KR20220050191A - A composition containing an inorganic solid electrolyte, a sheet for an all-solid secondary battery, an electrode sheet for an all-solid secondary battery and an all-solid secondary battery, and a sheet for an all-solid secondary battery and a method for manufacturing an all-solid secondary battery - Google Patents

Abstract

An inorganic solid electrolyte-containing composition comprising an inorganic solid electrolyte and a specific compound (SA) having at least one specific functional group, a sheet for an all-solid secondary battery, an electrode sheet for an all-solid secondary battery, and an all-solid-state secondary battery using the inorganic solid electrolyte-containing composition A solid secondary battery, a sheet for an all-solid secondary battery, and a method for manufacturing an all-solid secondary battery are provided.

Description

A composition containing an inorganic solid electrolyte, a sheet for an all-solid secondary battery, an electrode sheet for an all-solid secondary battery and an all-solid secondary battery, and a sheet for an all-solid secondary battery and a method for manufacturing an all-solid secondary battery

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

In an all-solid-state secondary battery, all of the negative electrode, the electrolyte, and the positive electrode are made of a solid, and thus safety and reliability, which are problems of a battery using an organic electrolyte, can be greatly improved. It is also believed that it is possible to increase the lifespan. In addition, the all-solid-state secondary battery can have a structure in which an electrode and an electrolyte are directly arranged and arranged in series. Therefore, compared with the secondary battery using an organic electrolyte solution, high energy density-ization is attained, and application to an electric vehicle, a large storage battery, etc. is anticipated.

In such an all-solid secondary battery, as a material for forming the constituent layers (a solid electrolyte layer, a negative electrode active material layer, a positive electrode active material layer, etc.), a solid particle material such as an inorganic solid electrolyte, an active material, and a conductive aid is used. Therefore, in addition to the solid particulate material, materials such as a binder for binding the solid particulate material and a dispersing agent for dispersing in a dispersion medium are usually used as the material for forming such a constituent layer (constituent layer forming material).

For example, Patent Document 1 discloses a positive electrode active material, an inorganic solid electrolyte having ion conductivity of a metal belonging to Group 1 or 2 of the periodic table, a conductive auxiliary, and a dispersant comprising a compound having a specific functional group A material for a positive electrode containing Patent Document 2 discloses (A) an inorganic solid electrolyte having ionic conductivity of a metal belonging to Group 1 or Group 2 of the periodic table, (B) a fluorine-containing compound satisfying specific conditions at a specific content, (C ) a solid electrolyte composition containing a dispersion medium. Patent Document 3 describes a solid electrolyte composition comprising an inorganic solid electrolyte (A) having ion conductivity of a metal belonging to Group 1 or 2 of the periodic table, and a compound (B) represented by a specific formula as a polymer dispersant. has been

In addition, a material using a solid electrolyte surface-treated with a solid electrolyte in advance, rather than a material used in combination with an inorganic solid electrolyte or the like, as the constituent layer-forming material has also been proposed. For example, in Patent Document 4, a solution containing a solid electrolyte to be coated for a lithium battery in which the surface of a sulfide-based solid electrolyte containing at least lithium and phosphorus is coated with a fluorine-containing silane compound or a fluorine-containing acrylic resin, and a binder This is described.

Patent Document 1: International Publication No. 2016/194759 Patent Document 2: International Publication No. 2018/016544 Patent Document 3: International Publication No. 2016/136089 Patent Document 4: Japanese Patent Application Laid-Open No. 2010-033732

In a structural layer formed of a solid particle material (simply also referred to as solid particles), in general, interfacial contact between solid particles (for example, between inorganic solid electrolytes, between inorganic solid electrolytes and active materials, between active materials) The status is not good enough. In addition, when the constituent layers of the all-solid-state secondary battery, particularly the active material layer, expand and contract by charging and discharging (contraction and expansion of the active material according to the release and absorption of ions of metals belonging to Group 1 or Group 2 of the periodic table), solid particles The state of contact between each other gradually deteriorates. In particular, the (negative electrode) active material capable of forming an alloy with lithium exhibits high ionic conductivity and has been attracting attention in that it contributes to the improvement of basic battery performance. The contact state is significantly lowered. It is thought that such a fall of the contact state of solid particle|grains originates in the void generation|occurrence|production between solid particles in a constituent layer gradually, and not only raises the resistance of an all-solid-state secondary battery, but also reduces cycling characteristics.

An object of the present invention is to provide an inorganic solid electrolyte-containing composition capable of realizing a constituent layer capable of suppressing the generation of voids due to charging and discharging of an all-solid-state secondary battery by using it as a material for forming a constituent layer of an all-solid-state secondary battery. do. Further, the present invention provides a sheet for an all-solid secondary battery, an electrode sheet for an all-solid secondary battery, and an all-solid secondary battery using this inorganic solid electrolyte-containing composition, and a method for manufacturing an all-solid secondary battery sheet and an all-solid secondary battery make it a task

As a result of repeated various studies by the present inventors, an inorganic solid electrolyte-containing composition using a compound (SA) having a specific molecular structure and introducing a specific functional group in combination with the inorganic solid electrolyte is an all-solid-state secondary battery It has been found that by using as a material for forming a constituent layer of , the frictional resistance between solid particles is reduced and a constituent layer in which voids are less likely to occur during expansion and contraction of the constituent layer due to charging and discharging can be realized. In addition, it has been found that by employing the constituent layer formed of the inorganic solid electrolyte-containing composition as a sheet for an all-solid secondary battery or a constituent layer of an all-solid secondary battery, it is possible to lower the resistance and improve the cycle characteristics of the all-solid-state secondary battery. . The present invention has been further studied and completed based on these findings.

That is, the above problem was solved by the following means.

<1> Inorganic solid electrolyte containing an inorganic solid electrolyte having ion conductivity of a metal belonging to Group 1 or 2 of the periodic table, and at least one compound (SA) selected from the following (A) to (C) composition.

(A): the compound represented by the following formula (1)

Formula (1) R-A-X

In the formula (1), R represents an aliphatic hydrocarbon group having 6 or more carbon atoms that does not have a fluorine atom (provided that it does not include a steroid ring structure), or a group containing a fluorinated hydrocarbon group and a hydrocarbon group not having a fluorine atom. indicates. A represents a divalent linking group containing no aromatic ring structure. X represents a functional group represented by the following functional group group (I).

(B): perfluoropolyether, polychlorotrifluoroethylene or polytetrafluoroethylene having at least one functional group among the functional groups included in the following functional group group (I)

(C): organopolysiloxane having at least one functional group among the functional groups included in the following functional group group (I)

<Functional group (I)>

An acidic group, a group having a basic nitrogen atom, an amide group, a urea group, a urethane group, an alkoxysilyl group, an epoxy group, an isocyanate group, a hydroxyl group, or a (meth)acryloyloxy group

<2> Ratio of the content [SE] of the inorganic solid electrolyte and the total content [SA] of the compound (SA) in 100 mass % of the solid content of the composition containing the inorganic solid electrolyte: [SA]/[SE] is 0.0003 to 0.11 Phosphorus, the inorganic solid electrolyte-containing composition according to <1>.

<3> The inorganic solid electrolyte-containing composition according to <1> or <2>, comprising a polymer binder.

<4> Ratio of content [BR] of polymer binder and total content of compound (SA) [SA] in 100 mass % of solid content of the inorganic solid electrolyte-containing composition: [BR]/[SA] of 0.2 to 5 , the inorganic solid electrolyte-containing composition according to <3>.

<5> The inorganic solid electrolyte-containing composition according to any one of <1> to <4>, comprising an active material.

<6> The inorganic solid electrolyte-containing composition according to <5>, wherein the active material is an active material containing elemental silicon or elemental tin.

<7> The inorganic solid electrolyte-containing composition according to any one of <1> to <6>, wherein the compound (SA) contains a compound represented by Formula (1).

<8> The inorganic solid electrolyte-containing composition according to any one of <1> to <7>, wherein the inorganic solid electrolyte is a sulfide-based inorganic solid electrolyte.

<9> The inorganic solid electrolyte-containing composition according to any one of <1> to <8>, comprising a dispersion medium.

<10> The inorganic solid electrolyte-containing composition according to any one of <1> to <9>, wherein the dispersion medium is selected from a ketone compound, an aliphatic compound, and an ester compound.

<11> 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 <10>.

<12> An electrode sheet for an all-solid secondary battery having an active material layer composed of the inorganic solid electrolyte-containing composition according to <5> or <6>.

<13> An all-solid-state secondary battery comprising a positive electrode active material layer, a solid electrolyte layer, and a negative electrode active material layer in this order,

An all-solid-state secondary battery, wherein at least one 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 <10>.

<14> A method for producing a sheet for an all-solid-state secondary battery, wherein the composition containing the inorganic solid electrolyte according to any one of <1> to <10> is formed into a film.

<15> The manufacturing method of an all-solid-state secondary battery, which manufactures an all-solid-state secondary battery through the manufacturing method as described in said <14>.

When the inorganic solid electrolyte-containing composition of the present invention is used as a material for forming a constituent layer of an all-solid-state secondary battery, it is possible to realize a constituent layer capable of suppressing the generation of voids due to charging and discharging of the all-solid-state secondary battery. Moreover, the all-solid-state secondary battery which shows low resistance and excellent cycling characteristics can be implement|achieved by using the sheet|seat for all-solid-state secondary batteries and the electrode sheet for all-solid-state secondary batteries of this invention as a structural layer of an all-solid-state secondary battery. In addition, the all-solid-state secondary battery of the present invention exhibits low resistance and excellent cycle characteristics.

Moreover, each manufacturing method of the sheet|seat for all-solid-state secondary batteries of this invention and an all-solid-state secondary battery can manufacture the sheet|seat for all-solid-state secondary batteries and all-solid-state secondary batteries which show the outstanding characteristic mentioned above.

The above and other features and advantages of the present invention will become more apparent from the following description with reference to the accompanying drawings as appropriate.

1 is a longitudinal cross-sectional view schematically showing an all-solid-state secondary battery according to a preferred embodiment of the present invention.
2 is a longitudinal cross-sectional view schematically showing an all-solid-state secondary battery (coin battery) manufactured in Examples.

In the present invention, the numerical range indicated using “to” means a range including the numerical values before and after “to” as the lower limit and the upper limit.

In the present invention, the expression of a compound (for example, when referring to a compound at the end) is used in a sense including the compound itself, its salt, and its ion. 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 methacrylic. It is the same also about (meth)acrylate.

In this invention, about a substituent, a coupling group, etc. which do not specify substitution or unsubstitution (henceforth a substituent etc.), it means that you may have an appropriate substituent for the group. Therefore, in the present invention, even when simply described as a YYY group, the YYY group includes, in addition to the aspect not having a substituent, an aspect having a substituent further. This has the same meaning for a compound that does not specify substitution or unsubstitution. As a preferable substituent, the substituent Z mentioned later is mentioned, for example.

In the present invention, when a plurality of substituents and the like indicated by a specific symbol exist, or when a plurality of substituents are defined simultaneously or alternatively, each of the substituents and the like may be the same as or different from each other. Moreover, even if it is a case where it is not specifically demonstrated, when a some substituent etc. are adjacent, it is the meaning which may form a ring by mutually connecting or condensed ring.

In this invention, although polymer means a polymer, it has the same meaning as what is called a high molecular compound. In addition, the polymer binder (simply referred to as a binder) means a binder composed of a polymer, and includes the polymer itself and a binder formed including the polymer.

[Composition containing inorganic solid electrolyte]

The inorganic solid electrolyte-containing composition of the present invention comprises an inorganic solid electrolyte having ion conductivity of a metal belonging to Group 1 or Group 2 of the periodic table, and at least one compound selected from (A) to (C) described below (SA) ) contains

In the inorganic solid electrolyte-containing composition of the present invention, the state of content of the inorganic solid electrolyte and the compound (SA) is not particularly limited, and even if the solid particles such as the inorganic solid electrolyte and the compound (SA) are independently present (dispersed) do. That is, although the compound (SA) may or may not adsorb|suck or adhere to the surface of a solid particle, it is preferable that it adsorb|sucks or adheres.

The inorganic solid electrolyte-containing composition of the present invention can form a constituent layer that does not easily generate voids even after repeated charging and discharging of an all-solid-state secondary battery, and an active material layer that expands and contracts during charging and discharging, particularly a negative electrode active material with large expansion and contraction Generation|occurrence|production of a space|gap can be suppressed also about a layer, and the desired contact state of solid particles can be maintained. An all-solid-state secondary battery having such a structural layer can realize low resistance and improved cycle characteristics by using the inorganic solid electrolyte-containing composition of the present invention as a structural layer-forming material of the all-solid-state secondary battery.

The above-mentioned effects are realized by using the compound (SA) described later in combination with the inorganic solid electrolyte in the inorganic solid electrolyte-containing composition of the present invention in combination. Although the details of the reason are not yet clear, it thinks as follows.

That is, in the constituent layer formed of the inorganic solid electrolyte-containing composition, the compound (SA) used in combination with solid particles such as an inorganic solid electrolyte (further, coexistable active material and conductive aid) is a functional group of the solid particles ( In particular, inorganic solid electrolyte), usually adhered or adsorbed to the surface. The solid particles adsorbed by the compound (SA), etc., by the interposition of the compound (SA), with respect to other solid particles located in the vicinity (for example, inorganic solid electrolytes, inorganic solid electrolytes and active materials, active materials) It shows high sliding property (slip property) (it shows small surface frictional resistance). As a result, it is considered that the desired contact state between solid particles can be maintained even by expansion and contraction of the constituent layer.

For example, if the active material layer is specifically described, the active material layer expanded by charging of the all-solid-state secondary battery migrates so that the solid particles do not generate voids due to discharge and contracts in a high-density state. Since an all-solid-state secondary battery is normally pressurized, the shrinkage|contraction with respect to a dense active material layer is encouraged. Such shrinkage of the dense active material layer can be repeatedly realized as long as the compound (SA) is interposed between the solid particles.

As described above, the constituent layer containing the compound (SA) can suppress the generation of voids due to charging and discharging of the all-solid-state secondary battery, particularly the voids during shrinkage, and as a result, the all-solid-state secondary battery is charged. Even if it discharges, the desired contact state of solid particles can be maintained. For this reason, the all-solid-state secondary battery provided with the structural layer formed from the inorganic solid electrolyte containing composition of this invention can make low-resistance reduction and cycling characteristics compatible at a high level.

Although detailed later, the said effect of this invention becomes more excellent when a polymer binder is used together, especially an inorganic solid electrolyte, the said compound (SA), and a polymer binder are used together in a specific content ratio.

The inorganic solid electrolyte-containing composition of the present invention is a sheet for an all-solid-state secondary battery (including an electrode sheet for an all-solid-state secondary battery) or as a material for forming a solid electrolyte layer or an active material layer of an all-solid secondary battery (composition layer forming material) It can be used preferably. In particular, it can be preferably used as a material for forming a negative electrode sheet for an all-solid secondary battery or a negative electrode active material layer containing a negative electrode active material having a large expansion and contraction due to charging and discharging, and in this aspect, while exhibiting a high active material capacity, low resistance and High cycle characteristics can be achieved.

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, in addition to the aspect that does not contain water, an aspect in which the moisture content (also referred to as water content) is preferably 500 ppm or less. In the non-aqueous composition, the moisture 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 represents the amount of water contained in the inorganic solid electrolyte-containing composition (mass ratio with respect to the inorganic solid electrolyte-containing composition), specifically, a value measured by filtration through a 0.02 μm membrane filter and using Karl Fischer titration do it with

The inorganic solid electrolyte-containing composition of the present invention also includes an embodiment in which an active material, furthermore, a conductive support agent, etc., is included in addition to the inorganic solid electrolyte (the composition of this embodiment is referred to as a composition for electrodes).

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

<Inorganic solid electrolyte>

The inorganic solid electrolyte-containing composition of the present invention contains an inorganic solid electrolyte.

In the present invention, the inorganic solid electrolyte is an inorganic solid electrolyte, and the solid electrolyte is a solid electrolyte capable of moving ions therein. Since the main ion-conducting material does not contain organic substances, organic solid electrolytes (polyelectrolytes such as polyethylene oxide (PEO), etc., lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), etc.) electrolyte salts) are clearly distinguished. In addition, since the inorganic solid electrolyte is solid in a steady state, it is not normally dissociated or liberated into cations and anions. In this respect, it is clearly distinguished from inorganic electrolyte salts (LiPF ₆ , LiBF ₄ , lithium bis(fluorosulfonyl)imide (LiFSI), LiCl, etc.) . The inorganic solid electrolyte is not particularly limited as long as it has ion conductivity of a metal belonging to Group 1 or 2 of the periodic table, and generally does not have electron conductivity. When the all-solid-state 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 usually used for an all-solid secondary battery can be appropriately selected and used. Examples of the inorganic solid electrolyte include (i) a sulfide-based inorganic solid electrolyte, (ii) an oxide-based inorganic solid electrolyte, (iii) a halide-based inorganic solid electrolyte, and (iv) a hydride-based inorganic solid electrolyte. A sulfide-based inorganic solid electrolyte is preferable from the viewpoint of being able to form a better interface between the active material and the inorganic solid electrolyte.

(i) sulfide-based inorganic solid electrolyte

The sulfide-based inorganic solid electrolyte preferably contains a sulfur atom, has ion conductivity of a metal belonging to Group 1 or Group 2 of the periodic table, and has electronic insulation properties. The sulfide-based inorganic solid electrolyte preferably contains at least Li, S and P as elements and has lithium ion conductivity, but may contain elements other than Li, S and P depending on the purpose or case.

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

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

In the formula, L represents an element selected from Li, Na and K, and Li is preferable. M represents an element selected from B, Zn, Sn, Si, Cu, Ga, Sb, Al, and Ge. A represents an element selected from I, Br, Cl and F. a1 to e1 represent the compositional ratio of each element, and a1:b1:c1:d1:e1 satisfies 1 to 12:0 to 5:1:2 to 12:0 to 10. 1-9 are preferable and, as for a1, 1.5-7.5 are more preferable. 0-3 are preferable and, as for b1, 0-1 are more preferable. 2.5-10 are preferable and, as for d1, 3.0-8.5 are more preferable. 0-5 are preferable and, as for e1, 0-3 are more preferable.

The composition ratio of each element can be controlled by adjusting the compounding quantity of the raw material compound at the time of manufacturing a sulfide type inorganic solid electrolyte as follows.

The sulfide-based inorganic solid electrolyte may be amorphous (glass) or crystallized (glass-ceramics), or may be partially crystallized. For example, Li-P-S-based glass containing Li, P and S, or Li-P-S-based glass ceramics containing Li, P and S can be used.

The sulfide-based inorganic solid electrolyte is, for example, lithium sulfide (Li ₂ S), phosphorus sulfide (eg, diphosphorus pentasulfide (P ₂ S ₅ )), simple phosphorus, single sulfur, sodium sulfide, hydrogen sulfide , lithium halide (eg, LiI, LiBr, LiCl) and the sulfide of the element represented by M (eg, SiS ₂ , SnS, GeS ₂ ) It can be prepared by reaction of at least two or more raw materials.

In Li-PS-based glass and Li-PS-based glass ceramics, the ratio of Li ₂ S and P ₂ S ₅ is the molar ratio of Li ₂ S:P ₂ S ₅ , preferably 60:40 to 90:10. , More preferably 68:32 to 78:22. By making the ratio of Li ₂ S and P ₂ S ₅ into this range, lithium ion conductivity can be made high. Specifically, the lithium ion conductivity may be preferably 1×10 ⁻⁴ S/cm or more, more preferably 1×10 ⁻³ S/cm or more. Although there is no particular upper limit, it is practical that it is 1x10 ^-1 S/cm or less.

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

(ii) oxide-based inorganic solid electrolyte

The oxide-based inorganic solid electrolyte preferably contains an oxygen atom, has ion conductivity of a metal belonging to Group 1 or Group 2 of the periodic table, and has electronic insulation properties.

The oxide-based inorganic solid electrolyte has an ionic conductivity of preferably 1×10 ^-6 S/cm or more, more preferably 5×10 ^-6 S/cm or more, and particularly preferably 1×10 ^-5 S/cm or more. Do. Although the upper limit is not particularly limited, it is practical that it is 1×10 ⁻¹ S/cm or less.

Specific examples of the compound include, for example, Li _xa La _ya TiO _{3 [} xa satisfies 0.3≤xa≤0.7, and ya satisfies 0.3≤ya≤0.7] (LLT); Li _xb La _yb Zr _zb M ^bb _mb O _nb (M ^bb is at least one element selected from Al, Mg, Ca, Sr, V, Nb, Ta, Ti, Ge, In, and Sn. xb is 5≤xb ≤10, yb satisfies 1≤yb≤4, zb satisfies 1≤zb≤4, mb satisfies 0≤mb≤2, and nb satisfies 5≤nb≤20. ); Li _xc B _yc M ^cc _zc O _nc (M ^cc is at least one element selected from C, S, Al, Si, Ga, Ge, In and Sn. xc satisfies 0<xc≤5, and yc is 0<yc≤1 satisfies, 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 is 0≤zd≤2 , ad satisfies 0≤ad≤1, md satisfies 1≤md≤7, and nd satisfies 3≤nd≤13); Li _(3-2xe) M ^ee _xe D ^ee O (xe represents a number from 0 to 0.1, and M ^ee represents a divalent metal atom. D ^ee represents a halogen atom or a combination of two or more halogen atoms. indicates); Li _xf Si _yf O _zf (xf satisfies 1≤xf≤5, yf satisfies 0<yf≤3, and zf satisfies 1≤zf≤10); Li _xg S _yg O _zg (xg satisfies 1≤xg≤3, yg satisfies 0<yg≤2, and zg satisfies 1≤zg≤10); Li ₃ BO ₃ ; Li ₃ BO ₃ -Li ₂ SO ₄ ; Li ₂ OB ₂ O ₃ —P ₂ O ₅ ; Li ₂ O—SiO ₂ ; Li ₆ BaLa ₂ Ta ₂ O ₁₂ ; Li ₃ PO _(4-3/2w) N _w (w is w<1); Li _3.5 Zn _0.25 GeO ₄ having a LISICON (Lithium super ionic conductor) type crystal structure; La _0.55 Li _0.35 TiO ₃ having a perovskite crystal structure; LiTi ₂ P ₃ O ₁₂ having a Natrium super ionic conductor (NASICON) 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, yh satisfies 0≤yh≤1 .); Li ₇ La ₃ Zr ₂ O ₁₂ (LLZ) having a garnet-type crystal structure, and the like.

