WO2021261526A1 - Composition contenant un électrolyte solide inorganique, feuille pour batterie secondaire entièrement solide, batterie secondaire entièrement solide, et procédés de production de feuille pour batterie secondaire entièrement solide et batterie secondaire entièrement solide - Google Patents

Composition contenant un électrolyte solide inorganique, feuille pour batterie secondaire entièrement solide, batterie secondaire entièrement solide, et procédés de production de feuille pour batterie secondaire entièrement solide et batterie secondaire entièrement solide Download PDF

Info

Publication number
WO2021261526A1
WO2021261526A1 PCT/JP2021/023810 JP2021023810W WO2021261526A1 WO 2021261526 A1 WO2021261526 A1 WO 2021261526A1 JP 2021023810 W JP2021023810 W JP 2021023810W WO 2021261526 A1 WO2021261526 A1 WO 2021261526A1
Authority
WO
WIPO (PCT)
Prior art keywords
solid electrolyte
group
secondary battery
polymer
hydrogen
Prior art date
Application number
PCT/JP2021/023810
Other languages
English (en)
Japanese (ja)
Inventor
浩司 安田
宏顕 望月
陽 串田
Original Assignee
富士フイルム株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 富士フイルム株式会社 filed Critical 富士フイルム株式会社
Priority to JP2022532519A priority Critical patent/JP7407286B2/ja
Publication of WO2021261526A1 publication Critical patent/WO2021261526A1/fr

