JP6587555B2 - Solid electrolyte composition, sheet for all-solid secondary battery and all-solid-state secondary battery using the same, and method for producing them - Google Patents

Description

  The present invention relates to a solid electrolyte composition, a sheet for an all-solid secondary battery using the same, an all-solid secondary battery, and a method for producing them.

A lithium ion secondary battery is a storage battery that includes a negative electrode, a positive electrode, and an electrolyte sandwiched between the negative electrode and the positive electrode, and enables charging and discharging by reciprocating lithium ions between the two electrodes. Conventionally, an organic electrolytic solution has been used as an electrolyte in a lithium ion secondary battery. However, the organic electrolyte is liable to leak, and there is a possibility that a short circuit may occur inside the battery due to overcharge or overdischarge, resulting in ignition, and further improvements in reliability and safety are required.
Under such circumstances, an all-solid secondary battery using an inorganic solid electrolyte in place of the organic electrolyte has attracted attention. All-solid-state secondary batteries are composed of a solid negative electrode, electrolyte, and positive electrode, which can greatly improve safety and reliability, which is a problem of batteries using organic electrolytes, and can also extend the service life. It will be. Furthermore, the all-solid-state secondary battery can have a structure in which electrodes and an electrolyte are directly arranged in series. Therefore, it is possible to increase the energy density as compared with a secondary battery using an organic electrolyte, and application to an electric vehicle, a large storage battery, and the like is expected.

  In such an all-solid secondary battery, any one of the active material layer of the negative electrode, the solid electrolyte layer, and the active material layer of the positive electrode is formed of binder particles (such as an inorganic solid electrolyte or an active material and a specific polymer compound). It has been proposed to form a material containing a binder). For example, Patent Document 1 describes a solid battery containing a hydrocarbon polymer having a crosslinked structure as a binder. Patent Document 2 discloses a solid secondary obtained from a composition for a solid electrolyte sheet in which a solid electrolyte and a binder composed of a fluorine compound (such as polyvinylidene fluoride (PVDF)) are dispersed in a fluorine solvent. A battery is described.

JP 2014-112485 A JP 2010-146823 A

  In recent years, development of all-solid-state secondary batteries is progressing rapidly, and performance required for all-solid-state secondary batteries is also increasing. In particular, with the increase in the types of products to which all-solid secondary batteries are applied, development of all-solid secondary batteries that can withstand use under harsh conditions is desired. However, the all-solid-state secondary batteries described in Patent Documents 1 and 2 need to be improved for use under severe conditions.

  The present invention can realize good cycle characteristics in an all-solid secondary battery both when used at a high temperature (for example, 60 ° C.) for a certain period of time and when used at a high potential (for example, 4.3 V). It is an object to provide a solid electrolyte composition. Moreover, this invention makes it a subject to provide the sheet | seat for all-solid-state secondary batteries and the all-solid-state secondary battery using the said solid electrolyte composition. Furthermore, this invention makes it a subject to provide the manufacturing method of each of the said sheet | seat for all-solid-state secondary batteries, and an all-solid-state secondary battery.

  By using a specific inorganic solid electrolyte and an organometallic compound having a specific structure, the present inventors can suppress an increase in interfacial resistance accompanying charge / discharge, and are all solids when operating at high temperatures. It has been found that the cycle characteristics of the secondary battery can be improved and that the all-solid secondary battery cycle characteristics when operating at a high potential can be improved. The present invention has been further studied based on these findings and has been completed.

That is, the above problem has been solved by the following means.
(1) An inorganic solid electrolyte having conductivity of metal ions belonging to Group 1 or Group 2 of the periodic table, and Fe, V, Cr, Mo represented by the following general formula (A1) or (A2) A solid electrolyte composition containing an organometallic compound having Hf, Zr, Ti or Y ,
The solid electrolyte composition whose content of the inorganic solid electrolyte in a solid electrolyte composition is 1 mass% or more .

In the above formula, M represents Fe, V, Cr, Mo, Hf, Zr, Ti or Y.
R ^A11 represents an alkyl group, an alkylsilyl group, an alkenyl group, an alkynyl group, an alkoxy group, an alkylsulfanyl group, an amino group, a cyano group, a carboxyl group, a carbonyl group-containing group, a sulfonyl group-containing group, a phosphanyl group, or a halogeno group. . R ^A11 may form an aliphatic or aromatic ring.
a is an integer of 0-5.
X and Y each independently contain a hydrogen atom, alkyl group, alkenyl group, alkoxy group, alkylamino group, silylamino group, alkylsulfanyl group, sulfonic acid group, isocyanate group, isothiocyanate group, sulfanyl group, phosphinyl group, carbonyl group A group, a halogeno group, an aryl group, —S _x H or a heteroaryl group; x is an integer of 2-8. Furthermore, X and Y may be connected to each other.
m and n are integers of 0 to 3, and m + n is 0 to 3.
T ^A11 is a hydrogen atom, alkyl group, alkenyl group, alkoxy group, alkylamino group, silylamino group, sulfonic acid group, isocyanate group, isothiocyanate group, sulfanyl group, phosphinyl group, carbonyl group-containing group, halogeno group, aryl group , A heteroaryl group, or a group represented by the following general formula (CP).
c is an integer of 0-2.

In the above formula, R ^A12 represents the same group as R ^A11 . * Represents a bond that bonds to M. b is an integer of 0-5. R ^A11 and R ^A12 may be linked to each other.

In the above formula, M represents Fe, V, Cr, Mo, Hf, Zr, Ti or Y. R ³ and R ⁴ represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, an alkylsilyl group, or a halogeno group. R ³ and R ⁴ may be linked to each other. p is an integer of 1 to 4 .
(2 ) The solid electrolyte composition according to (1) , wherein the organometallic compound is a transition metal metallocene.
( 3 ) The solid electrolyte composition according to (1) , wherein the organometallic compound is represented by any one of the following general formulas (Ia-1) to (Ia-3).

In said formula, M, X, and Y are synonymous with M, X, and Y in general formula (A1). m1 and n1 are integers of 0-2, and m1 + n1 is 0-2. m2 and n2 are integers of 0 to 3, and m2 + n2 is 2 or 3.
( 4 ) The solid electrolyte composition according to any one of (1) to ( 3 ), which contains an electrode active material.
( 5 ) The solid electrolyte composition according to ( 4 ), wherein the electrode active material is a positive electrode active material.
( 6 ) A sheet for an all-solid-state secondary battery having a layer of the solid electrolyte composition according to any one of (1) to ( 5 ) on a substrate or a metal foil.
( 7 ) An all-solid secondary battery comprising a positive electrode active material layer, a negative electrode active material layer, and a solid electrolyte layer,
An all-solid-state secondary battery, wherein at least one of the positive electrode active material layer, the negative electrode active material layer, and the solid electrolyte layer is a layer made of the solid electrolyte composition according to any one of (1) to ( 5 ).
( 8 ) The manufacturing method of the sheet | seat for all-solid-state secondary batteries which arrange | positions the solid electrolyte composition as described in any one of (1)-( 5 ) on a base material or metal foil, and forms this into a film.
( 9 ) A method for producing an all-solid secondary battery, wherein an all-solid secondary battery is produced through the production method according to ( 8 ).

In this specification, a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
In the present specification, when “acryl” or “(meth) acryl” is simply described, it means methacryl and / or acryl. The term “acryloyl” or “(meth) acryloyl” simply means methacryloyl and / or acryloyl.
In the present specification, when there are a plurality of substituents, linking groups, etc. (hereinafter referred to as substituents, etc.) indicated by specific symbols, or when a plurality of substituents etc. are specified simultaneously or alternatively, It means that a substituent etc. may mutually be same or different. The same applies to the definition of the number of substituents and the like.

When the solid electrolyte composition of the present invention is used as a material for a solid electrolyte layer or an active material layer of an all-solid-state secondary battery, it can be used for a certain period of time at a high temperature and has a high potential (for example, 4.3 V). Even when used in the above, an excellent effect is achieved that good cycle characteristics can be realized. Moreover, the sheet | seat for all-solid-state secondary batteries and all-solid-state secondary battery of this invention exhibit the outstanding performance using the solid electrolyte composition which has said outstanding effect.
Moreover, according to the manufacturing method of this invention, the sheet | seat for all-solid-state secondary batteries and all-solid-state secondary battery of this invention can each be manufactured suitably.

It is a longitudinal cross-sectional view which shows typically the all-solid-state secondary battery which concerns on preferable embodiment of this invention. It is a longitudinal cross-sectional view which shows typically the all-solid-state secondary battery (coin battery) produced in the Example.

  The solid electrolyte composition of the present invention includes a specific inorganic solid electrolyte and an organometallic compound having a transition element or a rare earth element represented by the general formula (A1) or (A2) (hereinafter also referred to as a specific organometallic compound). .). Hereinafter, the preferable embodiment will be described. First, an all-solid secondary battery using the solid electrolyte composition of the present invention will be described.

[All-solid secondary battery]
The all solid state secondary battery of the present invention includes a positive electrode, a negative electrode facing the positive electrode, and a solid electrolyte layer between the positive electrode and the negative electrode. The positive electrode has a positive electrode active material layer on a positive electrode current collector. The negative electrode has a negative electrode active material layer on a negative electrode current collector.
At least one of the negative electrode active material layer, the positive electrode active material layer, and the solid electrolyte layer is formed of the solid electrolyte composition of the present invention to be described later, that is, formed by coating the solid electrolyte composition of the present invention. It is preferable that it is a layer. Among them, the negative electrode active material layer and / or the positive electrode active material layer is more preferably formed of the solid electrolyte composition of the present invention, and the positive electrode active material layer is more preferably formed of the solid electrolyte composition of the present invention. .
The active material layer and / or the solid electrolyte layer formed of the solid electrolyte composition are preferably the same as those in the solid content of the solid electrolyte composition with respect to the component species to be contained and the content ratio thereof.
Hereinafter, preferred embodiments of the present invention will be described, but the present invention is not limited thereto.

FIG. 1 is a cross-sectional view schematically showing an all solid state secondary battery (lithium ion secondary battery) according to a preferred embodiment of the present invention. The all-solid-state secondary battery 10 of the present embodiment includes a negative electrode current collector 1, a negative electrode active material layer 2, a solid electrolyte layer 3, a positive electrode active material layer 4, and a positive electrode current collector 5 stacked in this order as viewed from the negative electrode side. The adjacent layers are in direct contact with each other. 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 discharging, lithium ions (Li ⁺ ) accumulated in the negative electrode are returned to the positive electrode side, and electrons can be supplied to the working part 6. In the example of the illustrated all-solid-state secondary battery, a light bulb is used as a model for the operating portion 6 and is lit by discharge.

In the present invention, by using the specific organometallic compound in combination with an inorganic solid electrolyte, the all-solid-state secondary battery exhibits excellent charge / discharge characteristics even at high temperature operation and high potential operation.
Although its action and mechanism are not clear but estimated, it can be considered as follows. In other words, the specific organometallic compound selectively reacts at the electrode site (particularly the positive electrode surface) and / or the solid electrolyte surface with high reaction activity, thereby causing side reactions such as decomposition of the inorganic solid electrolyte accompanying charge / discharge. It is presumed that the increase in interfacial resistance is suppressed. In particular, it is considered that side reactions such as decomposition of the inorganic solid electrolyte can be effectively suppressed even at a high temperature operation of 60 ° C. and a high potential operation of 4.3 V.
The all-solid-state secondary battery of the present invention contains the above-mentioned specific organometallic compound and an inorganic solid electrolyte, which can suppress side reactions such as decomposition of the inorganic solid electrolyte accompanying an electric reaction, and can suppress an increase in interface resistance. It is an all-solid-state secondary battery having a layer (a layer made of the solid electrolyte composition of the present invention). Here, it is meant to include an all-solid secondary battery that has been subjected to initialization, which will be described later, and in which the increase in interface resistance is suppressed.

The thicknesses of the positive electrode active material layer 4, the solid electrolyte layer 3, and the negative electrode active material layer 2 are not particularly limited. Considering general battery dimensions, the thickness of each layer is preferably 10 to 1,000 μm, and more preferably 20 μm or more and less than 500 μm. In the all solid state secondary battery of the present invention, it is more preferable that the thickness of at least one of the positive electrode active material layer 4, the solid electrolyte layer 3 and the negative electrode active material layer 2 is 50 μm or more and less than 500 μm.
In the present invention, either or both of the positive electrode active material layer and the negative electrode active material layer may be simply referred to as an active material layer or an electrode active material layer. In addition, either or both of the positive electrode active material and the negative electrode active material may be simply referred to as an active material or an electrode active material.

