JPWO2020110993A1 - Electrodes for inorganic solid electrolyte secondary batteries, and inorganic solid electrolyte secondary batteries - Google Patents

Abstract

Provided is a novel electrode for a solid electrolyte secondary battery that exhibits excellent charge / discharge characteristics in a solid electrolyte secondary battery. An electrode for a solid electrolyte secondary battery comprising an electrode material layer containing an ion conductive polymer material having an ethylene oxide unit in a side chain and an ion conductive polymer material and a lithium salt compound, and an active material.

Description

The present invention relates to an electrode for an inorganic solid electrolyte secondary battery, a method for producing the same, and an inorganic solid electrolyte secondary battery.

Conventionally, as a non-aqueous electrolyte secondary battery typified by a lithium ion battery, a solution or a paste-like electrolyte has been used from the viewpoint of ionic conductivity. However, since there is a risk of equipment damage due to liquid leakage, various safety measures are required, which is a barrier to the development of large batteries.

On the other hand, solid electrolytes in which electrolytes such as polymer solid electrolytes and inorganic solid electrolytes are solidified have been proposed. Polymer solid electrolytes generally have advantages such as excellent flexibility, bendability, and moldability, and increase the degree of freedom in designing applied devices. However, due to poor load characteristics and low temperature characteristics, high temperature is high. It has the disadvantage that it is limited to operating battery applications. On the other hand, the inorganic solid electrolyte has higher ionic conductivity than the polymer solid electrolyte, but the electrolyte is crystalline or amorphous, and it is difficult to alleviate the volume change due to the positive and negative electrode active materials during charging and discharging. Since the interface resistance between the electrode and the electrolyte is high, there is a problem that the charge / discharge characteristics are insufficient.

As a method for reducing the resistance at the interface between the inorganic solid electrolyte and the electrode, for example, in Patent Document 1, the active material is dispersed in a solvent containing a lithium ion conductive binder, a sulfide-based solid electrolyte is added, and after heating and drying. , Forming an active material sheet. However, when the active material and the lithium ion conductive binder are dispersed to prepare an electrode, voids are formed in the electrode. In the electrolytic solution system, the voids in the electrode are filled with the organic electrolytic solution, which contributes to the ionic conductivity in the electrode. However, since the voids are present in the electrode containing the sulfide-based solid electrolyte, the voids are particularly present. , It becomes a disadvantageous factor for the volume energy density. Further, the amount of the sulfide-based solid electrolyte added is 25 to 100 parts by mass with respect to 100 parts by mass of the active material, and the amount of the active material of the electrode is small, which is not suitable for a battery having a high energy density.

Further, for example, in Patent Document 2, a polymer compound, an electrolyte salt, and an electrode active material are put into a diluent, and after heating and stirring, a coated electrode active material is obtained. This method is effective for the binding property between active substances, but as in Patent Document 1, voids are formed in the electrodes.

Further, as a method of impregnating the electrode with the polymer solid electrolyte, for example, in the example of Patent Document 3, _{there is a description of impregnating polyethylene oxide in a monomer form and LiBF 4} for polymerization, but polyethylene oxide is further polymerized. There is no known way to do it. Further, polyethylene oxide cannot be crosslinked even if a polymerization initiator such as peroxide is used. Polyethylene oxide has high crystallinity, and when it becomes a melting point (60 ° C.) or lower, it loses its flexibility and its binding property becomes weak as it crystallizes. Further, when the temperature exceeds the melting point, the polyethylene oxide melts, so that the shape cannot be maintained, and there is a problem that the binding property is weakened. With polyethylene oxide, it is difficult to reduce the interface resistance of the inorganic solid electrolyte.

Japanese Unexamined Patent Publication No. 2010-33918 Japanese Unexamined Patent Publication No. 2016-197590 Japanese Unexamined Patent Publication No. 2000-138073

An object of the present invention is to provide a novel electrode for an inorganic solid electrolyte secondary battery that exhibits excellent charge / discharge characteristics in an inorganic solid electrolyte secondary battery. Further, it is also an object of the present invention to provide a method for manufacturing an electrode for the inorganic solid electrolyte secondary battery and an inorganic solid electrolyte secondary battery using the electrode for the inorganic solid electrolyte secondary battery.

The present inventor has made diligent studies to solve the above problems. As a result, the electrode for a solid electrolyte secondary battery provided with an electrode material layer containing an ionic conductive polymer having an ethylene oxide unit in the side chain and an ionic conductive polymer material containing a lithium salt compound and an active material has become a solid electrolyte secondary. It has been found that the next battery exhibits excellent charge / discharge characteristics. The present invention has been completed by further studies based on such findings.

That is, the present invention provides the inventions of the following aspects.
Item 1. An electrode for an inorganic solid electrolyte secondary battery, comprising an electrode material layer containing an ionic conductive polymer having an ethylene oxide unit in a side chain and an ionic conductive polymer material containing a lithium salt compound, and an active material.
Item 2. The active material is LiMO ₂ , LiM ₂ O ₄ , Li ₂ MO ₃ , LiMEO ₄ (M in the formula is composed of a transition metal and contains at least one of Co, Mn, Ni, Cr, Fe and Ti). Item 2. The electrode for an inorganic solid electrolyte secondary battery according to Item 1, wherein E is at least one selected from the group consisting of at least one of P and Si).
Item 3. Item 2. The electrode for an inorganic solid electrolyte secondary battery according to Item 1, wherein the active material is at least one selected from the group consisting of a carbon material, a silicon-based compound, and a tin-based compound.
Item 4. Item 2. The electrode for an inorganic solid electrolyte secondary battery according to any one of Items 1 to 3, wherein the ionic conductive polymer is a polyether having an ethylene oxide unit in the side chain.
Item 5. Item 6. The electrode for an inorganic solid electrolyte secondary battery according to any one of Items 1 to 4, which is used for a solid electrolyte secondary battery together with an inorganic solid electrolyte.
Item 6. Item 5. The electrode for an inorganic solid electrolyte secondary battery according to Item 5, wherein the inorganic solid electrolyte is an oxide-based solid electrolyte or a sulfide-based solid electrolyte.
Item 7. A method for producing an electrode for an inorganic solid electrolyte secondary battery, comprising a step of impregnating a layer containing an active material with an ionic conductive polymer material having an ionic conductive polymer having an ethylene oxide unit in a side chain and an ionic conductive polymer material containing a lithium salt compound.
Item 8. Item 2. The method for producing an electrode for an inorganic solid electrolyte secondary battery, which comprises a step of cross-linking the layer impregnated with the ion conductive polymer material by heating or irradiation with active energy rays.
Item 9. An inorganic solid electrolyte secondary battery comprising the electrode for the inorganic solid electrolyte secondary battery according to any one of Items 1 to 6.

