JP2016149238A - Solid electrolyte composition, battery electrode sheet and all solid secondary battery, and battery electrode sheet and method for producing all solid secondary battery - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a solid electrolyte composition that is used as a constituent material of a negative electrode active layer to enable implementation of an all-solid secondary battery which has large battery capacity and capacity density and is excellent in cycle characteristic, an electrode sheet for a battery and an all-solid secondary battery that use the solid electrolyte composition, and a method of manufacturing the electrode sheet for a battery and the all-solid secondary battery.SOLUTION: A solid electrolyte composition contains inorganic solid electrolyte having the conductivity of ions of metal belonging to the first group or second group in the periodic table, at least one kind of active material represented by formula (1), and particulate polymer, an electrode sheet for a battery and an all-solid secondary battery that use the solid electrolyte composition, and a method of manufacturing the all-solid secondary battery. SiMformula (1) (x ranges from 0.01 to 1 and represents the mole fraction; and M represents any one or combination of chalcogen element, metalloid element, alkali metal element, alkali metal earth element and transition metal element).SELECTED DRAWING: Figure 1

Description

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

An electrolyte solution is used for the lithium ion battery. Attempts have been made to replace the electrolytic solution with a solid electrolyte to obtain an all-solid-state secondary battery in which the constituent materials are all solid. One of the advantages of the technology using an inorganic solid electrolyte is reliability. A flammable material such as a carbonate-based solvent is used as a medium for the electrolytic solution used in the lithium ion secondary battery. Although various safety measures have been taken, it cannot be said that there is no risk of malfunctions during overcharge, and further measures are desired. An all-solid-state secondary battery that can make the electrolyte nonflammable is positioned as a fundamental solution.
A further advantage of the all-solid-state secondary battery is that it is suitable for increasing the energy density by stacking electrodes. Specifically, a battery having a structure in which an electrode and an electrolyte are directly arranged in series can be obtained. At this time, since the metal package for sealing the battery cell, the copper wire and the bus bar for connecting the battery cell can be omitted, the energy density of the battery is greatly increased. In addition, good compatibility with the positive electrode material capable of increasing the potential is also mentioned as an advantage.

  From the above advantages, the development of a next-generation lithium ion secondary battery has been vigorously advanced (Non-patent Document 1). On the other hand, in an inorganic all-solid secondary battery, since the electrolyte is a hard solid, there is a point that needs to be improved.

  For example, the interfacial resistance between the solid particles and between the solid particles and the current collector is increased. In order to improve this, Patent Document 1 proposes an all-solid-state secondary battery produced using a binder composed of a particulate polymer containing a surfactant having a polyoxyethylene chain.

  In addition, a graphite material is often used as an active material for the negative electrode, but improvements for further increasing the capacity are being promoted. Since Si has a large theoretical capacity, it is one of the materials expected as an active material for the negative electrode. For example, Patent Document 2 proposes a battery manufactured using silicon (Si) as a negative electrode active material.

JP 2013-008611 A JP 2013-2111238 A

NEDO Technology Development Organization, Fuel Cell / Hydrogen Technology Development Department, Energy Storage Technology Development Office “NEDO Next-Generation Automotive Storage Battery Technology Development Roadmap 2008” (June 2009)

However, the all-solid-state secondary battery disclosed in Patent Document 1 has a room for further improvement in the size of the battery capacity, although the interface resistance is suppressed.
On the other hand, in the said patent document 2, the binding property of a binder and a negative electrode active material is insufficient, and there exists room for the further improvement of a battery cycle characteristic.

  Accordingly, the present invention provides a solid electrolyte composition capable of realizing an all-solid-state secondary battery having a large battery capacity and capacity density and excellent cycle characteristics when used as a constituent material of a negative electrode active material layer, and a battery using the same It aims at providing the manufacturing method of the electrode sheet for batteries, an all-solid-state secondary battery, and the electrode sheet for batteries, and an all-solid-state secondary battery.

<1> An inorganic solid electrolyte having conductivity of metal ions belonging to Group 1 or Group 2 of the periodic table, at least one active material represented by the following formula (1), and a particulate polymer Solid electrolyte composition.

Si _x M _(1-x) Formula (1)

  In the formula (1), x represents a number of 0.01 or more and less than 1, and means a mole fraction. M represents a chalcogen element, a metalloid element, an alkali metal element, an alkaline earth metal element, a transition metal element, or a combination thereof.

<2> The solid electrolyte composition according to <1>, wherein x is 0.1 or more and 0.99 or less in the formula (1).
<3> The solid electrolyte composition according to <1> or <2>, further comprising a conductive additive.
<4> The solid electrolyte composition according to any one of <1> to <3>, wherein the active material is an alloy containing Si element.
<5> The solid electrolyte composition according to any one of <1> to <4>, wherein an average particle size of the active material is 0.1 to 60 μm.
<6> The solid electrolyte composition according to any one of <1> to <5>, wherein an average particle size of the particulate polymer is 0.02 μm or more.
<7> The solid electrolyte composition according to any one of <1> to <6>, wherein the glass transition temperature of the particulate polymer is 50 ° C. or less.
<8> The solid electrolyte composition according to any one of <1> to <7>, wherein the particulate polymer has a unit structure represented by the following group I.

R ¹ , R ² , R ⁵ and R ⁶ each independently represents an alkylene group, an arylene group or a combination thereof. R ³ represents an alkyl group, an alkenyl group, an aryl group or an aralkyl group. R ⁴ represents an aromatic or aliphatic tetravalent linking group. R ⁷ represents an alkyl group, an alkenyl group, an aryl group or an aralkyl group. * Represents a binding site.

<9> A positive electrode active material layer, an inorganic solid electrolyte layer, and a negative electrode active material layer, wherein the negative electrode active material layer includes at least one active material represented by the following formula (1) and a particulate polymer. Solid secondary battery.

Si _x M _(1-x) Formula (1)

  In the formula (1), x represents a number of 0.01 or more and less than 1, and M represents a chalcogen element, a metalloid element, an alkali metal element, an alkaline earth metal element, a transition metal element, or a combination thereof. .

<10> An electrode sheet for a battery in which the solid electrolyte composition according to any one of <1> to <8> is formed on a current collector.
<11> A method for producing an electrode sheet for a battery, wherein the solid electrolyte composition according to any one of <1> to <8> is formed on a current collector.
<12> An all-solid secondary battery comprising the battery electrode sheet according to <10>.
<13> A method for producing an all-solid secondary battery, comprising producing an all-solid secondary battery using the battery electrode sheet according to <10>.

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

  The solid electrolyte composition of the present invention can be suitably used as a constituent material of the negative electrode active material layer of an all-solid secondary battery. The all solid state secondary battery of the present invention has a large capacity density and excellent cycle characteristics. Moreover, the battery electrode sheet of the present invention enables the production of an all-solid secondary battery having the above-described excellent performance. Moreover, according to the manufacturing method of this invention, the battery electrode sheet of this invention and the all-solid-state secondary battery which has said outstanding performance can be manufactured efficiently.

It is sectional drawing which shows typically the all-solid-state lithium ion secondary battery which concerns on preferable embodiment of this invention. It is a sectional side view which shows typically the testing apparatus utilized in the Example.

  The solid electrolyte composition of the present invention includes an inorganic solid electrolyte having conductivity of metal ions belonging to Group 1 or Group 2 of the periodic table, and at least one active material represented by the following formula (1) And a particulate polymer. Hereinafter, preferred embodiments thereof will be described. First, an example of an all-solid secondary battery which is a preferred application mode thereof will be described.

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 this 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 in order from the negative electrode side. Each layer is in contact with each other and has a laminated structure. With such a structure, at the time of charging, electrons (e ⁻ ) are supplied to the negative electrode side, and lithium ions (Li ⁺ ) are accumulated therein. On the other hand, at the time of discharge, lithium ions (Li ⁺ ) accumulated in the negative electrode are returned to the positive electrode side, and electrons are supplied to the working part 6. In the illustrated example, a light bulb is illustrated as the operation site 6, but this is turned on by discharge. The solid electrolyte composition of the present invention is preferably used as a constituent material of the negative electrode active material layer.

  The 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, but are preferably 1,000 μm or less, more preferably 1 to 1,000 μm in consideration of general battery dimensions, 3-400 micrometers is still more preferable.

<Solid electrolyte composition>
(Inorganic solid electrolyte)
The inorganic solid electrolyte is a solid electrolyte made of an inorganic substance, and the solid electrolyte is a solid electrolyte that can move ions inside. From this point of view, it may be called an ion conductive inorganic solid electrolyte in consideration of the distinction from a lithium salt described later.

Since inorganic solid electrolytes do not contain organic substances (carbon atoms), organic solid electrolytes, polymer electrolytes typified by PEO (polyethylene oxide), etc., organic electrolytes typified by LiTFSI (lithium bistrifluoromethanesulfonimide), etc. It is clearly distinguished from 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 , LiFSI [lithium bis (fluorosulfonyl) imide], 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 contains a metal belonging to Group 1 or Group 2 of the periodic table and has conductivity of this metal ion (preferably lithium ion), and does not have electron conductivity. Things are common.

  The inorganic solid electrolyte used in the present invention has conductivity of ions of metals belonging to Group 1 or Group 2 of the Periodic Table. As the inorganic solid electrolyte, a solid electrolyte material applied to this type of product can be appropriately selected and used. Typical examples of inorganic solid electrolytes include (i) sulfide-based inorganic solid electrolytes and (ii) oxide-based inorganic solid electrolytes.

(I) Sulfide-based inorganic solid electrolyte A sulfide-based inorganic solid electrolyte (hereinafter, also simply referred to as a sulfide solid electrolyte) contains a sulfur atom (S) and belongs to Group 1 or Group 2 of the periodic table. Those having the ionic conductivity of the metal to which they belong and having electronic insulation are preferred. For example, a lithium ion conductive inorganic solid electrolyte that satisfies the composition formula represented by the following formula (A) can be given.

Li _a Y _{b Pc} S _d (A)

  In formula (A), Y represents an element selected from B, Zn, Si, Cu, Ga, and Ge. a to d represent the composition ratio of each element, and a: b: c: d satisfies 1 to 12: 0 to 1: 1: 2 to 9, respectively.

  In the formula (A), the composition ratio of Li, Y, P and S is preferably such that b is 0, more preferably b = 0 and the composition of a, c and d is a: c: d = 1. -9: 1: 3-7, more preferably b = 0 and a: c: d = 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 in producing the sulfide-based solid electrolyte.

  The sulfide-based solid electrolyte may be amorphous (glass) or crystallized (glass ceramic), or only a part may be crystallized.

The ratio of Li ₂ S to P ₂ S ₅ in the Li—PS glass and the Li—PS glass glass ceramic 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 75:25. By setting the ratio of Li ₂ S to P ₂ S ₅ within this range, the lithium ion conductivity can be increased. Specifically, the lithium ion conductivity can be preferably 1 × 10 ⁻² S / m or more, more preferably 0.1 S / m or more.

Specific examples of the compound include those using a raw material composition containing, for example, Li ₂ S and a sulfide of an element belonging to Group 13 to Group 15.
More specifically, for _{example, Li 2 S-P 2 S} 5, Li 2 S-GeS 2, Li 2 S-GeS 2 -ZnS, Li 2 S-Ga 2 S 3, Li 2 S-GeS 2 -Ga _{2 S 3, Li 2 S-} GeS 2 -P 2 S 5, Li 2 S-GeS 2 -Sb 2 S 5, Li 2 S-GeS 2 -Al 2 S 3, Li 2 S-SiS 2, Li 2 S _{-Al 2 S 3, Li 2 S} -SiS 2 -Al 2 S 3, Li 2 S-SiS 2 -P 2 S 5, Li 2 S-SiS 2 -LiI, Li 2 S-SiS 2 -Li 4 SiO 4 _{, Li 2 S-SiS 2 -Li} 3 PO 4, Li 10 GeP 2 S 12 and the like. Among them, Li ₂ S—P ₂ S ₅ , Li ₂ S—GeS ₂ —Ga ₂ S ₃ , Li ₂ S—GeS ₂ —P ₂ S ₅ , Li ₂ S—SiS ₂ —P ₂ S ₅ , Li _{2 S-SiS 2 -Li 4 SiO 4} , Li 2 S-SiS 2 -Li 3 crystalline and or amorphous material composition consisting of PO ₄ are preferred as they have a high lithium ion conductivity.
Examples of a method for synthesizing a sulfide solid electrolyte material using such a raw material composition include an amorphization method. Examples of the amorphization method include a mechanical milling method and a melt quenching method. Among these, the mechanical milling method is preferable because processing at normal temperature is possible and the manufacturing process can be simplified.