[Current collector (metal foil)]
The positive electrode current collector 5 and the negative electrode current collector 1 are preferably electronic conductors.
In the present invention, either or both of the positive electrode current collector and the negative electrode current collector may be simply referred to as a current collector.
Materials for forming the positive electrode current collector include aluminum, aluminum alloy, stainless steel, nickel and titanium, as well as the surface of aluminum or stainless steel treated with carbon, nickel, titanium or silver (formation of a thin film) Among them, aluminum and aluminum alloys are more preferable.
In addition to aluminum, copper, copper alloy, stainless steel, nickel and titanium, etc., the material for forming the negative electrode current collector is treated with carbon, nickel, titanium or silver on the surface of aluminum, copper, copper alloy or stainless steel. What was made to do is preferable, and aluminum, copper, copper alloy, and stainless steel are more preferable.

The current collector is usually in the form of a film sheet, but a net, a punched one, a lath, a porous body, a foam, a fiber group molded body, or the like can also be used.
Although the thickness of a collector is not specifically limited, 1-500 micrometers is preferable. Moreover, it is also preferable that the current collector surface is roughened by surface treatment.

  In the present invention, a functional layer, a member, or the like is appropriately interposed or disposed between or outside each of the negative electrode current collector, the negative electrode active material layer, the solid electrolyte layer, the positive electrode active material layer, and the positive electrode current collector. May be. Each layer may be composed of a single layer or a plurality of layers.

[Case]
The basic structure of the all-solid-state secondary battery can be manufactured by arranging each of the above layers. Depending on the application, it may be used as an all-solid secondary battery as it is, but in order to obtain a dry battery, it is further sealed in a suitable housing. The housing may be metallic or made of resin (plastic). When using a metallic thing, the thing made from an aluminum alloy and stainless steel can be mentioned, for example. The metallic housing is preferably divided into a positive-side housing and a negative-side housing, and electrically connected to the positive current collector and the negative current collector, respectively. The casing on the positive electrode side and the casing on the negative electrode side are preferably joined and integrated through a gasket for preventing a short circuit.

[Solid electrolyte composition]
The solid electrolyte composition of the present invention is as described above, and will be specifically described below.
(Inorganic solid electrolyte)
The solid electrolyte composition of the present invention contains an inorganic solid electrolyte.
The solid electrolyte of the inorganic solid electrolyte is a solid electrolyte that can move ions inside. Since it does not contain organic substances as the main ionic conductivity material, organic solid electrolytes (polymer electrolytes typified by polyethylene oxide (PEO), etc., and organics typified by lithium bis (trifluoromethanesulfonyl) imide (LiTFSI), etc. It is clearly distinguished from the electrolyte salt). Further, since the inorganic solid electrolyte is solid in a steady state, it is not dissociated or released into cations and anions. In this respect, it is also clearly distinguished from inorganic electrolyte salts (LiPF ₆ , LiBF ₄ , lithium bis (fluorosulfonyl) imide (LiFSI), LiCl, etc.) in which cations and anions are dissociated or liberated in the electrolyte and polymer. . The inorganic solid electrolyte is not particularly limited as long as it has conductivity of ions of metal elements belonging to Group 1 or Group 2 of the Periodic Table, and generally does not have electron conductivity. When the all solid state secondary battery of the present invention is a lithium ion battery, the inorganic solid electrolyte preferably has an ionic conductivity of lithium ions.
As the inorganic solid electrolyte, a solid electrolyte material usually used for an all-solid secondary battery can be appropriately selected and used. Typical examples of inorganic solid electrolytes include (i) sulfide-based inorganic solid electrolytes and (ii) oxide-based inorganic solid electrolytes. In the present invention, a sulfide-based inorganic solid electrolyte is preferably used from the viewpoint that a better interface can be formed between the active material and the inorganic solid electrolyte.
(I) Sulfide-based inorganic solid electrolyte The sulfide-based inorganic solid electrolyte contains a sulfur atom (S) and has ionic conductivity of a metal element belonging to Group 1 or Group 2 of the periodic table, And what has electronic insulation is preferable. The sulfide-based inorganic solid electrolyte preferably contains at least Li, S and P as elements and has lithium ion conductivity. However, depending on the purpose or the case, other than Li, S and P may be used. An element may be included.
For example, a lithium ion conductivity inorganic solid electrolyte satisfying the composition represented by the following formula (1) can be mentioned and is preferable.

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 preferred.
M represents an element selected from B, Zn, Sn, Si, Cu, Ga, Sb, Al, and Ge. Among these, B, Sn, Si, Al, or Ge is preferable, and Sn, Al, or Ge is more preferable.
A represents I, Br, Cl or F, preferably I or Br, and particularly preferably I.
L, M, and A can each be one or more of the above elements.
a1 to e1 indicate 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 further preferably 1 to 9, and more preferably 1.5 to 4. b1 is preferably 0 to 0.5. Further, d1 is preferably 3 to 7, and more preferably 3.25 to 4.5. Further, e1 is preferably 0 to 3, and more preferably 0 to 1.

  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 is a1: c1: d1 = 1-9: 1: 3-7, more preferably b1 = 0, e1 = 0 and a1: c1: d1 = 1.5-4: 1: 3.25-4. 5. As will be described later, the composition ratio of each element can be controlled by adjusting the blending amount of the raw material compound when producing the sulfide-based inorganic solid electrolyte.

The sulfide-based inorganic solid electrolyte may be amorphous (glass) or crystallized (glass ceramic), or only a part may be crystallized. For example, Li-PS-based glass containing Li, P, and S, or Li-PS-based glass ceramics containing Li, P, and S can be used.
The sulfide-based inorganic solid electrolyte includes [1] lithium sulfide (Li ₂ S) and phosphorus sulfide (for example, diphosphorus pentasulfide (P ₂ S ₅ )), [2] lithium sulfide and at least one of simple phosphorus and simple sulfur, Or [3] It can be produced by the reaction of lithium sulfide, phosphorus sulfide (for example, diphosphorus pentasulfide (P ₂ S ₅ )), at least one of elemental phosphorus and elemental sulfur.

The ratio of Li ₂ S to P ₂ S ₅ in the Li—PS glass and Li—PS glass ceramics is a molar ratio of Li ₂ S: P ₂ S ₅ , preferably 65:35 to 35:35. 85:15, more preferably 68:32 to 77:23. By setting the ratio of Li ₂ S to P ₂ S ₅ within this range, the lithium ion conductivity can be further 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 S / cm or less.

Specific examples of the compound of the sulfide-based inorganic solid electrolyte include, for example, those using a raw material composition containing Li ₂ S and a sulfide of an element belonging to Group 13 to Group 15. it can. More _{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 S-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 - _{l 2 S 3, Li 2 S} -SiS 2 -P 2 S 5, Li 2 S-SiS 2 -P 2 S 5 -LiI, Li 2 S-SiS 2 -LiI, Li 2 S-SiS 2 -Li 4 SiO _4, such as _{Li 2 S-SiS 2 -Li 3} PO 4 and _Li 10 _GeP 2 _{S 12} and the like. Among them, Li ₂ S—P ₂ S ₅ , Li ₂ S—GeS ₂ —Ga ₂ S ₃ , 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-LiI-Li 2 O-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 and / or crystalline composition of amorphous, amorphous, or a mixture of crystalline and amorphous, comprising Li ₂ S—GeS ₂ —P ₂ S ₅ , Li ₁₀ GeP ₂ S ₁₂ has high lithium ion conductivity. Since it has, it is preferable. Examples of a method for synthesizing a sulfide-based inorganic solid electrolyte material using such a raw material composition include an amorphization method. Examples of the amorphization method include a mechanical milling method 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.
Among _{them, Li 2 S-P 2 S} 5, LGPS (Li 10 GeP 2 S 12) and _{Li 2 S-P 2 S 5} -SiS 2 and the like are preferable.

(Ii) Oxide-based inorganic solid electrolyte The oxide-based inorganic solid electrolyte contains an oxygen atom (O) and has ionic conductivity of a metal element belonging to Group 1 or Group 2 of the periodic table, And what has electronic insulation is preferable.
The oxide-based inorganic solid electrolyte preferably has an ionic conductivity of 1 × 10 ⁻⁶ S / cm or more, more preferably 5 × 10 ⁻⁶ S / cm or more, and 1 × 10 ⁻⁵ S. / Cm or more is particularly preferable. Although an upper limit is not specifically limited, It is practical that it is 1 * 10 < ^-1 > S / cm or less.

As a specific compound example, for example, Li _xa La _ya TiO ₃ [xa satisfies 0.3 ≦ xa ≦ 0.7, and ya satisfies 0.3 ≦ ya ≦ 0.7. (LLT); Li _xb La _yb Zr _zb M ^bb _{mb Onb} (M ^bb is one or more elements selected from Al, Mg, Ca, Sr, V, Nb, Ta, Ti, Ge, In and Sn) Xb satisfies 5 ≦ xb ≦ 10, yb satisfies 1 ≦ yb ≦ 4, zb satisfies 1 ≦ zb ≦ 4, mb satisfies 0 ≦ mb ≦ 2, and nb satisfies 5 ≦ nb ≦ 20. Li _xc B _yc M ^cc _{zc Onc} (M ^cc is one or more elements selected from C, S, Al, Si, Ga, Ge, In and Sn. Xc is 0 ≦ xc ≦ 5 Yc satisfies 0 ≦ yc ≦ 1, zc satisfies 0 ≦ zc ≦ 1, and nc satisfies 0 ≦ nc ≦ 6); Li _xd (Al, Ga) _yd (Ti, Ge) _zd Si _ad P _{md Ond} (xd satisfies 1 ≦ xd ≦ 3, yd Satisfies 0 ≦ yd ≦ 1, zd satisfies 0 ≦ zd ≦ 2, ad satisfies 0 ≦ ad ≦ 1, md satisfies 1 ≦ md ≦ 7, and nd satisfies 3 ≦ nd ≦ 13.) ^{_{; Li (3-2xe) M ee xe}} D ee O (xe represents a number of 0 to ^{0.1, M ee} is ^{.D ee} halogen atom or two or more halogen atoms representing a divalent metal atom Li _xf Si _yf O _zf (xf satisfies 1 ≦ xf ≦ 5, yf satisfies 0 <yf ≦ 3, and zf satisfies 1 ≦ zf ≦ 10); Li _xg S _yg O _zg (xg satisfies 1 ≦ xg ≦ 3, yg satisfies 0 <yg ≦ 2, and zg satisfies 1 ≦ zg ≦ 10); Li ₃ BO ₃ ; Li ₃ BO ₃ —Li ₂ SO ₄ ; _{Li 2 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); LISICON Li 3.5} Zn 0.25 GeO with (Lithium super ionic conductor) type crystal structure ₄ ; La _0.55 Li _0.35 TiO ₃ having a perovskite-type crystal structure; LiTi ₂ P ₃ O ₁₂ having a NASICON (Natrium super ionic conductor) type crystal structure; Li _{1 + xh + yh} (Al, Ge) _xh (Ti, Ge) _2-xh Si _yh P _3-yh O ₁₂ (xh satisfies 0 ≦ xh ≦ 1 and yh satisfies 0 ≦ yh ≦ 1) And Li ₇ La ₃ Zr ₂ O ₁₂ (LLZ) having a garnet-type crystal structure.
Phosphorus compounds containing Li, P and O are also desirable. For example, lithium phosphate (Li ₃ PO ₄ ); LiPON obtained by substituting a part of oxygen of lithium phosphate with nitrogen; LiPOD ¹ (D ¹ is preferably Ti, V, Cr, Mn, Fe, Co, Ni, And at least one element selected from Cu, Zr, Nb, Mo, Ru, Ag, Ta, W, Pt, and Au.
Furthermore, LiA ¹ ON (A ¹ is one or more elements selected from Si, B, Ge, Al, C, and Ga) can be preferably used.
Among _them, (is as M bb, xb, yb, zb , mb and nb ^{_{above.) LLT, Li xb La yb}} Zr zb M bb mb O nb, LLZ, Li 3 BO 3, Li 3 BO 3 -Li ₂ SO ₄ and _{Li xd (Al, Ga) yd} (Ti, Ge) zd Si ad P md O nd (xd, yd, zd, ad, md and nd are as defined above.) is preferred, LLZ, LLT _{, LAGP (Li 1.5 Al 0.5 Ge} 1.5 (PO 4) 3) and _{LATP ([Li 1.4 Ti 2 Si} 0.4 P 2.6 O 12] -AlPO 4) is more preferable.

