, manufactured by Tokyo Chemical Industry Co., Ltd.)
- Component M4 -
DMBA: 2,2-bis(hydroxymethyl)butyric acid (manufactured by Tokyo Chemical Industry Co., Ltd.)
- Component M5 -
G-1000: Polybutadiene modified with hydroxyl groups at both ends NISSO-PB G-1000 (trade name, number average molecular weight 1400, manufactured by Nippon Soda Co., Ltd.)
Epol: Hydrogenated polybutadiene modified with both terminal hydroxyl groups (manufactured by Idemitsu Kosan Co., Ltd., number average molecular weight 2500)
R-45HT: Hydrogenated polybutadiene modified with hydroxyl groups on both ends (trade name: poly bd R-46HT, manufactured by Idemitsu Kosan Co., Ltd., number average molecular weight 2800)
- Component M6 -
BDO: 1,4-butanediol (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)
The BDO-derived component corresponds to component M4 (the component represented by formula (I-3A) above), but is classified as "component M6" for convenience in that it does not have a functional group.
BDA: 1,4-butanediamine (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)
The BDA-derived component corresponds to the component represented by formula (I-4) above.
KF-6001: modified silicone oil (product name, manufactured by Shin-Etsu Chemical Co., Ltd., number average molecular weight 900)

[Synthesis Example A: Synthesis of sulfide-based inorganic solid electrolyte]
Sulfide-based inorganic solid electrolytes are disclosed in T.W. Ohtomo, A.; Hayashi, M.; Tatsumisago, Y.; Tsuchida, S.; Hama, K.; Kawamoto, Journal of Power Sources, 233, (2013), pp231-235; Hayashi, S.; Hama, H.; Morimoto, M.; Tatsumisago, T.; Minami, Chem. Lett. , (2001), pp872-873.
Specifically, in a glove box under an argon atmosphere (dew point −70° C.), 2.42 g of lithium sulfide (Li ₂ S, manufactured by Aldrich, purity >99.98%) and diphosphorus pentasulfide (P ₂ S ₅ , manufactured by Aldrich, purity >99%) was weighed, put into an agate mortar, and mixed for 5 minutes using an agate pestle. The mixing ratio of Li ₂ S and P ₂ S ₅ was Li ₂ S:P ₂ S ₅ =75:25 in terms of molar ratio.
Next, 66 zirconia beads with a diameter of 5 mm were charged into a 45 mL zirconia container (manufactured by Fritsch), the entire mixture of lithium sulfide and phosphorus pentasulfide was charged, and the container was completely sealed under an argon atmosphere. . The container is set in a planetary ball mill P-7 manufactured by Fritsch (trade name, manufactured by Fritsch), and mechanical milling is performed at a temperature of 25 ° C. and a rotation speed of 510 rpm for 20 hours to obtain a yellow powdery sulfide-based inorganic solid electrolyte. (Li--P--S glass, hereinafter sometimes referred to as LPS.) 6.20 g was obtained. The particle size of the Li—P—S glass was 2.5 μm.

[Example 1]
In Example 1, the prepared binder was used to prepare an inorganic solid electrolyte-containing composition, a negative electrode composition, and a positive electrode composition to manufacture an all-solid secondary battery.

<Preparation of Inorganic Solid Electrolyte-Containing Composition>
180 zirconia beads with a diameter of 5 mm were put into a zirconia 45 mL container (manufactured by Fritsch), 4.85 g of LPS synthesized in the above synthesis example, and 0.15 g of the binder (dispersion or solution) shown in Table 2 (solid content mass ), and 11.0 g of butyl butyrate. After that, this container was set in a planetary ball mill P-7 (trade name) manufactured by Fritsch. The mixture was mixed for 10 minutes at a temperature of 25° C. and a rotation speed of 150 rpm to prepare inorganic solid electrolyte-containing compositions C-1 to C-7 and BC-1 to BC-6, respectively.

<Table abbreviations>
LPS: Li-P-S glass synthesized in Synthesis Example A

<Preparation of solid electrolyte sheet for all-solid secondary battery>
Using a Baker-type applicator (trade name: SA-201, manufactured by Tester Sangyo Co., Ltd.), each inorganic solid electrolyte-containing composition obtained above was applied to an aluminum foil having a thickness of 20 μm, and heated at 80 ° C. for 2 hours. to dry the inorganic solid electrolyte-containing composition (remove the dispersion medium). Thereafter, the dried inorganic solid electrolyte-containing composition is heated and pressurized for 10 seconds at a temperature of 120° C. and a pressure of 600 MPa using a heat press to obtain a solid electrolyte sheet S-1 for an all-solid secondary battery. ~S-7 and BS-1 to BS-6 were produced, respectively. The film thickness of the solid electrolyte layer was 50 μm.