Moreover, the phosphorus compound containing Li, P and O is also preferable. lithium phosphate (Li ₃ PO ₄ ); LiPON in which a part of oxygen in lithium phosphate is substituted with nitrogen; LiPOD ¹ (D ¹ is, preferably, one or more selected from Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zr, Nb, Mo, Ru, Ag, Ta, W, Pt and Au element.) and the like.

Further, LiA ¹ ON (A ¹ is at least one element selected from Si, B, Ge, Al, C, and Ga.) and the like can also be preferably used.

(iii) halide-based inorganic solid electrolyte

The halide-based inorganic solid electrolyte is preferably a compound containing a halogen atom, having ion conductivity of a metal belonging to Group 1 or Group 2 of the periodic table, and having electronic insulating properties.

Although it does not restrict|limit especially as a halide-type inorganic solid electrolyte, For example, LiCl, LiBr, LiI, ADVANCED MATERIALS, 2018, ₃₀ , _Li3YBr6 , _Li3YCl6 Compounds, such as described in _1803075 , are mentioned. . 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 is preferably a compound that contains a hydrogen atom, has ion conductivity of a metal belonging to Group 1 or 2 of the periodic table, and has electronic insulation properties.

Although it does not restrict|limit especially as a hydride _- type inorganic solid electrolyte, For example, LiBH4, Li4 ₍ BH4) _3I , _{3LiBH4 -} LiCl, etc. are mentioned.

The inorganic solid electrolyte is preferably particles. In this case, although the particle diameter (volume average particle diameter) in particular of an inorganic solid electrolyte is not restrict|limited, It is preferable that it is 0.01 micrometer or more, and it is more preferable that it is 0.1 micrometer or more. As an upper limit, it is preferable that it is 100 micrometers or less, and it is more preferable that it is 50 micrometers or less.

The measurement of the particle diameter of the inorganic solid electrolyte is performed in the following procedure. The inorganic solid electrolyte particles are prepared by diluting a 1 mass % dispersion in a 20 mL sample bottle using water (heptane in the case of a substance unstable to water). The dispersion liquid sample after dilution is irradiated with 1 kHz ultrasonic wave for 10 minutes, and is used for a test immediately after that. Using this dispersion sample, using a laser diffraction/scattering particle size distribution analyzer LA-920 (trade name, manufactured by HORIBA), data retrieval was performed 50 times using a quartz cell for measurement at a temperature of 25°C, and the volume average particle diameter to get For other detailed conditions, etc., if necessary, refer to the description of Japanese Industrial Standards (JIS) Z 8828:2013 "Particle diameter analysis-dynamic light scattering method". 5 samples per level are produced and the average value is adopted.

The inorganic solid electrolyte may contain 1 type, and may contain 2 or more types.

In the case of forming the solid electrolyte layer, the mass (mg) (weight per unit area) of the inorganic solid electrolyte per unit area (cm ² ) of the solid electrolyte layer is not particularly limited. According to the designed battery capacity, it can determine suitably, for example, it can be set as 1-100 mg/cm< ² >.

However, when the inorganic solid electrolyte containing composition contains the active material mentioned later, it is preferable that the total amount of an active material and an inorganic solid electrolyte is the said range as for the weight per unit area of an inorganic solid electrolyte.

The content of the inorganic solid electrolyte in the composition containing the inorganic solid electrolyte is not particularly limited, but from the viewpoint of binding properties and further dispersibility, in 100% by mass of solid content, it is preferably 50% by mass or more, and 70% by mass or more It is more preferable, and it is especially preferable that it is 90 mass % or more. As an upper limit, from the same viewpoint, it is preferable that it is 99.9 mass % or less, It is more preferable that it is 99.5 mass % or less, It is especially preferable that it is 99 mass % or less.

However, when the inorganic solid electrolyte-containing composition contains an active material to be described later, the content of the inorganic solid electrolyte in the inorganic solid electrolyte-containing composition is preferably within the above range of the total content of the active material and the inorganic solid electrolyte.

In the present invention, 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. under a nitrogen atmosphere under an atmospheric pressure of 1 mmHg for 6 hours. Typically, components other than the dispersion medium mentioned later are pointed out.

<Compound (SA)>

The inorganic solid electrolyte-containing composition of the present invention contains any one or more of the following compounds (A) to (C) as the specific compound (SA).

(A): The compound represented by Formula (1) mentioned later

(B): perfluoropolyether, polychlorotrifluoroethylene, polytetrafluoroethylene having at least one functional group among the functional groups included in the following functional group group (I)

(C): organopolysiloxane having at least one functional group among the functional groups included in the following functional group group (I)

In the present invention, the compound included in (A), (B) or (C) is sometimes referred to as a compound group (A), (B) or (C) for convenience.

The compound (SA) contained in the inorganic solid electrolyte-containing composition of the present invention may be one or more, for example, one to three. In the case of containing two or more, it may be selected from the same compound group (any one of (A)-(C)), and may be selected from the different compound group.

As described above, each of the compounds of (A) to (C) below exhibits a common effect of suppressing the generation of voids due to charging and discharging of an all-solid-state secondary battery by being used in combination with an inorganic solid electrolyte in the constituent layer. . A compound (A) is preferable at the point which is excellent in this effect.

The functional group contained in the compound (SA) is at least one of the functional groups included in the following functional group group (I). The functional group included in the following group (I) has a property of interacting with and adsorbing an inorganic solid electrolyte, an active material, and furthermore a conductive aid. Although this interaction is not particularly limited, for example, one by hydrogen bonding, one by acid-base ionic bond, one by covalent bond, one by π-π interaction by aromatic rings, Or the thing by a minority-minority interaction, etc. are mentioned. When these functional groups interact, the chemical structure of the functional group may or may not change. For example, in the ?-? interaction or the like, the functional group usually does not change and maintains the structure as it is. On the other hand, in the interaction by a covalent bond etc., active hydrogens, such as a carboxylic acid group, normally become an anion from which it escaped (a functional group changes), and couple|bonds with solid particle.

The number of functional groups in one molecule of the compound is not particularly limited as long as it is one or more, and is appropriately set. For example, the number of the functional groups which a compound (A) has can be made into 1-6 pieces, and 1 or 2 pieces are more preferable. The number of functional groups in the compound (B) and the compound (C) cannot be determined unequivocally depending on the polymer structure, for example, can be 1 to 100, and the compound (B) is 1 or two are preferred.

<Functional group (I)>

An acidic group, a group having a basic nitrogen atom, an amide group, a urea group, a urethane group, an alkoxysilyl group, an epoxy group, an isocyanate group, a hydroxyl group, or a (meth)acryloyloxy group

It does not restrict|limit especially as an acidic group, For example, a carboxylic acid group (-COOH), a sulfonic acid group (sulfo group: -SO ₃ H), a phosphoric acid group (phospho group: -OPO(OH) ₂ ), a phosphonic acid group, and phosphonic acid group A fin acid group is mentioned, A carboxylic acid group is preferable.

Examples of the group having a basic nitrogen atom include an amino group, a pyridyl group, an imino group, and an amidine group (-C(=NR)-NR ₂ ). The amino group has the same meaning as the amino group of the substituent Z described later, but an unsubstituted amino group or an alkylamino group is preferable. Three R of the amidine group each represents a hydrogen atom or a substituent (for example, a group selected from the substituent Z described later).

Examples of the urea group include -NR ¹⁵ CONR ¹⁶ R ¹⁷ (here, R ¹⁵ , R ¹⁶ and R ¹⁷ are a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 or more carbon atoms, or an aralkyl group having 7 or more carbon atoms. shown.) is mentioned as a preferable example. The urea group is more preferably -NR ¹⁵ CONHR ¹⁷ (herein, R ¹⁵ and R ¹⁷ represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 or more carbon atoms, or an aralkyl group having 7 or more carbon atoms.) ^-NHCONHR17 (here, ^R17 represents a hydrogen atom or a C1-C10 alkyl group, a C6 or more aryl group, and a C7 or more aralkyl group.) is especially preferable.

Examples of the urethane group include -NHCOOR ¹⁸ , -NR ¹⁹ COOR ²⁰ , -OCONHR ²¹ , -OCONR ²² R ²³ (wherein R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² and R ²³ are A group containing at least an imino group and a carbonyl group, such as an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 or more carbon atoms, and an aralkyl group having 7 or more carbon atoms), is mentioned as a preferable example. As the urethane group, -NHCOOR ¹⁸ , -OCONHR ²¹ (here, R ¹⁸ and R ²¹ represent an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 or more carbon atoms, or an aralkyl group having 7 or more carbon atoms.) etc. are more preferable; -NHCOOR ¹⁸ and -OCONHR ²¹ (here, R ¹⁸ and R ²¹ represent an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 or more carbon atoms, or an aralkyl group having 7 or more carbon atoms.) and the like are particularly preferable.

Although it does not restrict|limit especially as an amide group, For example, -CONR ¹⁶ R ¹⁷ , -NR ¹⁵ -COR ¹⁸ (R ¹⁵ to R ¹⁸ are the same as above.) A carbonyl group, such as an amino group, or an imino group The group is mentioned as a preferable example. As an amide group, -NR ¹⁵ -COR ¹⁸ is preferable, and -NHCOR ¹⁸ is more preferable.

It does not restrict|limit especially as an alkoxysilyl group, A mono-, di- or tri- alkoxysilyl group is mentioned, Preferably a C1-C20 alkoxysilyl group is mentioned, More preferably, a C1-C6 alkoxysilyl group is mentioned. For example, each group illustrated by methoxysilyl, ethoxysilyl, t-butoxysilyl, cyclohexyl silyl, and also the substituent Z mentioned later is mentioned.

Examples of the (meth)acryloyloxy group include acryloyloxy and methacryloyloxy.

The acidic group, the group which has a basic nitrogen atom, a hydroxyl group, etc. may form the salt.

An acidic group, an alkoxysilyl group, an amide group, a urea group, a urethane group, or an epoxy group is preferable, and, as for the functional group which a compound (SA) has, an acidic group is more preferable.

A compound (A) is a compound represented by following (1).

Formula (1) R-A-X

In the formula (1), R represents an aliphatic hydrocarbon group having 6 or more carbon atoms that does not have a fluorine atom (provided that it does not include a steroid ring structure), or a group containing a fluorinated hydrocarbon group and a hydrocarbon group not having a fluorine atom. indicates. A represents a divalent linking group containing no aromatic ring structure. X represents the functional group represented by the said functional group group (I).

R is an aliphatic hydrocarbon group having 6 or more carbon atoms that does not have a fluorine atom (however, it does not include a steroid ring structure.) The group in any one of the forms (referred to as a 2nd form for convenience) which takes the group containing a hydrocarbon group is taken.

In the first aspect, R is an aliphatic hydrocarbon group. Thereby, interaction between the solid particles adsorbed by the compound (SA) in the constituent layer with respect to other solid particles existing in the vicinity thereof is reduced, and frictional resistance between the solid particles can be reduced.

The aliphatic hydrocarbon group employable as R is not particularly limited, and may be an aliphatic saturated hydrocarbon group (alkyl group) or an aliphatic unsaturated hydrocarbon group (alkenyl group, alkynyl group). Among these, an alkyl group or an alkenyl group is preferable, and an alkyl group is more preferable.

Moreover, linear or branched form may be sufficient as an aliphatic hydrocarbon group, and cyclic|annular form may be sufficient as it, and may contain a cyclic structure in part. However, this aliphatic hydrocarbon group does not contain the steroid ring structure (steroid skeleton) shown below. The term "not including a steroid ring structure" means that the aliphatic hydrocarbon group does not contain a steroid ring structure in its structure, and that the aliphatic hydrocarbon group itself is not a group of a steroid ring structure. It is preferable that an aliphatic hydrocarbon group does not contain a cyclic structure, and an acyclic hydrocarbon group (linear or branched hydrocarbon group) is more preferable. As an aspect in which the aliphatic hydrocarbon group does not contain a cyclic structure, the aspect which does not contain a condensed ring structure, Preferably it is bicyclic or more, More preferably, it is three or more rings is also mentioned. This condensed ring structure may be aliphatic or aromatic.

From the point of reduction of the frictional resistance with respect to solid particle|grains, linear or branched form is preferable, and, as for the aliphatic hydrocarbon group, linear form is more preferable.

[Formula 1]

Carbon number of an aliphatic hydrocarbon group is 6 or more, 8 or more are preferable, 12 or more are more preferable, and 18 or more are more preferable from the point of the reduction of the frictional resistance of a solid particle, and cycling characteristics. On the other hand, the upper limit in particular of carbon number is although it does not restrict|limit, 30 or less are preferable, 25 or less are more preferable, and 22 or less are still more preferable.

The number of carbon atoms in the aliphatic hydrocarbon group means the number of carbon atoms constituting the aliphatic hydrocarbon group, and when the aliphatic hydrocarbon group has a substituent, the number of carbon atoms constituting the substituent is not included. However, when the aliphatic hydrocarbon group is a branched hydrocarbon group, the number of carbon atoms constituting the branched chain is included (eg, in the case of a 2-ethylhexyl group, the number of carbon atoms is 8).

Although the aliphatic hydrocarbon group may have a substituent, it does not have a fluorine atom and a steroid ring structure as a substituent. The substituent which the aliphatic hydrocarbon group may have is not particularly limited as long as the effect of the present invention is not impaired. For example, the substituent Z mentioned later is mentioned, Groups other than the functional group contained in the said functional group group (I), and groups other than an aryl group are preferable. That is, it is preferable that the aliphatic hydrocarbon group does not have a functional group contained in the functional group group (I) as a substituent, an aryl group, or a group containing these.

In the second aspect, as the group containing a fluorinated hydrocarbon group and a hydrocarbon group not having a fluorine atom, which can be employed as R, a group consisting of a fluorinated hydrocarbon group and a hydrocarbon group not having a fluorine atom, and further other than these groups and both forms of groups comprising other groups of groups (ie, groups other than fluorohydrocarbon groups and other groups other than hydrocarbon groups having no fluorine atom). Another group is usually bonded between a fluorinated hydrocarbon group and a hydrocarbon group having no fluorine atom. It does not restrict|limit especially as another group, A linking group which can be employ|adopted as A mentioned later is mentioned. In this invention, the group which consists of a fluorohydrocarbon group and the hydrocarbon group which does not have a fluorine atom is preferable.

The hydrocarbon group before fluorination and the hydrocarbon group not having a fluorine atom constituting the fluorinated hydrocarbon group are not particularly limited, and may be an aromatic hydrocarbon group, but are preferably an aliphatic hydrocarbon group. Thereby, the frictional resistance of solid particles can be reduced.

This aliphatic hydrocarbon group is not restrict|limited in particular, An aliphatic saturated hydrocarbon group may be sufficient, and an aliphatic unsaturated hydrocarbon group may be sufficient as it. Among these, an alkyl group or an alkenyl group is preferable, and an alkyl group is more preferable. Further, the aliphatic hydrocarbon group may be linear, branched, or cyclic, and may include a cyclic structure in a part, but is preferably linear or branched, and more preferably linear. The aliphatic hydrocarbon group in a 2nd aspect may contain the steroid ring structure.

The fluorinated hydrocarbon group in the second aspect is a fluorinated hydrocarbon group, and the number of carbon atoms is not particularly limited. The number of carbon atoms in the fluorohydrocarbon group can be, for example, 1 or more, and 2 or more are preferable, and 4 or more are more preferable from the viewpoint of reduction of frictional resistance of solid particles, low resistance, and cycle characteristics, 5 or more are more preferable. On the other hand, although the upper limit in particular of carbon number is not restrict|limited, 20 or less are preferable, 15 or less are more preferable, and 8 or less are still more preferable.

In the fluorinated hydrocarbon group, all the hydrogen atoms of the hydrocarbon group before fluorination may be substituted with fluorine atoms (perfluorohydrocarbon group), or a part thereof may be substituted with fluorine atoms. In this invention, a perfluoro hydrocarbon group is preferable at the point which can reduce the frictional resistance of solid particle effectively. In addition, when a part of hydrogen atoms is substituted by the fluorine atom, the remaining hydrogen atoms may be substituted by substituents other than a fluorine atom.

The hydrocarbon group which does not have a fluorine atom in a 2nd aspect should just be a hydrocarbon group other than a fluorinated hydrocarbon group, and although it may have a substituent, a hydrocarbon group (unsubstituted hydrocarbon group) which does not have a substituent is preferable. . The number of carbon atoms in the hydrocarbon group having no fluorine atom can be, for example, 1 or more, and 2 or more are preferable from the viewpoints of reduction of frictional resistance of solid particles, low resistance, and cycle characteristics. On the other hand, although the upper limit in particular of carbon number is not restrict|limited, 20 or less are preferable, 10 or less are more preferable, and 6 or less are still more preferable.

The combination in particular of the hydrocarbon group which does not have a fluorine atom in a 2nd aspect is not restrict|limited, The combination of the above-mentioned preferable things is mentioned. Among them, both the hydrocarbon group and the hydrocarbon group not having a fluorine atom constituting the fluorinated hydrocarbon group are preferably aliphatic hydrocarbon groups, more preferably alkyl groups, more preferably linear or branched alkyl groups, It is especially preferable that it is a linear alkyl group.

In the second aspect, the bonding mode between the fluorinated hydrocarbon group and the hydrocarbon group not having a fluorine atom is not particularly limited, and the other hydrocarbon group is bonded as a side chain of one hydrocarbon group (for example, as a whole, branched chain form) Although a hydrocarbon group may be formed), it is preferable to couple|bond in linear form (preferably to form a linear hydrocarbon group as a whole). Moreover, although any hydrocarbon group may couple|bond with the coupling group A of said Formula (1), from the point of reduction of the frictional resistance of solid particles, the hydrocarbon group which does not have a fluorine atom couple|bonds with the coupling group A, and a fluorohydrocarbon group is terminal. It is desirable to be (free).

The total number of carbon atoms as a group containing a fluorinated hydrocarbon group and a hydrocarbon group not having a fluorine atom is appropriately determined within the range of the total number of carbon atoms that a fluorinated hydrocarbon group and a hydrocarbon group not having a fluorine atom can take, preferably , has the same meaning as the range of carbon number of the aliphatic hydrocarbon group in the first aspect. In the present invention, the meaning of the total number of carbon atoms is the same as the meaning of the carbon number of the aliphatic hydrocarbon group in the first aspect, and does not include the number of carbon atoms constituting the substituent.

In the present invention, the hydrocarbon group may contain one or more heteroatoms (atoms other than a carbon atom and other than a hydrogen atom, for example, an oxygen atom, a sulfur atom, a nitrogen atom, and a silicon atom) in the molecular chain. However, it is one of the preferable aspects that it does not contain.

A in Formula (1) represents the divalent coupling group which does not contain an aromatic ring structure, and it is preferable that it is an aliphatic group.

Although it does not restrict|limit especially as a linking group which can be taken as A, For example, an alkylene group (C1-C20 is preferable, 1-12 are more preferable, and 1-6 are still more preferable), an alkenylene group ( 2-18 are preferable, as for carbon number, 2-10 are more preferable, 2-6 are still more preferable), an oxygen atom, a sulfur atom, an imino group (-NR ^N -), a carbonyl group, a phosphoric acid linking group (-OP ( OH)(O)-O-), a phosphonic acid linking group (-P(OH)(O)-O-), or a group relating to a combination thereof.

The alkylene group and the alkenylene group that can be taken as the linking group may each be linear, branched or cyclic, but from the viewpoint of reducing the frictional resistance of solid particles, the alkylene group is preferably linear or branched, The alkenylene group is preferably linear. Examples of the cyclic alkylene group include a cyclohexane ring group and a norbornene ring group, and examples of the cyclic alkenylene group include a cyclohexene ring group and a norbornene ring group.

As the group related to the combination of each group, a group formed by combining an alkylene group, an alkenylene group, a carbonyl group, an oxygen atom, a sulfur atom and an imino group is preferable, and an alkylene group, an alkenylene group, a carbonyl group, an oxygen atom and an imino group are preferable. A group formed by combining an ano group is more preferable, a group containing a -CO-O- group is still more preferable, and a group formed by combining an -CO-O- group with an alkylene group or an alkenylene group is particularly preferable. In the group containing the -CO-O- group, the -CO-O- group is preferably bonded to R in the formula (1), and it is more preferable that the oxygen atom in the -CO-O- group is bonded to R in the formula (1). desirable. Examples of the group containing a -CO-O- group include those shown for each compound used in Examples, but are not limited thereto.