  The inorganic solid electrolyte is preferably a particle. The volume average particle diameter of the particulate 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. In addition, the measurement of the volume average particle diameter of an inorganic solid electrolyte is performed in the following procedures. The inorganic solid electrolyte particles are prepared by diluting a 1 mass% dispersion in a 20 mL sample bottle using water (heptane in the case of a substance unstable to water). The diluted dispersion sample is irradiated with 1 kHz ultrasonic waves for 10 minutes and used immediately after that. Using this dispersion sample, using a laser diffraction / scattering particle size distribution measuring device LA-920 (trade name, manufactured by HORIBA), data acquisition was performed 50 times using a quartz cell for measurement at a temperature of 25 ° C. Obtain the volume average particle size. For other detailed conditions and the like, refer to the description of JISZ8828: 2013 “Particle Size Analysis—Dynamic Light Scattering Method” as necessary. Five samples are prepared for each level, and the average value is adopted.

The content of the inorganic solid electrolyte in the solid electrolyte composition is 5% by mass or more at a solid content of 100% by mass when considering both reduction of interface resistance and battery characteristic maintenance effect (improvement of cycle characteristics). Is more preferable, 70% by mass 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.
Moreover, the content of the inorganic solid electrolyte in the solid electrolyte composition is preferably 1% by mass or more, more preferably 5% by mass or more, and further preferably 10% by mass or more. As an upper limit, it is preferable that it is 80 mass% or less, It is more preferable that it is 60 mass% or less, It is further more preferable that it is 50 mass% or less.
However, when the positive electrode active material or the negative electrode active material is contained, the content of the inorganic solid electrolyte in the solid electrolyte composition is such that the total content of the positive electrode active material or the negative electrode active material and the inorganic solid electrolyte is in the above range. Is preferred.
In the present specification, the solid content means a component that does not volatilize or evaporate when subjected to a drying treatment at 170 ° C. for 6 hours in a nitrogen atmosphere. Typically, it refers to components other than the dispersion medium described below.
An inorganic solid electrolyte may be used individually by 1 type, or may be used in combination of 2 or more type.

(Organic metal compound)
The solid electrolyte composition of the present invention contains an organometallic compound having a transition element or a rare earth element represented by the following general formula (A1) or (A2).

In the above formula, M represents a transition element or a rare earth element.
R ^A11 is an alkyl group, alkylsilyl group, alkenyl group, alkynyl group, alkoxy group, alkylsulfanyl group, amino group, cyano group (—CN), carboxyl group, carbonyl group-containing group, sulfonyl group-containing group, phosphanyl (—PH ₂ ) represents a group or a halogeno group. R ^A11 may form an aliphatic or aromatic ring.
a is an integer of 0-5.
X and Y are each independently a hydrogen atom, alkyl group, alkenyl group, alkoxy group, alkylamino group, silylamino group, alkylsulfanyl group, sulfonic acid group (—SO ₃ H), isocyanate group (—NCO), isothiocyanate group (-NCS), sulfanyl group (-SH), a phosphinyl group _{(-P (= O) H 2} ), indicating a carbonyl group-containing group, a halogeno group, an aryl group, a -S _x H or heteroaryl group. x is an integer of 2 to 8, and an integer of 2 to 4 is preferable. Furthermore, X and Y may be connected to each other.
m and n are integers of 0 to 3, and m + n is 0 to 3.
T ^A11 is a hydrogen atom, an alkyl group, an alkenyl group, an alkoxy group, an alkylamino group, a silylamino group, a sulfonic acid group (—SO ₃ H), an isocyanate group (—NCO), an isothiocyanate group (—NCS), or a sulfanyl group. (-SH), a phosphinyl group _{(-P (= O) H 2} ), indicating a carbonyl group-containing group, a halogeno group, an aryl group, a heteroaryl group, or a group represented by the following general formula (CP),.
c is an integer of 0-2.

In the above formula, R ^A12 represents the same group as R ^A11 . * Represents a bond that bonds to M. b is an integer of 0-5. R ^A11 and R ^A12 may be linked to each other.

In the above formula, M represents a transition element or a rare earth element. R ³ and R ⁴ represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, an alkylsilyl group, or a halogeno group. R ³ and R ⁴ may be linked to each other. p is an integer of 1 to 4.

  Transition elements or rare earth elements in M include Ti, V, Cr, Fe, Zr, Ta, Mo, Ru, Eu, Hf, Er, La, Ce, Sm, Nb, Nd, Yb, Gd, Lu, and Y. Ti, V, Fe, Zr, Ru, Hf, Er, Nb and Gd are more preferable, and Ti, V, Zr, Hf and Er are further preferable.

For each substituent in R ^A11 , X, Y, T ^A11 , R ³ and R ⁴ , the description of the substituent Z described later can be preferably applied. The more preferable number of carbon atoms and the like of each substituent in R ^A11 , X, Y, T ^A11 , R ³ and R ⁴ are shown below.
The alkyl group preferably has 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms, and particularly preferably 1 to 3 carbon atoms. Examples include methyl, ethyl, n-propyl, isopropyl, n-butyl and t-butyl.
The alkylsilyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and particularly preferably 1 to 3 carbon atoms. An example is trimethylsilyl.
The alkenyl group preferably has 2 to 20 carbon atoms, and more preferably has 2 to 3 carbon atoms. For example, you may have substituents, such as an acyl group.
The alkoxy group preferably has 1 to 8 carbon atoms, and examples thereof include methoxy, ethoxy, propoxy, butoxy and isopropoxy.
The alkylsulfanyl group preferably has 1 to 8 carbon atoms, and more preferably 1 to 3 carbon atoms. An example is methanesulfanyl.
The amino group preferably has 0 to 10 carbon atoms, and examples thereof include dimethylamino.
The carbonyl group-containing group is preferably represented by —COOR, —OCOR, —COR, —NRCOR or —CONR ₂ (where R is a hydrogen atom, an alkyl group or a cycloalkyl group), and —COOR, —OCOR or —CONR ₂ is particularly preferable. The alkyl group in R preferably has 1 to 8 carbon atoms, and the cycloalkyl group preferably has 3 to 12 carbon atoms.
The sulfonyl group-containing group preferably has 1 to 10 carbon atoms, and examples thereof include methanesulfonyl.
Halogeno groups include fluoro, chloro, bromo and iodo, with fluoro being preferred.
The alkylamino group preferably has 1 to 8 carbon atoms, and examples thereof include N, N-dimethylamino and N, N-diethylamino.
The silylamino group preferably has 0 to 20 carbon atoms and is substituted with 1 to 3 groups selected from the group consisting of an alkylamino group, an arylamino group, an arylalkylamino group and a monovalent heterocyclic amino group Groups. Examples include trimethylsilylamino, triethylsilylamino, tert-butyldimethylsilylamino, triphenylsilylamino and diphenylmethylsilylamino.
Examples of the aryl group include aryl groups having 6 to 10 carbon atoms, which may have a substituent such as an alkoxy group. Specific examples include phenyl, tolyl and naphthyl, and phenyl or naphthyl is preferred.
The heteroaryl group is preferably a heteroaryl group having 3 to 6 ring atoms, preferably 2 to 20 carbon atoms, and examples of the heteroatoms in the ring include an oxygen atom, a nitrogen atom, and a sulfur atom. preferable. Specific heteroaryl rings include indole, carbazole, oxazole and thiophenine.

R ^A11 is preferably an alkyl group, an alkylsilyl group, an alkenyl group, an alkynyl group, an alkoxy group, an alkylsulfanyl group, an amino group, a carboxyl group, a carbonyl group-containing group, a sulfonyl group-containing group, a phosphanyl group, or a halogeno group. A group, an alkylsilyl group, a phosphanyl group and an amino group are more preferred.
X and Y are preferably an alkyl group, an alkenyl group, an alkylamino group, a silylamino group, an alkylsulfanyl group, an aryl group, an isothiocyanate group and —S _x H, and an alkyl group, an alkenyl group, an alkylamino group, a silylamino group and An isothiocyanate group is more preferred.
Examples of the divalent substituent formed by linking X and Y to each other include an alkenylene group (having preferably 2 to 12 carbon atoms, such as vinylene, 1,2-bis (trimethylsilyl) vinylene, butadienylene, 1,4 -Bis (trimethylsilyl) butadienylene and 2,3-dimethyl-1,4-bis (trimethylsilyl) butadienylene) and -S _y- (y is an integer of 4-8, for example, pentasulfanediyl And the like, and alkenylene groups are preferred.
T ^A11 is preferably a hydrogen atom, an alkyl group, or a group represented by the formula (CP).
As R ³ and R ⁴ , a hydrogen atom, an alkyl group, and an alkylsilyl group are preferable, and an alkyl group and an alkylsilyl group are more preferable.

a is preferably an integer of 0 to 4, more preferably 0 or 1.
m and n are preferably an integer of 1 to 3, and more preferably 1 or 2. m + n is preferably an integer of 1 to 3.
c is preferably 0 or 1, and more preferably 1.
In addition, when c is 0, m + n is preferably 2 or 3, when c is 1, m + n is preferably an integer of 0 to 2, and when c is 2, m + n is preferably 0.
b is preferably an integer of 0 to 3.
p is preferably an integer of 2 to 4.

  The organometallic compound represented by the general formula (A1) is preferably represented by any one of the following general formulas (Ia-1) to (Ia-3).

  In said formula, M, X, and Y are synonymous with M, X, and Y in general formula (A1). m1 and n1 are integers of 0-2, and m1 + n1 is 0-2. m2 and n2 are integers of 0 to 3, and m2 + n2 is 2 or 3.

  m1 and n1 are preferably 0 or 1, and m1 + n1 is preferably 0 or 2. m2 and n2 are preferably 1 or 2, and m2 + n2 is preferably 3.

The specific organometallic compound used in the present invention is presumed to suppress side reactions in the all-solid secondary battery by the following mechanism.
That is, it is considered that a specific organometallic compound selectively reacts with a reaction active site in an active material and / or an inorganic solid electrolyte present in the vicinity. More specifically, it is presumed that a metal compound (or an ion thereof) generated by elimination of a cyclopentadienyl ring or the like from a specific organometallic compound caps the reaction active site.
In general, elimination of a cyclopentadienyl ring or the like from an organometallic compound requires the presence of a medium (electrolytic solution or the like) that can dissolve these ligands around the organometallic compound. it is conceivable that. For this reason, in an all-solid battery formed only of solids, there is a concern that reaction such as capping of reaction active sites does not occur, and the organometallic compound itself becomes a foreign substance and deteriorates battery performance. However, in the all-solid-state secondary battery of the present invention, it was found that a specific organometallic compound contributes to good cycle characteristics rather than a decrease in battery performance, probably because of the polarity of the inorganic solid electrolyte.

  The organometallic compound used in the present invention is more preferably a transition metal metallocene. That is, the organometallic compound represented by the general formula (A1), particularly the organometallic compound represented by the general formula (Ia-1) or (Ia-3) is preferable.

  Specific examples of the organometallic compound used in the present invention are listed below, but the present invention is not construed as being limited thereto.

