WO2015147282A1

WO2015147282A1 - All-solid-state secondary cell, cell electrode sheet and solid electrolyte composition used in said cell, method for manufacturing cell electrode sheet, and method for manufacturing all-solid-state secondary cell

Info

Publication number: WO2015147282A1
Application number: PCT/JP2015/059680
Authority: WO
Inventors: 智則三村; 宏顕望月; 雅臣牧野; 目黒　克彦
Original assignee: 富士フイルム株式会社
Priority date: 2014-03-28
Filing date: 2015-03-27
Publication date: 2015-10-01
Also published as: JP2015191866A; JP6096701B2

Abstract

　An all-solid-state secondary cell provided with a positive electrode active layer, a negative electrode active layer, and a solid electrolyte layer, wherein at least one of the positive electrode active layer, the negative electrode active layer, and the solid electrolyte layer contains a binder and an inorganic solid electrolyte having conductivity for ions of a metal from Group 1 or Group 2 of the periodic table, the binder containing a compound having a structure in which a linear molecule penetrates a cyclic molecule.

Description

All-solid secondary battery, solid electrolyte composition and battery electrode sheet used therefor, method for producing battery electrode sheet, and method for producing all-solid secondary battery

The present invention relates to an all-solid secondary battery, a solid electrolyte composition and a battery electrode sheet used therefor, a method for producing a battery electrode sheet, and a method for producing an all-solid secondary battery.

Currently, many lithium ion batteries that are widely used use an electrolytic solution. Attempts have been made to replace this electrolytic solution with a solid electrolyte and make all the constituent materials solid. Among them, reliability is first mentioned as an advantage of a technique using an inorganic solid electrolyte. A flammable material such as a carbonate-based solvent is used as a medium for the electrolytic solution used in the lithium ion secondary battery. Although various measures have been taken, further measures in preparation for overcharge are desired. As a solution to this problem, an all-solid secondary battery made of an inorganic compound capable of making the electrolyte nonflammable is positioned. In addition, it is an advantage that the inorganic solid electrolyte exhibits higher ionic conductivity than the polymer electrolyte.
A further advantage of the all-solid-state secondary battery is that it is suitable for increasing the energy density by stacking electrodes. Specifically, a battery having a structure in which an electrode and an electrolyte are directly arranged in series can be obtained. At this time, since the metal package for sealing the battery cell, the copper wire and the bus bar for connecting the battery cell can be omitted, the energy density of the battery is greatly increased. In addition, good compatibility with the positive electrode material capable of increasing the potential is also mentioned as an advantage.

Developed as a next-generation lithium ion secondary battery due to the above-described advantages, it has been vigorously developed (Non-patent Document 1). On the other hand, an inorganic all-solid secondary battery has a disadvantage because the electrolyte is a hard solid. For example, the interface resistance between solid particles is increased. In order to improve this, there is an example using a specific polymer compound as a binder. Specifically, Patent Document 1 uses a surfactant having a polyoxyethylene chain. Patent Document 2 discloses the use of a hydrogenated butadiene copolymer.

JP 2013-008611 A JP 2011-134675 A

The increase in the interfacial resistance in the all-solid-state secondary battery may be improved accordingly by the technique of the above patent document. However, the binder made of the polymer compound disclosed in the above document cannot satisfy the recent high demand level, and further improvement is desired.
Therefore, the present invention achieves high ionic conductivity in an all-solid-state secondary battery regardless of the pressurization of the active material layer and the inorganic solid electrolyte layer, and further has good bending durability and material binding properties. It is an object of the present invention to provide an all-solid secondary battery realized, a solid electrolyte composition and a battery electrode sheet used therefor, a method for producing a battery electrode sheet, and a method for producing an all-solid secondary battery.

The above problem has been solved by the following means.
[1] An all-solid-state secondary battery comprising a positive electrode active material layer, a negative electrode active material layer, and a solid electrolyte layer, wherein at least one of the positive electrode active material layer, the negative electrode active material layer, and the solid electrolyte layer is periodic An all-solid secondary comprising an inorganic solid electrolyte having conductivity of metal ions belonging to the first or second group of the table and a binder, wherein the binder comprises a compound having a structure in which a linear molecule penetrates a cyclic molecule. battery.
[2] The all solid state secondary battery according to [1], wherein the cyclic molecule is cyclodextrin or a derivative thereof.
[3] The linear molecule is a polyolefin, polyether, polyester, polysiloxane, polycarbonate, polyacrylate, polyurethane, polyurea, polymer having a heterocyclic ring in the main chain, or a compound containing a polyene structure [1] or [2 ] The all-solid-state secondary battery as described in above.
[4] The all-solid secondary battery according to any one of [1] to [3], wherein the molecular weight of the linear molecule is 10,000 or more.
[5] A crosslinked structure in which the cyclic molecule or linear molecule is at least one of the following reactive substituent (A) and the following reactive linking group (B), or the reactive substituent or reactive linking group The all-solid-state secondary battery according to any one of [1] to [4].
Reactive substituent (A)
Amino group, thiol group, tetrahydrofuryl group, oxetane group, epoxy group, hydroxyl group, isocyanate group, carboxyl group, phosphoric acid group, sulfonic acid group, phosphonic acid group, alkenyl group-containing group reactive linking group (B)
The imino group, alkenylene group-containing group [6] The all-solid-state secondary battery according to any one of [1] to [5], which has a bulky substituent at the end of the linear molecule.
[7] The all-solid-state secondary battery according to any one of [1] to [6], wherein the cyclic molecule has a structure represented by any of the following formulas (2-1) to (2-4): .

L ^A is a preceding linking group.
Ar ² is a cyclic structural group.
R ^A1 to R ^A4 are a hydrogen atom, a halogen atom, a methyl group, an ethyl group, a cyano group, or a hydroxyl group.
Ring α is a cyclic structure group containing one or more X ^A1 , and forms a ring structure with an oxygen atom, a sulfur atom, an imino group, a carbonyl group, an alkylene group, an alkenylene group, an arylene group, or a combination thereof.
X ^A1 and X ^A2 each independently represent a hetero atom-containing linking group.
[8] In the compound having a structure in which a linear molecule penetrates the cyclic molecule, the linear molecule is a polymer compound having a plurality of monomers, and the ratio of the linear molecule to the cyclic molecule is a linear molecule. The all-solid-state secondary battery according to any one of [1] to [7], wherein the ratio of moles of monomer units constituting the number of cyclic molecules is 100: 0.1 to 100: 70 .
[9] The entire linear molecule according to any one of [1] to [8], wherein the linear molecule is a compound having a structure represented by any of the following formulas (1-1) to (1-5): Solid secondary battery.

L ¹ is an alkylene group or an alkenylene group. L ² is a linking group. R ³¹ and R ³² are each independently a hydrogen atom, a hydroxyl group, an alkyl group, an alkenyl group, an aryl group, or an aralkyl group. R ⁴¹ , R ⁴² , R ⁵¹ and R ⁵² are each independently a hydrogen atom, a halogen atom, a cyano group, a hydroxyl group, an alkyl group, an aryl group or an aralkyl group. A plurality of L ¹ , L ² , R ³¹ , R ³² , R ⁴¹ , R ⁴² , R ⁵¹ , R ⁵² in the molecule may be the same as or different from each other.
[10] The all-solid-state secondary battery according to [5], wherein the reactive substituent (A) is at least one of the following functional groups.
Functional group: thiol group, epoxy group, hydroxyl group, isocyanate group, carboxyl group, phosphoric acid group, sulfonic acid group, phosphonic acid group, alkenyl group-containing group [11] The binder is added to 100 parts by mass of the inorganic solid electrolyte. The all-solid-state secondary battery according to any one of [1] to [10], which is contained in an amount of 0.1 to 20 parts by mass.
[12] The all-solid-state secondary battery according to [10], wherein the reactive substituent (A) is at least one of the following functional groups.
Functional group Carboxyl group, phosphoric acid group, sulfonic acid group, phosphonic acid group [13] All solid described in any one of [1] to [12], wherein the inorganic solid electrolyte is an oxide-based inorganic solid electrolyte Secondary battery.
[14] The all-solid-state secondary battery according to [13], wherein the inorganic solid electrolyte is selected from the following formulae.
・ Li _xa La _ya TiO ₃
xa = 0.3 to 0.7, ya = 0.3 to 0.7
・ Li ₇ La ₃ Zr ₂ O ₁₂
・ Li _3.5 Zn _0.25 GeO ₄
・ LiTi ₂ P ₃ O ₁₂
Li _{1 + xh + yh} (Al, Ga) _xh (Ti, Ge) ₂ _-xh Si _yh P ₃ _-yh O ₁₂
0 ≦ xh ≦ 1, 0 ≦ yh ≦ 1
・ Li ₃ PO ₄
・ LiPON
・ LiPOD ¹
D ¹ is Ti, V, Cr, Mn, Fe, Co, Ni, Cu,
Zr, Nb, Mo, Ru, Ag, Ta, W, Pt, and Au
At least one selected from LiA ¹ ON
A ¹ is at least one selected from Si, B, Ge, Al, C, Ga and the like [15] a solid electrolyte composition for an all-solid-state secondary battery, and is a first group or second group in the periodic table A solid electrolyte composition comprising a binder containing an inorganic solid electrolyte having conductivity of metal ions belonging to the group and a compound having a structure in which a linear molecule penetrates a cyclic molecule.
[16] The solid electrolyte composition according to [15], further containing a dispersion medium.
[17] The solid electrolyte composition according to [16], wherein the dispersion medium is selected from alcohol compound solvents, ether compound solvents, amide compound solvents, ketone compound solvents, aromatic compound solvents, aliphatic compound solvents, and nitrile compound solvents. object.
[18] The solid electrolyte composition according to any one of [15] to [17], further comprising a radical polymerization initiator and / or a crosslinking agent.
[19] The solid electrolyte composition according to any one of [15] to [18], wherein the binder is contained in an amount of 0.1 to 20 parts by mass with respect to 100 parts by mass of the inorganic solid electrolyte. .
[20] The solid electrolyte composition according to any one of [15] to [19], wherein the cyclic molecule is cyclodextrin or a derivative thereof.
[21] The linear molecule is a polyolefin, polyether, polyester, polysiloxane, polycarbonate, polyacrylate, polyurethane, polyurea, a polymer having a heterocyclic ring in the main chain, or a compound containing a polyene structure [15] to [20] Solid electrolyte composition as described in any one of these.
[22] The cyclic molecule or linear molecule has a crosslinked structure via at least one of the following reactive substituent (A) and the following reactive linking group (B) or the reactive substituent [15]. The solid electrolyte composition according to any one of to [21].
Reactive substituent (A)
Amino group, thiol group, tetrahydrofuryl group, oxetane group, epoxy group, hydroxyl group, isocyanate group, carboxyl group, phosphoric acid group, sulfonic acid group, phosphonic acid, alkenyl group-containing group reactive linking group (B)
Imino group, alkenylene group-containing group [23] The solid electrolyte composition according to any one of [15] to [22], which has a bulky substituent at the end of the linear molecule.
[24] The solid according to any one of [15] to [23], wherein the linear molecule is a compound containing a structure represented by any of the following formulas (1-1) to (1-5): Electrolyte composition.

L ¹ is an alkylene group or an alkenylene group. L ² is a linking group. R ³¹ and R ³² are each independently a hydrogen atom, a hydroxyl group, an alkyl group, an alkenyl group, an aryl group, or an aralkyl group. R ⁴¹ , R ⁴² , R ⁵¹ and R ⁵² are each independently a hydrogen atom, a halogen atom, a cyano group, a hydroxyl group, an alkyl group, an aryl group or an aralkyl group. A plurality of L ¹ , L ² , R ³¹ , R ³² , R ⁴¹ , R ⁴² , R ⁵¹ , R ⁵² in the molecule may be the same as or different from each other.
[25] The solid electrolyte composition according to [22], wherein the reactive substituent (A) is at least one of the following functional groups.
Functional group: thiol group, epoxy group, hydroxyl group, isocyanate group, carboxyl group, phosphoric acid group, sulfonic acid group, phosphonic acid group, alkenyl group-containing group [26] The reactive substituent (A) has the following functional group: The solid electrolyte composition according to [25], which is at least one of them.
Functional group carboxyl group, phosphoric acid group, sulfonic acid group, phosphonic acid group [27] [15] to [26] A solid electrode composition according to any one of [27], [15] to [26] .
[28] A method for producing an electrode sheet for a battery, wherein the solid electrolyte composition according to any one of [15] to [27] is formed on a metal foil.
[29] The method for producing an electrode sheet for a battery according to [28], wherein the formed solid electrolyte composition is heated at 80 ° C. or higher.
[30] A method for producing an all-solid secondary battery, wherein an all-solid secondary battery is produced through the method for producing an electrode sheet for a battery according to [28] or [29].

In this specification, when there are a plurality of substituents or linking groups indicated by a specific symbol, or when a plurality of substituents (the definition of the number of substituents is the same) is specified simultaneously or alternatively, each substitution The groups and the like may be the same as or different from each other. Further, when a plurality of substituents and the like are close to each other, they may be bonded to each other or condensed to form a ring.

The all-solid-state secondary battery of the present invention achieves high ionic conductivity regardless of the pressurization of the active material layer and the inorganic solid electrolyte layer, and is excellent in bending durability and material binding.
According to the solid electrolyte composition, the battery electrode sheet, the battery electrode sheet manufacturing method and the all solid secondary battery manufacturing method of the present invention, the battery electrode sheet and the all solid secondary battery are preferably manufactured. be able to.
The above and other features and advantages of the present invention will become more apparent from the following description, with reference where appropriate to the accompanying drawings.

FIG. 1 is a cross-sectional view schematically showing an all solid lithium ion secondary battery according to a preferred embodiment of the present invention. FIG. 2 is a molecular structure diagram schematically showing a crosslinked product of a polyrotaxane compound according to a preferred embodiment of the present invention. FIG. 3 is a cross-sectional view schematically showing a test apparatus used in the examples.

The all-solid-state secondary battery of the present invention includes a positive electrode active material layer, a negative electrode active material layer, and a solid electrolyte layer, and any one of the layers contains an inorganic solid electrolyte having ion conductivity and a specific binder. To do. Hereinafter, preferred embodiments will be described with reference to the drawings.