In this invention, it is preferable that it is 1-36, as for the total number of the atoms which comprise a coupling group, it is more preferable that it is 1-24, It is more preferable that it is 1-12, It is especially preferable that it is 1-6. It is preferable that it is 10 or less, and, as for the number of connection atoms of a coupling group, it is more preferable that it is 8 or less. As a lower limit, it is 1 or more. The number of connecting atoms refers to the minimum number of atoms connecting R and X in Formula (1). For example, in the case of a linking group consisting of a cyclohexane ring and a -CO-O- group of Compound A-08 used in Examples, the number of atoms constituting the linking group is 19, but the number of linking atoms is 4.

The linking group that can be employed as A is preferably an alkylene group, an oxygen atom, or a group formed by combining an -CO-O- group with an alkylene group or an alkenylene group, and from the viewpoint of reducing the frictional resistance of solid particles, an alkylene group is more desirable.

However, in Formula (1), when R-A-group takes a single group (excluding an aralkyl group), let A be the minimum unit of the said coupling group contained in a single group, and let the remainder be R. For example, when the R-A- group is an alkyl group as a whole (an undecanyl group in the compound A-01 used in the Examples), let A be a methylene group (the minimum unit of an alkylene group as a linking group), and the remaining groups (compound A-01) decanyl) is denoted by R.

Although the coupling group employable as A may have a substituent, it is preferable that it does not have a substituent. As a substituent which A may have, the substituent Z other than the group which can be employ|adopted as said R other than the functional group selected from the said functional group group (I) is mentioned.

X in Formula (1) represents the functional group contained in the functional group group (I) mentioned above. It is as above-mentioned as a functional group, and a preferable thing is also the same.

As a compound (A), you may have a substituent. It does not restrict|limit especially as a substituent unless the effect of this invention is impaired, For example, the substituent Z mentioned later is mentioned, Groups other than the functional group contained in the said functional group group (I), and groups other than an aryl group desirable.

The compound (A) is preferably a low-molecular compound, and its molecular weight is appropriately determined. As molecular weight, it can be 150-1000, for example.

The compound (B) is perfluoropolyether, polychlorotrifluoroethylene or polytetrafluoroethylene, and perfluoropolyether is preferable.

Although it does not specifically limit as perfluoropolyether, The polymer which has alkylene oxide, arylene oxide, etc. as a structural component is mentioned. The compound (B) is not particularly limited as long as it is a polymer having a fluorinated constituent. For example, carbon number of the alkylene group in an alkylene oxide is not specifically limited, For example, it can be set as 1-10, and it is preferable that it is 1-6. Carbon number of the arylene group in arylene oxide is not specifically limited, For example, it can be 6-10.

The compound (B) has a functional group selected from the functional group group (I). The functional group may be introduced into any of the constituents forming the compound (B), but is preferably introduced at the end of the main chain of the polymer chain.

Although the number average molecular weight in particular of a compound (B) is not restrict|limited, For example, it can be 1000-50000.

Examples of the perfluoropolyether include a fluorolink (registered commercial law) series (PFPE, manufactured by Solvey) and a product manufactured by MORESCO. As polychlorotrifluoroethylene, the Neopren PCTFE M series (made by Daikin Corporation) is mentioned, for example. Examples of the polytetrafluoroethylene include the polyflon PTFE series (manufactured by Daikin Corporation), and further, the one made by Shamrock Technologies.

Although the organopolysiloxane in particular of a compound (C) is not restrict|limited, It is a polymer which has a siloxane structure and has at least 1 functional group among the functional groups contained in functional group group (I).

As for the siloxane structure which an organopolysiloxane has, _the structural unit represented by -Si( ^RS2 )-O- is mentioned, for example. In this structural unit, R ^S represents a hydrogen atom or a substituent, and the substituent is not particularly limited, and a hydroxy group or an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6, more preferably 1 to 3 It is especially preferable.), an alkenyl group (C2-C12 is preferable, 2-6 are more preferable, and 2 or 3 is especially preferable.), an alkoxy group (C1-C24 is preferable, 1-12 are More preferably, 1-6 are more preferable, and 1-3 are especially preferable.), an aryl group (C6-C22 is preferable, 6-14 are more preferable, and 6-10 are especially preferable.) , an aryloxy group (C6-22 is preferable, 6-14 are more preferable, and 6-10 are especially preferable.), an aralkyl group (C7-23 are preferable, 7-15 are more preferable, 7-11 are especially preferable.), The group etc. which are represented by the substituent ZC or -R ¹¹ -X in Formula (2) mentioned later are further mentioned. Among these, the group represented by a C1-C3 alkyl group, a phenyl group, substituent ZC, or -R ¹¹ -X is more preferable, and the group represented by a C1-C3 alkyl group or -R ¹¹ -X is still more preferable.

The siloxane structure is preferably a polymer chain having two or more structural units, and the degree of polymerization of all structural units forming the polymer chain is not particularly limited, but is preferably 1 to 1000, more preferably 1 to 500 It is preferable, and it is especially preferable that it is 1-200. The number average molecular weight of the polymer chain is not particularly limited, and is preferably 400 or more, more preferably 800 or more, and still more preferably 2,000 or more. It does not restrict|limit especially as an upper limit, It is preferable that it is 500,000 or less, It is more preferable that it is 100,000 or less, It is especially preferable that it is 50,000 or less. The number average molecular weight of a polymer chain can be measured as a number average molecular weight in terms of standard polystyrene so that it may mention later.

As for organopolysiloxane, the polymer represented by following formula (2) is preferable.

[Formula 2]

In Formula (2), R ¹⁵ represents an alkyl group or an aryl group, and an alkyl group is preferable. The alkyl group and the aryl group employable as R ¹⁵ have the same meaning as the alkyl group and the aryl group that can be employed as R ^S in the structural unit, respectively, and the preferable ones are also the same. However, R ¹⁵ is particularly preferably methyl. Although two R ¹⁵ couple|bonded with the same silicon atom may be respectively same or different, it is preferable that all are methyl.

R ¹⁶ represents an alkyl group or an aryl group, and an alkyl group is preferable. Two R ¹⁶ couple|bonded with the same silicon atom may be respectively same or different. The alkyl group and the aryl group employable as R ¹⁶ have the same meaning as the alkyl group and the aryl group employable as R ^S in the structural unit, respectively, and the preferable ones are also the same.

R ¹¹ represents a linking group. Although it does not restrict|limit especially as a coupling group employable as R ¹¹ , For example, C1-C30 alkylene group, C3-C12 cycloalkylene group, C6-C24 arylene group, C3-C12 hetero Arylene group, ether group (-O-), sulfide group (-S-), phosphiniden group (-PR-: R is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms), silylene group (-SiR ^S1 R ^S2 -: R ^S1 , R ^S2 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms), a carbonyl group, an imino group (-NR ^N -: R ^N is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 10 carbon atoms) Or, it is preferable that it is the coupling group which combined these 2 or more (preferably 2-10 pieces). Among them, an alkylene group, an imino group, an ether group, a sulfide group or a carbonyl group, or a linking group obtained by combining two or more (preferably 2 to 5) of these groups is preferable.

X has the same meaning as X in the formula (1).

ZC represents group represented by the following formula (Z).

[Formula 3]

In formula (Z), R ¹⁷ and R ¹⁸ each represent an alkyl group or an aryl group. The alkyl group and the aryl group which can be employed as R ¹⁷ and R ¹⁸ have the same meaning as the alkyl group and the aryl group which can be employed as R ^S in the siloxane structure, respectively, and the preferable ones are also the same. R ¹⁷ and R ¹⁸ may be the same or different. R ¹⁹ represents an unsubstituted alkyl group having 1 to 4 carbon atoms. y2 is an integer of 1-100, Preferably it is an integer of 1-50, More preferably, it is an integer of 1-20.

In Formula (2), x1, x2, and x3 are each an integer of 0 or more.

The integer of 0-50 is preferable and, as for x1, the integer of 0-20 is more preferable.

The integer of 0-50 is preferable and, as for x2, the integer of 0-20 is more preferable.

The integer of 1-500 is preferable and, as for x3, the integer of 1-200 is more preferable.

The integer of 0-200 is preferable, as for x4, the integer of 0-100 is more preferable, and the integer of 0-30 is still more preferable.

x1, x2, x3, and x4 are an integer of 1-500 in total, Preferably it is an integer of 1-200, More preferably, it is an integer of 1-100.

When x1 and x3 each employ|adopt an integer of 2 or more, in Formula 2, two ZC or R< ¹⁵ > couple|bonded with the same silicon atom may mutually be same or different.

y1 is an integer of 1-30, Preferably it is an integer of 1-20, More preferably, it is an integer of 1-10.

In Formula (2), Y represents the group represented by -R ¹¹ -X mentioned above, or R ¹⁶ , and two Y may be same or different, respectively.

The polymer represented by formula (2) has at least one group represented by -R ¹¹ -X in one molecule, for example, in formula (2), X ₄ and y1 are at least 1, or at least two Y One takes the group represented by -R ¹¹ -X. That is, when x4 is 0, any one of two Ys represents a group represented by -R ¹¹ -X, or when both Ys are R ¹⁶ , x4 and y1 are integers of 1 or more.

Each of the compounds (A) to (C) may be a commercially available product or may be synthesized as appropriate. The synthesis method in particular is not restrict|limited, A well-known method can be selected and conditions can be set suitably.

-substituent Z-

an alkyl group (preferably an alkyl group having 1 to 20 carbon atoms, for example, methyl, ethyl, isopropyl, t-butyl, pentyl, heptyl, 1-ethylpentyl, benzyl, 2-ethoxyethyl, 1-carboxymethyl, etc.); An alkenyl group (preferably an alkenyl group having 2 to 20 carbon atoms, for example, vinyl, allyl, oleyl, etc.), an alkynyl group (preferably an alkynyl group having 2 to 20 carbon atoms, such as ethynyl) , butadiynyl, phenylethynyl, etc.), a cycloalkyl group (preferably a cycloalkyl group having 3 to 20 carbon atoms, for example, cyclopropyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, etc., in the present specification When referring to an alkyl group, it is usually meant to include a cycloalkyl group, but is described separately here.), an aryl group (preferably an aryl group having 6 to 26 carbon atoms, for example, phenyl, 1-naphthyl, 4-methoxy phenyl, 2-chlorophenyl, 3-methylphenyl, etc.), an aralkyl group (preferably an aralkyl group having 7 to 23 carbon atoms, for example, benzyl, phenethyl, etc.), a heterocyclic group (preferably a heterocyclic group having 2 to 20 carbon atoms) cyclic, and more preferably 5 or 6 membered heterocyclic group having at least one oxygen atom, sulfur atom, nitrogen atom.Heterocyclic group includes aromatic heterocyclic group and aliphatic heterocyclic group. For example, tetrahydro pyran ring group, tetrahydrofuran ring group, 2-pyridyl, 4-pyridyl, 2-imidazolyl, 2-benzimidazolyl, 2-thiazolyl, 2-oxazolyl, pyrrolidone group, etc.), alkoxy group (preferably a C1-C20 alkoxy group, for example, methoxy, ethoxy, isopropyloxy, benzyloxy, etc.), an aryloxy group (preferably a C6-C26 aryloxy group, for example , phenoxy, 1-naphthyloxy, 3-methylphenoxy, 4-methoxyphenoxy, etc. In the present specification, the term aryloxy group includes aryloxy group), heterocyclic oxy group (The group in which an -O- group is bonded to the heterocyclic group), an alkoxycarbonyl group (preferably an alkoxycarbonyl group having 2 to 20 carbon atoms, for example, ethoxycarbonyl, 2-ethylhexyloxycarbonyl, dodecyloxy carbonyl, etc.), an aryloxycarbonyl group (wind Directly an aryloxycarbonyl group having 6 to 26 carbon atoms, for example, phenoxycarbonyl, 1-naphthyloxycarbonyl, 3-methylphenoxycarbonyl, 4-methoxyphenoxycarbonyl, etc.), hetero A ring oxycarbonyl group (a group in which an -O-CO- group is bonded to the heterocyclic group), an amino group (preferably an amino group having 0 to 20 carbon atoms, an alkylamino group, an arylamino group, for example, 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, for example, N, N-dimethylsulfamoyl, N-phenylsulfamoyl, etc.), an acyl group (alkylcarbonyl group, alkenylcarbonyl group, alkynylcarbonyl group, arylcarbonyl group, heterocyclic carbonyl group, preferably having 1 carbon atom) acyl groups of ~20, for example, acetyl, propionyl, butyryl, octanoyl, hexadecanoyl, acryloyl, methacryloyl, crotonoyl, benzoyl, naphthoyl, nicotinyl, etc.), acyloxy A group (including an alkylcarbonyloxy group, an alkenylcarbonyloxy group, an alkynylcarbonyloxy group, an arylcarbonyloxy group, and a heterocyclic carbonyloxy group, preferably an acyloxy group having 1 to 20 carbon atoms, for example, Acetyloxy, propionyloxy, butyryloxy, octanoyloxy, hexadecanoyloxy, acryloyloxy, methacryloyloxy, crotonoyloxy, benzoyloxy, naphthoyloxy, nicotinyloxy, etc.), aryl A loyloxy group (preferably an aryloxy group having 7 to 23 carbon atoms, such as benzoyloxy), 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 an acylamino group having 1 to 20 carbon atoms, for example, acetylamino, benzoylamino, etc.), an alkylthio group (preferably 1 to 20 carbon atoms) of an alkylthio group, for example, methylthio, ethylthio, isopropylthio, benzylthio, etc.), an arylthio group (preferably an arylthio group having 6 to 26 carbon atoms, for example, phenylthio Oh, 1-naphthylthio, 3-methylphenylthio, 4-methoxyphenylthio, etc.), a heterocyclic thio group (the heterocyclic group A group to which -S- is bonded), an alkylsulfonyl group (preferably an alkylsulfonyl group having 1 to 20 carbon atoms, for example, methylsulfonyl, ethylsulfonyl, etc.), an arylsulfonyl group (preferably having 6 to 22 carbon atoms) of an arylsulfonyl group, for example, benzenesulfonyl, etc.), an alkylsilyl group (preferably an alkylsilyl group having 1 to 20 carbon atoms, for example, monomethylsilyl, dimethylsilyl, trimethylsilyl, triethylsilyl) etc.), an arylsilyl group (preferably an arylsilyl group having 6 to 42 carbon atoms, such as triphenylsilyl), an alkoxysilyl group (preferably an alkoxysilyl group having 1 to 20 carbon atoms, such as mono Methoxysilyl, dimethoxysilyl, trimethoxysilyl, triethoxysilyl, etc.), an aryloxysilyl group (preferably an aryloxysilyl group having 6 to 42 carbon atoms, for example, triphenyloxysilyl, etc.); A phosphoryl group (preferably a phosphate group having 0 to 20 carbon atoms, for example, -OP(=O)( ^RP ) ₂ ), a phosphonyl group (preferably a phosphonyl group having 0 to 20 carbon atoms, for example , -P(=O)(R ^P ) ₂ ), a phosphinyl group (preferably a phosphinyl group having 0 to 20 carbon atoms, for example, -P( ^RP ) ₂ ), a phosphonic acid group (preferably A phosphonic acid group having 0 to 20 carbon atoms, for example, -PO (OR ^P ) ₂ ), a sulfo group (sulfonic acid group), a carboxy group, a hydroxy group, a sulfanyl group, a cyano group, a halogen atom (eg A fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc.) are mentioned. R ^P is a hydrogen atom or a substituent (preferably a group selected from the substituent Z).

Moreover, the said substituent Z may further substitute by each group mentioned by these substituent Z.

The said alkyl group, an alkylene group, an alkenyl group, an alkenylene group, an alkynyl group, and/or an alkynylene group may be cyclic|annular or a chain|strand shape may be sufficient as them, and may be linear or may be branched.

The content of the compound (SA) in the inorganic solid electrolyte-containing composition is not particularly limited, but from the viewpoint of reducing the frictional resistance of the solid particles, it is preferably 0.1 mass% or more, and 0.2 mass% or more in 100 mass% of the solid content. More preferably, it is especially preferable that it is 0.4 mass % or more. As an upper limit, it is preferable that it is 10 mass % or less from the point of reduction of battery resistance, It is more preferable that it is 4 mass % or less, It is more preferable that it is 2.5 mass % or less, It is especially preferable that it is 1.2 mass % or less.

In the inorganic solid electrolyte-containing composition of the present invention, the ratio of the content [SE] of the inorganic solid electrolyte to the total content [SA] of the compound (SA) in 100% by mass of the solid content: [SA]/[SE] is, Although not particularly limited, from the viewpoint of reduction of frictional resistance of solid particles, low resistance and cycle characteristics, it is preferable that it is 0.0003 to 0.11, and further reduction of frictional resistance of solid particles, and low resistance and improvement of cycle characteristics are achieved at a high level. It is more preferable that it is 0.003-0.05 at the point compatible with it, It is more preferable that it is 0.007-0.05, It is especially preferable that it is 0.01-0.03.

When the inorganic solid electrolyte-containing composition of the present invention contains the following polymer binder, the total content of the polymer binder [BR] and the compound (SA) in 100% by mass of the solid content of the inorganic solid electrolyte-containing composition [SA] Ratio of: [BR]/[SA] is not particularly limited, but is preferably 0.05 to 15 in terms of reduction of frictional resistance of solid particles, low resistance, and cycle characteristics, and additional It is more preferable that it is 0.1-10, it is more preferable that it is 0.2-5, and it is especially preferable that it is 0.8-5 at the point which can make both reduction and low resistance and cycle characteristic improvement at a high level.

<Polymer binder>

It is preferable that the inorganic solid electrolyte containing composition of this invention contains a polymer binder. By containing a polymer binder, the binding property of solid particle|grains can be improved and it contributes to improvement, such as cycling characteristics.

It does not restrict|limit especially as a polymer which forms a polymer binder, Various polymers normally used for the structural layer of an all-solid-state secondary battery are mentioned. For example, sequential polymerization (polycondensation, polyaddition or addition condensation)-based polymers such as polyurethane, polyurea, polyamide, polyimide, polyester, polyether, polycarbonate, and further, fluorine-based polymers ( fluorine-containing polymer), a hydrocarbon-based polymer, a vinyl-based polymer, and a chain polymerization-based polymer such as a (meth)acrylic polymer.

Examples of the polymers of polyurethane, polyurea, polyamide, and polyimide that can be taken as the sequential polymerization polymer include a polymer having a hard segment and a soft segment described in Japanese Patent Application Laid-Open No. 2015-088480 and each polymer described in International Publication No. 2018/147051, International Publication No. 2018/020827, and International Publication No. 2015/046313.

Examples of the fluorinated polymer include polytetrafluoroethylene (PTFE), polyvinylidene difluoride (PVdF), a copolymer of polyvinylidene difluoride and hexafluoropropylene (PVdF-HFP); and a copolymer of polyvinylidene difluoride, hexafluoropropylene, and tetrafluoroethylene (PVdF-HFP-TFE). PVdF-HFP WHEREIN: Although the copolymerization ratio [PVdF:HFP] (mass ratio) of PVdF and HFP is not specifically limited, 9:1-5:5 are preferable and 9:1-7:3 are more preferable. In PVdF-HFP-TFE, the copolymerization ratio of PVdF and HFP and TFE [PVdF:HFP:TFE] (mass ratio) is not particularly limited, but is preferably 20 to 60:10 to 40:5 to 30.

Examples of the hydrocarbon-based polymer include polyethylene, polypropylene, natural rubber, polybutadiene, polyisoprene, polystyrene, polystyrene-butadiene copolymer, styrene-based thermoplastic elastomer, polybutylene, and acrylonitrile butadiene. copolymers or hydrogenated (hydrogenated) polymers thereof. Although it does not restrict|limit especially as a styrene-type thermoplastic elastomer or its hydride, For example, Styrene-ethylene-butylene-styrene block copolymer (SEBS), Styrene-isoprene-styrene block copolymer (SIS) , styrene-isobutylene-styrene block copolymer (SIBS), hydrogenated SIS, styrene-butadiene-styrene block copolymer (SBS), hydrogenated SBS, styrene-ethylene-ethylene-propylene-styrene Block copolymer (SEEPS), styrene-ethylene-propylene-styrene block copolymer (SEPS), styrene-butadiene rubber (SBR), hydrogenated styrene-butadiene rubber (HSBR), further each of the above and random copolymers corresponding to block copolymers. In the present invention, it is preferable that the hydrocarbon-based polymer does not have an unsaturated group bonded to the main chain (eg, 1,2-butadiene constituent) from the viewpoint of suppressing the formation of chemical crosslinking.

Examples of the vinyl-based polymer include a polymer containing, for example, 50 mol% or more of a vinyl-based monomer other than the (meth)acrylic compound (M1). As a vinyl-type monomer, the vinyl compound etc. which are mentioned later are mentioned. Specific examples of the vinyl-based polymer include polyvinyl alcohol, polyvinyl acetal, polyvinyl acetate, or a copolymer containing these.

This vinyl-based polymer is, in addition to the component derived from the vinyl-based monomer, a component derived from the (meth)acrylic compound (M1) that forms the (meth)acrylic polymer described later, and further, a component derived from the macromonomer described later ( MM) is preferred. It is preferable that content of the structural component derived from a vinyl-type monomer is the same as content of the structural component derived from the (meth)acryl compound (M1) in a (meth)acryl polymer. Although content in particular of the structural component derived from (meth)acrylic compound (M1) will not restrict|limit if it is less than 50 mol% in a polymer, It is preferable that it is 0-40 mol%, and it is more preferable that it is 5-35 mol%. It is preferable that content of a structural component (MM) is the same as content in a (meth)acryl polymer.