In the present specification, a substituent that does not specify substitution or non-substitution (the same applies to a linking group) means that the group may have an appropriate substituent. This is also synonymous for compounds that do not specify substituted or unsubstituted. Preferred substituents include the following substituent Z.
Examples of the substituent Z 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, etc.), an alkynyl group (preferably an alkynyl group having 2 to 20 carbon atoms, such as ethynyl, butadiynyl, phenylethynyl, etc.), A cycloalkyl group (preferably a cycloalkyl group having 3 to 20 carbon atoms, such as cyclopropyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, etc., but in this specification, an alkyl group usually means a cycloalkyl group) ), An aryl group (preferably Aryl groups having 6 to 26 atoms such as phenyl, 1-naphthyl, 4-methoxyphenyl, 2-chlorophenyl, 3-methylphenyl, etc., aralkyl groups (preferably aralkyl groups having 7 to 23 carbon atoms, for example, Benzyl, phenethyl, etc.), a heterocyclic group (preferably a heterocyclic group having 2 to 20 carbon atoms, preferably 5 or 6 having at least one selected from an oxygen atom, a sulfur atom and a nitrogen atom as a ring-constituting atom A membered heterocyclic group is preferable, for example, tetrahydropyranyl, tetrahydrofuranyl, 2-pyridyl, 4-pyridyl, 2-imidazolyl, 2-benzimidazolyl, 2-thiazolyl, 2-oxazolyl, pyrrolidone group, etc.), an alkoxy group ( Preferably an alkoxy group having 1 to 20 carbon atoms such as methoxy, ethoxy, Propyloxy, benzyloxy, etc.), an aryloxy group (preferably an aryloxy group having 6 to 26 carbon atoms, such as phenoxy, 1-naphthyloxy, 3-methylphenoxy, 4-methoxyphenoxy, etc., but in this specification, An alkoxy group usually means an aryloyl group), an alkoxycarbonyl group (preferably an alkoxycarbonyl group having 2 to 20 carbon atoms, such as ethoxycarbonyl, 2-ethylhexyloxycarbonyl, etc.), an aryloxycarbonyl group ( Preferably, the aryloxycarbonyl group having 6 to 26 carbon atoms such as phenoxycarbonyl, 1-naphthyloxycarbonyl, 3-methylphenoxycarbonyl, 4-methoxyphenoxycarbonyl, etc.), amino group (preferably carbon atom) Including an amino group having 0 to 20 atoms, an alkylamino group, an arylamino group, for example, amino, N, N-dimethylamino, N, N-diethylamino, N-ethylamino, anilino, etc.), sulfamoyl group (preferably A sulfamoyl group having 0 to 20 carbon atoms such as N, N-dimethylsulfamoyl, N-phenylsulfamoyl and the like, an acyl group (preferably an acyl group having 1 to 20 carbon atoms such as acetyl and propionyl) , Butyryl, etc.), an aryloyl group (preferably an aryloyl group having 7 to 23 carbon atoms, such as benzoyl, etc., but in this specification, an acyl group usually means an aryloyl group. ), An acyloxy group (preferably an acyloxy group having 1 to 20 carbon atoms such as acetyloxy), an aryloyloxy group (preferably an aryloyloxy group having 7 to 23 carbon atoms such as benzoyloxy, etc. In this specification, an acyloxy group usually means an aryloyloxy group.), A carbamoyl group (preferably a carbamoyl group having 1 to 20 carbon atoms, such as N, N-dimethylcarbamoyl, N-phenylcarbamoyl, etc. ), An acylamino group (preferably an acylamino group having 1 to 20 carbon atoms, such as acetylamino, benzoylamino, etc.), an alkylsulfanyl group (preferably an alkylsulfanyl group having 1 to 20 carbon atoms, such as methylsulfanyl, ethyl Sulfanyl, isopropyl Sulfanyl, benzylsulfanyl, etc.), arylsulfanyl groups (preferably arylsulfanyl groups having 6 to 26 carbon atoms, such as phenylsulfanyl, 1-naphthylsulfanyl, 3-methylphenylsulfanyl, 4-methoxyphenylsulfanyl, etc.), alkylsulfonyl A group (preferably an alkylsulfonyl group having 1 to 20 carbon atoms, such as methylsulfonyl or ethylsulfonyl), an arylsulfonyl group (preferably an arylsulfonyl group having 6 to 22 carbon atoms, such as benzenesulfonyl), an alkyl, etc. A silyl group (preferably an alkylsilyl group having 1 to 20 carbon atoms, such as monomethylsilyl, dimethylsilyl, trimethylsilyl, triethylsilyl, etc.), an arylsilyl group (preferably 6 to 4 carbon atoms) Arylsilyl groups such as triphenylsilyl), alkoxysilyl groups (preferably alkoxysilyl groups having 1 to 20 carbon atoms such as monomethoxysilyl, dimethoxysilyl, trimethoxysilyl, triethoxysilyl, etc.), aryl An oxysilyl group (preferably an aryloxysilyl group having 6 to 42 carbon atoms, such as triphenyloxysilyl), a phosphoryl group (preferably a phosphoryl group having 0 to 20 carbon atoms, such as -OP (= O) ^(R _P) 2), a phosphonyl group (preferably a phosphonyl group having 0-20 carbon atoms, for ^{example, -P (= O) (R} P) 2), a phosphinyl group (preferably phosphinyl of 0-20 carbon atoms group, for example, ^-P (R _P) 2), (meth) acryloyl group, (meth) acryloyloxy group, ( (Meth) acryloylumimino group ((meth) acrylamide group), hydroxy group, sulfanyl group, carboxy group, phosphoric acid group, phosphonic acid group, sulfonic acid group, cyano group, halogen atom (for example, fluorine atom, chlorine atom, bromine atom, Iodine atom etc.).
In addition, each of the groups listed as the substituent Z may be further substituted with the above-described substituent Z.
When the compound, substituent, linking group and the like include an alkyl group, an alkylene group, an alkenyl group, an alkenylene group, an alkynyl group and / or an alkynylene group, these may be cyclic or linear, and may be linear or branched. It may be substituted as described above or unsubstituted.

  The organometallic compound used in the present invention includes a method in which a base is allowed to act on cyclopentadiene, a method of mixing a metal chloride (for example, iron (II) chloride), and a metallocene halide (for example, zirconocene dichloride and a nucleophilic compound). (For example, dimethylamine or methyl iodide) can be synthesized by a conventional method such as a method of reacting.

  The content of the organometallic compound used in the present invention in the solid electrolyte composition reacts with a reaction active site that causes a side reaction and effectively suppresses the side reaction. The content is preferably 01% by mass or more, more preferably 0.1% by mass or more, and particularly preferably 0.5% by mass or more. Moreover, since there exists a possibility that the resistance component which inhibits the movement of lithium ion may increase when there is too much content and battery performance may fall, it is preferable that the upper limit of the said content is 10 mass% or less. The content is more preferably at most 3 mass%, particularly preferably at most 3 mass%.

In addition, when the solid electrolyte composition of this invention contains the below-mentioned active material, it is also preferable to use the active material coat | covered with the organometallic compound used for this invention.
In this case, the content of the organometallic compound used in the present invention in the solid electrolyte composition is appropriately 0.01 mass at a solid content of 100 mass% in order to cause a reaction with a reactive site that contributes to a decrease in battery performance. % Or more is preferable, 0.05 mass% or more is more preferable, and 0.1 mass% or more is particularly preferable. Moreover, as an upper limit of the said content, 20 mass% or less is preferable, 10 mass% or less is more preferable, and 5 mass% or less is especially preferable.

  The organometallic compounds used in the present invention may be used singly or in combination of two or more. Moreover, you may use together with the other functional additive mentioned later.

  As described above, the all-solid secondary battery formed using the solid electrolyte composition containing the organometallic compound used in the present invention exhibits excellent charge / discharge characteristics even at high temperature operation and high potential operation.

(binder)
The solid electrolyte composition of the present invention preferably contains a binder.
The binder used in the present invention is not particularly limited as long as it is an organic polymer.
The binder that can be used in the present invention is preferably a binder that is usually used as a binder for a positive electrode or a negative electrode of a battery material, and is not particularly limited. For example, a binder made of a resin described below is preferable.

Examples of the fluorine-containing resin include polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVdF), and a copolymer of polyvinylidene fluoride and hexafluoropropylene (PVdF-HFP). Examples of the thermoplastic resin include polyethylene, polypropylene, styrene butadiene rubber (SBR), hydrogenated styrene butadiene rubber (HSBR), butylene rubber, acrylonitrile butadiene rubber, polybutadiene, polyisoprene, and the like.
Examples of the acrylic resin include poly (meth) methyl acrylate, poly (meth) ethyl acrylate, poly (meth) acrylate isopropyl, poly (meth) acrylate isobutyl, poly (meth) butyl acrylate, poly (meth) ) Hexyl acrylate, poly (meth) acrylate octyl, poly (meth) acrylate dodecyl, poly (meth) acrylate stearyl, poly (meth) acrylate 2-hydroxyethyl, poly (meth) acrylic acid, poly (meth) ) Benzyl acrylate, poly (meth) acrylate glycidyl, poly (meth) acrylate dimethylaminopropyl, and copolymers of monomers constituting these resins.
Further, copolymers with other vinyl monomers are also preferably used. Examples thereof include poly (meth) acrylate methyl-polystyrene copolymer, poly (meth) acrylate methyl-acrylonitrile copolymer, poly (meth) acrylate butyl-acrylonitrile-styrene copolymer, and the like.

In addition to the above radical polymerization polymer, a polycondensation polymer can also be used. As the polycondensation polymer, for example, urethane resin, urea resin, amide resin, imide resin, polyester resin, and the like can be suitably used.
The polycondensation polymer preferably has a hard segment part and a soft segment part. The hard segment site indicates a site capable of forming an intermolecular hydrogen bond, and the soft segment site generally indicates a flexible site having a glass transition temperature (Tg) of room temperature (25 ± 5 ° C.) or lower and a molecular weight of 400 or higher.
These may be used individually by 1 type, or may be used in combination of 2 or more type.

  The upper limit of the glass transition temperature of the binder is preferably 50 ° C or lower, more preferably 0 ° C or lower, and most preferably -20 ° C or lower. The lower limit is preferably −100 ° C. or higher, more preferably −70 ° C. or higher, and particularly preferably −50 ° C. or higher.

The glass transition temperature (Tg) is measured under the following conditions using a dry sample and a differential scanning calorimeter “X-DSC7000” (trade name, manufactured by SII Nanotechnology Co., Ltd.). The measurement is performed twice on the same sample, and the second measurement result is adopted.
Measurement chamber atmosphere: Nitrogen (50 mL / min)
Temperature increase rate: 5 ° C / min
Measurement start temperature: -100 ° C
Measurement end temperature: 200 ° C
Sample pan: Aluminum pan Mass of measurement sample: 5 mg
Calculation of Tg: Tg is calculated by rounding off the decimal point of the intermediate temperature between the descent start point and descent end point of the DSC chart.

The water concentration of the polymer constituting the binder used in the present invention is preferably 100 ppm (mass basis) or less, and Tg is preferably 100 ° C. or less.
The polymer constituting the binder used in the present invention may be crystallized and dried, or a polymer solution may be used as it is. It is preferable that the amount of metal catalyst (urethanization, polyesterification catalyst = tin, titanium, bismuth) is small. It is preferable that the metal concentration in the copolymer be 100 ppm (mass basis) or less by reducing the amount during polymerization or removing the catalyst by crystallization.

  The solvent used for the polymerization reaction of the polymer is not particularly limited. It is desirable to use a solvent that does not react with the inorganic solid electrolyte and the active material and that does not decompose them. For example, hydrocarbon solvents (toluene, heptane, xylene), ester solvents (ethyl acetate, propylene glycol monomethyl ether acetate), ether solvents (tetrahydrofuran, dioxane, 1,2-diethoxyethane), ketone solvents (acetone) , Methyl ethyl ketone, cyclohexanone), nitrile solvents (acetonitrile, propionitrile, butyronitrile, isobutyronitrile), halogen solvents (dichloromethane, chloroform) and the like.

The polymer constituting the binder used in the present invention preferably has a mass average molecular weight of 10,000 or more, more preferably 20,000 or more, and even more preferably 50,000 or more. As an upper limit, 1,000,000 or less is preferable, 200,000 or less is more preferable, and 100,000 or less is more preferable.
In the present invention, the molecular weight of the polymer means a mass average molecular weight unless otherwise specified.

The content of the binder in the solid electrolyte composition is 0.01% by mass with respect to 100% by mass of the solid component in consideration of good reduction in interface resistance and its maintainability when used in an all-solid secondary battery. The above is preferable, 0.1% by mass or more is more preferable, and 1% by mass or more is more preferable. As an upper limit, from a viewpoint of a battery characteristic, 20 mass% or less is preferable, 10 mass% or less is more preferable, and 10 mass% or less is further more preferable.
In the present invention, the mass ratio [(mass of inorganic solid electrolyte + mass of electrode active material) / mass of binder] of the total mass (total amount) of the inorganic solid electrolyte and the electrode active material to be included if necessary with respect to the mass of the binder is: A range of 1,000 to 1 is preferred. This ratio is more preferably 500 to 2, and further preferably 100 to 10.