  Examples of the sulfide solid electrolyte include T.I. Ohtomo, A .; Hayashi, M .; Tatsumisago, Y. et al. Tsuchida, S .; Hama, 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, and the like.

(Ii) Oxide-based inorganic solid electrolyte The oxide-based inorganic solid electrolyte (hereinafter, also simply referred to as “oxide-based solid electrolyte”) contains an oxygen atom (O), and is group 1 or group 2 of the periodic table. It is preferable to include a metal belonging to the above, to have ionic conductivity, and to have electronic insulation.

Specifically, for example, Li _xa La _ya TiO ₃ [xa = 0.3 to 0.7, ya = 0.3 to 0.7] (LLT), Li ₇ La ₃ Zr ₂ O ₁₂ (LLZ), Li _3.5 Zn _0.25 GeO ₄ having a LIICON (Lithium super ionic conductor) type crystal structure, LiTi ₂ P ₃ O ₁₂ having a NASICON (Natium super ionic conductor) type crystal structure, Li _{1 + xb + bb (Ti, Ge) 2-xb} Si yb P 3-yb O 12 ( provided that, 0 ≦ xb ≦ 1,0 ≦ yb ≦ 1), Li 7 La 3 Zr 2 O 12 having a garnet-type crystal structure.
A phosphorus compound containing Li, P and O is also preferable. For example, lithium phosphate (Li ₃ PO ₄ ), LiPON obtained by substituting a part of oxygen atoms of lithium phosphate with nitrogen atoms, LiPOD (D is Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zr, Nb, Mo, Ru, Ag, Ta, W, Pt, Au or the like is selected. Moreover, LiAON (A shows at least 1 sort (s) chosen from Si, B, Ge, Al, C, Ga, etc.) etc. can be used preferably.
Among them, Li _{1 + xb + yb} (Al, Ga) _xb (Ti, Ge) _2-xb Si _yb P _3-yb O ₁₂ (where 0 ≦ xb ≦ 1, 0 ≦ yb ≦ 1) is high in lithium ion conduction. It is preferable because it has good properties, is chemically stable, and is easy to handle. These may be used alone or in combination of two or more.

The lithium ion conductivity of the oxide-based solid electrolyte is preferably 1 × 10 ⁻⁴ S / m or more, more preferably 1 × 10 ⁻³ S / m or more, and further preferably 5 × 10 ⁻³ S / m or more.

  The average particle size of the inorganic solid electrolyte is not particularly limited, but is preferably 0.01 μm or more, and more preferably 0.1 μm or more. As an upper limit, 100 micrometers or less are preferable and 50 micrometers or less are more preferable.

The concentration of the inorganic solid electrolyte in the solid electrolyte composition is preferably 50% by mass or more, and 80% by mass or more in 100% by mass of the solid component, considering both battery performance and reduction / maintenance effect of interface resistance. More preferably, 90 mass% or more is further more preferable. From the same viewpoint, the upper limit is preferably 99.9% by mass or less, more preferably 99% by mass or less, and further preferably 98% by mass or less.
In the present specification, the solid component refers to a component that does not disappear by volatilization or evaporation when dried at 170 ° C. for 6 hours. Typically, it refers to components other than the dispersion medium described below.

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

  The solid electrolyte composition of the present invention contains at least one active material represented by the following formula (1).

Si _x M _(1-x) Formula (1)

  In the formula (1), x represents a number of 0.01 or more and less than 1, and means a mole fraction. M represents a chalcogen element, a metalloid element, an alkali metal element, an alkaline earth metal element, a transition metal element, or a combination thereof.

M is preferably a chalcogen element such as O, S or Se, a metalloid element such as B or Ge, an alkali metal element such as Li or Na, an alkaline earth metal element such as Mg or Ca, Ti, V, It can be selected from transition metal elements such as Mn, Fe, Co, Ni and Cu. Further, a combination of two or more of these elements may be used.
Of these, chalcogen elements and transition metal elements are preferable, and transition metal elements are more preferable. Among the transition metal elements, the first transition metal element is preferable, Ti, V, Mn, Fe, Co, Ni, and Cu are more preferable, and Ti, Mn, Fe, Co, and Ni are particularly preferable.

  x is preferably 0.1 or more and less than 1, more preferably 0.1 or more and 0.99 or less, further preferably 0.2 or more and 0.98 or less, and particularly preferably 0.3 or more and 0.95 or less.

  The particle diameter of the active material represented by the formula (1) is not particularly limited, but the average particle diameter is preferably 0.1 μm to 60 μm, more preferably 0.2 μm to 50 μm, and particularly preferably 0.5 μm to 20 μm.

  In order to obtain a predetermined particle size, a well-known pulverizer or classifier is used. For example, a mortar, a ball mill, a sand mill, a vibrating ball mill, a satellite ball mill, a planetary ball mill, a swirling air flow type jet mill or a sieve is preferably used. When pulverizing, wet pulverization in the presence of water or an organic solvent such as methanol can be performed as necessary. In order to obtain a desired particle 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 size of the active material represented by the formula (1) is measured by the same method as the method for measuring the average particle size of the particulate polymer shown in the section of Examples described later.

  The mole fraction of the active material represented by the formula (1) can be calculated from an inductively coupled plasma (ICP) emission spectroscopic analysis method as a measurement method and a mass difference between powders before and after firing as a simple method.

  The active material represented by the formula (1) is preferably an alloy containing Si element. This is because Si has poor electron conductivity, so that it is possible to impart electron conductivity by alloying. Here, the alloy containing Si element has one or more metal elements and metalloid elements in pure Si consisting of a single Si element, and as its state, a solid solution in which a plurality of elements are dissolved, Examples of crystals include eutectics in which the metal elements of each component are independent, and intermetallic compounds that are bonded to a certain level at the element level.

  Alloys can be prepared by melting and mixing several kinds of metals, sintering by mixing raw metal powders and heating them below their melting point, alloy plating by chemical methods, and mechanically using ball mill equipment. And mechanical alloying to be mixed.

  As a method for imparting electronic conductivity other than when the active material represented by the formula (1) is an alloy, the solid electrolyte composition of the present invention may contain a conductive additive. As a general conductive auxiliary agent, carbon fibers such as graphite, carbon black, acetylene black, ketjen black, and carbon nanotube, metal powder, metal fibers, polyphenylene derivatives, and the like, which are electron conductive materials, can be included. .

  The active material represented by the formula (1) is more preferably represented by the following formulas.

(SA-1) Si _a O _{1-a
(SA-2) Ni b Ti} c Si 1-b-c
_{(SA-3) Cr b Ti} c Si 1-b-c
(SA-4) Si _a Mn _1-a
(SA-5) Si _a Ni _1-a
(SA-6) Si _a Mg _1-a
(SA-7) Si _a Ge _1-a

  Here, a, b and c represent mole fractions, and a, b and c each independently represent a number of 0.01 or more and less than 1. However, 1-bc is greater than zero.

  Although the specific example of the active material represented by Formula (1) used for this invention below is given, this invention is not limited and interpreted by this.

Si _0.4 O _0.6
Si _0.5 O _0.5
Si _0.6 O _0.4
Si _0.7 O _0.3
Si _0.8 O _0.2
Si _0.9 O _0.1
Ni _0.04 Ti _0.04 Si _0.92
Ni _0.08 Ti _0.04 Si _0.88
Ni _0.08 Ti _0.08 Si _0.84
Cr _0.04 Ti _0.04 Si _0.92
Mn _0.1 Si _0.9
Ni _0.1 Si _0.9
Mg _0.1 Si _0.9
Ge _0.1 Si _0.9

  In the present invention, the active material represented by the formula (1) may be used alone, but it is preferable to use a combination of two or more, and a combination of two or more is used, and the formula (1 ), M is more preferably a transition metal element.

  Although the density | concentration of a negative electrode active material is not specifically limited, 10-80 mass% is preferable in 100 mass% of solid components in the solid electrolyte composition for forming a negative electrode active material layer, and 20-70 mass% is more preferable.

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. It can be arbitrarily determined according to the designed battery capacity.

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

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

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

Li _a1 M ¹ O _b1 Formula (MA)

Wherein (MA), ^{M 1} are as defined above ^{M a,} and the preferred range is also the same. a1 represents 0 to 1.2 (preferably 0.2 to 1.2), and preferably 0.6 to 1.1. b1 represents 1-3 and 2 is preferable. A part of M ¹ may be substituted with the mixed element M ^b .
The transition metal oxide represented by the formula (MA) typically has a layered rock salt structure.

  The transition metal oxide represented by the formula (MA) is more preferably represented by the following formulas.

_{(MA-1) Li g CoO} k
_{(MA-2) Li g NiO} k
_{(MA-3) Li g MnO} k
_{(MA-4) Li g Co} j Ni 1-j O k
_{(MA-5) Li g Ni} j Mn 1-j O k
_{(MA-6) Li g Co} j Ni i Al 1-j-i O k
_{(MA-7) Li g Co} j Ni i Mn 1-j-i O k

Here, g has the same meaning as a1 above, and the preferred range is also the same. j represents 0.1 to 0.9. i represents 0 to 1; However, 1-j-i is 0 or more. k has the same meaning as b1, and the preferred range is also the same.
Specific examples of these transition metal compounds include LiCoO ₂ (lithium cobaltate [LCO]), LiNi ₂ O ₂ (lithium nickelate) LiNi _0.85 Co _0.01 Al _0.05 O ₂ (nickel cobalt aluminum acid Lithium [NCA]), LiNi _0.33 Co _0.33 Mn _0.33 O ₂ (nickel manganese lithium cobaltate [NMC]), LiNi _0.5 Mn _0.5 O ₂ (lithium manganese nickelate) .

  The transition metal oxide represented by the formula (MA) partially overlaps, but when represented by changing the notation, those represented by the following are also preferable examples.

(I) Li _g Ni _xc Mn _yc Co _zc O ₂ (xc> 0.2, yc> 0.2, zc ≧ 0, xc + yc + zc = 1)
Representative:
_{Li g Ni 1/3 Mn 1/3 Co 1/3} O 2
Li _g Ni _1/2 Mn _1/2 O ₂

_{(Ii) Li g Ni xd Co} yd Al zd O 2 (xd> 0.7, yd>0.1,0.1> zd ≧ 0.05, xd + yd + zd = 1)
Representative:
_{Li g Ni 0.8 Co 0.15 Al 0.05} O 2

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

Li _c1 M ² ₂ O _d1 Formula (MB)

Wherein (MB), ^{M 2} are as defined above ^{M a,} and the preferred range is also the same. c1 represents 0-2, 0.2-2 are preferable and 0.6-1.5 are more preferable. d1 represents 3-5, and 4 is preferable.

  The transition metal oxide represented by the formula (MB) is more preferably represented by the following formulas.

_{(MB-1) Li m Mn} 2 O n
_{(MB-2) Li m Mn} p Al 2-p O n
_{(MB-3) Li m Mn} p Ni 2-p O n

m is synonymous with c1, and its preferable range is also the same. n is synonymous with d1, and a preferable range is also the same. p represents 0-2.
Examples of these transition metal oxides include LiMn ₂ O ₄ and LiMn _1.5 Ni _0.5 O ₄ .

  Preferred examples of the transition metal oxide represented by the formula (MB) include those represented by the following formulas.

(A) LiCoMnO ₄
(B) Li ₂ FeMn ₃ O ₈
(C) Li ₂ CuMn ₃ O ₈
(D) Li ₂ CrMn ₃ O ₈
(E) Li ₂ NiMn ₃ O ₈

  Of these, an electrode containing Ni is more preferable from the viewpoint of high capacity and high output.

[Transition metal oxide represented by formula (MC)]
The lithium-containing transition metal oxide is preferably a lithium-containing transition metal phosphate, and among them, one represented by the following formula (MC) is also preferable.

Li _e1 M ³ (PO ₄ ) _f1 Formula (MC)

  In the formula (MC), e1 represents 0 to 2 (preferably 0.2 to 2), and preferably 0.5 to 1.5. f1 represents 1-5, and 1-2 are preferable.

M ³ represents one or more elements selected from the group consisting of V, Ti, Cr, Mn, Fe, Co, Ni, and Cu. M ³ represents, other mixing element ^{M b} above, Ti, Cr, Zn, Zr, may be substituted by other metals such as Nb. Specific examples include, for example, olivine-type iron phosphates such as LiFePO ₄ and Li ₃ Fe ₂ (PO ₄ ) ₃ , iron pyrophosphates such as LiFeP ₂ O ₇ , cobalt phosphates such as LiCoPO ₄ , and Li _3. Monoclinic Nasicon type vanadium phosphate salts such as V ₂ (PO ₄ ) ₃ (lithium vanadium phosphate) can be mentioned.