As the (meth)acrylic polymer, at least one (meth)acrylic compound (M1) selected from a (meth)acrylic acid compound, a (meth)acrylic acid ester compound, a (meth)acrylamide compound, and a (meth)acrylnitrile compound A polymer obtained by (co)polymerization is preferable. Moreover, the (meth)acrylic polymer which consists of a copolymer of a (meth)acrylic compound (M1) and another polymeric compound (M2) is also preferable. The other polymerizable compound (M2) is not particularly limited, and a vinyl compound such as a styrene compound, a vinyl naphthalene compound, a vinyl carbazole compound, an allyl compound, a vinyl ether compound, a vinyl ester compound, or an itaconic acid dialkyl compound. can be heard As a vinyl compound, the "vinyl-type monomer" described in Unexamined-Japanese-Patent No. 2015-88486 is mentioned, for example.

Also preferred is a (meth)acrylic polymer having a constituent (MM) derived from a macromonomer. As such a (meth)acrylic polymer, for example, a macromonomer having a mass average molecular weight of 1,000 or more is introduced as a side chain component described in International Publication No. 2016/132872, and has at least one of the following functional groups (b) polymers can be mentioned.

Functional group (b): carboxyl group, sulfonic acid group, phosphoric acid group, phosphonic acid group

In the (meth)acrylic polymer, the content of the component derived from the (meth)acrylic compound (M1) is preferably 50 mol% or more, and the content of other polymerizable compounds (M2) is not particularly limited, but examples include For example, it can be set as 50 mol% or less, and it is preferable that it is less than 50 mol%. It is preferable that content of a structural component (MM) is 1-70 mass %.

As the polymer binder, polyurethane, fluorine-based polymer or hydrocarbon-based polymer is preferable, and polyurethane, PVdF-HFP, SEBS, SBS, SBR or HSBR is more preferable, polyurethane, PVdF-HFP or SEBS is more preferred, and polyurethane or PVdF-HFP is particularly preferred.

The main chain forming the sequential polymerization polymer is not particularly limited, and two or more components represented by any of the following formulas (I-1) to (I-4) (preferably 2 to 8 types, more preferably is 2 to 4) a main chain formed by combining, or a main chain formed by sequentially polymerizing a carboxylic dianhydride represented by the following formula (I-5) and a diamine compound deriving a component represented by the following formula (I-6) is preferred Do. Examples of the polymer having such a main chain include polyurethane, polyurea, polyamide, polyimide, polyester, and polycarbonate. The combination of each component is appropriately selected according to the type of polymer. As the main chain made of polycarbonate, a component represented by the following formula (I-2) in which oxygen atoms are introduced at both ends of R ^P1 or a component represented by formula (I-3) as R ^P1 is adopted by the following formula (I- The main chain which has the structural component represented by 2), and the structural component represented by following formula (I-3) is mentioned. One type of component in the combination of components means the number of types of component represented by any one of the following formulas, and even if it has two types of components represented by one of the following formulas, two types of components does not interpret that

[Formula 4]

In the formula, R ^P1 and R ^P2 each represents a molecular chain having a molecular weight or a mass average molecular weight of 20 or more and 200,000 or less. Although the molecular weight of this molecular chain cannot be determined uniquely because it depends on the kind etc., For example, 30 or more are preferable, 50 or more are more preferable, 100 or more are still more preferable, and 150 or more are especially preferable. As an upper limit, 100,000 or less are preferable and 10,000 or less are more preferable. The molecular weight of the molecular chain is measured with respect to the raw material compound before introduction into the main chain of the polymer.

The molecular chain that can be taken as R ^P1 and R ^P2 is not particularly limited, but a hydrocarbon chain, a polyalkylene oxide chain, a polycarbonate chain or a polyester chain is preferable, and a hydrocarbon chain or a polyalkylene oxide chain is More preferably, a hydrocarbon chain, a polyethylene oxide chain, or a polypropylene oxide chain is more preferable.

A hydrocarbon chain that can be taken as R ^P1 and R ^P2 means a chain of hydrocarbons composed of carbon atoms and hydrogen atoms, and more specifically, at least two atoms of a compound composed of carbon atoms and hydrogen atoms (for example, For example, a hydrogen atom) or a group (for example, a methyl group) means a structure from which it is removed. However, in the present invention, the hydrocarbon chain includes, for example, a chain having a group containing an oxygen atom, a sulfur atom, or a nitrogen atom in the chain, like a hydrocarbon group represented by the following formula (M2). A terminal group that may be at the end of the hydrocarbon chain is not included in the hydrocarbon chain. This hydrocarbon chain may have a carbon-carbon unsaturated bond, and may have the ring structure of an aliphatic ring and/or an aromatic ring. That is, the hydrocarbon chain may be a hydrocarbon chain composed of hydrocarbons selected from aliphatic hydrocarbons and aromatic hydrocarbons.

As such a hydrocarbon chain, any one satisfying the above molecular weight may be used, and both hydrocarbon chains of a chain consisting of a hydrocarbon group of low molecular weight and a hydrocarbon chain consisting of a hydrocarbon polymer (also referred to as a hydrocarbon polymer chain) are included. .

The low molecular weight hydrocarbon chain is a chain consisting of a normal (non-polymerizable) hydrocarbon group, and examples of the hydrocarbon group include an aliphatic or aromatic hydrocarbon group, and specifically, an alkylene group ( 1-12 are preferable, as for carbon number, 1-6 are more preferable, 1-3 are more preferable), an arylene group (as for carbon number, 6-22 are preferable, 6-14 are preferable, 6-10 are more preferred), or a group consisting of a combination thereof is preferred. As the hydrocarbon group forming the low molecular weight hydrocarbon chain that can be taken as R ^P2 , an alkylene group is more preferable, an alkylene group having 2 to 6 carbon atoms is still more preferable, and an alkylene group having 2 or 3 carbon atoms is particularly preferable. . This hydrocarbon chain may have a polymer chain (for example, (meth)acryl polymer) as a substituent.

It does not restrict|limit especially as an aliphatic hydrocarbon group, For example, the hydrogen reduction body of the aromatic hydrocarbon group represented by the following formula (M2), the partial structure which a well-known aliphatic diisocyanate compound has (for example, group consisting of isophorone); and the like. Moreover, the hydrocarbon group which the structural component of each example described below has is mentioned.

The aromatic hydrocarbon group includes, for example, a hydrocarbon group included in the constituent components of each example described below, and an arylene group (for example, one hydrogen atom The group removed above, specifically, a phenylene group, a tolylene group, or a xylylene group) or a hydrocarbon group represented by the following formula (M2) is preferable.

[Formula 5]

In formula (M2), X represents a single bond, -CH ₂ -, -C(CH ₃ ) ₂ -, -SO ₂ -, -S-, -CO- or -O-, and from the viewpoint of binding property, -CH ₂ - or -O- is preferable, and -CH ₂ - is more preferable. The alkylene group illustrated 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, and a hydrogen atom is preferable. The substituent that can be taken as R ^M2 to R ^M5 is not particularly limited, and includes a substituent Z described later, for example, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, -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 (eg, a fluorine atom; A chlorine atom and a bromine atom) are mentioned preferably. As -N(R ^M6 ) ₂ , an alkylamino group (the number of carbon atoms is preferably 1 to 20, more preferably 1 to 6) or an arylamino group (the number of carbon atoms is preferably 6 to 40, more preferably 6 to 20). do) can be heard.

The hydrocarbon polymer chain is a polymer chain formed by polymerization of (at least two) polymerizable hydrocarbons, and is not particularly limited as long as it is a chain made of a hydrocarbon polymer having a larger number of carbon atoms than the low molecular weight hydrocarbon chain described above. is a chain consisting of a hydrocarbon polymer composed of at least 30, more preferably at least 50 carbon atoms. The upper limit in particular of the number of carbon atoms which comprises a hydrocarbon polymer is not restrict|limited, For example, it can be 3,000 pieces. The hydrocarbon polymer chain is preferably a chain composed of a hydrocarbon polymer composed of aliphatic hydrocarbons, whose main chain satisfies the above-mentioned number of carbon atoms, and a polymer composed of aliphatic saturated hydrocarbons or aliphatic unsaturated hydrocarbons (preferably It is more preferable that it is a chain|strand which consists of elastomer). Specific examples of the polymer include a diene polymer having a double bond in the main chain, and a non-diene polymer having no double bond in the main chain. Examples of the diene-based polymer include a styrene-butadiene copolymer, a styrene-ethylene-butadiene copolymer, a copolymer of isobutylene and isoprene (preferably butyl rubber (IIR)); butadiene polymer, isoprene polymer, ethylene-propylene-diene copolymer, etc. are mentioned. Examples of the non-diene-based polymer include olefin-based polymers such as ethylene-propylene copolymers and styrene-ethylene-butylene copolymers, and hydrogenated products of the diene-based polymers.

The hydrocarbon chain which can be taken as R ^P1 and R ^P2 may have a substituent as mentioned later, and it is preferable to have an ether group, a carbonyl group, or both. In particular, the hydrocarbon chain employable as R ^P2 of the structural component represented by the formula (I-3) or (I-4) is an ether group, a carbonyl group, or both (for example, a -CO-O- group These are mentioned, Preferably, it is preferable to have a carboxy group). It is preferable to have an atom, such as a hydrogen atom, or a substituent (for example, the substituent Z mentioned later) at the edge part of the said ether group and a carbonyl group.

It is preferable to have a reactive group at the terminal, and, as for the hydrocarbon used as a hydrocarbon chain, it is more preferable to have a terminal reactive group which can be polycondensable. The terminal reactive group capable of polycondensation or polyaddition forms a group bonded to R ^P1 or R ^P2 in the above formulas by polycondensation or polyaddition. As such a terminal reactive group, an isocyanate group, a hydroxyl group, a carboxy group, an amino group, an acid anhydride, etc. are mentioned, Especially, a hydroxyl group is preferable.

As a hydrocarbon polymer having a terminal reactive group, all are brand names, for example, NISSO-PB series (manufactured by Nippon Soda Corporation), Claysol series (manufactured by Tomoe Kogyo Co., Ltd.), PolyVEST-HT series (manufactured by Evonik Corporation), poly-bd The series (manufactured by Idemitsu Kosan Corporation), the poly-ip series (manufactured by Idemitsu Kosan Corporation), EPOL (manufactured by Idemitsu Kosan Corporation), and the polytail series (manufactured by Mitsubishi Chemical Corporation) are suitably used.

As a polyalkylene oxide chain (polyalkyleneoxy chain), the chain|strand which consists of a well-known polyalkyleneoxy group is mentioned. It is preferable that carbon number of the alkyleneoxy group in a polyalkyleneoxy chain is 1-10, It is more preferable that it is 1-6, It is more preferable that it is 2 or 3 (polyethyleneoxy chain or polypropyleneoxy chain). The polyalkyleneoxy chain may be a chain composed of one type of alkyleneoxy group, or a chain composed of two or more types of alkyleneoxy groups (for example, a chain composed of an ethyleneoxy group and a propyleneoxy group).

As a polycarbonate chain|strand or polyester chain, the chain|strand which consists of well-known polycarbonate or polyester is mentioned.

It is preferable that the polyalkyleneoxy chain, the polycarbonate chain, or the polyester chain each have an alkyl group (as for carbon number, 1-12 are preferable, and 1-6 are more preferable) at the terminal.

The ends of the polyalkyleneoxy chains, polycarbonate chains and polyester chains that can be taken as R ^P1 and R ^P2 are appropriately changed to conventional chemical structures that can be introduced into the constituents represented by the above formulas as R ^P1 and R ^P2 . can For example, the polyalkyleneoxy chain is introduced as R ^P1 or R ^P2 of the above constituent with the terminal oxygen atom removed.

Inside or at the terminal of the alkyl group included in the molecular chain, an ether group (-O-), a thioether group (-S-), a carbonyl group (>C=O), an imino group (>NR ^N : R ^N 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< The above molecular chains may be formed.

R ^P1 is preferably a hydrocarbon chain among the molecular chains, more preferably a low molecular weight hydrocarbon chain, still more preferably a hydrocarbon chain consisting of an aliphatic or aromatic hydrocarbon group, and an aromatic hydrocarbon group A hydrocarbon chain formed is particularly preferable.

Among the 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 low molecular weight hydrocarbon chain and a low molecular weight The aspect including molecular chains other than the hydrocarbon chain of molecular weight, respectively is more preferable. In this aspect, as for the structural component represented by any one of Formula (I-3), Formula (I-4), and Formula (I-6), R ^P2 is a low molecular weight hydrocarbon group, and R ^P2 is a structural component At least two kinds of constituents that are molecular chains other than the low molecular weight hydrocarbon chain are included.

The specific example of the structural component represented by said Formula (I-1) is shown below. Moreover, as a raw material compound (diisocyanate compound) which derives the structural component represented by the said Formula (I-1), the diamond represented by Formula (M1) described in International Publication No. 2018/020827, for example. An isocyanate compound and its specific example, further, polymeric 4,4'- diphenylmethane diisocyanate etc. are mentioned. In addition, in this invention, the component represented by Formula (I-1) and the raw material compound which derives it are not limited to the following specific examples and those described in the said document.

[Formula 6]

The raw material compound (carboxylic acid or its acid chloride, etc.) for deriving the component represented by the formula (I-2) is not particularly limited, and for example, described in paragraph [0074] of International Publication No. 2018/020827, compounds of carboxylic acids or acid chlorides and specific examples thereof.

The specific example of the structural component represented by said Formula (I-3) or Formula (I-4) is shown below. Moreover, as a raw material compound (diol compound or diamine compound) which derives the structural component represented by the said Formula (I-3) or Formula (I-4), each is not restrict|limited in particular, For example, International Publication Each compound described in No. 2018/020827 and specific examples thereof are mentioned, and further, dihydroxyoxamide is also mentioned. In the present invention, the constituent components represented by the formula (I-3) or (I-4) and the raw material compound derived therefrom are not limited to those described in the following specific examples and the above literature.

Moreover, in the following specific example, when it has a structure repeatedly in a component, the repeating number is an integer of 1 or more, and it is set suitably in the range which satisfy|fills the molecular weight or carbon atom number of the said molecular chain.

[Formula 7]

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

[Formula 8]

In formulas (i) to (iix), X ¹ represents a single bond or a divalent linking group. As a divalent coupling group, a C1-C6 alkylene group (for example, methylene, ethylene, propylene) is preferable. As propylene, 1,3-hexafluoro-2,2-propanediyl is preferable. 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, * represents a binding site with a carbonyl group in formula (1-5). The substituent that can be employed as R ^X and R ^Y is not particularly limited, and includes a substituent Z described later, and an alkyl group (the number of carbon atoms is preferably 1 to 12, more preferably 1 to 6, and 1 to 3 more preferably) or an aryl group (as for carbon number, 6-22 are preferable, 6-14 are more preferable, and 6-10 are still more preferable) are mentioned preferably.

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

R ^P1 , R ^P2 , and R ^P3 may each have a substituent. It does not restrict|limit especially as this substituent, For example, the substituent Z mentioned later is mentioned, The said substituent which can be employ|adopted as R ^M2 is mentioned suitably.

As shown below, in addition to the structural component represented by Formula (I-1), polyurethane is said Formula (I-3) or Formula (I-4), Preferably it is Formula (I-3) As a component to appear, R ^P2 is a chain consisting of a low molecular weight hydrocarbon group (as a functional group, preferably a group having an ether group or a carbonyl group or both, more preferably a group containing a carboxy group) A component preferably represented by the following formula (I-3A)), and a component in which R ^P2 is the above hydrocarbon polymer chain as a molecular chain (a component preferably represented by the following formula (I-3C)); It is preferable that R ^P2 has at least 1 sort(s) of the structural component (The structural component preferably represented by a following formula (I-3B)) which is the said polyalkylene oxide chain as a molecular chain.

[Formula 9]

In formula (I-1), R ^P1 is as described above. In the formula (I-3A), R ^P2A represents a chain (preferably an aliphatic hydrocarbon group) consisting of a low molecular weight hydrocarbon group, and as the functional group, preferably at least selected from the functional group group (Ia) to be described later. It has one group, more preferably a group containing an ether group or a carbonyl group or both, more preferably a carboxy group. For example, bis(hydroxymethyl)acetic acid compounds, such as 2, 2-bis (hydroxymethyl) butyric acid, are mentioned. In the formula (I-3B), R ^P2B represents a polyalkyleneoxy chain. In the formula (I-3C), R ^P2C represents a hydrocarbon polymer chain. A chain consisting 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, respectively, in the formula (I-3) It has the same meaning as the aliphatic hydrocarbon group, polyalkyleneoxy chain, and hydrocarbon polymer chain that can be taken as R ^P2 of R P2 , and the preferred ones are also the same.

In addition, content of the structural component represented by said each formula in a polyurethane is mentioned later.

It is preferable that polyurethane has a structural component containing a polyether structure in a principal chain. Among them, it is preferable to have at least two types of polyether structures in the main chain.

In the present invention, the "polyether structure" refers to a structure (also referred to as a polyalkyleneoxy chain or an alkylene oxide chain) formed by connecting two or more alkyleneoxy groups, for example, -(O-alkylene group). ) n-structure (n represents 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 types of polyalkyleneoxy chains (different in chemical structure). In this invention, it is preferable that it is a single polyalkyleneoxy chain.

The "polyether structure" is appropriately introduced into the main chain of the polymer via an atom or a linking group. As an atom and a linking group at this time, it has the same meaning as given for X in Formula (I-7) mentioned later.

It does not restrict|limit especially as a structural component containing a polyether structure, A structural component derived from polyether polyols, such as polyalkylene glycol, a structural component derived from polyether polyamine, etc. are mentioned.

In the present invention, "at least two types" with respect to the polyether structure means that (alkylene groups) have different chemical structures from each other, regardless of the movement of the constituents forming the main chain and the position introduced into the main chain. It means that the number of types of polyether structure is at least 2 types, and even if polyether structure which has the same chemical structure is introduce|transduced into a different structural component, even if it introduce|transduces two or more in one structural component, let it be 1 type.

The number of types of the polyether structure which a polyurethane has should just be 2 types or more, It is preferable that it is 2 types or 3 types, It is more preferable that it is 2 types.

The alkyleneoxy group forming the polyether structure is not particularly limited, and for example, a polyalkylene oxide chain that can be employed as R ^P2 is mentioned, and the number of carbon atoms of the alkylene group in the alkyleneoxy group is 1 to It is preferable that it is 6, and it is more preferable that it is 2-4.

Although it does not restrict|limit especially as a combination of a polyether structure, At least 2 types of polyether structures chosen from a polyethyleneoxy chain|strand, a polypropyleneoxy chain, and a polytetramethyleneoxy chain|strand are preferable. A combination containing a polyethyleneoxy chain and a polypropyleneoxy chain or polytetramethyleneoxy chain is more preferable, and a combination containing a polyethyleneoxy chain and a polypropyleneoxy chain is still more preferable.

Although the (number average) molecular weight in particular of at least 2 types of polyether structures is not restrict|limited, It is preferable that it is 400 or less, It is more preferable that it is 350 or less, It is more preferable that it is 300 or less, It is especially preferable that it is 250 or less. (Number average) Although the minimum in particular of molecular weight is not restrict|limited, Actually, it is preferable that it is 100 or more, and it is more preferable that it is 150 or more.

In this invention, the (number average) molecular weight of at least 2 types of polyether structures means the sum total of the product of the (number average) molecular weight of each polyether structure, and a mole fraction.

The (number average) molecular weight of each polyether structure is a compound (usually, a hydrogen atom bonded to each end) that induces a component containing a polyether structure (not in a state introduced into the main chain) by the method described later. It is set as the value measured with respect to a compound, for example, polyether polyol mentioned later).

Although the (number average) molecular weight of each polyether structure is not specifically limited, It is set suitably within the range which satisfy|fills the above-mentioned "number average molecular weight of at least two types of polyether structures".

In addition, the polymerization degree of each polyether structure will not be restrict|limited in particular if it is 2 or more, It is set suitably within the range which satisfy|fills the above-mentioned "number average molecular weight of at least two types of polyether structures". Although polymerization degree changes also with carbon number of an alkyleneoxy group, etc., for example, it is preferable that it is 2-10, It is more preferable that it is 3-8, It is still more preferable that it is 2-5.

As a structural component containing a polyether structure, the structural component represented by following formula (I-7) is mentioned, for example.

[Formula 10]

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 from each other. n1 and n2 represent polymerization degrees.

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 becomes a group containing a single bond or a linking group, and when the terminal of the alkyleneoxy group is an alkylene group, it becomes a group containing an oxygen atom or a nitrogen atom or a linking group. Examples of the group containing a linking group that can be employed 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. Although it does not restrict|limit especially as this coupling group, For example, the group in which one hydrogen atom was removed from each group mentioned by the substituent Z is mentioned, Preferably, an alkylene group which can be employ|adopted as R ^P4A or R ^P4B is mentioned. there is. Two Xs in the structural component represented by the said Formula (I-7) may be same or different.

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

Each of n1 and n2 represents a polymerization degree, n1 is a number greater than or equal to 2, n2 is a number greater than 0 or 1, and may be a number greater than or equal to two.

When n2 is 0, the structural component represented by Formula (I-7) becomes a structural component containing a single polyalkyleneoxy chain. This aspect WHEREIN: It is preferable to have 2 types or 3 types, and, as for the principal chain of a polyurethane, it has at least 2 types of different structural components represented by said Formula (I-7), and it is more preferable to have 2 types. This aspect WHEREIN: It is preferable that the structural component represented by Formula (I-7) is a structural component derived from at least 2 types selected from polyethylene glycol, polypropylene glycol, and polytetramethylene ether glycol. . Moreover, you may have a structural component represented by Formula (I-7) whose n2 is a number exceeding 1.