It is also preferred that the binder used in the present invention is a polymer particle that maintains the particle shape. In the present invention, poly (meth) methyl acrylate (PMMA), poly (methyl methacrylate-methacrylic acid) copolymer (PMMA-PMA) or poly (methyl methacrylate-ethyl methacrylate phosphate) copolymer (PMMA). -PHM) is preferably used.
Here, the “polymer particles” refer to particles that do not completely dissolve even when added to the dispersion medium described later, and are dispersed in the dispersion medium in the form of particles and exhibit an average particle diameter of more than 0.01 μm.

  The shape of the polymer particles is not limited as long as the polymer particles are kept solid. The polymer particles may be monodispersed or polydispersed. The polymer particles may be spherical or flat and may be amorphous. The surface of the polymer particles may be smooth or may have an uneven shape. The polymer particles may have a core-shell structure, and the core (inner core) and the shell (outer shell) may be made of the same material or different materials. Moreover, it may be hollow and the hollow ratio is not limited.

The polymer particles can be synthesized by a method of polymerizing in the presence of a surfactant, an emulsifier or a dispersant, or a method of depositing in a crystalline form as the molecular weight increases.
Moreover, you may use the method of crushing the existing polymer mechanically, or the method of making a polymer liquid fine particle by reprecipitation.

  The average particle diameter of the polymer particles is preferably 0.01 μm to 100 μm, more preferably 0.05 μm to 50 μm, further preferably 0.1 μm to 20 μm, and particularly preferably 0.2 μm to 10 μm.

Unless otherwise specified, the average particle diameter of the polymer particles used in the present invention is based on the measurement conditions and definitions described below.
Dilute the 1% by weight dispersion of polymer particles in a 20 ml sample bottle using any solvent (dispersion medium used to prepare the solid electrolyte composition, eg, heptane). The diluted dispersion sample is irradiated with 1 kHz ultrasonic waves for 10 minutes and used immediately after that. Using this dispersion sample, using a laser diffraction / scattering particle size distribution measuring device LA-920 (trade name, manufactured by HORIBA), data acquisition was performed 50 times using a quartz cell for measurement at a temperature of 25 ° C. Let the obtained volume average particle diameter be an average particle diameter. For other detailed conditions and the like, refer to the description of JISZ8828: 2013 “Particle Size Analysis—Dynamic Light Scattering Method” as necessary. Five samples are prepared for each level and measured, and the average value is adopted.
In addition, the measurement from the produced all-solid-state secondary battery is performed, for example, after disassembling the battery and peeling off the electrode, then measuring the electrode material according to the measurement method of the average particle diameter of the polymer particles, This can be done by eliminating the measured value of the average particle diameter of the particles other than the polymer particles that have been measured.

  In addition, a commercial item can be used for the binder used for this invention. Moreover, it can also prepare by a conventional method.

(Dispersion medium)
The solid electrolyte composition of the present invention preferably contains a dispersion medium.
The dispersion medium only needs to disperse each of the above components, and examples thereof include various organic solvents. Specific examples of the dispersion medium include the following.
Examples of the alcohol compound solvent include methyl alcohol, ethyl alcohol, 1-propyl alcohol, 2-propyl alcohol, 2-butanol, ethylene glycol, propylene glycol, glycerin, 1,6-hexanediol, cyclohexanediol, sorbitol, xylitol, Examples include 2-methyl-2,4-pentanediol, 1,3-butanediol, and 1,4-butanediol.
Examples of ether compound solvents include alkylene glycol alkyl ethers (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.), dialkyl ethers (dimethyl ether, diethyl ether, diisopropyl ether, dibutyl ether, etc.), cyclic ethers (tetrahydrofuran, geo Sun (1,2, including 1,3- and 1,4-isomers of), etc.).
Examples of the amide compound solvent include N, N-dimethylformamide, N-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 and the like.
Examples of the amino compound solvent include triethylamine, diisopropylethylamine, tributylamine and the like.
Examples of the ketone compound solvent include acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone.
Examples of the aromatic compound solvent include benzene, toluene, xylene and the like.
Examples of the aliphatic compound solvent include hexane, heptane, octane, decane, and the like.
Examples of the nitrile compound solvent include acetonitrile, propyronitrile, isobutyronitrile, and the like.
Examples of the ester compound solvent include ethyl acetate, butyl acetate, propyl acetate, butyl butyrate, and butyl pentanoate.
Examples of the non-aqueous dispersion medium include the above aromatic compound solvents and aliphatic compound solvents.

  In the present invention, an amino compound solvent, an ether compound solvent, a ketone compound solvent, an aromatic compound solvent, and an aliphatic compound solvent are preferable, and an ether compound solvent, an aromatic compound solvent, and an aliphatic compound solvent are more preferable. In the present invention, it is preferable to further select the specific organic solvent using a sulfide-based inorganic solid electrolyte. By selecting this combination, the functional group active for the sulfide-based inorganic solid electrolyte is not included, so that the sulfide-based inorganic solid electrolyte can be handled stably, which is preferable.

The dispersion medium preferably has a boiling point of 50 ° C. or higher, more preferably 70 ° C. or higher, at normal pressure (1 atm). The upper limit is preferably 250 ° C. or lower, and more preferably 220 ° 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 the present invention, the content of the dispersion medium in the solid electrolyte composition can be appropriately set in consideration of the balance between the viscosity of the solid electrolyte composition and the drying load. Generally, 20-99 mass% is preferable in a solid electrolyte composition, 25-70 mass% is more preferable, and 30-60 mass parts is especially preferable.

(Active material)
The solid electrolyte composition of the present invention may contain an active material capable of inserting and releasing ions of metal elements belonging to Group 1 or Group 2 of the periodic table. Examples of the active material include a positive electrode active material and a negative electrode active material, and a transition metal oxide that is a positive electrode active material or a metal oxide that is a negative electrode active material is preferable.
In the present invention, a solid electrolyte composition containing an active material (positive electrode active material, negative electrode active material) may be referred to as an electrode layer composition (positive electrode layer composition, negative electrode layer composition).

-Positive electrode active material-
The positive electrode active material that may be contained in the solid electrolyte composition of the present invention is preferably one that can reversibly insert and release lithium ions. The material is not particularly limited as long as it has the above characteristics, and may be a transition metal oxide or an element that can be complexed with Li such as sulfur.
Among them, as the positive electrode active material, it is preferable to use a transition metal oxide, and a transition metal oxide having a transition metal element M ^a (one or more elements selected from Co, Ni, Fe, Mn, Cu and V). More preferred. In addition, this transition metal oxide includes an element M ^b (an element of the first (Ia) group of the metal periodic table other than lithium, an element of the second (IIa) group, Al, Ga, In, Ge, Sn, Pb, Elements such as Sb, Bi, Si, P or B) may be mixed. The mixing amount, 0~30mol% is preferred for the amount of the transition metal element ^{M a (100mol%).} What was mixed and synthesize | combined so that the molar ratio of Li / Ma might be 0.3-2.2 is more preferable.
Specific examples of the transition metal oxide include (MA) a transition metal oxide having a layered rock salt structure, (MB) a transition metal oxide having a spinel structure, (MC) a lithium-containing transition metal phosphate compound, (MD And lithium-containing transition metal halide phosphate compounds and (ME) lithium-containing transition metal silicate compounds.

(MA) As specific examples of transition metal oxides having a layered rock salt structure, LiCoO ₂ (lithium cobaltate [LCO]), LiNi ₂ O ₂ (lithium nickelate) LiNi _0.85 Co _0.10 Al _0.05 O ₂ (nickel cobalt lithium aluminum oxide [NCA]), LiNi _1/3 Co _1/3 Mn _1/3 O ₂ (nickel manganese lithium cobalt oxide [NMC]) and LiNi _0.5 Mn _0.5 O ₂ (manganese) Lithium nickelate).
Specific examples of transition metal oxides having (MB) spinel structure include LiCoMnO _4, Li ₂ FeMn ₃ O ₈ , Li ₂ CuMn ₃ O ₈ , Li ₂ CrMn ₃ O ₈ and Li ₂ NiMn ₃ O _8. .
Examples of (MC) lithium-containing transition metal phosphate compounds include olivine-type phosphate iron salts such as LiFePO ₄ and Li ₃ Fe ₂ (PO ₄ ) ₃ , iron pyrophosphates such as LiFeP ₂ O ₇ , LiCoPO _{4, and the} like. And monoclinic Nasicon type vanadium phosphate salts such as Li ₃ V ₂ (PO ₄ ) ₃ (Vanadium Lithium Phosphate).
(MD) as the lithium-containing transition metal halogenated phosphate compound, for _example, Li 2 FePO ₄ F such fluorinated phosphorus iron _salt, Li 2 MnPO ₄ hexafluorophosphate manganese salts such as F and _Li 2 CoPO ₄ F Cobalt fluorophosphates such as
Examples of the (ME) lithium-containing transition metal silicate compound include Li ₂ FeSiO ₄ , Li ₂ MnSiO _4, and Li ₂ CoSiO ₄ .
In the present invention, a transition metal oxide having a (MA) layered rock salt structure is preferable, and LCO, NMC or NMC is more preferable.

  The shape of the positive electrode active material is not particularly limited, but is preferably particulate. The volume average particle diameter (sphere conversion average particle diameter) of the positive electrode active material is not particularly limited. For example, the thickness can be 0.1 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 volume average particle diameter (sphere conversion average particle diameter) of the positive electrode active material particles can be measured using a laser diffraction / scattering particle size distribution analyzer LA-920 (trade name, manufactured by HORIBA).

The positive electrode active materials may be used alone or in combination of two or more.
When forming the positive electrode active material layer, the mass (mg) (weight per unit area) of the positive electrode active material per unit area (cm ² ) of the positive electrode active material layer is not particularly limited. This can be determined as appropriate according to the designed battery capacity.

  Content in the solid electrolyte composition of a positive electrode active material is not specifically limited, 10-95 mass% is preferable in solid content of 100 mass%, 30-90 mass% is more preferable, 50-85 mass is further Preferably, 70-80 mass% is especially preferable.

-Negative electrode active material-
The negative electrode active material that may be contained in the solid electrolyte composition of the present invention is preferably one that can reversibly insert and release lithium ions. The material is not particularly limited as long as it has the above characteristics, and is a carbonaceous material, a metal oxide such as tin oxide, a silicon oxide, a metal composite oxide, a lithium simple substance and a lithium alloy such as a lithium aluminum alloy, and , Metals such as Sn, Si, and In that can form an alloy with lithium. Among these, a carbonaceous material or a lithium composite oxide is preferably used from the viewpoint of reliability. 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. For example, various synthetics such as petroleum pitch, carbon black such as acetylene black (AB), graphite (natural graphite, artificial graphite such as vapor-grown graphite), PAN (polyacrylonitrile) -based resin, furfuryl alcohol resin, etc. The carbonaceous material which baked resin can be mentioned. Furthermore, various carbon fibers such as PAN-based carbon fiber, cellulose-based carbon fiber, pitch-based carbon fiber, vapor-grown carbon fiber, dehydrated PVA (polyvinyl alcohol) -based carbon fiber, lignin carbon fiber, glassy carbon fiber, and activated carbon fiber. Examples thereof include mesophase microspheres, graphite whiskers, and flat graphite.

  These carbonaceous materials can be divided into non-graphitizable carbonaceous materials and graphite-based carbonaceous materials according to the degree of graphitization. Further, the carbonaceous material preferably has an interplanar spacing, density, and crystallite size described in JP-A-62-222066, JP-A-2-6856, and / or 3-45473. . The carbonaceous material does not need to be a single material, and a mixture of natural graphite and artificial graphite described in JP-A-5-90844 and graphite having a coating layer described in JP-A-6-4516 are 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 an apex in the region of 20 ° to 40 ° in terms of 2θ values, 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 compound group consisting of the above amorphous oxide and chalcogenide, an amorphous oxide of a semimetal element and a chalcogenide are more preferable, and an element of Groups 13 (IIIB) to 15 (VB) of the periodic table, Al , Ga, Si, Sn, Ge, Pb, Sb and Bi are used alone or in combination of two or more thereof, and chalcogenides are particularly preferable. 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 ₈ Bi ₂ O ₃ , Sb ₂ O ₈ Si ₂ O ₃ , Bi ₂ O ₄ , SnSiO ₃ , GeS, SnS, SnS ₂ , PbS, PbS ₂ , Sb ₂ S ₃ , Sb ₂ S ₅ and SnSiS ₃ are preferred. Moreover, these may be a complex oxide with lithium oxide, for example, Li ₂ SnO ₂ .