FIG. 1 is a cross-sectional view schematically showing an all solid state secondary battery (lithium ion secondary battery) according to a preferred embodiment of the present invention. The all-solid-state secondary battery 10 of the present embodiment includes a negative electrode current collector 1, a negative electrode active material layer 2, an inorganic solid electrolyte layer 3, a positive electrode active material layer 4, and a positive electrode current collector 5 in that order as viewed from the negative electrode side. Have in. Each layer is in contact with each other and has a laminated structure. By adopting such a structure, at the time of charging, electrons (e ⁻ ) are supplied to the negative electrode side, and lithium ions (Li ⁺ ) are accumulated therein. On the other hand, at the time of discharge, lithium ions (Li ⁺ ) accumulated in the negative electrode are returned to the positive electrode side, and electrons are supplied to the working part 6. In the example shown in the figure, a light bulb is adopted as the operation part 6 and is turned on by discharge. The solid electrolyte composition of the present invention is preferably used as a constituent material of the negative electrode active material layer, the positive electrode active material layer or the inorganic solid electrolyte layer, and among them, the inorganic solid electrolyte layer, the positive electrode active material layer, and the negative electrode active material layer. It is preferable to use as all constituent materials. Note that the positive electrode active material layer and the negative electrode active material layer may be collectively referred to as an “active material layer”. In addition, the inorganic solid electrolyte layer may be referred to as “solid electrolyte layer” or “electrolyte layer”.

The thicknesses of the positive electrode active material layer 4 and the negative electrode active material layer 2 can be determined according to the target battery capacity. In consideration of general element dimensions, it is preferably 1 μm or more, and more preferably 3 μm. As an upper limit, it is preferable that it is 1000 micrometers or less, and it is more preferable that it is 400 micrometers or less.
On the other hand, the inorganic solid electrolyte layer 3 is desirably as thin as possible while preventing a short circuit between the positive and negative electrodes. Furthermore, it is preferable that the effect of the present invention is remarkably exhibited. Specifically, it is preferably 1 μm or more, and more preferably 3 μm or more. As an upper limit, it is preferable that it is 1000 micrometers or less, and it is more preferable that it is 400 micrometers or less.

<Solid electrolyte composition>
The solid electrolyte composition of the present invention refers to a composition containing an inorganic solid electrolyte. It is used as a material for forming at least one of the inorganic solid electrolyte layer, the positive electrode active material layer, and the negative electrode active material layer of the all solid state secondary battery of the present invention. The solid electrolyte composition is not limited to a solid, and may be liquid or pasty.
(Inorganic solid electrolyte)
An inorganic solid electrolyte is an inorganic solid electrolyte. In the present specification, the term “solid electrolyte” means a solid electrolyte capable of moving ions therein. From this viewpoint, the inorganic solid electrolyte may be referred to as an ion conductive inorganic solid electrolyte in consideration of the distinction from the electrolyte salt (supporting electrolyte) described later. The ionic conductivity of the inorganic solid electrolyte is not particularly limited, but is preferably 1 × 10 ⁻⁶ S / cm or more, more preferably 1 × 10 ⁻⁵ S / cm or more in lithium ions. More preferably, it is 10 ⁻⁴ S / cm or more, and particularly preferably 1 × 10 ⁻³ S / cm or more. There is no particular upper limit, but 1 S / cm or less is practical. Unless otherwise specified, the ion conductivity measurement method is based on the non-pressurized conditions measured in Examples described later.

Since inorganic solid electrolytes do not contain organic compounds such as polymer compounds and complex salts, they are clear from organic solid electrolytes (polymer electrolytes typified by PEO (polyethylene oxide), organic electrolyte salts typified by LiTFSI, etc.) Are distinguished. In addition, since the inorganic solid electrolyte is a non-dissociable solid in a steady state, it does not dissociate or release into cations and anions even in the liquid. In this respect, it is also clearly distinguished from inorganic electrolyte salts (LiPF ₆ , LiBF ₄ , LiFSI, LiCl, etc.) in which cations and anions are dissociated or liberated in the electrolytic solution or polymer. In general, the inorganic solid electrolyte has conductivity of metal ions (preferably lithium ions) belonging to Group 1 or Group 2 of the periodic table, but does not have electronic conductivity.

In the present invention, the electrolyte layer or the active material layer contains a metal ion (preferably lithium ion) conductive inorganic solid electrolyte belonging to Group 1 or Group 2 of the Periodic Table. As the inorganic solid electrolyte, a solid electrolyte material applied to this type of product can be appropriately selected and used. Typical examples of the inorganic solid electrolyte include (i) sulfide-based inorganic solid electrolyte (sometimes referred to as sulfide solid electrolyte) and (ii) oxide-based inorganic solid electrolyte (sometimes referred to as oxide solid electrolyte). As mentioned.

(I) Sulfide-based inorganic solid electrolyte A sulfide solid electrolyte contains sulfur (S), has ionic conductivity of a metal belonging to Group 1 or Group 2 of the periodic table, and has electronic insulation. Those having properties are preferred. For example, a lithium ion conductive inorganic solid electrolyte that satisfies the composition represented by the following formula (1) can be given.

L _a1 M _b1 P _c1 S _d1 A _e1 (1)

(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. Among them, B, Sn, Si, Al, and Ge are preferable, and Sn, Al, and Ge are more preferable, A represents I, Br, Cl, and F, I and Br are preferable, and I is particularly preferable. E1 represents the composition ratio of each element, and a1: b1: c1: d1: e1 satisfies 1 to 12: 0 to 1: 1: 2 to 12: 0 to 5. a1 is more preferably 1 to 9 1.5 to 4 is more preferable, b1 is preferably 0 to 0.5, d1 is further preferably 3 to 7, more preferably 3.25 to 4.5, and e1 is further preferably 0 to 3. 0 to 1 are more preferable.)

In the formula (1), the composition ratio of L, M, P, S and A is preferably such that b1 and e1 are 0, more preferably b1 = 0 and e1 = 0 and the ratio of a1, c1 and d1 ( a1: c1: d1) is a1: c1: d1 = 1-9: 1: 3-7, more preferably b1 = 0, e1 = 0 and a1: c1: d1 = 1.5-4: 1 : 3.25 to 4.5. The composition ratio of each element can be controlled by adjusting the blending amount of the raw material compound when producing the sulfide-based solid electrolyte as described below.

The sulfide-based solid electrolyte may be amorphous (glass) or crystallized (glass ceramics), or only part of it may be crystallized.

The ratio of Li ₂ S to P ₂ S ₅ in the Li—PS system glass and the Li—PS system glass ceramic is a molar ratio of Li ₂ S: P ₂ S ₅ , preferably 65:35 to 85:15, more preferably 68:32 to 75:25. By setting the ratio of Li ₂ S to P ₂ S ₅ within this range, the lithium ion conductivity can be increased. Specifically, the lithium ion conductivity can be preferably 1 × 10 ⁻⁴ S / cm or more, more preferably 1 × 10 ⁻³ S / cm or more. Although there is no upper limit, it is practical that it is 1 × 10 ⁻¹ or less.

Specific examples of the compound include those using a raw material composition containing, for example, Li ₂ S and a sulfide of an element belonging to Group 13 to Group 15. Specifically, Li ₂ S—P ₂ S ₅ , Li ₂ S—LiI—P ₂ S ₅ , Li ₂ S—LiI—Li ₂ O—P ₂ S ₅ , Li ₂ S—LiBr—P ₂ S ₅ Li ₂ S—Li ₂ O—P ₂ S ₅ , Li ₂ S—Li ₃ PO ₄ —P ₂ S ₅ , Li ₂ S—P ₂ S ₅ —P ₂ O ₅ , Li ₂ SP—P ₂ S ₅ —SiS ₂ , Li ₂ S—P ₂ S ₅ —SnS, Li ₂ S—P ₂ S ₅ —Al ₂ S ₃ , Li ₂ S—GeS ₂ , Li ₂ S—GeS ₂ —ZnS, Li ₂ S—Ga ₂ S ₃ , Li ₂ S—GeS ₂ —Ga ₂ S ₃ , Li ₂ S—GeS ₂ —P ₂ S ₅ , Li ₂ S—GeS ₂ —Sb ₂ S ₅ , Li ₂ S—GeS ₂ —Al ₂ S _{_{_{3, Li 2 S-SiS 2}}} , Li 2 S-Al 2 S 3, Li 2 S-SiS 2 -Al _{_{_{_{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, Examples include Li ₂ S—SiS ₂ —Li ₃ PO ₄ and Li ₁₀ GeP ₂ S ₁₂ . Among them, Li ₂ S—P ₂ S ₅ , Li ₂ S—GeS ₂ —Ga ₂ S ₃ , Li ₂ S—LiI—P ₂ S ₅ , Li ₂ S—LiI—Li ₂ O—P ₂ S ₅ , Li ₂ S—SiS ₂ —P ₂ S ₅ , Li ₂ S—SiS ₂ —Li ₄ SiO ₄ , Li ₂ S—SiS ₂ —Li ₃ PO ₄ , Li ₂ S—Li ₃ PO ₄ —P ₂ S ₅ , A crystalline and / or amorphous raw material composition comprising Li ₂ S—GeS ₂ —P ₂ S ₅ or Li ₁₀ GeP ₂ S ₁₂ is preferred because it has high lithium ion conductivity. Examples of a method for synthesizing a sulfide solid electrolyte material using such a raw material composition include an amorphization method. Examples of the amorphization method include a mechanical milling method and a melt quenching method, and among them, the mechanical milling method is preferable. This is because processing at room temperature is possible, and the manufacturing process can be simplified.

The sulfide solid electrolyte is more preferably represented by the following formula (2).
Li _l P _m _Sn formula (2)
In the formula, l to n represent the composition ratio of each element, and l: m: n satisfies 2 to 4: 1: 3 to 10.

(Ii) Oxide-based inorganic solid electrolyte An oxide-based solid electrolyte contains oxygen (O), has ion conductivity of a metal belonging to Group 1 or Group 2 of the periodic table, and is an electron What has insulation is preferable.

Specific examples of the compound include Li _xa La _ya TiO ₃ [xa = 0.3 to 0.7, ya = 0.3 to 0.7] (LLT), Li _xb La _yb Zr _zb M ^bb _mb O _nb ( ^Mbb is at least one element selected from Al, Mg, Ca, Sr, V, Nb, Ta, Ti, Ge, In, and Sn, xb satisfies 5 ≦ xb ≦ 10, and yb satisfies 1 ≦ yb. ≦ 4, zb satisfies 1 ≦ zb ≦ 4, mb satisfies 0 ≦ mb ≦ 2, nb satisfies 5 ≦ nb ≦ 20), Li _xc B _yc M ^cc _zc _Onc (M ^cc is C, S, Al, Si, Ga, Ge, In, Sn are at least one element, xc satisfies 0 ≦ xc ≦ 5, yc satisfies 0 ≦ yc ≦ 1, and zc satisfies 0 ≦ zc ≦ met 1, nc satisfies 0 ≦ nc ≦ 6.), Li xd ( _{_{l, Ga) yd (Ti,}} Ge) zd Si ad P md O nd ( provided that, 1 ≦ xd ≦ 3,0 ≦ yd ≦ 1,0 ≦ zd ≦ 2,0 ≦ ad ≦ 1,1 ≦ md ≦ 7, 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 Represents a combination of two or more halogen atoms.), Li _xf Si _yf O _zf (1 ≦ xf ≦ 5, 0 <yf ≦ 3, 1 ≦ zf ≦ 10), Li _xg S _yg O _zg (1 ≦ xg ≦ 3, 0 <yg ≦ 2, 1 ≦ zg ≦ 10), Li ₃ BO ₃ —Li ₂ SO ₄ , Li ₂ O—B ₂ O ₃ —P ₂ O ₅ , Li ₂ O—SiO ₂ , Li ₆ BaLa ₂ _{_{_{_{ta 2 O 12, Li 3 PO}}}} (4-3 / 2w) N w (w is w <1), LI ICON (Lithium super ionic conductor) type _Li 3.5 _Zn 0.25 GeO ₄ having a crystal structure, _La 0.55 _Li 0.35 _TiO 3 having a perovskite crystal structure, NASICON (Natrium super ionic conductor) type crystal structure LiTi ₂ P ₃ O ₁₂ , Li _{1 + xh + yh} (Al, Ga) _xh (Ti, Ge) _2-xh Si _yh P _3-yh O ₁₂ (where 0 ≦ xh ≦ 1, 0 ≦ yh ≦ 1), garnet Examples include Li ₇ La ₃ Zr ₂ O ₁₂ having a type crystal structure. Phosphorus compounds containing Li, P and O are also desirable. For example, lithium phosphate (Li ₃ PO ₄ ), LiPON obtained by replacing a part of oxygen of lithium phosphate with nitrogen, LiPOD ¹ (D ¹ is Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zr) , Nb, Mo, Ru, Ag, Ta, W, Pt, Au, etc.). LiA ¹ ON (A ¹ is at least one selected from Si, B, Ge, Al, C, Ga, etc.) and the like can also be preferably used.
Among them, Li _xa La _ya TiO ₃ [xa = 0.3 to 0.7, ya = 0.3 to 0.7] (LLT), Li _xb La _yb Zr _zb M ^bb _mb _Onb (M ^bb is Al , Mg, Ca, Sr, V, Nb, Ta, Ti, Ge, In, Sn, xb satisfies 5 ≦ xb ≦ 10, yb satisfies 1 ≦ yb ≦ 4, zb Satisfies 1 ≦ zb ≦ 4, mb satisfies 0 ≦ mb ≦ 2, nb satisfies 5 ≦ nb ≦ 20), Li ₇ La ₃ Zr ₂ O ₁₂ (LLZ), Li ₃ BO ₃ , Li ₃ _{_{_{_{BO 3 -Li 2 SO 4, Li}}}} xd (Al, Ga) yd (Ti, Ge) zd Si ad P md O nd ( provided that, 1 ≦ xd ≦ 3,0 ≦ yd ≦ 1,0 ≦ zd ≦ 2,0 ≦ ad ≦ 1, 1 ≦ md ≦ 7, 3 ≦ nd ≦ 13) are preferred . These may be used alone or in combination of two or more.

The ionic conductivity of the lithium ion conductive oxide-based inorganic solid electrolyte is preferably 1 × 10 ⁻⁶ S / cm or more, more preferably 1 × 10 ⁻⁵ S / cm or more. X 10 ⁻⁵ S / cm or more is particularly preferable.

In the present invention, it is particularly preferable to use an oxide-based inorganic solid electrolyte. Since the oxide-based inorganic solid electrolyte generally has a higher hardness, the interface resistance is likely to increase in the all-solid secondary battery. By applying the present invention, the effect becomes more prominent. In particular, it is assumed that an oxide-based inorganic solid electrolyte and the following specific binder act to form a more suitable adsorption state. Also from this viewpoint, it is particularly preferable to use an oxide-based inorganic solid electrolyte.
The said inorganic solid electrolyte may be used individually by 1 type, or may be used in combination of 2 or more type.