According to the present invention, it is possible to provide a novel electrode for an inorganic solid electrolyte secondary battery that exhibits excellent charge / discharge characteristics in the inorganic solid electrolyte secondary battery. Further, according to the present invention, it is also possible to provide a method for manufacturing the electrode for the inorganic solid electrolyte secondary battery and an inorganic solid electrolyte secondary battery using the electrode for the inorganic solid electrolyte secondary battery.

The electrode for an inorganic solid electrolyte secondary battery of the present invention comprises an ionic conductive polymer material containing an ionic conductive polymer having an ethylene oxide unit in a side chain and a lithium salt compound, and an electrode material layer containing an active material. It is a feature. The electrode for an inorganic solid electrolyte secondary battery of the present invention has such a configuration, so that the inorganic solid electrolyte secondary battery can exhibit excellent charge / discharge characteristics.

More specifically, in the electrode for an inorganic solid electrolyte secondary battery of the present invention (hereinafter, may be referred to as “the electrode of the present invention”), in addition to the active material, the above-mentioned ion conductive polymer is further used. Since the material is contained in the electrode material layer, the electrode material such as the active material contained in the electrode material layer (specifically, the active material particles, the binder, the conductive auxiliary agent, the thickener, the inorganic solid electrolyte, etc.) It is considered that the voids of)) are filled with the ion conductive polymer material, the interfacial resistance inside the electrode material layer is effectively reduced, and as a result, excellent charge / discharge characteristics are exhibited. Further, the inorganic solid electrolyte secondary battery may be used in a high temperature environment (for example, a high temperature environment of 100 ° C. or higher), but by using the electrode of the present invention, excellent charge / discharge characteristics are exhibited in the high temperature environment. To. Hereinafter, the electrode for an inorganic solid electrolyte secondary battery of the present invention, a method for producing the same, and an inorganic solid electrolyte secondary battery using the electrode for the inorganic solid electrolyte secondary battery of the present invention will be described in detail.

In this specification, the numerical value connected by "-" means a numerical range including the numerical values before and after "-" as the lower limit value and the upper limit value. When multiple lower limit values and multiple upper limit values are described separately, any lower limit value and upper limit value can be selected and connected by "~".

The electrode of the present invention includes an ionic conductive polymer material containing an ionic conductive polymer having an ethylene oxide unit in a side chain and a lithium salt compound, and an electrode material layer containing an active material. More specifically, the electrode of the present invention includes a current collector in addition to the electrode material layer, and the electrode material layer is formed on the current collector. Details of the ionic conductive polymer material will be described later.

The electrode of the present invention can be either a positive electrode or a negative electrode in an inorganic solid electrolyte secondary battery. In the positive electrode, a positive electrode material layer is formed on the current collector, and in the negative electrode, a negative electrode material layer is formed on the current collector. When the electrode of the present invention is a positive electrode, the positive electrode material layer contains the above-mentioned ion conductive polymer material and the positive electrode active material. When the electrode of the present invention is a negative electrode, the negative electrode material layer contains the ion conductive polymer material and the negative electrode active material.

A known current collector can be used for the positive electrode and the negative electrode. Specifically, for the positive electrode, a metal such as aluminum, nickel, stainless steel, gold, platinum, or titanium is used as a current collector. For the negative electrode, a metal such as copper, nickel, stainless steel, gold, platinum, or titanium is used as a current collector.

Further, the positive electrode material layer and the negative electrode material layer each contain at least a positive electrode active material and a negative electrode active material in addition to the above-mentioned ion conductive polymer material, and further contain a conductive auxiliary agent, a binder, and a thickener. Alternatively, an inorganic solid electrolyte described later may be contained, if necessary.

The positive electrode active material used in the present invention is a lithium metal-containing composite oxide powder having a composition of any one of _{LiMO 2} , LiM ₂ O ₄ , Li ₂ MO ₃ , and LiMEO _4. Here, M in the formula is mainly composed of a transition metal and contains at least one of Co, Mn, Ni, Cr, Fe and Ti. M is made of a transition metal, but Al, Ga, Ge, Sn, Pb, Sb, Bi, Si, P, B and the like may be added in addition to the transition metal. E contains at least one of P and Si. The particle size of the positive electrode active material is preferably 50 μm or less, more preferably 20 μm or less. These active materials have an electromotive force of 3 V (vs. Li / Li +) or more.

Specific examples of the positive electrode active material include lithium cobalt oxide, lithium nickel oxide, nickel / cobalt / lithium manganate (ternary system), spinel-type lithium manganate, and lithium iron phosphate.

The negative electrode active material used in the present invention is a carbon material (natural graphite, artificial graphite, amorphous carbon, etc.) having a structure (interlayer compound) capable of storing and releasing alkali metal ions such as lithium ions, or lithium ions. It is a metal such as lithium, aluminum-based compound, tin-based compound, silicon-based compound, and titanium-based compound that can store and release alkali metal ions. In the case of powder, the particle size is preferably 10 nm or more and 100 μm or less, and more preferably 20 nm or more and 20 μm or less. Further, it may be used as a mixed active material of a metal and a carbon material.

When a conductive auxiliary agent is used, a known conductive auxiliary agent can be used, and conductive carbon black such as graphite, furnace black, acetylene black, and Ketjen black, carbon fiber such as carbon nanotube, or metal powder can be used. Can be mentioned. These conductive auxiliaries may be used alone or in combination of two or more.

The binder is one or more selected from, for example, fluororesin such as PVdF, fluororubber, acrylic rubber, modified acrylic rubber, styrene-butadiene rubber, acrylic polymer, vinyl polymer, and the above-mentioned ion conductive polymer. Compounds can be used. For these binders, the active material is added in an amount of 100 parts by mass, preferably 5 parts by mass or less, more preferably 3 parts by mass or less, for example, 0.01 to 2 parts by mass.

Specific examples of the thickener include carboxymethyl cellulose, methyl cellulose, hydroxymethyl cellulose, ethyl cellulose and salts thereof (alkali metal salts such as sodium salt, ammonium salts), polyvinyl alcohol, polyacrylate, polyethylene oxide and the like. The thickener may be used alone or in combination of two or more. These thickeners are added in an amount of 100 parts by mass, preferably 5 parts by mass or less, more preferably 3 parts by mass or less, for example, 0.01 to 2 parts by mass. Further, when the viscosity of the coating liquid is low, a thickener can be used in combination.