This aspect WHEREIN: The (number average) molecular weight of the structural component from which 2 or more types differ by 2 or more types represented by Formula (I-7), and the (number average) molecular weight of each component are, respectively, at least 2 types of polyether structures mentioned above, respectively. It has the same meaning as the (number average) molecular weight of , and the preferable range is also the same. In addition, n1 in the structural component from which 2 or more types represented by Formula (I-7) differ is respectively set suitably within the range which satisfy|fills the (number average) molecular weight, and the polymerization degree of the above-mentioned polyether structure and It has the same meaning, and the preferable range is also the same.

When n2 is a number exceeding 1, the structural component represented by Formula (I-7) becomes a structural component containing the copolymer of 2 types of polyalkyleneoxy chain|strands. The bonding mode in particular of two polyalkyleneoxy chains in a copolymer is not restrict|limited, A random bond may be sufficient, a block bond may be sufficient, and an alternating bond may be sufficient. This aspect WHEREIN: It is preferable that the principal chain of a polyurethane just needs to have at least 1 type of structural component represented by the said Formula (I-7), and it is preferable to have 1 type. This aspect WHEREIN: As a structural component represented by Formula (I-7), the structural component which consists of a copolymer of a polyethyleneoxy chain|strand and a polypropyleneoxy chain|strand is mentioned, for example.

The (number average) molecular weight of the structural component represented by Formula (I-7) has the same meaning as the (number average) molecular weight of the polyether structure of at least 2 types mentioned above, and a preferable range is also the same. In addition, the (number average) molecular weight of two polyalkyleneoxy chains has the same meaning as the (number average) molecular weight of each polyether structure mentioned above, respectively, and a preferable range is also the same. When it has two or more same polyalkyleneoxy chain|strands, let the (number average) molecular weight of a polyalkyleneoxy chain|strand be a total molecular weight. In addition, n1 and n2 are respectively set suitably within the range which satisfy|fills the (number average) molecular weight, and has the same meaning as the polymerization degree of the polyether structure mentioned above, and a preferable range is also the same.

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 above formula (I The structural component represented by -7) may contain 3 or more types of polyether structures.

Although the specific example of the structural component represented by said Formula (I-7) is shown below, this invention is not limited to this. In the following specific examples, although the polymerization degree of the alkyleneoxy group is abbreviate|omitted, it is set in the above-mentioned range.

[Formula 11]

Polyurethane may have structural components other than the structural component represented by said each formula. Such a constituent component is not particularly limited as long as it can sequentially polymerize with the raw material compound that induces the constituent component represented by each of the above formulas.

Although (total) content of the structural component represented by each said Formula (1-1) - Formula (I-7) in a polyurethane is not specifically limited, It is preferable that it is 5-100 mass %, and 10-100 mass It is more preferable that it is %, It is more preferable that it is 50-100 mass %, It is more preferable that it is 80-100 mass %. The upper limit of this content can also be made into 90 mass % or less, irrespective of said 100 mass %, for example.

Although content of structural components other than the structural component represented by said each formula in a polyurethane is not specifically limited, It is preferable that it is 50 mass % or less.

When polyurethane has a structural component represented by any one of said Formula (I-1) - Formula (I-6), the content in particular is not restrict|limited, It can set in the following range.

That is, the content in particular of the structural component represented by Formula (I-1) or Formula (I-2) in polyurethane, or the structural component derived from carboxylic dianhydride represented by Formula (I-5) is not restrict|limited in particular, , It is preferable that it is 10-50 mol%, It is more preferable that it is 20-50 mol%, It is more preferable that it is 30-50 mol%.

In polyurethane, content of the structural component represented by Formula (I-3), Formula (I-4) or Formula (I-6) in particular is not restrict|limited, respectively, It is preferable that it is 0-50 mol%, , more preferably 5 to 40 mol%, and still more preferably 10 to 30 mol%.

Of the constituents represented by the formula (I-3) or (I-4), R ^P2 is a chain consisting of a low molecular weight hydrocarbon group (for example, a constituent represented by the formula (I-3A)), Although content in particular in polyurethane is not restrict|limited, For example, it is preferable that it is 0-50 mol%, It is more preferable that it is 1-30 mol%, It is more preferable that it is 2-20 mol%, 4 More preferably, it is ~10 mol%.

Among the constituents represented by the formula (I-3) or (I-4), R ^P2 as a molecular chain is the polyalkyleneoxy chain (for example, a constituent represented by the formula (I-3B)) Although content in particular in polyurethane is not restrict|limited, For example, it is preferable that it is 0-50 mol%, It is more preferable that it is 0-45 mol%, It is more preferable that it is 0-43 mol% .

Of the constituents represented by the formula (I-3) or (I-4), R ^P2 is a molecular chain of the hydrocarbon polymer chain (for example, a constituent represented by the formula (I-3C)) , The content in polyurethane is not particularly limited, but for example, it is preferably 0 to 50 mol%, more preferably 1 to 45 mol%, still more preferably 3 to 40 mol%, , more preferably 3 to 30 mol%, particularly preferably 3 to 20 mol%, and most preferably 3 to 10 mol%.

Although the (total) content in polyurethane of the structural component which has a polyether structure, for example, the structural component represented by Formula (I-7) is not restrict|limited, For example, it is 10-60 mol% It is preferable, It is more preferable that it is 20-55 mol%, It is more preferable that it is 30-50 mol%, It is especially preferable that it is 35-45 mol%.

When polyurethane has two or more different structural components represented by Formula (I-7), content of each structural component is suitably determined within the range which satisfy|fills the said (total) content. For example, when having two different constituents represented by formula (I-7), the content of one constituent (preferably a constituent having a polyether structure formed with an alkyleneoxy group having a large molecular weight) is For example, it is preferable that it is 5-30 mol%, It is more preferable that it is 10-25 mol%, It is more preferable that it is 15-20 mol%. The content of the other component (preferably, a component having a polyether structure formed with an alkyleneoxy group having a small molecular weight) is, for example, preferably 10 to 50 mol%, and 15 to 40 mol% It is more preferable, and it is more preferable that it is 20-30 mol%. Moreover, ratio in particular of content of one structural component and the other structural component [one structural component: other structural component] is although it does not restrict|limit, For example, it is preferable that it is 10:90-80:20, 20 : It is more preferable that it is 80-70:30.

On the other hand, when polyurethane has three or more different constituents represented by formula (I-7), a constituent having a polyether structure formed with an alkyleneoxy group having the smallest molecular weight is used as the other constituent, , let other structural components be said one structural component.

In addition, when the component represented by Formula (I-7) also corresponds to the component represented by Formula (I-3B), content of the component represented by Formula (I-7) is represented by Formula (I-3B) Irrespective of the said content of a structural component, let it be the said content demonstrated by the structural component represented by the said Formula (I-7).

In addition, when polyurethane has two or more structural components represented by each formula, let the said content of each structural component be sum total content.

-Functional group-

It is preferable that polyurethane has a functional group for improving the wettability with respect to the surface of solid particles, such as an inorganic solid electrolyte, or adsorption property. Examples of such a functional group include a group that exhibits physical interaction such as hydrogen bonding on the surface of the solid particle and a group that can form a chemical bond with a group that exists on the surface of the solid particle, specifically, the following functional group group ( It is more preferred to have at least one group selected from Ia). However, it is preferable not to have two or more types of groups which can form a bond with functional groups from a viewpoint of expressing more effectively the wettability with respect to the surface of a solid particle or adsorption property.

<Functional group (Ia)>

Carboxylic group, sulfonic acid group (-SO ₃ H), phosphoric acid group (-PO ₄ H ₂ ), amino group (-NH ₂ ), hydroxyl group, sulfanyl group, isocyanato group, alkoxysilyl group and three or more condensed ring structures group to have

The salt may be sufficient as the group which can form salts, such as a carboxy group, a sulfonic acid group, a phosphoric acid group, a hydroxyl group, and a sulfanyl group, For example, a sodium salt, a calcium salt, etc. are mentioned.

The alkoxysilyl group should just be a silyl group in which the Si atom is substituted with at least one alkoxy group (the number of carbon atoms is preferably 1 to 12), and examples of other substituents on the Si atom include an alkyl group, an aryl group, and the like. As an alkoxysilyl group, the description of the alkoxysilyl group in the substituent Z mentioned later is applicable preferably, for example.

The group having a condensed ring structure of three or more rings is preferably a group having a cholesterol ring structure or a structure in which an aromatic ring of three or more rings is condensed, more preferably a cholesterol residue or a pyrenyl group.

A carboxyl group, a sulfonic acid group (-SO ₃ H), a phosphoric acid group (-PO ₄ H ₂ ), a hydroxyl group, and an alkoxysilyl group have high adsorption properties with an inorganic solid electrolyte or a positive electrode active material, and a group having a condensed ring structure of three or more rings is a negative electrode active material It has high adsorption properties. An amino group (-NH ₂ ), a sulfanyl group, and an isocyanato group have high adsorption properties with the inorganic solid electrolyte.

Polyurethane may have the functional group selected from the said functional group group (Ia) in any structural component which forms a polymer, and may have it in any of the main chain or side chain of a polymer. As a structural component which has the said functional group, the structural component represented, for example by Formula (I-3A) is mentioned.

Although content in particular of the functional group selected from the functional group group (Ia) in polyurethane is not restrict|limited, For example, Polyurethane of the structural component which has a functional group selected from the said functional group group (Ia) 0.01-50 mol% is preferable, as for the ratio in all the components which comprise, 0.02-49 mol% is preferable, 0.1-40 mol% is more preferable, 1-30 mol% is still more preferable, 3-25 mol% % by mole is particularly preferred.

Polyurethane (each component and raw material compound) may have a substituent. Although it does not restrict|limit especially as a substituent, Preferably, the group chosen from the following substituent Z is mentioned.

Polyurethane can be synthesized by selecting a raw material compound by a known method according to the type of bond possessed by the main chain and subjecting the raw material compound to polyaddition or polycondensation. As a synthesis method, reference can be made to International Publication No. 2018/151118, for example.

As the above-mentioned preferable polyurethane, for example, 2 to each polyurethane described in International Publication Nos. 2018/020827 and 2015/046313, and further, Japanese Patent Application Laid-Open No. 2015-088480, for example. and the like in which the polyether structure of the species is introduced into the main chain.

(Physical properties or properties of the polymer binder or the fluorine-based copolymer forming the polymer binder, etc.)

The water concentration of the polymer binder is preferably 100 ppm (based on mass) or less. Moreover, this polymer binder may crystallize and dry a fluorine-type copolymer, and may use a polymer binder dispersion liquid as it is.

It is preferable that a fluorine-type copolymer is amorphous. In the present invention, the term "amorphous" of a polymer typically means that an endothermic peak due to crystal melting is not observed when measured at a glass transition temperature.

Although the shape in particular of a polymer binder is not restrict|limited, Particulate|particulate form may be sufficient. Although flat, amorphous, etc. may be sufficient as the particle shape at this time, spherical shape or granular form is preferable. The particle diameter of the particulate polymer binder is not particularly limited, but is preferably 0.1 nm or more, more preferably 1 nm or more, still more preferably 5 nm or more, particularly preferably 10 nm or more, and most preferably 50 nm or more. As an upper limit, it is preferable that it is 1.0 micrometer or less, It is more preferable that it is 700 nm or less, It is especially preferable that it is 500 nm or less.

The average particle diameter of the composite polymer particles can be measured in the same way as the average particle diameter of the inorganic solid electrolyte.

In addition, the average particle diameter of the polymer binder in the structural layer of an all-solid-state secondary battery is, for example, after the battery is disassembled and the structural layer containing the polymer binder is peeled off, the structural layer is measured and measured in advance. It can measure by excluding the measured value of the particle diameter of particle|grains other than the used polymer binder.

Although the mass average molecular weight of a polymer is not restrict|limited in particular, For example, 5,000 or more are preferable, 10,000 or more are more preferable, 20,000 or more are still more preferable, 50,000 or more are especially preferable. As an upper limit, although 5,000,000 or less are substantial, 3,000,000 or less are preferable, 1,000,000 or less are more preferable, and 500,000 or less are especially preferable.

-Measurement of molecular weight-

In the present invention, unless otherwise specified, the molecular weight of the polymer and the polymer chain refers to the mass average molecular weight or the number average molecular weight in terms of standard polystyrene by gel permeation chromatography (GPC). As the measurement method, it is basically set as a value measured by the method of the following condition 1 or condition 2 (priority). However, depending on the type of polymer, 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

Measuring temperature: 40℃

Carrier flow rate: 1.0ml/min

Sample concentration: 0.1% by mass

Detector: RI (Refractive Index) Detector

(Condition 2)

Column: A column to which TOSOH TSKgel Super HZM-H, TOSOH TSKgel Super HZ4000, and TOSOH TSKgel Super HZ2000 (all trade names, manufactured by Tosoh Corporation) is connected is used.

Carrier: tetrahydrofuran

Measuring temperature: 40℃

Carrier flow rate: 1.0ml/min

Sample concentration: 0.1% by mass

Detector: RI (Refractive Index) Detector

A non-crosslinked polymer or a crosslinked polymer may be sufficient as the polymer which forms a polymer binder. Moreover, when crosslinking of a polymer advances by heating or application of a voltage, it may be set as the molecular weight larger than the said molecular weight. Preferably, the polymer has a mass average molecular weight within the above-mentioned range at the start of use of the all-solid-state secondary battery.

The inorganic solid electrolyte-containing composition of the present invention may contain one polymer binder or may contain a plurality of polymer binders.

The content of the polymer binder in the inorganic solid electrolyte-containing composition is not particularly limited, but from the viewpoint of binding properties and resistance, it is preferably 0.1 to 10.0 mass%, and 0.2 to 5.0 mass%, based on 100 mass% of the solid content. It is more preferable, and it is still more preferable that it is 0.3-4.0 mass %.

In the present invention, the mass ratio of the total mass (total amount) of the inorganic solid electrolyte and the active material to the mass of the binder [(the mass of the inorganic solid electrolyte + the mass of the active material)/(the total mass of the binder)] is 1,000 to 1 range is preferred. Also, as for this ratio, 500-2 are more preferable, and 100-10 are still more preferable.

<dispersion hawk>

The inorganic solid electrolyte-containing composition of the present invention may be a solid mixture without containing a dispersion medium for dispersing each of the above components, but preferably contains a dispersion medium, and is a slurry in which solid particles such as an inorganic solid electrolyte are dispersed in a dispersion medium it is preferable

As the dispersion medium, any organic compound exhibiting a liquid phase in the environment of use may be sufficient, for example, various organic solvents may be mentioned. Specifically, an alcohol compound, an ether compound, an amide compound, an amine compound, a ketone compound, an aromatic compound, an aliphatic compound a compound, a nitrile compound, an ester compound, etc. are mentioned.

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 from the viewpoint of exhibiting excellent dispersibility. A non-polar dispersion medium generally refers to a property with low affinity for water, but in the present invention, for example, an ester compound, a ketone compound, an ether compound, an aromatic compound, an aliphatic compound, etc. are mentioned.

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

As the ether compound, for example, alkylene glycol (diethylene glycol, triethylene glycol, polyethylene glycol, dipropylene glycol, etc.), alkylene glycol monoalkyl ether (ethylene glycol, etc.) Cole monomethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, diethylene glycol monomethyl ether, dipropylene glycol monomethyl ether, tripropylene glycol mono Methyl 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 ether (tetrahydrofuran, dioxane (each of 1,2-, 1,3- and 1,4-) isomers are included) and the like).

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

Examples of the amine compound include triethylamine, diisopropylethylamine, and tributylamine.

Examples of the ketone compound include acetone, methyl ethyl ketone, methyl isobutyl ketone (MIBK), cyclopentanone, cyclohexanone, cycloheptanone, dipropyl ketone, dibutyl ketone, diisopropyl ketone, diisobutyl ketone (DIBK), isobutyl propyl ketone, sec-butyl propyl ketone, pentyl propyl ketone, butyl propyl ketone, and the like.

As an aromatic compound, benzene, toluene, xylene, etc. are mentioned, for example.

Examples of the aliphatic compound include hexane, heptane, octane, nonane, decane, dodecane, cyclohexane, methylcyclohexane, ethylcyclohexane, cycloheptane, cyclooctane, decalin, Paraffin, gasoline, naphtha, kerosene, light oil, etc. are mentioned.

As a nitrile compound, acetonitrile, propionitrile, isobutyronitrile, etc. are mentioned, for example.

As the ester compound, for example, ethyl acetate, butyl acetate, propyl acetate, propyl butyrate, isopropyl butyrate, butyl butyrate, isobutyl butyrate, butyl pentanoate, ethyl isobutyrate, propyl isobutyrate, isobutyrate and isopropyl butyrate, isobutyl isobutyrate, propyl pivalate, isopropyl pivalate, butyl pivalate, isobutyl pivalate, and the like.

In this invention, especially, an ether compound, a ketone compound, an aromatic compound, an aliphatic compound, and an ester compound are preferable, and a ketone compound, an aliphatic compound, or an ester compound is more preferable.

Carbon number in particular of the compound which comprises a dispersion medium is not restrict|limited, 2-30 are preferable, 4-20 are more preferable, 6-15 are still more preferable, 7-12 are especially preferable.

It is preferable that the boiling point in normal pressure (1 atm) of a dispersion medium is 50 degreeC or more, and, as for the dispersion medium, it is more preferable that it is 70 degreeC or more. It is preferable that it is 250 degrees C or less, and, as for an upper limit, it is more preferable that it is 220 degrees C or less.

When the inorganic solid electrolyte-containing composition of the present invention contains a dispersion medium, the dispersion medium may be at least one or two or more. Moreover, content in particular of a dispersion medium is not restrict|limited, It can set suitably. For example, in an inorganic solid electrolyte containing composition, 20-80 mass % is preferable, 30-70 mass % is more preferable, 40-60 mass % is especially preferable.

<Active material>

The inorganic solid electrolyte-containing composition of the present invention may contain an active material capable of intercalating and releasing ions of metals belonging to Group 1 or Group 2 of the periodic table. Although demonstrated below as an active material, a positive electrode active material and a negative electrode active material are mentioned.

In this invention, the inorganic solid electrolyte containing composition containing an active material (a positive electrode active material or a negative electrode active material) may be called the composition for electrodes (composition for positive electrodes or the composition for negative electrodes).

(Positive electrode active material)

The positive electrode active material is an active material capable of intercalating and releasing ions of a metal belonging to Group 1 or 2 of the periodic table, and preferably capable of reversibly intercalating and releasing lithium ions. The material is not particularly limited as long as it has the above characteristics, and may be an element capable of being complexed with Li such as a transition metal oxide, an organic substance, or sulfur by decomposing a battery.

Among them, it is preferable to use a transition metal oxide as the positive electrode active material, and a transition metal oxide having a transition metal element M ^a (at least one element selected from Co, Ni, Fe, Mn, Cu and V) is more preferable. Further, in this transition metal oxide, an element M ^b (element of group 1 (Ia) of the periodic table of metals other than lithium, element of group 2 (IIa), Al, Ga, In, Ge, Sn, Pb, Sb, Bi) , elements such as Si, P and B) may be mixed. As ^a mixing amount, 0-30 mol% is preferable with respect to the quantity (100 mol%) of transition metal element Ma. It is more preferable to mix and synthesize so that the molar ratio of Li/M ^a may be 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, and (MD) a lithium-containing transition metal halide. and rosenated phosphoric acid compounds and (ME) lithium-containing transition metal silicic acid compounds.

(MA) Specific examples of the transition metal oxide having a layered rock salt structure, LiCoO ₂ (lithium cobaltate [LCO]), LiNi ₂ O ₂ (lithium nickelate), LiNi _0.85 Co _0.10 Al _0.05 O ₂ (nickel cobalt aluminum lithium acid [NCA]), LiNi _1/3 Co _1/3 Mn _1/3 O ₂ (lithium nickel manganese cobaltate [NMC]), and LiNi _0.5 Mn _0.5 O ₂ (lithium manganese nickelate). .

(MB) Specific examples of transition metal oxides having a spinel structure, LiMn ₂ O ₄ (LMO), LiCoMnO ₄ , Li ₂ FeMn ₃ O ₈ , Li ₂ CuMn ₃ O ₈ , Li ₂ CrMn ₃ O ₈ and Li ₂ NiMn ₃ O ₈ .

(MC) Examples of the lithium-containing transition metal phosphate compound include olivine-type iron phosphate salts such as LiFePO ₄ and Li ₃ Fe ₂ (PO ₄ ) ₃ , iron pyrophosphates such as LiFeP ₂ O ₇ , and phosphoric acid such as LiCoPO ₄ . and monoclinic Nasicon-type vanadium phosphate salts such as cobalts and Li ₃ V ₂ (PO ₄ ) ₃ (lithium vanadium phosphate).

(MD) Examples of the lithium-containing transition metal halide phosphate compound include iron fluorophosphate salts such as Li ₂ FePO ₄ F, manganese fluorophosphate salts such as Li ₂ MnPO ₄ F, and fluorides such as Li ₂ CoPO ₄ F and cobalt phosphate.

(ME) As a lithium containing transition metal _silicic acid compound, _Li2FeSiO4 , _{Li2MnSiO4 , Li2CoSiO4 etc.} are mentioned, for example.

In the present invention, (MA) a transition metal oxide having a layered rock salt structure is preferable, and LCO or NMC is more preferable.