The average particle size of the inorganic solid electrolyte is not particularly limited, but is preferably 0.01 μm or more, and more preferably 0.1 μm or more. 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 concentration of the inorganic solid electrolyte in the solid electrolyte composition is preferably 50% by mass or more and 100% by mass in 100% by mass of the solid component when considering both the battery performance and the reduction / maintenance effect of the interface resistance. % Or more is more preferable, and 90% by mass or more is particularly preferable. As an upper limit, it is preferable that it is 99.9 mass% or less from the same viewpoint, 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 used together with a positive electrode active material or a negative electrode active material to be described later, the sum is preferably in the above concentration range.

(Specific binder)
In the present invention, a compound having a structure in which a linear molecule penetrates a cyclic molecule is used as the binder of the inorganic solid electrolyte. This compound is called pseudorotaxane or polypseudorotaxane, and a compound in which the terminal is blocked with a bulky substituent so that the cyclic molecule does not escape from the linear molecule is sometimes called rotaxane, polyrotaxane or the like. In this specification, these cross-linked products are collectively referred to as polyrotaxane compounds. A preferred polyrotaxane compound of the present invention is schematically shown in FIG. The polyrotaxane compound of the present embodiment has a structure in which linear molecules 21 are inserted through a plurality of cyclic molecules 22. The end of the linear molecule is sealed with a terminal substituent 24 to prevent the cyclic molecule from falling off. Adjacent polyrotaxane compounds 20 are connected to each other by a cross-linked chain (linked chain by a reactive group) 23. Thus, in this embodiment, the binder comprised with the crosslinked material 200 of the polyrotaxane compound is comprised. Thus, by using a cyclic molecule of a polyrotaxane compound as a crosslinking point, a crosslinked product having a movable crosslinking point is obtained, which has an effect of uniforming the tension between the polymers and exhibits specific mechanical properties. By using such a polyrotaxane compound as a binder, good binding properties are expressed. Such a cross-linked structure may be added in advance as a cross-linked structure, or may be formed in the state of a solid electrolyte composition paste, or may be cross-linked after forming it into an electrode sheet. In this specification, the term “binder” is used in a broad sense to include both an uncrosslinked polyrotaxane compound and a crosslinked product thereof. When distinguishing, it calls an uncrosslinked binder (uncrosslinked polyrotaxane compound) and a crosslinked binder (crosslinked polyrotaxane compound), respectively.

-Linear molecule The linear molecule is preferably a polyolefin, polyether, polyester, polysiloxane, polycarbonate, polyacrylate, polyurethane, polyurea, polymer having a heterocyclic ring in the main chain, or a compound containing a polyene structure.

The polyolefin is preferably a compound having a repeating unit represented by the following formula (1-1).

L ¹ is an alkylene group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, particularly preferably 1 to 3 carbon atoms) or an alkenylene group (preferably having 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms). Is particularly preferred). A plurality of L ^{1 in the} molecule may be the same as or different from each other. L ¹ may further have a substituent T described later. This repeating unit is preferably present in the molecule in a molar ratio of 50% or more, more preferably 60% or more, and particularly preferably 70% or more. The upper limit is 100%.

The polyether is preferably a compound having a repeating unit represented by the following formula (1-2).

L ² is a linking group, an alkylene group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, particularly preferably 1 to 4 carbon atoms), or an alkenylene group (preferably having 2 to 12 carbon atoms, preferably having 2 to 6 carbon atoms). More preferably, it is preferably 2 to 4), an arylene group (preferably having 6 to 22 carbon atoms, more preferably 6 to 14 and particularly preferably 6 to 10), or a group relating to a combination thereof. The above linking group may further have a substituent T described later. A plurality of L ² in the molecule may be the same or different from each other. Moreover, said coupling group (an alkylene group, an alkenylene group, an arylene group) may interpose the coupling group containing a hetero atom. Examples of the linking group containing a hetero atom include an oxygen atom, a sulfur atom, an imino group (NR ^N ), an ammonium linking group (NR ^N ₂ ⁺ · M ⁻ ), and a carbonyl group. Here, ^RN is an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, particularly preferably 1 to 3 carbon atoms), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, 2 or 3 is particularly preferred), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 14 carbon atoms, particularly preferably 6 to 10 carbon atoms), an aralkyl group (preferably having 7 to 23 carbon atoms, more preferably 7 to 15 carbon atoms). 7 to 11 are particularly preferable). Incidentally, it is also synonymous ^{R N} to be described later. M ⁻ is a counter anion and can be exemplified by PF ₆ ^— .
This repeating unit is preferably present in the molecule in a molar ratio of 50% or more, more preferably 60% or more, and particularly preferably 70% or more. The upper limit is 100%.

The polysiloxane is preferably a compound having a repeating unit represented by the following formula (1-3).

R ³¹ and R ³² each independently represent a hydrogen atom, a hydroxyl group, an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and particularly preferably 1 to 3 carbon atoms), an alkenyl group (having 2 to 12 carbon atoms). Preferably 2 to 6, more preferably 2 or 3, particularly an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 14 carbon atoms, particularly preferably 6 to 10 carbon atoms), an aralkyl group (7 to 7 carbon atoms). 23 is preferable, 7 to 15 is more preferable, and 7 to 11 is particularly preferable. The alkyl group, alkenyl group, aryl group and aralkyl group may further have a substituent T described later. A plurality of R ³¹ and R ^{32 in the} molecule may be the same as or different from each other.
This repeating unit is preferably present in the molecule in a molar ratio of 50% or more, more preferably 60% or more, and particularly preferably 70% or more. The upper limit is 100%.

The compound containing a polyene structure is preferably a compound having a repeating unit represented by the following formula (1-4) or (1-5).

R ⁴¹ , R ⁴² , R ⁵¹ and R ⁵² are each independently a hydrogen atom, a halogen atom, a cyano group, a hydroxyl group or an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and particularly preferably 1 to 3 carbon atoms). Preferably), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 14 carbon atoms, particularly preferably 6 to 10 carbon atoms), an aralkyl group (preferably having 7 to 23 carbon atoms, more preferably 7 to 18 carbon atoms, and 7 to 12 carbon atoms). Is particularly preferred). This alkyl group, aryl group, and aralkyl group may further have a substituent T described later. A plurality of R ⁴¹ , R ⁴² , R ⁵¹ and R ^{52 in the} molecule may be the same as or different from each other.
This repeating unit is preferably present in the molecule in a molar ratio of 50% or more, more preferably 60% or more, and particularly preferably 70% or more. The upper limit is 100%.

The polyester is preferably a compound having a repeating unit represented by the following formula (1-6).

L ⁶ is a group having the same meaning as L ² .
This repeating unit is preferably present in the molecule in a molar ratio of 50% or more, more preferably 60% or more, and particularly preferably 70% or more. The upper limit is 100%.

Polycarbonate, polyurethane, and polyurea are preferably compounds having a repeating unit represented by the following formula (1-7).

L ⁷ is a group having the same meaning as L ² . X, Y are each independently O or NR ^N.
This repeating unit is preferably present in the molecule in a molar ratio of 50% or more, more preferably 60% or more, and particularly preferably 70% or more. The upper limit is 100%.

The polyacrylate is preferably a compound having a repeating unit represented by the following formula (1-8).

L ⁸ is a group having the same meaning as L ² . R ⁸¹ is a hydrogen atom, a halogen atom, a methyl group, an ethyl group, a cyano group, or a hydroxyl group. R ⁸² each independently represents a hydrogen atom, an alkyl group (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, particularly preferably 1 to 3 carbon atoms), an alkenyl group (preferably 2 to 12 carbon atoms, preferably 2 to 6 carbon atoms). More preferably, 2 or 3 is particularly preferred), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 14 and particularly preferably 6 to 10), and an aralkyl group (preferably having 7 to 23 carbon atoms, preferably 7 to 7 carbon atoms). 18 is more preferable, and 7 to 12 is particularly preferable.) And a polyether group (polyethylene oxide, polypropylene oxide, and polybutylene oxide are preferable). The alkyl group, alkenyl group, aryl group and aralkyl group may further have a substituent T described later. A plurality of R ⁸¹ and R ^{82 in the} molecule may be the same as or different from each other.
This repeating unit is preferably present in the molecule in a molar ratio of 50% or more, more preferably 60% or more, and particularly preferably 70% or more. The upper limit is 100%.

The polymer having a heterocyclic ring in the main chain is preferably a compound having a repeating unit represented by the following formula (1-9).

Ar ¹ is a heterocyclic group, a heteroaliphatic cyclic group (preferably having 1 to 12 carbon atoms, more preferably 2 to 5), or a heteroaromatic cyclic group (preferably having 1 to 12 carbon atoms, preferably having 2 to 5 carbon atoms). More preferred). The heterocyclic group may be a cation or a structure with a counter anion. Examples of heterocycles include thiophene rings, pyridine rings (may be pyridinium rings), pyrrole rings (may be pyrrolium rings), furan rings, pyrazine rings (may be pyrazinium rings), pyrimidine rings (may be pyrimidinium rings), piperidine Ring (may be piperidinium ring), tetrahydrofuran ring, tetrahydropyran ring, pyrrolidine ring (may be pyrrolidinium ring), imidazole ring (may be imidazolinium ring), pyrazole ring (may be pyrazolinium ring), morpholine ring (also morpholinium ring) Good). The hetero atom of the heteroaliphatic ring group or heteroaromatic ring group is preferably an oxygen atom, a sulfur atom, a nitrogen atom or a combination thereof. Heterocyclic group may have a substituent T described later without going through or via a linking group L ^2.
Z is preferably a single bond, an alkylene group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, particularly preferably 1 to 3 carbon atoms), O, S, NR ^N , CO, or a combination thereof. A single bond or an alkylene group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and particularly preferably 1 to 3 carbon atoms) is more preferable.
This repeating unit is preferably present in the molecule in a molar ratio of 50% or more, more preferably 60% or more, and particularly preferably 70% or more. The upper limit is 100%.

Examples of linear molecules include polyethers such as polyethylene glycol, polypropylene glycol and polytetrahydrofuran, polyolefins such as polyethylene and polypropylene, celluloses such as carboxymethyl cellulose, hydroxyethyl cellulose and hydroxypropyl cellulose, polyammonium salts, polydimethyl Preferable examples include polysiloxanes such as siloxane, polythiophenes, polymethacrylates such as polymethyl methacrylate, polyacrylic acid, polyesters, and polycarbonates. Furthermore, polyacrylates, polysiloxanes, polycarbonates and polyethers are preferred, and polyethers are particularly preferred. In the present specification, the acrylate means that the carbon at the α-position may have an arbitrary substituent, and examples thereof include the above ^R81 .

Examples of structural units of linear molecules that are preferably employed in the present invention are shown below, but the present invention is not construed as being limited thereto.

The weight average molecular weight of the linear molecule is preferably 1,000 or more, more preferably 5,000 or more, and particularly preferably 10,000 or more. The upper limit is preferably 1,000,000 or less, more preferably 500,000 or less, and particularly preferably 300,000 or less. By setting it within this range, it is preferable that the cyclic molecule (the inclusion compound) moves freely on the linear molecule. In the present specification, the molecular weight is based on the conditions measured in Examples described below unless otherwise specified.

The structural unit constituting the cyclic molecule includes, for example, a linking group having a hetero atom (oxygen atom, NR ^N , sulfur atom, CO is preferred), a heteroaliphatic ring group (preferably having 1 to 12 carbon atoms, preferably having 2 to 6 carbon atoms). More preferably), a heteroaromatic cyclic group (preferably having 1 to 12 carbon atoms, more preferably 2 to 6 carbon atoms), an alkylene group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and particularly preferably 1 to 3 carbon atoms). ), An alkenylene group (preferably having 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, particularly preferably 2 or 3), and an aromatic group (preferably having 6 to 22 carbon atoms, more preferably 6 to 14 carbon atoms, and 6 to 10 carbon atoms). Are particularly preferred) and combinations thereof. The hetero atom of the heteroaliphatic ring group or heteroaromatic ring group is preferably an oxygen atom, a sulfur atom, or a nitrogen atom. The heteroaliphatic ring group and heteroaromatic ring group are preferably 4- to 7-membered rings, and more preferably 5- or 6-membered rings. Each of the above linking groups may have a substituent T described later.

-Cyclic molecule The cyclic molecule preferably has a structure in which a plurality of structural units are linked to form a ring, and the structural units in the cyclic molecule may be the same or different.

The structural unit of the cyclic molecule is preferably represented by any of the following formulas. The following formula may be a double cyclic structure, such as a structure (c) as a structural unit, or may be a multiple cyclic structure such as triple or quadruple. In that case, the structural unit of each formula may be interpreted as having a multiple structure.

L ^A is a group having the same meaning as L ² above.

Ar ² is a cyclic structure group, a heteroaliphatic ring group (preferably having 1 to 12 carbon atoms, more preferably 2 to 6), or a heteroaromatic ring group (preferably having 1 to 12 carbon atoms, more preferably 2 to 6 carbon atoms). And an aromatic group (preferably 6 to 22 carbon atoms, more preferably 6 to 14 carbon atoms, and particularly preferably 6 to 10 carbon atoms). The hetero atom of the heteroaliphatic ring group or heteroaromatic ring group is preferably an oxygen atom, a sulfur atom, or a nitrogen atom. The heteroaliphatic ring group and heteroaromatic ring group are preferably 4- to 7-membered rings, and more preferably 5- or 6-membered rings. The cyclic molecule may have a linking group in addition to the structural unit described above or below, and an oxygen atom, a sulfur atom, an imino group (NR ^N ), a carbonyl group, an alkylene group (preferably having 1 to 12 carbon atoms, 1 to 6 is more preferable, and 1 to 3 is particularly preferable), or a combination thereof.
R ^A1 to R ^A4 are groups having the same meaning as R ⁸¹ .