The method for producing the electrode including the current collector and the electrode material layer is not particularly limited, and a general method can be used. For example, a paste (coating liquid) of an electrode material consisting of a positive electrode active material or a negative electrode active material, a conductive auxiliary agent, a binder, water or a solvent such as N-methyl-2-pyrrolidone (NMP), and if necessary, a thickener and the like. ) Is uniformly applied on the surface of the current collector to an appropriate thickness by a doctor blade method or a silk screen method.

For example, in the doctor blade method, a negative electrode active material powder, a positive electrode active material powder, a conductive auxiliary agent, a binder, etc. are dispersed in water to form a slurry, applied to a metal electrode substrate, and then a blade having a predetermined slit width is more appropriate. Uniform to thickness. After applying the active material, the electrodes are dried under hot air at 100 ° C. or reduced pressure at 80 ° C. in order to remove excess organic solvent. The dried electrode is press-molded by a press device to form an electrode precursor in which an electrode material layer is laminated on a current collector.

In the electrode of the present invention, the electrode material layer of the electrode precursor thus formed is impregnated with the ionic conductive polymer material to suitably produce an electrode containing the ionic conductive polymer material and the active material. be able to. That is, when the electrode material layer is formed by using the conventional method for manufacturing the electrode material layer described above, voids such as active material particles are formed between the electrode materials constituting the electrode material layer. In the electrode of the present invention, since the voids of the electrode material are filled with the ion conductive polymer material, the interfacial resistance inside the electrode material layer can be efficiently reduced.

The ionic conductive polymer material comprises an ionic conductive polymer having an ethylene oxide unit in the side chain and a lithium salt compound. Specifically, the ionic conductive polymer material of the present invention is a mixture of an ionic conductive polymer having an ethylene oxide unit in the side chain and a lithium salt compound.

In the electrode of the present invention, the content of the ionic conductive polymer material contained in the electrode material layer is not particularly limited, but is preferable with respect to 100 parts by mass of the active material from the viewpoint of suitably improving charge / discharge characteristics. It is 5 to 50 parts by mass, more preferably 15 to 30 parts by mass.

Examples of the ion conductive polymer having an ethylene oxide unit in the side chain include a polyether having an ethylene oxide unit in the side chain, a borate ester having an ethylene oxide unit in the side chain, and a polyolefin having an ethylene oxide unit in the side chain, which are preferable. Is a polyether having ethylene oxide units in its side chain.

The polyether having an ethylene oxide unit in the side chain preferably contains a structural unit formed from an epoxy compound having an ethylene oxide unit in the side chain. That is, the ionic conductive polymer is preferably a polymer having at least a monomer of an epoxy compound having an ethylene oxide unit in the side chain.

Examples of the epoxy compound having an ethylene oxide unit in the side chain include a monomer represented by the following formula (2), which may be represented by the following formula (2), and if necessary, the following formula (1) and the following formula (3). The branched polyether using the represented monomer is a polyether (i) having an ethylene oxide unit in the side chain. As the monomer represented by the formulas (1) to (3), only one kind may be used, or two or more kinds may be mixed and used.

[In the formula (2), R is −CH ₂ O (CH ₂ CH ₂ O) _n R ⁴ , R ⁴ is an alkyl group having 1 to 6 carbon atoms, and n is a number of 0 to 12. ]

[In formula (3), R ⁵ represents a group containing an ethylenically unsaturated group. ]

Examples of the monomer of the formula (3) include allyl glycidyl ether, 4-vinylcyclohexyl glycidyl ether, α-terpinyl glycidyl ether, cyclohexenylmethyl glycidyl ether, p-vinylbenzyl glycidyl ether, allylphenyl glycidyl ether, and vinyl glycidyl. Ether, 3,4-epoxy-1-butene, 3,4-epoxy-1-pentene, 4,5-epoxy-2-pentene, 1,2-epoxy-5,9-cyclododecandien, 3,4- Epoxy-1-vinylcyclohexene, 1,2-epoxy-5-cyclooctene, glycidyl acrylate, glycidyl methacrylate, glycidyl sorbate, glycidyl silicate, glycidyl crotonate, glycidyl-4-hexenoate are used. Preferred are allyl glycidyl ether, glycidyl acrylate, and glycidyl methacrylate.

The synthesis of the polyether (i) having an ethylene oxide unit in the side chain can be carried out, for example, as follows. As a ring-opening polymerization catalyst, a catalyst system mainly composed of organoaluminum, a catalyst system mainly composed of organozinc, a coordination anion initiator such as an organotin-phosphate condensate catalyst system, or potassium containing ^{K + as a counter ion.} Polyether (i) is obtained by reacting each monomer in the presence or absence of a catalyst at a reaction temperature of 10 to 120 ° C. with stirring using an anion initiator such as alkoxide, diphenylmethyl potassium, or potassium hydroxide. ) Is obtained. From the viewpoint of the degree of polymerization and the properties of the obtained copolymer, the coordination anion initiator is preferable, and the organic tin-phosphate ester condensate catalyst system is particularly preferable because it is easy to handle.

In the polyether (i) having an ethylene oxide unit in the side chain, the repeating unit (A) derived from the monomer of the formula (1), the repeating unit (B) derived from the monomer of the formula (2), and the repeating unit (B). The molar ratio with the repeating unit (C) derived from the monomer of the formula (3) is (A) 95 to 5 mol%, (B) 5 to 95 mol%, and (C) 0 to 20 mol%. Suitable and preferably (A) 92-9 mol%, (B) 7-90 mol%, and (C) 1-15 mol%, more preferably (A) 88-18 mol%, (B) 10. ~ 80 mol%, and (C) 2-15 mol%. When the repeating unit (A) is 95 mol% or less, it does not cause an increase in the glass transition temperature and crystallization of the oxyethylene chain, and as a result, it is preferable in terms of ionic conductivity.

Specific examples of the polyether (i) having an ethylene oxide unit in the side chain include ethylene oxide / diethylene glycol methyl glycidyl ether / allyl glycidyl ether ternary copolymer, ethylene oxide / diethylene glycol methyl glycidyl ether / glycidyl methacrylate ternary copolymer, and the like. Examples thereof include ethylene oxide / diethylene glycol methyl glycidyl ether / glycidyl acrylate ternary copolymer.