  In addition, said a1, c1, g, m, and e1 value showing the composition of Li are the values which change with charging / discharging, and are typically evaluated by the value of the stable state when Li is contained. In the formulas (a) to (e), the composition of Li is shown as a specific value, which also changes depending on the operation of the battery.

  The average particle diameter (sphere conversion average particle diameter) of the positive electrode active material used in the all solid secondary battery of the present invention is not particularly limited. In addition, 0.1 micrometers-50 micrometers are preferable. In order to make the positive electrode active substance have a predetermined particle size, a normal 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 average particle diameter of the positive electrode active material particles is measured by the same method as the method for measuring the average particle diameter of the particulate polymer shown in the section of the examples described later.

  Although the density | concentration of a positive electrode active material is not specifically limited, 10-90 mass% is preferable in a solid component 100 mass% in the solid electrolyte composition for forming a positive electrode active material layer, and 20-80 mass% is more preferable.

Moreover, you may make a positive electrode active material layer contain a conductive support agent suitably as needed. Common conductive aids may include electron conductive materials such as graphite, carbon black, acetylene black, ketjen black, carbon fiber, metal powder, metal fiber, polyphenylene derivative, and the like.
In addition, the structure of the solid electrolyte composition for forming a positive electrode active material layer can use the same thing as the structure of the solid electrolyte composition of this invention other than an active material.

(Particulate polymer)
The particulate polymer used in the present invention plays a role as a binder bound to the inorganic solid electrolyte, optionally in combination with an additive or the like (hereinafter, the particulate polymer may be referred to as “binder”).
(I) Particulate polymer A
The particulate polymer used in the present invention may be an organic polymer particle or an organic-inorganic hybrid polymer particle as long as it shows a good binding property between the active material and the inorganic solid electrolyte as a binder. Polymer particles are preferred.
The structure is not particularly limited as long as it is organic polymer particles. For example, fluorine resin (polyvinylene difluoride (PVdF), etc.), hydrocarbon resin (hydrogenated styrene butadiene rubber (HSBR), styrene butadiene rubber (SBR), etc.), acrylic resin, styrene resin, amide type Examples include resins, imide resins, urethane resins, urea resins, ester resins, ether resins, phenol resins, epoxy resins, carbonate resins, silicone resins, or combinations thereof. Among these, acrylic resins or urethane resins are particularly preferable, and urethane resins are most preferable.
In the present invention, the resin used for the particulate polymer is not limited to one type, but may be two or more types, or a combination thereof.

  Here, the particulate polymer used in the present invention may be any polymer particle of a block copolymer, an alternating copolymer, or a random copolymer.

In addition, when a sulfide-based solid electrolyte is used, the water content of the particulate polymer from the viewpoint of suppressing the generation of hydrogen sulfide due to the reaction between the sulfide-based solid electrolyte and water and suppressing the decrease in ionic conductivity. Is preferably 100 ppm or less.
The water content was determined by using the Karl Fischer liquid Aquamicron AX (trade name, manufactured by Mitsubishi Chemical Corporation) as a sample after drying the polymer in a vacuum at 80 ° C. with the Karl Fischer method. ) And the water content (g) is divided by the sample mass (g).

  The glass transition temperature of the particulate polymer used in the present invention is preferably 50 ° C. or lower, more preferably −200 ° C. or higher and 40 ° C. or lower, and further preferably −150 ° C. or higher and 30 ° C. or lower. When the glass transition temperature is within the above range, good ionic conductivity can be obtained. In addition, the glass transition temperature of the particulate polymer used for this invention is measured by the method shown by the term of the below-mentioned Example.

The weight average molecular weight of the particulate polymer used in the present invention is preferably from 5,000 to 1,000,000, more preferably from 10,000 to 500,000, and even more preferably from 30,000 to 200,000. .
When the weight average molecular weight of the particulate polymer is within the above range, better binding properties are exhibited and handling properties (manufacturability) are improved.
In addition, the weight average molecular weight of the particulate polymer used for this invention is measured by the method shown by the term of the below-mentioned Example.

The shape of the particulate polymer used in the present invention is not limited as long as it can bind an active material and an inorganic solid electrolyte as a binder.
The particulate polymer may be spherical or flat, and may be amorphous. Further, the surface of the particulate polymer may be smooth or may have an uneven shape. Furthermore, the inside of the particulate polymer may be filled with the same material as the side wall or may be filled with a different material. Moreover, it may be hollow and the hollow ratio is not limited.
The particulate polymer may be monodispersed or polydispersed.

The particulate polymer used in the present invention can be synthesized by a method of polymerizing a polymerizable monomer in the presence of a surfactant, an emulsifier or a dispersing agent, a method of depositing in a crystalline form as the molecular weight increases, and the like.
Alternatively, the existing polymer may be mechanically crushed to form a particulate polymer, or the polymer dissolved in the polymer solution may be reprecipitated to form the particulate polymer.

The average particle diameter of the particulate polymer used in the present invention is not particularly limited, but is preferably 0.02 μm or more, more preferably 0.05 μm to 50 μm, and more preferably 0.07 μm to 20 μm when dispersed in a dispersion medium described later. Is more preferable, and 0.1 μm to 10 μm is particularly preferable.
The average particle diameter of the particulate polymer is measured by the same method as the method for measuring the volume average particle diameter of the particulate polymer shown in the Examples section below.

  In the present invention, the particulate polymer preferably has a unit structure represented by the following group I.

R ¹ , R ² , R ⁵ and R ⁶ each independently represents an alkylene group, an arylene group or a combination thereof. R ³ represents an alkyl group, an alkenyl group, an aryl group or an aralkyl group. R ⁴ represents an aromatic or aliphatic tetravalent linking group. R ⁷ represents an alkyl group, an alkenyl group, an aryl group or an aralkyl group. * Represents a binding site.

R ^{1, R} 2, ^{R 5} and the carbon number of the alkylene group for ^{R 6} is preferably 1 to 20, more preferably 1 to 12, 1 to 6 is particularly preferred.

R ^{1, R} 2, ^{R 5} and the carbon number of the arylene group in ^{R 6} is preferably 6 to 22, more preferably 6 to 14, 6 to 10 are particularly preferred.

R ^{1, R} 2, ^{R 5} and the carbon number of combining an alkylene group and an arylene group in ^{R 6} is preferably 7-42, more preferably 7-28, particularly preferably 7-16.

The number of carbon atoms in the alkyl group for R ^3, preferably 1 to 20, more preferably 1 to 12, 1 to 6 is particularly preferred.

R number of carbon atoms of the alkenyl group in ³ is preferably 2 to 20, more preferably 2 to 12, 2 to 6 is particularly preferred.

The number of carbon atoms of the aryl group for R ^3, preferably 6 to 22, more preferably 6 to 14, 6 to 10 are particularly preferred.

The number of carbon atoms of the aralkyl group for R ^3, preferably 7-42, more preferably 7-28, particularly preferably 7-16.

R ⁴ is preferably a linking group represented by any one of the following formulas (i) to (iii).

In formulas (i) to (iii), X ¹ represents a single bond or a divalent linking group. As a bivalent coupling group, a C1-C6 alkylene group (for example, a methylene group, ethylene group, a propylene group) is preferable. As the propylene group, a 1,3-hexafluoro-2,2-propanediyl group is preferable. L represents —CH ₂ ═CH ₂ — or —CH ₂ —. R ^X and R ^Y each independently represents a hydrogen atom or a substituent. * Represents a binding site with a carbonyl group.

The substituent in R ^X and R ^Y is an alkyl group (the number of carbon atoms is preferably 1 to 12, more preferably 1 to 6, and further preferably 1 to 3) or an aryl group (the number of carbon atoms is preferably 6 to 22). 6-14 are more preferable, and 6-10 are more preferable.

The number of carbon atoms of the alkyl group in R ⁷ is preferably 1 to 20, more preferably 1 to 12, 1 to 6 is particularly preferred.

The number of carbon atoms of the alkenyl group for R ⁷ is preferably 2 to 20, more preferably 2 to 12, 2 to 6 is particularly preferred.

The number of carbon atoms of the aryl group in R ⁷ is preferably 6 to 22, more preferably 6 to 14, 6 to 10 are particularly preferred.

The number of carbon atoms of the aralkyl group in R ⁷ is preferably 7-42, more preferably 7-28, particularly preferably 7-16.

  What was obtained by the above-mentioned method may be used for the particulate polymer used for this invention, and a common commercial item may be used. Hereinafter, although the specific example of the particulate polymer used for this invention is given, this invention is not limited to these.

Fluorine-based resin As the fluorine-based resin that can be used as the particulate polymer in the present invention, Microdispers-200 (polytetrafluoroethylene (PTFE) particles, average particle size: 200 nm, manufactured by Techno Chemical Co., Ltd.), Micro Disperse-3000 (PTFE particles, average particle size: 3 μm, manufactured by Techno Chemical Co., Ltd.), Micro Disperse-8000 (PTFE particles, average particle size: 8 μm, manufactured by Techno Chemical Co., Ltd.), Disperse Easy-300 (PTFE particles, average particle diameter: 200 nm, manufactured by Techno Chemical Co., Ltd.), Fluon AD911E (produced by Asahi Glass Co., Ltd.), Fluon AD915E (produced by Asahi Glass Co., Ltd.), Fluon AD916E (produced by Asahi Glass Co., Ltd.), Fluon AD939E (Asahi Glass Co., Ltd.) )), Argoflo F (PTFE particles, average particle size: 15 to 35 μm, manufactured by Solvay), Algoflon S (PTFE particles, average particle size: 15 to 35 μm, manufactured by Solvay), Lubron L-2 (PTFE particles, Average particle size: 3.5 μm, manufactured by Daikin Corp.), Lubron L-5 (PTFE particles, average particle size: 5 μm, manufactured by Daikin Corp.), Lubron L-5F (PTFE particles, average particle size: 4. 5 μm, manufactured by Daikin Co., Ltd. (both are trade names), etc., and are available as commercial products.

Hydrocarbon resins As hydrocarbon resins that can be used as the particulate polymer in the present invention, soft beads (manufactured by Sumitomo Seika Co., Ltd.), Syxen (polyolefin emulsion, manufactured by Sumitomo Seika Co., Ltd.), Sephorjon G (Polyolefin emulsion, manufactured by Sumitomo Seika Co., Ltd.), Sepolex IR100 (polyisoprene latex, manufactured by Sumitomo Seika Co., Ltd.), Sepolex CSM (chlorosulfonated polyethylene latex, manufactured by Sumitomo Seika Co., Ltd.), Frocene (polyethylene) Powder, manufactured by Sumitomo Seika Co., Ltd.), Flowsen UF (polyethylene powder, manufactured by Sumitomo Seika Co., Ltd.), flowbrene (polypropylene powder, manufactured by Sumitomo Seika Co., Ltd.), flow beads (polyethylene-acrylic copolymer powder) , Manufactured by Sumitomo Seika Co., Ltd.) (all are trade names), etc., available as commercial products Kill.