Although the shape in particular of a positive electrode active material is not restrict|limited, A particulate form is preferable. The particle diameter (volume average particle diameter) of a positive electrode active material in particular is not restrict|limited. For example, it can be set as 0.1-50 micrometers. The particle diameter of the positive electrode active material particles can be measured in the same manner as the particle diameter of the inorganic solid electrolyte. In order to make a positive electrode active material into a predetermined particle diameter, a normal grinder or classifier is used. For example, a mortar, a ball mill, a sand mill, a vibrating ball mill, a satellite ball mill, a planetary ball mill, a swirling air flow type jet mill or a sieve etc. are used suitably. At the time of grinding, wet grinding in which a dispersion medium such as water or methanol is coexisted can also be performed. In order to set it as a desired particle diameter, it is preferable to classify. The classification is not particularly limited, and can be performed using a sieve, a wind classifier, or the like. Classification can be used both dry and wet.

You may use the positive electrode active material obtained by the baking method, after washing|cleaning with water, acidic aqueous solution, alkaline aqueous solution, and an organic solvent.

A positive electrode active material may be used individually by 1 type, and may be used in combination of 2 or more type.

In the case of forming the positive electrode active material layer, the mass (mg) (weight per unit area) of the positive electrode active material per unit area (cm ² ) of the positive electrode active material layer is not particularly limited. According to the designed battery capacity, it can determine suitably, for example, it can be set as 1-100 mg/cm< ² >.

The content in particular of the positive electrode active material in the inorganic solid electrolyte-containing composition is not limited, and in 100 mass % of solid content, 10-97 mass % is preferable, 30-95 mass % is more preferable, 40-93 mass is It is more preferable, and 50-90 mass % is especially preferable.

(Negative electrode active material)

The negative electrode active material is an active material capable of intercalating and releasing ions of a metal belonging to Group 1 or 2 of the periodic table, and preferably capable of reversibly intercalating and releasing lithium ions. The material is not particularly limited as long as it has the above characteristics, and examples thereof include a carbonaceous material, a metal oxide, a metal composite oxide, a lithium single element, a lithium alloy, a negative electrode active material capable of forming an alloy with lithium (alloyable), and the like. Among them, a carbonaceous material, a metal composite oxide, or a single lithium is preferably used from the viewpoint of reliability. An active material capable of being alloyed with lithium is preferable from the viewpoint that the capacity of the all-solid-state secondary battery can be increased. In the structural layer formed of the solid electrolyte composition of the present invention, solid particles are strongly bound to each other, and therefore, a negative electrode active material capable of forming an alloy with lithium can be used as the negative electrode active material. This makes it possible to increase the capacity of the all-solid-state secondary battery and increase the lifespan of the battery.

The carbonaceous material used as the 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 PAN (polyacrylonitrile) resin or furfuryl alcohol resin, etc. and carbonaceous materials obtained by calcining various synthetic resins of In addition, various carbon fibers such as PAN-based carbon fibers, cellulosic carbon fibers, pitch-based carbon fibers, vapor-grown carbon fibers, dehydrated PVA (polyvinyl alcohol)-based carbon fibers, lignin carbon fibers, glassy carbon fibers and activated carbon fibers, Mesophase microspheres, graphite whiskers, flat graphite, and the like can also be mentioned.

These carbonaceous materials can also be divided into non-graphitizable carbonaceous materials (also referred to as hard carbon) and graphite-based carbonaceous materials according to the degree of graphitization. The carbonaceous material preferably has the interplanar spacing or density and crystallite size described in Japanese Patent Application Laid-Open Nos. 62-22066, Hei-2-6856, and 3-45473. The carbonaceous material does not need to be a single material, and a mixture of natural graphite and artificial graphite described in Japanese Patent Application Laid-Open No. Hei 5-90844, graphite having a coating layer described in Japanese Patent Application Laid-Open No. Hei6-4516, etc. may be used. may be

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 applied as the negative electrode active material is not particularly limited as long as it is an oxide capable of occluding and releasing lithium, and an oxide of a metal element (metal oxide), a composite oxide of a metal element, or a composite of a metal element and a metalloid element oxides (collectively referred to as metal composite oxides) and oxides of semimetal elements (semimetal oxides) are mentioned. As these oxides, an amorphous oxide is preferable, and a chalcogenide which is a reaction product of a metal element and the element of Group 16 of the periodic table is also mentioned preferably. In the present invention, the semimetal element refers to an element exhibiting intermediate properties between a metallic element and a non-metallic element, and usually includes six elements of boron, silicon, germanium, arsenic, antimony and tellurium, and further contains the three elements selenium, polonium and astatine. In addition, amorphous means having a wide scattering band which has a peak in the region of 20° to 40° in 2θ value by X-ray diffraction method using CuKα rays, and may have a crystalline diffraction line. It is preferable that the strongest intensity among the crystalline diffraction lines seen at 40° to 70° at the 2θ value is 100 times or less, and 5 times or less, the intensity of the diffraction line at the apex of the broad scattering band seen at 20° to 40° at the 2θ value. It is more preferable, and it is especially preferable that it does not have a crystalline diffraction line.

Among the compound group consisting of the amorphous oxide and the chalcogenide, an amorphous oxide of a semimetal element or the chalcogenide is more preferable, and an element of groups 13 (IIIB) to 15 (VB) of the periodic table (eg, Al , Ga, Si, Sn, Ge, Pb, Sb, and Bi), or a (composite) oxide composed of a combination of two or more thereof, or a chalcogenide is particularly preferable. Specific examples of preferred amorphous oxides and chalcogenides include, for example, Ga ₂ O ₃ , GeO, PbO, PbO ₂ , Pb ₂ O ₃ , Pb ₂ O ₄ , Pb ₃ O ₄ , Sb ₂ O ₃ , Sb ₂ O ₄ , Sb ₂ O ₈ Bi ₂ O ₃ , Sb ₂ O ₈ Si ₂ O ₃ , Sb ₂ O ₅ , Bi ₂ O ₃ , Bi ₂ O ₄ , GeS, PbS, PbS ₂ , Sb ₂ S ₃ or Sb ₂ S ₅ is preferably mentioned.

Examples of negative electrode active materials that can be used together with amorphous oxides centered on Sn, Si, and Ge include carbonaceous materials capable of occluding and/or releasing lithium ions or lithium metal, lithium simplex, lithium alloys, negative electrode active materials capable of alloying with lithium can be suitably cited.

Oxides of metals or semimetal elements, particularly metal (composite) oxides and chalcogenides, which contain at least one of titanium and lithium as constituent components are preferable from the viewpoint of high current density charge/discharge characteristics. As the metal composite oxide (lithium composite metal oxide) containing lithium, for example, a composite oxide of lithium oxide and the metal (composite) oxide or the chalcogenide, more specifically, Li ₂ SnO ₂ . .

As for a negative electrode active material, for example, a metal oxide, the thing containing a titanium element (titanium oxide) is also mentioned preferably. Specifically, Li ₄ Ti ₅ O ₁₂ (lithium titanate [LTO]) has excellent rapid charge/discharge characteristics in that the volume fluctuation during occlusion/release of lithium ions is small, and deterioration of the electrode is suppressed to prevent lithium ion secondary batteries. It is preferable in that the lifespan of the improvement becomes possible.

As a lithium alloy as a negative electrode active material, if it is an alloy normally used as a negative electrode active material of a secondary battery, it will not restrict|limit, For example, a lithium aluminum alloy is mentioned.

The negative electrode active material capable of forming an alloy with lithium is not particularly limited as long as it is normally used as a negative electrode active material of a secondary battery. Such an active material has a large expansion and contraction due to charging and discharging of an all-solid-state secondary battery and accelerates the decrease in cycle characteristics. deterioration can be suppressed. Examples of such an active material include a (negative electrode) active material (alloy, etc.) having elemental silicon or tin element, and metals such as Al and In, and a negative electrode active material having elemental silicon (element silicon) that enables higher battery capacity containing active material), and more preferably an active material containing elemental silicon in which the content of elemental silicon is 50 mol% or more of all constituent elements.

In general, a negative electrode containing these negative electrode active materials (for example, a Si negative electrode containing an active material containing elemental silicon, a Sn negative electrode containing an active material containing an element tin, etc.) , more Li ions can be occluded. That is, the occlusion amount of Li ions 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.

Examples of the silicon element-containing active material include silicon materials such as Si and SiOx (0<x≤1), and further, silicon-containing alloys containing titanium, vanadium, chromium, manganese, nickel, copper, lanthanum, and the like. (For example, LaSi ₂ , VSi ₂ , La-Si, Gd-Si, Ni-Si) or a structured active material (for example, LaSi ₂ /Si), in addition to silicon such as SnSiO ₃ , SnSiS ₃ The active material containing an element and a tin element, etc. are mentioned. In addition, since SiOx itself can be used as a negative electrode active material (semimetal oxide), and Si is generated by operation of an all-solid secondary battery, it can be used as a negative electrode active material (its precursor material) that can be alloyed with lithium. there is.

As a negative electrode active material which has a tin element, Sn, _SnO , SnO2, SnS, _SnS2 , and the active material etc. containing the said silicon element and a tin element further are mentioned, for example. Moreover, complex oxide _with lithium oxide, for example, _Li2SnO2 can also be mentioned.

In the present invention, the above-mentioned negative electrode active material can be used without particular limitation, but in terms of battery capacity, as the negative electrode active material, a negative electrode active material capable of alloying with lithium is a preferred embodiment, and among them, the silicon material or silicon-containing alloy (silicon alloy containing an element) is more preferable, and it is still more preferable to include silicon (Si) or a silicon-containing alloy.

The chemical formula of the compound obtained by the above calcination method can be calculated from the mass difference of the powder before and after calcining as an inductively coupled plasma (ICP) emission spectroscopy as a measuring method and as a simple method.

Although the shape in particular of a negative electrode active material is not restrict|limited, A particulate form is preferable. Although the volume average particle diameter in particular of a negative electrode active material is not restrict|limited, 0.1-60 micrometers is preferable. The volume average particle diameter of the negative electrode active material particles can be measured in the same manner as the average particle diameter of the inorganic solid electrolyte. In order to set it as a predetermined particle diameter, similarly to a positive electrode active material, a normal grinder or classifier is used.

The said negative electrode active material may be used individually by 1 type, and may be used in combination of 2 or more type.

In the case of forming the negative electrode active material layer, the mass (mg) (weight per unit area) of the negative electrode active material per unit area (cm ² ) of the negative electrode active material layer is not particularly limited. According to the designed battery capacity, it can determine suitably, for example, it can be set as 1-100 mg/cm< ² >.

The content in particular of the negative electrode active material in the inorganic solid electrolyte-containing composition is not limited, and in 100 mass % of solid content, it is preferable that it is 10-90 mass %, 20-85 mass % is more preferable, 30-80 mass % is more preferable, and it is still more preferable that it is 40-75 mass %.

In the present invention, when the negative electrode active material layer is formed by charging the secondary battery, ions of a metal belonging to Group 1 or Group 2 of the periodic table generated in the all-solid secondary battery may be used instead of the negative electrode active material. A negative electrode active material layer can be formed by combining this ion with an electron and making it precipitate as a metal.

(Coating of active material)

The surface of the positive electrode active material and the negative electrode active material may be surface-coated with another metal oxide. As a surface coating material, the metal oxide containing Ti, Nb, Ta, W, Zr, Al, Si, or Li, etc. are mentioned. Specifically, a spinel titanate, a tantalum-based oxide, a niobium-based oxide, a lithium niobate-based compound, etc. may be mentioned, and specifically, Li ₄ Ti ₅ O ₁₂ , Li ₂ Ti ₂ O ₅ , LiTaO ₃ , LiNbO ₃ , LiAlO ₂ , Li ₂ ZrO ₃ , Li ₂ WO ₄ , Li ₂ TiO ₃ , Li ₂ B ₄ O ₇ , Li ₃ PO ₄ , Li ₂ MoO ₄ , Li ₃ BO ₃ , LiBO ₂ , Li ₂ CO ₃ , Li ₂ SiO ₃ , SiO ₂ , TiO ₂ , ZrO ₂ , Al ₂ O ₃ , B ₂ O ₃ and the like.

Moreover, the electrode surface containing a positive electrode active material or a negative electrode active material may be surface-treated with sulfur or phosphorus.

In addition, the surface of the particle|grain surface of a positive electrode active material or a negative electrode active material may be surface-treated with actinic ray or an active gas (plasma etc.) before and after the said surface coating.

<Challenge Preparation>

It is preferable that the inorganic solid electrolyte containing composition of this invention contains a conductive support agent, For example, it is preferable that the silicon atom containing active material as a negative electrode active material is used together with a conductive support agent.

There is no restriction|limiting in particular as a conductive support agent, What is known as a general conductive support agent can be used. For example, electronic conductive materials such as natural graphite and artificial graphite, carbon black such as acetylene black, Ketjen black, and furnace black, amorphous carbon such as needle coke, vapor-grown carbon fiber or carbon nanotube, etc. A carbonaceous material such as carbon fibers, graphene or fullerene may be used, a metal powder such as copper or nickel may be used, or a metal fiber may be used, and a conductive polymer such as polyaniline, polypyrrole, polythiophene, polyacetylene, or polyphenylene derivative may be used. .

In the present invention, when the active material and the conductive aid are used together, among the conductive aids, insertion and release of metal ions (preferably Li ions) belonging to Group 1 or Group 2 of the periodic table when the battery is charged and discharged This does not occur and the thing which does not function as an active material is made into a conductive support agent. Therefore, among the conductive aids, those that can function as an active material in the active material layer when the battery is charged and discharged are classified as active materials other than conductive aids. When a battery is charged and discharged, whether or not it functions as an active material is not unique, but is determined by the combination with an active material.

The conductive support agent may contain 1 type, and may contain 2 or more types.

Although the shape in particular of a conductive support agent is not restrict|limited, A particulate form is preferable.

When the inorganic solid electrolyte containing composition of this invention contains a conductive support agent, as for content of the conductive support agent in an inorganic solid electrolyte containing composition, 0-10 mass % is preferable in 100 mass % of solid content.

<Lithium salt>

It is also preferable that the inorganic solid electrolyte-containing composition of the present invention contains a lithium salt (supporting electrolyte).

As a lithium salt, the lithium salt normally used for this kind of product is preferable, and there is no restriction|limiting in particular, For example, the lithium salt of Paragraph 0082-0085 of Unexamined-Japanese-Patent No. 2015-088486 is preferable.

When the inorganic solid electrolyte containing composition of this invention contains lithium salt, 0.1 mass part or more is preferable with respect to 100 mass parts of solid electrolytes, and, as for content of lithium salt, 5 mass parts or more is more preferable. As an upper limit, 50 mass parts or less are preferable and 20 mass parts or less are more preferable.

<Dispersant>

The inorganic solid electrolyte-containing composition of the present invention may contain a dispersing agent as appropriate. When the inorganic solid electrolyte-containing composition of the present invention contains a polymer binder, since this poster also functions as a dispersing agent, it is not necessary to contain a dispersing agent other than the polymer binder, but may contain a dispersing agent. As a dispersing agent, what is normally used for an all-solid-state secondary battery can be appropriately selected and used. In general, a compound intended for particle adsorption, steric repulsion and/or electrostatic repulsion is preferably used.

<Other additives>

The inorganic solid electrolyte-containing composition of the present invention comprises, as other components other than the above components, suitably an ionic liquid, a thickener, a crosslinking agent (such as a crosslinking reaction by radical polymerization, condensation polymerization or ring-opening polymerization), a polymerization initiator (acid) or one that generates radicals by heat or light, etc.), an antifoaming agent, a leveling agent, a dehydrating agent, an antioxidant, and the like. An ionic liquid is contained in order to improve ionic conductivity more, A well-known thing in particular can be used without restrict|limiting. Moreover, you may contain polymers other than the polymer contained in the above-mentioned binder, the binder normally used, etc.

(Preparation of inorganic solid electrolyte-containing composition)

The inorganic solid electrolyte-containing composition of the present invention comprises an inorganic solid electrolyte and the above-mentioned compound (SA), preferably a polymer binder, a dispersion medium, an active material depending on the use, a conductive aid, and further suitably a lithium salt, any other component can be prepared as a mixture, preferably as a slurry, by mixing, for example, with various mixers commonly used.

The mixing method in particular is not restrict|limited, You may mix collectively, and you may mix sequentially. Although the environment in particular for mixing is not restrict|limited, Under dry air, under inert gas, etc. are mentioned.

[Sheet for all-solid-state secondary batteries]

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

The solid electrolyte sheet for an all-solid-state secondary battery of the present invention may be a sheet having a solid electrolyte layer, a sheet having a solid electrolyte layer formed on a substrate, or a sheet having no substrate but formed of a solid electrolyte layer . The solid electrolyte sheet for all-solid-state secondary batteries may have other layers other than a solid electrolyte layer. As another layer, a protective layer (release sheet), an electrical power collector, a coating layer, etc. are mentioned, for example.

Examples of the solid electrolyte sheet for an all-solid secondary battery of the present invention include a sheet having, on a substrate, a layer composed of the inorganic solid electrolyte-containing composition of the present invention, usually a solid electrolyte layer, and a protective layer in this order. . It is preferable that the solid electrolyte layer which the solid electrolyte sheet for all-solid-state secondary batteries has is formed from the inorganic solid electrolyte containing composition of this invention. Although content of each component in this solid electrolyte layer is not specifically limited, Preferably, it has the same meaning as content of each component in solid content of the inorganic solid electrolyte containing composition of this invention. The layer thickness of each layer which comprises the solid electrolyte sheet for all-solid-state secondary batteries is the same as the layer thickness of each layer demonstrated in the all-solid-state secondary battery mentioned later.

The base material is not particularly limited as long as it can support the solid electrolyte layer, and examples of the material described in the current collector described later include a sheet body (plate body) such as an organic material, an inorganic material, and the like. As an organic material, various polymers etc. are mentioned, Specifically, a polyethylene terephthalate, a polypropylene, polyethylene, a cellulose, etc. are mentioned. As an inorganic material, glass, a ceramic, etc. are mentioned, for example.

The electrode sheet for an all-solid-state secondary battery of the present invention (simply also referred to as "electrode sheet") may be an electrode sheet having an active material layer, and may be a sheet in which an active material layer is formed on a base material (current collector), or may not have a base material. Instead, it may be a sheet formed of an active material layer. This electrode sheet is usually a sheet having a current collector and an active material layer, but an embodiment having a current collector, an active material layer and a solid electrolyte layer in this order, and a current collector, an active material layer, a solid electrolyte layer and an active material layer in this order Also included are aspects with It is preferable that the solid electrolyte layer and active material layer which an electrode sheet has are formed from the inorganic solid electrolyte containing composition of this invention. Although content of each component in this solid electrolyte layer or active material layer is not specifically limited, Preferably, it has the same meaning as content of each component in solid content of the inorganic solid electrolyte containing composition (composition for electrodes) of this invention. The layer thickness of each layer which comprises the electrode sheet of this invention is the same as the layer thickness of each layer demonstrated in the all-solid-state secondary battery mentioned later. The electrode sheet of this invention may have the other layer mentioned above.

In the all-solid-state secondary battery sheet of the present invention, at least one of the solid electrolyte layer and the active material layer is formed of the inorganic solid electrolyte-containing composition of the present invention, and preferably, the active material layer is formed of the inorganic solid electrolyte-containing composition of the present invention . Therefore, the constituent layer formed of the inorganic solid electrolyte-containing composition of the present invention can realize a large layer density ratio as shown in the Examples to be described later. By using the sheet for an all-solid-state secondary battery of the present invention as a constituent layer of an all-solid-state secondary battery, the excellent cycle characteristics and low resistance of the all-solid-state secondary battery can be realized. In particular, a negative electrode sheet for an all-solid secondary battery and an all-solid-state secondary battery in which a negative electrode active material is formed of the inorganic solid electrolyte-containing composition of the present invention, even when a negative electrode active material capable of forming an alloy with lithium is used as the negative electrode active material, high active material capacity and low resistance and high cycle characteristics can be achieved.

[Method for producing sheet for all-solid-state secondary battery]

The manufacturing method in particular of the sheet|seat for all-solid-state secondary batteries of this invention is not restrict|limited, It can manufacture by forming said each layer using the inorganic solid electrolyte containing composition of this invention. For example, when the inorganic solid electrolyte-containing composition of the present invention is a solid mixture, a method of forming the composition by pressure molding on a substrate or a current collector is exemplified. On the other hand, when the inorganic solid electrolyte-containing composition of the present invention contains a dispersion medium, a layer comprising the inorganic solid electrolyte-containing composition is preferably formed (applied and dried) on a substrate or a current collector (another layer may be interposed). The method of forming (coating-dried layer) is mentioned. Thereby, the sheet|seat for all-solid-state secondary batteries which has a base material or an electrical power collector, and an application dry layer can be produced. Here, the coating dry layer is a layer formed by applying the inorganic solid electrolyte-containing composition of the present invention and drying the dispersion medium (that is, using the inorganic solid electrolyte-containing composition of the present invention, the inorganic solid electrolyte of the present invention) A layer comprising a composition in which the dispersion medium is removed from the containing composition). In the active material layer and the applied dry layer, the dispersion medium may remain as long as the effect of the present invention is not impaired, and the residual amount can be, for example, 3% by mass or less in each layer.

In the manufacturing method of the sheet|seat for all-solid-state secondary batteries of this invention, each process, such as application|coating and drying, is demonstrated in the manufacturing method of the following all-solid-state secondary battery.

In the manufacturing method of the sheet|seat for all-solid-state secondary batteries of this invention, you can also pressurize the coating-dried layer obtained by making it above. The pressurization conditions etc. are demonstrated in the manufacturing method of the all-solid-state secondary battery mentioned later.

Moreover, in the manufacturing method of the sheet|seat for all-solid-state secondary batteries of this invention, a base material, a protective layer (especially peeling sheet), etc. can also be peeled.