It is also preferable that the negative electrode active material contains a titanium atom. More specifically, Li ₄ Ti ₅ O ₁₂ (lithium titanate [LTO]) is excellent in rapid charge / discharge characteristics due to small volume fluctuations during the insertion and release of lithium ions, and the deterioration of the electrodes is suppressed, and the lithium ion secondary This is preferable in that the battery life can be improved.

  In the present invention, hard carbon or graphite is preferably used, and graphite is more preferably used. In the present invention, the carbonaceous materials may be used singly or in combination of two or more.

  The shape of the negative electrode active material is not particularly limited, but is preferably particulate. The average particle size of the negative electrode active material is preferably 0.1 to 60 μm. In order to obtain a predetermined particle size, a normal 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, and a sieve are 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 diameter, 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 average particle diameter of the negative electrode active material particles can be measured by the same method as the above-described method for measuring the volume average particle diameter of the positive electrode active material.

  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 centered on Sn, Si, and Ge include carbon materials that can occlude and release lithium ions or lithium metal, lithium, lithium alloys, and lithium. An alloyable metal is preferable.

  In the present invention, it is preferable to apply a Si-based negative electrode. In general, a Si negative electrode can occlude more Li ions than a carbon negative electrode (such as graphite and acetylene black). That is, the amount of Li ion occlusion per unit weight increases. Therefore, the battery capacity can be increased. As a result, there is an advantage that the battery driving time can be extended.

The said negative electrode active material may be used individually by 1 type, or may be used in combination of 2 or more type.
When forming the negative electrode active material layer, the mass (mg) (weight per unit area) of the negative electrode active material per unit area (cm ² ) of the negative electrode active material layer is not particularly limited. This can be determined as appropriate according to the designed battery capacity.

  Content in a solid electrolyte composition of a negative electrode active material is not specifically limited, It is preferable that it is 10-80 mass% in solid content 100 mass%, 20-80 mass% is more preferable, 30-80 It is more preferable that it is mass%, and it is further more preferable that it is 40-75 mass%.

(Conductive aid)
The solid electrolyte composition of the present invention may contain a conductive auxiliary agent used for improving the electronic conductivity of the active material, if necessary. As the conductive auxiliary agent, a general conductive auxiliary agent can be used. For example, graphites such as natural graphite and artificial graphite, carbon blacks such as acetylene black, ketjen black and furnace black, amorphous carbon such as needle coke, vapor grown carbon fiber and carbon nanotubes, which are electron conductive materials Carbon fibers such as graphene and carbonaceous materials such as graphene and fullerene, metal powders such as copper and nickel, or metal fibers may be used, and conductive polymers such as polyaniline, polypyrrole, polythiophene, polyacetylene, and polyphenylene derivatives May be used. Moreover, 1 type of these may be used and 2 or more types may be used.
When the solid electrolyte composition of this invention contains a conductive support agent, 0-10 mass% is preferable for content of the conductive support agent in a solid electrolyte composition.

(Lithium salt)
The solid electrolyte composition of the present invention preferably contains a lithium salt (supporting electrolyte).
As a lithium salt, the lithium salt normally used for this kind of product is preferable, and there is no restriction | limiting in particular, For example, the lithium salt demonstrated with the said binder particle | grain is mentioned.
This lithium salt is not included in the binder particles (the polymer forming the binder particles) (for example, it is present alone in the solid electrolyte layer composition), and the lithium salt is included in the binder particles. Is different.
The content of the lithium salt is preferably 0 part by mass or more and more preferably 5 parts by mass or more with respect to 100 parts by mass of the solid electrolyte. As an upper limit, 50 mass parts or less are preferable, and 20 mass parts or less are more preferable.

(Dispersant)
The solid electrolyte composition of the present invention may contain a dispersant. By adding the dispersant, even when the concentration of either the electrode active material or the inorganic solid electrolyte is high, the aggregation can be suppressed, and a uniform active material layer and solid electrolyte layer can be formed.
As the dispersant, those usually used for all-solid secondary batteries can be appropriately selected and used. For example, it is composed of a low molecule or oligomer having a molecular weight of 200 or more and less than 3000, and contains a functional group represented by the functional group (I) and an alkyl group having 8 or more carbon atoms or an aryl group having 10 or more carbon atoms in the same molecule. Those are preferred.
Functional group (I): acidic group, group having basic nitrogen atom, (meth) acryloyl group, (meth) acrylamide group, alkoxysilyl group, epoxy group, oxetanyl group, isocyanate group, cyano group, sulfanyl group and hydroxy Group (an acidic group, a group having a basic nitrogen atom, an alkoxysilyl group, a cyano group, a sulfanyl group and a hydroxy group are preferred, and a carboxy group, a sulfonic acid group, a cyano group, an amino group and a hydroxy group are more preferred).
In the all solid state secondary battery of the present invention, when there is a layer containing a dispersant, the content of the dispersant in the layer is preferably 0.2 to 10% by mass.

(Preparation of solid electrolyte composition)
The solid electrolyte composition of the present invention can be produced by mixing or adding an inorganic solid electrolyte and a specific organometallic compound and, if necessary, other components such as a dispersion medium. For example, it can manufacture by mixing the said component using various mixers. The mixing conditions are not particularly limited, and examples thereof include a ball mill, a bead mill, a planetary mixer, a blade mixer, a roll mill, a kneader, and a disk mill.
In the method for producing a solid electrolyte composition, when an active material is contained, it is preferable to add and mix after mixing an inorganic solid electrolyte, a specific organometallic compound, and, if necessary, a dispersion medium. As another aspect, after mixing (stirring) an active material (preferably positive electrode active material), a specific organometallic compound, and a dispersion medium at 10 to 50 ° C. for 1 to 10 hours, the dispersion medium is distilled off. It is also preferable to include a step of coating (modifying) a specific organometallic compound on the active material by vacuum drying. In the production method including this step, a solid electrolyte composition is produced by mixing or adding an active material and an inorganic solid electrolyte coated (modified) with a specific organometallic compound and, if necessary, other components. it can.

[All-solid-state secondary battery sheet]
The all-solid-state secondary battery sheet of the present invention may be a sheet used for an all-solid-state secondary battery, and includes various modes depending on the application. For example, a sheet preferably used for a solid electrolyte layer (also referred to as a solid electrolyte sheet for an all-solid secondary battery), a sheet preferably used for an electrode or a laminate of an electrode and a solid electrolyte layer (an electrode sheet for an all-solid secondary battery) Etc. In the present invention, these various sheets may be collectively referred to as an all-solid secondary battery sheet.

The sheet for an all-solid-state secondary battery of the present invention is a sheet having a solid electrolyte layer or an active material layer (electrode layer) on a substrate. The all-solid-state secondary battery sheet may have other layers as long as it has a substrate and a solid electrolyte layer or an active material layer. It classifies into the secondary battery electrode sheet. Examples of other layers include a protective layer, a current collector, and a coat layer (current collector, solid electrolyte layer, active material layer) and the like.
Examples of the solid electrolyte sheet for an all-solid secondary battery used in the present invention include a sheet having a solid electrolyte layer and a protective layer in this order on a substrate.
The substrate is not particularly limited as long as it can support the solid electrolyte layer, and examples thereof include the materials described in the above current collector, sheet bodies (plate bodies) such as organic materials and inorganic materials, and the like. Examples of the organic material include various polymers, and specific examples include polyethylene terephthalate, polypropylene, polyethylene, and cellulose. Examples of the inorganic material include glass and ceramic.

The configuration and layer thickness of the solid electrolyte layer of the all-solid-state secondary battery sheet are the same as the configuration and layer thickness of the solid electrolyte layer described in the all-solid-state secondary battery of the present invention.
This sheet is obtained by forming (coating and drying) the solid electrolyte composition of the present invention on a base material (which may be via another layer) to form a solid electrolyte layer on the base material. It is done. That is, the sheet for an all-solid secondary battery of the present invention has a layer formed by coating the solid electrolyte composition of the present invention on a substrate or a metal foil. The all-solid-state secondary battery sheet of the present invention has an effect of suppressing side reactions such as decomposition of an inorganic solid electrolyte accompanying an electric reaction and suppressing an increase in interface resistance when an all-solid-state secondary battery is formed. .
Here, the solid electrolyte composition of the present invention can be prepared by the above-described method.

The electrode sheet for an all-solid secondary battery of the present invention (also simply referred to as “the electrode sheet of the present invention”) is a metal as a current collector for forming the active material layer of the all-solid-state secondary battery of the present invention. An electrode sheet having an active material layer on a foil. This electrode sheet is usually a sheet having a current collector and an active material layer, but an embodiment having a current collector, an active material layer, and a solid electrolyte layer in this order, and a current collector, an active material layer, and a solid electrolyte The aspect which has a layer and an active material layer in this order is also included.
The configuration and the layer thickness of each layer constituting the electrode sheet are the same as the configuration and the layer thickness of each layer described in the all solid state secondary battery of the present invention.
The electrode sheet is obtained by forming (coating and drying) the solid electrolyte composition containing the active material of the present invention on a metal foil to form an active material layer on the metal foil.

[Manufacture of all-solid-state secondary battery and electrode sheet for all-solid-state secondary battery]
Manufacture of the all-solid-state secondary battery and the electrode sheet for all-solid-state secondary batteries can be performed by a conventional method. Specifically, the all-solid-state secondary battery and the all-solid-state secondary battery electrode sheet can be manufactured by forming each of the above layers using the solid electrolyte composition of the present invention. In addition, any layer of a positive electrode active material layer, a solid electrolyte layer, and a negative electrode active material layer should just be formed using the solid electrolyte composition of this invention. This will be described in detail below.

The all-solid-state secondary battery of the present invention is produced by a method including (intervening) the step of applying the solid electrolyte composition of the present invention onto a metal foil to be a current collector and forming (forming) a coating film. it can.
For example, a positive electrode active material layer is formed by applying a solid electrolyte composition containing a positive electrode active material as a positive electrode material (positive electrode layer composition) on a metal foil that is a positive electrode current collector. A positive electrode sheet for a secondary battery is prepared. Next, a solid electrolyte composition for forming a solid electrolyte layer is applied on the positive electrode active material layer to form a solid electrolyte layer. Furthermore, a solid electrolyte composition containing a negative electrode active material is applied as a negative electrode material (negative electrode layer composition) on the solid electrolyte layer to form a negative electrode active material layer. An all-solid secondary battery having a structure in which a solid electrolyte layer is sandwiched between a positive electrode active material layer and a negative electrode active material layer is obtained by stacking a negative electrode current collector (metal foil) on the negative electrode active material layer. Can do. If necessary, this can be enclosed in a housing to obtain a desired all-solid secondary battery.
Moreover, the formation method of each layer is reversed, and a negative electrode active material layer, a solid electrolyte layer, and a positive electrode active material layer are formed on the negative electrode current collector, and the positive electrode current collector is stacked to manufacture an all-solid secondary battery. You can also

Another method includes the following method. That is, a positive electrode sheet for an all-solid secondary battery is produced as described above. Further, a negative electrode active material layer is formed by applying a solid electrolyte composition containing a negative electrode active material as a negative electrode material (a composition for a negative electrode layer) on a metal foil that is a negative electrode current collector. A negative electrode sheet for a secondary battery is prepared. Next, a solid electrolyte layer is formed on one of the active material layers of these sheets as described above. Furthermore, the other of the positive electrode sheet for an all solid secondary battery and the negative electrode sheet for an all solid secondary battery is laminated on the solid electrolyte layer so that the solid electrolyte layer and the active material layer are in contact with each other. In this way, an all-solid secondary battery can be manufactured.
Another method includes the following method. That is, as described above, a positive electrode sheet for an all-solid secondary battery and a negative electrode sheet for an all-solid secondary battery are produced. Separately from this, a solid electrolyte composition is applied on a substrate to produce a solid electrolyte sheet for an all-solid secondary battery comprising a solid electrolyte layer. Furthermore, it laminates | stacks so that the solid electrolyte layer peeled off from the base material may be pinched | interposed with the positive electrode sheet for all-solid-state secondary batteries, and the negative electrode sheet for all-solid-state secondary batteries. In this way, an all-solid secondary battery can be manufactured.