Acrylic resin As acrylic resins that can be used as the particulate polymer in the present invention, Art Pearl GR (manufactured by Negami Kogyo Co., Ltd.), Art Pearl SE (manufactured by Negami Kogyo Co., Ltd.), Art Pearl G (Negami Kogyo Co., Ltd.) Art Pearl GR (manufactured by Negami Kogyo Co., Ltd.), Art Pearl GR (manufactured by Negami Kogyo Co., Ltd.), Art Pearl GS (manufactured by Negami Kogyo Co., Ltd.), Art Pearl J (Negami Kogyo Co., Ltd.) ), Art Pearl MF (Negami Kogyo Co., Ltd.), Art Pearl BE (Negami Kogyo Co., Ltd.), Tufic AR-650 (Toyobo Co., Ltd.), Tuftic AR-750 (Toyobo Co., Ltd.) ), Tuftic FH-S (manufactured by Toyobo Co., Ltd.), Chemisnow MP-1451 (manufactured by Soken Chemical Co., Ltd.), Chemisnow MP-2200 (manufactured by Soken Chemical Co., Ltd.), Chemisnow MP-1000 ( Kenken Chemical Co., Ltd.), Chemisnow MP-2701 (manufactured by Soken Chemical Co., Ltd.), Chemisnow MP-5000 (manufactured by Soken Chemical Co., Ltd.), Chemisnow MP-5500 (manufactured by Soken Chemical Co., Ltd.), Chemisnow MP- 300 (manufactured by Soken Chemical Co., Ltd.), Chemisnow KMR-3TA (manufactured by Soken Chemical Co., Ltd.), Chemisnow MX-80H3wT (manufactured by Soken Chemical Co., Ltd.), Chemisnow MX-150 (manufactured by Soken Chemical Co., Ltd.), Chemisnow MX-180TA (manufactured by Soken Chemical Co., Ltd.), Chemisnow MX-300 (manufactured by Soken Chemical Co., Ltd.), Chemisnow MX-500 (manufactured by Soken Chemical Co., Ltd.), Chemisnow MX-500H (manufactured by Soken Chemical Co., Ltd.) Chemisnow MX-1000 (manufactured by Soken Chemical Co., Ltd.), Chemisnow MX-1500H (manufactured by Soken Chemical Co., Ltd.), Chemisnow MX-2000 (manufactured by Soken Chemical Co., Ltd.), Snow MX-3000 (manufactured by Soken Chemical Co., Ltd.), FS-101 (manufactured by Nippon Paint Co., Ltd.), FS-102 (manufactured by Nippon Paint Co., Ltd.), FS-106 (manufactured by Nippon Paint Co., Ltd.), FS -107 (manufactured by Nippon Paint), FS-201 (manufactured by Nippon Paint), FS-301 (manufactured by Nippon Paint), FS-501 (manufactured by Nippon Paint), FS-701 (Manufactured by Nippon Paint), MG-155E (manufactured by Nippon Paint), MG-451 (manufactured by Nippon Paint), MG-351 (manufactured by Nippon Paint), Techpolymer MBX (Sekisui Kasei Kogyo Co., Ltd.), Techpolymer SBX (Sekisui Kasei Kogyo Co., Ltd.), Techpolymer MSX (Sekisui Kasei Kogyo Co., Ltd.), Techpolymer SSX (Sekisui Kasei Kogyo Co., Ltd.) , Techpolymer BMX ( Sekisui Plastics Co., Ltd.), Techpolymer ABX (Sekisui Plastics Co., Ltd.), Techpolymer ARX (Sekisui Plastics Co., Ltd.), Techpolymer AFX (Sekisui Plastics Co., Ltd.) ), Techpolymer MB (manufactured by Sekisui Plastics Industry Co., Ltd.), Techpolymer MBP (manufactured by Sekisui Chemicals Co., Ltd.), Advancel HB-2051 (manufactured by Sekisui Chemical Co., Ltd.), Hayabies L-11 (Hayakawa) Rubber Co., Ltd.), Hayabies M-11 (Hayakawa Rubber Co., Ltd.), Aron T Series (Toa Gosei Co., Ltd.), Aron A Series (Toa Gosei Co., Ltd.), Aron SD-10 (Toa Gosei) Synthetic Co., Ltd.), Aron AC Series (Toa Gosei Co., Ltd.), Jurimer AC Series (Toa Gosei Co., Ltd.), Eposta MA (Nippon Shokubai Co., Ltd.), Eposta MX (Nippon Shokubai Co., Ltd.) Product name) There is etc., available as a commercial product.

As the acrylic resin particles, particles having the structure shown below are preferable.
The numbers in the structure of the following particles represent the molar ratio of structural units in parentheses, and the particles may be any of a block copolymer, an alternating copolymer, and a random copolymer.

  Moreover, the acrylic latex obtained by superposing | polymerizing the acrylic monomer as described in Japanese Patent Application No. 2013-198397 can also be used suitably.

Styrenic resin Examples of the styrenic resin that can be used as the particulate polymer in the present invention include Chemisnow KSR-3A (trade name, manufactured by Soken Chemical Co., Ltd.), Eposta ST (manufactured by Nippon Shokubai Co., Ltd.), and the like. Available as a commercial product.

Amide resin As amide resin that can be used as the particulate polymer in the present invention, Sephojon PA (copolymer nylon emulsion, manufactured by Sumitomo Seika Co., Ltd.), Trepearl PAI (polyamideimide particles, manufactured by Toray Industries, Inc.) (Both are trade names) and are available as commercial products.

Imide resin As imide resin that can be used as the particulate polymer in the present invention, polyimide powder P84 (R) NT (manufactured by Daicel Evonik Co., Ltd.), polyimide powder PIP-3 (manufactured by Seishin Enterprise Co., Ltd.) , Polyimide powder PIP-25 (manufactured by Seishin Enterprise Co., Ltd.), polyimide powder PIP-60 (manufactured by Seishin Enterprise Co., Ltd.), polyimide powder UIP-R (manufactured by Ube Industries), polyimide powder UIP-S (Ube) Manufactured by Kosan Co., Ltd. (both are trade names), etc., and are available as commercial products.

Urethane resin As urethane resin that can be used as the particulate polymer in the present invention, dimic beads UCN-8070CM (average particle size: 7 μm, manufactured by Dainichi Seika Co., Ltd.), dimic beads UCN-8150CM (average) Particle size: 15 μm, manufactured by Dainichi Seika Co., Ltd.), Art Pearl C (manufactured by Negami Kogyo Co., Ltd.), Art Pearl P (manufactured by Negami Kogyo Co., Ltd.), Art Pearl JB (manufactured by Negami Kogyo Co., Ltd.), Art Pearl U (Negami Kogyo Co., Ltd.), Art Pearl CE (Negami Kogyo Co., Ltd.), Art Pearl AK (Negami Kogyo Co., Ltd.), Art Pearl HI (Negami Kogyo Co., Ltd.), Art Pearl MM (Negami Kogyo Co., Ltd.), Art Pearl FF (Negami Kogyo Co., Ltd.), Art Pearl TK (Negami Kogyo Co., Ltd.), Art Pearl C-TH (Negami Kogyo Co., Ltd.), A Topal RW (Negami Kogyo Co., Ltd.), Art Pearl RX (Negami Kogyo Co., Ltd.), Art Pearl RY (Negami Kogyo Co., Ltd.), Art Pearl RZ (Negami Kogyo Co., Ltd.), Art Pearl RU (Negami Kogyo Co., Ltd.), Art Pearl RV (Negami Kogyo Co., Ltd.), Art Pearl BP (Negami Kogyo Co., Ltd.), Grosdale S Series (Mitsui Chemicals Co., Ltd.), Grosdale M Series (Mitsui Chemicals Co., Ltd.), Grosdale V Series (Mitsui Chemicals Co., Ltd.), Grosdale T Series (Mitsui Chemicals Co., Ltd.), Infinergy (BASF Co., Ltd.) (all trade names) , Available as a commercial product.

As the urethane resin particles, particles having the structure shown below are preferable.
The numbers in the structure of the following particles represent the molar ratio of structural units in parentheses, and the particles may be any of a block copolymer, an alternating copolymer, and a random copolymer.
Urethane resin particles having these chemical structures are generally obtained by polymerizing a diisocyanate compound and a diol compound and then mechanically pulverizing or dispersing the obtained polyurethane resin in a poor solvent.

Urea-based resin The urea-based resin particles that can be used as the particulate polymer in the present invention preferably include particles having the structure shown below.
The numbers in the structure of the following particles represent the molar ratio of structural units in parentheses, and the particles may be any of a block copolymer, an alternating copolymer, and a random copolymer.
Urea-based resin particles having these chemical structures are generally obtained by polymerizing a diisocyanate compound and a diamine compound and then mechanically pulverizing or dispersing the obtained polyurea resin in a poor solvent.

Ester-based resin Examples of ester-based resins that can be used as the particulate polymer in the present invention include Sepoljon ES (trade name, copolymerized polyester emulsion, manufactured by Sumitomo Seika Co., Ltd.), and are commercially available.

Ether-based resin The ether-based resin that can be used as the particulate polymer in the present invention includes Trepal PPS (polyphenylene sulfide particles, manufactured by Toray Industries, Inc.), Trepal PES (Polyethersulfone particles, manufactured by Toray Industries, Inc.) (any Is also available as a commercial product.

Phenol resin As the phenol resin that can be used as the particulate polymer in the present invention, LPS series (manufactured by Lignite Co., Ltd.), Marilyn FM series (manufactured by Gunei Chemical Industry Co., Ltd.), Marilyn HF series (Gunei Chemical Industry Co., Ltd.) (Buy Co., Ltd.) (all are trade names), etc., and are available as commercial products.

Epoxy Resin As an epoxy resin that can be used as the particulate polymer in the present invention, there is Trepearl EP (epoxy resin particles, manufactured by Toray Industries, Inc.) (all are trade names), which are available as commercial products.

Polycarbonate resin The polycarbonate resin that can be used as the particulate polymer in the present invention can be synthesized, for example, by the method described in International Publication 2011/004730. Specifically, it is possible to polymerize by reacting an epoxy compound with carbon dioxide.

Silicone Resin Silicone resins that can be used as the particulate polymer in the present invention include Seahoster KE-E series (manufactured by Nippon Shokubai Co., Ltd.), Seahoster KE-W series (manufactured by Nippon Shokubai Co., Ltd.), Seahoster KE. -P series (manufactured by Nippon Shokubai Co., Ltd.), Seahoster KE-S series (manufactured by Nippon Shokubai Co., Ltd.), silicone composite powder KMP-600 (manufactured by Shin-Etsu Silicone), silicone composite powder KMP-601 (Shin-Etsu Silicone) ), Silicone composite powder KMP-602 (Shin-Etsu Silicone Co., Ltd.), silicone composite powder KMP-605 (Shin-Etsu Silicone Co., Ltd.), silicone composite powder X-52-7030 (Shin-Etsu Silicone Co., Ltd.) Manufactured), Silicone Resin Powder KMP-590 (Shin-Etsu Silicone) ), Silicone Resin Powder KMP-701 (Shin-Etsu Silicone Co., Ltd.), Silicone Resin Powder X-52-854 (Shin-Etsu Silicone Co., Ltd.), Silicone Resin Powder X-52-1621 (Shin-Etsu Silicone ( Co., Ltd.), Silicone Rubber Powder KMP-597 (Shin-Etsu Silicone Co., Ltd.), Silicone Rubber Powder KMP-598 (Shin-Etsu Silicone Co., Ltd.), Silicone Rubber Powder KMP-594 (Shin-Etsu Silicone Co., Ltd.), Silicone rubber powder X-52-875 (manufactured by Shin-Etsu Silicone Co., Ltd.), Charine R-170S (silicone acrylic copolymer, manufactured by Nissin Chemical Industry Co., Ltd.) (both trade names) are available as commercial products it can.

Hereinafter, although the specific example of the particulate polymer used for this invention is shown, this invention is limited to this and is not interpreted.
In addition, the number in a compound represents the molar ratio of the structural unit in a parenthesis, and xx represents the integer of 1-300.

(Ii) Particulate polymer B
In the present invention, the following polymers may be used as the particulate polymer. In the polymer constituting the particulate polymer, a repeating unit derived from the macromonomer (X) having a number average molecular weight of 1,000 or more is incorporated as a side chain component.

  As the number average molecular weight of the macromonomer (X) used in the present invention, a value measured by the following method is adopted. The number average molecular weight of the macromonomer (X) used in the present invention is measured by the same method as the method for measuring the weight average molecular weight shown in the Examples section described later.

-Main chain component The main chain of a polymer is not specifically limited, A normal polymer component can be applied. The monomer constituting the main chain component is preferably a monomer having a polymerizable unsaturated bond, and for example, various vinyl monomers and acrylic monomers can be applied. In the present invention, it is particularly preferable to use an acrylic monomer. More preferably, it is preferable to use a monomer selected from a (meth) acrylic acid monomer, a (meth) acrylic acid ester monomer, and (meth) acrylonitrile. The number of polymerizable groups is not particularly limited, but is preferably 1 to 4.

  The polymer preferably has at least one of the following functional group (b). This functional group group may be contained in the main chain or may be contained in a side chain described later, but is preferably contained in the main chain. In this way, the inclusion of a specific functional group in the main chain or the like allows interaction with hydrogen atoms, oxygen atoms, and sulfur atoms that are considered to exist on the surface of the solid electrolyte, active material, and current collector. It can be expected to have an effect of strengthening, improving the binding property and lowering the interface resistance.

Functional group (b)
Carbonyl group, amino group, sulfonic acid group, phosphoric acid group, hydroxy group, ether group, cyano group, thiol group

Examples of the carbonyl group-containing group include a carboxyl group, a carbonyloxy group, an amide group, etc., preferably having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, and particularly preferably 1 to 6 carbon atoms.
The amino group preferably has 0 to 12 carbon atoms, more preferably 0 to 6 and particularly preferably 0 to 2.
The sulfonic acid group may be its ester or salt. In the case of ester, C1-C24 is preferable, 1-12 are more preferable, and 1-6 are especially preferable.
The phosphate group may be its ester or salt. In the case of ester, C1-C24 is preferable, 1-12 are more preferable, and 1-6 are especially preferable.
In addition, the said functional group may exist as a substituent or may exist as a coupling group. For example, the amino group may exist as a divalent imino group or a trivalent nitrogen atom.