<Preparation of positive electrode composition>
180 zirconia beads with a diameter of 5 mm were placed in a zirconia 45 mL container (manufactured by Fritsch), 2.7 g of LPS synthesized in Synthesis Example A, and KYNAR FLEX 2500-20 (trade name) as a solid content mass of 0.00. 3 g, and 22 g of butyl butyrate. This container was set in a planetary ball mill P-7 (trade name) manufactured by Fritsch, and mixed at a temperature of 25° C. and a rotation speed of 300 pm for 60 minutes. After that, 7.0 g of LiNi _1/3 Co _1/3 Mn _1/3 O ₂ (NMC) was added as a positive electrode active material. Mixing was continued for 5 minutes at 25° C. and 100 rpm. Thus, a positive electrode composition (slurry) was prepared.
"KYNAR FLEX 2500-20" used as the polymer forming the binder does not satisfy the 10 times tensile hysteresis loss and the 30 times tensile hysteresis loss by the above measuring method.

<Preparation of positive electrode sheet for all-solid secondary battery>
Using a baker applicator (trade name: SA-201), the positive electrode composition prepared on an aluminum foil having a thickness of 20 μm is applied and heated at 80 ° C. for 2 hours to dry the positive electrode composition (dispersion medium removed). Thereafter, the dried positive electrode composition is pressed at 25° C. using a heat press (10 MPa, 1 minute) to obtain a positive electrode sheet for an all-solid secondary battery having a positive electrode active material layer with a thickness of 80 μm. made.

<Preparation of negative electrode composition>
180 zirconia beads with a diameter of 5 mm were placed in a zirconia 45 mL container (manufactured by Fritsch), 4.0 g of LPS synthesized in Synthesis Example A, and 0.3 g of a binder (dispersion or solution) shown in Table 3 (solid portion), and 12.0 g of butyl butyrate. This container was set in a planetary ball mill P-7 (trade name) manufactured by Fritsch, and mixed at a temperature of 25° C. and a rotation speed of 300 pm for 60 minutes. After that, 5.3 g of silicon as a negative electrode active material and 0.4 g of acetylene black (manufactured by Denka Co., Ltd.) as a conductive agent were added. Mixing was carried out at 100 rpm for 10 minutes to prepare negative electrode compositions U-1 to U-7 and V-1 to V-6, respectively.

<Table abbreviations>
Si: powder (trade name: APS, average particle size 1 to 5 μm, manufactured by Alfa Aesar)
LPS: Li-P-S-based glass synthesized in Synthesis Example A AB: Acetylene black (manufactured by Denka)

<Preparation of negative electrode sheet for all-solid secondary battery>
Using a baker applicator (trade name: SA-201), the negative electrode composition prepared on a copper foil having a thickness of 20 μm is applied and heated at 80° C. for 2 hours to dry the negative electrode composition (dispersion medium removed). Thereafter, the dried negative electrode composition is pressed at 25° C. using a heat press (10 MPa, 1 minute) to obtain a negative electrode sheet PU for an all-solid secondary battery having a negative electrode active material layer with a thickness of 80 μm. -1 to PU-7 and PV-1 to PV-6 were produced.

<Preparation of Negative Electrode Sheet for All-Solid Secondary Battery Equipped with Solid Electrolyte Layer>
Next, on the negative electrode active material layer of each all-solid secondary battery negative electrode sheet shown in the "negative electrode active material layer" column of Table 4, the all-solid secondary battery solid electrolyte shown in the "solid electrolyte layer" column of Table 4 The sheets were stacked so that the solid electrolyte layer was in contact with the negative electrode active material layer, and were transferred (laminated) by pressing with a press at a temperature of 25° C. and a pressure of 50 MPa. The obtained laminate was further pressed at a temperature of 25° C. and a pressure of 600 MPa to prepare a negative electrode sheet for an all-solid secondary battery having a solid electrolyte layer. In each sheet, the thickness of the solid electrolyte layer was 50 μm, and the thickness of the negative electrode active material layer was 75 μm.

[Test example: Measurement of battery resistance before and after bending]
<Bending test of negative electrode sheet for all-solid secondary battery>
A rectangular test piece having a width of 3 cm and a length of 14 cm was cut out from each negative electrode sheet for an all-solid secondary battery having the solid electrolyte layer. Using a cylindrical mandrel tester (product code 056, mandrel diameter 10 mm, manufactured by Allgood), the cut test piece is tested according to Japanese Industrial Standards (JIS) K5600-5-1 (flex resistance (cylindrical mandrel: type 2 ), the same test as International Standard (ISO) 1519). Then, the bent sheet was put back. This flexion and restoration was repeated 10 times. The test piece was set so that the solid electrolyte layer was on the opposite side of the mandrel (the substrate was on the mandrel side) and the width direction of the test piece was substantially parallel to the central axis of the mandrel.
In this way, a test piece subjected to the bending test was produced.