  An all-solid-state secondary battery can also be manufactured by a combination of the above forming methods. For example, as described above, a positive electrode sheet for an all-solid secondary battery, a negative electrode sheet for an all-solid secondary battery, and a solid electrolyte sheet for an all-solid secondary battery are produced. Then, after laminating the solid electrolyte layer peeled off from the base material on the negative electrode sheet for an all solid secondary battery, an all solid secondary battery can be produced by pasting the positive electrode sheet for the all solid secondary battery. it can. In this method, the solid electrolyte layer can be laminated on the positive electrode sheet for an all-solid secondary battery, and bonded to the negative electrode sheet for an all-solid secondary battery.

(Formation of each layer (film formation))
The method for applying the solid electrolyte composition is not particularly limited, and can be appropriately selected. Examples thereof include coating (preferably wet coating), spray coating, spin coating coating, dip coating, slit coating, stripe coating, and bar coating coating.
At this time, the solid electrolyte composition may be dried after being applied, or may be dried after being applied in multiple layers. The drying temperature is not particularly limited. The lower limit is preferably 30 ° C or higher, more preferably 60 ° C or higher, and still more preferably 80 ° C or higher. The upper limit is preferably 300 ° C. or lower, more preferably 250 ° C. or lower, and further preferably 200 ° 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. Further, it is preferable because the temperature is not excessively raised and each member of the all-solid-state secondary battery is not damaged. Thereby, in the all-solid-state secondary battery, excellent overall performance can be obtained, and good binding properties and good ionic conductivity can be obtained even without pressure.

It is preferable to pressurize each layer or all-solid secondary battery after producing the applied solid electrolyte composition or all-solid secondary battery. Moreover, it is also preferable to pressurize in the state which laminated | stacked each layer. Examples of the pressurizing method include a hydraulic cylinder press. The applied pressure is not particularly limited and is generally preferably in the range of 50 to 1500 MPa.
Moreover, you may heat the apply | coated solid electrolyte composition simultaneously with pressurization. It does not specifically limit as heating temperature, Generally, it is the range of 30-300 degreeC. It is also possible to press at a temperature higher than the glass transition temperature of the inorganic solid electrolyte.
The pressurization may be performed in a state where the coating solvent or the dispersion medium is dried in advance, or may be performed in a state where the solvent or the dispersion medium remains.
In addition, each composition may be apply | coated simultaneously and application | coating drying press may be performed simultaneously and / or sequentially. You may laminate | stack by transfer after apply | coating to a separate base material.

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

(Initialization)
The all solid state secondary battery manufactured as described above is preferably initialized after manufacture or before use. The initialization is not particularly limited, and can be performed, for example, by performing initial charging / discharging in a state in which the press pressure is increased, and then releasing the pressure until the general use pressure of the all-solid secondary battery is reached.

[Use of all-solid-state secondary batteries]
The all solid state secondary battery of the present invention can be applied to various uses. Although there is no particular limitation on the application mode, for example, when installed in an electronic device, a notebook computer, pen input personal computer, mobile personal computer, electronic book player, mobile phone, cordless phone, pager, handy terminal, mobile fax, mobile phone Copy, portable printer, headphone stereo, video movie, LCD TV, handy cleaner, portable CD, mini-disc, electric shaver, transceiver, electronic notebook, calculator, memory card, portable tape recorder, radio and backup power supply. Other consumer products include automobiles, electric vehicles, motors, lighting equipment, toys, game equipment, road conditioners, watches, strobes, cameras, and medical equipment (such as pacemakers, hearing aids, and shoulder grinders). Furthermore, it can be used for various military uses or 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 safety is essential, and further compatibility of battery performance is required. In addition, electric vehicles and the like are equipped with a high-capacity secondary battery and are expected to be charged every day at home, and further safety is required against overcharging. According to the present invention, it is possible to exhibit the excellent effect correspondingly to such a usage pattern.

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 includes an organic (polymer) all-solid-state secondary battery using a polymer compound such as polyethylene oxide as an electrolyte, and an inorganic all-solid-state using the above-described Li-PS-based glass, LLT, LLZ, It is divided into secondary batteries. In addition, application of a polymer compound to an inorganic all-solid secondary battery is not hindered, and the polymer compound can be applied as a positive electrode active material, a negative electrode active material, and / or binder particles of inorganic solid electrolyte particles.
The inorganic solid electrolyte is distinguished from the above-described electrolyte (polymer electrolyte) using a polymer compound such as polyethylene oxide as an ion conductive medium, and the inorganic compound serves as an ion conductive medium. Specific examples include the Li—PS—S glass, 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. In this case, this is called “electrolyte salt” or “supporting electrolyte”. Examples of the electrolyte salt include LiTFSI (lithium bistrifluoromethanesulfonylimide).
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 and uneven distribution may partially occur within a range in which a desired effect is achieved. In particular, when it is referred to as a solid electrolyte composition, it basically refers to a composition (typically a paste) that is a material for forming a solid electrolyte layer or the like, and an electrolyte layer or the like formed by curing the composition. Shall not be included in this.

  Below, based on an Example, it demonstrates still in detail about this invention. The present invention is not construed as being limited thereby. In the following examples, “part” and “%” representing the composition are based on mass unless otherwise specified. “Room temperature” means 25 ° C.

[Example 1]
<Synthesis of sulfide-based inorganic solid electrolyte>
-Synthesis of Li-PS-based glass-
As a sulfide-based inorganic solid electrolyte, T.I. Ohtomo, A .; Hayashi, M .; Tatsumisago, Y. et al. Tsuchida, S .; HamGa, K .; Kawamoto, Journal of Power Sources, 233, (2013), pp231-235 and A.K. Hayashi, S .; Hama, H .; Morimoto, M .; Tatsumisago, T .; Minami, Chem. Lett. , (2001), pp 872-873, Li-PS glass was synthesized with reference to non-patent literature.
Specifically, in a glove box under an argon atmosphere (dew point −70 ° C.), 2.42 g of lithium sulfide (Li ₂ S, manufactured by Aldrich, purity> 99.98%), diphosphorus pentasulfide (P ₂ S) ₅ , 3.90 g manufactured by Aldrich, purity> 99%) was weighed, put into an agate mortar, and mixed for 5 minutes using an agate pestle. The mixing ratio of Li ₂ S and P ₂ S ₅ was Li ₂ S: P ₂ S ₅ = 75: 25 in terms of molar ratio.
66 zirconia beads having a diameter of 5 mm were introduced into a 45 mL container (made by Fritsch) made of zirconia, the whole mixture of the above lithium sulfide and diphosphorus pentasulfide was introduced, and the container was sealed under an argon atmosphere. This container is set in a planetary ball mill P-7 (trade name) manufactured by Frichtu, and mechanical milling is performed at a temperature of 25 ° C. and a rotation speed of 510 rpm for 20 hours to obtain a yellow powder sulfide solid electrolyte (Li-PS system). 6.20 g of glass) was obtained.

Example 1
<Preparation of each composition>
(1) Preparation of oxide solid electrolyte composition (SO-1) 180 zirconia beads having a diameter of 5 mm were put into a 45 mL container (made by Fritsch) made of zirconia, and an oxide-based inorganic solid electrolyte LLT (made by Toshima Seisakusho) 9.1 g, PVdF-HFP (polyvinylidene fluoride hexafluoropropylene copolymer (manufactured by Arkema Co., Ltd.)) 0.8 g was added as a binder, and 20 g of ethyl methyl ketone was added as a dispersion medium. 0.1 g of compound (I-1) was added, and then the vessel was set on a planetary ball mill P-7 (trade name) manufactured by Fritsch, and the mixing was continued for 2 hours at a temperature of 25 ° C. and a rotational speed of 300 rpm. An electrolyte composition (SO-1) was prepared.
An oxide solid electrolyte composition described in Table 1 below was prepared in the same manner as in the oxide solid electrolyte composition (SO-1) except that the additive was changed to the configuration described in Table 1 below.

(2) Preparation of Sulfide Solid Electrolyte Composition (SS-1) 180 zirconia beads having a diameter of 5 mm were put into a 45 mL container (manufactured by Fritsch) made of zirconia, and the sulfide-based inorganic solid electrolyte Li- synthesized above was prepared. 9.3 g of PS glass, 0.7 g of PVdF-HFP (polyvinylidene fluoride hexafluoropropylene copolymer (manufactured by Arkema Co., Ltd.)) as a binder, 15.0 g of heptane as a dispersion medium, and further as an additive 0.1 g of Exemplified Compound (I-1) was charged, and then this vessel was set in a planetary ball mill P-7 (manufactured by Fritsch) and stirred for 2 hours at a temperature of 25 ° C. and a rotation speed of 300 rpm. An electrolyte composition (SS-1) was prepared.
A sulfide solid electrolyte composition described in Table 2 below was prepared in the same manner as the sulfide solid electrolyte composition (SS-1) except that the additive was changed to the configuration described in Table 2 below.

(3) Preparation of composition for positive electrode (SOA-1) 180 zirconia beads having a diameter of 5 mm were put into a 45 mL container (manufactured by Fritsch) made of zirconia, and an oxide-based inorganic solid electrolyte LLT (manufactured by Toshima Seisakusho). 9 g, 0.15 g of PVdF-HFP (polyvinylidene fluoride hexafluoropropylene copolymer (manufactured by Arkema Co., Ltd.)) was added as a binder, and 20 g of ethyl methyl ketone was added as a dispersion medium. -1) 0.1 g was added, and then the container was set on a planetary ball mill P-7 (trade name) manufactured by Fritsch, and mixing was continued for 2 hours at a temperature of 25 ° C. and a rotation speed of 300 rpm. 7.9 g (manufactured by Nippon Chemical Industry Co., Ltd.) was put into a container, and further using a planetary ball mill at a temperature of 25 ° C. and a rotation speed of 200 rpm. Stirring was continued for 20 minutes to prepare a positive electrode composition (SOA-1).
A positive electrode composition described in Table 3 below was prepared in the same manner as the positive electrode composition (SOA-1) except that the additives and the positive electrode active material were changed to the configurations described in Table 3 below.

(4) Preparation of composition for positive electrode (SSA-1) Into a 45 mL zirconia container (manufactured by Fritche), 180 pieces of zirconia beads having a diameter of 5 mm were charged, and 1.9 g of the Li-PS system glass synthesized above. Then, 0.001 g of Exemplified Compound (I-1) as an additive, 0.15 g of PVdF-HFP as a binder were added, and 20 g of toluene was added as a dispersion medium. After that, this container was set on a planetary ball mill P-7 (manufactured by Fritsch) and stirred for 2 hours at a temperature of 25 ° C. and a rotation speed of 300 rpm, and then NMC (manufactured by Nippon Chemical Industry Co., Ltd.) as an active material. 9 g was charged into a container, and further stirred using a planetary ball mill at a temperature of 25 ° C. and a rotation speed of 200 rpm for 15 minutes to prepare a positive electrode composition (SSA-1).
A positive electrode composition described in the following Table 4 was prepared in the same manner as the positive electrode composition (SSA-1) except that the additives, the positive electrode active material, and the dispersion medium were changed to the configurations described in the following Table 4.

(5) Preparation of composition for positive electrode (SSA′-1) In a 300 mL three-necked flask, 10 g of NMC (manufactured by Nippon Chemical Industry Co., Ltd.) as a positive electrode active material, 0.06 g of exemplary compound (I-1) as an additive, 90 ml of tetrahydrofuran was added as a dispersion medium and stirred for 2 hours. Thereafter, the dispersion medium was distilled off and vacuum drying was performed to obtain a positive electrode active material modified with the exemplary compound.
In the preparation of the positive electrode composition (SSA-1), except that 7.9 g of this modified positive electrode active material was used instead of the positive electrode active material NMC, it was the same as the positive electrode composition (SSA-1), A positive electrode composition (SSA′-1) was prepared.
A positive electrode composition (SSA'-2) was prepared in the same manner as the positive electrode composition (SSA'-1) except that (I-14) or (I-19) was used instead of the exemplified compound (I-1). ) And (SSA'-3) were prepared.