Ring α is a cyclic structural group containing one or more X ^A1 , and forms a ring structure with an oxygen atom, a sulfur atom, an imino group (NR ^N ), a carbonyl group, an alkylene group, an alkenylene group, an arylene group, or a combination thereof. ing. Among them, an alkylene group having 2 to 12 carbon atoms, an oxygen atom, a sulfur atom, a carbonyl group, an imino group, or a combination thereof is preferable, and a combination of an alkylene group having 3 to 6 carbon atoms and an oxygen atom is particularly preferable. . Examples of the ring α include a 3-membered ring to an 8-membered ring, and among them, a 5-membered ring or a 6-membered ring is preferable. Specific examples include a glucose ring, a fructose ring, a galactose ring, and a mannose ring. May be accompanied by a substituent T of any later without going through or over an exemplary cyclic groups further either a single bond or a linking group L ² above.
X ^A1 and X ^A2 each independently represent a hetero atom-containing linking group, preferably an oxygen atom, a sulfur atom, or an imino group (NR ^N ), and particularly preferably an oxygen atom.
Ring α is preferably the following formula (d). X ^d2 , X ^d3 and X ^d6 are each independently a hydrogen atom or a group having the same meaning as R ⁸² . L ^d2 , L ^d3 , and L ^d6 are each independently a single bond, a carbonyl group, or an imino group (NR ^N ).

Ar ² is preferably any one of the following formulas (a) to (d).

Among the cyclic molecules, cyclodextrins such as α-cyclodextrin, β-cyclodextrin, and γ-cyclodextrin, crown ethers, cucurbiturils, cyclophanes, and calixarenes are preferable. Furthermore, cyclodextrin is preferred.

In the cyclic molecule, the number of structural units is not particularly limited, but is preferably 2 or more, more preferably 3 or more, and particularly preferably 4 or more. The upper limit is preferably 30 or less, more preferably 20 or less, and particularly preferably 15 or less.

Preferred examples of the cyclic molecule are exemplified below, but the present invention is not construed as being limited thereto.

-Terminal group It is preferable that said polyrotaxane compound has a bulky substituent (terminal group) in the terminal. By doing in this way, it can fix so that a cyclic molecule may not slip from a linear molecule. Although the molecular weight of a terminal group is not specifically limited, It is preferable that it is 70 or more, and it is more preferable that it is 100 or more. The upper limit is practically 1000 or less. The bulkiness of the terminal group may be determined in relation to the size of the ring of the cyclic molecule, and may be a size that does not allow the cyclic molecule to escape. The molecular weight of the terminal group can be set with respect to the number of linked atoms of the cyclic molecule in the relationship of molecular weight of the terminal group> number of linked atoms × 3. Molecular weight of terminal group> number of connected atoms × 5 is preferable, and molecular weight of terminal group> number of connected atoms × 8 is more preferable. As an upper limit, the molecular weight of the terminal group <the number of connected atoms × 100 is practical. The number of linking atoms is the number of atoms involved in linking constituting the ring. Compound A-1 is 30, A-4 is 21, A-5 is 21, and A-12 is 28.

When a substituent is introduced at both ends of the linear molecule of the binder, a bulky one is preferable to prevent the cyclic molecule from falling off the linear molecule. It is preferable that the terminal group is appropriately selected from substituents having such a size that the cyclic molecule differs depending on the size of the opening of the cyclic molecule and the cyclic molecule cannot be removed. Specific examples include a phenyl group-containing group, a cyclodextrin structure-containing group, and an adamantane structure-containing group. Among them, nitrophenyl groups such as 2,4-dinitrophenyl group, 3,5-dinitrophenyl group, 2,4,6-trinitrophenyl group; triphenylmethyl group (trityl group), 3,5-dimethyl Examples include groups including phenyl group, 3,5-tertbutylphenyl group, adamantyl group, pyrene group, naphthalene group, fluorescein group, cyclodextrin group and the like.

The method for substituting the end of the linear molecule with a bulky substituent is not particularly limited. For example, by using a polymer having amino groups at both ends of polyethylene glycol as a linear molecule and reacting the amino groups at both ends with 2,4-dinitrophenyl fluoride, 2,4 as the above-mentioned bulky blocking group. -The end can be substituted with a dinitrophenyl group. Further, instead of the above 2,4-dinitrophenyl fluoride, trityl bromide, 2,4,6-trinitrophenyl fluoride, 3,5-dimethylbenzoic acid chloride, 3,5-tertbutylbenzoic acid chloride, If 1-fluoropyrene or the like is used, the terminal can be substituted with a trityl group, 2,4,6-trinitrophenyl group, or pyrene group, respectively.
Further, an adamantyl group and a cyclodextrin can be introduced by reacting a carboxylic acid group at both ends with adamantylamine and cyclodextrin, respectively, by using a polymer having a carboxyl group at both ends of polyethylene glycol as a linear molecule.

There is no particular limitation on the method of clathrating linear molecules to the cyclic molecules, and known methods can be applied. When α-, β-, or γ-cyclodextrin is used as the cyclic molecule and polyethers are used as the linear molecule, both components can be obtained by stirring and mixing in an aqueous medium to cause a reaction. In particular, when polypropylene glycol is used as the linear molecule, it may be in a dispersed state, so it is preferable to perform ultrasonic stirring.

When the linear molecule is a polymer compound having a plurality of monomers, the ratio of the linear molecule and the cyclic molecule in the binder is (number of moles of monomer units constituting the linear molecule): (cyclic molecule) The ratio is preferably 100: 0.1 to 100: 70, more preferably 100: 0.5 to 100: 50, and particularly preferably 100: 1 to 100: 40. The ratio of linear molecules to cyclic molecules can be measured by 1H- and 13C-NMR spectra, light absorption, elemental analysis and the like.

The polyrotaxane compound can be applied to the present invention with appropriate reference to known literature. For example, WO08 / 108411 for the production method of polyrotaxane, WO10 / 024431 for the production method of polyrotaxane without solvent, WO11 / 105532 for the photocrosslinkable polyrotaxane, WO06-090819 for the polymer electrolyte of polyrotaxane, and JP2003-257236A JP, 2004-327271, A, etc. can be referred to.

・ Reactive groups (functional groups)
The cyclic molecule or linear molecule preferably has a reactive group, and among them, the cyclic molecule preferably has a reactive group. The reactive group preferably has a function of linking and crosslinking the polyrotaxane compound by performing a treatment such as heating. At this time, it is preferable that the cyclic molecules are linked and crosslinked as described above. Reactive group of the linking group having a hetero atom (O, S, CO, NR N and the like) may be introduced into a linear molecule and cyclic molecule by intervening and said L ^2.

The reactive group is preferably a hetero atom (B, O, S, N, P, etc.) or a substituent or linking group having an unsaturated bond. Especially, it is preferable to have at least any one of the following reactive substituent (A) and the following reactive coupling group (B).
Reactive substituent [functional group] (A)
Amino group (NR ^N ₂ ), thiol group (sulfide group) (SH), tetrahydrofuryl group, oxetane group, epoxy group, isocyanate group, carboxyl group, phosphoric acid group, sulfonic acid group, phosphonic acid group, hydroxyl group, Alkenyl group-containing group (vinyl group, allyl group, acryloyl group, acryloyloxy, etc.)
Reactive linking group [functional group] (B)
Imino group (NR ^N ), alkenylene group-containing group (preferably having 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and particularly preferably 2 or 3 carbon atoms)

Among them, reactive groups are hydroxyl group, alkenyl group-containing group (vinyl group, allyl group), acryloyl group, acryloyloxy group, epoxy group, thiol group, isocyanate group, carboxyl group, phosphate group, sulfonate group. A phosphonic acid group is preferred. In the present specification, the term “acrylic or acryloyl” means that the α-position carbon may have a predetermined substituent. For example, it is meant to include those having an R ⁸¹ group at the α-position. For example, a methacryloyl group and a methacryloyloxy group are included.
The reactive group is preferably a thiol group, epoxy group, hydroxyl group, isocyanate group, carboxyl group, phosphoric acid group, sulfonic acid group, phosphonic acid group, or alkenyl group-containing group, carboxyl group, phosphoric acid group, sulfone group. Particularly preferred are acid groups and phosphonic acid groups.

Preferred examples of the reactive group are illustrated below, but the present invention is not construed as being limited thereto.

A known method can be adopted as the condition for introducing the reactive group.
For example, when a reactive group is newly introduced into an inclusion compound using α-cyclodextrin as a cyclic molecule and polyethylene glycol substituted at both ends as a linear molecule, the inclusion compound is dissolved in dimethyl sulfoxide. The reactive group M-4 can be introduced by adding 2-isocyanatoethyl methacrylate and bismuth tris (2-ethylhexanoate) to this solution and reacting them. In the same manner, M-3 can be introduced by using 2-isocyanatoethyl acrylate instead of 2-isocyanatoethyl methacrylate. M-1 and M-2 can be introduced by reacting methacrylic acid chloride or acrylic acid chloride in DMF. M-6 can be introduced by reacting 3-mercaptopropylmethyldimethoxysilane in ethanol / water. M-7 to M-11 can be introduced in the same manner. M-12 can be introduced by reacting succinic anhydride in dimethyl sulfoxide.
When crown ether is used as the cyclic molecule, the crown ether derivative having a hydroxyl group introduced therein is dissolved in dimethyl sulfoxide, and 2-isocyanatoethyl methacrylate and bismuth tris (2-ethylhexanoate) are added to this solution and reacted. The reactive group M-4 can be introduced with Similarly, other cyclic molecules can introduce a reactive group M-4 by introducing 2-isocyanatoethyl methacrylate and bismuth tris (2-ethylhexanoate) after introducing a hydroxyl group and reacting them.

The solid electrolyte composition of the present invention preferably contains a radical polymerization initiator.
The radical polymerization initiator is preferably added for the purpose of reacting the reactive group.
As the radical polymerization initiator, a commonly used one may be used, but as the thermal radical polymerization initiator that is cleaved by heat to generate an initiation radical, methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, acetylacetone peroxide, cyclohexanone peroxide are used. Ketone peroxides such as oxide and methylcyclohexanone peroxide; hydroperoxides such as 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide and t-butyl hydroperoxide; diisobutyryl peroxide Bis-3,5,5-trimethylhexanoyl peroxide, lauroyl peroxide, benzoyl peroxide and m-toluylbenzoyl peroxide Acyl peroxides; dicumyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 1,3-bis (t-butylperoxyisopropyl) hexane, t-butylcumyl peroxide, Dialkyl peroxides such as di-t-butyl peroxide and 2,5-dimethyl-2,5-di (t-butylperoxy) hexene; 1,1-di (t-butylperoxy-3,5,5- Peroxyketals such as trimethyl) cyclohexane, 1,1-di-t-butylperoxycyclohexane and 2,2-di (t-butylperoxy) butane; t-hexylperoxypivalate, t-butylperoxypivalate, , 1,3,3-Tetramethylbutylperoxy-2-ethylhexanoate, t-amino Peroxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, t-butylperoxyisobutyrate, di-t-butylperoxyhexahydroterephthalate, 1,1,3,3-tetramethylbutyl Peroxy-3,5,5-trimethylhexanoate, t-amylperoxy-3,5,5-trimethylhexanoate, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxyacetate, alkyl peresters such as t-butylperoxybenzoate and dibutylperoxytrimethyladipate; 1,1,3,3-tetramethylbutylperoxyneodicarbonate, α-cumylperoxyneodicarbonate, t-butylperoxyneodicarbonate, di-3 -Me Xylbutylperoxydicarbonate, di-2-ethylhexylperoxydicarbonate, bis (1,1-butylcyclohexaoxydicarbonate), diisopropyloxydicarbonate, t-amylperoxyisopropylcarbonate, t-butylperoxyisopropylcarbonate, t- Peroxycarbonates such as butylperoxy-2-ethylhexyl carbonate and 1,6-bis (t-butylperoxycarboxy) hexane; 1,1-bis (t-hexylperoxy) cyclohexane and (4-t-butylcyclohexyl) per Examples thereof include oxydicarbonate.
Specific examples of the azo compound used as an azo-based (AIBN or the like) polymerization initiator include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), 2, 2'-azobis (2,4-dimethylvaleronitrile), 1,1'-azobis-1-cyclohexanecarbonitrile, dimethyl-2,2'-azobisisobutyrate, 4,4'-azobis-4-cyano Examples include valeric acid, 2,2′-azobis- (2-amidinopropane) dihydrochloride, and the like (see JP 2010-189471 A). Alternatively, dimethyl-2,2′-azobis (2-methylpropinate) (trade name V-601, manufactured by Wako Pure Chemical Industries, Ltd.) is also preferably used.

As the radical polymerization initiator, in addition to the thermal radical polymerization initiator, a radical polymerization initiator that generates an initiation radical by light, electron beam, or radiation can be used.
Examples of such radical polymerization initiators include benzoin ether, 2,2-dimethoxy-1,2-diphenylethane-1-one [IRGACURE651, trade name, manufactured by Ciba Specialty Chemicals Co., Ltd.], 1-hydroxy-cyclohexyl -Phenyl-ketone [IRGACURE 184, trade name, manufactured by Ciba Specialty Chemicals Co., Ltd.], 2-hydroxy-2-methyl-1-phenyl-propan-1-one [DAROCUR 1173, manufactured by Ciba Specialty Chemicals Co., Ltd., Trademarks], 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one [IRGACURE2959, trade name, manufactured by Ciba Specialty Chemicals Co., Ltd.], 2 -Hydroxy-1- [4- [4- (2-H Roxy-2-methyl-propionyl) -benzyl] phenyl] -2-methyl-propan-1-one (IRGACURE127, trade name, manufactured by Ciba Specialty Chemicals), 2-methyl-1- (4-methylthiophenyl) ) -2-morpholinopropan-1-one [IRGACURE907, trade name, manufactured by Ciba Specialty Chemicals Co., Ltd.], 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 [ IRGACURE369, manufactured by Ciba Specialty Chemicals, Inc., trademark], 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-monophorinyl) phenyl] -1-butanone [IRGACURE 379, trade name, manufactured by Ciba Specialty Chemicals Co., Ltd.] 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (DAROCUR TPO, trade name, manufactured by Ciba Specialty Chemicals), bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide [IRGACURE819, Ciba Trademarks, Specialty Chemicals, Inc.], bis (η ⁵ -2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) Titanium [IRGACURE784, manufactured by Ciba Specialty Chemicals, Inc., trademark], 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)] [IRGACURE OXE 01, Ciba Specialty Chemicals Co., Ltd., Trademark], D Non, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) [IRGACURE OXE 02, manufactured by Ciba Specialty Chemicals Co., Ltd. , Trademark] and the like.
The amount of the radical polymerization initiator is not particularly limited, but is preferably 0.01% by mass or more in the composition, more preferably 0.02% by mass or more, and 0.05% by mass or more. Is particularly preferred. The upper limit is preferably 20% by mass or less, more preferably 10% by mass or less, and particularly preferably 5% by mass or less.
The radical polymerization initiator may be used alone or in combination of two or more.