  As a vinyl-type monomer which makes said polymer, what is represented by a following formula (b-1) is preferable.

In the formula, R ^a1 represents a hydrogen atom, a hydroxy group, a cyano group, a halogen atom, an alkyl group (preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, and particularly preferably 1 to 6 carbon atoms), an alkenyl group (2 carbon atoms). To 24, more preferably 2 to 12, and particularly preferably 2 to 6, an alkynyl group (preferably having 2 to 24 carbon atoms, more preferably 2 to 12 and particularly preferably 2 to 6), or an aryl group ( C6-C22 is preferable and 6-14 are more preferable. Of these, a hydrogen atom or an alkyl group is preferable, and a hydrogen atom or a methyl group is more preferable.

R ^a2 is a hydrogen atom, an alkyl group (preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, particularly preferably 1 to 6 carbon atoms), an alkenyl group (preferably 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms). ), Aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 14 carbon atoms), aralkyl group (preferably having 7 to 23 carbon atoms, more preferably 7 to 15 carbon atoms), cyano group, carboxyl group, hydroxy group, thiol Group, sulfonic acid group, phosphoric acid group, phosphonic acid group, aliphatic heterocyclic group containing oxygen atom (preferably having 2 to 12 carbon atoms, more preferably 2 to 6), or amino group (NR ^N ₂ : R ^N is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms according to the definition described later. Of these, a methyl group, an ethyl group, a propyl group, a butyl group, a cyano group, an ethenyl group, a phenyl group, a carboxyl group, a thiol group, a sulfonic acid group, and the like are preferable.
R ^a2 may further have a substituent T described later. Of these, a carboxyl group, a halogen atom (fluorine atom or the like), a hydroxy group, an alkyl group, or the like may be substituted.
The carboxyl group, hydroxy group, sulfonic acid group, phosphoric acid group, and phosphonic acid group may be esterified with, for example, an alkyl group having 1 to 6 carbon atoms.
The aliphatic heterocyclic group containing an oxygen atom is preferably an epoxy group-containing group, an oxetane group-containing group, a tetrahydrofuryl group-containing group, or the like.

L ¹ is an arbitrary linking group, and examples of the linking group L described later can be given. Specifically, an alkylene group having 1 to 6 (preferably 1 to 3) carbon atoms, an alkenylene group having 2 to 6 (preferably 2 to 3) carbon atoms, and 6 to 24 (preferably 6 to 10) carbon atoms. Arylene group, oxygen atom, sulfur atom, imino group (NR ^N ), carbonyl group, phosphate linking group (—O—P (OH) (O) —O—), phosphonic acid linking group (—P (OH) ( O) -O-), or a group relating to a combination thereof. The linking group may have an arbitrary substituent. The preferable number of connecting atoms and the number of connecting atoms are the same as described later. As an arbitrary substituent, the substituent T is mentioned, For example, an alkyl group or a halogen atom is mentioned.

  n is 0 or 1.

  As the acrylic monomer constituting the polymer, those represented by any of the following formulas (b-2) to (b-6) in addition to the formula (b-1) are preferable.

R ^a1 and n have the same ^meaning as in the above formula (b-1).
R ^a3 has the same ^{meaning as} R ^a2 in formula (b-1). However, preferred examples thereof include a hydrogen atom, an alkyl group, an aryl group, a carboxyl group, a thiol group, a phosphoric acid group, a phosphonic acid group, an aliphatic heterocyclic group containing an oxygen atom, and an amino group (NR ^N ₂ ). Is mentioned.
L ² is an arbitrary linking group, and an example of L ¹ in formula (b-1) is preferable, an oxygen atom, an alkylene group having 1 to 6 carbon atoms (preferably 1 to 3), and 2 to 6 carbon atoms ( A group relating to an alkenylene group, a carbonyl group, an imino group (NR ^N ), or a combination thereof of 2 to 3) is more preferable.
L ³ is a linking group, and an example of L ² is preferable, and an alkylene group having 1 to 6 (preferably 1 to 3) carbon atoms is more preferable.
L ⁴ has the same meaning as L ¹ in formula (b-1).
R ^a4 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms (preferably 1 to 3), a hydroxyl group-containing group having 0 to 6 carbon atoms (preferably 0 to 3), or 0 to 6 carbon atoms (preferably 0). To 3) a carboxyl group-containing group or a (meth) acryloyloxy group. In addition, R ^a4 may be a linking group of the above L ¹ and may form a dimer at this portion.
m represents an integer of 1 to 300, preferably an integer of 1 to 200, and more preferably an integer of 1 to 100.

  In the above formulas (b-1) to (b-6), any group that may take a substituent such as an alkyl group, an aryl group, an alkylene group, or an arylene group may be substituted as long as the effects of the present invention are maintained. It may have a group. Examples of the optional substituent include the substituent T described later, specifically, a halogen atom, a hydroxy group, a carboxyl group, a thiol group, an acyl group, an acyloxy group, an alkoxy group, an aryloxy group, and an aryloyl group. And may have any substituent such as an aryloyloxy group and an amino group.

  Examples of the monomer constituting the main chain component are listed below, but the present invention is not construed as being limited thereto. M in the following formula is synonymous with m in the above formulas (b-3) and (b-4).

・ Side chain component (macromonomer (X))
The macromonomer has a number average molecular weight of 1,000 or more, more preferably 2,000 or more, and particularly preferably 3,000 or more. The upper limit is preferably 500,000 or less, more preferably 100,000 or less, and particularly preferably 30,000 or less. When the polymer has a side chain component having a molecular weight in the above range, it can be more uniformly dispersed in an organic solvent and can be mixed and applied with solid electrolyte particles.

  The SP value of the macromonomer (X) is preferably 10 or less, and more preferably 9.5 or less. Although there is no particular lower limit, it is practical that it is 5 or more.

-SP value definition-
In this specification, unless otherwise specified, the SP value is obtained by the Hoy method (HL Hoy Journal of Paining, 1970, Vol. 42, 76-118). The SP value is shown with the unit omitted, but the unit is cal ^1/2 cm ^−3/2 . Note that the SP value of the side chain component (X) is not substantially different from the SP value of the raw material monomer forming the side chain, and may be evaluated accordingly.

  The SP value is an index indicating the characteristic of being dispersed in an organic solvent. Here, by setting the side chain component to a specific molecular weight or more, preferably to the SP value or more, the binding property with the solid electrolyte is improved, thereby improving the affinity with the solvent and stably dispersing. This is preferable.

  The macromonomer (X) preferably includes a repeating unit derived from a monomer selected from a (meth) acrylic acid monomer, a (meth) acrylic acid ester monomer, and (meth) acrylonitrile. The macromonomer (X) is a polymerizable double bond and a linear hydrocarbon structural unit S having 6 or more carbon atoms (preferably an alkylene group having 6 to 30 carbon atoms, more preferably 8 to 24 carbon atoms). Of the alkylene group). Thus, when the macromonomer which makes a side chain has the linear hydrocarbon structural unit S, the effect | action that the affinity with a solvent becomes high and a dispersion stability improves can be anticipated.

  The macromonomer (X) preferably has a site represented by the following formula (b-11).

R ^a11 has the same ^{meaning as} R ^a1 in formula (b-1). * Is a connecting part.

  The macromonomer (X) preferably has a site represented by any one of the following formulas (b-12a) to (b-12c). Hereinafter, these sites may be referred to as “specific polymerizable sites”.

R ^b2 has the same ^{meaning as} R ^a1 in formula (b-1). * Is a connecting part. ^RN has the same definition as the substituent T described later. An arbitrary substituent T may be substituted on the benzene ring of the formula (b-12c).
The structure part present at the end of the bond part of * is not particularly limited as long as the molecular weight as a macromonomer is satisfied, but a structure part composed of a carbon atom, an oxygen atom, and a hydrogen atom is preferable. At this time, it may have a substituent T described later, and may have, for example, a halogen atom (fluorine atom).

  Said macromonomer (X) is a compound which has a repeating unit represented by either of following formula (b-13a)-(b-13c) and (b-14a)-(b-14c). preferable.

R ^b2 and R ^b3 have the same ^meaning as R ^a1 .
An arbitrary substituent T may be substituted on the benzene ring of the formulas (b-13c) and (b-14c).

  Although na is not specifically limited, Preferably it is an integer of 1-6, More preferably, it is 1 or 2.

Ra represents a substituent (preferably an organic group) when na is 1, and represents a linking group when na is 2 or more.
Rb is a divalent linking group.
When Ra and Rb are linking groups, examples of the linking group include the following linking group L. Specifically, an alkane linking group having 1 to 30 carbon atoms (an alkylene group in the case of divalent), a cycloalkane linking group having 3 to 12 carbon atoms (a cycloalkylene group in the case of divalent), and an aryl having 6 to 24 carbon atoms. Linking group (arylene group in the case of divalent), heteroaryl linking group having 3 to 12 carbon atoms (heteroarylene group in the case of divalent), ether group (-O-), sulfide group (-S-), phosphinidene group ( -PR-: R is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms), a silylene group (-SiRR'-: R, R 'is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms), a carbonyl group, an imino group ( -NR ^N -: ^{R N} is as defined in below, here, the alkyl group of which a hydrogen atom or 1 to 6 carbon atoms is preferably an aryl group), or a combination thereof having 6 to 10 carbon atoms. Among them, an alkane linking group having 1 to 30 carbon atoms (an alkylene group in the case of divalent), an aryl linking group having 6 to 24 carbon atoms (an arylene group in the case of divalent), an ether group, a carbonyl group, or a combination thereof. It is preferable.
The linking group constituting Ra and Rb is preferably a linking structure composed of a carbon atom, an oxygen atom, and a hydrogen atom. Or it is also preferable that the coupling group which comprises Ra and Rb is a structure part which has the below-mentioned repeating unit (b-15). When Ra and Rb are linking groups, the number of atoms constituting the linking group and the number of linking atoms are as defined for the linking group L described later.

When Ra is a monovalent substituent, examples of the substituent T described later are exemplified, and among them, an alkyl group, an alkenyl group, and an aryl group are preferable. At this time, even if the linking group L is present and substituted, the linking group L may be present in the substituent.
Alternatively, when Ra is a monovalent substituent, the structure of —Rb—Rc or a structure having a repeating unit (b-15) described later is also preferred. Here, Rc includes examples of the substituent T described later, and among them, an alkyl group, an alkenyl group or an aryl group is preferable.

  At this time, each of Ra and Rb preferably contains at least a linear hydrocarbon structural unit having 1 to 30 carbon atoms (preferably an alkylene group), and preferably contains the linear hydrocarbon structural unit S. More preferred. In addition, each of Ra to Rc may have a linking group or a substituent, and examples thereof include a linking group L and a substituent T described later.

The macromonomer (X) preferably further has a repeating unit represented by the following formula (b-15).

^{Wherein, R b3} is the same meaning as ^{R b3} in the above formula (b-14a) ~ (b -14c).

R ^b4 represents a hydrogen atom or a substituent T described later, and is preferably a hydrogen atom, an alkyl group, an alkenyl group, or an aryl group. When R ^b4 is an alkyl group, an alkenyl group or an aryl group, it may further have a substituent T described later, and may have, for example, a halogen atom or a hydroxy group.

X represents a linking group, and examples of the linking group L can be given. Preferred are an ether group, a carbonyl group, an imino group, an alkylene group, an arylene group, or a combination thereof. Specific examples of the linking group in combination include a linking group composed of a carbonyloxy group, an amide group, an oxygen atom, a carbon atom, and a hydrogen atom. When R ^b4 and X contain carbon, the preferred carbon number is the same as the substituent T and linking group L described later. The preferable number of constituent atoms and the number of connecting atoms of the connecting group are also synonymous.

Examples of the substituent include a structure in which an arbitrary substituent is arranged at the terminal of the above linking group. Examples of the terminal substituent include the substituent T described later, and the example of R ¹ in the above formula (b-1) is preferable.
In addition, in this specification, it uses for the meaning containing the salt and its ion other than the said compound itself about the display of a compound (For example, when attaching | subjecting and attaching | subjecting a compound and an end). In addition, it is meant to include derivatives in which a part thereof is changed, such as introduction of a substituent, within a range where a desired effect is exhibited.

  In the present specification, a substituent that does not specify substitution / non-substitution (the same applies to a linking group) means that the group may have an arbitrary substituent. This is also synonymous for compounds that do not specify substitution / non-substitution. Preferred substituents include the following substituent T.