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H01M10/0562—Solid materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to an inorganic solid electrolyte-containing composition, an all-solid-state secondary battery sheet and an all-solid-state secondary battery, and a method for manufacturing an all-solid-state secondary battery sheet and an all-solid-state secondary battery.
  • the all-solid-state secondary battery consists of a negative electrode, an electrolyte, and a positive electrode, all of which are solid, and can greatly improve the safety and reliability of batteries using organic electrolytes. It is also said that it will be possible to extend the service life. Further, the all-solid-state secondary battery can have a structure in which electrodes and electrolytes are directly arranged side by side and arranged in series. Therefore, it is possible to increase the energy density as compared with a secondary battery using an organic electrolytic solution, and it is expected to be applied to an electric vehicle, a large storage battery, or the like.
  • examples of the substance forming the constituent layer include an inorganic solid electrolyte, an active material, and the like.
  • this inorganic solid electrolyte particularly an oxide-based inorganic solid electrolyte and a sulfide-based inorganic solid electrolyte, has been attracting attention as an electrolyte material having high ionic conductivity approaching that of an organic electrolytic solution.
  • a material for forming a constituent layer of an all-solid-state secondary battery (constituent layer forming material)
  • a material containing the above-mentioned inorganic solid electrolyte and the like has been proposed.
  • Patent Document 1 describes an inorganic solid electrolyte (A) having the conductivity of an ion of a metal belonging to Group 1 or Group 2 of the Periodic Table, and a macromonomer having a number average molecular weight of 1,000 or more as a side chain component.
  • a solid electrolyte composition comprising a binder particle (B) having an average particle diameter of 10 nm or more and 1,000 nm or less, which is composed of a polymer incorporating (X), and a dispersion medium (C).
  • the constituent layer of the all-solid secondary battery is formed of solid particles (inorganic solid electrolyte, active material, conductive auxiliary agent, etc.), the interfacial contact state between the solid particles is restricted, and the interfacial resistance increases (ion conductivity). Is likely to decrease). As the interfacial resistance between solid particles increases, the battery resistance of the all-solid-state secondary battery also increases. Further, the increase in battery resistance is further accelerated by the voids between the solid particles generated by the charging and discharging of the all-solid-state secondary battery, which in turn leads to the deterioration of the cycle characteristics of the all-solid-state secondary battery.
  • the increase in battery resistance is not only due to the interfacial contact between solid particles, but also due to the non-uniform presence (arrangement) of solid particles in the constituent layer, and the surface smoothness (also referred to as surface flatness) of the constituent layer. ) Is also a factor. Therefore, when the constituent layer is formed of the constituent layer forming material, the constituent layer forming material has a characteristic (dispersion) that stably maintains not only the dispersibility of the solid particles immediately after preparation but also the dispersibility of the solid particles immediately after preparation (dispersion). Stability) and the property of easily forming a coating film having a flat surface (good surface property) (surface smoothness) are also required.
  • Patent Document 1 has not been examined based on such a viewpoint. Moreover, in recent years, research and development such as high performance and practical application of electric vehicles have progressed rapidly, and the demand for battery performance (for example, cycle characteristics) required for all-solid-state secondary batteries has become higher.
  • the present invention is an inorganic solid electrolyte-containing composition having excellent dispersion stability and surface smoothness, and by using it as a material for forming a constituent layer of an all-solid secondary battery, it is possible to further suppress an increase in battery resistance and an excellent cycle. It is an object of the present invention to provide an inorganic solid electrolyte-containing composition capable of realizing the characteristics.
  • the present invention also provides a method for manufacturing an all-solid-state secondary battery sheet and an all-solid-state secondary battery, and an all-solid-state secondary battery sheet and an all-solid-state secondary battery using this inorganic solid electrolyte-containing composition. The challenge is to provide.
  • the hydrogen-binding group (BHa) introduced into the side chain of the polymer is utilized to dissolve the binder constituent component containing this polymer in the dispersion medium. It has been found that by expressing the property, it is possible to form a coating film having a flat surface while suppressing reaggregation or sedimentation of solid particles such as an inorganic solid electrolyte over time.
  • the hydrogen-binding group (BHa) is used to reduce the solubility of the binder constituent in the dispersion medium, and the binder is solidified or precipitated as a polymer binder. Therefore, it was found that the inorganic solid electrolytes can be bound to each other while suppressing the increase in the interfacial resistance.
  • this inorganic solid electrolyte-containing composition as a constituent layer forming material, a constituent layer having a flat surface on which solid particles are bound to each other while suppressing an increase in interfacial resistance between solid particles can be formed over time.
  • C1 A polymer C1-1 having at least one hydrogen-binding group (BHa) capable of forming two or more hydrogen bonds in a side chain, and a hydrogen bond having an active hydrogen atom and containing the active hydrogen atom.
  • Compound C1-2 having a CRogP value of 1.5 or more and having a hydrogen-binding group (BHb) capable of forming a hydrogen bond with the sex group (BHa).
  • C2 Polymer C2 having two or more hydrogen-bonding groups (BHa) capable of forming two or more hydrogen bonds in the side chain and having an SP value of 22.5 or less.
  • C3 Two or more of the above polymers C1-1, or one or more of the above polymers C1-1 and one or more of the above polymers C2 ⁇ 2>
  • ⁇ 3> The inorganic solid electrolyte-containing composition according to ⁇ 2>, wherein a hydrogen-bonding group (BHa) is introduced into the constituents.
  • BHa hydrogen-bonding group
  • ⁇ 4> The composition containing an inorganic solid electrolyte according to any one of ⁇ 1> to ⁇ 3>, wherein the inorganic solid electrolyte is a sulfide-based inorganic solid electrolyte.
  • ⁇ 5> The inorganic solid electrolyte-containing composition according to any one of ⁇ 1> to ⁇ 4>, wherein the dispersion medium contains at least one selected from a ketone compound, an aliphatic compound and an ester compound.
  • ⁇ 6> The inorganic solid electrolyte-containing composition according to any one of ⁇ 1> to ⁇ 5>, which contains an active substance.
  • ⁇ 7> The inorganic solid electrolyte-containing composition according to any one of ⁇ 1> to ⁇ 6>, which contains a conductive auxiliary agent.
  • ⁇ 8> An all-solid-state secondary battery sheet having a layer composed of the inorganic solid electrolyte-containing composition according to any one of ⁇ 1> to ⁇ 7> above.
  • ⁇ 9> An all-solid-state secondary battery including a positive electrode active material layer, a solid electrolyte layer, and a negative electrode active material layer in this order.
  • At least one layer of the positive electrode active material layer, the solid electrolyte layer, and the negative electrode active material layer is a layer composed of the inorganic solid electrolyte-containing composition according to any one of ⁇ 1> to ⁇ 7>.
  • Solid secondary battery. ⁇ 10> A method for producing a sheet for an all-solid secondary battery, which forms a film of the inorganic solid electrolyte-containing composition according to any one of ⁇ 1> to ⁇ 7>.
  • ⁇ 11> A method for manufacturing an all-solid-state secondary battery, wherein the all-solid-state secondary battery is manufactured through the manufacturing method according to ⁇ 10> above.
  • the present invention is an inorganic solid electrolyte-containing composition having excellent dispersion stability and surface smoothness, and by using it as a constituent layer forming material for an all-solid secondary battery, further suppression of an increase in battery resistance (ion conductivity). ) And an inorganic solid electrolyte-containing composition capable of achieving excellent cycle characteristics can be provided. Further, the present invention can provide an all-solid-state secondary battery sheet and an all-solid-state secondary battery having a layer composed of the inorganic solid electrolyte-containing composition. Furthermore, the present invention can provide a sheet for an all-solid-state secondary battery and a method for producing an all-solid-state secondary battery using this inorganic solid electrolyte-containing composition.
  • FIG. 2 is a vertical sectional view schematically showing the coin-type all-solid-state secondary battery produced in the examples.
  • FIG. 3 is a diagram illustrating a layer thickness measurement point in the surface smoothness test in the example.
  • the numerical range represented by using "-" means a range including the numerical values before and after "-" as the lower limit value and the upper limit value.
  • the indication of a compound is used to mean that the compound itself, its salt, and its ion are included. Further, it is meant to include a derivative which has been partially changed, such as by introducing a substituent, as long as the effect of the present invention is not impaired.
  • (meth) acrylic means one or both of acrylic and methacrylic. The same applies to (meth) acrylate.
  • substituents or the like may be the same or different from each other. Means that.
  • the polymer means a polymer, but is synonymous with a so-called polymer compound.
  • the polymer binder means a binder composed of a polymer, and includes the polymer itself and a binder formed containing the polymer.
  • the polymer binder is formed from a binder component described later, and in the case of the binder component (C1), the polymer binder may or may not contain compound C1-2.
  • the composition containing an inorganic solid electrolyte of the present invention contains an inorganic solid electrolyte having ionic conductivity of a metal belonging to Group 1 or Group 2 of the Periodic Table, a binder component, and a dispersion medium.
  • the binder component contained in the inorganic solid electrolyte-containing composition constitutes a polymer binder in the constituent layer formed of the inorganic solid electrolyte-containing composition, and the inorganic solid electrolyte (further, an active material that can coexist).
  • Conductive aid for example, inorganic solid electrolytes to each other, inorganic solid electrolytes to live materials, active materials to each other
  • the binder constituent component contains a compound or a combination of compounds specified in at least one of the following (C1) to (C3) in the composition containing an inorganic solid electrolyte.
  • each compound specified in any of (C1) to (C3) can be appropriately combined, but the compound specified in any of (C1) to (C3) or a combination of compounds is included. Is good.
  • (C1) A polymer C1-1 having at least one hydrogen-binding group (BHa) capable of forming two or more hydrogen bonds in a side chain, and an active hydrogen atom containing the active hydrogen atom.
  • Combination of compound C1-2 having a CRogP value of 1.5 or more (C2) having a hydrogen-binding group (BHb) capable of forming a hydrogen bond with a binding group (BHa)
  • C3 Two or more kinds of polymers C1-1 or a combination of one or more kinds of polymers C1-1 and one or more kinds of polymers C2
  • the binder component and the polymer binder may or may not have a function of binding solid particles to each other.
  • the composition containing an inorganic solid electrolyte of the present invention is preferably a slurry in which the inorganic solid electrolyte is dispersed in a dispersion medium.
  • the binder component defined by any one of (C1) to (C3) above exhibits solubility (solubleness) in the dispersion medium contained in the inorganic solid electrolyte-containing composition, and is inorganic. It is dissolved in a dispersion medium in the solid electrolyte-containing composition.
  • the fact that the binder component is dissolved in the dispersion medium means, for example, that the solubility is 50% or more in the solubility measurement.
  • the binder component dissolved in the composition containing an inorganic solid electrolyte has a function of adsorbing to solid particles such as an inorganic solid electrolyte and dispersing it in a dispersion medium. This makes it possible to improve the dispersion stability and surface smoothness (also referred to as dispersion characteristics) of the composition containing an inorganic solid electrolyte.
  • the adsorption of the binder constituents to the solid particles includes not only physical adsorption but also chemical adsorption (adsorption by chemical bond formation, adsorption by electron transfer, etc.).
  • the composition containing an inorganic solid electrolyte of the present invention is excellent in dispersion stability and surface smoothness.
  • this inorganic solid electrolyte-containing composition as a constituent layer forming material, an all-solid-state secondary battery sheet having a constituent layer having a flat surface and excellent surface properties, and an all-solid-state battery having low resistance and excellent cycle characteristics.
  • a secondary battery can be realized.
  • the active material layer formed on the current collector is formed of the inorganic solid electrolyte-containing composition of the present invention, the adhesion between the current collector and the active material layer is also excellent, and the cycle characteristics are further improved. Can be planned.
  • the polymer C1-1 contained in the binder constituent is usually completely dissolved in the dispersion medium because the hydrogen-bonding group (BHa) tends to form a hydrogen bond in the molecule. do not do.
  • BHa hydrogen-bonding group
  • a compound C1-2 or a polymer (a different kind of polymer C1-1 or a polymer C2, etc.) capable of forming a hydrogen bond is allowed to coexist with the polymer C1-1, the intramolecular hydrogen bond of the polymer C1-1 is formed.
  • the hydrogen-bonding group easily forms a hydrogen bond between the molecules in the composition containing an inorganic solid electrolyte, and is a dispersion medium. It is considered that the solubility in the hydrogen is increased. It is considered that the polymers C1-1 and C2 that have formed intermolecular hydrogen bonds have increased solubility in the dispersion medium and are dissolved in the dispersion medium, and are appropriately adsorbed on the solid particles while maintaining the dissolved state in the dispersion medium. Be done.
  • the polymer C1-1 is formed when the constituent layer is formed (for example, when the composition containing an inorganic solid electrolyte is applied and further dried). And it is considered that the intermolecular hydrogen bond formed in C2 is cleaved and an intramolecular hydrogen bond is formed instead. As intramolecular hydrogen bonds are formed, each polymer becomes unable to maintain its solubility in the dispersion medium and solidifies or precipitates to form a polymer binder, partially without covering the entire surface of the solid particles. It is considered to be coated (adsorbed).
  • the contact between the solid particles is not hindered by the presence of the polymer binder, and the ionic conduction path due to the contact between the solid particles is sufficiently constructed (the increase in the interfacial resistance between the solid particles is suppressed), and the solid particles are separated from each other.
  • the composition containing an inorganic solid electrolyte of the present invention can maintain the dispersion characteristics even when the constituent layer is formed, and suppresses the variation in the contact state of the solid particles in the constituent layer (arrangement of the solid particles in the constituent layer). It is considered that uniform contact (adhesion) of solid particles can be ensured.
  • the inorganic solid electrolyte-containing composition is easy to form a film, and the inorganic solid electrolyte-containing composition flows appropriately (leveling) at the time of film formation, and the uneven surface caused by insufficient flow or excessive flow.
  • the constituent layer is free from roughness and surface roughness due to clogging of the ejection portion during film formation (excellent flatness of the film formation surface). In this way, it is considered that an all-solid-state secondary battery sheet having a flat surface (uniform layer thickness) and a low resistance (high conductivity) constituent layer can be realized.
  • An all-solid-state secondary battery provided with a constituent layer exhibiting the above-mentioned characteristics exhibits excellent cycle characteristics even after repeated charging and discharging under normal conditions.
  • a further increase in battery resistance and a decrease in cycle characteristics become noticeable at an early stage due to high-output charging / discharging (high-speed charging / discharging) for practical use.
  • the all-solid-state secondary battery of the present invention enables high-speed charging / discharging at a large current in addition to charging / discharging under normal conditions.
  • the generation of voids due to expansion and contraction of the active material or the like is effectively suppressed, and excellent cycle characteristics can be realized.
  • the constituent layer is formed while maintaining a highly (uniform) dispersed state immediately after preparation. Therefore, the contact (adhesion) of the polymer binder to the surface of the current collector is not hindered by the solid particles that have been preferentially settled, and the polymer binder is in contact with the surface of the current collector (adhesion) in a state of being dispersed with the solid particles. It is thought that it can be done.
  • the electrode sheet for an all-solid-state secondary battery in which the active material layer is formed on the current collector with the inorganic solid electrolyte-containing composition of the present invention can realize strong adhesion between the current collector and the active material.
  • the all-solid secondary battery in which the active material layer is formed on the current collector with the inorganic solid electrolyte-containing composition of the present invention exhibits strong adhesion between the current collector and the active material, and has cycle characteristics and conductivity. Further improvement can be realized.
  • the composition containing an inorganic solid electrolyte of the present invention is a material for forming a solid electrolyte layer or an active material layer of an all-solid-state secondary battery sheet (including an all-solid-state secondary battery electrode sheet) or an all-solid-state secondary battery. It can be preferably used as a constituent layer forming material). In particular, it can be preferably used as a material for forming a negative electrode sheet for an all-solid-state secondary battery or a negative electrode active material layer containing a negative electrode active material having a large expansion and contraction due to charging and discharging. Can be achieved.
  • the composition containing an inorganic solid electrolyte of the present invention is preferably a non-aqueous composition.
  • the non-aqueous composition includes not only a water-free aspect but also a form in which the water content (also referred to as water content) is preferably 500 ppm or less.
  • the water content is more preferably 200 ppm or less, further preferably 100 ppm or less, and particularly preferably 50 ppm or less.
  • the water content indicates the amount of water contained in the inorganic solid electrolyte-containing composition (mass ratio to the inorganic solid electrolyte-containing composition), and specifically, is filtered through a 0.02 ⁇ m membrane filter and Karl Fischer.
  • the value shall be the value measured using titration.
  • the composition containing an inorganic solid electrolyte of the present invention also includes an embodiment containing an active material, a conductive auxiliary agent, and the like in addition to the inorganic solid electrolyte (the composition of this embodiment is referred to as an electrode composition).
  • the composition of this embodiment is referred to as an electrode composition.
  • the inorganic solid electrolyte-containing composition of the present invention contains an inorganic solid electrolyte.
  • the inorganic solid electrolyte is an inorganic solid electrolyte
  • the solid electrolyte is a solid electrolyte capable of transferring ions inside the solid electrolyte. Since it does not contain organic substances as the main ionic conductive material, it is an organic solid electrolyte (polyelectrolyte represented by polyethylene oxide (PEO), organic represented by lithium bis (trifluoromethanesulfonyl) imide (LiTFSI), etc.). It is clearly distinguished from (electrolyte salt).
  • PEO polyethylene oxide
  • LiTFSI lithium bis (trifluoromethanesulfonyl) imide
  • the inorganic solid electrolyte is a solid in a steady state, it is usually not dissociated or liberated into cations and anions. In this respect, it is also clearly distinguished from the electrolyte or inorganic electrolyte salts (LiPF 6 , LiBF 4 , Lithium bis (fluorosulfonyl) imide (LiFSI), LiCl, etc.) that are dissociated or liberated into cations and anions in the polymer. Will be done.
  • the inorganic solid electrolyte is not particularly limited as long as it has the ionic conductivity of a metal belonging to Group 1 or Group 2 of the Periodic Table, and is generally one having no electron conductivity.
  • the inorganic solid electrolyte preferably has ionic conductivity of lithium ions.
  • a solid electrolyte material usually used for an all-solid secondary battery can be appropriately selected and used.
  • examples of the inorganic solid electrolyte include (i) a sulfide-based inorganic solid electrolyte, (ii) an oxide-based inorganic solid electrolyte, (iii) a halide-based inorganic solid electrolyte, and (iv) a hydride-based inorganic solid electrolyte.
  • the sulfide-based inorganic solid electrolyte is preferable from the viewpoint that a better interface can be formed between the active material and the inorganic solid electrolyte.
  • the sulfide-based inorganic solid electrolyte contains a sulfur atom, has ionic conductivity of a metal belonging to Group 1 or Group 2 of the Periodic Table, and is electronically insulated. Those having sex are preferable.
  • the sulfide-based inorganic solid electrolyte preferably contains at least Li, S and P as elements and has lithium ion conductivity, but other than Li, S and P may be used depending on the purpose or case. It may contain an element.
  • Examples of the sulfide-based inorganic solid electrolyte include a lithium ion conductive inorganic solid electrolyte satisfying the composition represented by the following formula (S1).
  • L a1 M b1 P c1 S d1 A e1 (S1)
  • L represents an element selected from Li, Na and K, with Li being preferred.
  • M represents an element selected from B, Zn, Sn, Si, Cu, Ga, Sb, Al and Ge.
  • A represents an element selected from I, Br, Cl and F.
  • a1 to e1 indicate the composition ratio of each element, and a1: b1: c1: d1: e1 satisfy 1 to 12: 0 to 5: 1: 2 to 12: 0 to 10.
  • a1 is preferably 1 to 9, more preferably 1.5 to 7.5.
  • b1 is preferably 0 to 3, more preferably 0 to 1.
  • d1 is preferably 2.5 to 10, more preferably 3.0 to 8.5.
  • e1 is preferably 0 to 5, more preferably 0 to 3.
  • composition ratio of each element can be controlled by adjusting the blending amount of the raw material compound when producing the sulfide-based inorganic solid electrolyte as described below.
  • the sulfide-based inorganic solid electrolyte may be amorphous (glass) or crystallized (glass-ceramic), or only a part thereof may be crystallized.
  • Li—P—S based glass containing Li, P and S, or Li—P—S based glass ceramics containing Li, P and S can be used.
  • Sulfide-based inorganic solid electrolytes include, for example, lithium sulfide (Li 2 S), phosphorus sulfide (for example, diphosphorus pentasulfide (P 2 S 5 )), simple phosphorus, simple sulfur, sodium sulfide, hydrogen sulfide, and lithium halide (eg, lithium halide). It can be produced by the reaction of at least two or more raw materials in the sulfides of the elements represented by LiI, LiBr, LiCl) and M (for example, SiS 2 , SnS, GeS 2).
  • the ratio of Li 2 S and P 2 S 5 is, Li 2 S: at a molar ratio of P 2 S 5, preferably 60: 40 ⁇ It is 90:10, more preferably 68:32 to 78:22.
  • the lithium ion conductivity can be made high.
  • the lithium ion conductivity can be preferably 1 ⁇ 10 -4 S / cm or more, and more preferably 1 ⁇ 10 -3 S / cm or more. There is no particular upper limit, but it is practical that it is 1 ⁇ 10 -1 S / cm or less.
  • Li 2 S-P 2 S 5 Li 2 S-P 2 S 5 -LiCl, Li 2 S-P 2 S 5 -H 2 S, Li 2 S-P 2 S 5 -H 2 S-LiCl, Li 2 S-LiI-P 2 S 5 , Li 2 S-LiI-Li 2 O-P 2 S 5 , Li 2 S-LiBr-P 2 S 5 , Li 2 S-Li 2 O-P 2 S 5 , Li 2 S-Li 3 PO 4- P 2 S 5 , Li 2 S-P 2 S 5 -P 2 O 5 , Li 2 S-P 2 S 5- SiS 2 , Li 2 S-P 2 S 5- SiS 2 -LiCl, Li 2 S-P 2 S 5 -SnS, Li 2 S-P 2 S 5 -Al 2 S 3, Li 2 S-GeS 2,
  • the mixing ratio of each raw material does not matter.
  • an amorphization method can be mentioned.
  • the amorphization method include a mechanical milling method, a solution method and a melt quenching method. This is because processing at room temperature is possible and the manufacturing process can be simplified.
  • the oxide-based inorganic solid electrolyte contains an oxygen atom, has ionic conductivity of a metal belonging to Group 1 or Group 2 of the Periodic Table, and is electronically insulated. Those having sex are preferable.
  • the oxide-based inorganic solid electrolyte preferably has an ionic conductivity of 1 ⁇ 10 -6 S / cm or more, more preferably 5 ⁇ 10 -6 S / cm or more, and 1 ⁇ 10 -5 S. It is particularly preferable that it is / cm or more.
  • the upper limit is not particularly limited, but it is practical that it is 1 ⁇ 10 -1 S / cm or less.