[All-solid-state secondary battery]

The all-solid-state secondary battery of the present invention has a positive electrode active material layer, a negative electrode active material layer facing the positive electrode active material layer, and a solid electrolyte layer disposed between the positive electrode active material layer and the negative electrode active material layer. The 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 and constitutes the negative electrode.

It is preferable that at least one of the negative electrode active material layer, the positive electrode active material layer and the solid electrolyte layer is formed of the inorganic solid electrolyte-containing composition of the present invention, and the negative electrode active material layer is formed of the inorganic solid electrolyte-containing composition of the present invention. It is also one of the preferred embodiments that all the layers are formed of the inorganic solid electrolyte-containing composition of the present invention. The active material layer or solid electrolyte layer formed of the inorganic solid electrolyte-containing composition of the present invention is preferably the same as that in the solid content of the inorganic solid electrolyte-containing composition of the present invention with respect to the component species to be contained and the content ratio thereof. 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, a known material can be used.

The thickness of the negative electrode active material layer, the solid electrolyte layer, and the positive electrode active material layer is not particularly limited, respectively. When the dimension of a general all-solid-state secondary battery is considered, 10-1,000 micrometers is preferable, respectively, and, as for the thickness of each layer, 20 micrometers or more and less than 500 micrometers are more preferable. In the all-solid-state secondary battery of this invention, it is more preferable that the thickness of at least 1 layer among a positive electrode active material layer and a negative electrode active material layer is 50 micrometers or more and less than 500 micrometers.

The positive electrode active material layer and the negative electrode active material layer may each have a current collector on the opposite side to the solid electrolyte layer.

<case>

The all-solid-state secondary battery of the present invention may be used as an all-solid-state secondary battery in the state of the above structure depending on the application. However, in order to form a dry cell, it is preferable to use the battery by enclosing it in a more suitable case. The case may be metallic or may be made of resin (plastic). When using a metallic thing, the thing made from an aluminum alloy or stainless steel is mentioned, for example. The metallic case is preferably divided into a case on the positive electrode side and a case on the negative electrode side, and electrically connected to the positive electrode current collector and the negative electrode current collector, respectively. It is preferable that the case by the side of a positive electrode and the case by the side of a negative electrode are joined through the gasket for short circuit prevention, and are integrated.

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

1 is a cross-sectional view schematically illustrating an all-solid-state secondary battery (lithium ion secondary battery) according to a preferred embodiment of the present invention. All-solid-state secondary battery 10 of this embodiment, viewed from the negative electrode side, negative electrode current collector 1, negative electrode active material layer 2, solid electrolyte layer 3, positive electrode active material layer 4, positive electrode current collector ( 5) in this order. Each layer is in contact with each other and has an adjacent structure. By employing such a structure, electrons (e ⁻ ) are supplied to the negative electrode side during charging, and lithium ions (Li ⁺ ) are accumulated there. On the other hand, during discharge, lithium ions (Li ⁺ ) accumulated in the negative electrode return to the positive electrode side, and electrons are supplied to the operation site 6 . In the illustrated example, a light bulb is modeled for the actuating part 6, and it is made to light by discharge.

When an all-solid-state secondary battery having the layer structure shown in Fig. 1 is put in a 2032-type coin case, this all-solid-state secondary battery is called a laminate for all-solid-state secondary batteries, and this laminate for all-solid-state secondary batteries is put in a 2032-type coin case The manufactured battery is called an all-solid-state secondary battery and is sometimes called separately.

(Positive electrode active material layer, solid electrolyte layer, negative electrode active material layer)

In the all-solid-state secondary battery 10, the positive electrode active material layer, the solid electrolyte layer, and the negative electrode active material layer are all formed of the inorganic solid electrolyte-containing composition of the present invention. This all-solid-state secondary battery 10 exhibits excellent battery performance. The inorganic solid electrolyte, the compound (SA), and the polymer binder contained in the positive electrode active material layer 4 , the solid electrolyte layer 3 , and the negative electrode active material layer 2 may each be the same or different from each other.

In the present invention, any one or both of the positive electrode active material layer and the negative electrode active material layer may be simply referred to as an active material layer or an electrode active material layer in some cases. Moreover, any one or both of a positive electrode active material and a negative electrode active material may be put together and simply called an active material or an electrode active material.

In the present invention, when the constituent layer is formed of the inorganic solid electrolyte-containing composition of the present invention, an all-solid-state secondary battery having excellent cycle characteristics and low resistance can be realized.

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

The positive electrode current collector 5 and the negative electrode current collector 1 are preferably electron conductors.

In the present invention, any one or both of the positive electrode current collector and the negative electrode current collector may be simply referred to as a current collector in some cases.

As a material for forming the positive electrode current collector, in addition to aluminum, aluminum alloy, stainless steel, nickel and titanium, etc., it is preferable that the surface of aluminum or stainless steel is treated with carbon, nickel, titanium or silver (thin film is formed), , Among them, aluminum and aluminum alloys are more preferable.

As a material for forming the negative electrode current collector, in addition to aluminum, copper, copper alloy, stainless steel, nickel and titanium, etc., it is preferable that the surface of aluminum, copper, copper alloy or stainless steel is treated with carbon, nickel, titanium or silver, Aluminum, copper, copper alloys and stainless steel are more preferred.

As the shape of the current collector, a film sheet-like one is usually used, but a net, a punched one, a lath body, a porous body, a foam body, a molded body of a group of fibers, and the like can also be used.

Although the thickness in particular of an electrical power collector is not restrict|limited, 1-500 micrometers is preferable. Moreover, it is also preferable that the surface of an electrical power collector forms unevenness|corrugation by surface treatment.

In the all-solid-state secondary battery 10 , the positive electrode active material layer may be formed of a known constituent layer forming material.

In the present invention, functional layers, members, etc. may be appropriately interposed or disposed between or outside each layer 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. Moreover, each layer may be comprised by a single layer, and may be comprised by multiple layers.

[Production of all-solid-state secondary battery]

An all-solid-state secondary battery can be manufactured according to a conventional method. Specifically, an all-solid-state secondary battery can be manufactured by forming each of the above layers using the inorganic solid electrolyte-containing composition or the like of the present invention. Hereinafter, it demonstrates in detail.

The all-solid-state secondary battery of the present invention includes a step of appropriately applying the inorganic solid electrolyte-containing composition of the present invention on a substrate (eg, metal foil serving as a current collector), and forming a coating film (film forming) It can be manufactured by performing the (intervening) method (the manufacturing method of the sheet|seat for all-solid-state secondary batteries of this invention).

For example, on a metal foil serving as a positive electrode current collector, as a material for a positive electrode (composition for a positive electrode), an inorganic solid electrolyte-containing composition containing a positive electrode active material is applied, a positive electrode active material layer is formed, and a positive electrode sheet for an all-solid secondary battery is produced do. Next, on this positive electrode active material layer, the inorganic solid electrolyte containing composition for forming a solid electrolyte layer is apply|coated, and a solid electrolyte layer is formed. Moreover, on the solid electrolyte layer, as a material for negative electrodes (composition for negative electrodes), the inorganic solid electrolyte containing composition containing a negative electrode active material is apply|coated, and a negative electrode active material layer is formed. By superposing a negative electrode current collector (metal foil) on the negative electrode active material layer, an all-solid-state secondary battery having a structure in which a solid electrolyte layer is sandwiched between the positive electrode active material layer and the negative electrode active material layer can be obtained. This can also be enclosed in a case and it can also be set as a desired all-solid-state secondary battery.

Moreover, 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 a negative electrode collector, and a positive electrode collector can be superposed|stacked, and an all-solid-state secondary battery can also be manufactured.

As another method, the following method is mentioned. That is, it is carried out as mentioned above, and the positive electrode sheet for all-solid-state secondary batteries is produced. Moreover, on the metal foil which is a negative electrode collector, the inorganic solid electrolyte containing composition containing a negative electrode active material is apply|coated as a negative electrode material (negative electrode composition), a negative electrode active material layer is formed, and the negative electrode sheet for all-solid-state secondary batteries is produced. Next, a solid electrolyte layer is formed on the active material layer on either one of these sheets as described above. Moreover, on the solid electrolyte layer, the other of the positive electrode sheet for all-solid-state secondary batteries and the negative electrode sheet for all-solid-state secondary batteries is laminated|stacked so that a solid electrolyte layer and an active material layer may contact. In this way, an all-solid-state secondary battery can be manufactured.

As another method, the following method is mentioned. That is, as mentioned above, the positive electrode sheet for all-solid-state secondary batteries and the negative electrode sheet for all-solid-state secondary batteries are produced. Moreover, separately from this, an inorganic solid electrolyte containing composition is apply|coated on a base material, and the solid electrolyte sheet for all-solid-state secondary batteries which consists of a solid electrolyte layer is produced. Moreover, it laminates|stacks so that the solid electrolyte layer peeled from a base material may be pinched|interposed with the positive electrode sheet for all-solid-state secondary batteries and the negative electrode sheet for all-solid-state secondary batteries. In this way, an all-solid-state secondary battery can be manufactured.

Moreover, as mentioned above, the positive electrode sheet for all-solid-state secondary batteries, the negative electrode sheet for all-solid-state secondary batteries, and the solid electrolyte sheet for all-solid-state secondary batteries are produced. Next, the positive electrode sheet for an all-solid-state secondary battery or the negative electrode sheet for an all-solid-state secondary battery and the solid electrolyte sheet for an all-solid-state secondary battery are overlapped and pressed in a state in which the positive electrode active material layer or the negative electrode active material layer and the solid electrolyte layer are in contact. In this way, the solid electrolyte layer is transferred to the positive electrode sheet for all-solid-state secondary batteries or the negative electrode sheet for all-solid-state secondary batteries. Then, the solid electrolyte layer from which the base material of the solid electrolyte sheet for all-solid-state secondary batteries was peeled and the negative electrode sheet for all-solid-state secondary batteries or the positive electrode sheet for all-solid-state secondary batteries (in a state in which the negative electrode active material layer or the positive electrode active material layer was brought into contact with the solid electrolyte layer) ) overlap and pressurize. In this way, an all-solid-state secondary battery can be manufactured. The pressurization method, pressurization conditions, etc. in particular in this method are not restrict|limited, The method demonstrated in pressurization of the apply|coated composition mentioned later, pressurization conditions, etc. are applicable.

The solid electrolyte layer or the like may be formed, for example, by press-molding an inorganic solid electrolyte-containing composition or the like on a substrate or an active material layer under pressure conditions to be described later, or a sheet molded body of a solid electrolyte or an active material may be used.

In the above production method, the inorganic solid electrolyte-containing composition of the present invention may be used in any one of the composition for a positive electrode, the composition containing an inorganic solid electrolyte, and the composition for a negative electrode, and the composition containing the inorganic solid electrolyte of the present invention is added to the composition for a negative electrode. It is preferable to use it, and the inorganic solid electrolyte-containing composition of the present invention may be used for any composition.

When a solid electrolyte layer or an active material layer is formed with a composition other than the solid electrolyte composition of this invention, the composition etc. which are normally used are mentioned as the material. In addition, ions of metals belonging to Group 1 or 2 of the periodic table that are accumulated in the negative electrode current collector through initialization or charging during use, which will be described later, without forming a negative electrode active material layer during manufacturing of the all-solid-state secondary battery, are combined with electrons A negative electrode active material layer can also be formed by bonding and depositing on a negative electrode collector etc. as a metal.

<Formation of each layer (film formation)>

The coating method in particular of the composition containing an inorganic solid electrolyte is not restrict|limited, It can select suitably. For example, application|coating (preferably wet application|coating), spray application|coating, spin coat application|coating, dip coat application|coating, slit application|coating, stripe application|coating, and bar coat application|coating are mentioned.

At this time, the inorganic solid electrolyte-containing composition may be subjected to a drying treatment after each application, or may be subjected to a drying treatment after multilayer application. The drying temperature is not particularly limited. 30 degreeC or more is preferable, as for a minimum, 60 degreeC or more is more preferable, and 80 degreeC or more is still more preferable. 300 degrees C or less is preferable, as for an upper limit, 250 degrees C or less is more preferable, and 200 degrees C or less is still more preferable. By heating in such a temperature range, a dispersion medium can be removed and it can be set as a solid state (coating-dried layer). Moreover, since the temperature is not made high too much and each member of an all-solid-state secondary battery is not damaged, since it is completed, it is preferable. Thereby, in an all-solid-state secondary battery, the outstanding overall performance can be shown, and favorable binding property and favorable ionic conductivity can be acquired also in non-pressurization.

It is preferable to pressurize each layer or the all-solid-state secondary battery after applying the inorganic solid electrolyte-containing composition, after overlapping the constituent layers, or after manufacturing the all-solid-state secondary battery. As a pressurization method, a hydraulic cylinder press machine etc. are mentioned. It does not restrict|limit especially as a pressing force, Generally, it is preferable that it is the range of 5-1500 MPa.

Moreover, you may heat the applied inorganic solid electrolyte containing composition simultaneously with pressurization. It does not restrict|limit especially as a heating temperature, Usually, it is the range of 30-300 degreeC. The pressing may be performed at a temperature higher than the glass transition temperature of the inorganic solid electrolyte. In addition, it can also be pressed at a temperature higher than the glass transition temperature of the polymer contained in the binder. However, in general, it is a temperature which does not exceed the melting|fusing point of this polymer.

Pressurization may be performed in a state in which the application solvent or dispersion medium has been dried in advance, or may be performed in a state in which the solvent or dispersion medium remains.

In addition, each composition may be apply|coated simultaneously, and may perform an application|coating drying press simultaneously and/or sequentially. After apply|coating to another base material, you may laminate|stack by transcription|transfer.

The atmosphere during the manufacturing process, for example, heating or pressurization, is not particularly limited, and in the atmosphere, in dry air (dew point -20°C or less), in an inert gas (eg, in argon gas, in helium gas, in nitrogen gas). etc. may be any.

For the press time, high pressure may be applied for a short time (eg, within several hours), or medium pressure may be applied for a long period of time (one day or more). In addition to the all-solid-state secondary battery sheet, for example, in the case of an all-solid-state secondary battery, in order to continuously apply an intermediate pressure, a restraint tool (screw clamping pressure, etc.) of the all-solid-state secondary battery may be used.

The press pressure may be uniform or different with respect to the portion to be pressed, such as a sheet surface.

The press pressure can be changed according to the area or layer thickness of the part to be pressed. It is also possible to change the same site to different pressures in stages.

The press surface may be smooth or may be roughened.

<Reset>

It is preferable that the all-solid-state secondary battery manufactured as mentioned above performs initialization after manufacture or before use. Initialization is not particularly limited, and can be performed, for example, by first charging and discharging in a state in which the press pressure is raised, and then releasing the pressure until it reaches the general operating pressure of the all-solid-state secondary battery.

[Use of all-solid-state secondary battery]

The all-solid-state secondary battery of the present invention can be applied to various uses. Although there is no particular limitation on the application mode, for example, when mounted on an electronic device, a notebook computer, a pen input computer, a mobile computer, an electronic book player, a mobile phone, a cordless phone, a pager, a portable communication terminal , portable fax machines, portable copiers, portable printers, headphone stereos, video movies, LCD televisions, handy cleaners, portable CDs, mini disks, electric shavers, transceivers, electronic notebooks, calculators, memory cards, portable tape recorders, radios, backup power supplies, etc. can be heard Examples of other consumer products include automobiles, electric vehicles, motors, lighting equipment, toys, game devices, road conditioners, watches, strobes, cameras, medical devices (pacemakers, hearing aids, shoulder massagers, etc.). In addition, it can be used for various military purposes and space applications. Moreover, it can also be combined with a solar cell.

Example

Hereinafter, although this invention is demonstrated in more detail based on an Example, this invention is not limited and interpreted by this. In the following examples, "parts" and "%" indicating the composition are based on mass unless otherwise specified. In the present invention, "room temperature" means 25 ℃.

1. Synthesis of sulfide-based inorganic solid electrolyte

[Synthesis Example A]

Sulfide-based inorganic solid electrolytes are disclosed in T. Ohtomo, A. Hayashi, M. Tatsumisago, Y. Tsuchida, S. Hama, K. Kawamoto, Journal of Power Sources, 233, (2013), pp 231-235, and, A Hayashi, S. Hama, H. Morimoto, M. Tatsumisago, T. Minami, Chem. Lett., (2001), pp 872-873 was synthesized with reference to the non-patent literature.

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%) 3.90 g each 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 set to Li ₂ S:P ₂ S ₅ =75:25 in molar ratio.

Next, 66 zirconia beads with a diameter of 5 mm were put into a 45 mL container made of zirconia (manufactured by Fritz), the total amount of the mixture of lithium sulfide and diphosphorus pentasulfide was put, and the container was sealed in an argon atmosphere. This container was set in a planetary ball mill P-7 (trade name, manufactured by Fritz Corporation), and mechanical milling was performed for 20 hours at a temperature of 25° C. and a rotation speed of 510 rpm. Hereinafter, it is sometimes referred to as LPS.) 6.20 g was obtained. The ionic conductivity was 0.28 mS/cm, and the average particle diameter of the Li-P-S-based glass according to the above measurement method was 15 μm.

2. Synthesis or Preparation of Compound (SA)

Compounds (SA) A-1 to A-28, B-01 to B-02, and C-01 to C-04 shown below were each dissolved in (dispersion medium) toluene to prepare a solution having a concentration of 3% by mass.

[Formula 12]

[Formula 13]

[Formula 14]

Each compound represented by said A-01 - A-28 is a compound represented by Formula (1) mentioned above.

<Preparation or synthesis of each compound>

(1) Compounds A-01 to A-04 and A-20 to A-24

A commercially available compound (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) was used as each compound.

(2) compound A-05

Compound A-05 was synthesized according to the method described in the following literature.

Literature: Analytical chemistry, 1998, vol. 60, 2509-2512

(3) Compounds A-06 to A-18

In the synthesis of compound A-05, compounds A-06 to A-18 were synthesized in the same manner as in A-05, except that the alcohol compounds and acid anhydrides forming A-06 to A-18 were changed. .

(4) compound A-19

It was synthesized according to the method described in the following literature.

Literature: Journal of the American Society for Mass Spectrometry, 2014, vol. 25, 751-757

(5) Compounds A-25 to A-28

Compounds A-25 to A-28 were synthesized according to the methods described in each of the following documents, respectively.

(Compound A-25) Literature: Organic and Biomolecular chemistry, 2014, vol. 12, 261-264

(Compound A-26) Literature: Molecules, 2016, vol. 21(1), 24

(Compound A-27) Literature: Bulletin de la Societe Chimique de France, 1988, 671-680

(Compound A-28): Tetrahedron Letters, 1986, vol. 27, 6329-6332

As the above-mentioned compound (B) (fluorine-based polymer), each of the following compounds B-01 and B-02 was prepared.

B-01: Fluorolink (registered trademark) F10 (perfluoropolyether, phosphate group-containing, manufactured by Solvey)

B-02: Fluorolink (registered trademark) S10 (perfluoropolyether, alkoxysilyl group-containing, manufactured by Solvey)

As the above-mentioned compound (C) (organopolysiloxane), each of the following compounds C-01 to C-04 was prepared.

C-01: X-22-162C (reactive silicone oil at both ends, reactive groups are carboxyl groups, manufactured by Shin-Etsu Chemical Co., Ltd.)

C-02: X-22-163A (reactive silicone oil at both ends, reactive groups are epoxy groups, manufactured by Shin-Etsu Chemical Co., Ltd.)

C-03: X-22-164C (reactive silicone oil at both ends, reactive group is methacryloyloxy group, manufactured by Shin-Etsu Chemical Co., Ltd.)

C-04: KF-2201 (branched reactive silicone oil, reactive group (phenolic) hydroxyl group, manufactured by Shin-Etsu Chemical Co., Ltd.)

[Example 1]

<Preparation of compositions S-1 to S-44 and cS-1 to cS-3 for negative electrodes>

Into a 45 mL container made of zirconia (manufactured by Frich), 180 zirconia beads having a diameter of 5 mm were put in, 4.0 g of the LPS synthesized in Synthesis Example A above, and the content of the solution of the compound (SA) shown in Table 1 is shown in Table 1. 22 g of the quantity used as (solid content) and butyl butyrate were injected|thrown-in. This vessel was set in a planetary ball mill P-7 (trade name) manufactured by Fritz Corporation, and stirred at 25°C at a rotational speed of 300 rpm for 60 minutes. Thereafter, 5.3 g of silicon (Si, manufactured by Aldrich, Ltd.) and graphite (CGB20, trade name, manufactured by Nippon Kokuen Corporation) as a negative electrode active material and acetylene black (made by Denka Corporation) as a conductive aid are used as a negative electrode active material in an amount shown in Table 1, a binder The butyl butyrate dispersion liquid of PVdF-HFP (manufactured by Akema Corporation, KYNER FLEX 2500-20) was added in an amount corresponding to the content (solid content) shown in Table 1, and the container was set in a planetary ball mill P-7, 25 ° C., The mixture was mixed at a rotation speed of 100 rpm for 10 minutes. In this way, compositions S-1 to S-44 for negative electrodes and cS-1 to cS-3 were prepared as non-aqueous compositions, respectively.

<Preparation of composition S-45 for negative electrodes>

In the adjustment of the composition S-3 for the negative electrode, the binder PVdF-HFP is changed to the polyurethane binder B-1 synthesized in Synthesis Example 1 below, and the mixture amount of the binder and the mixture amount of butyl butyrate so that the solid content is the same Except having adjusted, it carried out similarly to preparation of the said composition S-3 for negative electrodes, and prepared the composition S-45 for negative electrodes as a non-aqueous composition.