The weight average molecular weight of the polyether (i) having an ethylene oxide unit in the side chain is not particularly limited, but may be 10,000 to 3 million, more preferably 50,000 to 2.5 million, and 100,000 to 2 million. It is particularly preferable to have. The weight average molecular weight is calculated by gel permeation chromatography (GPC) in terms of standard polystyrene using dimethylformamide (DMF) as the solvent.

The content of the ionic conductive polymer contained in the ionic conductive polymer material is 100 parts by mass, preferably 5 to 95 parts by mass, and more preferably 10 to 90 parts by mass with respect to the entire conductive polymer material.

The ionic conductive polymer may contain a crosslinked product.

As the lithium salt compound, a lithium salt compound having a wide potential window, which is generally used for lithium ion batteries, is suitable. Examples of the lithium salt compound include LiBF ₄ , LiPF ₆ , LiClO ₄ , LiCF ₃ SO ₃ , LiN (CF ₃ SO ₂ ) ₂ (LiTFSI), LiN (SFO ₂ ) ₂ (LiFSI), LiN (C ₂ F _5). Examples include, but are not limited to, SO ₂ ) ₂ , LiN [CF ₃ SC (C ₂ F ₅ SO ₂ ) ₃ ] _2. These may be used alone or in combination of two or more.

As the content of lithium chloride contained in the ionic conductive polymer material, the value of the number of moles of the lithium salt compound / the total number of moles of ether oxygen atoms of the ionic conductive polymer is preferably 0.0001 to 5, and more preferably 0.0001 to 5. The range of 0.001 to 0.5 is good.

Further, the ion conductive polymer material may contain a molten salt at room temperature. A room temperature molten salt is a salt that is at least partially liquid at room temperature, and the room temperature is a temperature range in which a power source is expected to operate normally. The temperature range in which the power supply is expected to operate normally is such that the upper limit is about 120 ° C., in some cases about 60 ° C., and the lower limit is about −40 ° C., and in some cases about −20 ° C.

The room temperature molten salt is also called an ionic liquid, and pyridine-based, aliphatic amine-based, and alicyclic amine-based quaternary ammonium organic cations are known. Examples of the quaternary ammonium organic cation include imidazolium ions such as dialkyl imidazolium and trialkyl imidazolium, tetraalkylammonium ions, alkylpyridinium ions, pyrazolium ions, pyrrolidinium ions and piperidinium ions. In particular, the imidazolium cation is preferable.

Examples of the tetraalkylammonium ion include, but are limited to, trimethylethylammonium ion, trimethylethylammonium ion, trimethylpropylammonium ion, trimethylhexylammonium ion, tetrapentylammonium ion, triethylmethylammonium ion and the like. is not it.

The alkylpyridinium ions include N-methylpyridinium ion, N-ethylpyridinium ion, N-propylpyridinium ion, N-butylpyridinium ion, 1-ethyl-2methylpyridinium ion, and 1-butyl-4-methyl. Examples thereof include, but are not limited to, pyridinium ion, 1-butyl-2,4 dimethylpyridinium ion and the like.

Examples of the imidazolium cation include 1,3-dimethylimidazolium ion, 1-ethyl-3-methylimidazolium ion, 1-methyl-3-ethylimidazolium ion, 1-methyl-3-butylimidazolium ion, 1-. Butyl-3-methylimidazolium ion, 1,2,3-trimethylimidazolium ion, 1,2-dimethyl-3-ethylimidazolium ion, 1,2-dimethyl-3-propylimidazolium ion, 1-butyl- Examples include, but are not limited to, 2,3-dimethylimidazolium ion.

The room temperature molten salt having these cations may be used alone or in combination of two or more.

When the ion conductive polymer material contains a molten salt at room temperature, the content thereof is preferably 10 to 1000 parts by mass, and more preferably 20 to 500 parts by mass with respect to 100 parts by mass of the ion conductive polymer.

The ionic conductive polymer material may contain a plasticizer or the like. The plasticizer is not particularly limited, but a dicyano compound and a branched ether compound are preferable. When adding a plasticizer, it is preferable to crosslink the ionic conductive polymer. This cross-linking is a chemical cross-linking and can suppress the outflow of the plasticizer from the ionic conductive polymer material.

Examples of the dicyano compound include succinonitrile, glutaronitrile, adiponitrile, 1,5-dicyanopentane, 1,6-dicyanohexane, 1,7-dicyanoheptane, 1,8-dicyanooctane and the like. Examples of the branched ether compound include the following multi-branched ether compounds.

When the ionic conductive polymer material contains a plasticizer, the content of the plasticizer is preferably 10 to 1000 parts by mass, more preferably 20 to 500 parts by mass with respect to 100 parts by mass of the ionic conductive polymer. ..

A thermal reaction initiator, a photoreaction initiator, and a cross-linking aid may be used to form the ionic conductive polymer material.

As the thermal reaction initiator, a radical initiator selected from organic peroxides, azo compounds and the like is used. As the organic peroxide, those usually used for cross-linking applications such as ketone peroxide, peroxyketal, hydroperoxide, dialkyl peroxide, diacyl peroxide, and peroxy ester are used, and the azo compound is azonitrile. Compounds, azoamide compounds, azoamidine compounds, etc., which are usually used for cross-linking applications, are used. The amount of the radical initiator added varies depending on the type, but is usually in the range of 0.1 to 10 parts by mass with the ion conductive polymer as 100 parts by mass.

As the photoreaction initiator, radical initiators such as alkylphenone-based, benzophenone-based, acylphosphine oxide-based, titanosen, triazines, bisimidazoles, and oxime esters are used. The amount of these radical polymerization initiators added varies depending on the type, but is usually in the range of 0.01 to 5.0 parts by mass with the ionic conductive polymer as 100 parts by mass.

Examples of the cross-linking aid include ethylene glycol diacrylate, ethylene glycol dimethacrylate, oligoethylene glycol diacrylate, oligoethylene glycol dimethacrylate, trimethylolpropane triacrylate, allyl methacrylate, allyl acrylate, diallyl malate, triallyl isocyanurate, and maleimide. , Phenylmaleimide, maleic anhydride and the like can be arbitrarily used.

The ionic conductive polymer material may contain a solvent for dissolving an ionic conductive polymer having an ethylene oxide unit in the side chain and a lithium salt compound for the method described later, and acetonitrile, toluene, tetrahydrofuran (THF), dioxane. , Dimethyl sulfoxide (DMSO), water and other highly polar solvents can be used.