  • Li xa La ya TiO 3 [xa satisfies 0.3 ⁇ xa ⁇ 0.7, and ya satisfies 0.3 ⁇ ya ⁇ 0.7.
  • LLT Li xb Layb Zr zb M bb mb Onb
  • M bb is one or more elements selected from Al, Mg, Ca, Sr, V, Nb, Ta, Ti, Ge, In and Sn.
  • Xb satisfies 5 ⁇ xb ⁇ 10, yb satisfies 1 ⁇ yb ⁇ 4, zb satisfies 1 ⁇ zb ⁇ 4, mb satisfies 0 ⁇ mb ⁇ 2, and nb satisfies 5 ⁇ nb ⁇ 20. Satisfies.); Li xc Byc M cc zc Onc (M cc is one or more elements selected from C, S, Al, Si, Ga, Ge, In and Sn.
  • Xc is 0 ⁇ xc ⁇ 5 , Yc satisfies 0 ⁇ yc ⁇ 1, zc satisfies 0 ⁇ zc ⁇ 1, nc satisfies 0 ⁇ nc ⁇ 6); Li xd (Al, Ga) yd (Ti, Ge) zd Si.
  • Li xf Si yf O zf (xf satisfies 1 ⁇ xf ⁇ 5, yf satisfies 0 ⁇ yf ⁇ 3 , zf satisfies 1 ⁇ zf ⁇ 10);.
  • Li xg S yg O zg (xg satisfies 1 ⁇ xg ⁇ 3, yg satisfies 0 ⁇ yg ⁇ 2, zg satisfies 1 ⁇ zg ⁇ 10.
  • Li 7 La 3 Zr 2 O 12 (LLZ) having a garnet-type crystal structure.
  • Phosphorus compounds containing Li, P and O are also desirable.
  • lithium phosphate Li 3 PO 4
  • LiPON in which a part of the oxygen element of lithium phosphate is replaced with a nitrogen element
  • LiPOD 1 LiPON in which a part of the oxygen element of lithium phosphate is replaced with a nitrogen element
  • LiPOD 1 is preferably Ti, V, Cr, Mn, Fe, Co, It is one or more elements selected from Ni, Cu, Zr, Nb, Mo, Ru, Ag, Ta, W, Pt and Au
  • LiA 1 ON A 1 is one or more elements selected from Si, B, Ge, Al, C and Ga
  • the halide-based inorganic solid electrolyte contains a halogen atom, has the conductivity of an ion of a metal belonging to Group 1 or Group 2 of the Periodic Table, and has electrons. Insulating compounds are preferred.
  • the halide-based inorganic solid electrolyte is not particularly limited, and examples thereof include compounds such as Li 3 YBr 6 and Li 3 YCl 6 described in LiCl, LiBr, LiI, ADVANCED MATERIALS, 2018, 30, 1803075. Of these, Li 3 YBr 6 and Li 3 YCl 6 are preferable.
  • the hydride-based inorganic solid electrolyte contains a hydrogen atom, has ionic conductivity of a metal belonging to Group 1 or Group 2 of the Periodic Table, and is electronically insulated. A compound having a property is preferable.
  • the hydride-based inorganic solid electrolyte is not particularly limited, and examples thereof include LiBH 4 , Li 4 (BH 4 ) 3 I, and 3LiBH 4- LiCl.
  • the inorganic solid electrolyte is preferably particles.
  • the average particle size (volume average particle size) of the inorganic solid electrolyte is not particularly limited, but is preferably 0.01 ⁇ m or more, and more preferably 0.1 ⁇ m or more.
  • the upper limit is preferably 100 ⁇ m or less, and more preferably 50 ⁇ m or less.
  • the average particle size of the inorganic solid electrolyte is measured by the following procedure. Inorganic solid electrolyte particles are prepared by diluting a 1% by mass dispersion in a 20 mL sample bottle with water (heptane in the case of a water-unstable substance).
  • the diluted dispersion sample is irradiated with 1 kHz ultrasonic waves for 10 minutes, and immediately after that, it is used for the test.
  • data was captured 50 times using a laser diffraction / scattering particle size distribution measuring device LA-920 (trade name, manufactured by HORIBA) using a measuring quartz cell at a temperature of 25 ° C. Obtain the volume average particle size.
  • JIS Japanese Industrial Standards
  • Z 8828 2013 "Particle size analysis-Dynamic light scattering method” as necessary. Five samples are prepared for each level and the average value is adopted.
  • the inorganic solid electrolyte may contain one kind or two or more kinds.
  • the mass (mg) (grain amount) of the inorganic solid electrolyte per unit area (cm 2) of the solid electrolyte layer is not particularly limited. It can be appropriately determined according to the designed battery capacity, and can be, for example, 1 to 100 mg / cm 2 .
  • the amount of the inorganic solid electrolyte is preferably in the above range as the total amount of the active material and the inorganic solid electrolyte.
  • the content of the inorganic solid electrolyte in the composition containing the inorganic solid electrolyte is not particularly limited, but is 50% by mass or more at 100% by mass of the solid content in terms of binding property and dispersibility. Is more preferable, 70% by mass or more is more preferable, and 90% by mass or more is particularly preferable. From the same viewpoint, the upper limit is preferably 99.9% by mass or less, more preferably 99.5% by mass or less, and particularly preferably 99% by mass or less.
  • the content of the inorganic solid electrolyte in the inorganic solid electrolyte-containing composition is such that the total content of the active material and the inorganic solid electrolyte is in the above range. Is preferable.
  • the solid content refers to a component that does not disappear by volatilizing or evaporating when the composition containing an inorganic solid electrolyte is dried at 150 ° C. under a nitrogen atmosphere at 1 mmHg for 6 hours. .. Typically, it refers to a component other than the dispersion medium described later.
  • the inorganic solid electrolyte-containing composition of the present invention is a compound specified in at least one of the following (C1) to (C3) as a component constituting the polymer binder that functions as a binder in the constituent layer. Or it contains a combination of compounds.
  • the composition containing an inorganic solid electrolyte contains a binder component, it includes an embodiment in which a part of the binder component forms a polymer binder.
  • the binder component forms a polymer binder at the time of film formation of the composition containing an inorganic solid electrolyte. It is considered that this is because intramolecular hydrogen bonds are selectively formed in the polymer C1-1 or C2.
  • the polymer binder contained in the constituent layer thus formed can be said to be a (intramolecular) hydrogen bond of the polymer C1-1 or C2 defined by any one of (C1) to (C3).
  • the polymer binder is not uniquely determined by the type of compound specified in any of (C1) to (C3), the type or combination of hydrogen-bonding groups, etc., and in the present invention, (meth). Hydrogen bonds of acrylic polymers or vinyl polymers are preferred.
  • the polymer C1-1 or C2 having a hydrogen-bonding group (BHa) decreases in solubility in a dispersion medium as the number of intramolecular hydrogen bonds formed increases, and dissolves in the dispersion medium as the number of intermolecular hydrogen bonds formed increases. It is thought that sex will increase. Therefore, according to the present invention, the solubility of the polymer C1-1 or C2 in the dispersion medium can be controlled by increasing or decreasing the amount of hydrogen bonds in the molecule. As a result, it is possible to improve the dispersion characteristics of the composition containing an inorganic solid electrolyte, and to realize the function of binding solid particles to each other in the constituent layer and the suppression of an increase in interfacial resistance.
  • the polymer binder contained in the constituent layer may be one kind or two or more kinds. In the present invention, when the constituent layer contains a polymer binder, it includes an embodiment in which the binder constituent component is contained (residual).
  • the binder component is at least one of a combination of compounds specified in (C1) below, a compound specified in (C2), and a combination of compounds specified in (C3).
  • the compound C1-2 easily forms an intermolecular hydrogen bond with the polymer C1-1 in the inorganic solid electrolyte-containing composition (dispersion medium) and dissolves in the dispersion medium.
  • compound C1-2 can be said to be a compatibilizer for polymer C1-1.
  • -Polymer C1-1- Polymer C1-1 has at least one hydrogen-bonding group (BHa) in the side chain capable of forming two or more hydrogen bonds.
  • the hydrogen-bonding group (BHa) is not particularly limited as long as it is a substituent or a linking group capable of forming two or more hydrogen bonds.
  • This hydrogen-bonding group (BHa) is an acceptor site (unshared electron pair) that accepts a hydrogen atom and a donor site (hydrogen bondable hydrogen atom) that supplies a hydrogen atom in one substituent (linking group). It is a substituent containing at least one of the above, and preferably at least one hydrogen-bonding group (BHa) is a group containing one or more acceptor sites and one or more donor sites.
  • the hydrogen-bonding group (BHa) usually forms a hydrogen bond with another hydrogen-bonding group (BHa) or the hydrogen-bonding group (BHb) possessed by the compound C1-2 described later, but the effects of the present invention can be achieved.
  • a part of the hydrogen-bonding group (BHa) may form a hydrogen bond within one group as long as it is not impaired.
  • the number of hydrogen bonds that can be formed by the hydrogen-bonding group (BHa) may be 2 or more, and is preferably 3 or more, preferably 4 or more, in terms of ease of forming hydrogen bonds. More preferred.
  • the upper limit is not particularly limited, but is practically 10 or less, and is preferably 5 or less in terms of enhancing the solubility in the inorganic solid electrolyte-containing composition.
  • the total number of acceptor and donor sites of a hydrogen-bonding group (BHa) is usually synonymous with the number of hydrogen bonds that a hydrogen-bonding group (BHa) can form.
  • the combination of the acceptor site and the donor site of the hydrogen-bonding group (BHa) is not particularly limited and is appropriately determined, but includes both the acceptor site and the donor site in that a strong hydrogen bond can be formed.
  • a combination is preferable, and in the molecular chain constituting the hydrogen-bonding group, the acceptor site (excluding the hetero atom covalently bonded to the hydrogen atom of the donor site) and the donor site are alternately arranged (for example, a urea group and a urethane group). ) Is more preferable.
  • the donor site is not particularly limited, and examples thereof include a hydrogen atom capable of hydrogen bonding, and usually a hydrogen atom bonded to a hetero atom such as oxygen or nitrogen (active hydrogen atom).
  • a hydrogen atom co-bonded with a nitrogen atom a hydrogen atom co-bonded with an oxygen atom, a hydrogen atom co-bonded with a sulfur atom, a hydrogen atom co-bonded with a phosphorus atom, and the like can be mentioned.
  • a hydrogen atom covalently bonded to a nitrogen atom or a hydrogen atom covalently bonded to an oxygen atom is preferable in that it forms a stronger hydrogen bond with the acceptor moiety.
  • the nitrogen atom to which the hydrogen atom is covalently bonded is not limited to the primary or secondary amino group, and if the hydrogen atom is covalently bonded, it is contained in a functional group such as a urethane group or a urea group. Includes the nitrogen atom. The same applies to the phosphorus atom.
  • Examples of the hydrogen-bonding group (BHa) include a group composed of an appropriate combination of an acceptor site and a donor site.
  • Specific examples of the hydrogen-binding group (BHa) are not particularly limited, but for example, an acidic group such as a hydroxyl group or a carboxy group, a sulfanyl group, a primary or secondary amino group, or a primary or secondary amide group (amide bond).
  • examples of generally well-known nucleobases adenin and chimin / guanine and cytosine
  • lane supramolecular chemistry Choemistry Dojin 1997; by JM Lehn, translated by Takato Takeuchi). Chapter 9, pp.
  • Ra represents a hydrogen atom or a substituent (preferably selected from the substituent Z described later), and a hydrogen atom is preferable.
  • substituents such as hydroxyl groups and sulfanyl groups, substituents such as amide groups, urethane groups and urea groups or linking groups (bonds) are preferable.
  • the polymer C1-1 may have at least one hydrogen-bonding group (BHa) as described above, and may have 2 to 5 hydrogen-bonding groups (BHa). Improvement of dissolution in the dispersion medium by preferentially forming intermolecular hydrogen bonds in the composition containing an inorganic solid electrolyte, and reduction of solubility in the dispersion medium by preferentially forming intramolecular hydrogen bonds in the film forming process. Considering this, one type is preferable.
  • the number of hydrogen-bonding groups (BHa) contained in one molecule of the polymer C1-1 may be one or more, but it is preferably two or more in that a strong hydrogen bond can be formed.
  • the number of hydrogen-bonding groups (BHa) cannot be uniquely determined, but is appropriately determined depending on the number of hydrogen-bonding groups (BHa) possessed by the hydrogen-bonding constituents described later, the content of the hydrogen-bonding constituents, and the like. Will be done.
  • This hydrogen-bonding group (BHa) is contained in the side chain of the polymer C1-1, and is preferably introduced as a linking group or a (terminal) substituent in the side chain, and is introduced as a linking group in the side chain. It is more preferable that it is.
  • the main chain of a polymer means a linear molecular chain in which all other molecular chains constituting the polymer can be regarded as a branched chain or a pendant with respect to the main chain. Although it depends on the mass average molecular weight of the molecular chain regarded as a branched chain or a pendant chain, the longest chain among the molecular chains constituting the polymer is typically the main chain. However, the terminal group of the polymer terminal is not included in the main chain. Further, the side chain of the polymer means a molecular chain other than the main chain, and includes a short molecular chain and a long molecular chain.
  • having a hydrogen-bonding group (BHa) in the side chain of the polymer means that the hydrogen-bonding group (BHa) is indirectly bonded to an atom constituting the main chain of the polymer. It does not include an embodiment that directly bonds to an atom constituting the main chain.
  • the ester bond the one directly bonded to the atom constituting the main chain of the (meth) acrylic monomer is described above.
  • the hydrogen-bonding group (BHa) may be contained in the main chain of the polymer, but it is preferable that the hydrogen-bonding group (BHa) is not contained.
  • the group that links the main chain of the polymer with the hydrogen-bonding group (BHa) introduced as a linking group or a (terminal) substituent is not particularly limited and is appropriately selected.
  • an alkylene group preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, further preferably 1 to 3
  • an alkenylene group preferably 2 to 6 carbon atoms, more preferably 2 to 3 carbon atoms
  • an arylene preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, further preferably 1 to 3
  • an alkenylene group preferably 2 to 6 carbon atoms, more preferably 2 to 3 carbon atoms
  • R N represents a hydrogen atom, an alkyl group or carbon number of 1 to 6 carbon atoms 6 to 10 aryl groups are shown), carbonyl group, phosphate linking group (-OP (OH) (O) -O-), phosphonic acid linking group (-P (OH) (O) -O- ) Or a group related to a combination thereof.
  • Polyalkylene oxy chains can also be formed by combining alkylene groups and oxygen atoms.
  • a group composed of a combination of an alkylene group, an arylene group, a carbonyl group, an oxygen atom, a sulfur atom and an imino group is preferable, and a group composed of a combination of an alkylene group, an arylene group, a carbonyl group, an oxygen atom and an imino group is preferable.
  • -CO-O-group, -CO-N (R N) - (the R N are as defined above.) or groups are more preferred include an arylene group, -CO-O-alkylene group, - A CO-N ( RN ) -alkylene group or the like is particularly preferable.
  • the number of atoms constituting the linking group is preferably 1 to 36, more preferably 1 to 24, and even more preferably 1 to 12.
  • the number of linked atoms of the group to be linked is preferably 10 or less, and more preferably 8 or less.
  • the lower limit is 1 or more.
  • a hydrogen-bonding group (BHa) is introduced as a linking group
  • the terminal substituent to be bonded to the hydrogen-bonding group (BHa) is not particularly limited and is appropriately selected.
  • a group selected from the following substituent Z is mentioned, and among them, an alkyl group, an aralkyl group, an aryl group, a heterocyclic group and the like are preferably mentioned.
  • the polymer C1-1 may have a hydrogen-bonding group (acceptor site) capable of forming one hydrogen bond in addition to the hydrogen-bonding group (BHa).
  • the polymer C1-1 preferably has a small SP value in the composition containing an inorganic solid electrolyte in that the solubility in the dispersion medium is enhanced by improving the affinity with the dispersion medium.
  • the SP according to the calculation method described later is used.
  • the value is 21.0MPa 1/2 or less, and more preferably 20.5 MPa 1/2 or less.
  • the lower limit is not particularly limited, for example, is preferably 13.0 MPa 1/2 or more, more preferably 16.0MPa 1/2 or more, further not less 18.0 MPa 1/2 or more preferable.
  • the polymer C1-1 a commercially available product may be used, or a synthetic product may be used.
  • the content of the polymer C1-1 in the composition containing an inorganic solid electrolyte is not particularly limited, and is appropriately determined according to the dispersion characteristics, battery performance, and the like.
  • the content of the polymer C1-1 is 0.1 to 10.
  • the total content with the compound C1-2 in terms of the degree of improvement in dispersion characteristics, resistance, cycle characteristics, etc. at a solid content of 100% by mass. It is preferably 0% by mass, more preferably 0.2 to 5.0% by mass, and even more preferably 0.3 to 4.0% by mass.
  • the content of the polymer C1-1 in the composition containing an inorganic solid electrolyte is not particularly limited, but is 0.1 to 9 at a solid content of 100% by mass in terms of improvement in dispersion characteristics, resistance, cycle characteristics, and the like. It is preferably 9.9% by mass, more preferably 0.15 to 4.95% by mass, and even more preferably 0.25 to 3.96% by mass.
  • the mass ratio of the content of the polymer C1-1 to the content of the compound C1-2 [content of the polymer C1-1: content of the compound C1-2] is not particularly limited, but is a hydrogen-binding group ( In terms of the number of BHa) and (BHb), solubility in a dispersion medium due to the formation of hydrogen bonds, and the like, for example, it is preferably 50:50 to 99: 1, and preferably 70:30 to 97: 3. More preferably, it is 85:15 to 95: 5.
  • the content of the polymer C1-1 is the total amount including the polymer C1-1 forming the hydrogen bond.
  • This compound C1-2 contains an active hydrogen atom and has a hydrogen-bonding group (BHb) capable of forming a hydrogen bond with the hydrogen-bonding group (BHa) of the polymer C1-1.
  • the hydrogen-bonding group (BHb) contained in this compound C1-2 is different from the hydrogen-bonding group (BHa) in that it easily forms an intermolecular hydrogen bond with the polymer C1-1 in the inorganic solid electrolyte-containing composition. It is preferably a different group.
  • the hydrogen-bonding group (BHb) has an active hydrogen atom.
  • the active hydrogen atom may be any hydrogen atom capable of forming a hydrogen bond with the above-mentioned hydrogen-bonding group (BHa), usually the above-mentioned acceptor site, and each hydrogen atom described as a donor site of the hydrogen-bonding group (BHa). And the like, a hydrogen atom covalently bonded to a nitrogen atom or an oxygen atom is preferable in that a stronger hydrogen bond is formed with a hydrogen-bonding group (BHa).
  • the number of active hydrogen atoms contained in one hydrogen-bonding group (BHb) is not particularly limited, and is usually 1 to 8, preferably 1 or 2.
  • Examples of the hydrogen-binding group (BHb) having such an active hydrogen atom include a group containing a nitrogen atom, an oxygen atom, a sulfur atom or a phosphorus atom to which a hydrogen atom is covalently bonded, and specific examples thereof. Examples include an acidic group such as a hydroxyl group and a carboxy group, a sulfanyl group, a primary or secondary amino group, an alkylenediamine structure, and an alkyleneaminoether structure.
  • the hydrogen-bonding group (BHb) may further include the above-mentioned acceptor site, donor site, or the like to form the above-mentioned hydrogen-bonding group (BHa).
  • the amino group as the hydrogen-bonding group (BHb) may be an amide group which is the hydrogen-bonding group (BHa) or an amino group constituting a urethane group.
  • the group containing such an amino group include those described in the above-mentioned hydrogen-bonding group (BHa), and specific examples thereof include a primary or secondary amide group, a urethane group, and a urea group.
  • the hydrogen-bonding group (BHb) is preferably a hydroxyl group or a group containing an amino group or an amino group in that a strong hydrogen bond is formed with the hydrogen-bonding group (BHa).
  • Compound C1-2 may have one or more hydrogen-bonding groups (BHb), but is one in that it can form an efficient hydrogen bond with the polymer C1-1. Is preferable.
  • the combination of the hydrogen-bonding group (BHa) of the polymer C1-1 and the hydrogen-bonding group (BHb) of the compound C1-2 is not particularly limited and is appropriately set.
  • a combination of a preferable hydrogen-bonding group (BHa) and a preferable hydrogen-bonding group (BHb) is preferable, and any one of a hydroxyl group, a urethane group, and a urea group as the hydrogen-bonding group (BHa) is preferable.
  • a combination with a hydroxyl group as a hydrogen-bonding group (BHb) or an amino group or a group containing an amino group is more preferable.
  • Compound C1-2 has a CRogP value of 1.5 or more.
  • the composition is soluble in the dispersion medium of the inorganic solid electrolyte-containing composition and is compatible with the polymer C1-1 to increase the solubility of the polymer C1-1 in the dispersion medium, which contributes to the improvement of the dispersion characteristics.
  • the CLogP value is preferably 1.7 or more, more preferably 1.9 or more, and even more preferably 2.0 or more.
  • the upper limit is not particularly limited, but it is practically 12.0 or less, and preferably 6.0 or less.
  • the CLogP value is a value obtained by calculation of the common logarithm LogP of 1-octanol and the partition coefficient P to water.
  • the structure is drawn using ChemDraw of PerkinElmer Co., Ltd., and the calculated value is used.
  • the ClogP value is the sum of the products of the ClogP value of each compound and the mass fraction.
  • the compound C1-2 is not particularly limited as long as it satisfies the ClogP value and has the hydrogen-bonding group (BHb), and may be a low molecular weight compound (non-polymerizable compound) or a high molecular weight compound.
  • a small molecule compound is preferable because it can effectively reinforce the improvement of the dispersion characteristics by the polymer C1-1.
  • the low molecular weight compound is not particularly limited, and a compound in which the hydrogen-bonding group (BHb) is introduced as a substituent or a linking group (bond) into an appropriate basic skeleton is used.
  • the low molecular weight compound include an amine compound having an amino group (including a compound having an amino bond introduced as a linking group), an alcohol compound having a hydroxyl group, a thiol compound having a sulfanyl group, and a carboxy compound having a carboxy group.
  • Examples thereof include an acid compound, a sulfonic acid compound having a sulfo group, a phosphoric acid compound having a phosphoric acid group, and a phosphonic acid compound having a phosphonic acid group.
  • These compounds may be either an aliphatic compound or an aromatic compound, and the above-mentioned hydrogen-binding group (BHb) may be added to a compound such as an aliphatic saturated hydrocarbon, an aliphatic unsaturated hydrocarbon, an aromatic hydrocarbon, or an aromatic heterocycle. ) Is introduced.
  • alcohol compounds or amine compounds such as aliphatic saturated hydrocarbons, aliphatic unsaturated hydrocarbons, aromatic hydrocarbons and aromatic heterocycles are preferable, and alcohol compounds or amine compounds of aliphatic saturated hydrocarbons are more preferable. Chained or cyclic aliphatic saturated hydrocarbon alcohol compounds or amine compounds are more preferred.
  • the molecular weight and chemical structure of the small molecule compound are not particularly limited as long as they satisfy the ClogP value, and can be appropriately set.
  • the molecular weight can be 1000 or less, preferably 100 to 400.
  • the low molecular weight compound may have a substituent other than the hydrogen-bonding group (BHb) as long as it satisfies the ClogP value, and may have, for example, a group selected from the substituent Z described later. ..
  • the inorganic solid electrolyte-containing composition of the present invention may contain one or more compounds C1-2.
  • the content of the compound C1-2 in the composition containing an inorganic solid electrolyte is not particularly limited, and the solid content is 100% by mass in terms of solubility of the polymer C1-1 in a dispersion medium due to the formation of hydrogen bonds. It is preferably 0.05 to 8.0% by mass, more preferably 0.10 to 4.0% by mass, and even more preferably 0.15 to 3.0% by mass.
  • the content of the compound C1-2 is the total amount including the compound C1-2 forming the hydrogen bond.
  • the combination of the polymer C1-1 and the compound C1-2 is not particularly limited as long as it is a combination capable of forming a hydrogen bond, and for example, a preferable combination of the polymer C1-1 and a preferable combination of the compound C1-2. Can be mentioned.
  • the polymer C2 has two or more hydrogen-bonding groups (BHa) in the side chain capable of forming two or more hydrogen bonds.
  • This polymer C2 may be the same as the polymer C1-1 having two or more hydrogen-bonding groups (BHa).
  • the aspect of having the hydrogen-bonding group (BHa) of the polymer C2 and further the hydrogen-bonding group (BHa) in the side chain is the same as that of the polymer C1-1.
  • the polymer C2 may have at least two hydrogen-bonding groups (BHa), and may improve dissolution in a dispersion medium by preferentially forming intermolecular hydrogen bonds in an inorganic solid electrolyte-containing composition. Considering the reduction of solubility in the dispersion medium by preferentially forming intramolecular hydrogen bonds in the film forming process, it is preferable to have 2 to 5 types, and it is more preferable to have 2 or 3 types. preferable. It is preferable that the two or more hydrogen-bonding groups (BHa) possessed by the polymer C2 are different groups from each other in that a strong hydrogen-bonding property can be formed and the polymer C2 can be effectively solidified or precipitated.