The cross-linked product of the polyrotaxane compound is preferably obtained by cross-linking the cyclic molecule in the polyrotaxane compound as a cross-linking point. The form of crosslinking is not particularly limited, and reactive groups (functional groups) may react with each other to crosslink, reactive groups may react with other reactive groups, and reactive groups react with crosslinking agents. And may be cross-linked. A well-known thing can be used as a crosslinking agent. Specific examples include polyfunctional carboxylic acid chlorides such as trimesic acid chloride and terephthalic acid chloride, molecules having reactive halogen atoms such as epichlorohydrin, dibromobenzene and cyanuric chloride, and polyfunctional aldehydes such as glutaraldehyde. Polyfunctional isocyanates such as phenylene diisocyanate and tolylene diisocyanate, polyfunctional vinyls such as 1,1′-carbonyldiimidazole polyfunctional imidazoles, divinyl sulfone, triethylene glycol dimethacrylate, divinylbenzene, tetramethoxysilane, Examples include alkoxysilanes such as tetraethoxysilane.

A well-known method can be adopted for the crosslinking reaction. For example, when cross-linking an inclusion compound using α-cyclodextrin as a cyclic molecule, M-4 as a reactive group, and polyethylene glycol having both ends substituted as a linear molecule, The crosslinking reaction can be carried out by dissolving in dimethylformamide, adding dimethyl-2,2′-azobis (2-methylpropinate) and heating to react at 80 ° C. Similarly, a crosslinking reaction can be performed for M-1 to M-3 and M-8 to M-10. Further, the crosslinking reaction can be similarly carried out by adding a crosslinking agent such as triethylene glycol dimethacrylate, divinylbenzene, polyethylene glycol dimethacrylate and the like.
When cross-linking an inclusion compound using α-cyclodextrin as a cyclic molecule, M-6 as a reactive group, and polyethylene glycol substituted at both ends as a linear molecule, the inclusion compound is dimethylformamide A cross-linking reaction is performed by adding a polyfunctional vinyl compound such as triethylene glycol divinyl ether, adding dimethyl-2,2′-azobis (2-methylpropinate), and heating and reacting at 80 ° C. Can do.
When cross-linking an inclusion compound using α-cyclodextrin as a cyclic molecule and polyethylene glycol substituted at both ends as a linear molecule, the inclusion compound is dissolved in an alkaline aqueous solution, and epichlorohydrin or chloride is dissolved in the aqueous solution. A crosslinking reaction can be performed by adding cyanur and stirring at room temperature. Further, the crosslinking reaction can be similarly carried out using dimethyl sulfoxide as a solvent and 1,1′-carbonyldiimidazole or tolylene diisocyanate as a crosslinking agent.

In the present specification, the term “crosslinked structure” means a linked structure formed by the reaction of the reactive substituent. There are various cross-linking structures, and reactive groups may react to cross-link as described above, or reactive groups may react with other reactive groups, and reactive groups and cross-linking agents react. And may be cross-linked. Examples of the atoms constituting the crosslinked structure include carbon atoms, oxygen atoms, sulfur atoms, nitrogen atoms, halogen atoms, silicon atoms, and hydrogen atoms. The number of atoms forming the crosslinked structure is preferably 1 to 2000, more preferably 1 to 1000.

The crosslinking of the binder can be carried out by any method, and examples thereof include a heating method, a light irradiation method, and a crosslinking accelerator addition method. In the case of heating, it is preferable to heat at 60 ° C or higher, and more preferable to heat at 80 ° C or higher. An upper limit of 200 ° C. or lower is practical, and 150 ° C. or lower is more practical. The heating time is preferably 1 minute or longer, more preferably 3 minutes or longer, and particularly preferably 5 minutes or longer. The upper limit is practically 24 hours or less.

The blending amount of the binder is preferably 0.1 parts by mass or more, and 0.3 parts by mass or more with respect to 100 parts by mass of the inorganic solid electrolyte (including this when an active material is used). More preferred is 1 part by mass or more. The upper limit is preferably 20 parts by mass or less, more preferably 10 parts by mass or less, and particularly preferably 5 parts by mass or less.
For the solid electrolyte composition, in the solid content, the binder is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, and particularly preferably 1% by mass or more. preferable. The upper limit is preferably 20% by mass or less, more preferably 10% by mass or less, and particularly preferably 5% by mass or less. By using the binder in the above range, it is possible to more effectively achieve both the adhesion of the inorganic solid electrolyte and the suppression of the interface resistance.

¡Binders may be used alone or in combination of a plurality of types. Further, it may be used in combination with other particles.

In the present invention, the binder may be in the form of particles. The average particle size of the particles is preferably 1,000 nm or less, more preferably 750 nm or less, further preferably 500 nm or less, further preferably 300 nm or less, and particularly preferably 200 nm or less. The lower limit is preferably 10 nm or more, more preferably 20 nm or more, further preferably 30 nm or more, and particularly preferably 50 nm or more.
When the inorganic solid electrolyte is in the form of particles, the binder preferably has a smaller particle size than the average particle size of the inorganic solid electrolyte.
The measurement from the created all-solid-state secondary battery is, for example, after disassembling the battery and peeling off the electrode, then measuring the electrode material according to the method of particle size measurement of the binder described later, and measuring in advance. This can be done by eliminating the measured value of the particle size of the particles other than the binder.
In addition, in this specification, it uses for the meaning containing the salt and its ion other than the said compound itself about the display of a compound (For example, when attaching | subjecting and attaching | subjecting a compound and an end). In addition, it is meant to include derivatives in which a part thereof is changed, such as introduction of a substituent, within a range where a desired effect is exhibited.
In the present specification, a substituent that does not specify substitution / non-substitution (the same applies to a linking group) means that the group may have an arbitrary substituent. This is also synonymous for compounds that do not specify substitution / non-substitution. Preferred substituents include the following substituent T.
Examples of the substituent T include the following.
An alkyl group (preferably an alkyl group having 1 to 20 carbon atoms, such as methyl, ethyl, isopropyl, t-butyl, pentyl, heptyl, 1-ethylpentyl, benzyl, 2-ethoxyethyl, 1-carboxymethyl, etc.), alkenyl A group (preferably an alkenyl group having 2 to 20 carbon atoms such as vinyl, allyl, oleyl and the like), an alkynyl group (preferably an alkynyl group having 2 to 20 carbon atoms such as ethynyl, butadiynyl, phenylethynyl and the like), A cycloalkyl group (preferably a cycloalkyl group having 3 to 20 carbon atoms, such as cyclopropyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, etc.), an aryl group (preferably an aryl group having 6 to 26 carbon atoms, for example, Phenyl, 1-naphthyl, 4-methoxyphenyl, -Chlorophenyl, 3-methylphenyl, etc.), heterocyclic groups (preferably heterocyclic groups of 2 to 20 carbon atoms, preferably 5- or 6-membered heterocycles having at least one oxygen atom, sulfur atom, nitrogen atom) A cyclic group is preferred, for example, 2-pyridyl, 4-pyridyl, 2-imidazolyl, 2-benzimidazolyl, 2-thiazolyl, 2-oxazolyl, etc.), an alkoxy group (preferably an alkoxy group having 1 to 20 carbon atoms, for example, Methoxy, ethoxy, isopropyloxy, benzyloxy, etc.), aryloxy groups (preferably aryloxy groups having 6 to 26 carbon atoms, such as phenoxy, 1-naphthyloxy, 3-methylphenoxy, 4-methoxyphenoxy, etc.), An alkoxycarbonyl group (preferably an alkoxycarbonyl group having 2 to 20 carbon atoms) Nyl groups such as ethoxycarbonyl, 2-ethylhexyloxycarbonyl and the like, amino groups (preferably containing an amino group having 0 to 20 carbon atoms, alkylamino group, arylamino group, such as amino, N, N-dimethyl) Amino, N, N-diethylamino, N-ethylamino, anilino, etc.), sulfamoyl groups (preferably sulfamoyl groups having 0 to 20 carbon atoms, such as N, N-dimethylsulfamoyl, N-phenylsulfamoyl, etc.) ), An acyl group (preferably an acyl group having 1 to 20 carbon atoms, such as acetyl, propionyl, butyryl, benzoyl, etc.), an acyloxy group (preferably an acyloxy group having 1 to 20 carbon atoms, such as acetyloxy, benzoyl) Oxy, etc.), a carbamoyl group (preferably a C 1-20 carbon Rubamoyl groups such as N, N-dimethylcarbamoyl and N-phenylcarbamoyl), acylamino groups (preferably acylamino groups having 1 to 20 carbon atoms such as acetylamino and benzoylamino), sulfonamide groups (preferably A sulfamoyl group having 0 to 20 carbon atoms, such as methanesulfonamide, benzenesulfonamide, N-methylmethanesulfonamide, N-ethylbenzenesulfonamide, etc., an alkylthio group (preferably an alkylthio group having 1 to 20 carbon atoms, For example, methylthio, ethylthio, isopropylthio, benzylthio, etc.), arylthio groups (preferably arylthio groups having 6 to 26 carbon atoms, such as phenylthio, 1-naphthylthio, 3-methylphenylthio, 4-methoxyphenylthio, etc.), Alkyl group or arylsulfonyl group (preferably an alkyl or arylsulfonyl group having 1 to 20 carbon atoms, such as methylsulfonyl, ethylsulfonyl, benzenesulfonyl, etc.), hydroxyl group, cyano group, halogen atom (for example, fluorine atom, chlorine atom, Bromine atom, iodine atom, etc.), more preferably alkyl group, alkenyl group, aryl group, heterocyclic group, alkoxy group, aryloxy group, alkoxycarbonyl group, amino group, acylamino group, phosphonic acid group, sulfonic acid group , Phosphoric acid group, carboxyl group, hydroxyl group or halogen atom.
In addition, each of the groups listed as the substituent T may be further substituted with the substituent T described above.
When a compound or a substituent / linking group includes an alkyl group / alkylene group, an alkenyl group / alkenylene group, an alkynyl group / alkynylene group, etc., these may be cyclic or linear, and may be linear or branched These may be substituted as described above or may be unsubstituted. In this case, an alkyl group, an alkylene group, an alkenyl group, an alkenylene group, an alkynyl group, an alkynylene group is a group containing a hetero atom (e.g., O, S, CO, NR ^N and the like) be separated by a, with this A ring structure may be formed. Moreover, when an aryl group, a heterocyclic group, etc. are included, they may be monocyclic or condensed and may be similarly substituted or unsubstituted.

(Electrolyte salt [supporting electrolyte])
The solid electrolyte composition according to the present invention may contain an electrolyte salt (supporting electrolyte). The electrolyte salt is preferably a lithium salt. As the lithium salt, a lithium salt usually used in this type of product is preferable, and there is no particular limitation, but for example, the following are preferable.

(L-1) Inorganic lithium salts: inorganic fluoride salts such as LiPF ₆ , LiBF ₄ , LiAsF ₆ , LiSbF ₆ ; perhalogenates such as LiClO ₄ , LiBrO ₄ , LiIO ₄ ; inorganic chloride salts such as LiAlCl ₄ etc.

(L-2) Fluorine-containing organic lithium salt: perfluoroalkane sulfonate such as LiCF ₃ SO ₃ ; LiN (CF ₃ SO ₂ ) ₂ , LiN (CF ₃ CF ₂ SO ₂ ) ₂ , LiN (FSO ₂ ) ₂ , Perfluoroalkanesulfonylimide salts such as LiN (CF ₃ SO ₂ ) (C ₄ F ₉ SO ₂ ); perfluoroalkanesulfonylmethide salts such as LiC (CF ₃ SO ₂ ) ₃ ; Li [PF ₅ (CF ₂ CF ₂ CF ₃ )], Li [PF ₄ (CF ₂ CF ₂ CF ₃ ) ₂ ], Li [PF ₃ (CF ₂ CF ₂ CF ₃ ) ₃ ], Li [PF ₅ (CF ₂ CF ₂ CF ₂ CF ₃ _{_{_{_{)], Li [PF 4 (}}}} CF 2 CF 2 CF 2 CF 3) 2], Li [PF 3 (CF 2 CF 2 CF 2 CF 3) 3] fluoroalkyl fluoride such as potash Acid salts, and the like.

(L-3) Oxalatoborate salt: lithium bis (oxalato) borate, lithium difluorooxalatoborate and the like.
Among these, LiPF ₆ , LiBF ₄ , LiAsF ₆ , LiSbF ₆ , LiClO ₄ , Li (Rf ¹ SO ₃ ), LiN (Rf ¹ SO ₂ ) ₂ , LiN (FSO ₂ ) ₂ , and LiN (Rf ¹ SO ₂ ) (Rf ² SO ₂ ), preferably LiPF ₆ , LiBF ₄ , LiN (Rf ¹ SO ₂ ) ₂ , LiN (FSO ₂ ) ₂ , and LiN (Rf ¹ SO ₂ ) (Rf ² SO ₂ ) More preferred are imide salts. Here, Rf ¹ and Rf ² each represent a perfluoroalkyl group.

The content of the lithium salt is preferably 0.1 parts by mass or more and more preferably 0.5 parts by mass or more with respect to 100 parts by mass of the inorganic solid electrolyte. As an upper limit, it is preferable that it is 10 mass parts or less, and it is more preferable that it is 5 mass parts or less.
In addition, the electrolyte used for electrolyte solution may be used individually by 1 type, or may combine 2 or more types arbitrarily.