As described above, the method for including the ionic conductive polymer material in the voids between the electrode materials is not particularly limited, but the ionic conductive polymer having an ethylene oxide unit in the side chain and the lithium salt compound are completely dissolved by the solvent. This can be done by impregnating the layer containing the active material (more specifically, the voids of the electrode material constituting the electrode material layer precursor) with the solution (composition). The impregnation condition is to allow the voids to contain the ionic conductive polymer and the lithium salt compound at the lowest possible temperature (preferably below room temperature) while slowly evaporating the solvent. Further, when the electrode material layer is a thick film, it can be performed under reduced pressure.

When cross-linking an ionic conductive polymer having an ethylene oxide unit in the side chain, the layer impregnated with the ionic conductive polymer material can be cross-linked by heating or irradiation with active energy rays (ultraviolet irradiation or the like).

Inorganic Solid Electrolyte Secondary Battery The inorganic solid electrolyte secondary battery of the present invention includes the electrode for the inorganic solid electrolyte secondary battery of the present invention. More specifically, it comprises a positive electrode and a negative electrode (at least one of which is composed of the electrodes of the present invention) and an inorganic solid electrolyte disposed between the positive electrode and the negative electrode. Of the positive electrode and the negative electrode, known electrodes used in the solid electrolyte secondary battery can be used as the electrodes that do not use the electrodes of the present invention. The electrodes for the inorganic solid electrolyte secondary battery of the present invention are as described above.

The electrode of the present invention used in the inorganic solid electrolyte secondary battery of the present invention has an electrode material layer in which the above-mentioned ion conductive polymer material is contained in the electrode material layer in addition to the active material. The voids of the electrode material (specifically, active material particles, binders, conductive aids, thickeners, inorganic solid electrolytes, etc.) contained in the electrode material are filled with the ionic conductive polymer material, and the inside of the electrode material layer is filled. It is considered that the interfacial resistance of the above is effectively reduced, and as a result, excellent charge / discharge characteristics are exhibited. Further, the solid electrolyte secondary battery of the present invention may be used in a high temperature environment (for example, a high temperature environment of 100 ° C. or higher), but by using the electrode of the present invention, excellent charge / discharge characteristics can be obtained in a high temperature environment. It is demonstrated.

Examples of the inorganic solid electrolyte include an oxide-based solid electrolyte and a sulfide-based solid electrolyte. The inorganic solid electrolyte is generally an aggregate of inorganic solid particles constituting the electrolyte.

The oxide-based solid electrolyte is particularly limited as long as it contains oxygen, has ionic conductivity of a metal belonging to Group 1 or Group 2 of the Periodic Table, and has electron insulation. It's not a thing.

Specific compounds included in the oxide-based solid electrolyte, Li _x La _y TiO ₃ [x = 0.3~0.7, y = 0.3~0.7] (LLT), Li _x La _y Zr _z M _m O _n (M satisfies Al, Mg, Ca, Sr, V, Nb, Ta, Ti, Ge, in, represents at least one element of Sn x is a 5 ≦ x ≦ 10, y satisfies 1 ≦ y ≦ 4, z satisfies 1 ≦ z ≦ 4, m satisfies 0 ≦ m ≦ 2, n satisfies 5 ≦ n ≦ 20.) Li x B y M z O n ( wherein Medium M is at least one element of C, S, Al, Si, Ga, Ge, In, Sn, x satisfies 0 ≦ x ≦ 5, y satisfies 0 ≦ y ≦ 1, and z is 0. meet ≦ z ≦ 1, n satisfies 0 ≦ n ≦ 6.), Li x (Al, Ga) y (Ti, Ge) z Si a P m O n ( however, 1 ≦ x ≦ 3,0 ≦ y ≦ 1, 0 ≦ z ≦ 2, 0 ≦ a ≦ 1, 1 ≦ m ≦ 7, 3 ≦ n ≦ 13), Li _(3-2x) M _x DO (x is 0 or more and 0.1 or less) M represents a divalent metal atom; D represents a halogen atom or a combination of two or more kinds of halogen atoms), Li _{x S y} O _z (1 ≦ x ≦ 5, 0 <y ≦ 3, 1). ≤z ≤ 10), Li _x S _y O _z (1 ≤ x ≤ 3, 0 <y ≤ 2, 1 ≤ z ≤ 10), Li ₃ BO ₃ -Li ₂ SO ₄ , Li _{2 OB 2} O ₃ -P ₂ O ₅ , Li ₂ O-SiO ₂ , Li ₆ BaLa ₂ Ta ₂ O ₁₂ , Li ₃ PO _{(4-3 / 2w)} N _w (w is w <1), LISION (Lithium super ionic compound) type Li _3.5 Zn _0.25 GeO _{4 with a crystal structure, La 0.55} Li _{0.35 TIO 3} with a perovskite type crystal structure, _{LiTi 2} P ₃ O ₁₂ with a NASION (Naturium superionic compound) type crystal structure, Li _{(1 + x + y) )} (Al, Ga) _x (Ti, Ge) _(2-x) Si _y P _(3-y) O ₁₂ (where 0 ≦ x ≦ 1, 0 ≦ y ≦ 1), Li with a garnet-type crystal structure ₇ La ₃ Zr ₂ O1 _{2 and the} like can be mentioned. Phosphorus compounds containing Li, P and O are also desirable. For example, lithium phosphate (Li ₃ PO ₄ ), LiPON in which a part of oxygen of lithium phosphate is replaced with nitrogen, LiPOD (D is Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zr, Nb). , Mo, Ru, Ag, Ta, W, Pt, Au and the like (at least one selected from) and the like. Further, LiAON (A is at least one selected from Si, B, Ge, Al, C, Ga and the like) and the like can also be preferably used.

Among them, Li _x La _y TiO ₃ [x = 0.3~0.7, y = 0.3~0.7] _{(LLT), Li x La y} Zr z M m O n (M is Al, Mg , Ca, Sr, V, Nb, Ta, Ti, Ge, In, Sn, x is 5 ≦ x ≦ 10, y is 1 ≦ y ≦ 4, and z is 1. ≤z≤4, m satisfies _{0≤m≤2, n satisfies 5≤n≤20), Li 7} La ₃ Zr ₂ O ₁₂ (LLZ), Li ₃ BO ₃ , Li ₃ BO _{3 -Li 2 SO 4, Li 3 BO} 3 -Li 2 CO 3, Li x (Al, Ga) y (Ti, Ge) z Si a P m O n ( however, 1 ≦ x ≦ 3,0 ≦ y ≦ 1 , 0 ≦ z ≦ 2, 0 ≦ a ≦ 1, 1 ≦ m ≦ 7, 3 ≦ n ≦ 13) are preferable. These may be used alone or in combination of two or more.