  • BHa hydrogen-bonding groups
  • the combination of two or more hydrogen-bonding groups (BHa) is not particularly limited, and the hydrogen-bonding group (BHa) of the polymer C1-1 and the hydrogen-bonding property of the compound C1-2 described above are not particularly limited. Preferred combinations with the group (BHb) are mentioned.
  • the number of hydrogen-bonding groups (BHa) contained in one molecule of the polymer C2 may be at least one for each type of hydrogen-bonding group, but is two or more in that strong hydrogen bonds can be formed. Is preferable.
  • the number of hydrogen-bonding groups (BHa) cannot be uniquely determined, but is appropriately determined depending on the number of hydrogen-bonding groups (BHa) and the content of hydrogen-bonding components described later in the hydrogen-bonding components. Will be done.
  • the polymer C2 may have a hydrogen-bonding group capable of forming one hydrogen bond in addition to the hydrogen-bonding group (BHa).
  • the SP value of the polymer C2 according to the calculation method described later is 22.5 MPa 1/2 or less.
  • the affinity for the dispersion medium is enhanced, and particularly when an intermolecular hydrogen bond is formed, the solubility in the dispersion medium is enhanced, and the dispersion characteristics can be improved.
  • SP values of polymers C2 is preferably at 21.0MPa 1/2 or less, and more preferably 20.5 MPa 1/2 or less.
  • the lower limit is not particularly limited, for example, is preferably 13.0 MPa 1/2 or more, more that it is 16.0MPa 1/2 or more is more preferably 18.0 MPa 1/2 or more preferable.
  • the structural unit for specifying the SP value is determined. That is, in the present invention, when the SP value of the polymer is calculated, when the polymer (segment) is a chain-growth polymer, it is the same structural unit as the constituent component derived from the raw material compound, but the polymer is a step-growth polymer. In the case, the unit is different from the constituents derived from the raw material compound. For example, taking polyurethane as a step-growth polymerization polymer as an example, the structural unit for specifying the SP value is defined as follows.
  • one —NH—CO— group is bonded to an —O— group and the remaining —NH-CO—group is added to the constituent unit derived from the polyisocyanate compound.
  • the removed unit (unit having one urethane bond) is used.
  • the constituent unit derived from the polyol compound the -CO-NH- group was bonded to one —O— group with respect to the constituent component derived from the polyol compound, and the remaining —O— group was removed.
  • the unit (a unit having one urethane bond).
  • the constituent unit is determined in the same manner as that of polyurethane.
  • SP value of polymer It is calculated from the following formula using the structural unit determined as described above and the obtained SP value. The following values were determined in compliance with the literature, in terms of the SP value of the structural units in the SP value (MPa 1/2) (e.g., 1cal 1/2 cm -3/2 ⁇ 2.05J 1/2 cm -3 / 2 ⁇ 2.05 MPa 1/2 )).
  • SP p 2 (SP 1 2 x W 1 ) + (SP 2 2 x W 2 ) + ...
  • SP 1 , SP 2 Indicates the SP value of the constituent unit
  • W 1 , W 2 Indicates the mass fraction of the constituent unit.
  • the mass fraction of the constituent unit is the mass fraction in the polymer of the constituent component (raw material compound leading to this constituent) corresponding to the constituent unit.
  • the SP value of the polymer can be adjusted depending on the type or composition of the polymer (type and content of constituents) and the like.
  • the SP value of the polymer is calculated by the above formula for all the constituent units.
  • the SP value (MM excluded) calculated by the above formula may be obtained by excluding the component corresponding to the component derived from the macromonomer (MM). can.
  • the SP value (MM exclusion) calculated in this way the dispersion characteristic can be further improved.
  • the SP value (excluding MM) may be in the same range as the above SP value, but is preferably 13.0 to 22.5 MPa 1/2 , and 16.0 to 21.0 MPa 1/2 . It is more preferably 17.5 to 20.5 MPa 1/2 .
  • the inorganic solid electrolyte-containing composition of the present invention may contain one or more polymers C2.
  • the content of the polymer C2 in the composition containing an inorganic solid electrolyte is not particularly limited, and is appropriately determined according to the dispersion characteristics, battery performance, and the like.
  • the solid content is preferably 0.1 to 10.0% by mass, preferably 0.2 to 5.0% by mass. More preferably, it is more preferably 0.3 to 4.0% by mass.
  • the content of the polymer C2 is the total amount including the polymer C2 forming the hydrogen bond.
  • the binder component (C3) will be described.
  • One aspect of (C3) is to use two or more kinds of polymers C1-1 in combination, and instead of the compound C1-2 used in combination with the polymer C1-1 in the above (C1), another polymer C1-1.
  • Polymer C1-1 is as described above.
  • the polymer C1-1 used in combination of two types is preferably of a different type, and examples thereof include combinations of polymers having different types or compositions and different types of hydrogen-bonding groups (BHa), and a strong hydrogen bond can be formed. Therefore, a combination of different types of hydrogen-bonding groups (BHa) is more preferable.
  • BHa hydrogen-bonding group
  • C1-1 hydrogen-bonding group of the polymer C1-1 and the hydrogen bond of the compound C1-2 in the above-mentioned (C1) are not particularly limited.
  • Preferred combinations with the sex group (BHb) can be mentioned.
  • the polymer C1-1 contained in the inorganic solid electrolyte-containing composition may be of 2 or more types, and may be 2 to 5 types. It is preferably 2, 3 or 4 types.
  • the total content of the polymer C1-1 in the inorganic solid electrolyte-containing composition is not particularly limited, and is appropriately determined according to the dispersion characteristics, battery performance, and the like.
  • the solid content is preferably 0.1 to 10.0% by mass, preferably 0.2 to 5.0% by mass. More preferably, it is more preferably 0.3 to 4.0% by mass.
  • the ratio of the contents of two or more kinds of polymers C1-1 is not particularly limited, and the number of hydrogen-bonding groups (BHa) possessed by the polymer C1-1, solubility in a dispersion medium by forming hydrogen bonds, and the like can be determined. It will be decided as appropriate in consideration. For example, when two kinds are used in combination, the ratio of the content (% by mass) of one polymer to the other polymer is preferably 1:10 to 10: 1, and preferably 1: 5 to 5: 1. Is more preferable, and 1: 3 to 3: 1 is even more preferable.
  • the content of the polymer C1-1 is the total amount including the polymer C1-1 forming the hydrogen bond.
  • Another aspect of (C3) is to use one or more polymers C1-1 and one or more polymers C2 in combination.
  • the polymers C1-1 and C2 are as described above.
  • the hydrogen-bonding group (BHa) possessed by the polymer C1-1 and the hydrogen-bonding group (BHa) possessed by the polymer C2 are preferably of different types in that strong hydrogen bonds can be formed.
  • the combination of different types of hydrogen-bonding groups (BHa) is the same as in the above aspect.
  • the polymers C1-1 and C2 contained in the inorganic solid electrolyte-containing composition may be one or more kinds, respectively, and may be 2 to 5 kinds, but one kind is preferable.
  • the total content of the polymers C1-1 and C2 in the inorganic solid electrolyte-containing composition is not particularly limited and is appropriately determined according to the dispersion characteristics, battery performance and the like.
  • the solid content is preferably 0.1 to 10.0% by mass, preferably 0.2 to 5.0% by mass. More preferably, it is more preferably 0.3 to 4.0% by mass.
  • the ratio of the contents of the polymers C1-1 and the polymer C2 is not particularly limited, and the number of hydrogen-bonding groups (BHa) possessed by the polymers C1-1 and C2 and the solubility in the dispersion medium by forming hydrogen bonds.
  • Etc. which are appropriately determined, and examples thereof include the ratio in the above aspect.
  • the content of the polymers C1-1 and C2 is the total amount including the polymer C1-1 forming the hydrogen bond.
  • the polymers C1-1 and C2 are the same except for the number of types of hydrogen-bonding groups (BHa) described above, and will be described together.
  • the polymer is a polymer having the above-mentioned hydrogen-bonding group (BHa) in the side chain, and a polymer usually used as a binder for an all-solid-state secondary battery can be used without particular limitation.
  • Specific examples of such polymers include sequential polymerization (hypercondensation, polyaddition or addition condensation) polymers such as polyurethane, polyurea, polyamide, polyimide, polyester, polyether, and polycarbonate, and further, fluoropolymers (fluorine-containing polymers).
  • Examples thereof include chain polymers such as polymers), hydrocarbon polymers, vinyl polymers, and (meth) acrylic polymers. Of these, vinyl polymers or (meth) acrylic polymers are preferred.
  • the polymer constituting the polymer preferably has a component derived from a (meth) acrylic monomer or a vinyl monomer, and has a component derived from these monomers in an amount of 50% by mass or more in the polymer ((meth) acrylic polymer or. Vinyl polymer) is preferred.
  • the bonding mode (arrangement) of the copolymer components is not particularly limited, and any of a random copolymer, an alternate copolymer, a block copolymer, a graft copolymer and the like can be used. But it may be.
  • the (meth) acrylic monomer includes a monomer having a (meth) acryloyloxy group or a (meth) acryloylamino group, a (meth) acrylonitrile compound, and the like.
  • the (meth) acrylic monomer is not particularly limited, and is, for example, a (meth) acrylic compound (M) such as a (meth) acrylic acid compound, a (meth) acrylic acid ester compound, a (meth) acrylamide compound and a (meth) acrylonitrile compound. ), And among them, the (meth) acrylic acid ester compound is preferable.
  • the (meth) acrylic acid ester compound is not particularly limited, and examples thereof include esters such as aliphatic or aromatic hydrocarbons or aliphatic or aromatic heterocyclic compounds, and these hydrocarbons, heterocyclic compounds and the like.
  • the number of carbon atoms, the type or number of heteroatoms of the above is not particularly limited, and is appropriately set. For example, the number of carbon atoms can be 1 to 30.
  • the vinyl monomer is a monomer containing a vinyl group other than the (meth) acrylic compound (M), and is not particularly limited.
  • a vinyl group-containing aromatic compound styrene compound, vinyl naphthalene compound, etc.
  • Heterocyclic compounds vinylcarbazole compounds, vinylpyridine compounds, vinylimidazole compounds, vinyl group-containing aromatic heterocyclic compounds such as N-vinylcaprolactam, vinyl group-containing non-aromatic heterocyclic compounds, etc.
  • allyl compounds vinyl ether compounds, vinyl ketones, etc.
  • vinyl compounds such as compounds, vinyl ester compounds, dialkyl itaconates, and unsaturated carboxylic acid anhydrides.
  • Examples of the vinyl compound include "vinyl-based monomers" described in JP-A-2015-88486.
  • the polymer is an aliphatic hydrocarbon (preferably alkyl) having 4 or more carbon atoms among the (meth) acrylic acid ester compounds in terms of developing or improving the solubility in a dispersion medium. It is preferable to have a constituent component derived from a (meth) acrylic acid ester compound.
  • the aliphatic hydrocarbon group preferably has 6 or more carbon atoms, and more preferably 10 or more carbon atoms.
  • the upper limit is not particularly limited, and is preferably 20 or less, and more preferably 14 or less.
  • the aliphatic hydrocarbon having 4 or more carbon atoms may have a branched chain structure or a cyclic structure, but a linear structure is preferable.
  • the (meth) acrylic monomer into which a hydrogen-bonding group (BHa) is introduced is an aliphatic hydrocarbon (preferably alkyl) (meth) acrylic acid ester having 3 or less carbon atoms. It is preferably a compound.
  • the polymer preferably has a constituent component derived from a styrene compound in terms of resistance and cycle characteristics, and further in improving the strength of the polymer binder, and the constituent component derived from the (meth) acrylic monomer and /
  • the polymer may have other copolymerizable constituents.
  • the hydrogen-bonding group (BHa) may be introduced into any component as long as it is a component constituting the polymer, but is introduced into a component derived from a (meth) acrylic monomer or a vinyl monomer. Is preferable.
  • a component having a hydrogen-bonding group (BHa) introduced from a component derived from a (meth) acrylic monomer or a vinyl monomer having no hydrogen-bonding group (BHa) introduced hydrogen-bonding property is used for convenience. It is called a component.
  • the hydrogen-bonding component is a component having a main chain of the polymer, a hydrogen-bonding group (BHa), and a group linking them.
  • this hydrogen-binding component is a component derived from the (meth) acrylic monomer
  • a hydrogen-binding group (BHa) is linked to the side chain terminal group of the component derived from the (meth) acrylic compound (M).
  • examples include the constituents introduced as groups or (terminal) substituents.
  • a hydrogen-binding group (BHa) is used as a linking group or a (terminal) substituent on the side chain terminal group of the component derived from the vinyl compound.
  • Examples include the introduced constituents.
  • a hydrogen-bonding group (BHa) is introduced as a linking group
  • the terminal group can be the above-mentioned terminal substituent.
  • Preferred examples of the polymer include vinyl polymer and (meth) acrylic polymer.
  • the vinyl polymer is not particularly limited, and examples thereof include a polymer containing a vinyl monomer other than the (meth) acrylic compound (M) in an amount of, for example, 50% by mass or more.
  • Examples of the vinyl monomer include the above-mentioned vinyl compounds and the like.
  • the vinyl polymer includes polyvinyl alcohol, polyvinyl acetal, polyvinyl acetate, a copolymer containing these, and the like.
  • the vinyl polymer preferably has a constituent component derived from the vinyl monomer and a hydrogen-binding constituent component, and further, a constituent component derived from the (meth) acrylic compound (M) forming the (meth) acrylic polymer described later, which will be described later. It may have a constituent component (MM) derived from the macromonomer.
  • the content of the constituents in the vinyl polymer is not particularly limited, and is appropriately selected in consideration of the solubility in the dispersion medium, the SP value, etc., and is, for example, in the following range in 100% by mass of all the constituents. Can be set.
  • the content of the constituents derived from the vinyl monomer (when the hydrogen-bonding constituents also correspond to these constituents, the contents of the hydrogen-bonding constituents are added up. The same shall apply hereinafter) is the dispersion characteristic and further the resistance.
  • it is preferable that the content of the constituent component derived from the (meth) acrylic compound (M) in the (meth) acrylic polymer is the same.
  • the content of the constituents derived from the styrene compound among the vinyl monomers in the vinyl polymer is appropriately set in consideration of the range of the contents of the constituents derived from the vinyl monomer, but has resistance and cycle characteristics. In this respect, it is preferably 50 to 90% by mass, more preferably 53 to 80% by mass, and particularly preferably 55 to 75% by mass.
  • the content of the hydrogen-bonding constituent component in the vinyl polymer is appropriately determined in consideration of the content of the constituent component derived from the vinyl monomer or the (meth) acrylic compound (M) described later.
  • the polymers C1-1 and C2 are preferably 3 to 40% by mass, more preferably 5 to 35% by mass, respectively.
  • the content of the component derived from the (meth) acrylic compound (M) (when the hydrogen-bonding component also corresponds to this component, the contents of the hydrogen-bonding component are added up.
  • the content of the polymer is not particularly limited as long as it is less than 50% by mass, but is preferably 0 to 47% by mass, more preferably 15 to 45% by mass.
  • the content of the constituents derived from the (meth) acrylic acid ester compound of the aliphatic hydrocarbon having 4 or more carbon atoms in the vinyl polymer is the above-mentioned (meth) acrylic compound (meth).
  • the content of the constituent component derived from M is preferably 5 to 45% by mass, more preferably 8 to 35% by mass, and particularly preferably 10 to 25% by mass.
  • the content of the component (MM) is preferably the same as the content in the (meth) acrylic polymer. When other constituents are contained, the content thereof is appropriately determined.
  • the (meth) acrylic polymer is not particularly limited, but for example, a polymer obtained by polymerizing at least one (co) of the above-mentioned (meth) acrylic compound (M) is preferable. Further, a (meth) acrylic polymer composed of a copolymer of the (meth) acrylic compound (M) and another polymerizable compound (N) is also preferable. The other polymerizable compound (N) is not particularly limited, and examples thereof include the above-mentioned vinyl compounds.
  • the (meth) acrylic polymer has a component derived from the above-mentioned low molecular weight (without polymerized chain) monomer and does not have a component (MM) derived from a macromonomer having a polymerized chain.
  • the macromonomer is not particularly limited, and examples thereof include a (meth) acrylic monomer or a vinyl monomer having a polymer chain having a number average molecular weight of 1,000 or more, and specific examples thereof include the macromonomer described in Patent Document 1. X) can be mentioned. Examples of the (meth) acrylic polymer include those described in Japanese Patent No. 6295332.
  • the content of the constituent component in the (meth) acrylic polymer is not particularly limited in consideration of the solubility in the dispersion medium, the SP value, etc., and is appropriately selected. Can be set in the range of.
  • the content of the constituent component derived from the (meth) acrylic compound (M) in the (meth) acrylic polymer is not particularly limited and may be 100% by mass, but may have dispersion characteristics, resistance and cycle characteristics. In this respect, it is preferably 1 to 90% by mass, more preferably 10 to 80% by mass, and particularly preferably 20 to 70% by mass.
  • the content of the constituent component derived from the (meth) acrylic acid ester compound of the aliphatic hydrocarbon having 4 or more carbon atoms in the (meth) acrylic polymer is derived from the above (meth) acrylic compound (M). It is appropriately set in consideration of the range of the content of the constituent components. For example, it is preferably 10 to 95% by mass, more preferably 30 to 85%, and particularly preferably 40 to 80% by mass.
  • the content of the hydrogen-bonding constituent component in the (meth) acrylic polymer is appropriately determined in consideration of the content of the (meth) acrylic compound (M) or the vinyl monomer described later.
  • the polymers C1-1 and C2 are preferably 3 to 40% by mass, more preferably 5 to 35% by mass, respectively. It is particularly preferably about 30% by mass.
  • the content of the constituent component derived from the polymerizable compound (N) in the (meth) acrylic polymer is not particularly limited, but is preferably 1% by mass or more and less than 50% by mass, preferably 10% by mass or more and 50% by mass. It is more preferably less than%, and particularly preferably 20% by mass or more and less than 50% by mass.
  • the content of the component (MM) is preferably 0 to 50% by mass, more preferably 0 to 30% by mass. When other constituents are contained, the content thereof is appropriately determined.
  • the polymer may have a substituent.
  • the substituent is not particularly limited, and a group selected from the following substituent Z is preferable. Since the polymer binder composed of a polymer has a function of binding solid particles as described above, the polymer does not have a substituent (for example, a polar group such as a carboxy group) that exhibits adsorptivity to the solid particles. You may.
  • -Substituent Z- Alkyl groups preferably alkyl groups having 1 to 20 carbon atoms, such as methyl, ethyl, isopropyl, t-butyl, pentyl, heptyl, 1-ethylpentyl, benzyl, 2-ethoxyethyl, 1-carboxymethyl, etc.
  • alkenyl groups preferably alkyl groups having 1 to 20 carbon atoms, such as methyl, ethyl, isopropyl, t-butyl, pentyl, heptyl, 1-ethylpentyl, benzyl, 2-ethoxyethyl, 1-carboxymethyl, etc.
  • an alkenyl group having 2 to 20 carbon atoms for example, vinyl, allyl, oleyl, etc.
  • an alkynyl group preferably an alkynyl group having 2 to 20 carbon atoms, for example, ethynyl, butadynyl, phenylethynyl, etc.
  • a cycloalkyl group having 3 to 20 carbon atoms for example, cyclopropyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, etc., is usually used as an alkyl group in the present specification, but it is described separately here.
  • An aryl group (preferably an aryl group having 6 to 26 carbon atoms, for example, phenyl, 1-naphthyl, 4-methoxyphenyl, 2-chlorophenyl, 3-methylphenyl, etc.), an aralkyl group (preferably 7 carbon atoms).
  • ⁇ 23 Aralkyl groups such as benzyl, phenethyl, etc.
  • heterocyclic groups preferably heterocyclic groups having 2 to 20 carbon atoms, more preferably 5 or 5 having at least one oxygen atom, sulfur atom, nitrogen atom. It is a 6-membered heterocyclic group.
  • the heterocyclic group includes an aromatic heterocyclic group and an aliphatic heterocyclic group.
  • a tetrahydropyran ring group for example, a tetrahydropyran ring group, a tetrahydrofuran ring group, 2-pyridyl, 4-pyridyl, 2-. Imidazolyl, 2-benzoimidazolyl, 2-thiazolyl, 2-oxazolyl, pyrrolidone group, etc.), alkoxy group (preferably an alkoxy group having 1 to 20 carbon atoms, for example, methoxy, ethoxy, isopropyloxy, benzyloxy, etc.), aryloxy group.
  • an aryloxy group having 6 to 26 carbon atoms for example, phenoxy, 1-naphthyloxy, 3-methylphenoxy, 4-methoxyphenoxy, etc.
  • the aryloxy group in the present specification means that the aryloxy group is included.
  • a heterocyclic oxy group a group in which an —O— group is bonded to the above heterocyclic group
  • an alkoxycarbonyl group preferably an alkoxycarbonyl group having 2 to 20 carbon atoms, for example, ethoxycarbonyl, 2-ethylhexyloxycarbonyl.
  • aryloxycarbonyl groups preferably aryloxycarbonyl groups with 6-26 carbon atoms, such as phenoxycarbonyl, 1-naphthyloxycarbonyl, 3-me Chilphenoxycarbonyl, 4-methoxyphenoxycarbonyl, etc.
  • heterocyclic oxycarbonyl group group in which -O-CO- group is bonded to the above heterocyclic group
  • amino group preferably amino group having 0 to 20 carbon atoms, alkyl
  • Sulfamoyl group of, for example, N, N-dimethylsulfamoyl, N-phenylsulfamoyl, etc.
  • acyl group alkylcarbonyl group, alkenylcarbonyl group, alkynylcarbonyl group, arylcarbonyl group, heterocyclic carbonyl group, etc.
  • an acyl group having 1 to 20 carbon atoms for example, acetyl, propionyl, butyryl, octanoyl, hexadecanoyl, acryloyl, methacryloyl, crotonoyle, benzoyl, naphthoyl, nicotinoyyl, etc., and an acyloxy group (alkylcarbonyloxy group, alkenylcarbonyloxy).
  • a carbamoyl group having 1 to 20 carbon atoms for example, N, N-dimethylcarbamoyl, N-phenylcarbamoyl, etc.
  • an acylamino group preferably an acylamino group having 1 to 20 carbon atoms, for example, acetylamino, benzoylamino, etc.
  • An alkylthio group preferably an alkylthio group having 1 to 20 carbon atoms, for example, methylthio, ethylthio, isopropylthio, benzylthio, etc.
  • an arylthio group preferably an arylthio group having 6 to 26 carbon atoms, for example, phenylthio, 1-naphthylthio.
  • heterocyclic thio group group in which -S- group is bonded to the above heterocyclic group
  • alkylsulfonyl group preferably an alkylsulfonyl group having 1 to 20 carbon atoms.
  • methylsulfonyl, ethyls Luhonyl, etc. arylsulfonyl groups (preferably arylsulfonyl groups having 6 to 22 carbon atoms, such as benzenesulfonyl), alkylsilyl groups (preferably alkylsilyl groups having 1 to 20 carbon atoms, such as monomethylsilyl and dimethylsilyl).
  • Trimethylsilyl, triethylsilyl, etc. Trimethylsilyl, triethylsilyl, etc.
  • arylsilyl group preferably arylsilyl group having 6 to 42 carbon atoms, for example, triphenylsilyl group, etc.
  • alkoxysilyl group preferably alkoxysilyl group having 1 to 20 carbon atoms, for example, Monomethoxysilyl, dimethoxysilyl, trimethoxysilyl, triethoxysilyl, etc.
  • aryloxysilyl group preferably aryloxysilyl group having 6 to 42 carbon atoms, for example, triphenyloxysilyl group, etc.
  • phosphoryl group preferably carbon
  • a phosphonyl group preferably a phosphonyl group having 0-20 carbon atoms, for example, -P (
  • RP is a hydrogen atom or a substituent (preferably a group selected from the substituent Z). Further, each of the groups listed in these substituents Z may be further substituted with the above-mentioned substituent Z.
  • the alkyl group, alkylene group, alkenyl group, alkenylene group, alkynyl group and / or alkynylene group may be cyclic or chain-like, or may be linear or branched.
  • the polymer preferably has the following physical properties or properties.
  • the water concentration of the polymer is preferably 100 ppm (mass basis) or less.
  • the polymer may be crystallized and dried, or the polymer solution may be used as it is.
  • the polymer is preferably amorphous. In the present invention, the polymer being "amorphous" typically means that no endothermic peak due to crystal melting is observed when measured at the glass transition temperature.
  • the polymer may be a non-crosslinked polymer or a crosslinked polymer. Further, when the cross-linking of the polymer progresses by heating or application of a voltage, the molecular weight may be larger than the above molecular weight. Preferably, the polymer has a mass average molecular weight in the range described below at the start of use of the all-solid-state secondary battery.