Examples of the substituent T include the following.
An alkyl group (preferably an alkyl group having 1 to 20 carbon atoms, such as methyl, ethyl, isopropyl, t-butyl, pentyl, heptyl, 1-ethylpentyl, benzyl, 2-ethoxyethyl, 1-carboxymethyl, etc.), alkenyl A group (preferably an alkenyl group having 2 to 20 carbon atoms, such as vinyl, allyl, oleyl, 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.), an aryl group (preferably an aryl group having 6 to 26 carbon atoms, for example, Phenyl, 1-naphthyl, 4-methoxyphenyl, -Chlorophenyl, 3-methylphenyl, etc.), a heterocyclic group (preferably a heterocyclic group having 2 to 20 carbon atoms, preferably a 5- or 6-membered heterocycle having at least one oxygen atom, sulfur atom, nitrogen atom) A cyclic group is preferable, for example, tetrahydropyran, tetrahydrofuran, 2-pyridyl, 4-pyridyl, 2-imidazolyl, 2-benzimidazolyl, 2-thiazolyl, 2-oxazolyl and the like, an alkoxy group (preferably having 1 to 20 carbon atoms) Alkoxy groups such as methoxy, ethoxy, isopropyloxy, benzyloxy and the like, aryloxy groups (preferably aryloxy groups having 6 to 26 carbon atoms, such as phenoxy, 1-naphthyloxy, 3-methylphenoxy, 4- Methoxyphenoxy, etc.), alkoxycarbonyl groups (preferred Or an alkoxycarbonyl group having 2 to 20 carbon atoms such as ethoxycarbonyl, 2-ethylhexyloxycarbonyl, etc., an aryloxycarbonyl group (preferably an aryloxycarbonyl group having 6 to 26 carbon atoms such as phenoxycarbonyl, 1-naphthyloxycarbonyl, 3-methylphenoxycarbonyl, 4-methoxyphenoxycarbonyl, etc.), an amino group (preferably containing an amino group having 0 to 20 carbon atoms, an alkylamino group, an arylamino group, such as amino, N , N-dimethylamino, N, N-diethylamino, N-ethylamino, anilino, etc.), sulfamoyl groups (preferably sulfamoyl groups having 0 to 20 carbon atoms, such as N, N-dimethylsulfamoyl, N-phenyl) Sulfamoyl etc.), acyl group (Preferably an acyl group having 1 to 20 carbon atoms, such as acetyl, propionyl, butyryl, etc.), an aryloyl group (preferably an aryloyl group having 7 to 23 carbon atoms, such as benzoyl), an acyloxy group (preferably carbon An acyloxy group having 1 to 20 atoms, such as acetyloxy, an aryloyloxy group (preferably an aryloyloxy group having 7 to 23 carbon atoms, such as benzoyloxy), and a carbamoyl group (preferably having carbon atoms) 1-20 carbamoyl groups such as N, N-dimethylcarbamoyl, N-phenylcarbamoyl, etc.), acylamino groups (preferably acylamino groups having 1-20 carbon atoms such as acetylamino, benzoylamino, etc.), alkylthio groups (Preferably an alkylthio group having 1 to 20 carbon atoms For example, methylthio, ethylthio, isopropylthio, benzylthio, etc.), arylthio groups (preferably arylthio groups having 6 to 26 carbon atoms, such as phenylthio, 1-naphthylthio, 3-methylphenylthio, 4-methoxyphenylthio, etc.), An alkylsulfonyl group (preferably an alkylsulfonyl group having 1 to 20 carbon atoms, such as methylsulfonyl and ethylsulfonyl), an arylsulfonyl group (preferably an arylsulfonyl group having 6 to 22 carbon atoms, such as benzenesulfonyl); An alkylsilyl group (preferably an alkylsilyl group having 1 to 20 carbon atoms, such as monomethylsilyl, dimethylsilyl, trimethylsilyl, triethylsilyl, etc.), an arylsilyl group (preferably an arylsilyl group having 6 to 42 carbon atoms) For instance, triphenylsilyl, etc.), a phosphoryl group (preferably a phosphate group 0-20 carbon atoms, for ^{example, -OP (= O) (R} P) 2), phosphonyl group (preferably 0 to 20 carbon atoms the phosphonyl group, for ^{example, -P (= O) (R} P) 2), a phosphinyl group (preferably a phosphinyl group having 0 to 20 carbon atoms, for example, ^-P (R _P) 2), (meth) acryloyl groups , (Meth) acryloyloxy group, hydroxyl group, cyano group, halogen atom (for example, fluorine atom, chlorine atom, bromine atom, iodine atom).
In addition, each of the groups listed as the substituent T may be further substituted with the substituent T described above.

When a compound or a substituent / linking group includes an alkyl group / alkylene group, an alkenyl group / alkenylene group, an alkynyl group / alkynylene group, etc., these may be cyclic or linear, and may be linear or branched These may be substituted as described above or may be unsubstituted.
Each substituent defined in the present specification may be substituted through the following linking group L within the scope of the effects of the present invention, or the linking group L may be present in the structure thereof. For example, the alkyl group / alkylene group, alkenyl group / alkenylene group and the like may further have the following hetero-linking group interposed in the structure.

Examples of the linking group L include a hydrocarbon linking group [an alkylene group having 1 to 10 carbon atoms (more preferably 1 to 6 carbon atoms, still more preferably 1 to 3), an alkenylene group having 2 to 10 carbon atoms (more preferably carbon atoms). 2 to 6, more preferably 2 to 4), an alkynylene group having 2 to 10 carbon atoms (more preferably 2 to 6, more preferably 2 to 4 carbon atoms), and an arylene group having 6 to 22 carbon atoms (more preferably). Is a carbon number 6-10)], hetero linking group [carbonyl group (—CO—), thiocarbonyl group (—CS—), ether group (—O—), thioether group (—S—), imino group (— NR ^N- ), imine linking group (R ^N -N = C <, -N = C (R ^N )-), sulfonyl group (-SO _2- ), sulfinyl group (-SO-), phosphate linking group ( -O-P (OH) (O) -O-), phosphonic acid Yuimoto (-P (OH) (O) -O-)], or a linking group is preferably a combination thereof. In addition, when condensing and forming a ring, the said hydrocarbon coupling group may form the double bond and the triple bond suitably, and may connect. The ring to be formed is preferably a 5-membered ring or a 6-membered ring. As the five-membered ring, a nitrogen-containing five-membered ring is preferable, and examples of the compound forming the ring include pyrrole, imidazole, pyrazole, indazole, indole, benzimidazole, pyrrolidine, imidazolidine, pyrazolidine, indoline, carbazole, or these And derivatives thereof. Examples of the 6-membered ring include piperidine, morpholine, piperazine, and derivatives thereof. Moreover, when an aryl group, a heterocyclic group, etc. are included, they may be monocyclic or condensed and may be similarly substituted or unsubstituted.

^RN is a hydrogen atom or a substituent. Examples of the substituent include an alkyl group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12, more preferably 1 to 6 and particularly preferably 1 to 3), and an alkenyl group (preferably having 2 to 24 carbon atoms and 2 -12 are more preferable, 2-6 are more preferable, 2-3 are particularly preferable, and an alkynyl group (C2-C24 is preferable, 2-12 are more preferable, 2-6 are more preferable, and 2-3 are Particularly preferred), an aralkyl group (preferably 7 to 22 carbon atoms, more preferably 7 to 14 carbon atoms, particularly preferably 7 to 10 carbon atoms), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 14 carbon atoms, and 6 to 6 carbon atoms). 10 is particularly preferred).

^RP is a hydrogen atom, a hydroxyl group, or a substituent. Examples of the substituent include an alkyl group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12, more preferably 1 to 6 and particularly preferably 1 to 3), and an alkenyl group (preferably having 2 to 24 carbon atoms and 2 -12 are more preferable, 2-6 are more preferable, 2-3 are particularly preferable, and an alkynyl group (C2-C24 is preferable, 2-12 are more preferable, 2-6 are more preferable, and 2-3 are Particularly preferred), an aralkyl group (preferably 7 to 22 carbon atoms, more preferably 7 to 14 carbon atoms, particularly preferably 7 to 10 carbon atoms), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 14 carbon atoms, and 6 to 6 carbon atoms). 10 is particularly preferred), an alkoxy group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12, even more preferably 1 to 6 and particularly preferably 1 to 3), an alkenyloxy group (having carbon numbers). To 24, more preferably 2 to 12, more preferably 2 to 6, particularly preferably 2 to 3, and alkynyloxy group (2 to 24 carbon atoms are preferred, 2 to 12 are more preferred, and 2 to 6 are preferred). More preferably, 2 to 3 are particularly preferable), an aralkyloxy group (preferably 7 to 22 carbon atoms, more preferably 7 to 14 carbon atoms, particularly preferably 7 to 10 carbon atoms), an aryloxy group (preferably 6 to 22 carbon atoms, 6 to 14 are more preferable, and 6 to 10 are particularly preferable.

In the present specification, the number of atoms constituting the linking group is preferably 1 to 36, more preferably 1 to 24, still more preferably 1 to 12, and 1 to 6. Is particularly preferred. The number of linking atoms in the linking group is preferably 10 or less, and more preferably 8 or less. The lower limit is 1 or more. The number of connected atoms refers to the minimum number of atoms that are located in a path connecting predetermined structural portions and are involved in the connection. For example, in the case of —CH ₂ —C (═O) —O—, the number of atoms constituting the linking group is 6, but the number of linking atoms is 3.
Specific examples of combinations of linking groups include the following. Oxycarbonyl group (—OCO—), carbonate group (—OCOO—), amide group (—CONH—), urethane group (—NHCOO—), urea group (—NHCONH—), (poly) alkyleneoxy group (— ( Lr-O) x-), carbonyl (poly) oxyalkylene group (-CO- (O-Lr) x-, carbonyl (poly) alkyleneoxy group (-CO- (Lr-O) x-), carbonyloxy ( Poly) alkyleneoxy group (—COO— (Lr—O) x—), (poly) alkyleneimino group (— (Lr—NR ^N ) x), alkylene (poly) iminoalkylene group (—Lr— (NR ^N —) lr) x-), carbonyl (poly) iminoalkylene group ^{(-CO- (NR N -Lr) x-} ), carbonyl (poly) alkyleneimino group (-CO- ^(lr-NR N) -), (Poly) ester group (-(CO-O-Lr) x-,-(O-CO-Lr) x-,-(O-Lr-CO) x-,-(Lr-CO-O) x -, - (Lr-O -CO) x -), ( poly) amide group ^{(- (CO-NR N -Lr} ) x -, - (NR N -CO-Lr) x -, - (NR N - ^{Lr-CO) x -, -} (Lr-CO-NR N) x -, - (Lr-NR N -CO) x-) is .x which is such an integer of 1 or more, preferably from 1 to 500, 1-100 are more preferable.

Lr is preferably an alkylene group, an alkenylene group or an alkynylene group. 1-12 are preferable, as for carbon number of Lr, 1-6 are more preferable, and 1-3 are especially preferable. A plurality of Lr, R ^N , R ^P , x, etc. need not be the same. The direction of the linking group is not limited by the above description, and may be understood as appropriate according to a predetermined chemical formula.

  As the macromonomer, a macromonomer having an ethylenically unsaturated bond at the terminal may be used. Here, the macromonomer is composed of a polymer chain portion and a polymerizable functional group portion having an ethylenically unsaturated bond at its terminal.

The copolymerization ratio of the repeating unit derived from the macromonomer (X) is not particularly limited, but is preferably 1% by mass or more, more preferably 3% by mass or more in the particulate polymer, and more preferably 5% by mass or more. It is particularly preferred that As an upper limit, it is preferable that it is 50 mass% or less, It is more preferable that it is 30 mass% or less, It is especially preferable that it is 20 mass% or less.
The estimated structural formulas of the macromonomer synthesized below and (ii) the polymer belonging to the particulate polymer B are shown below.

The content of the particulate polymer in the solid electrolyte composition is preferably 0.1 parts by mass or more with respect to 100 parts by mass of the inorganic solid electrolyte (including this when an active material is used). The amount is more preferably 3 parts by mass or more, and particularly preferably 1 part by mass or more. The upper limit is preferably 20 parts by mass or less, more preferably 10 parts by mass or less, and particularly preferably 5 parts by mass or less.
For the solid electrolyte composition, in the solid content, the particulate polymer is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, and 1% by mass or more. Is particularly preferred. The upper limit is preferably 20% by mass or less, more preferably 10% by mass or less, and particularly preferably 5% by mass or less.

By using the particulate polymer within the above range, it is possible to more effectively achieve both the binding property of the inorganic solid electrolyte and the suppression property of the interface resistance.
In addition, as mentioned above, you may use the binder applied to this invention combining another binder and various additives other than what consists of said specific particulate polymer. The above blending amount is defined as the amount of particulate polymer, but may be read as the total amount of binder.