The sulfide-based solid electrolyte is particularly limited as long as it contains sulfur, has ionic conductivity of a metal belonging to Group 1 or Group 2 of the Periodic Table, and has electron insulation. It's not a thing. For example, a lithium ion conductive inorganic solid electrolyte satisfying the composition represented by the following formula can be mentioned.

Li _a M _b P _c S _d A _e

In the formula, M represents an element selected from B, Zn, Sn, Si, Cu, Ga, Sb, Al and Ge. Among them, B, Sn, Si, Al and Ge are preferable, and Sn, Al and Ge are more preferable. A indicates I, Br, Cl, F, and I and Br are preferable, and I is particularly preferable. a to e indicate the composition ratio of each element, and a: b: c: d: e satisfies 1 to 12:00 to 1: 1: 2 to 12:00 to 5. Further, a is preferably 1 to 9, and more preferably 1.5 to 4. b is preferably 0 to 0.5. d is further preferably 3 to 7, more preferably 3.25 to 4.5. e is further preferably 0 to 3, more preferably 0 to 2.

In the formula, the composition ratios of Li, M, P, S and A are preferably 0 for b and e, more preferably b = 0 and e = 0 and the ratio of a, c and d (a: c). : D) is a: c: d = 1 to 9: 1: 3 to 7, more preferably b = 0, e = 0 and a: c: d = 1.5 to 4: 1: 3. It is 25 to 4.5.

When the inorganic solid electrolyte is in the form of particles, the particle size thereof is, for example, 0.01 to 100 μm, preferably 0.1 to 20 μm.

In the solid electrolyte secondary battery of the present invention, ionic conductivity having an ethylene oxide unit in the side chain containing a lithium salt compound at least one between the positive electrode and the inorganic solid electrolyte and between the negative electrode and the inorganic solid electrolyte. A crosslinked film of polymer material may be placed. The crosslinked film of the ionic conductive polymer material is a crosslinked film of a composition containing a lithium salt compound and an ionic conductive polymer. By arranging the crosslinked film, the interfacial resistance of the electrode and the inorganic solid electrolyte can be further reduced.

The cross-linked film is formed by cross-linking a composition containing at least a lithium salt compound and an ionic conductive polymer having ethylene oxide units in the side chains. That is, the crosslinked film is a crosslinked film of a composition containing a lithium salt compound and an ionic conductive polymer. The lithium salt compound and the ionic conductive polymer are as described above.

The content of the ionic conductive polymer contained in the crosslinked film is 100 parts by mass, preferably 10 to 90 parts by mass, and more preferably 20 to 80 parts by mass with respect to the entire crosslinked film.

Content of Lithium Chloride in Crosslinked Film The value of the number of moles of the lithium salt compound / the total number of moles of ether oxygen atoms of the ionic conductive polymer is preferably 0.0001 to 5, and more preferably 0.001 to 0. A range of 5 is good.

Further, the crosslinked film may contain a molten salt at room temperature. The room temperature molten salt is as described above.

When the crosslinked film contains a molten salt at room temperature, the content thereof is preferably 10 to 1000 parts by mass, and more preferably 20 to 500 parts by mass with respect to 100 parts by mass of the ionic conductive polymer.

The crosslinked film may contain a plasticizer or the like. The plasticizer is as described above.

When the crosslinked film contains a plasticizer, the content of the plasticizer is preferably 10 to 1000 parts by mass, more preferably 20 to 500 parts by mass with respect to 100 parts by mass of the ionic conductive polymer.

A cross-linking film may be formed by blending a reaction initiator or a cross-linking aid with a composition containing a lithium salt compound and an ionic conductive polymer. Examples of the reaction initiator include a thermal reaction initiator and a photoreaction initiator.

The thermal reaction initiator, photoreaction initiator, and cross-linking aid are as described above.

An organic solvent may be blended in the composition containing the lithium salt compound and the ionic conductive polymer, and the organic solvent includes toluene, xylene, benzene, acetonitrile, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and THF ( Tetrahydrofuran).

As a method for producing a crosslinked film, for example, an ionic conductive polymer, a reaction initiator, and a lithium salt compound, if necessary, are mixed and dissolved in an organic solvent to form a composition, and a substrate (for example, PET film or Teflon) is prepared. A method of casting a composition on a (registered trademark) plate or the like, removing the solvent, and then heating or irradiating with an active energy ray such as ultraviolet rays to prepare a crosslinked film can be mentioned. Further, the composition can be directly cast on the surface of the inorganic solid electrolyte to prepare a crosslinked film.

The film thickness of the crosslinked film is preferably in the range of 0.1 μm to 200 μm, more preferably 0.5 μm to 100 μm.

Examples of the laminated configuration of the inorganic solid electrolyte secondary battery of the present invention include the following configurations.
Laminated structure in which a positive electrode, an inorganic solid electrolyte, and a negative electrode are laminated in order;
Laminated structure in which a positive electrode, a crosslinked film, an inorganic solid electrolyte, a crosslinked film, and a negative electrode are laminated in order;
A laminated structure in which a positive electrode, a crosslinked film, an inorganic solid electrolyte, and a negative electrode are laminated in this order;
A laminated structure in which a positive electrode, an inorganic solid electrolyte, a crosslinked film, and a negative electrode are laminated in this order.

In the inorganic solid electrolyte secondary battery of the present invention, it is preferable that the inorganic solid electrolyte and the above-mentioned crosslinked film are in contact with each other. The inorganic solid electrolyte is generally formed of an aggregate of inorganic solid particles constituting the electrolyte, and voids are present between the particles. Since the crosslinked film is a crosslinked product of a composition containing an ionic conductive polymer containing a lithium salt compound, it has ionic conductivity and high flexibility as compared with an inorganic material. .. Therefore, the crosslinked film has a large contact area with the inorganic solid electrolyte, and as a result, the interfacial resistance of the inorganic solid electrolyte is effectively reduced, and the inorganic solid electrolyte secondary battery of the present invention has excellent charge / discharge characteristics. It is thought that it will be demonstrated. Since the active material particles contained in the electrode material layer also form voids, it is preferable that the crosslinked film is in contact with the electrode material layer of the electrode in the inorganic solid electrolyte secondary battery of the present invention. It is also preferred that the crosslinked film is in contact with both the electrode material layer and the inorganic solid electrolyte.