  • the mass average molecular weight of the polymer is not particularly limited. For example, 15,000 or more is preferable, 30,000 or more is more preferable, and 50,000 or more is further preferable.
  • the upper limit is substantially 5,000,000 or less, preferably 4,000,000 or less, more preferably 3,000,000 or less, still more preferably 1,000,000 or less.
  • the molecular weights of the polymer, the polymer chain and the macromonomer refer to the mass average molecular weight or the number average molecular weight in terms of standard polystyrene by gel permeation chromatography (GPC) unless otherwise specified.
  • GPC gel permeation chromatography
  • condition 1 or condition 2 (priority) method is basically mentioned.
  • an appropriate eluent may be appropriately selected and used depending on the type of polymer or macromonomer.
  • the polymer can be synthesized by selecting a raw material compound (monomer) by a known method and polymerizing the raw material compound.
  • the method for incorporating the hydrogen-bonding group is not particularly limited, and for example, a method of copolymerizing a compound having a hydrogen-bonding group, a method of using a polymerization initiator or a chain transfer agent having (producing) a hydrogen-bonding group, and a method of using a chain transfer agent. Examples thereof include a method using a polymer reaction.
  • Specific examples of the polymer and combinations of the components constituting the polymer binder include those shown in Examples, but the present invention is not limited thereto.
  • composition containing an inorganic solid electrolyte of the present invention may contain a component constituting one kind of polymer binder, or may contain a component constituting a plurality of kinds of polymer binders.
  • the content of the binder components in the inorganic solid electrolyte-containing composition is as described above, but assuming that these components form a polymer binder, the inorganic solid electrolyte-containing composition (constructive layer) of the polymer binder.
  • the content thereof is preferably 0.1 to 10.0% by mass, preferably 0.2 to 5% by mass, based on the total mass of the composition (constructive layer) in terms of dispersion characteristics, resistance reduction and cycle characteristics. It is more preferably 0.0% by mass, and even more preferably 0.3 to 4.0% by mass.
  • the solid content of 100% by mass is preferably 0.1 to 10.0% by mass, more preferably 0.3 to 8% by mass, and 0.5 to 7% by mass for the same reason. % Is more preferable.
  • the mass ratio of the total content of the inorganic solid electrolyte and the active material to the above-mentioned content of the polymer binder at 100% by mass of the solid content [(mass of the inorganic solid electrolyte + mass of the active material) / (mass of the polymer binder). Mass)] is preferably in the range of 1,000 to 1. This ratio is more preferably 500 to 2, and even more preferably 100 to 10.
  • the inorganic solid electrolyte-containing composition of the present invention preferably contains a dispersion medium that dissolves or disperses each of the above components.
  • the dispersion medium may be any organic compound that is liquid in the environment of use, and examples thereof include various organic solvents. Specific examples thereof include alcohol compounds, ether compounds, amide compounds, amine compounds, ketone compounds, and aromatic compounds. , Fat group compounds, nitrile compounds, ester compounds and the like.
  • the dispersion medium may be a non-polar dispersion medium (hydrophobic dispersion medium) or a polar dispersion medium (hydrophilic dispersion medium), but a non-polar dispersion medium is preferable because it can exhibit excellent dispersion characteristics.
  • the non-polar dispersion medium generally refers to a property having a low affinity for water, but in the present invention, for example, an ester compound, a ketone compound, an ether compound, an aromatic compound, an aliphatic compound and the like can be mentioned, and among them, a ketone.
  • an ester compound, a ketone compound, an ether compound, an aromatic compound, an aliphatic compound and the like can be mentioned, and among them, a ketone.
  • Compounds, aliphatic compounds and ester compounds are preferably mentioned.
  • Examples of the alcohol compound include methyl alcohol, ethyl alcohol, 1-propyl alcohol, 2-propyl alcohol, 2-butanol, ethylene glycol, propylene glycol, glycerin, 1,6-hexanediol, cyclohexanediol, sorbitol, xylitol, and 2 -Methyl-2,4-pentanediol, 1,3-butanediol, 1,4-butanediol can be mentioned.
  • ether compound examples include alkylene glycol (diethylene glycol, triethylene glycol, polyethylene glycol, dipropylene glycol, etc.), alkylene glycol monoalkyl ether (ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, etc.).
  • alkylene glycol diethylene glycol, triethylene glycol, polyethylene glycol, dipropylene glycol, etc.
  • alkylene glycol monoalkyl ether ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, etc.
  • amide compound examples include N, N-dimethylformamide, N-methyl-2-pyrrolidone, 2-pyrrolidinone, 1,3-dimethyl-2-imidazolidinone, ⁇ -caprolactam, formamide, N-methylformamide and acetamide. , N-Methylacetamide, N, N-dimethylacetamide, N-methylpropaneamide, hexamethylphosphoric triamide and the like.
  • Examples of the amine compound include triethylamine, diisopropylethylamine, tributylamine and the like.
  • Examples of the ketone compound include acetone, methyl ethyl ketone, methyl isobutyl ketone (MIBK), cyclopentanone, cyclohexanone, cycloheptanone, dipropyl ketone, dibutyl ketone, diisopropyl ketone, diisobutyl ketone (DIBK), isobutylpropyl ketone, sec-. Examples thereof include butyl propyl ketone, pentyl propyl ketone and butyl propyl ketone.
  • Examples of the aromatic compound include benzene, toluene, xylene and the like.
  • Examples of the aliphatic compound include hexane, heptane, octane, nonane, decane, dodecane, cyclohexane, methylcyclohexane, ethylcyclohexane, cycloheptane, cyclooctane, decalin, paraffin, gasoline, naphtha, kerosene, and light oil.
  • Examples of the nitrile compound include acetonitrile, propionitrile, isobutyronitrile and the like.
  • ester compound examples include ethyl acetate, butyl acetate, propyl acetate, propyl butyrate, isopropyl butyrate, butyl butyrate, isobutyl butyrate, butyl pentanate, ethyl isobutyrate, propyl isobutyrate, isopropyl isobutyrate, isobutyl isobutyrate, and pivalic acid.
  • Examples thereof include propyl, isopropyl pivalate, butyl pivalate, and isobutyl pivalate.
  • ether compounds, ketone compounds, aromatic compounds, aliphatic compounds and ester compounds are preferable, and ester compounds, ketone compounds or ether compounds are more preferable.
  • the number of carbon atoms of the compound constituting the dispersion medium is not particularly limited, and is preferably 2 to 30, more preferably 4 to 20, further preferably 6 to 15, and particularly preferably 7 to 12.
  • the dispersion medium preferably has an SP value (unit: MPa 1/2 ) of 15 to 21, more preferably 16 to 20, and even more preferably 17 to 19 in terms of dispersion characteristics.
  • the difference (absolute value) between the SP values of the polymer C1-1 or C2 and the dispersion medium is not particularly limited, but is preferably 3 or less, preferably 0 to 2. It is more preferably 5 and even more preferably 0 to 2.0.
  • the difference (absolute value) of the SP value preferably includes the smallest value (absolute value) within the above range, and all the differences (absolute value) are included within the above range. May be good.
  • the SP value of the dispersion medium is a value obtained by converting the SP value calculated by the Hoy method described above into the unit MPa 1/2.
  • the SP value of the dispersion medium means the SP value of the entire dispersion medium, and is the product of the SP value of each dispersion medium and the mass fraction.
  • the sum is the sum. Specifically, it is calculated in the same manner as the above-mentioned method for calculating the SP value of the polymer, except that the SP value of each dispersion medium is used instead of the SP value of the constituent component.
  • the SP value (unit omitted) of the dispersion medium is shown below.
  • MIBK diisopropyl ether (16.8), dibutyl ether (17.9), diisopropyl ketone (17.9), DIBK (17.9), butyl butyrate (18.6), butyl acetate (18) .9), Toluene (18.5), Ethylcyclohexane (17.1), Cyclooctane (18.8), Isobutyl ethyl ether (15.3), N-Methylpyrrolidone (NMP, SP value: 25.4)
  • the dispersion medium preferably has a boiling point of 50 ° C. or higher at normal pressure (1 atm), and more preferably 70 ° C. or higher.
  • the upper limit is preferably 250 ° C. or lower, and more preferably 220 ° C. or lower.
  • the composition containing an inorganic solid electrolyte of the present invention may contain at least one dispersion medium and may contain two or more.
  • the content of the dispersion medium in the composition containing an inorganic solid electrolyte is not particularly limited and can be appropriately set.
  • 20 to 80% by mass is preferable, 30 to 70% by mass is more preferable, and 40 to 60% by mass is particularly preferable.
  • the composition containing an inorganic solid electrolyte of the present invention may also contain an active material capable of inserting and releasing ions of a metal belonging to Group 1 or Group 2 of the Periodic Table.
  • the active material include a positive electrode active material and a negative electrode active material, which will be described below.
  • an inorganic solid electrolyte-containing composition containing an active material positive electrode active material or negative electrode active material
  • an electrode composition positive electrode composition or negative electrode composition
  • the positive electrode active material is an active material capable of inserting and releasing ions of a metal belonging to Group 1 or Group 2 of the Periodic Table, and is preferably a material capable of reversibly inserting and releasing lithium ions.
  • the material is not particularly limited as long as it has the above-mentioned characteristics, and may be a transition metal oxide, an organic substance, an element that can be composited with Li such as sulfur, or the like by decomposing the battery.
  • the 1 (Ia) group elements of the transition metal oxide to elemental M b (Table metal periodic other than lithium, the elements of the 2 (IIa) group, Al, Ga, In, Ge , Sn, Pb, Elements such as Sb, Bi, Si, P and B) may be mixed.
  • the mixing amount is preferably 0 to 30 mol% relative to the amount of the transition metal element M a (100 mol%). That the molar ratio of li / M a was synthesized were mixed so that 0.3 to 2.2, more preferably.
  • transition metal oxide examples include (MA) a transition metal oxide having a layered rock salt type structure, (MB) a transition metal oxide having a spinel type structure, (MC) a lithium-containing transition metal phosphoric acid compound, and (MD). ) Lithium-containing transition metal halide phosphoric acid compound, (ME) lithium-containing transition metal silicic acid compound and the like can be mentioned.
  • transition metal oxide having a layered rock salt structure examples include LiCoO 2 (lithium cobalt oxide [LCO]), LiNi 2 O 2 (lithium nickel oxide), LiNi 0.85 Co 0.10 Al 0. 05 O 2 (Nickel Lithium Cobalt Lithium Aluminate [NCA]), LiNi 1/3 Co 1/3 Mn 1/3 O 2 (Nickel Manganese Lithium Cobalt Oxide [NMC]) and LiNi 0.5 Mn 0.5 O 2 ( Lithium manganese nickel oxide).
  • LiCoO 2 lithium cobalt oxide
  • LiNi 2 O 2 lithium nickel oxide
  • LiNi 0.85 Co 0.10 Al 0. 05 O 2 Nickel Lithium Cobalt Lithium Aluminate [NCA]
  • LiNi 1/3 Co 1/3 Mn 1/3 O 2 Nickel Manganese Lithium Cobalt Oxide [NMC]
  • LiNi 0.5 Mn 0.5 O 2 Lithium manganese nickel oxide
  • transition metal oxide having a spinel structure LiMn 2 O 4 (LMO) , LiCoMnO 4, Li 2 FeMn 3 O 8, Li 2 CuMn 3 O 8, Li 2 CrMn 3 O 8 and Li 2 Nimn 3 O 8 may be mentioned.
  • the (MC) lithium-containing transition metal phosphate compound include olivine-type iron phosphate salts such as LiFePO 4 and Li 3 Fe 2 (PO 4 ) 3 , iron pyrophosphates such as LiFeP 2 O 7 , LiCoPO 4, and the like.
  • Examples thereof include cobalt phosphates of Li 3 V 2 (PO 4 ) 3 (lithium vanadium phosphate) and other monoclinic pyanicon-type vanadium phosphate salts.
  • (MD) as the lithium-containing transition metal halogenated phosphate compound for example, Li 2 FePO 4 F such fluorinated phosphorus iron salt, Li 2 MnPO 4 hexafluorophosphate manganese salts such as F and Li 2 CoPO 4 F
  • Examples thereof include cobalt fluoride phosphates such as.
  • Examples of the (ME) lithium-containing transition metal silicic acid compound include Li 2 FeSiO 4 , Li 2 MnSiO 4 , and Li 2 CoSiO 4 .
  • a transition metal oxide having a (MA) layered rock salt type structure is preferable, and LCO or NMC is more preferable.
  • the shape of the positive electrode active material is not particularly limited, but is preferably in the form of particles.
  • the average particle size (volume average particle size) of the positive electrode active material is not particularly limited. For example, it can be 0.1 to 50 ⁇ m.
  • the average particle size of the positive electrode active material particles can be measured in the same manner as the average particle size of the above-mentioned inorganic solid electrolyte.
  • a normal crusher or classifier is used to make the positive electrode active material a predetermined particle size. For example, a mortar, a ball mill, a sand mill, a vibrating ball mill, a satellite ball mill, a planetary ball mill, a swirling airflow type jet mill, a sieve, or the like is preferably used.
  • wet pulverization in which a dispersion medium such as water or methanol coexists can also be performed. It is preferable to perform classification in order to obtain a desired particle size.
  • the classification is not particularly limited, and can be performed using a sieve, a wind power classifier, or the like. Both dry and wet classifications can 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 positive electrode active material one type may be used alone, or two or more types may be used in combination.
  • the mass (mg) (grain amount) of the positive electrode active material per unit area (cm 2) of the positive electrode active material layer is not particularly limited. It can be appropriately determined according to the designed battery capacity, and can be, for example, 1 to 100 mg / cm 2 .
  • the content of the positive electrode active material in the composition containing an inorganic solid electrolyte is not particularly limited, and is preferably 10 to 97% by mass, more preferably 30 to 95% by mass, and 40 to 93% by mass in terms of solid content of 100% by mass. Is more preferable, and 50 to 90% by mass is particularly preferable.
  • the negative electrode active material is an active material capable of inserting and releasing ions of a metal belonging to Group 1 or Group 2 of the Periodic Table, and is preferably a material capable of reversibly inserting and releasing lithium ions.
  • the material is not particularly limited as long as it has the above-mentioned characteristics, and is a negative electrode activity capable of forming an alloy with a carbonaceous material, a metal oxide, a metal composite oxide, a single lithium substance, a lithium alloy, or lithium. Substances and the like can be mentioned. Of these, carbonaceous materials, metal composite oxides or elemental lithium are preferably used from the viewpoint of reliability.
  • An active material that can be alloyed with lithium is preferable in that the capacity of the all-solid-state secondary battery can be increased. Since the constituent layer formed of the composition containing the inorganic solid electrolyte of the present invention can maintain a strong bonded state between the solid particles, a negative electrode active material capable of forming an alloy with lithium can be used as the negative electrode active material. This makes it possible to increase the capacity of the all-solid-state secondary battery and extend the life of the battery.
  • the carbonaceous material used as the negative electrode active material is a material substantially composed of carbon.
  • carbon black such as acetylene black (AB)
  • graphite artificial graphite such as natural graphite and vapor-grown graphite
  • PAN polyacrylonitrile
  • a carbonaceous material obtained by firing a resin can be mentioned.
  • various carbon fibers such as PAN-based carbon fiber, cellulose-based carbon fiber, pitch-based carbon fiber, gas phase-grown carbon fiber, dehydrated PVA (polyvinyl alcohol) -based carbon fiber, lignin carbon fiber, glassy carbon fiber and activated carbon fiber.
  • carbonaceous materials can also be divided into non-graphitizable carbonaceous materials (also referred to as hard carbon) and graphite-based carbonaceous materials depending on the degree of graphitization. Further, the carbonaceous material preferably has the plane spacing or density and the crystallite size described in JP-A No. 62-22066, JP-A No. 2-6856, and JP-A-3-45473.
  • the carbonaceous material does not have to be a single material, and a mixture of natural graphite and artificial graphite described in JP-A-5-90844, graphite having a coating layer described in JP-A-6-4516, and the like should be used. You can also.
  • As the carbonaceous material hard carbon or graphite is preferably used, and graphite is more preferably used.
  • the metal or semi-metal element oxide applied as the negative electrode active material is not particularly limited as long as it is an oxide capable of storing and releasing lithium, and is a composite of a metal element oxide (metal oxide) and a metal element.
  • metal oxide metal oxide
  • examples thereof include oxides or composite oxides of metal elements and semi-metal elements (collectively referred to as metal composite oxides) and oxides of semi-metal elements (semi-metal oxides).
  • metal composite oxides oxides or composite oxides of metal elements and semi-metal elements
  • oxides of semi-metal elements semi-metal elements
  • amorphous oxides are preferable, and chalcogenides, which are reaction products of metal elements and elements of Group 16 of the Periodic Table, are also preferable.
  • the metalloid element means an element exhibiting properties intermediate between a metalloid element and a non-metalloid element, and usually contains six elements of boron, silicon, germanium, arsenic, antimony and tellurium, and further selenium. , Polonium and Asstatin.
  • amorphous means an X-ray diffraction method using CuK ⁇ rays, which has a broad scattering zone having a peak in a region of 20 ° to 40 ° in 2 ⁇ value, and a crystalline diffraction line is used. You may have.
  • the strongest intensity of the crystalline diffraction lines seen at the 2 ⁇ value of 40 ° to 70 ° is 100 times or less the diffraction line intensity of the apex of the broad scattering zone seen at the 2 ⁇ value of 20 ° to 40 °. It is preferable that it is 5 times or less, and it is particularly preferable that it does not have a crystalline diffraction line.
  • the amorphous oxide of the metalloid element or the chalcogenide is more preferable, and the elements of the Group 13 (IIIB) to 15 (VB) of the Periodic Table (for example).
  • the elements of the Group 13 (IIIB) to 15 (VB) of the Periodic Table for example.
  • Al, Ga, Si, Sn, Ge, Pb, Sb and Bi) alone or a combination of two or more of them (composite) oxides, or chalcogenides are particularly preferred.
  • preferable amorphous oxides and chalcogenides include, for example, Ga 2 O 3 , GeO, PbO, PbO 2 , Pb 2 O 3 , Pb 2 O 4 , Pb 3 O 4 , Sb 2 O 3 , Sb 2.
  • Negative negative active materials that can be used in combination with amorphous oxides such as Sn, Si, and Ge include carbonaceous materials capable of storing and / or releasing lithium ions or lithium metals, lithium alone, lithium alloys, and lithium.
  • a negative electrode active material that can be alloyed with is preferably mentioned.
  • the oxide of a metal or a metalloid element contains at least one of titanium and lithium as a constituent component from the viewpoint of high current density charge / discharge characteristics.
  • the lithium-containing metal composite oxide include a composite oxide of lithium oxide and the metal (composite) oxide or the chalcogenide, and more specifically, Li 2 SnO 2.
  • the negative electrode active material for example, a metal oxide, contains a titanium element (titanium oxide).
  • Li 4 Ti 5 O 12 (lithium titanate [LTO]) has excellent rapid charge / discharge characteristics because the volume fluctuation of lithium ions during occlusion and discharge is small, and deterioration of the electrodes is suppressed and lithium ion secondary. It is preferable in that the battery life can be improved.
  • the lithium alloy as the negative electrode active material is not particularly limited as long as it is an alloy usually used as the negative electrode active material of the secondary battery, and examples thereof include a lithium aluminum alloy containing lithium as a base metal and aluminum added in an amount of 10% by mass. Be done.
  • the negative electrode active material that can be alloyed with lithium is not particularly limited as long as it is usually used as the negative electrode active material of the secondary battery. Such an active material has a large expansion and contraction due to charging and discharging of the all-solid-state secondary battery and accelerates the deterioration of the cycle characteristics.
  • the inorganic solid electrolyte-containing composition of the present invention contains the above-mentioned binder constituent component, It is possible to suppress the deterioration of cycle characteristics.
  • Examples of such an active material include a (negative electrode) active material having a silicon element or a tin element (alloy, etc.), and metals such as Al and In, and a negative electrode active material having a silicon element that enables a higher battery capacity.
  • a silicon element-containing active material is preferable, and a silicon element-containing active material having a silicon element content of 50 mol% or more of all constituent elements is more preferable.
  • a negative electrode containing these negative electrode active materials for example, a Si negative electrode containing a silicon element-containing active material, a Sn negative electrode containing a tin element active material, etc.
  • a carbon negative electrode graphite, acetylene black, etc.
  • silicon element-containing active material examples include silicon materials such as Si and SiOx (0 ⁇ x ⁇ 1), and silicon-containing alloys containing titanium, vanadium, chromium, manganese, nickel, copper, lanthanum, and the like (for example,). LaSi 2 , VSi 2 , La-Si, Gd-Si, Ni-Si) or organized active material (eg LaSi 2 / Si), as well as other silicon and tin elements such as SnSiO 3 , SnSiS 3 and the like. Examples include active materials containing the above.
  • SiOx itself can be used as a negative electrode active material (semi-metal oxide), and since Si is generated by the operation of an all-solid secondary battery, a negative electrode active material that can be alloyed with lithium (its). It can be used as a precursor substance).
  • the negative electrode active material having a tin element include Sn, SnO, SnO 2 , SnS, SnS 2 , and the above-mentioned active material containing a silicon element and a tin element.
  • a composite oxide with lithium oxide for example, Li 2 SnO 2 can also be mentioned.
  • the above-mentioned negative electrode active material can be used without particular limitation, but in terms of battery capacity, a negative electrode active material that can be alloyed with silicon is a preferred embodiment as the negative electrode active material.
  • a negative electrode active material that can be alloyed with silicon is a preferred embodiment as the negative electrode active material.
  • the above silicon material or a silicon-containing alloy (alloy containing a silicon element) is more preferable, and it is further preferable to contain silicon (Si) or a silicon-containing alloy.
  • the chemical formula of the compound obtained by the above firing method can be calculated from the inductively coupled plasma (ICP) emission spectroscopic analysis method as a measurement method and the mass difference of the powder before and after firing as a simple method.
  • ICP inductively coupled plasma
  • the shape of the negative electrode active material is not particularly limited, but it is preferably in the form of particles.
  • the average particle size (volume average particle size) of the negative electrode active material is not particularly limited, but is preferably 0.1 to 60 ⁇ m.
  • the average particle size of the negative electrode active material particles can be measured in the same manner as the average particle size of the above-mentioned inorganic solid electrolyte. In order to obtain a predetermined particle size, a normal crusher or classifier is used as in the case of the positive electrode active material.
  • the negative electrode active material may be used alone or in combination of two or more.
  • the mass (mg) (grain amount) 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 appropriately determined according to the designed battery capacity, and can be, for example, 1 to 100 mg / cm 2 .
  • the content of the negative electrode active material in the composition containing an inorganic solid electrolyte is not particularly limited, and is preferably 10 to 90% by mass, more preferably 20 to 85% by mass, and 30 to 30% by mass in terms of solid content of 100% by mass. It is more preferably 80% by mass, and even more preferably 40 to 75% by mass.
  • the negative electrode active material layer when the negative electrode active material layer is formed by charging the secondary battery, instead of the negative electrode active material, a metal belonging to Group 1 or Group 2 of the periodic table generated in the all-solid secondary battery is used. Ions can be used. By combining these ions with electrons and precipitating them as a metal, a negative electrode active material layer can be formed.
  • the surfaces of the positive electrode active material and the negative electrode active material may be surface-coated with another metal oxide.
  • the surface coating agent include metal oxides containing Ti, Nb, Ta, W, Zr, Al, Si or Li. Specific examples thereof include spinel titanate, tantalum oxide, niobate oxide, lithium niobate compound and the like, and specific examples thereof include Li 4 Ti 5 O 12 , Li 2 Ti 2 O 5 and LiTaO 3.
  • the surface of the electrode containing the positive electrode active material or the negative electrode active material may be surface-treated with sulfur or phosphorus.
  • the particle surface of the positive electrode active material or the negative electrode active material may be surface-treated with active light rays or an active gas (plasma or the like) before and after the surface coating.