(Dispersion medium)
In the solid electrolyte composition according to the present invention, a dispersion medium in which the above components are dispersed may be used. When producing an all-solid secondary battery, it is preferable to add a dispersion medium to the solid electrolyte composition to make a paste from the viewpoint of uniformly coating the solid electrolyte composition to form a film. When forming the solid electrolyte layer of the all-solid secondary battery, the dispersion medium is removed by drying.
Examples of the dispersion medium include water-soluble or water-insoluble organic solvents. Specific examples include the following.
Alcohol compound solvent Methyl alcohol, ethyl alcohol, 1-propyl alcohol, 2-propyl alcohol, 2-butanol, ethylene glycol, propylene glycol, glycerin, 1,6-hexanediol, cyclohexanediol, sorbitol, xylitol, 2-methyl- 2,4-pentanediol, 1,3-butanediol, 1,4-butanediol, etc. ・ Ether compound solvents (including hydroxyl group-containing ether compounds)
Dimethyl ether, diethyl ether, diisopropyl ether, dibutyl ether, t-butyl methyl ether, cyclohexyl methyl ether, anisole, tetrahydrofuran, alkylene glycol alkyl ether (ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol, dipropylene glycol, propylene glycol monomethyl ether , Diethylene glycol monomethyl ether, triethylene glycol, polyethylene glycol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether, etc.) Amide compound solvents N, N-dimethylformamide, 1-methyl-2-pyrrolidone, 2-pyrrolidinone, 1,3-dimethyl-2-imidazolidinone, 2-pyrrolidinone, ε-caprolactam, formamide, N-methylformamide, acetamide , N-methylacetamide, N, N-dimethylacetamide, N-methylpropanamide, hexamethylphosphoric triamide, etc.Ketone compound solvents Acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.Aromatic compound solvents benzene, toluene, etc. Aliphatic compound solvent Hexane, heptane, cyclohexane, methylcyclohexane, octane, pentane, cyclopentane, etc. ・ Nitrile compound solvent Acetonitrile

In the present invention, it is particularly preferable to use an ether compound solvent, a ketone compound solvent, an aromatic compound solvent, or an aliphatic compound solvent. The dispersion medium preferably has a boiling point of 50 ° C. or higher, more preferably 80 ° C. or higher at normal pressure (1 atm). The upper limit is preferably 220 ° C. or lower, and more preferably 180 ° C. or lower. The said dispersion medium may be used individually by 1 type, or may be used in combination of 2 or more type.
In this invention, the quantity of the dispersion medium in a solid electrolyte composition can be made into arbitrary quantity with the balance of the viscosity of a solid electrolyte composition, and a dry load. Generally, it is preferably 20 to 99% by mass in the solid electrolyte composition.

(Positive electrode active material)
The solid electrolyte composition may contain a positive electrode active material to form a positive electrode active material layer. Thereby, it can be set as the composition for positive electrode materials. It is preferable to use a transition metal oxide for the positive electrode active material, and it is preferable to have a transition element M ^a (one or more elements selected from Co, Ni, Fe, Mn, Cu, and V). Further, mixed element M ^b (elements of the first (Ia) group of the metal periodic table other than lithium, elements of the second (IIa) group, Al, Ga, In, Ge, Sn, Pb, Sb, Bi, Si , P, B, etc.) may be mixed. Examples of the transition metal oxide include specific transition metal oxides including those represented by any of the following formulas (MA) to (MC), or other transition metal oxides such as V ₂ O ₅ and MnO _2. Is mentioned. As the positive electrode active material, a particulate positive electrode active material may be used. Specifically, a transition metal oxide capable of reversibly inserting and releasing lithium ions can be used, but the specific transition metal oxide is preferably used.

The transition metal oxides, oxides containing the above transition element M ^a is preferably exemplified. At this time, a mixed element M ^b (preferably Al) or the like may be mixed. The mixing amount is preferably 0 to 30 mol% with respect to the amount of the transition metal. That the molar ratio of li / ^{M a} was synthesized were mixed so that 0.3 to 2.2, more preferably.

[Transition metal oxide represented by formula (MA) (layered rock salt structure)]
As the lithium-containing transition metal oxide, those represented by the following formula are preferable.
Li _a M ¹ O _b (MA)

Wherein, ^{M 1} is as defined above Ma. a represents 0 to 1.2 (preferably 0.2 to 1.2), and preferably 0.6 to 1.1. b represents 1 to 3 and is preferably 2. A part of M ¹ may be substituted with the mixed element M ^b . The transition metal oxide represented by the above formula (MA) typically has a layered rock salt structure.

The transition metal oxide is more preferably one represented by the following formulas.
_{(MA-1) Li g CoO} k
_{(MA-2) Li g NiO} k
_{(MA-3) Li g MnO} k
_{_{_{(MA-4) Li g Co}}} j Ni 1-j O k
_{_{_{(MA-5) Li g Ni}}} j Mn 1-j O k
_{_{_{(MA-6) Li g Co}}} j Ni i Al 1-j-i O k
_{_{_{(MA-7) Li g Co}}} j Ni i Mn 1-j-i O k

Here, g has the same meaning as a. j represents 0.1 to 0.9. i represents 0 to 1; However, 1-ji is 0 or more. k has the same meaning as b above. Specific examples of the transition metal compound include LiCoO ₂ (lithium cobaltate [LCO]), LiNi ₂ O ₂ (lithium nickelate) LiNi _0.85 Co _0.01 Al _0.05 O ₂ (nickel cobalt aluminum acid Lithium [NCA]), LiNi _0.33 Co _0.33 Mn _0.33 O ₂ (lithium nickel manganese cobaltate [NMC]), LiNi _0.5 Mn _0.5 O ₂ (lithium manganese nickelate).

The transition metal oxide represented by the formula (MA) partially overlaps, but when represented by changing the notation, those represented by the following are also preferable examples.
_{_{_{_{(I) Li g Ni x Mn}}}} y Co z O 2 (x> 0.2, y> 0.2, z ≧ 0, x + y + z = 1)
Representative:
_{_{_{_{Li g Ni 1/3 Mn 1/3 Co 1/3}}}} O 2
Li _g Ni _{_1/2} Mn _1/2 O ₂
_{_{_{_{(Ii) Li g Ni x Co}}}} y Al z O 2 (x> 0.7, y>0.1,0.1> z ≧ 0.05, x + y + z = 1)
Representative:
_{_{_{_{Li g Ni 0.8 Co 0.15 Al 0.05}}}} O 2

[Transition metal oxide represented by formula (MB) (spinel structure)]
Among the lithium-containing transition metal oxides, those represented by the following formula (MB) are also preferable.
Li _c M ² ₂ O _d (MB)

Wherein, ^{M 2} is as defined above Ma. c represents 0 to 2 (preferably 0.2 to 2), and preferably 0.6 to 1.5. d represents 3 to 5 and is preferably 4.

The transition metal oxide represented by the formula (MB) is more preferably one represented by the following formulas.
_{_{(MB-1) Li m Mn}} 2 O n
_{_{_{(MB-2) Li m Mn}}} p Al 2-p O n
_{_{_{(MB-3) Li m Mn}}} p Ni 2-p O n

m is synonymous with c. n is synonymous with d. p represents 0-2. Specific examples of the transition metal compound are LiMn ₂ O ₄ and LiMn _1.5 Ni _0.5 O ₄ .

Preferred examples of the transition metal oxide represented by the formula (MB) include those represented by the following.
(A) LiCoMnO ₄
(B) Li ₂ FeMn ₃ O ₈
(C) Li ₂ CuMn ₃ O ₈
(D) Li ₂ CrMn ₃ O ₈
(E) Li ₂ NiMn ₃ O ₈
Of these, an electrode containing Ni is more preferable from the viewpoint of high capacity and high output.

[Transition metal oxide represented by formula (MC)]
As the lithium-containing transition metal oxide, it is also preferable to use a lithium-containing transition metal phosphor oxide, and among them, one represented by the following formula (MC) is also preferable.
Li _e M ³ (PO ₄ ) _f ... (MC)

In the formula, e represents 0 to 2 (preferably 0.2 to 2), and is preferably 0.5 to 1.5. f represents 1 to 5, and preferably 0.5 to 2.

The M ³ represents one or more elements selected from V, Ti, Cr, Mn, Fe, Co, Ni, and Cu. The ^{M 3} are, in addition to the mixing element ^{M b} above, Ti, Cr, Zn, Zr, may be substituted by other metals such as Nb. Specific examples include, for example, olivine-type iron phosphates such as LiFePO ₄ and Li ₃ Fe ₂ (PO ₄ ) ₃ , iron pyrophosphates such as LiFeP ₂ O ₇ , cobalt phosphates such as LiCoPO ₄ , and Li _3. Monoclinic Nasicon type vanadium phosphate salts such as V ₂ (PO ₄ ) ₃ (lithium vanadium phosphate) can be mentioned.
The a, c, g, m, and e values representing the composition of Li are values that change due to charge and discharge, and are typically evaluated as values in a stable state when Li is contained. In the above formulas (a) to (e), the composition of Li is shown as a specific value, but this also varies depending on the operation of the battery.

The average particle size of the positive electrode active material is not particularly limited, but is preferably 0.1 μm to 50 μm. In order to make the positive electrode active material have a predetermined particle size, an ordinary pulverizer or classifier may be used. The positive electrode active material obtained by the firing method may be used after being washed with water, an acidic aqueous solution, an alkaline aqueous solution, or an organic solvent.

The concentration of the positive electrode active material is not particularly limited, but is preferably 20 to 90% by mass, and more preferably 40 to 80% by mass in 100% by mass of the solid component in the solid electrolyte composition.
The positive electrode active materials may be used alone or in combination of two or more.

(Negative electrode active material)
It is good also as a composition for forming a negative electrode active material layer by making a solid electrolyte composition contain a negative electrode active material. Thereby, it can be set as the composition for negative electrode materials. As the negative electrode active material, those capable of reversibly inserting and releasing lithium ions are preferable. The material is not particularly limited, and is a carbonaceous material, a metal oxide such as tin oxide or silicon oxide, a metal composite oxide, a lithium alloy such as lithium alone or a lithium aluminum alloy, and a lithium such as Sn, Si, or In. And metals capable of forming an alloy. Of these, carbonaceous materials or lithium composite oxides are preferably used from the viewpoint of reliability. In addition, the metal composite oxide is preferably capable of inserting and extracting lithium. The material is not particularly limited, but preferably contains titanium and / or lithium as a constituent component from the viewpoint of high current density charge / discharge characteristics.

The carbonaceous material used as the negative electrode active material is a material substantially made of carbon. Examples thereof include carbonaceous materials obtained by baking various synthetic resins such as artificial pitches such as petroleum pitch, natural graphite, and vapor-grown graphite, and PAN-based resins and furfuryl alcohol resins. Furthermore, various carbon fibers such as PAN-based carbon fiber, cellulose-based carbon fiber, pitch-based carbon fiber, vapor-grown carbon fiber, dehydrated PVA-based carbon fiber, lignin carbon fiber, glassy carbon fiber, activated carbon fiber, mesophase micro Examples thereof include spheres, graphite whiskers, and flat graphite.

These carbonaceous materials can be divided into non-graphitizable carbon materials and graphite-based carbon materials depending on the degree of graphitization. Further, the carbonaceous material preferably has a face spacing, density, and crystallite size described in JP-A-62-222066, JP-A-2-6856, and 3-45473. The carbonaceous material does not have to be a single material, and a mixture of natural graphite and artificial graphite described in JP-A-5-90844, graphite having a coating layer described in JP-A-6-4516, or the like is used. You can also.

As the metal oxide and metal composite oxide applied as the negative electrode active material, an amorphous oxide is particularly preferable, and chalcogenite, which is a reaction product of a metal element and an element of Group 16 of the periodic table, is also preferably used. It is done. The term “amorphous” as used herein means an X-ray diffraction method using CuKα rays, which has a broad scattering band having a peak in the region of 20 ° to 40 ° in terms of 2θ, and is a crystalline diffraction line. You may have. The strongest intensity of crystalline diffraction lines seen from 2 ° to 40 ° to 70 ° is 100 times the diffraction line intensity at the peak of the broad scattering band seen from 2 ° to 20 °. It is preferable that it is 5 times or less, and it is particularly preferable not to have a crystalline diffraction line.

Among the group of compounds consisting of the above amorphous oxide and chalcogenide, amorphous metal oxides and chalcogenides are more preferable, and elements in groups 13 (IIIB) to 15 (VB) of the periodic table are preferable. Particularly preferred are oxides and chalcogenides composed of one kind of Al, Ga, Si, Sn, Ge, Pb, Sb, Bi or a combination of two or more kinds thereof. Specific examples of preferable amorphous oxides and chalcogenides include, for example, Ga ₂ O ₃ , SiO, GeO, SnO, SnO ₂ , 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 ₅ , Bi ₂ O ₃ , Bi ₂ O ₄ , SnSiO ₃ , GeS, SnS, SnS ₂ , PbS, PbS ₂ , Sb ₂ S ₃ , Sb ₂ S ₅ , such as SnSiS ₃ may preferably be mentioned. Moreover, these may be a complex oxide with lithium oxide, for example, Li ₂ SnO ₂ .

The average particle size of the negative electrode active material is preferably 0.1 μm to 60 μm. To obtain a predetermined particle size, a well-known pulverizer 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 is preferably used. When pulverizing, wet pulverization in the presence of water or an organic solvent such as methanol can be performed as necessary. In order to obtain a desired particle size, classification is preferably performed. The classification method is not particularly limited, and a sieve, an air classifier, or the like can be used as necessary. Classification can be used both dry and wet.

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

Examples of the negative electrode active material that can be used in combination with the amorphous oxide negative electrode active material centering on Sn, Si, and Ge include carbon materials that can occlude and release lithium ions or lithium metal, lithium, lithium alloys, lithium A metal that can be alloyed with is preferable.

The negative electrode active material preferably contains a titanium atom. More specifically, since Li ₄ Ti ₅ O ₁₂ has a small volume fluctuation at the time of occlusion and release of lithium ions, it has excellent rapid charge / discharge characteristics, suppresses electrode deterioration, and improves the life of lithium ion secondary batteries. This is preferable. By combining a specific negative electrode and a specific electrolyte, the stability of the secondary battery is improved even under various usage conditions.

In the all solid state secondary battery of the present invention, it is also preferable to apply a negative electrode active material containing Si element. In general, a Si negative electrode can occlude more Li ions than current carbon negative electrodes (graphite, acetylene black, etc.). That is, since the amount of Li ion storage per weight increases, the battery capacity can be increased. As a result, there is an advantage that the battery driving time can be extended, and use in a battery for vehicles is expected in the future. On the other hand, it is known that the volume change associated with insertion and extraction of Li ions is large. In one example, the volume expansion of the carbon negative electrode is about 1.2 to 1.5 times, and the volume of Si negative electrode is about three times. There is also an example. By repeating this expansion and contraction (repeating charge and discharge), the durability of the electrode layer is insufficient, and for example, contact shortage is likely to occur, and cycle life (battery life) is shortened.
According to the solid electrolyte composition according to the present invention, even in an electrode layer in which such expansion / contraction increases, the high durability (strength) can be exhibited, and the excellent advantages can be exhibited more effectively. is there.

The concentration of the negative electrode active material is not particularly limited, but is preferably 10 to 80% by mass, more preferably 20 to 70% by mass in 100% by mass of the solid component in the solid electrolyte composition.