[Formula 15]

[Synthesis Example 1: Synthesis of polyurethane B-1 and preparation of binder dispersion B-1 composed of polyurethane B-1]

(Synthesis of Polyurethane B-1)

In a 300 mL three-neck flask, 2.92 g of polyethylene glycol (PEG200 (trade name), number average molecular weight 200, manufactured by Fujifilm Wako Junyaku) and polytetramethylene ether glycol (number average molecular weight 250, manufactured by SIGMA-Aldrich) 3.65 g, NISSO-PB G-1000 (trade name, manufactured by Nippon Soda Co., Ltd.) 3.78 g, 2,2-bis(hydroxymethyl)butyric acid (made by Tokyo Kasei Kogyo Co., Ltd.) 0.60 g, THF (tetrahydrofuran) It was dissolved in 80.85 g. To this solution, 9.26 g of diphenylmethane diisocyanate (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) was added, stirred at 60°C, and dissolved uniformly.

To the obtained solution, 65 mg of Neostan U-600 (trade name, manufactured by Nitto Chemical Corporation) was added, and the mixture was stirred at 60°C for 5 hours. To this solution, 0.96 g of methanol was added, the polymer terminal was sealed, the polymerization reaction was stopped, and a 20% by mass THF solution (polymer solution) of the polymer B-1 was obtained.

(Preparation of binder dispersion B-1)

15.00 g of the polymer solution obtained above was diluted with 15.00 g of THF, and while stirring, 90.00 g of butyl butyrate was added dropwise over 1 hour to obtain an emulsion of polymer B-1. This emulsion was concentrated to about 70 g, butyl butyrate was added, and the total amount was 100.00 g to obtain a 3% by mass butyl butyrate dispersion (binder dispersion B-1) of the binder composed of polymer B-1.

<Production of negative electrode sheet for all-solid-state secondary battery>

Each composition for negative electrode obtained above is applied on a stainless steel foil (negative electrode current collector) having a thickness of 10 μm using a Baker-type applicator (trade name: SA-201, manufactured by Tester Sangyo), and heated at 100° C. for 2 hours, The composition for negative electrodes was dried (dispersion medium was removed). Then, using a heat press machine, the dried composition for negative electrodes is pressurized at 25° C. (20 MPa, 1 minute), and negative electrode sheets PS-1 to PS-45 for all-solid secondary batteries having a negative electrode active material layer having a layer thickness of 50 μm; and PcS-1 to PcS-3 were respectively produced.

The compound used for the preparation of the composition cS-2 for negative electrodes and the preparation of the negative electrode sheet PcS-2 for all-solid secondary batteries (the chemical structure is shown below). cA-01 is not the compound (SA) specified in the present invention, but Table 1 For convenience, it is shown in the column of compound (SA).

[Formula 16]

[Table 1]

<Comment in table>

Content is content in 100 mass % of solid content of the composition for negative electrodes, and a unit is mass %.

The conductive support agent is acetylene black (manufactured by Denka Corporation).

The binder is a polymer binder made of PVdF-HFP or a polyurethane binder B-1.

<Preparation of inorganic solid electrolyte-containing composition>

In a 45 mL container made of zirconia (manufactured by Fritz), 180 zirconia beads with a diameter of 5 mm were put, 4.85 g of the LPS synthesized in Synthesis Example A above, 0.15 g of the following polymer binder solution (solid mass), and butyl butyrate 16.0 g was added. Thereafter, this container was set in a planetary ball mill P-7 manufactured by Fritz Corporation, and mixed for 10 minutes at a temperature of 25°C and a rotation speed of 150 rpm to prepare an inorganic solid electrolyte-containing composition.

(Polymer binder solution)

A polymer binder solution having a solid content concentration of 3% by mass prepared by dissolving PVdF-HFP (manufactured by Akema Corporation, KYNER FLEX 2500-20) in butyl butyrate

<Production of solid electrolyte sheet for all-solid-state secondary battery>

The inorganic solid electrolyte-containing composition obtained above was applied on an aluminum foil having a thickness of 20 μm using an applicator (trade name: SA-201), heated at 80° C. for 2 hours, and the inorganic solid electrolyte-containing composition was dried (dispersion medium was removed). ) was made. Thereafter, using a heat press machine, the dried inorganic solid electrolyte-containing composition was heated and pressurized for 10 seconds at a temperature of 120°C and a pressing force of 600 MPa to prepare a solid electrolyte sheet for an all-solid secondary battery. The layer thickness of the solid electrolyte layer was 50 µm.

<Production of a negative electrode sheet for an all-solid secondary battery having a solid electrolyte layer>

On the negative electrode active material layer of each negative electrode sheet for an all-solid-state secondary battery shown in Table 2, the solid electrolyte sheet for an all-solid-state secondary battery prepared above was superposed so that the solid electrolyte layer was in contact with the negative electrode active material layer, and using a press machine, the temperature was After transferring (laminated) by pressurizing at 25°C and a pressing force of 50 MPa, it was further pressurized at a temperature of 25°C and a pressing force of 600 MPa. In this way, the solid electrolyte layer with a layer thickness of 50 micrometers was laminated|stacked on the negative electrode active material layer of the negative electrode sheet for all-solid-state secondary batteries.

<Preparation of the composition for positive electrodes>

In a 45 mL container made of zirconia (manufactured by Fritz), 180 zirconia beads with a diameter of 5 mm were put, 2.8 g of LPS synthesized in Synthesis Example A, 0.2 g of the following polymer binder solution (solid content mass), and 22 g of butyl butyrate put in This vessel was set in a planetary ball mill P-7 (trade name) manufactured by Fritz, and stirred at 25°C at a rotational speed of 300 rpm for 60 minutes. Then, 7.0 g of LiNi _1/3 Co _1/3 Mn _1/3 O ₂ (NMC, manufactured by Aldrich) was put into this container as a positive electrode active material, and in the same manner, the container was placed in a planetary ball mill P-7. It was set and mixed for 5 minutes at 25 degreeC and rotation speed of 100 rpm. In this way, the composition for positive electrodes was prepared.

(binder solution)

A polymer binder solution having a solid content concentration of 3% by mass prepared by dissolving PVdF-HFP (manufactured by Akema Corporation, KYNER FLEX 2500-20) in butyl butyrate

<Production of positive electrode sheet for all-solid-state secondary battery>

The composition for a positive electrode obtained above is applied on an aluminum foil (positive electrode current collector) having a thickness of 20 μm using a Baker-type applicator (trade name: SA-201), heated at 100° C. for 2 hours, and the composition for a positive electrode is dried ( the dispersion medium was removed). Then, using a heat press machine, the dried composition for positive electrodes was pressurized (10 MPa, 1 minute) at 25 degreeC, and the positive electrode sheet for all-solid-state secondary batteries which has a positive electrode active material layer with a film thickness of 80 micrometers was produced.

The produced positive electrode sheet for all-solid-state secondary batteries was punched out into the disk shape with a diameter of 14.0 mm, and the disk-shaped positive electrode sheet was obtained.

<Production of all-solid-state secondary battery>

Each of the prepared negative electrode sheets for all-solid-state secondary batteries having a solid electrolyte layer (the aluminum foil of the solid electrolyte sheet for all-solid-state secondary batteries has been peeled off) was cut out into a disk shape with a diameter of 14.5 mm. Next, as shown in Fig. 2, it was placed in a stainless steel 2032 type coin case 11 having spacers and washers (not shown in Fig. 2) introduced so that the negative electrode current collector of the cut-out disc-shaped sheet was on the bottom side. . A disk-shaped positive electrode sheet was superposed on the solid electrolyte layer of the disk-shaped sheet so that the solid electrolyte layer and the positive electrode active material layer were in contact, and the all-solid-state secondary battery laminate 12 (aluminum foil - positive electrode active material layer - solid electrolyte layer - A negative electrode active material layer-laminated body made of stainless steel foil) was formed. Then, by caulking the 2032-type coin case 11, the all-solid-state secondary battery No. 1 shown in FIG. 1-45 and c1-c3 were prepared, respectively. The all-solid-state secondary battery manufactured in this way has the layer structure shown in FIG.

The manufactured all-solid-state secondary battery No. The following characteristics were evaluated for 1-45 and c1-c3, and the results are shown in Table 2.

In Table 2, the ratio of the content [SE] of the inorganic solid electrolyte to the content [SA] of the compound (SA) in 100 mass % of the solid content of the inorganic solid electrolyte-containing composition (negative electrode active material layer): [SA]/[ SE], and the ratio of the content [BR] of the polymer binder and the content [SA] of the compound (SA): [BR]/[SA] are calculated and shown, respectively.

In addition, the compound described in the "compound (SA)" column in Table 2 represents the compound (SA) contained in the negative electrode active material layer.

<Evaluation 1: Layer Density Test>

In the following procedure, the solid electrolyte molded body pellets for evaluation were produced using the compound (SA) corresponding to each all-solid-state secondary battery shown in Table 2.

Specifically, 3.0 g of zirconia beads with a diameter of 3 mm were put into a 5 mL conical tube, and the LPS (0.8 g) synthesized in Synthesis Example A (0.8 g) was used in the production of each of the solid secondary batteries shown in Table 2. A butyl butyrate solution or dispersion (8.2 mg (solid mass)) of the compound (SA), and further butyl butyrate (amount adjusted so that the solid content concentration of the obtained inorganic solid electrolyte containing composition might be 20 mass %) was added. Thereafter, this centrifugal needle tube was set in a test tube mixer Se-04 (trade name, manufactured by Taitech Corporation) and mixed for 30 minutes to prepare an inorganic solid electrolyte-containing composition. The obtained inorganic solid electrolyte containing composition was collect|recovered in the aluminum cup, it dried on a hot plate at 100 degreeC for 2 hours, and obtained the powder of the inorganic solid electrolyte containing composition. The powder obtained by using a press machine was pressurized at 25 degreeC and 200 MPa or 600 MPa of pressing force, and solid electrolyte molded body pellets for evaluation (film thickness 300-500 micrometers) were respectively produced.

Next, the layer density of each produced pellets of the solid electrolyte molded body for evaluation was calculated according to the mass of the powder/volume of the pellets by measuring the total thickness of the pellets after molding and estimating the volume.

Ratio of the layer density D ₂₀₀ of the pellets produced by pressing at a pressure of 200 MPa to the layer density D ₆₀₀ of the pellets produced by pressing at a pressure of 600 MPa with respect to the pellets for evaluation produced using the same compound (SA) : _D200 / _D600 was calculated.

In this test, the closer this ratio: D ₂₀₀ /D ₆₀₀ is to 1, the smaller the surface resistance between the inorganic solid electrolytes is, and when used as a constituent layer of an all-solid-state secondary battery, it expands even once it expands. It is thought that it becomes easy to shrink|contract to the former dense structural layer (a structural layer with few voids). The following evaluation criteria "C" or higher is the pass level of this test. A result is shown in Table 3.

-Evaluation standard-

A: 0.9≤D ₂₀₀ /D ₆₀₀ <1.0

B: 0.8≤D ₂₀₀ /D ₆₀₀ <0.9

C: 0.7≤D ₂₀₀ /D ₆₀₀ <0.8

D: D ₂₀₀ /D ₆₀₀ <0.7

<Evaluation 2: Evaluation of Active Material Capacity>

All-solid-state secondary battery No. As the battery characteristics of 1-45 and c1-c3, the theoretical capacity of the active material was calculated and evaluated as follows. It indicates that the higher the capacity, the higher the energy density.

-Calculation of theoretical capacity-

It was computed from the saturation composition at the time of insertion of lithium.

Graphite: Since graphite becomes C→LiC ₆ , the amount of Li insertion per 1 g of graphite becomes 1340 (coulombs) ([(1(g)/6 (Li insertion amount per graphite molecule))/12 (graphite molecular weight) ]×96500 (Faraday constant)).

Since 3.6 coulombs is 1 mAh, the theoretical capacity of graphite is 372 (mAh/g) (1340/3.6).

Silicon: Since silicon becomes Si→Li _4.4 Si, the amount of Li insertion per 1 g of silicon becomes 15110 (coulombs) ([(1(g)×4.4 (Li insertion amount per silicon molecule))/28.1 (silicon molecular weight) )]×96500 (Faraday constant)).

Thus, the theoretical capacity of silicon is 4197 (mAh/g) (15110/3.6).

-Evaluation standard-

A: 1500mAh/g≤active material theoretical capacity

B: 400mAh/g≤active material theoretical capacity <1500mAh/g

C: Active material theoretical capacity <400 mAh/g

<Evaluation 3: Evaluation of resistance>

All-solid-state secondary battery No. As battery characteristics of 1-45 and c1-c3, the resistance was measured, and the height of battery resistance was evaluated.

The resistance of each all-solid-state secondary battery was evaluated by a charge-discharge evaluation device: TOSCAT-3000 (trade name, manufactured by Toyo Systems Co., Ltd.). Charging was performed at a current density of 0.1 mA/cm ² until the battery voltage reached 4.2 V. Discharge was performed until the battery voltage reached 2.5V with a current density of 0.2 mA/cm ² . This charging and discharging were repeated as 1 cycle of charging and discharging, 2 cycles of charging and discharging were carried out, and the battery voltage after 5 mAh/g (electrical quantity per 1 g of mass of active material) discharging in the 2nd cycle was read. The resistance of the all-solid-state secondary battery was evaluated according to which of the following evaluation criteria this battery voltage was included.

In the present invention, the higher the battery voltage, the lower the resistance, and the evaluation criterion "C" or more is a pass.

-Evaluation standard-

A: 4.0V≤cell voltage

B: 3.7V≤Battery Voltage<4.0V

C: 3.5V≤Battery Voltage <3.7V

D: 2.5V≤Battery Voltage<3.5V

E: Cannot charge and discharge

<Evaluation 4: Evaluation of cycle characteristics>

All-solid-state secondary battery No. As the battery characteristics of 1-45 and c1-c3, the discharge capacity retention rate was measured, and cycle characteristics were evaluated.

Specifically, the discharge capacity retention rate of each all-solid-state secondary battery was measured by a charge-discharge evaluation apparatus: TOSCAT-3000 (trade name, manufactured by Toyo Systems Co., Ltd.) in an environment of 25°C. Charging was performed at a current density of 0.1 mA/cm ² until the battery voltage reached 4.2 V. Discharge was performed at a current density of 0.1 mA/cm ² until the battery voltage reached 2.5 V. One cycle of charge and discharge was performed by making this 1 charge and 1 discharge into 1 charge/discharge cycle, and the all-solid-state secondary battery was initialized.

The all-solid-state secondary battery after initialization was repeatedly charged and discharged under the same conditions as the above charge/discharge conditions. When the discharge capacity (initial discharge capacity) of the first charge/discharge cycle after initialization is 100%, the number of charge/discharge cycles when the discharge capacity retention rate (discharge capacity with respect to the initial discharge capacity) reaches (decreases) 75% , Cycle characteristics were evaluated according to which of the following evaluation criteria was included.

In this test, the larger the number of charge/discharge cycles, the better the battery performance (cycle characteristics), and even if the charge/discharge is repeated multiple times (even in long-term use), the initial battery performance can be maintained. The following evaluation criteria "C" or higher is the pass of this test.

In addition, the all-solid-state secondary battery No. All of the initial discharge capacities of 1-45 showed a value sufficient to function as an all-solid-state secondary battery.

-Evaluation standard-

(1) When silicon is used as a negative electrode active material

A: 100 cycles ≤ the number of charge/discharge cycles

B: 50 cycles ≤ the number of charge/discharge cycles < 100 cycles

C: 10 cycles ≤ number of charge/discharge cycles < 50 cycles

D: number of charge/discharge cycles <10 cycles

(2) When graphite is used as a negative electrode active material

A: 500 cycles ≤ number of charge/discharge cycles

B: 200 cycles ≤ the number of charge/discharge cycles < 500 cycles

C: 100 cycles ≤ the number of charge/discharge cycles < 200 cycles

D: number of charge/discharge cycles <100 cycles

[Table 2]

From the results shown in Table 2, the following can be seen.

Since the inorganic solid electrolyte-containing composition of the comparative example in which a compound other than the compound (SA) prescribed in the present invention was used together with respect to the inorganic solid electrolyte or the inorganic solid electrolyte-containing composition of the comparative example in which the compound (LB) was not used together, the layer density ratio was small, It can be seen that the dense constituent layer cannot be formed unless a high pressure is applied, so that the once expanded constituent layer is difficult to contract in the dense constituent layer before expansion. The all-solid-state secondary battery of the comparative example which has the structural layer formed from these inorganic solid electrolyte containing composition cannot make resistance and cycling characteristics compatible.

On the other hand, in the inorganic solid electrolyte-containing composition of the present invention in which the compound (SA) specified in the present invention is used in combination with respect to the inorganic solid electrolyte, the layer density ratio is large, so it is not significantly affected by the pressure height and has a dense structural layer. can be formed, and it can be seen that the once expanded component layer tends to contract to the dense component layer before expansion. It turns out that the all-solid-state secondary battery of this invention which has a structural layer formed from these inorganic solid electrolyte containing composition can implement|achieve coexistence of low resistance and excellent cycling characteristics. In particular, even when Si having large expansion and contraction due to charging and discharging is used as the negative electrode active material, it is possible to achieve both low resistance and excellent cycle characteristics while exhibiting high active material capacity. Therefore, even in an inorganic solid electrolyte-containing composition containing an ordinary active material or not containing an active material, it is easy to restore to a dense constituent layer, and low resistance and excellent cycle characteristics can be imparted to an all-solid-state secondary battery. Able to know.

Although the present invention has been described along with its embodiments, it is not intended to limit the invention in any detail of the description unless otherwise specified, and I think that it should be interpreted broadly without going against the spirit and scope of the invention as set forth in the appended claims. .

This application claims the priority based on Japanese Patent Application No. 2019-177551 for which the patent application was carried out in Japan on September 27, 2019, which takes in the content as a part of description of this specification with reference here.

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 working area
10 All-solid-state secondary battery
11 2032 type coin case
12 All-solid-state secondary battery laminate
13 Coin-type all-solid-state secondary battery

Claims (15)

An inorganic solid electrolyte-containing composition comprising: an inorganic solid electrolyte having ion conductivity of a metal belonging to Group 1 or 2 of the periodic table; and at least one compound (SA) selected from the following (A) to (C).
(A): the compound represented by the following formula (1)
Equation (1) RAX
In the formula (1), R represents an aliphatic hydrocarbon group having 6 or more carbon atoms that does not have a fluorine atom (provided that it does not include a steroid ring structure), or a group containing a fluorinated hydrocarbon group and a hydrocarbon group not having a fluorine atom. indicates. A represents a divalent linking group containing no aromatic ring structure. X represents a functional group represented by the following functional group group (I).
(B): perfluoropolyether, polychlorotrifluoroethylene or polytetrafluoroethylene having at least one functional group among the functional groups included in the following functional group group (I)
(C): organopolysiloxane having at least one functional group among the functional groups included in the following functional group group (I)
<Functional group (I)>
An acidic group, a group having a basic nitrogen atom, an amide group, a urea group, a urethane group, an alkoxysilyl group, an epoxy group, an isocyanate group, a hydroxyl group, or a (meth)acryloyloxy group The method according to claim 1,
The ratio of the content [SE] of the inorganic solid electrolyte to the total content [SA] of the compound (SA) in 100% by mass of the solid content of the inorganic solid electrolyte-containing composition: [SA]/[SE] is 0.0003 to 0.11 A composition containing phosphorus and an inorganic solid electrolyte. The method according to claim 1 or 2,
A composition containing an inorganic solid electrolyte, comprising a polymer binder. 4. The method according to claim 3,
The ratio of the content [BR] of the polymer binder to the total content [SA] of the compound (SA) in 100% by mass of the solid content of the inorganic solid electrolyte-containing composition: [BR]/[SA] is 0.2 to 5 , a composition containing an inorganic solid electrolyte. 5. The method according to any one of claims 1 to 4,
An inorganic solid electrolyte-containing composition comprising an active material. 6. The method of claim 5,
The composition containing an inorganic solid electrolyte, wherein the active material is an active material containing elemental silicon or elemental tin. 7. The method according to any one of claims 1 to 6,
The inorganic solid electrolyte containing composition in which the said compound (SA) contains the compound represented by the said Formula (1). 8. The method according to any one of claims 1 to 7,
The inorganic solid electrolyte is a sulfide-based inorganic solid electrolyte, an inorganic solid electrolyte-containing composition. 9. The method according to any one of claims 1 to 8,
A composition containing an inorganic solid electrolyte, comprising a dispersion medium. 10. The method of claim 9,
The composition containing an inorganic solid electrolyte, wherein the dispersion medium is selected from ketone compounds, aliphatic compounds and ester compounds. The sheet for all-solid-state secondary batteries which has a layer comprised from the inorganic solid electrolyte containing composition in any one of Claims 1-10. The electrode sheet for all-solid-state secondary batteries which has an active material layer comprised from the inorganic solid electrolyte containing composition of Claim 5 or 6. An all-solid-state secondary battery comprising a positive electrode active material layer, a solid electrolyte layer, and a negative electrode active material layer in this order,
11. An all-solid-state secondary battery, wherein at least one of the positive electrode active material layer, the solid electrolyte layer, and the negative electrode active material layer is a layer composed of the inorganic solid electrolyte-containing composition according to any one of claims 1 to 10. The manufacturing method of the sheet|seat for all-solid-state secondary batteries which forms into a film the inorganic solid electrolyte containing composition of any one of Claims 1-10. The manufacturing method of an all-solid-state secondary battery which manufactures an all-solid-state secondary battery through the manufacturing method of Claim 14.

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