  • the inorganic solid electrolyte-containing composition of the present invention preferably contains a conductive auxiliary agent, and for example, a silicon atom-containing active material as a negative electrode active material is preferably used in combination with the conductive auxiliary agent.
  • the conductive auxiliary agent is not particularly limited, and those known as general conductive auxiliary agents can be used.
  • electron conductive materials such as natural graphite, artificial graphite and other graphite, acetylene black, ketjen black, furnace black and other carbon blacks, needle coke and other atypical carbon, vapor-grown carbon fiber or carbon nanotubes.
  • It may be a carbon fiber such as carbon fiber, a carbon material such as graphene or fullerene, a metal powder such as copper or nickel, or a metal fiber, and a conductive polymer such as polyaniline, polypyrrole, polythiophene, polyacetylene, or polyphenylene derivative. May be used.
  • a conductive auxiliary agent is one that does not insert and release ions) and does not function as an active material.
  • conductive auxiliary agents those that can function as an active material in the active material layer when the battery is charged and discharged are classified as active materials rather than conductive auxiliary agents. Whether or not the battery functions as an active material when it is charged and discharged is not unique and is determined by the combination with the active material.
  • the conductive auxiliary agent may contain one kind or two or more kinds.
  • the shape of the conductive auxiliary agent is not particularly limited, but is preferably in the form of particles.
  • the content of the conductive auxiliary agent in the inorganic solid electrolyte-containing composition is preferably 0 to 10% by mass with respect to 100% by mass of the solid content.
  • the inorganic solid electrolyte-containing composition of the present invention preferably contains a lithium salt (supporting electrolyte).
  • the lithium salt the lithium salt usually used for this kind of product is preferable, and there is no particular limitation, and for example, the lithium salt described in paragraphs 882 to 856 of JP-A-2015-084886 is preferable.
  • the content of the lithium salt is preferably 0.1 part by mass or more, more preferably 5 parts by mass or more, based on 100 parts by mass of the solid electrolyte.
  • the upper limit is preferably 50 parts by mass or less, more preferably 20 parts by mass or less.
  • the inorganic solid electrolyte-containing composition of the present invention does not have to contain a dispersant other than the binder constituent component.
  • the dispersant usually used for an all-solid-state secondary battery can be appropriately selected and used.
  • compounds intended for particle adsorption, steric repulsion and / or electrostatic repulsion are preferably used.
  • the composition containing an inorganic solid electrolyte of the present invention has an ionic liquid, a thickener, and a cross-linking agent (such as those that undergo a cross-linking reaction by radical polymerization, condensation polymerization, or ring-opening polymerization) as appropriate as components other than the above-mentioned components.
  • a cross-linking agent such as those that undergo a cross-linking reaction by radical polymerization, condensation polymerization, or ring-opening polymerization
  • Polymerization initiators such as those that generate acids or radicals by heat or light
  • defoaming agents leveling agents, dehydrating agents, antioxidants and the like
  • the ionic liquid is contained in order to further improve the ionic conductivity, and known ones can be used without particular limitation. Further, it may contain a polymer other than the polymer forming the above-mentioned polymer binder, a commonly used binder and the like.
  • the composition containing an inorganic solid electrolyte of the present invention is a mixture of an inorganic solid electrolyte, a binder component, preferably a dispersion medium, a conductive auxiliary agent, and optionally a lithium salt, and any other components, for example, usually used.
  • a binder component preferably a dispersion medium, a conductive auxiliary agent, and optionally a lithium salt, and any other components, for example, usually used.
  • the active substance is further mixed.
  • the mixing method is not particularly limited, and may be mixed all at once or sequentially.
  • the mixing environment is not particularly limited, and examples thereof include under dry air and under inert gas.
  • the mixing conditions are not particularly limited, but conditions in which the binder constituents easily form intermolecular hydrogen bonds are preferable, and the type of hydrogen-bonding group (BHa) or (BHb), the content of each component, and the polymer C2 are used. It is appropriately set according to the SP value and the like.
  • the sheet for an all-solid-state secondary battery of the present invention is a sheet-like molded body that can form a constituent layer of an all-solid-state secondary battery, and includes various aspects depending on its use.
  • a sheet preferably used for a solid electrolyte layer also referred to as a solid electrolyte sheet for an all-solid secondary battery
  • an electrode or a sheet preferably used for a laminate of an electrode and a solid electrolyte layer (an electrode for an all-solid secondary battery).
  • Sheet and the like.
  • these various sheets are collectively referred to as an all-solid-state secondary battery sheet.
  • the solid electrolyte sheet for an all-solid secondary battery of the present invention may be a sheet having a solid electrolyte layer, and even a sheet having a solid electrolyte layer formed on a base material does not have a base material and is a solid electrolyte layer. It may be a sheet formed of.
  • the solid electrolyte sheet for an all-solid secondary battery may have another layer in addition to the solid electrolyte layer. Examples of the other layer include a protective layer (release sheet), a current collector, a coat layer, and the like.
  • the solid electrolyte sheet for an all-solid secondary battery of the present invention for example, a sheet having a layer composed of the inorganic solid electrolyte-containing composition of the present invention, a normal solid electrolyte layer, and a protective layer on a substrate in this order.
  • the layer thickness of each layer constituting the solid electrolyte sheet for an all-solid-state secondary battery is the same as the layer thickness of each layer described in the all-solid-state secondary battery described later.
  • the solid electrolyte layer of the solid electrolyte sheet for an all-solid secondary battery is preferably formed of the inorganic solid electrolyte-containing composition of the present invention. It is considered that the intermolecular hydrogen bond formed by the polymer C1-1 or C2 is cleaved and an intramolecular hydrogen bond is formed in the film forming process of the inorganic solid electrolyte-containing composition of the present invention. As the formation of this intramolecular hydrogen bond progresses, the solubility of the polymer C1-1 or C2 in the dispersion medium gradually decreases, and the solidification or precipitation is preferably carried out in the form of particles while maintaining the adsorption state with the solid particles.
  • the solid electrolyte layer composed of this inorganic solid electrolyte-containing composition preferably contains a polymer binder in which the binder constituents are hydrogen-bonded as particles.
  • the constituent layer formed of the inorganic solid electrolyte-containing composition of the present invention contains a polymer binder in which the polymers C1-1 or C2 are molecularly hydrogen-bonded, but the inorganic solid electrolyte-containing composition is contained.
  • the polymers C1-1 or C2 contained therein form a polymer binder, and the polymer C1-1 or C2 having no intramolecular hydrogen bond is used as long as the action and effect of the present invention are not impaired. It may be contained (residual).
  • the content of each component in the constituent layer is not particularly limited, but is preferably synonymous with the content of each component in the solid content of the inorganic solid electrolyte-containing composition of the present invention.
  • the content of the polymer binder is usually consistent with the total content of the binder constituents.
  • the base material is not particularly limited as long as it can support the solid electrolyte layer, and examples thereof include a material described in the current collector described later, a sheet body (plate-shaped body) such as an organic material and an inorganic material.
  • a material described in the current collector described later a sheet body (plate-shaped body) such as an organic material and an inorganic material.
  • the organic material include various polymers, and specific examples thereof include polyethylene terephthalate, polypropylene, polyethylene, and cellulose.
  • the inorganic material include glass, ceramic and the like.
  • the electrode sheet for an all-solid-state secondary battery (also simply referred to as “electrode sheet”) of the present invention may be an electrode sheet having an active material layer, and the active material layer is formed on a base material (current collector).
  • the sheet may be a sheet having no base material and may be formed from an active material layer.
  • This electrode sheet is usually a sheet having a current collector and an active material layer, but has an embodiment having a current collector, an active material layer and a solid electrolyte layer in this order, and a current collector, an active material layer and a solid electrolyte. An embodiment having a layer and an active material layer in this order is also included.
  • At least one of the solid electrolyte layer and the active material layer of the electrode sheet is formed of the inorganic solid electrolyte-containing composition of the present invention.
  • the presence state (hydrogen bond formation state) of the polymer binder is the solid electrolyte layer of the above-mentioned solid electrolyte sheet for an all-solid secondary battery. It is the same as the existence state in.
  • the content of each component in the solid electrolyte layer or the active material layer is not particularly limited, but the content of each component in the solid content of the inorganic solid electrolyte-containing composition (electrode composition) of the present invention is preferable.
  • the content of the polymer binder is usually consistent with the total content of the binder constituents.
  • the layer thickness of each layer constituting the electrode sheet of the present invention is the same as the layer thickness of each layer described in the all-solid-state secondary battery described later.
  • the electrode sheet of the present invention may have the other layers described above.
  • the solid electrolyte layer or the active material layer is not formed by the inorganic solid electrolyte-containing composition of the present invention, it is formed by a normal constituent layer forming material.
  • the sheet for an all-solid secondary battery of the present invention at least one of the solid electrolyte layer and the active material layer is formed of the inorganic solid electrolyte-containing composition of the present invention, while suppressing an increase in interfacial resistance between solid particles.
  • the surface of the solid particles firmly bonded to each other has a flat constituent layer.
  • This constituent layer preferably exhibits smoothness in which the maximum deviation value is less than 8% in the surface smoothness test in the examples described later. Therefore, by using the sheet for an all-solid-state secondary battery of the present invention as a constituent layer of an all-solid-state secondary battery, it is possible to realize low resistance (high conductivity) and excellent cycle characteristics of the all-solid-state secondary battery.
  • the active material layer and the current collector show strong adhesion and cycle. Further improvement of characteristics can be realized. Therefore, the sheet for an all-solid-state secondary battery of the present invention is suitably used as a sheet that can form a constituent layer of an all-solid-state secondary battery.
  • each layer constituting the all-solid-state secondary battery sheet may have a single-layer structure or a multi-layer structure.
  • the method for producing a sheet for an all-solid-state secondary battery of the present invention is not particularly limited, and can be produced by forming each of the above layers using the composition containing an inorganic solid electrolyte of the present invention.
  • a layer made of an inorganic solid electrolyte-containing composition is preferably formed on a base material or a current collector (which may be via another layer) by forming a film (coating and drying).
  • the method can be mentioned. This makes it possible to produce a sheet for an all-solid-state secondary battery having a base material or a current collector and a coating dry layer.
  • the coating dry layer is a layer formed by applying the inorganic solid electrolyte-containing composition of the present invention and drying the dispersion medium (that is, the inorganic solid electrolyte-containing composition of the present invention is used.
  • the dispersion medium may remain as long as the effect of the present invention is not impaired, and the residual amount may be, for example, 3% by mass or less in each layer.
  • this coated dry layer contains a polymer binder formed by hydrogen-bonding the polymers C1-1 or C2.
  • each step such as coating and drying will be described in the following method for manufacturing an all-solid-state secondary battery.
  • the adhesion between the current collector and the active material layer can be strengthened. ..
  • the coating dry layer obtained as described above can also be pressurized.
  • the pressurizing conditions and the like will be described later in the method for manufacturing an all-solid-state secondary battery.
  • the base material, the protective layer (particularly the release sheet) and the like can be peeled off.
  • the all-solid secondary battery of the present invention has a positive electrode active material layer, a negative electrode active material layer facing the positive electrode active material layer, and a solid electrolyte layer arranged between the positive electrode active material layer and the negative electrode active material layer.
  • the positive electrode active material layer is preferably formed on the positive electrode current collector and constitutes the positive electrode.
  • the negative electrode active material layer is preferably formed on the negative electrode current collector to form the negative electrode.
  • At least one layer of the negative electrode active material layer, the positive electrode active material layer and the solid electrolyte layer is formed of the inorganic solid electrolyte-containing composition of the present invention, and the solid electrolyte layer or at least the negative electrode active material layer and the positive electrode active material layer.
  • One is preferably formed of the composition containing the inorganic solid electrolyte of the present invention. It is also one of the preferred embodiments that all layers are formed of the inorganic solid electrolyte-containing composition of the present invention.
  • forming the constituent layer of the all-solid-state secondary battery with the composition containing the inorganic solid electrolyte of the present invention means that the sheet for the all-solid-state secondary battery of the present invention (provided that the composition containing the inorganic solid electrolyte of the present invention is used).
  • the embodiment in which the constituent layer is formed by the sheet) from which this layer is removed is included.
  • the active material layer or the solid electrolyte layer formed of the inorganic solid electrolyte-containing composition of the present invention preferably contains the component species and the content thereof in the solid content of the inorganic solid electrolyte-containing composition of the present invention. The same (although the content of the polymer binder usually corresponds to the total content of the binder components).
  • a known material can be used.
  • the thicknesses of the negative electrode active material layer, the solid electrolyte layer, and the positive electrode active material layer are not particularly limited.
  • each layer is preferably 10 to 1,000 ⁇ m, more preferably 20 ⁇ m or more and less than 500 ⁇ m, respectively, in consideration of the dimensions of a general all-solid-state secondary battery. In the all-solid-state secondary battery of the present invention, it is more preferable that the thickness of at least one of the positive electrode active material layer and the negative electrode active material layer is 50 ⁇ m or more and less than 500 ⁇ m.
  • the positive electrode active material layer and the negative electrode active material layer may each have a current collector on the opposite side of the solid electrolyte layer.
  • the all-solid-state secondary battery of the present invention may be used as an all-solid-state secondary battery with the above structure, but in order to form a dry battery, it should be further enclosed in a suitable housing.
  • the housing may be made of metal or resin (plastic).
  • a metallic material for example, an aluminum alloy or a stainless steel material can be mentioned.
  • the metallic housing is divided into a positive electrode side housing and a negative electrode side housing, and electrically connected to the positive electrode current collector and the negative electrode current collector, respectively. It is preferable that the housing on the positive electrode side and the housing on the negative electrode side are joined and integrated via a gasket for preventing a short circuit.
  • FIG. 1 is a schematic sectional view showing an all-solid-state secondary battery (lithium ion secondary battery) according to a preferred embodiment of the present invention.
  • the all-solid secondary battery 10 of the present embodiment has 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 this order when viewed from the negative electrode side. ..
  • Each layer is in contact with each other and has an adjacent structure.
  • the lithium ion (Li + ) accumulated in the negative electrode is returned to the positive electrode side, and electrons are supplied to the operating portion 6.
  • a light bulb is used as a model for the operating portion 6, and the light bulb is turned on by electric discharge.
  • an all-solid secondary battery laminate 12 When an all-solid secondary battery having the layer structure shown in FIG. 1 is placed in a 2032 type coin case, the all-solid secondary battery is referred to as an all-solid secondary battery laminate 12, and the all-solid secondary battery laminate is referred to as an all-solid secondary battery laminate 12.
  • a battery (for example, a coin-type all-solid-state secondary battery shown in FIG. 2) manufactured by putting 12 in a 2032-inch coin case 11 may be referred to as an all-solid-state secondary battery 13.
  • the all-solid secondary battery 10 In the all-solid secondary battery 10, all of the positive electrode active material layer, the solid electrolyte layer, and the negative electrode active material layer are formed of the inorganic solid electrolyte-containing composition of the present invention.
  • the presence state (hydrogen bond formation state) of the polymer binder in the positive electrode active material layer 4, the solid electrolyte layer 3 and the negative electrode active material layer 2 is the presence state in the solid electrolyte layer of the above-mentioned solid electrolyte sheet for an all-solid secondary battery. Is the same as.
  • the all-solid-state secondary battery 10 exhibits excellent battery performance.
  • the inorganic solid electrolyte and the polymer binder contained in the positive electrode active material layer 4, the solid electrolyte layer 3 and the negative electrode active material layer 2 may be of the same type or different from each other.
  • either or both of the positive electrode active material layer and the negative electrode active material layer may be simply referred to as an active material layer or an electrode active material layer.
  • either or both of the positive electrode active material and the negative electrode active material may be collectively referred to as an active material or an electrode active material.
  • the constituent layer is formed of the composition containing the inorganic solid electrolyte of the present invention, an all-solid-state secondary battery having low resistance and excellent cycle characteristics can be realized.
  • the negative electrode active material layer can be a lithium metal layer.
  • the lithium metal layer include a layer formed by depositing or molding a lithium metal powder, a lithium foil, a lithium vapor deposition film, and the like.
  • the thickness of the lithium metal layer can be, for example, 1 to 500 ⁇ m regardless of the thickness of the negative electrode active material layer.
  • the positive electrode current collector 5 and the negative electrode current collector 1 are preferably electron conductors.
  • either or both of the positive electrode current collector and the negative electrode current collector may be collectively referred to as a current collector.
  • a current collector As a material for forming a positive electrode current collector, in addition to aluminum, aluminum alloy, stainless steel, nickel and titanium, the surface of aluminum or stainless steel is treated with carbon, nickel, titanium or silver (a thin film is formed). Of these, aluminum and aluminum alloys are more preferable.
  • As a material for forming the negative electrode current collector in addition to aluminum, copper, copper alloy, stainless steel, nickel and titanium, carbon, nickel, titanium or silver is treated on the surface of aluminum, copper, copper alloy or stainless steel.
  • aluminum, copper, copper alloy and stainless steel are more preferable.
  • the shape of the current collector is usually a film sheet, but a net, a punched body, a lath body, a porous body, a foam body, a molded body of a fiber group, or the like can also be used.
  • the thickness of the current collector is not particularly limited, but is preferably 1 to 500 ⁇ m. Further, it is also preferable that the surface of the current collector is made uneven by surface treatment.
  • each layer may be composed of a single layer or a plurality of layers.
  • the all-solid-state secondary battery can be manufactured by a conventional method. Specifically, the all-solid-state secondary battery can be manufactured by forming each of the above layers using the inorganic solid electrolyte-containing composition or the like of the present invention. The details will be described below.
  • the inorganic solid electrolyte-containing composition of the present invention is appropriately applied onto a base material (for example, a metal foil serving as a current collector) to form a coating film (form a film).
  • a method including (via) a step a method for manufacturing a sheet for an all-solid-state secondary battery of the present invention
  • an inorganic solid electrolyte-containing composition containing a positive electrode active material is applied as a positive electrode material (positive electrode composition) on a metal foil which is a positive electrode current collector to form a positive electrode active material layer, and all solid batteries are formed.
  • a positive electrode sheet for the next battery is manufactured.
  • an inorganic solid electrolyte-containing composition for forming the solid electrolyte layer is applied onto the positive electrode active material layer to form the solid electrolyte layer.
  • an inorganic solid electrolyte-containing composition containing a negative electrode active material is applied onto the solid electrolyte layer as a negative electrode material (negative electrode composition) to form a negative electrode active material layer.
  • a negative electrode current collector metal foil
  • an all-solid secondary battery having a structure in which a solid electrolyte layer is sandwiched between the positive electrode active material layer and the negative electrode active material layer can be obtained. Can be done. This can be enclosed in a housing to obtain a desired all-solid-state secondary battery.
  • a negative electrode active material layer, a solid electrolyte layer and a positive electrode active material layer are formed on the negative electrode current collector, and the positive electrode current collector is superposed to manufacture an all-solid-state secondary battery. You can also do it.
  • Another method is as follows. That is, as described above, a positive electrode sheet for an all-solid-state secondary battery is manufactured. Further, an inorganic solid electrolyte-containing composition containing a negative electrode active material is applied as a negative electrode material (negative electrode composition) on a metal foil which is a negative electrode current collector to form a negative electrode active material layer, and all solid batteries are formed. A negative electrode sheet for the next battery is manufactured. Then, a solid electrolyte layer is formed on the active material layer of any one of these sheets as described above.
  • the other of the positive electrode sheet for the all-solid-state secondary battery and the negative electrode sheet for the all-solid-state secondary battery is laminated on the solid electrolyte layer so that the solid electrolyte layer and the active material layer are in contact with each other.
  • an all-solid-state secondary battery can be manufactured.
  • the following method can be mentioned. That is, as described above, a positive electrode sheet for an all-solid-state secondary battery and a negative electrode sheet for an all-solid-state secondary battery are manufactured. Separately from this, an inorganic solid electrolyte-containing composition is applied onto the substrate to prepare a solid electrolyte sheet for an all-solid secondary battery composed of a solid electrolyte layer.
  • the positive electrode sheet for the all-solid-state secondary battery and the negative electrode sheet for the all-solid-state secondary battery are laminated so as to sandwich the solid electrolyte layer peeled off from the base material. In this way, an all-solid-state secondary battery can be manufactured. Further, as described above, a positive electrode sheet for an all-solid-state secondary battery or a negative-negative sheet for an all-solid-state secondary battery, and a solid electrolyte sheet for an all-solid-state secondary battery are produced.