(Lithium salt)
The lithium salt that can be used in the present invention is preferably a lithium salt that is usually used in this type of product, and is not particularly limited. For example, those described below are preferable.

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

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

(L-3) Oxalatoborate salt: lithium bis (oxalato) borate, lithium difluorooxalatoborate and the like.
Among these, LiPF ₆ , LiBF ₄ , LiAsF ₆ , LiSbF ₆ , LiClO ₄ , Li (Rf ¹ SO ₃ ), LiN (Rf ¹ SO ₂ ) ₂ , LiN (FSO ₂ ) ₂ , and LiN (Rf ¹ SO ₂ ) (Rf ² SO ₂ ), preferably LiPF ₆ , LiBF ₄ , LiN (Rf ¹ SO ₂ ) ₂ , LiN (FSO ₂ ) ₂ , and LiN (Rf ¹ SO ₂ ) (Rf ² SO ₂ ) More preferred are imide salts. Here, Rf ¹ and Rf ² each independently represents a perfluoroalkyl group.
In addition, the electrolyte used for electrolyte solution may be used individually by 1 type, or may combine 2 or more types arbitrarily.

  The content of the lithium salt is preferably more than 0 parts by mass with respect to 100 parts by mass of the solid electrolyte, and more preferably 5 parts by mass or more. As an upper limit, 50 mass parts or less are preferable, and 20 mass parts or less are more preferable.

(Dispersion medium)
In the solid electrolyte composition of the present invention, a dispersion medium in which the above components are dispersed may be used. Examples of the dispersion medium include a water-soluble organic solvent. 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, 2 -Methyl-2,4-pentanediol, 1,3-butanediol, 1,4-butanediol.

  Examples of the ether compound solvent include alkylene glycol alkyl ether (ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol, dipropylene glycol, propylene glycol monomethyl ether, diethylene glycol monomethyl ether, triethylene glycol, polyethylene glycol, propylene glycol monomethyl ether, diethylene glycol, Propylene glycol monomethyl ether, tripropylene glycol monomethyl ether, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether, etc.), dimethyl ether, diethyl ether, tetrahydrofuran, cyclopentyl methyl ether, dimethoxyethane, and 1,4-dioxane.

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

  Examples of the ketone compound solvent include acetone, methyl ethyl ketone, methyl isobutyl ketone, diethyl ketone, dipropyl ketone, diisopropyl ketone, diisobutyl ketone, and cyclohexanone.

  Examples of the aromatic compound solvent include benzene, toluene, xylene, chlorobenzene, and dichlorobenzene.

  Examples of the aliphatic compound solvent include hexane, heptane, octane, decane, and dodecane.

  Examples of the nitrile compound solvent include acetonitrile, propionitrile, butyronitrile, isobutyronitrile, and benzonitrile.

In the present invention, among these, an ether compound solvent, a ketone compound solvent, an aromatic compound solvent, and an aliphatic compound solvent are preferably used, and an aromatic compound solvent and an aliphatic compound solvent are more preferably used. The dispersion medium preferably has a boiling point of 50 ° C. or higher, more preferably 80 ° C. or higher at normal pressure (1 atm). The upper limit is preferably 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 this invention, the quantity of the dispersion medium in a solid electrolyte composition can be made into arbitrary quantity with the balance of the viscosity of a solid electrolyte composition, and a dry load. Generally, it is preferable that it is 20-99 mass% in a solid electrolyte composition.

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

As the shape of the current collector, a film sheet shape is usually used, but a net, a punched material, a lath body, a porous body, a foamed body, a molded body of a fiber group, and the like can also be used.
Although it does not specifically limit as thickness of the said electrical power collector, 1 micrometer-500 micrometers are preferable. Moreover, it is also preferable that the current collector surface is roughened by surface treatment.

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

<Uses of all-solid-state secondary batteries>
The all solid state secondary battery according to 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, a pen input personal computer, a mobile personal computer, an electronic book player, a mobile phone, a cordless phone, a pager, a handy terminal, a mobile fax machine, a mobile phone Copy, portable printer, headphone stereo, video movie, LCD TV, handy cleaner, portable CD, minidisc, electric shaver, transceiver, electronic notebook, calculator, memory card, portable tape recorder, radio, backup power supply, memory card, etc. It is done. Other consumer products include automobiles, electric vehicles, motors, lighting equipment, toys, game equipment, road conditioners, watches, strobes, cameras, medical equipment (such as pacemakers, hearing aids, and shoulder grinders). Furthermore, it can be used for various military use and space use. Moreover, it can also combine with a solar cell.

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

According to a preferred embodiment of the present invention, the following applications are derived.
(1) A solid electrolyte composition (an electrode composition for a negative electrode) containing an active material capable of inserting and releasing ions of metals belonging to Group 1 or Group 2 of the Periodic Table.
(2) A battery electrode sheet obtained by forming the solid electrolyte composition on a metal foil.
(3) An all-solid secondary battery comprising a positive electrode active material layer, a negative electrode active material layer, and a solid electrolyte layer, wherein the negative electrode is a layer composed of the solid electrolyte composition.
(4) The manufacturing method of the battery electrode sheet which arrange | positions the said solid electrolyte composition on metal foil, and forms this into a film.
(5) The manufacturing method of the all-solid-state secondary battery which manufactures an all-solid-state secondary battery via the manufacturing method of the said battery electrode sheet.
Moreover, in preferable embodiment of this invention, it has the advantage that inhibitory factors, such as a side reaction accompanying it, can form a polymer particle without adding surfactant and can reduce it. In addition, the inversion emulsification step can be omitted, which leads to relatively improved production efficiency.

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

  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, “parts” and “%” are based on mass unless otherwise specified.

Synthesis of particulate polymer used in the present invention

Synthesis of Exemplary Compound (A-56) In a 200 mL three-neck flask, 13.2 g of dicyclohexylmethane-4,4′-diisocyanate, 2.6 g of 1,4-butanediol, polytetramethylene glycol (weight average molecular weight 650) 6 0.5 g, Blemmer GLM (trade name, manufactured by NOF Corporation) 0.8 g, 2,2- (bishydroxymethyl) propionic acid 0.7 g were added, and tetrahydrofuran 56 g was further added and dissolved by heating at 60 ° C. To this solution, 50 mg of Neostan U-600 (trade name, manufactured by Nitto Kasei Co., Ltd.) was added over 10 minutes, and the mixture was heated and stirred at 60 ° C. for 5 hours. 10 mL of methanol was added to the obtained polymer solution and stirred at 60 ° C. for 1 hour to stop the polymerization. This polymer solution was crystallized from 1 L of methanol, and the polymer solid was vacuum-dried at 80 ° C. for 6 hours to obtain a polymer represented by the exemplary compound (A-56). The weight average molecular weight of the obtained polymer was 126,900, and the glass transition temperature was −15 ° C.

Synthesis of Exemplary Compound (A-57) A polymer shown in Exemplary Compound (A-57) was obtained by a method similar to the synthesis of Exemplary Compound (A-56).

Synthesis of macromonomer used in the present invention

Synthesis of Exemplified Compound M-1 Glycidyl methacrylate (Tokyo Chemical Industry Co., Ltd.) was added to a self-condensate of 12-hydroxystearic acid (manufactured by Wako Pure Chemical Industries, Ltd.) (number average molecular weight converted to polystyrene by GPC: 2,000). )) Was reacted in toluene at 110 ° C. for 10 hours. Next, this reaction product was mixed with methyl methacrylate and glycidyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) at a ratio of 1: 0.99: 0.01 (molar ratio, reaction product: methyl methacrylate: glycidyl methacrylate). The mixture was stirred in toluene in the presence of azoisobutyronitrile at 80 ° C. for 8 hours to obtain a polymer. Next, this monomer was reacted with acrylic acid (manufactured by Wako Pure Chemical Industries, Ltd.) in toluene at 110 ° C. for 10 hours to synthesize macromonomer M-1. Macromonomer M-1 had an SP value of 9.3 and a number average molecular weight of 20,000.
The number average molecular weight was measured in the same manner as the weight average molecular weight measuring method described later.

Preparation of particulate polymer dispersion used in the present invention (1) Preparation of particulate polymer dispersion by ball mill method Into a 45 mL zirconia container (manufactured by Fritsch), 180 zirconia beads having a diameter of 5 mm are charged and exemplified compounds ( A-56) 1.0 g and 15.0 g of toluene as a dispersion medium were added. Thereafter, the container is set on a planetary ball mill P-7 (trade name) manufactured by Fritsch, and the mechanical dispersion is continued for 2 hours at a temperature of 25 ° C. and a rotation speed of 300 rpm, whereby the exemplified compound (A-56) is pulverized. A dispersion was prepared. The average particle diameter in terms of sphere of this particulate polymer was 0.96 μm.

For the exemplified compound (A-57), a particulate polymer dispersion was prepared in the same manner as described above.
In addition, the sphere conversion average particle diameter, the weight average molecular weight, the glass transition temperature, and the solid component concentration of the prepared exemplary compounds are collectively shown in Table 2 below.

(2) Preparation of particulate polymer dispersion by latex method In a 2 L three-necked flask equipped with a reflux condenser and a gas introduction cock, 7.2 g of 40% by mass of the macromonomer M-1 prepared above, acrylic acid 12.4 g of methyl (manufactured by Wako Pure Chemical Industries, Ltd.), 6.7 g of methyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.), 207 g of heptane (manufactured by Wako Pure Chemical Industries, Ltd.), azoiso After adding 1.4 g of butyronitrile and introducing nitrogen gas at a flow rate of 200 mL / min for 10 minutes, the temperature was raised to 100 ° C. In this container, a monomer mixture (93.1 g of a 40% by weight heptane solution of macromonomer M-1 prepared above, 222.8 g of methyl acrylate, 120.0 g of methyl methacrylate, 300.0 g of heptane, (Liquid mixed with 2.1 g of isobutyronitrile) was added dropwise over 4 hours. After completion of the dropwise addition, 0.5 g of azoisobutyronitrile was added. Thereafter, stirring was continued at 100 ° C. for 2 hours, followed by cooling to room temperature and filtering to obtain a dispersion of particulate polymer B-1. The solid content (particulate polymer B-1) concentration was 39.2%, and the sphere-converted average particle size was 0.20 μm.

Dispersions of particulate polymers B-2 and B-3 shown in Table 1 below were prepared in the same manner as the dispersion of particulate polymer B-1.
In addition, the sphere conversion average particle diameter, glass transition temperature, and solid component concentration of the prepared particulate polymers B-1 to B-3 are collectively shown in Table 2 below.

<Notes on Table 1>
MC1-3: monomer constituting the main chain, compound numbers refer to the examples of the above exemplified compounds MM: monomer constituting the side chain (macromonomer)

(Measurement of weight average molecular weight)
As the weight average molecular weight of the particulate polymer used in the present invention, a value measured by gel permeation chromatography (GPC) in terms of the following standard sample was adopted. The measurement apparatus and measurement conditions were based on the following condition 1 and were set to condition 2 depending on the solubility of the sample. However, depending on the polymer type, an appropriate carrier (eluent) and a column suitable for the carrier were selected as appropriate.
(Condition 1)
Measuring instrument: EcoSEC HLC-8320 (trade name, manufactured by Tosoh Corporation)
Column: Two TOSOH TSKgel Super AWM-H (trade name, manufactured by Tosoh Corporation) are connected Carrier: 10 mM LiBr / N-methylpyrrolidone Measurement temperature: 40 ° C.
Carrier flow rate: 1.0 ml / min
Sample concentration: 0.1% by mass
Detector: RI (refractive index) detector Standard sample: Polystyrene (Condition 2)
Measuring instrument: Same as above Column: TOSOH TSKgel Super HZM-H,
TOSOH TSKgel Super HZ4000,
TOSOH TSKgel Super HZ2000 (both trade names, manufactured by Tosoh Corporation)
Carrier: Tetrahydrofuran Measurement temperature: 40 ° C
Carrier flow rate: 1.0 ml / min
Sample concentration: 0.1% by mass
Detector: RI (refractive index) detector Standard sample: Polystyrene

<Measurement method of Tg>
The glass transition temperature (Tg) of the prepared particulate polymer was measured under the following conditions for the obtained particulate polymer using a differential scanning calorimeter “X-DSC7000” (manufactured by SII Nanotechnology Co., Ltd.). . The measurement was performed twice on the same sample, and the second measurement result was 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 was calculated by rounding off the decimal point of the intermediate temperature between the lowering start point and the lowering end point of the DSC chart.