Method for Manufacturing Solid Electrolyte Secondary Battery The method for manufacturing the solid electrolyte secondary battery of the present invention is not particularly limited, and is composed of at least a positive electrode, a negative electrode, and an inorganic solid electrolyte, and is manufactured by a known method. For example, in the case of a coin-type lithium ion battery, a positive electrode, an inorganic solid electrolyte, and a negative electrode are arranged and inserted into an outer can. After that, a storage battery can be obtained by joining the sealing body with a tab welding or the like, sealing the sealing body, and caulking. The shape of the battery is not limited, and examples thereof include a coin type, a cylindrical type, and a sheet type, and a structure in which two or more batteries are laminated may be used.

The present invention will be described in more detail in the following examples, but the present invention is not limited thereto.

In this example, a coin battery was manufactured, and the performance evaluation of the charge / discharge characteristics of the coin battery was performed by the following experiment.

[Evaluation of manufactured batteries]
As an evaluation of the manufactured battery, a charge / discharge test was performed using a charge / discharge device, and the charge capacity and the discharge capacity were determined.

After CCCV charging (0.01C cut) to 4.2V with a current equivalent to charge / discharge measurement 0.1C (10 hour rate), CCCV discharge (0.01C cut) to 2.5V with a current equivalent to 0.1C. ) Was performed. The test temperature was an environment of 100 ° C.

[Example of production of positive electrode precursor]
To 100 parts by mass of NCM (nickel / cobalt / lithium manganate = 5/2/3) as a positive electrode active material, 3 parts by mass of acetylene black and 3 parts by mass of graphite as a conductive auxiliary agent, and 3 parts by mass of PVdF as a binder are added, and a slurry is further added. Was added to the NMP solution so that the solid content concentration was 35% by mass, and the mixture was sufficiently mixed to obtain a slurry for a positive electrode. The obtained positive electrode slurry is applied onto an aluminum current collector having a thickness of 20 μm using a die coater, dried at 100 ° C. for 12 hours or more, and then pressed by a roll press machine to prepare a positive electrode having a thickness of 20 μm. did. The basis weight of the positive electrode active material is 6.6 mg / cm ² , the positive electrode density is 3.1 g / cm ³ , and the porosity is 26%.

[Example of Implementation of Negative Electrode Precursor]
100 parts by mass of artificial graphite (particle size 10 μm) as a negative electrode active material, 2 parts by mass of vapor-grown carbon fiber (VGCF) as a conductive auxiliary agent, 3 parts by mass of SBR as a binder, and 2 parts by mass of a sodium salt of carboxymethyl cellulose as a thickener. A portion was added, and water was further added so that the solid content concentration of the slurry was 35% by mass, and the mixture was sufficiently mixed to obtain a slurry for a negative electrode. The obtained negative electrode slurry was applied onto a copper current collector having a thickness of 16.5 μm using a die coater, dried at 100 ° C. for 12 hours or more, and then pressed by a roll press machine to obtain a negative electrode having a thickness of 22 μm. Was produced. The basis weight of the negative electrode active material is 3.1 mg / cm ² , the negative electrode density is 1.2 g / cm ³ , and the porosity is 23%.

[Example of Implementation of Positive Electrode for Solid Electrode Secondary Battery (Positive Electrode with Positive Electrode Precursor Impregnated with Ion Conductive Polymer and Lithium Salt Compound)]
As an ionic conductive polymer having an ethylene oxide unit in the side chain, ethylene oxide / diethylene glycol methyl glycidyl ether / allyl glycidyl ether = 80/17/3 mol% ternary copolymer (weight average molecular weight 1.5 million) 100 parts by mass, as a lithium salt compound Completely add 12 parts by mass of lithium borofluoride, 10 parts by mass of trimethyl propantriacrylate as a cross-linking aid, and 0.3 parts by mass of benzoyl peroxide (Nyper BMT, manufactured by Nichiyu Co., Ltd.) as a radical initiator to 900 parts by mass of acetonitrile. A coating solution for impregnating the electrode was prepared. The positive electrode precursor obtained in the production example was coated with an electrode impregnating coating solution so as to have a thickness of 140 μm. Then, by allowing it to stand for 2 hours, the voids in the positive electrode precursor were impregnated with the ionic conductive polymer and the lithium salt compound while removing the solvent. The impregnated ionic conductive polymer was crosslinked at 100 ° C. for 2 hours under reduced pressure to prepare a positive electrode for a solid electrolyte secondary battery. The cross section of the positive electrode was analyzed by SEM (scanning electron microscope). By SEM, an ionic conductive polymer was observed in the voids in the positive electrode.

[Example of comparative production of positive electrode for solid electrolyte secondary battery]
In the positive electrode for a solid electrolyte secondary battery of the embodiment, 100 parts by mass of polyethylene oxide (weight average molecular weight 1.1 million) is used instead of the ionic conductive polymer having an ethylene oxide unit in the side chain, and similarly for comparison. A positive electrode for a solid electrolyte secondary battery was prepared. SEM analysis was performed on the cross section of the positive electrode. Polyethylene oxide was observed in the voids in the positive electrode by SEM.

[Example of Implementation of Negative Electrode for Solid Electrode Secondary Battery (Negative Electrode with Negative Electrode Precursor Impregnated with Ion Conductive Polymer and Lithium Salt Compound)]
As an ionic conductive polymer having an ethylene oxide unit in the side chain, ethylene oxide / diethylene glycol methyl glycidyl ether / allyl glycidyl ether = 80/17/3 mol% ternary copolymer (weight average molecular weight 1.5 million) 100 parts by mass, as a lithium salt compound Completely dissolve 38 parts by mass of LiTFSI in 900 parts by mass of trimylol propantriacrylate as a cross-linking aid and 0.3 parts by mass of benzoylper oxide (Nyper BMT, manufactured by Nichiyu Co., Ltd.) as a radical initiator in 900 parts by mass of acetonitrile. A coating solution for impregnating the electrode was prepared. The negative electrode precursor obtained in the example of carrying out the negative electrode was coated with an electrode impregnating coating solution so as to have a thickness of 120 μm. Then, by allowing it to stand for 2 hours, the voids in the negative electrode precursor were impregnated with the ionic conductive polymer and the lithium salt compound while removing the solvent. An ionic conductive polymer having an ethylene oxide unit was crosslinked on the impregnated side chain at 100 ° C. for 2 hours under reduced pressure to prepare a negative electrode for a solid electrolyte secondary battery. The cross section of the negative electrode was analyzed by SEM-EDX (scanning electron microscope / energy dispersive X-ray spectroscopy). By SEM, an ionic conductive polymer was observed in the voids in the negative electrode, and by EDX, the distribution of F ions was observed in the voids, which confirmed that LiTFSI was contained in the voids.