<Production of all-solid secondary battery>
The all-solid secondary battery consists of each negative electrode sheet for an all-solid secondary battery (hereinafter referred to as a non-flexible sheet) having a solid electrolyte layer that has not been subjected to the bending test, and a test piece that has undergone the bending test ( hereinafter referred to as a bending test piece).
That is, a disc-shaped negative electrode sheet with a diameter of 14.5 mm was cut out from each of the non-flexing sheet and the bending test piece, and as shown in FIG. 2032 type coin case 11. Next, a positive electrode sheet for an all-solid secondary battery (positive electrode active material layer and aluminum foil already peeled off) punched out with a diameter of 14.0 mm was overlaid on the solid electrolyte layer of this disk-shaped negative electrode sheet. A stainless steel foil (positive electrode current collector) is further overlaid on it, and the all-solid secondary battery laminate 12 (copper foil-negative electrode active material layer-solid electrolyte layer-positive electrode active material layer-stainless steel foil laminate ) was formed. Thereafter, the 2032-type coin case 11 was crimped to manufacture the coin-type all-solid-state secondary batteries 101 to 108 and c11 to c16 shown in FIG. The coin-type all-solid-state secondary battery 13 manufactured in this manner has the layer structure shown in FIG.
Note that the same battery No. The all-solid secondary battery represented by the same negative electrode sheet No. A set of batteries manufactured using a non-flexing sheet or a bending test piece derived from the negative electrode sheet for an all-solid secondary battery represented by is included.

<Evaluation of battery resistance>
As the battery characteristics of the all-solid secondary batteries 101 to 108 and c11 to c16, the battery resistance was measured for each set of batteries manufactured using the non-flexing sheet or the bending test piece, and the change rate of the battery resistance was evaluated.
The resistance of each all-solid secondary battery was evaluated with a charge/discharge evaluation device: TOSCAT-3000 (trade name, manufactured by Toyo System Co., Ltd.). Specifically, each all-solid secondary battery was charged to a battery voltage of 4.2 V at a current density of 0.1 mA/cm ² . After that, the battery was discharged at a current density of 0.2 mA/cm ² until the battery voltage reached 2.5V. This cycle of charging and discharging was repeated for 2 cycles, and the battery voltage was read after discharging at 5 mAh/g (amount of electricity per 1 g of active material mass) in the second cycle.
The same battery No. In one set of all-solid-state secondary batteries represented by, the rate of change in battery voltage ([resistance value of all-solid-state secondary battery manufactured using bending test piece / all-solid-state secondary battery manufactured using non-flexing sheet resistance value]×100 (%)), and the bending durability of the all-solid-state secondary battery was evaluated based on which of the following evaluation ranks this rate of change was included in as a rate of change in resistance.
In this test, the higher the evaluation rank, the higher the flexing durability of the constituent layers, and the deterioration of battery performance (increase in battery resistance) due to the flexing and restoration that act during the preparation of the constituent layers can be suppressed. . The passing level of this test is an evaluation rank of "3" or higher.

- Evaluation rank -
8: 100% ≤ resistance change rate < 101%
7: 101% ≤ resistance change rate < 105%
6: 105% ≤ resistance change rate < 108%
5: 108% ≤ resistance change rate < 110%
4: 110% ≤ resistance change rate < 115%
3: 115% ≤ resistance change rate < 118%
2: 118% ≤ resistance change rate < 120%
1: 120% ≤ resistance change rate

The results shown in Table 4 reveal the following.
That is, the binder-free inorganic solid electrolyte-containing composition containing a polymer that satisfies the 10-times tensile hysteresis loss specified in the present invention can be used to form the constituent layers of an all-solid secondary battery, and the all-solid secondary battery can be obtained. As for the battery, the battery voltage after charging and discharging in the second charging and discharging cycle is lowered, and a constituent layer having excellent bending durability cannot be realized. Therefore, an all-solid secondary battery having a constituent layer formed of this inorganic solid electrolyte-containing composition has a large increase in battery voltage.
On the other hand, an inorganic solid electrolyte-containing composition containing a binder containing a polymer that satisfies the 10-fold tensile hysteresis loss specified in the present invention is used to form the constituent layers of an all-solid secondary battery. It is possible to realize excellent bending durability in the layer, and an all-solid-state secondary battery using this can prevent a decrease in battery voltage even when the constituent layers are bent and restored, and can exhibit excellent battery performance. I understand.
In particular, when the binder contained in the inorganic solid electrolyte-containing composition is a binder containing a polymer that satisfies the 30-times tensile hysteresis loss, the tensile elastic modulus and the breaking elongation in addition to the 10-times tensile hysteresis loss, the flex resistance of the constituent layers It can be seen that it is possible to achieve a higher level of performance and the battery performance of the all-solid secondary battery.