In the above-described embodiment, the solid electrolyte composition is shown in consideration of an example in which a positive electrode active material or a negative electrode active material is contained. However, the present invention is not construed as being limited thereto. For example, you may prepare the paste containing a positive electrode active material thru | or a negative electrode active material as a composition which does not contain the said binder. Moreover, you may make the active material layer of a positive electrode and a negative electrode contain a conductive support agent suitably as needed. As general electron conductive materials, carbon fibers such as graphite, carbon black, acetylene black, ketjen black, carbon nanotubes, metal powders, metal fibers, polyphenylene derivatives, and the like can be included.
The said negative electrode active material may be used individually by 1 type, or may be used in combination of 2 or more type.

<Current collector (metal foil)>
As the positive / negative current collector, an electron conductor that does not cause a chemical change is preferably used. As the current collector of the positive electrode, in addition to aluminum, stainless steel, nickel, titanium, etc., the surface of aluminum or stainless steel is preferably treated with carbon, nickel, titanium, or silver. Among them, aluminum and aluminum alloys are preferable. More preferred. As the negative electrode current collector, aluminum, copper, stainless steel, nickel, and titanium are preferable, and aluminum, copper, and a copper alloy are more preferable.

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

<Preparation of all-solid secondary battery>
The all-solid-state secondary battery may be manufactured by a conventional method. Specifically, there is a method in which the solid electrolyte composition is applied onto a metal foil serving as a current collector to form a battery electrode sheet having a coating film formed thereon. For example, a composition serving as a positive electrode material is applied onto a metal foil that is a positive electrode current collector and then dried to form a positive electrode layer. Next, the solid electrolyte composition is applied onto the positive electrode sheet for a battery and then dried to form a solid electrolyte layer. Furthermore, after applying the composition used as a negative electrode material on it, it dries and forms a negative electrode layer. A structure of an all-solid-state secondary battery in which a solid electrolyte layer is sandwiched between a positive electrode layer and a negative electrode layer can be obtained by stacking a current collector (metal foil) on the negative electrode side thereon. In addition, the application | coating method of said each composition should just follow a conventional method. At this time, a drying treatment may be performed after each application of the composition forming the positive electrode active material layer, the composition forming the inorganic solid electrolyte layer (solid electrolyte composition), and the composition forming the negative electrode active material layer. Then, after the multilayer coating, a drying process may be performed. Although drying temperature is not specifically limited, 30 degreeC or more is preferable and 60 degreeC or more is more preferable. The upper limit is preferably 300 ° C. or lower, and more preferably 250 ° C. or lower. By heating in such a temperature range, a dispersion medium can be removed and it can be set as a solid state. Thereby, in an all-solid secondary battery, good binding properties and non-pressurized ion conductivity can be obtained.

<Use of all-solid-state secondary battery>
The all solid state secondary battery according to the present invention can be applied to various uses. Although the application mode is not particularly limited, for example, when installed in an electronic device, a notebook computer, a pen input personal computer, a mobile personal computer, an electronic book player, a cellular phone, a cordless phone, a pager, a handy terminal, a portable fax machine, a portable copy, Examples include portable printers, headphone stereos, video movies, LCD TVs, handy cleaners, portable CDs, minidiscs, electric shavers, transceivers, electronic notebooks, calculators, memory cards, portable tape recorders, radios, backup power supplies, and memory cards. Other consumer products include automobiles, electric vehicles, motors, lighting equipment, toys, game equipment, road conditioners, watches, strobes, cameras, medical equipment (such as pacemakers, hearing aids, and shoulder grinders). Furthermore, it can be used for various military use and space use. Moreover, it can also combine with a solar cell.

In particular, it is preferably applied to applications that require high capacity and high rate discharge characteristics. For example, in power storage facilities and the like that are expected to increase in capacity in the future, high reliability is indispensable and further compatibility of battery performance is required. In addition, electric vehicles and the like are equipped with high-capacity secondary batteries and are expected to be charged every day at home, and thus more reliability is required for overcharging. According to the present invention, it is possible to exhibit the excellent effect correspondingly to such a usage pattern.

According to a preferred embodiment of the present invention, the following applications are derived.
A solid electrolyte composition (positive electrode or negative electrode composition) containing an active material capable of inserting and releasing metal ions belonging to Group 1 or Group 2 of the Periodic Table.
-The battery electrode sheet which formed the said solid electrolyte composition on metal foil.
-An all-solid secondary battery comprising a positive electrode active material layer, a negative electrode active material layer, and an inorganic solid electrolyte layer, wherein at least one of the positive electrode active material layer, the negative electrode active material layer, and the inorganic solid electrolyte layer is All-solid-state secondary battery made into the layer comprised with the solid electrolyte composition.
-The manufacturing method of the electrode sheet for batteries which arrange | positions the said solid electrolyte composition on metal foil, and forms this into a film.
-The manufacturing method of the all-solid-state secondary battery which manufactures an all-solid-state secondary battery via the manufacturing method of the said battery electrode sheet.

An all-solid secondary battery refers to a secondary battery in which the positive electrode, the negative electrode, and the electrolyte are all solid. In other words, it is distinguished from an electrolyte type secondary battery using a carbonate-based solvent as an electrolyte. In this, this invention presupposes an inorganic all-solid-state secondary battery. The all-solid-state secondary battery is classified into an organic (polymer) all-solid-state secondary battery that uses a polymer compound such as polyethylene oxide as an electrolyte, and an inorganic all-solid-state secondary battery that uses the above LLT, LLZ, or the like. . The application of the polymer compound to the inorganic all-solid secondary battery is not hindered, and the polymer compound can be applied as a binder for the positive electrode active material, the negative electrode active material, and the inorganic solid electrolyte particles.
The inorganic solid electrolyte is distinguished from an electrolyte (polymer electrolyte) using the above-described polymer compound as an ion conductive medium, and the inorganic compound serves as an ion conductive medium. Specific examples include the above LLT and LLZ. The inorganic solid electrolyte itself does not release cations (Li ions) but exhibits an ion transport function. On the other hand, a material that is added to the electrolytic solution or the solid electrolyte layer and serves as a source of ions that release cations (Li ions) is sometimes called an electrolyte, but it is distinguished from the electrolyte as the ion transport material. This is sometimes referred to as “electrolyte salt” or “supporting electrolyte”. Examples of the electrolyte salt include LiTFSI (lithium bistrifluoromethanesulfonimide).
In the present invention, the term “composition” means a mixture in which two or more components are uniformly mixed. However, as long as the uniformity is substantially maintained, aggregation or uneven distribution may partially occur within a range in which a desired effect is achieved.

Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not construed as being limited thereto. In addition, when it is set as a part and% in the display of a compounding quantity and a density | concentration, it shall be based on mass unless there is particular notice.

Example of polyrotaxane synthesis B-1
In 300 g of water, 10 g of polyethylene glycol bisamine having a weight average molecular weight of 20000 (synthesized according to JP 2009-507943) and 35 g of α-cyclodextrin (manufactured by Wako Pure Chemical Industries, Ltd.) were added and heated to 80 ° C. for dissolution. The solution was stirred for 2 hours, cooled to 5 ° C. and allowed to stand for 8 hours. The produced precipitate was dried, added to a solution of 25 g of 2,4-dinitrofluorobenzene (Wako Pure Chemical Industries, Ltd.) and 100 g of dimethylformamide (Wako Pure Chemical Industries, Ltd.) and stirred at room temperature for 12 hours. The reaction product was dissolved by adding 500 g of dimethyl sulfoxide (DMSO), and then poured into 10 kg of 0.1% strength saline to precipitate the product. The precipitate was washed with water and methanol 5 times each and then dried in vacuo at 50 ° C. for 8 hours. In this way, 30 g of a polyrotaxane compound in which α-cyclodextrin was penetrated by polyethylene glycol bisamine and 2,4-dinitrophenyl groups were bonded to both terminal amino groups was obtained. The composition ratio of the clathrate compound calculated from ¹ H-NMR was 100: 17 in terms of the ratio of the number of moles of ethylene oxide units to the number of moles of α-cyclodextrin molecules (the reactive group M-13 in Table 1 is cyclohexane). Dextrin hydroxyl group).

Functional group introduction example (M-4 alkenyl group-containing group) ... B-2
5 g of the polyrotaxane obtained above, 3 g of 2-isocyanatoethyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.), 0.03 g of bismuth tris (2-ethylhexanoate) (manufactured by Nitto Kasei Co., Ltd., Neostan U-600) were added to dimethyl It was dissolved in 30 g of sulfoxide, heated to 60 ° C. and stirred for 3 hours. The obtained solution was poured into 500 g of 0.1% strength saline to precipitate the product, and fractionated to obtain a polyrotaxane in which M-4 was introduced into the cyclic molecule.

Functional group introduction example (M-6 thiol group) B-3
5 g of the polyrotaxane obtained above was added to a mixed solution of 3 g of water and 27 g of ethanol, 3 g of 3-mercaptopropylmethyldimethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.) was further added, and the mixture was stirred at 50 ° C. for 1 hour. By separating the precipitate, a polyrotaxane in which M-6 was introduced into a cyclic molecule was obtained. M-7 can also be introduced in the same manner.

Functional group introduction example (M-12 carboxylic acid group) B-4
5 g of the polyrotaxane obtained above was dissolved in 30 g of dimethyl sulfoxide, and 1.1 g of triethylamine (manufactured by Wako Pure Chemical Industries, Ltd.) and 2.3 g of succinic anhydride (manufactured by Wako Pure Chemical Industries, Ltd.) were added at 40 ° C. Stir for 5 hours. The obtained solution was poured into 500 g of 0.1% strength saline to precipitate the product, and fractionated to obtain a polyrotaxane in which M-12 was introduced into the cyclic molecule.

Other binders (polyrotaxane compounds) were similarly prepared with reference to the above synthesis method.

(Preparation example of solid electrolyte composition)
180 pieces of zirconia beads having a diameter of 5 mm are put into a 45 mL container (manufactured by Fritsch) made of zirconia, 9.7 g of inorganic solid electrolyte LLT (manufactured by Toyoshima Seisakusho), 0.3 g of binder B-1 (solid weight), dispersed After charging 15.0 g of N-methylpyrrolidone as a medium, the container was set on a planetary ball mill manufactured by Fritsch, and mixing was continued at 300 rpm for 2 hours to obtain a solid electrolyte composition S-1.
The solid electrolyte compositions S-2 to S-10 and T-1 to T-3 shown in Table 2 below were also prepared in the same manner as the solid electrolyte composition S-1.

(Preparation Example of Composition for Secondary Battery Positive Electrode)
In a planetary mixer (TK Hibismix, manufactured by PRIMIX), 100 parts of the positive electrode active material (average particle size 10 μm) described in Table 4 below, 5 parts of acetylene black, 75 parts of the solid electrolyte composition S-1 obtained as described above , 270 parts of N-methylpyrrolidone was added and stirred at 40 rpm for 1 hour. A composition for a secondary battery positive electrode in 201 was prepared.
Test No. shown in Table 4 below. The compositions for secondary battery positive electrodes in 202 to 205 were similarly prepared.

(Preparation example of secondary battery negative electrode composition)
In a planetary mixer (TK Hibismix, manufactured by PRIMIX), 100 parts of the negative electrode active material (average particle size 6 μm) described in Table 4 below, 5 parts of acetylene black, 75 parts of the solid electrolyte composition S-1 obtained above , 270 parts of N-methylpyrrolidone was added and stirred at 40 rpm for 1 hour. A composition for a secondary battery negative electrode in 201 was prepared.
Test No. shown in Table 4 below. The secondary battery negative electrode compositions in 202 to 205 were prepared in the same manner.

(Example of making a positive electrode for a secondary battery)
The composition for a positive electrode of the secondary battery obtained above was applied onto an aluminum foil having a thickness of 20 μm with an applicator having an arbitrary clearance and dried at 80 ° C. for 2 hours. Then, it heated and pressurized so that it might become arbitrary density using the heat press machine, and the positive electrode for secondary batteries was obtained.

(Production example of electrode sheet for secondary battery)
On the positive electrode for secondary batteries obtained above, the solid electrolyte composition obtained above was applied with an applicator having an arbitrary clearance, heated at 80 ° C. for 2 hours, and dried.
Then, the composition for secondary battery negative electrodes obtained above was further applied, heated at 80 ° C. for 2 hours, and dried. A copper foil having a thickness of 20 μm was combined on the negative electrode layer, and heated and pressurized to a desired density using a heat press machine, to obtain an electrode sheet for a secondary battery.

(Example of production of solid electrolyte sheet)
The solid electrolyte composition S-1 obtained as described above was applied onto an aluminum foil having a thickness of 20 μm with an applicator having an arbitrary clearance, and dried at 80 ° C. for 2 hours. Thereafter, a copper foil having a thickness of 20 μm was combined, heated and pressurized to a desired density using a heat press machine, and the test nos. 101 solid electrolyte sheet was obtained.
Test No. shown in Table 3 below. The solid electrolyte sheets 102 to 112 and c11 to c13 were produced in the same manner.

<Measurement of molecular weight>
In the present invention, the molecular weight of the polymer means the weight average molecular weight unless otherwise specified, and the weight average molecular weight in terms of standard polystyrene is measured by gel permeation chromatography (GPC). The measurement method is a value measured by the method of Condition 1 below. However, an appropriate eluent may be selected and used depending on the polymer type.
(Condition 1)
Column: TOSOH TSKgel Super AWM-H carrier: 10 mM LiBr / N-methylpyrrolidone

<Evaluation of binding properties>
In the secondary battery electrode sheet manufacturing step, the binding property was evaluated using the electrode sheet in a state before applying the negative electrode composition (a state where the solid electrolyte composition was dried). An adhesive tape (cellophane tape (“CT24”, manufactured by Nichiban Co., Ltd.)) was applied to the cured solid electrolyte composition surface, and when peeled at a constant speed, the peeled area was visually confirmed. The area ratio of the part that was not peeled was evaluated as follows.
5: 0%
4: More than 0% and less than 5% 3: 5% or more and less than 20% 2: 20% or more and less than 50% 1: 50% or more

<Evaluation of bending durability>
An electrode sheet (composite solid electrolyte sheet, secondary battery electrode) was punched into a 4 cm square, wound around a SUS rod having a different thickness, and evaluated by the radius of the rod when each composition was peeled off from the electrode sheet.
5: No peeling 4: 0 mm or more and less than 2 mm 3: 2 mm or more and less than 5 mm 2: 5 mm or more and less than 30 mm 1: 50 mm or more

<Measurement of ionic conductivity>
The electrode sheet (composite solid electrolyte sheet, secondary battery electrode sheet) obtained above was cut into a disk shape having a diameter of 14.5 mm, and placed in a stainless steel 2032 type coin case incorporating a spacer and washer. Was made. From the outside of the coin battery, it was sandwiched between jigs capable of applying pressure between the electrodes, and used for various electrochemical measurements. The pressure between the electrodes was 500 kgf / cm ² .
It calculated | required by the alternating current impedance method in a 30 degreeC thermostat using the coin battery obtained above. At this time, the test body shown in FIG. 3 was used for pressurization of the battery. 11 is an upper support plate, 12 is a lower support plate, 13 is a coin battery, 14 is a coin case, 15 is an electrode sheet (solid electrolyte sheet or secondary battery electrode sheet), and S is a screw.
Table 3 shows the measurement results of the electrode binding properties of the solid electrolyte sheet, and the ionic conductivity in the pressurized and non-pressurized states. At this time, the measurement in the pressurized state is a case where measurement is performed with the coin battery sandwiched between the jigs, and the measurement in the non-pressurized state indicates that the coin battery is measured as it is.