[Example of Fabrication of Crosslinked Film of Ion Conductive Polymer Material]
As an ionic conductive polymer having an ethylene oxide unit in the side chain, ethylene oxide / diethylene glycol methylglycidyl ether / allylglycidyl ether = 80/17/3 mol% ternary copolymer (weight average molecular weight 1.5 million) 100 parts by mass, as a lithium salt compound 38 parts by mass of LiTFSI was dissolved in 10 parts by mass of trimethylolpropane triacrylate as a cross-linking aid, and 0.3 parts by mass of benzoyl peroxide (Nyper BMT, manufactured by Nichiyu Co., Ltd.) as a radical initiator in 900 parts by mass of acetonitrile. A solution was prepared. This solution was cast on a polytetrafluoroethylene mold, dried at room temperature, and then thermally crosslinked at 100 ° C. for 2 hours to prepare a crosslinked film of an ion conductive polymer material having a thickness of 20 μm.

Battery manufacturing example [Implementation manufacturing example 1 of solid electrolyte secondary battery]
In the dry room, the positive electrode obtained in the implementation example of the positive electrode for the solid electrolyte secondary battery, the crosslinked film of the ion conductive polymer material in the production example, and Li ₇ La ₃ Zr ₂ O ₁₂ (LLZ, Toyoshima Seisakusho) as the inorganic solid electrolyte. A 2032 type coin battery for testing was manufactured by laminating in this order a crosslinked film of the ion conductive polymer material of the production example and a metallic lithium foil as a negative electrode, and then caulking.
<Charging / discharging conditions>
Lower limit voltage 2.5V-Upper limit voltage 4.2V, 100 ° C
CC (0.1C) -CV (0.01C) charging CC (0.1C) -CV (0.01C) discharging <Charging / discharging test results>
Charge capacity 168mAh / g, discharge capacity 162mAh / g

[Implementation Manufacturing Example 2 of Solid Electrolyte Secondary Battery]
In the dry room, the positive electrode obtained in the implementation example of the positive electrode for the solid electrolyte secondary battery, the crosslinked film of the ion conductive polymer material in the production example, and Li ₇ La ₃ Zr ₂ O ₁₂ (LLZ, Toyoshima Seisakusho) as the inorganic solid electrolyte. (Thickness: 500 μm), crosslinked film of ion conductive polymer material in the production example, and negative electrode for solid electrolyte secondary battery. After laminating in this order, the negative electrode obtained in the production example was caulked to produce a 2032 type coin battery for testing. ..
<Charging / discharging conditions>
Lower limit voltage 2.5V-Upper limit voltage 4.2V, 100 ° C
CC (0.1C) -CV (0.01C) charging CC (0.1C) -CV (0.01C) discharging <Charging / discharging test results>
Charging capacity 155mAh / g Discharging capacity 140mAh / g

[Comparative Manufacturing Example 1 of Solid Electrolyte Secondary Battery]
In the dry room, a positive electrode using polyethylene oxide as a comparative example of a positive electrode for a solid electrolyte secondary battery, Li ₇ La ₃ Zr ₂ O ₁₂ (LLZ, manufactured by Toyoshima Seisakusho Co., Ltd., film thickness 500 μM) as an inorganic solid electrolyte, and ions of a production example. A crosslinked film made of a conductive polymer material and a metallic lithium foil as a negative electrode were laminated in this order, and then caulked to produce a 2032 type coin battery for testing.
<Charging / discharging conditions>
Lower limit voltage 2.5V-Upper limit voltage 4.2V, 100 ° C
CC (0.1C) -CV (0.01C) charging CC (0.1C) -CV (0.01C) discharging <Charging / discharging test results>
Charging capacity 100mAh / g Discharging capacity 50mAh / g

It can be seen that the electrodes in which the voids of the electrode material are filled with the ionic conductive polymer material clearly improve the charge and discharge capacities as compared with the electrodes not filled and the electrodes filled with polyethylene oxide. .. Since polyethylene oxide has high crystallinity and cannot be crosslinked, it is considered that the cause is that the shape cannot be maintained due to melting at a high temperature of 100 ° C. and the binding property is weakened. Since the ionic conductive polymer having an ethylene oxide unit in the side chain has flexibility and binding property, it can be said that it has an effect of lowering the resistance at the interface with the inorganic solid electrolyte.

The electrode for a solid electrolyte secondary battery of the present invention can exhibit excellent charge / discharge characteristics by being used as an electrode for a solid electrolyte secondary battery, and can be used in vehicles such as electric vehicles and hybrid electric vehicles, and at home. It can be suitably used for large battery applications such as storage batteries for storing electric power.

Claims (9)

An electrode for an inorganic solid electrolyte secondary battery, comprising an electrode material layer containing an ionic conductive polymer having an ethylene oxide unit in a side chain and an ionic conductive polymer material containing a lithium salt compound, and an active material. The active material is LiMO ₂ , LiM ₂ O ₄ , Li ₂ MO ₃ , LiMEO ₄ (M in the formula is composed of a transition metal and contains at least one of Co, Mn, Ni, Cr, Fe and Ti). The electrode for an inorganic solid electrolyte secondary battery according to claim 1, wherein E is at least one selected from the group consisting of at least one of P and Si). The electrode for an inorganic solid electrolyte secondary battery according to claim 1, wherein the active material is at least one selected from the group consisting of a carbon material, a silicon-based compound, and a tin-based compound. The electrode for an inorganic solid electrolyte secondary battery according to any one of claims 1 to 3, wherein the ion conductive polymer is a polyether having an ethylene oxide unit in the side chain. The electrode for an inorganic solid electrolyte secondary battery according to any one of claims 1 to 4, which is used for a solid electrolyte secondary battery together with an inorganic solid electrolyte. The electrode for an inorganic solid electrolyte secondary battery according to claim 5, wherein the inorganic solid electrolyte is an oxide-based solid electrolyte or a sulfide-based solid electrolyte. A method for producing an electrode for an inorganic solid electrolyte secondary battery, comprising a step of impregnating a layer containing an active material with an ionic conductive polymer material having an ionic conductive polymer having an ethylene oxide unit in a side chain and an ionic conductive polymer material containing a lithium salt compound. The method for producing an electrode for an inorganic solid electrolyte secondary battery according to claim 7, further comprising a step of cross-linking the layer impregnated with the ion conductive polymer material by heating or irradiation with active energy rays. An inorganic solid electrolyte secondary battery comprising the electrode for the inorganic solid electrolyte secondary battery according to any one of claims 1 to 6.