  • the positive electrode sheet for an all-solid secondary battery or the negative electrode sheet for an all-solid secondary battery and the solid electrolyte sheet for an all-solid secondary battery were brought into contact with the positive electrode active material layer or the negative electrode active material layer and the solid electrolyte layer. Put it on top of each other and pressurize it. In this way, the solid electrolyte layer is transferred to the positive electrode sheet for the all-solid-state secondary battery or the negative electrode sheet for the all-solid-state secondary battery.
  • the solid electrolyte layer from which the base material of the solid electrolyte sheet for the all-solid secondary battery is peeled off and the negative electrode sheet for the all-solid secondary battery or the positive electrode sheet for the all-solid secondary battery are attached (the negative electrode active material layer or the negative electrode active material layer to the solid electrolyte layer). Pressurize the positive electrode active material layer in contact with each other. In this way, an all-solid-state secondary battery can be manufactured.
  • the pressurizing method and pressurizing conditions in this method are not particularly limited, and the methods and pressurizing conditions described later in the pressurization of the applied composition can be applied.
  • the solid electrolyte layer or the like can be formed, for example, on a substrate or an active material layer by pressure-molding an inorganic solid electrolyte-containing composition or the like under pressure conditions described later, or sheet molding of a solid electrolyte or an active material. You can also use the body.
  • the inorganic solid electrolyte-containing composition of the present invention may be used for any one of the positive electrode composition, the inorganic solid electrolyte-containing composition and the negative electrode composition, and the present invention may be used as the inorganic solid electrolyte-containing composition.
  • the inorganic solid electrolyte-containing composition of the above can be used for any of the compositions.
  • the solid electrolyte layer or the active material layer is formed by a composition other than the composition containing an inorganic solid electrolyte of the present invention, examples thereof include commonly used compositions.
  • it belongs to the first group or the second group of the periodic table, which is accumulated in the negative electrode current collector by the initialization or the charging at the time of use, which will be described later, without forming the negative electrode active material layer at the time of manufacturing the all-solid secondary battery.
  • a negative electrode active material layer can also be formed by binding metal ions with electrons and precipitating them as a metal on a negative electrode current collector or the like.
  • the film formation (coating and drying) of the inorganic solid electrolyte-containing composition of the present invention is carried out while hydrogen-bonding the binder constituent components in the molecule and gradually solidifying or precipitating them.
  • the method of hydrogen bonding in the molecule is not particularly limited, and examples thereof include a method of selecting drying conditions in the film forming step.
  • the coating method of the composition containing an inorganic solid electrolyte or the like is not particularly limited and can be appropriately selected. Examples thereof include coating (preferably wet coating), spray coating, spin coating coating, dip coating coating, slit coating, stripe coating, and bar coat coating.
  • the coating conditions are appropriately determined, but it is preferable that the above-mentioned components constituting the polymer binder do not chemically react, and for example, the temperature conditions are preferably a temperature lower than the following drying temperature.
  • the applied inorganic solid electrolyte-containing composition is subjected to a drying treatment (heat treatment).
  • the drying treatment the polymer C1-1 or C2 among the binder constituents in the coated inorganic solid electrolyte-containing composition forms an intramolecular hydrogen bond while maintaining adsorption with the solid particles, for example, in the form of particles.
  • Solid particles can be solidified or precipitated to bind solid particles to each other while suppressing an increase in interfacial resistance. Due to the solidification or precipitation of such a polymer, the solid particles can be bound while suppressing the variation in the contact state and the increase in the interfacial resistance in combination with the excellent dispersion characteristics of the inorganic solid electrolyte-containing composition, and the surface can be surfaced.
  • a flat coated dry layer can be formed.
  • the composition containing an inorganic solid electrolyte of the present invention is heated in the drying treatment, the formation of intramolecular hydrogen bonds in the polymer among the binder constituents is promoted as the temperature rises, and the volatilization of the dispersion medium is also promoted. , It is considered that the solubility of the polymer in the dispersion medium gradually decreases. In this way, the binder constituents solidify or precipitate as a polymer binder.
  • the drying treatment may be carried out after each of the inorganic solid electrolyte-containing compositions has been applied, or may be carried out after the multi-layer coating.
  • the drying conditions are not particularly limited as long as the intermolecular hydrogen bonds can be cleaved to form an intramolecular hydrogen bond.
  • the drying temperature is appropriately set according to the type of hydrogen-bonding group (BHa) or (BHb), and is, for example, preferably 40 ° C. or higher, more preferably 60 ° C. or higher, still more preferably 80 ° C. or higher.
  • the upper limit is preferably 300 ° C. or lower, more preferably 250 ° C. or lower, and even more preferably 200 ° C. or lower.
  • the dispersion medium By heating in such a temperature range, the dispersion medium can be removed while the polymer C1-1 or C2 is intramolecularly hydrogen-bonded to form a coating dry layer. Further, it is preferable because the temperature is not too high and each member of the all-solid-state secondary battery is not damaged. As a result, in an all-solid-state secondary battery, it is possible to obtain excellent overall performance, good binding property, and good ionic conductivity even without pressurization.
  • the composition containing the inorganic solid electrolyte of the present invention is applied and dried as described above, it is possible to suppress the variation in the contact state and bind the solid particles, and the coated dry layer (inorganic solid electrolyte layer) having a flat surface. Can be formed.
  • the pressurizing method include a hydraulic cylinder press machine and the like.
  • the pressing force is not particularly limited, and is generally preferably in the range of 5 to 1500 MPa.
  • the applied inorganic solid electrolyte-containing composition may be heated at the same time as pressurization.
  • the heating temperature is not particularly limited, and is generally in the range of 30 to 300 ° C. It can also be pressed at a temperature higher than the glass transition temperature of the inorganic solid electrolyte. It is also possible to press at a temperature higher than the glass transition temperature of the polymer binder.
  • the temperature does not exceed the melting point of this polymer.
  • the pressurization may be performed in a state where the coating solvent or the dispersion medium is dried in advance, or may be performed in a state where the solvent or the dispersion medium remains.
  • each composition may be applied at the same time, and the application drying press may be performed simultaneously and / or sequentially. After being applied to different substrates, they may be laminated by transfer.
  • the atmosphere during the manufacturing process is not particularly limited, and is in air, in dry air (dew point -20 ° C or lower), in inert gas (for example, in argon gas, in helium gas, nitrogen). In gas), etc. may be used.
  • the pressing time may be short (for example, within several hours) and high pressure may be applied, or medium pressure may be applied for a long time (1 day or more).
  • a restraining tool for the all-solid-state secondary battery can be used in order to continue applying a medium pressure.
  • the press pressure may be uniform or different with respect to the pressed portion such as the seat surface.
  • the press pressure can be changed according to the area or film thickness of the pressed portion. It is also possible to change the same part step by step with different pressures.
  • the pressed surface may be smooth or roughened.
  • the all-solid-state secondary battery manufactured as described above is preferably initialized after manufacturing or before use. Initialization is not particularly limited, and can be performed, for example, by performing initial charging / discharging with the press pressure increased, and then releasing the pressure until the pressure reaches the general working pressure of the all-solid-state secondary battery.
  • the all-solid-state secondary battery of the present invention can be applied to various uses.
  • the application mode is not particularly limited, but for example, when it is mounted on an electronic device, it is a notebook computer, a pen input computer, a mobile computer, an electronic book player, a mobile phone, a cordless phone handset, a pager, a handy terminal, a mobile fax, or a mobile phone. Examples include copying, mobile printers, headphone stereos, video movies, LCD TVs, handy cleaners, portable CDs, mini discs, electric shavers, transceivers, electronic notebooks, calculators, memory cards, portable tape recorders, radios, backup power supplies, etc.
  • Other consumer products include automobiles, electric vehicles, motors, lighting equipment, toys, game equipment, road conditioners, watches, strobes, cameras, medical equipment (pacemakers, hearing aids, shoulder massagers, etc.). Furthermore, it can be used for various military demands and space. It can also be combined with a solar cell.
  • Synthesis Examples 8 and 9 Synthesis of Polymers PD-01 and PD-02
  • Synthesis Example 1 Similar to Synthesis Example 1 except that in Synthesis Example 1, a compound that derives each component so that the polymers PD-01 and PD-02 have the composition (type and content of the component) shown in the following chemical formula is used. Then, polymers PD-01 and PD-02 (acrylic polymer) were synthesized, respectively, to obtain polymers PD-01 and PD-02 as solids.
  • polymers P-08 to P-11 were synthesized as polymers C2 having two or more hydrogen-bonding groups (BHa) in the side chain and having an SP value of 22.5 or less.
  • Synthesis Examples 10 to 13 Synthesis of Polymers P-08 to P-11
  • a compound that guides each component so that the polymers P-08 to P-11 have the composition (type and content of the component) shown in the following chemical formula is used.
  • polymers P-08 to P-11 (acrylic polymer or vinyl polymer) were synthesized, respectively, and polymers P-08 to P-11 were obtained as solids.
  • a small molecule compound C1-2 having a hydrogen-bonding group (BHb) and having a CLogP value of 1.5 or more was prepared.
  • a monomer solution consisting of methyl methacrylate (60.0 g), hydroxyethyl acrylate (45.0 g), diisobutyl ketone (115.5 g) and V-601 (1.5 g) was placed in the three-necked flask for 2 hours. It was dropped at a constant velocity so that the dropping was completed. After the dropping of the monomer solution was completed, the mixture was stirred for 2 hours, then the temperature was raised to 90 ° C., and the mixture was further stirred for 2 hours. The resulting reaction mixture was filtered through a mesh with a mesh of 50 ⁇ m. In this way, a dispersion liquid T-5 of the binder particles cP-03 made of the polymer cP-03 having a solid content concentration of 30% by mass was prepared.
  • Table 1 shows the results of calculating the SP value (unit: MPa 1/2 ), mass average molecular weight, and ClogP value of compound C1-2 of each synthesized polymer based on the above method.
  • the above-mentioned SP value (excluding MM) is the same as the above-mentioned calculated SP value.
  • Binder Solution The binder solution shown in Table 1 was prepared using each polymer synthesized as described above.
  • Preparation Example 1 Preparation of Binder Solution S-1
  • the solid of the polymer P-01 synthesized in Synthesis Example 1 and n-hexanol (D-01) as compound C1-2 are mixed at a ratio of 10: 1 (mass ratio) and dissolved in butyl butyrate to dissolve the binder solution S-. 1 (solid content mass 3%) was obtained.
  • Preparation Examples 2 to 14 Preparation of binder solutions S-2-S-11 and T-1 to T-4] Binder solutions S-2 to S-11 and T in the same manner as in Preparation Example 1 except that the polymers P-01 and D-01 were changed to the polymers and compounds C1-2 shown in Table 1. -1 to T-4 (solid content 3% by mass) were obtained, respectively.
  • Binder Solutions S-12 and S-13 The binder solution S-12 was prepared by mixing the solid of the polymer P-07 synthesized in Synthesis Example 7 and the solid of the polymer PD-01 synthesized in Synthesis Example 8 at a ratio of 1: 1 (mass ratio) and dissolving them in butyl butyrate. (Solid content mass 3%) was obtained. Further, the binder solution S-13 (solid content 3% by mass) is also the solid of the polymer P-07 synthesized in the synthesis example 7 and the polymer PD-02 synthesized in the synthesis example 9 in the same manner as the above binder solution S-12. The solids were prepared by mixing 1: 1 (mass ratio) and dissolving in butyl butyrate.
  • Binder Solution S-14 to 17 The solid of the polymer P-08 synthesized in Synthesis Example 8 was dissolved in butyl butyrate to obtain a binder solution S-14 (solid content 3% by mass). Further, in the preparation of the binder solution S-14, the binder solutions S-15 to S-17 (similar to the preparation of the binder solution S-14) except that the polymer P-08 was changed to the polymer shown in Table 1. Solid content 3% by mass) was obtained respectively. In Table 1 below, "-" in each column means that it does not have the corresponding component. When the polymer has a plurality of hydrogen-bonding groups (BHa), they are described together using "/".
  • Li 2 S lithium sulfide
  • Aldrich Corp. purity> 99.98%
  • Example 1 Each composition shown in Tables 2-1 to 2-3 (collectively referred to as Table 2) was prepared as follows. In each of the prepared compositions, the binder constituents were dissolved in the dispersion medium. ⁇ Preparation of Inorganic Solid Electrolyte-Containing Composition> 60 g of zirconia beads having a diameter of 5 mm was put into a zirconia 45 mL container (manufactured by Fritsch), and 8.7 g of LPS synthesized in the above synthesis example A, each binder solution or binder shown in the "binder solution or dispersion" column of Table 2.
  • Butyl butyrate was added as a dispersion medium so that the content of the dispersion liquid (solid content mass) was 0.3 g and the content of butyl butyrate as a dispersion medium was 55% by mass. After that, this container was set in a planetary ball mill P-7 (trade name) manufactured by Fritsch. Inorganic solid electrolyte-containing compositions (slurries) K-1 to K-17 and Kc1 to Kc5 were prepared by mixing at a temperature of 25 ° C. and a rotation speed of 150 rpm for 10 minutes, respectively.
  • ⁇ Preparation of positive electrode composition 60 g of zirconia beads having a diameter of 5 mm was put into a 45 mL container made of zirconia (manufactured by Fritsch), 8.0 g of LPS synthesized in Synthesis Example A, and each binder solution or each binder solution shown in the "Binder solution or dispersion" column of Table 2. 0.4 g (solid content mass) of the binder dispersion was added. This container was set on a planetary ball mill P-7 (trade name) manufactured by Fritsch, and stirred at 25 ° C. at a rotation speed of 200 pm for 30 minutes.
  • NMC manufactured by Aldrich
  • AB acetylene black
  • butyl butyrate was added as a dispersion medium so that the 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 30 minutes.
  • PKc1 to PKc5 were prepared, respectively.
  • ⁇ Preparation of negative electrode composition 60 g of zirconia beads having a diameter of 5 mm was put into a 45 mL container made of zirconia (manufactured by Fritsch), 8.0 g of LPS synthesized in Synthesis Example A, and each binder solution or binder dispersion shown in the "Binder solution or dispersion” column of Table 2. 0.4 g (solid content mass) of the liquid was added.
  • This container was set on a planetary ball mill P-7 (trade name) manufactured by Fritsch, and mixed at a temperature of 25 ° C. and a rotation speed of 300 pm for 60 minutes.
  • the content of silicon (Si, manufactured by Aldrich) as a negative electrode active material was 9.5 g, VGCF (manufactured by Showa Denko) 1.0 g as a conductive auxiliary agent, and butyl butyrate as a dispersion medium in the composition was 48% by mass. Butyl butyrate was added as a dispersion medium so that the container was set in the planetary ball mill P-7 and mixed at a temperature of 25 ° C. and a rotation speed of 100 rpm for 10 minutes to prepare the negative electrode composition (slurry) NK-1. -NK-17 and NKc1 to NKc5 were prepared, respectively.
  • ⁇ Evaluation 2 Surface smoothness> A test piece having a length of 20 mm and a width of 20 mm was cut out from the solid electrolyte sheet for each all-solid-state secondary battery, the positive electrode sheet for each all-solid-state secondary battery, and the negative electrode sheet for each all-solid-state secondary battery.
  • the layer thickness at 5 points was measured using a constant pressure thickness measuring device (manufactured by Teclock Co., Ltd.), and the arithmetic mean value of the layer thickness was calculated. From each measured value and its arithmetic mean value, the large deviation value (maximum deviation value) among the deviation values (%) obtained by the following formula (a) or (b) is applied to the following evaluation criteria to obtain surface smoothness. evaluated.
  • the layer thickness was measured at the following "5 points" for each test piece. As shown in FIG. 3, first, three virtual lines y1, y2, and y3 that divide the vertical direction of the test piece TP into four equal parts are drawn, and then the horizontal direction of the test piece TP is divided into four equal parts in the same manner. Three virtual lines x1, x2 and x3 are drawn, and the surface of the test piece is divided into a grid pattern.
  • the measurement points are the intersection A of the virtual lines x1 and y1, the intersection B of the virtual lines x1 and y3, the intersection C of the virtual lines x2 and y2, the intersection D of the virtual lines x3 and y1, and the virtual lines x3 and y3.
  • E the intersection E with.
  • Evaluation criteria - A: Maximum deviation value ⁇ 3% B: 3% ⁇ maximum deviation value ⁇ 8% C: 8% ⁇ maximum deviation value ⁇ 13% D: 13% ⁇ maximum deviation value
  • An all-solid-state secondary battery (No. 101) having the layer structure shown in FIG. 1 was produced as follows.
  • the 2032 type coin case 11 was crimped to obtain the No. 2 shown in FIG.
  • the 101 all-solid-state secondary battery 13 was manufactured.
  • the all-solid-state secondary battery (half cell) manufactured in this manner has the layer structure shown in FIG. 1 (however, the lithium foil corresponds to the negative electrode active material layer 2 and the negative electrode current collector 1).
  • the positive electrode sheet No. 1 for an all-solid-state secondary battery provided with a solid electrolyte layer instead of 118, No. 1 shown in the “Electrode active material layer” column of Table 4.
  • the all-solid-state secondary battery (half cell) is the same as the production of the all-solid-state secondary battery (No. 101) except that the positive electrode sheet for the all-solid-state secondary battery provided with the solid-state electrolyte layer is used. No. 102 to 117 were manufactured respectively.
  • Negative electrode sheet No. 1 for an all-solid secondary battery provided with the solid electrolyte layer obtained above. 135 (the aluminum foil of the solid electrolyte-containing sheet has been peeled off) is cut into a disk shape with a diameter of 14.5 mm, and as shown in FIG. 2, 2032 made of stainless steel incorporating a spacer and a washer (not shown in FIG. 2). I put it in the mold coin case 11. Next, a positive electrode sheet (positive electrode active material layer) punched out from the positive electrode sheet for an all-solid-state secondary battery produced below with a diameter of 14.0 mm was laminated on the solid electrolyte layer. After further stacking the stainless steel foil on it, the 2032 type coin case 11 is crimped to obtain the all-solid-state secondary battery (full-cell) No. 2 shown in FIG. 118 was made.
  • a positive electrode sheet for a solid-state secondary battery used for manufacturing the all-solid-state secondary battery (No. 118) was prepared as follows. (Preparation of positive electrode composition) 180 zirconia beads having a diameter of 5 mm were put into a 45 mL container made of zirconia (manufactured by Fritsch), 2.7 g of LPS synthesized in the above synthesis example A, KYNAR FLEX 2500-20 (trade name, PVdF-HFP: polyfluoridene). Vinylidene hexafluoropropylene copolymer (manufactured by Arkema) was added as a solid content mass of 0.3 g, and butyl butyrate was added in an amount of 22 g.
  • This container was set on a planetary ball mill P-7 (trade name) manufactured by Fritsch, and stirred at 25 ° C. and a rotation speed of 300 rpm for 60 minutes. After that, 7.0 g of LiNi 1/3 Co 1/3 Mn 1/3 O 2 (NMC) was added as the positive electrode active material, and in the same manner, the container was set in the planetary ball mill P-7, and the temperature was 25 ° C. and the rotation speed. Mixing was continued at 100 rpm for 5 minutes to prepare a positive electrode composition.
  • NMC LiNi 1/3 Co 1/3 Mn 1/3 O 2
  • the positive electrode composition obtained above is applied onto an aluminum foil (positive electrode current collector) having a thickness of 20 ⁇ m with a baker-type applicator (trade name: SA-201, manufactured by Tester Sangyo Co., Ltd.) and heated at 100 ° C. for 2 hours. , The positive electrode composition was dried (dispersion medium was removed). Then, using a heat press machine, the dried positive electrode composition was pressurized at 25 ° C. (10 MPa, 1 minute) to prepare a positive electrode sheet for an all-solid secondary battery having a positive electrode active material layer having a film thickness of 80 ⁇ m. ..
  • the above all-solid-state secondary battery No. In the production of 118, the negative electrode sheet No. 1 for an all-solid secondary battery provided with a solid electrolyte layer. Instead of 135, No. 1 shown in the “Electrode active material layer” column of Table 4. All-solid-state secondary battery No. 1 except that the negative electrode sheet for the all-solid-state secondary battery provided with the solid-state electrolyte layer was used. In the same manner as in the production of 118, the all-solid-state secondary battery (full-cell) No. 119 to 134 and c101 to c105 were produced, respectively.
  • the passing level of this test is above the evaluation standard "C”.
  • the all-solid-state secondary battery c103 is included in the evaluation standard "D", and the number of charge / discharge cycles is 90.
  • the initial discharge capacities of 101 to 134 all showed sufficient values to function as an all-solid-state secondary battery.
  • - Evaluation criteria - A: 500 cycles or more B: 250 cycles or more, less than 500 cycles C: 150 cycles or more, less than 250 cycles D: 80 cycles or more, less than 150 cycles E: less than 80 cycles
  • ⁇ Evaluation 4 Ion conductivity measurement> The ionic conductivity of each manufactured all-solid-state secondary battery was measured. Specifically, for each all-solid-state secondary battery, AC impedance was measured with a voltage amplitude of 5 mV and a frequency of 1 MHz to 1 Hz using a 1255B FREQUENCY RESPONSE ANALYZER (trade name, manufactured by SOLARTRON) in a constant temperature bath at 30 ° C. As a result, the resistance of the sample for measuring ionic conductivity in the layer thickness direction was obtained, and the ionic conductivity was calculated by the following formula (1).
  • Ion conductivity ⁇ (mS / cm) 1000 x sample layer thickness (cm) / [resistance ( ⁇ ) x sample area (cm 2 )]
  • the sample layer thickness is measured before the laminate 12 is placed in the 2032 type coin case 11, and the value obtained by subtracting the layer thickness of the current collector (total layer thickness of the solid electrolyte layer and the electrode active material layer). ).
  • the sample area is the area of a disk-shaped sheet having a diameter of 14.5 mm. It was determined which of the following evaluation criteria the obtained ionic conductivity ⁇ was included in. The ionic conductivity ⁇ in this test passed the evaluation standard "C" or higher.
  • the all-solid-state secondary battery c103 is included in the evaluation standard "D", and the ionic conductivity ⁇ is 0.20 (mS / cm).
  • this inorganic solid electrolyte-containing composition for forming a constituent layer of an all-solid-state secondary battery, a constituent layer having a flat surface and low resistance can be formed, and the obtained all-solid-state secondary battery has excellent cycle characteristics. It can be seen that high ionic conductivity can be achieved.
  • the above-mentioned effect of the present invention is that the binder constituent component dissolves in a dispersion medium by forming an intermolecular hydrogen bond in the composition containing an inorganic solid electrolyte to exhibit excellent dispersion characteristics, while the molecule in the constituent layer. It is considered that the polymer binder is formed by forming the internal hydrogen bond, and the solid particles can be bound to each other while suppressing the increase in the interfacial resistance. Since the all-solid-state secondary battery of the present invention exhibits the above-mentioned excellent characteristics, it exhibits excellent cycle characteristics even under high-speed charge / discharge conditions.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Electrochemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Polymers & Plastics (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
  • Secondary Cells (AREA)
  • Conductive Materials (AREA)