(Measurement of volume average particle diameter of particulate polymer)
The volume average particle diameter of the particulate polymer is measured using the particulate polymer dispersion prepared above, and using a laser diffraction / scattering type particle size distribution analyzer LA-920 (trade name, manufactured by HORIBA). The volume average particle diameter (sphere conversion average particle diameter) of the polymer was measured. In Table 2 below, the measured sphere-converted average particle diameter is described as “particle diameter”.

<Measurement method of solid content concentration>
10 g of the produced particulate polymer dispersion was weighed on an aluminum cup, dried on a hot plate at 170 ° C. for 6 hours, and then the weight of the remaining amount excluding the weight of the aluminum cup was measured. The proportion of the remaining amount in 10 g initially weighed was defined as the solid content concentration.

<Notes on the table>
(1) PVDF: polyvinylidene fluoride (2) AcBu-MA-St: butyl acrylate-methacrylic acid-styrene copolymer According to the description in paragraph [0087] of JP2013-008611A, an emulsion polymerization method is used. Synthesized.
(3) In the dispersion liquid (C-1), since PVDF was dissolved in the dispersion medium, the sphere-converted average particle diameter in the dispersed state could not be measured.

Synthesis of sulfide-based inorganic solid electrolyte (Li-PS-based glass) Ohtomo, A .; Hayashi, M .; Tatsumisago, Y. et al. Tsuchida, S .; Hama, 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), pp872-873.

Specifically, in a glove box under an argon atmosphere (dew point −70 ° C.), 2.42 g of lithium sulfide (Li ₂ S, manufactured by Aldrich, purity> 99.98%), 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 mortar. Incidentally, Li ₂ S and _P 2 _{S 5} at a molar ratio of _{Li 2 S: P 2 S 5} = 75: was 25.
66 zirconia beads having a diameter of 5 mm were put into a 45 mL container (manufactured by Fritsch) made of zirconia, the whole mixture of lithium sulfide and diphosphorus pentasulfide was put therein, and the container was completely sealed under an argon atmosphere. A container is set in a planetary ball mill P-7 manufactured by Fricht Co., 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 material (Li—PS glass) 6.20 g. Got.

<Example 1>
Preparation of Secondary Battery Negative Electrode Composition (S-1) Into a zirconia 45 mL container (manufactured by Fritsch), 180 pieces of zirconia beads having a diameter of 5 mm were charged and 4.9 g of the Li-PS system glass synthesized above. The dispersion (B-1) was charged in such an amount that the amount of the particulate polymer B-1 was 0.2 g, and 12.3 g of heptane was added as a dispersion medium. The container was set on a planetary ball mill P-7 manufactured by Fricht Co., and mixing was continued for 2 hours at a temperature of 25 ° C. and a rotation speed of 300 rpm. After that, 2.2 g of acetylene black as a conductive additive and NiTiSi as an active material (average particle size of 3 μm) , Made by Nippon Steel & Sumikin Co., Ltd.), put the container in the planetary ball mill P-7, and continue mixing at a temperature of 25 ° C. and a rotation speed of 200 rpm for 15 minutes. The product (S-1) was prepared (hereinafter, the secondary battery negative electrode composition is also referred to as a negative electrode composition).

(3) Preparation of Composition for Negative Electrode (S-2) to (S-7), (T-1) and (T-2) The composition for negative electrode described above, except that the composition shown in Table 3 below was changed. Negative electrode compositions (S-2) to (S-7), (T-1), and (T-2) were prepared in the same manner as (S-1).

Table 3 below summarizes the components of the negative electrode composition.
Here, the negative electrode compositions (S-1) to (S-7) are the negative electrode compositions of the present invention, and the negative electrode compositions (T-1) and (T-2) are comparative negative electrode compositions. It is a thing.

<Notes on the table>
(1) Li-PS: Li-PS-based glass synthesized above (2) SiO: Silicon monoxide (SiO molar fraction, Si: 0.5, O: 0.5), average particle Diameter 5 μm, manufactured by Osaka Titanium Technologies Co., Ltd. (3) NiTiSi: Alloy made of Ni, Ti, Si (molar fraction of NiTiSi, Ni: 0.04, Ti: 0.04, Si: 0.92)
(4) AB: Acetylene black (5) VGCF: Vapor growth carbon fiber (6) Graphite: Nippon Graphite Industries Co., Ltd., average particle size 20 μm
(7) Si: manufactured by Toshima Seisakusho Co., Ltd., average particle size 75 μm

Preparation of Solid Electrolyte Composition (K-1) 180 zirconia beads having a diameter of 5 mm were put into a 45 mL container (manufactured by Fritsch) made of zirconia, and 9.0 g of the Li-PS system glass synthesized above and a dispersion liquid. (B-1) was charged in an amount such that the particulate polymer B-1 was 0.3 g, and 15.0 g of heptane was added as a dispersion medium. Thereafter, the container was set on a planetary ball mill P-7 manufactured by Fritsch, and stirring was continued for 2 hours at a temperature of 25 ° C. and a rotation speed of 300 rpm to prepare a solid electrolyte composition (K-1).

Preparation of composition for secondary battery positive electrode (U-1) Into a 45 mL container (manufactured by Fritsch) made of zirconia, 180 pieces of zirconia beads having a diameter of 5 mm were charged, and 2.7 g of the Li—PS system glass synthesized above. The dispersion (B-1) was charged in such an amount that 0.3 g of the particulate polymer B-1 and 12.3 g of heptane was added as a dispersion medium. The container is set in a planetary ball mill P-7 manufactured by Frichtu, and after mixing for 2 hours at a temperature of 25 ° C. and a rotation speed of 300 rpm, 7.0 g of NMC (manufactured by Nippon Chemical Industry Co., Ltd.) is charged as the active material. Similarly, a container was set in the planetary ball mill P-7, and mixing was continued at a temperature of 25 ° C. and a rotation speed of 200 rpm for 15 minutes to prepare a composition (U-1) for a secondary battery positive electrode (hereinafter referred to as a secondary battery). The positive electrode composition is also referred to as a positive electrode composition).

Preparation of positive electrode sheet for secondary battery The composition for positive electrode of the secondary battery prepared above was applied onto an aluminum foil having a thickness of 20 μm with an applicator with adjustable clearance, heated at 80 ° C. for 1 hour, and further at 110 ° C. The coating solvent was dried by heating for 1 hour. Then, it heated and pressurized so that it might become arbitrary density using the heat press machine, and produced the positive electrode sheet for secondary batteries.

Production of Secondary Battery Electrode Sheet On the positive electrode sheet for secondary battery produced above, the solid electrolyte composition prepared above was applied with an applicator with adjustable clearance, heated at 80 ° C. for 1 hour, and further 110 Heated at 0 ° C for 1 hour. Then, the composition for secondary battery negative electrodes prepared above was further applied on the dried solid electrolyte composition, heated at 80 ° C. for 1 hour, and further heated at 110 ° C. for 1 hour. A copper foil having a thickness of 20 μm was combined on the negative electrode active material layer, and heated and pressurized to a desired density using a heat press, and the test numbers of secondary battery electrode sheets shown in Table 4 below were obtained. 101-107 and c11-c12 were produced. The secondary battery electrode sheet has the configuration of FIG. Each of the positive electrode active material layer, the negative electrode active material layer, and the solid electrolyte layer has a film thickness described in Table 4.

Production of an all-solid secondary battery The secondary battery electrode sheet 15 produced above was cut into a disk shape having a diameter of 14.5 mm and placed in a stainless steel 2032 type coin case 14 incorporating a spacer and a washer. Using the test specimen shown, a restraint pressure (screw tightening pressure: 8 N) was applied from the outside of the coin case 14, and test Nos. Described in Table 4 below were applied. 101 to 107 and c11 to c12 all solid state secondary battery 13 were manufactured. In FIG. 2, 11 is an upper support plate, 12 is a lower support plate, and S is a screw.
Test No. manufactured above. The following evaluation was performed for the all-solid secondary batteries 101 to 107 and c11 to c12.

<Measurement of discharge capacity>
The all-solid-state secondary battery produced above was measured by a charge / discharge evaluation apparatus “TOSCAT-3000” (trade name) manufactured by Toyo System Co., Ltd.
Charging was performed at a current value of 0.2 mA until the battery voltage reached 4.2 V, and discharging was performed at a current value of 0.2 mA until the battery voltage reached 3.0 V. The same charge / discharge was repeated, and the discharge capacity at the third cycle was defined as the battery discharge capacity. In Table 4 below, the discharge capacity is described as “capacity”.

<Measurement of capacity density>
It calculated by dividing the capacity | capacitance measured above by the volume of the composition which comprises a battery.

<Evaluation of cycle characteristics>
The cycle characteristics of the all-solid secondary battery produced above were measured by a charge / discharge evaluation apparatus “TOSCAT-3000” (trade name) manufactured by Toyo System Co., Ltd.
Charging / discharging was performed in the same manner as the capacity calculation. The discharge capacity at the third cycle was set to 100, and the following criteria were evaluated from the number of cycles when the discharge capacity was less than 80. In addition, evaluation "C" or more is a pass level of this test.
A: 50 times or more B: 40 times or more and less than 50 times C: 30 times or more and less than 40 times D: Less than 30 times

<Notes on Table 4>
Weight per unit area: Means the mass (mg) of the negative electrode active material per unit area (cm ² ) of the negative electrode active material layer.

As is apparent from Table 4, test No. 1 using an active material containing Si satisfying the formula (1) of the present invention for the negative electrode. It can be seen that 101 to 107 have a large current density and excellent cycle characteristics.
On the other hand, since the active material in the negative electrode is graphite, c11 has a capacity density of Test No. It was low compared with 101-107. Moreover, although c12 used Si for the negative electrode as an active material in the negative electrode, it did not satisfy the formula (1) of the present invention, so the cycle characteristics did not reach the acceptable level.

DESCRIPTION OF SYMBOLS 1 Negative electrode collector 2 Negative electrode active material layer 3 Solid electrolyte layer 4 Positive electrode active material layer 5 Positive electrode collector 6 Working part 10 All-solid secondary battery 11 Upper support plate 12 Lower support plate 13 Coin battery 14 Coin case 15 Secondary Battery electrode sheet S Screw

Claims (13)

A solid electrolyte composition comprising an inorganic solid electrolyte having conductivity of metal ions belonging to Group 1 or Group 2 of the periodic table, at least one active material represented by the following formula (1), and a particulate polymer object.
Si _x M _(1-x) Formula (1)
In the formula (1), x represents a number of 0.01 or more and less than 1, and means a mole fraction. M represents a chalcogen element, a metalloid element, an alkali metal element, an alkaline earth metal element, a transition metal element, or a combination thereof.   2. The solid electrolyte composition according to claim 1, wherein in the formula (1), x is 0.1 or more and 0.99 or less.   Furthermore, the solid electrolyte composition of Claim 1 or 2 containing a conductive support agent.   The solid electrolyte composition according to claim 1, wherein the active material is an alloy containing Si element.   The solid electrolyte composition according to claim 1, wherein the active material has an average particle size of 0.1 to 60 μm.   The solid electrolyte composition according to any one of claims 1 to 5, wherein an average particle size of the particulate polymer is 0.02 µm or more.   The solid electrolyte composition according to claim 1, wherein the particulate polymer has a glass transition temperature of 50 ° C. or lower. The solid electrolyte composition according to any one of claims 1 to 7, wherein the particulate polymer has a unit structure represented by the following group I.

R ¹ , R ² , R ⁵ and R ⁶ each independently represents an alkylene group, an arylene group or a combination thereof. R ³ represents an alkyl group, an alkenyl group, an aryl group or an aralkyl group. R ⁴ represents an aromatic or aliphatic tetravalent linking group. R ⁷ represents an alkyl group, an alkenyl group, an aryl group or an aralkyl group. * Represents a binding site. A positive electrode active material layer, an inorganic solid electrolyte layer, and a negative electrode active material layer, and the negative electrode active material layer includes an active material represented by the following formula (1) and a particulate polymer. Next battery.
Si _x M _(1-x) Formula (1)
In the formula (1), x represents a number of 0.01 or more and less than 1, and M represents a chalcogen element, a metalloid element, an alkali metal element, an alkaline earth metal element, a transition metal element, or a combination thereof. .   The battery electrode sheet which formed the solid electrolyte composition of any one of Claims 1-8 into a film on the electrical power collector.   The manufacturing method of the electrode sheet for batteries which forms the solid electrolyte composition of any one of Claims 1-8 on a collector.   An all-solid-state secondary battery comprising the battery electrode sheet according to claim 10.   The manufacturing method of the all-solid-state secondary battery which manufactures an all-solid-state secondary battery using the battery electrode sheet of Claim 10.

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