While we have described our invention in conjunction with embodiments thereof, we do not intend to limit our invention in any detail to the description unless specified otherwise, which is contrary to the spirit and scope of the invention as set forth in the appended claims. I think it should be interpreted broadly.

This application claims priority based on Japanese Patent Application No. 2019-137624 filed in Japan on July 26, 2019, the contents of which are incorporated herein by reference. taken in 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 2032 Type Coin Case 12 All Solid Secondary Battery Laminate 13 Coin Type All-solid secondary battery

Claims (14)

An inorganic solid electrolyte-containing composition containing an inorganic solid electrolyte having ion conductivity of a metal belonging to Group 1 or Group 2 of the periodic table and a binder,
The binder contains a polymer having a tensile hysteresis loss of less than 40% in a stress-strain curve obtained by repeating tension and recovery ten times under the following measurement conditions in accordance with JIS K 7312-1996 , At least one bond selected from a urethane bond, a urea bond, an amide bond, an imide bond and an ester bond, and at least two polyether structures selected from a polyethyleneoxy chain, a polypropyleneoxy chain and a polytetramethyleneoxy chain. An inorganic solid electrolyte-containing composition having a chain, wherein the at least two polyether structures have a number average molecular weight of 400 or less .
<Measurement conditions>
Strip-shaped test piece: width 5 mm, length 50 mm, film thickness 80 μm
Distance between chucks: 30mm
Speed of tension and recovery: 3mm/min
Elongation: 10% The inorganic solid according to claim 1, wherein the polymer has a tensile hysteresis loss of less than 35% in a stress-strain curve obtained by repeating tension and recovery 30 times under the measurement conditions in accordance with JIS K 7312-1996. Electrolyte-containing compositions. 3. The inorganic solid electrolyte-containing composition according to claim 1, wherein said polymer has a tensile modulus of 400 MPa or more. The inorganic solid electrolyte-containing composition according to any one of claims 1 to 3, wherein the polymer has a breaking elongation of 300% or more. The polymer comprises 30 to 50 mol% of a component represented by the following formula (I-1), 4 to 10 mol% of a component represented by the following formula (I-3A), and the following formula (I-3B ) and 3 to 10 mol% of the constituent component represented by the following formula (I-3C), the inorganic solid electrolyte according to any one of claims 1 to 4. Containing composition.

In the formula, R ^P1 indicates a molecular chain having a molecular weight or a weight average molecular weight of 20 or more and 200,000 or less. R. ^P2A represents a chain composed of a low-molecular-weight hydrocarbon group and having at least one functional group selected from the following functional group group (I). R. ^P2B represents a polyalkyleneoxy chain (excluding the polyether structure). R. ^P2C indicates a hydrocarbon polymer chain.
<Functional group group (I)>
Carboxy groups, sulfonic acid groups, phosphoric acid groups, amino groups, hydroxy groups, sulfanyl groups, isocyanato groups, alkoxysilyl groups, and groups having three or more condensed ring structures The inorganic solid electrolyte-containing composition according to any one of claims 1 to 5, wherein the total content of the components containing the polyether structure is 10 to 60 mol%. The inorganic solid electrolyte-containing composition according to any one of claims 1 to 6, which contains an active material . 8. The composition containing an inorganic solid electrolyte according to claim 7, wherein said active material is an active material containing elemental silicon or elemental tin. The inorganic solid electrolyte-containing composition according to any one of claims 1 to 8, which contains a conductive aid. The inorganic solid electrolyte-containing composition according to any one of claims 1 to 9, wherein the inorganic solid electrolyte is a sulfide-based inorganic solid electrolyte. A sheet for an all-solid secondary battery having a layer composed of the inorganic solid electrolyte-containing composition according to any one of claims 1 to 10. An all-solid secondary battery comprising a positive electrode active material layer, a solid electrolyte layer and a negative electrode active material layer in this order,
At least one 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 inorganic solid electrolyte-containing composition according to any one of claims 1 to 10. Solid secondary battery. A method for producing a sheet for an all-solid secondary battery, comprising forming a film from the inorganic solid electrolyte-containing composition according to any one of claims 1 to 10. A method for manufacturing an all-solid secondary battery, comprising manufacturing an all-solid secondary battery through the manufacturing method according to claim 13 .

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