Abstract

L'invention concerne : une composition contenant un électrolyte solide inorganique qui contient un électrolyte solide inorganique, un milieu de dispersion, et des composants constituant un liant polymère, les composants constituant le liant polymère comprenant un polymère qui a une chaîne latérale ayant au moins un type de groupe de liaison à l'hydrogène capable de former deux liaisons hydrogène ou plus ; une feuille pour une batterie secondaire entièrement solide et une batterie secondaire entièrement solide à l'aide de la composition contenant un électrolyte solide inorganique ; et des procédés de production de la feuille pour une batterie secondaire entièrement solide et la batterie secondaire entièrement solide.
PCT/JP2021/023810 2020-06-26 2021-06-23 Composition contenant un électrolyte solide inorganique, feuille pour batterie secondaire entièrement solide, batterie secondaire entièrement solide, et procédés de production de feuille pour batterie secondaire entièrement solide et batterie secondaire entièrement solide WO2021261526A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2022532519A JP7407286B2 (ja) 2020-06-26 2021-06-23 無機固体電解質含有組成物、全固体二次電池用シート及び全固体二次電池、並びに、全固体二次電池用シート及び全固体二次電池の製造方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2020110647 2020-06-26
JP2020-110647 2020-06-26

Publications (1)

Publication Number Publication Date
WO2021261526A1 true WO2021261526A1 (fr) 2021-12-30

Family

ID=79281310

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2021/023810 WO2021261526A1 (fr) 2020-06-26 2021-06-23 Composition contenant un électrolyte solide inorganique, feuille pour batterie secondaire entièrement solide, batterie secondaire entièrement solide, et procédés de production de feuille pour batterie secondaire entièrement solide et batterie secondaire entièrement solide

Country Status (2)

Country Link
JP (1) JP7407286B2 (fr)
WO (1) WO2021261526A1 (fr)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015103451A (ja) * 2013-11-26 2015-06-04 三星電子株式会社Ｓａｍｓｕｎｇ Ｅｌｅｃｔｒｏｎｉｃｓ Ｃｏ．，Ｌｔｄ． 全固体二次電池および全固体二次電池の製造方法
JP2018088306A (ja) * 2016-11-28 2018-06-07 富士フイルム株式会社 固体電解質組成物、固体電解質含有シートおよび全固体二次電池、ならびに、固体電解質含有シートおよび全固体二次電池の製造方法
WO2019098009A1 (fr) * 2017-11-17 2019-05-23 富士フイルム株式会社 Composition d'électrolyte solide, feuille de batterie secondaire "tout solide", feuille d'électrode de batterie secondaire "tout solide", procédé de production d'une feuille de batterie secondaire "tout solide", et procédé de production d'une batterie secondaire "tout solide"
JP2019207840A (ja) * 2018-05-30 2019-12-05 トヨタ自動車株式会社 全固体電池

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015103451A (ja) * 2013-11-26 2015-06-04 三星電子株式会社Ｓａｍｓｕｎｇ Ｅｌｅｃｔｒｏｎｉｃｓ Ｃｏ．，Ｌｔｄ． 全固体二次電池および全固体二次電池の製造方法
JP2018088306A (ja) * 2016-11-28 2018-06-07 富士フイルム株式会社 固体電解質組成物、固体電解質含有シートおよび全固体二次電池、ならびに、固体電解質含有シートおよび全固体二次電池の製造方法
WO2019098009A1 (fr) * 2017-11-17 2019-05-23 富士フイルム株式会社 Composition d'électrolyte solide, feuille de batterie secondaire "tout solide", feuille d'électrode de batterie secondaire "tout solide", procédé de production d'une feuille de batterie secondaire "tout solide", et procédé de production d'une batterie secondaire "tout solide"
JP2019207840A (ja) * 2018-05-30 2019-12-05 トヨタ自動車株式会社 全固体電池

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
MINISTRY OF HEALTH, LABOUR AND WELFARE, MINISTRY OF ECONOMY, TRADE AND INDUSTRY, MINISTRY OF THE ENVIRONMENT GOVERNMENT OF JAPAN: "2,6-Di-t-butyl-4-methylphenol", RISK ASSESSMENT OF PRIORITY ASSESSMENT CHEMICAL SUBSTANCE (PHASE 1), 4 July 2015 (2015-07-04) *

Also Published As

Publication number Publication date
JP7407286B2 (ja) 2023-12-28
JPWO2021261526A1 (fr) 2021-12-30

Similar Documents

Publication Publication Date Title
JP7104800B2 (ja) 全固体二次電池の製造方法、並びに、全固体二次電池用電極シート及びその製造方法
WO2021100362A1 (fr) Composition contenant un électrolyte solide inorganique, feuille pour batteries secondaires entièrement solides, batterie secondaire entièrement solide, procédé de production de feuille pour batteries secondaires entièrement solides et procédé de production de batterie secondaire entièrement solide
WO2021039950A1 (fr) Composition contenant un électrolyte solide inorganique, feuille pour batteries secondaires à semi-conducteur, batterie secondaire à semi-conducteur et procédés de production de batterie secondaire à semi-conducteur et feuille pour batteries secondaires à semi-conducteur
WO2021039948A1 (fr) Procédé de production de composition d'électrode, procédé de fabrication de feuille d'électrode pour une batterie secondaire tout solide et procédé de fabrication de batterie secondaire tout solide
JP7165747B2 (ja) 電極用組成物、全固体二次電池用電極シート及び全固体二次電池、並びに、電極用組成物、全固体二次電池用電極シート及び全固体二次電池の各製造方法
WO2021039468A1 (fr) Composition contenant un électrolyte solide inorganique, feuille pour batteries secondaires entièrement solides, batterie secondaire entièrement solide, méthode de fabrication de feuille pour batteries secondaires entièrement solides, et méthode de fabrication de batterie secondaire entièrement solide
WO2021014852A1 (fr) Composition contenant un électrolyte solide inorganique, feuille pour batteries secondaires entièrement solides, feuille d'électrode pour batteries secondaires entièrement solides, batterie secondaire entièrement solide, procédé de production de feuille pour batteries secondaires entièrement solides et procédé de production de batterie secondaire entièrement solide
US20230041774A1 (en) Inorganic solid electrolyte-containing composition, sheet for all-solid state secondary battery, and all-solid state secondary battery, and manufacturing methods for sheet for all-solid state secondary battery and all-solid state secondary battery
JP6957742B2 (ja) 固体電解質組成物、全固体二次電池用シート及び全固体二次電池、並びに、全固体二次電池用シート若しくは全固体二次電池の製造方法
WO2022071392A1 (fr) Composition contenant un électrolyte solide inorganique, feuille pour batterie secondaire entièrement solide, et batterie secondaire entièrement solide, et procédés de production de feuille pour batterie secondaire entièrement solide et batterie secondaire entièrement solide
WO2020067106A1 (fr) Composition d'électrolyte solide, feuille pour batterie rechargeable à électrolyte solide, feuille d'électrode pour batterie rechargeable à électrolyte solide, batterie rechargeable à électrolyte solide, et procédés de fabrication de feuille pour batterie rechargeable à électrolyte solide et de batterie rechargeable à électrolyte solide
WO2021157278A1 (fr) Composition contenant un électrolyte solide inorganique, feuille pour batterie secondaire entièrement solide, batterie secondaire entièrement solide, et procédés de fabrication de feuille pour batterie secondaire entièrement solide et batterie secondaire entièrement solide
WO2021085549A1 (fr) Composition contenant un électrolyte solide inorganique, feuille pour batterie secondaire entièrement solide et batterie secondaire entièrement solide, et procédés de fabrication de feuille pour batterie secondaire entièrement solide et pour fabrication de batterie secondaire entièrement solide
US20210083323A1 (en) Solid electrolyte composition, solid electrolyte-containing sheet, all-solid state secondary battery, method of manufacturing solid electrolyte-containing sheet, and method of manufacturing all-solid state secondary battery
WO2021039949A1 (fr) Composition contenant un électrolyte solide inorganique, feuille pour batterie secondaire tout à l'état solide, batterie secondaire tout à l'état solide, et procédés de fabrication de feuille pour batterie secondaire tout à l'état solide et batterie secondaire tout à l'état solide
JP6982682B2 (ja) 固体電解質組成物、全固体二次電池用シート、及び全固体二次電池、並びに、全固体二次電池用シート若しくは全固体二次電池の製造方法
WO2021193751A1 (fr) Composition d'électrode, feuille d'électrode pour batterie secondaire entièrement solide et batterie secondaire entièrement solide, et procédés de fabrication de feuille d'électrode pour batterie secondaire entièrement solide et batterie secondaire entièrement solide
WO2021261526A1 (fr) Composition contenant un électrolyte solide inorganique, feuille pour batterie secondaire entièrement solide, batterie secondaire entièrement solide, et procédés de production de feuille pour batterie secondaire entièrement solide et batterie secondaire entièrement solide
WO2022085733A1 (fr) Composition d'électrode, feuille d'électrode pour batteries rechargeables entièrement solides, batterie rechargeable entièrement solide, procédé de production d'une feuille d'électrode pour batteries rechargeables entièrement solides et procédé de production d'une batterie rechargeable entièrement solide
WO2022059567A1 (fr) Composition contenant un électrolyte solide inorganique, feuille pour batteries rechargeables tout-solide, batterie rechargeable tout-solide, procédé de production de feuille pour batteries rechargeables tout-solide et procédé de production de batterie rechargeable tout-solide
WO2022071124A1 (fr) Composition contenant un électrolyte solide inorganique, feuille pour batteries secondaires entièrement solides, batterie secondaire entièrement solide, procédé de production de feuille pour batteries secondaires entièrement solides et procédé de production de batterie secondaire entièrement solide
WO2021193826A1 (fr) Composition contenant un électrolyte solide inorganique, feuille de batterie secondaire entièrement solide, batterie secondaire entièrement solide, et procédé de fabrication d'une feuille de batterie secondaire entièrement solide et d'une batterie secondaire entièrement solide
WO2022065477A1 (fr) Composition contenant un électrolyte solide inorganique, feuille pour batteries secondaires à l'état solide, batterie secondaire à l'état solide, et procédés de production de feuille pour batteries secondaires à l'état solide ou batterie secondaire à l'état solide
WO2022070850A1 (fr) Composition contenant un électrolyte solide inorganique, feuille pour batterie secondaire entièrement solide, batterie secondaire entièrement solide, méthode de production de feuille pour batterie secondaire entièrement solide et méthode de production de batterie secondaire entièrement solide
WO2023068237A1 (fr) Composition contenant un électrolyte solide inorganique, feuille pour batterie secondaire entièrement solide, et batterie secondaire entièrement solide, et procédés de production de feuille pour batterie secondaire entièrement solide et batterie secondaire entièrement solide

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 21828108

Country of ref document: EP

Kind code of ref document: A1

DPE1 Request for preliminary examination filed after expiration of 19th month from priority date (pct application filed from 20040101)
ENP Entry into the national phase

Ref document number: 2022532519

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 21828108

Country of ref document: EP

Kind code of ref document: A1