Amount introduced: Amount of cyclic molecule introduced: Number of moles of cyclic molecule when the number of moles of monomer units of the linear molecule is 100 The terminal group was a 2,4-dinitrophenyl group.
The molecular weight was determined by the GPC measurement, and values below 1000 were rounded off.

<Table notes>
Numbers in the table are mass ratios (%)
For compound numbers, refer to the examples of the above exemplified compounds. LLT: Li _0.33 La _0.55 TiO ₃
LLZ: _Li 7 _La 3 Zr2O ₁₂
NMP: N-methylpyrrolidone

PA: Polymer particles obtained by the following synthesis method In an autoclave, 700 parts of n-butyl acrylate, 200 parts of styrene, 5 parts of methacrylic acid, 10 parts of divinylbenzene, polyoxyethylene lauryl ether as an emulsifier (Emulgen, manufactured by Kao Corporation) 108, a nonionic surfactant, an alkyl group having 12 carbon atoms, an HLB value of 12.1) 25 parts, 1500 parts of ion-exchanged water, and 15 parts of azobisbutyronitrile as a polymerization initiator were charged and sufficiently stirred. Then, it superposed | polymerized by heating at 80 degreeC. Then, after the polymerization was started, the polymerization reaction was stopped by cooling to obtain a latex of polymer particles.

HBR: Polymer obtained by the following synthesis method 30 parts of cyclohexane and 10 parts of butadiene are added to an autoclave, and 30 parts of a 14% tetrahydrofuran solution of n-butyllithium is added. The temperature is raised to 70 ° C., and when the conversion rate reaches 100%, 30 parts of butadiene and 120 parts of tetrahydrofuran are further added, and the reaction is carried out at 70 ° C. When the conversion rate reached 100%, 30 parts of 20% dichlorosilane tetrahydrofuran solution was added and reacted for 20 minutes to obtain a triblock polymer. Thereafter, the reaction solution was brought to 70 ° C., and 3 parts of n-butyllithium, 3 parts of 2,6-di-t-butyl-p-cresol, 1 part of bis (cyclopentadienyl) titanium dichloride and 2 parts of diethylaluminum chloride were added. In addition, a block polymer was obtained by reacting at a hydrogen pressure of 10 kg / cm ² for 1 hour, evaporating and drying.

<Table notes>
For compound numbers, refer to the examples of the above exemplified compounds. TDI: Tolylene diisocyanate V-601:

Dimethyl

2,2′-azobis (2-methylpropionate)
TEGDV: Triethylene glycol divinyl ether TAC: Terephthalic acid chloride ECH: Epichlorohydrin Addition amount: Addition amount of additive:% by mass when binder weight is 100

<Table notes>
LMO: LiMn ₂ O ₄ lithium manganate LTO: Li ₄ Ti ₅ O ₁₂ lithium titanate (trade name “Enamite LT-106”, manufactured by Ishihara Sangyo Co., Ltd.)
LCO: LiCoO ₂ Lithium cobaltate NMC: Li (Ni _1/3 Mn _1/3 Co _1/3 ) O ₂
Nickel, manganese, lithium cobalt oxide graphite: Spheroidized graphite powder manufactured by Nippon Graphite Industries Co., Ltd .: Amount of additive added:% by mass when binder weight is 100

The following compound was synthesized and used instead of the polyrotaxane compound B-1 used in Test 102 above. As a result, it was confirmed that better performance than c11 to c13 was obtained in all of bending durability, binding property and ionic conductivity.

Amount introduced: amount of cyclic molecule introduced ... number of moles of cyclic molecule when the number of moles of monomer units of the linear molecule is 100.
Terminal group: 2,4-dinitrophenyl group

While this invention has been described in conjunction with its embodiments, we do not intend to limit our invention in any detail of the description unless otherwise specified and are contrary to the spirit and scope of the invention as set forth in the appended claims. I think it should be interpreted widely.

This application claims priority based on Japanese Patent Application No. 2014-070095 filed in Japan on March 28, 2014, which is hereby incorporated herein by reference. Capture as part.

DESCRIPTION OF SYMBOLS 1 Negative electrode collector 2 Negative electrode active material layer 3 Inorganic solid electrolyte layer 4 Positive electrode active material layer 5 Positive electrode collector 6 Working part 10 All-solid secondary battery 11 Upper support plate 12 Lower support plate 13 Coin cell (all-solid secondary battery)
14 Coin case 15 Electrode sheet S Screw 20 Polyrotaxane compound 21 Linear molecule 22 Cyclic molecule 23 Cross-linked chain (linkage chain by reactive group)
24 Terminal substituent 200 Cross-linked product of polyrotaxane compound

Claims

An all-solid secondary battery comprising a positive electrode active material layer, a negative electrode active material layer, and a solid electrolyte layer, wherein at least one of the positive electrode active material layer, the negative electrode active material layer, and the solid electrolyte layer is a periodic table. An all-solid secondary battery comprising an inorganic solid electrolyte having conductivity of metal ions belonging to Group 1 or Group 2 and a binder, wherein the binder comprises a compound having a structure in which a linear molecule penetrates a cyclic molecule.
The all-solid-state secondary battery according to claim 1, wherein the cyclic molecule is cyclodextrin or a derivative thereof.
The whole linear molecule according to claim 1 or 2, wherein the linear molecule is a polyolefin, a polyether, a polyester, a polysiloxane, a polycarbonate, a polyacrylate, a polyurethane, a polyurea, a polymer having a heterocyclic ring in the main chain, or a compound containing a polyene structure. Solid secondary battery.
The all-solid-state secondary battery according to any one of claims 1 to 3, wherein the molecular weight of the linear molecule is 10,000 or more.
The claim wherein the cyclic molecule or linear molecule has a crosslinked structure via at least one of the following reactive substituent (A) and the following reactive linking group (B), or the reactive substituent or reactive linking group. Item 5. The all solid state secondary battery according to any one of Items 1 to 4.
Reactive substituent (A)
Amino group, thiol group, tetrahydrofuryl group, oxetane group, epoxy group, hydroxyl group, isocyanate group, carboxyl group, phosphoric acid group, sulfonic acid group, phosphonic acid group, alkenyl group-containing group reactive linking group (B)
Imino group, alkenylene group-containing group
6. The all-solid-state secondary battery according to claim 1, which has a bulky substituent at the end of the linear molecule.
The all-solid-state secondary battery according to any one of claims 1 to 6, wherein the cyclic molecule has a structure represented by any of the following formulas (2-1) to (2-4).

L A is a preceding linking group.
Ar 2 is a cyclic structural group.
R A1 to R A4 are a hydrogen atom, a halogen atom, a methyl group, an ethyl group, a cyano group, or a hydroxyl group.
Ring α is a cyclic structure group containing one or more X A1 , and forms a ring structure with an oxygen atom, a sulfur atom, an imino group, a carbonyl group, an alkylene group, an alkenylene group, an arylene group, or a combination thereof.
X A1 and X A2 each independently represent a hetero atom-containing linking group.
In the compound having a structure in which a linear molecule penetrates the cyclic molecule, the linear molecule is a polymer compound having a plurality of monomers, and the ratio of the linear molecule and the cyclic molecule constitutes the linear molecule. 8. The all-solid-state secondary battery according to claim 1, wherein the ratio of the number of moles of monomer units to the number of cyclic molecules is 100: 0.1 to 100: 70.
9. The all solid state secondary battery according to claim 1, wherein the linear molecule is a compound including a structure represented by any of the following formulas (1-1) to (1-5).

L 1 is an alkylene group or an alkenylene group. L 2 is a linking group. R 31 and R 32 are each independently a hydrogen atom, a hydroxyl group, an alkyl group, an alkenyl group, an aryl group, or an aralkyl group. R 41 , R 42 , R 51 and R 52 are each independently a hydrogen atom, a halogen atom, a cyano group, a hydroxyl group, an alkyl group, an aryl group or an aralkyl group. A plurality of L 1 , L 2 , R 31 , R 32 , R 41 , R 42 , R 51 , R 52 in the molecule may be the same as or different from each other.
The all-solid-state secondary battery according to claim 5, wherein the reactive substituent (A) is at least one of the following functional groups.
Functional group Thiol group, epoxy group, hydroxyl group, isocyanate group, carboxyl group, phosphoric acid group, sulfonic acid group, phosphonic acid group, alkenyl group-containing group
The all-solid-state secondary battery according to any one of claims 1 to 10, wherein the binder is contained in an amount of 0.1 to 20 parts by mass with respect to 100 parts by mass of the inorganic solid electrolyte.
The all-solid-state secondary battery according to claim 10, wherein the reactive substituent (A) is at least one of the following functional groups.
Functional group Carboxyl group, phosphoric acid group, sulfonic acid group, phosphonic acid group
The all-solid-state secondary battery according to any one of claims 1 to 12, wherein the inorganic solid electrolyte is an oxide-based inorganic solid electrolyte.
The all-solid-state secondary battery according to claim 13, wherein the inorganic solid electrolyte is selected from the following formulae.
・ Li xa La ya TiO 3
xa = 0.3 to 0.7, ya = 0.3 to 0.7
・ Li 7 La 3 Zr 2 O 12
・ Li 3.5 Zn 0.25 GeO 4
・ LiTi 2 P 3 O 12
Li 1 + xh + yh (Al, Ga) xh (Ti, Ge) 2 -xh Si yh P 3 -yh O 12
0 ≦ xh ≦ 1, 0 ≦ yh ≦ 1
・ Li 3 PO 4
・ LiPON
・ LiPOD 1
D 1 is Ti, V, Cr, Mn, Fe, Co, Ni, Cu,
Zr, Nb, Mo, Ru, Ag, Ta, W, Pt, and Au
At least one selected from LiA 1 ON
A 1 is at least one selected from Si, B, Ge, Al, C, Ga and the like
A solid electrolyte composition for an all-solid-state secondary battery having a structure in which a linear molecule penetrates an inorganic solid electrolyte having a conductivity of metal ions belonging to Group 1 or Group 2 of the periodic table and a cyclic molecule. The solid electrolyte composition containing the binder containing the compound which has.
The solid electrolyte composition according to claim 15, further comprising a dispersion medium.
The solid electrolyte composition according to claim 16, wherein the dispersion medium is selected from an alcohol compound solvent, an ether compound solvent, an amide compound solvent, a ketone compound solvent, an aromatic compound solvent, an aliphatic compound solvent, and a nitrile compound solvent.
The solid electrolyte composition according to any one of claims 15 to 17, further comprising a radical polymerization initiator and / or a crosslinking agent.
The solid electrolyte composition according to any one of claims 15 to 18, wherein the binder is contained in an amount of 0.1 to 20 parts by mass with respect to 100 parts by mass of the inorganic solid electrolyte.
The solid electrolyte composition according to any one of claims 15 to 19, wherein the cyclic molecule is cyclodextrin or a derivative thereof.
The linear molecule is a polyolefin, polyether, polyester, polysiloxane, polycarbonate, polyacrylate, polyurethane, polyurea, a polymer having a heterocyclic ring in the main chain, or a compound containing a polyene structure. The solid electrolyte composition described in 1.
The cyclic molecule or linear molecule has a crosslinked structure via at least one of the following reactive substituent (A) and the following reactive linking group (B) or the reactive substituent: The solid electrolyte composition according to any one of the above.
Reactive substituent (A)
Amino group, thiol group, tetrahydrofuryl group, oxetane group, epoxy group, hydroxyl group, isocyanate group, carboxyl group, phosphoric acid group, sulfonic acid group, phosphonic acid, alkenyl group-containing group reactive linking group (B)
Imino group, alkenylene group-containing group
The solid electrolyte composition according to any one of claims 15 to 22, which has a bulky substituent at an end of the linear molecule.
The solid electrolyte composition according to any one of claims 15 to 23, wherein the linear molecule is a compound containing a structure represented by any of the following formulas (1-1) to (1-5).

L 1 is an alkylene group or an alkenylene group. L 2 is a linking group. R 31 and R 32 are each independently a hydrogen atom, a hydroxyl group, an alkyl group, an alkenyl group, an aryl group, or an aralkyl group. R 41 , R 42 , R 51 and R 52 are each independently a hydrogen atom, a halogen atom, a cyano group, a hydroxyl group, an alkyl group, an aryl group or an aralkyl group. A plurality of L 1 , L 2 , R 31 , R 32 , R 41 , R 42 , R 51 , R 52 in the molecule may be the same as or different from each other.
The solid electrolyte composition according to claim 22, wherein the reactive substituent (A) is at least one of the following functional groups.
Functional group Thiol group, epoxy group, hydroxyl group, isocyanate group, carboxyl group, phosphoric acid group, sulfonic acid group, phosphonic acid group, alkenyl group-containing group
The solid electrolyte composition according to claim 25, wherein the reactive substituent (A) is at least one of the following functional groups.
Functional group Carboxyl group, phosphoric acid group, sulfonic acid group, phosphonic acid group
An electrode sheet for a battery, wherein the solid electrolyte composition according to any one of claims 15 to 26 is formed on a metal foil.
A method for producing an electrode sheet for a battery, wherein the solid electrolyte composition according to any one of claims 15 to 27 is formed on a metal foil.
The method for producing an electrode sheet for a battery according to claim 28, wherein the formed solid electrolyte composition is heated at 80 ° C or higher.
A method for producing an all-solid-state secondary battery, wherein an all-solid-state secondary battery is produced via the method for producing an electrode sheet for a battery according to claim 28 or claim 29.