(6) Preparation of composition for negative electrode (SSB-1) Into a 45 mL zirconia container (manufactured by Fritche), 180 zirconia beads having a diameter of 5 mm were charged and 3.9 g of the Li-PS-based glass synthesized above. Then, 0.2 g of PVdF-HFP was added as a binder, 0.1 g of Exemplified Compound (I-1) was added as an additive, and 20 g of heptane was added as a dispersion medium. After that, this container was set on a planetary ball mill P-7 (manufactured by Fritsch) and stirred at a temperature of 25 ° C. and a rotation speed of 300 rpm for 2 hours. Then, 5.9 g of graphite was charged into the container as an active material, and further planetary Using a ball mill, stirring was continued for 15 minutes at a temperature of 25 ° C. and a rotation speed of 200 rpm to prepare a negative electrode composition (SSB-1).
A negative electrode composition described in Table 5 below was prepared in the same manner as the negative electrode composition (SSB-1) except that the additives, negative electrode active material, and dispersion medium were changed to the configurations described in Table 5 below.

<Comments on Tables 1-5>
I-1, 3-7, 9-16, 19-21 and 23-25: Illustrative compounds of the above organometallic compounds LLT: Li _0.33 La _0.55 TiO ₃ (manufactured by Toshima Seisakusho)
Li-PS: Sulfide-based inorganic solid electrolyte Li-PS-based glass eX-1 synthesized above: Organometallic compound (eX-1) described below
NMC: LiNi _1/3 Co _1/3 Mn _1/3 O ₂ nickel manganese lithium cobaltate LCO: LiCoO ₂ lithium cobaltate NCA: LiNi _0.85 Co _0.10 Al _0.05 O ₂ nickel cobalt aluminum lithium PVdF- HFP (polyvinylidene fluoride-hexafluoropropylene copolymer (trade name “KYNAR FLEX 2500-20” manufactured by Arkema Co., Ltd.)
“-”: Indicates that no component is contained.

<Creating a sheet>
−Preparation of positive electrode sheet for all solid state secondary battery−
The positive electrode composition prepared above was applied onto an aluminum foil (current collector) having a thickness of 20 μm by an applicator (trade name: SA-201 Baker type applicator, manufactured by Tester Sangyo Co., Ltd.) and heated at 80 ° C. for 1 hour. Further, the composition for positive electrode was dried by heating at 110 ° C. for 1 hour. Then, using a heat press machine, it pressurized, heating at 120 degreeC (180 Mpa, 1 minute), and produced the positive electrode sheet for all-solid-state secondary batteries with a thickness of 110 micrometers which has a laminated structure of a positive electrode active material layer / aluminum foil.

-Production of all-solid-state secondary battery sheet-
On the positive electrode sheet for an all-solid secondary battery produced above, the solid electrolyte composition prepared above was applied with an applicator (trade name: SA-201 Baker type applicator, manufactured by Tester Sangyo Co., Ltd.), and 1 at 80 ° C. After heating for a period of time, the mixture was further heated at 100 ° C. for 1 hour to form a solid electrolyte layer having a thickness of 50 μm. Thereafter, the negative electrode composition prepared above was further applied, heated at 80 ° C. for 1 hour, and further heated at 110 ° C. for 1 hour to form a negative electrode active material layer having a thickness of 100 μm. A copper foil having a thickness of 20 μm is combined on the negative electrode active material layer, and is pressed while heating at 120 ° C. using a heat press machine (540 MPa, 1 minute), and an all solid secondary battery sheet having the layer structure shown in FIG. Produced.

The all-solid-state secondary battery sheet produced above was cut into a disk shape having a diameter of 14.5 mm. The all-solid-state secondary battery sheet cut out into a disk shape having a diameter of 14.5 mm was placed in a stainless steel 2032 type coin case incorporating a spacer and a washer. In this way, a coin battery having the structure of FIG. 2 was produced.
Here, test no. 1-1 to 1-34 and 2-1 to 2-13 are the electrode sheet for an all-solid secondary battery and the all-solid secondary battery of the present invention. c1-1 to c1-8 and c2-1 to c2-4 are comparative all-solid-state secondary battery electrode sheets and all-solid-state secondary batteries.

<Battery characteristics test>
The following battery characteristic test was performed on the produced all-solid-state secondary battery (hereinafter also simply referred to as “battery”).

-Test Example 1. 4.3 V cycle test-
Using the battery prepared above, charging and discharging at 4.2 V to 3.0 V were repeated four times at 30 ° C. with a charging current value of 0.35 mA and a discharging current value of 0.7 mA.
Thereafter, as a cycle test, a test in which charging and discharging at 4.3 V to 3.0 V were repeated under a condition of charging and discharging current value of 0.7 mA in a 30 ° C. environment.
In this cycle test, the number of cycles at which the discharge capacity was 80% when the discharge capacity at the first cycle was 100% was evaluated. Tables 6 and 7 below list the number of cycles.
By this test, it is possible to observe battery deterioration due to a solid electrolyte side reaction when the battery is operated at 4.3 V (high potential).

-Test Example 2. 60 ° C.-4.2 V cycle test −
Using the battery prepared above, charging and discharging at 4.2 V to 3.0 V were repeated four times at 30 ° C. with a charging current value of 0.35 mA and a discharging current value of 0.7 mA. Using this battery, charging / discharging was performed at a charging current value of 0.35 mA and a discharging current value of 7 mA, and the discharge capacity was measured.
Then, the test which repeats charging / discharging of 4.2V-2.5V 50 times was implemented as a cycle test on 60 degreeC environment on the conditions of charge and discharge current value 0.7mA. Thereafter, charging and discharging were performed at a charging current value of 0.35 mA and a discharging current value of 7 mA, and the discharge capacity after the cycle test was measured.
The capacity retention rate during discharge before and after the 60 ° C. cycle test was evaluated by the following calculation formula. In Tables 6 and 7 below, the discharge capacity retention rate (%) is shown with the unit “%” omitted.

Discharge capacity maintenance rate (%) = Discharge capacity at 2C current value after 50 cycles
/ Discharge capacity at 2C current value before cycle test × 100

  By this test, it is possible to observe battery deterioration due to a solid electrolyte side reaction when the battery is operated at 60 ° C. (high temperature).

-Test Example 3. 4.2V cycle test-
Using the battery prepared above, charging and discharging at 4.2 V to 3.0 V were repeated four times at 30 ° C. with a charging current value of 0.35 mA and a discharging current value of 0.7 mA. Using this battery, charging / discharging was performed at a charging current value of 0.35 mA and a discharging current value of 7 mA, and the discharge capacity was measured.
Then, the test which repeats charging / discharging of 4.2V-2.5V 50 times on 30 degreeC environment on the conditions of charge and discharge current value 0.7mA as a cycle test was implemented. Thereafter, charging and discharging were performed at a charging current value of 0.35 mA and a discharging current value of 7 mA, and the discharge capacity after the cycle test was measured.
The capacity retention rate during discharge after the cycle test was evaluated by the following calculation formula. In Tables 6 and 7 below, the discharge capacity retention rate (%) is shown with the unit “%” omitted.

Discharge capacity maintenance rate (%) = Discharge capacity at 2C current value after 50 cycles
/ Discharge capacity at 2C current value before cycle test × 100

  By this test, it is possible to compare the degree of increase in resistance when the battery is operated at 4.2 V and 30 ° C.

From the results of Tables 6 and 7, using the solid electrolyte composition of the present invention containing an organic metal compound having a transition element or a rare earth element and an inorganic solid electrolyte, represented by the general formula (A1) or (A2), The all-solid-state secondary battery in which any one of the positive electrode active material layer, the solid electrolyte layer, and the negative electrode active material layer in the all-solid-state secondary battery is formed has increased resistance when the battery is operated at 4.2 V and 30 ° C. In addition, both high potential (4.3 V) operation and high temperature (60 ° C.) operation showed excellent cycle characteristics. Thus, the solid electrolyte composition of the present invention was able to produce an all-solid secondary battery with little battery deterioration even during high-potential operation and high-temperature operation.
On the other hand, none of the layers in the all solid state secondary battery contains the specific organometallic compound used in the present invention. c1-1 to 1-3, 1-5, 1-6 and c2-1 to 2-4, No. 2 using a positive electrode composition containing a metal complex which is not a specific organometallic compound. No. 1 using an all-solid-state secondary battery of c1-4 and a negative electrode composition containing a metal complex that is not a specific organometallic compound. The all solid state secondary battery of c1-7 was not sufficient in suppression of resistance increase in battery operation at 4.2 V and 30 ° C. and in cycle characteristics in high potential operation and high temperature operation.

DESCRIPTION OF SYMBOLS 1 Negative electrode current collector 2 Negative electrode active material layer 3 Solid electrolyte layer 4 Positive electrode active material layer 5 Positive electrode current collector 6 Working part 10 All solid secondary battery 11 Coin case 12 All solid secondary battery sheet 13 Battery characteristic test cell ( Coin battery)

Claims (9)

An inorganic solid electrolyte having conductivity of metal ions belonging to Group 1 or Group 2 of the periodic table, and Fe, V, Cr, Mo, Hf, represented by the following general formula (A1) or (A2) : A solid electrolyte composition containing an organometallic compound having Zr, Ti or Y ,
The solid electrolyte composition whose content of the said inorganic solid electrolyte in the said solid electrolyte composition is 1 mass% or more .

In the above formula, M represents Fe, V, Cr, Mo, Hf, Zr, Ti or Y.
R ^A11 represents an alkyl group, an alkylsilyl group, an alkenyl group, an alkynyl group, an alkoxy group, an alkylsulfanyl group, an amino group, a cyano group, a carboxyl group, a carbonyl group-containing group, a sulfonyl group-containing group, a phosphanyl group, or a halogeno group. . R ^A11 may form an aliphatic or aromatic ring.
a is an integer of 0-5.
X and Y each independently contain a hydrogen atom, alkyl group, alkenyl group, alkoxy group, alkylamino group, silylamino group, alkylsulfanyl group, sulfonic acid group, isocyanate group, isothiocyanate group, sulfanyl group, phosphinyl group, carbonyl group A group, a halogeno group, an aryl group, —S _x H or a heteroaryl group; x is an integer of 2-8. Furthermore, X and Y may be connected to each other.
m and n are integers of 0 to 3, and m + n is 0 to 3.
T ^A11 is a hydrogen atom, alkyl group, alkenyl group, alkoxy group, alkylamino group, silylamino group, sulfonic acid group, isocyanate group, isothiocyanate group, sulfanyl group, phosphinyl group, carbonyl group-containing group, halogeno group, aryl group , A heteroaryl group, or a group represented by the following general formula (CP).
c is an integer of 0-2.

In the above formula, R ^A12 represents the same group as R ^A11 . * Represents a bond that bonds to M. b is an integer of 0-5. R ^A11 and R ^A12 may be linked to each other.

In the above formula, M represents Fe, V, Cr, Mo, Hf, Zr, Ti or Y. R ³ and R ⁴ represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, an alkylsilyl group, or a halogeno group. R ³ and R ⁴ may be linked to each other. p is an integer of 1 to 4. The solid electrolyte composition according to claim 1 , wherein the organometallic compound is a transition metal metallocene. The solid electrolyte composition according to claim 1 , wherein the organometallic compound is represented by any one of the following general formulas (Ia-1) to (Ia-3).

In said formula, M, X, and Y are synonymous with M, X, and Y in the said general formula (A1). m1 and n1 are integers of 0-2, and m1 + n1 is 0-2. m2 and n2 are integers of 0 to 3, and m2 + n2 is 2 or 3. The solid electrolyte composition according to any one of claims 1 to 3 , comprising an electrode active material. The solid electrolyte composition according to claim 4 , wherein the electrode active material is a positive electrode active material. An all-solid-state secondary battery sheet comprising the solid electrolyte composition layer according to any one of claims 1 to 5 on a substrate or a metal foil. An all-solid secondary battery comprising a positive electrode active material layer, a negative electrode active material layer, and a solid electrolyte layer,
The all-solid-state secondary battery whose at least 1 layer of the said positive electrode active material layer, a negative electrode active material layer, and a solid electrolyte layer is a layer which consists of a solid electrolyte composition of any one of Claims 1-5 . The manufacturing method of the sheet | seat for all-solid-state secondary batteries which arrange | positions the solid electrolyte composition of any one of Claims 1-5 on a base material or 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 Claim 8 .

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