WO2023282312A1 - 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 - Google Patents

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 Download PDF

Info

Publication number
WO2023282312A1
WO2023282312A1 PCT/JP2022/026899 JP2022026899W WO2023282312A1 WO 2023282312 A1 WO2023282312 A1 WO 2023282312A1 JP 2022026899 W JP2022026899 W JP 2022026899W WO 2023282312 A1 WO2023282312 A1 WO 2023282312A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
solid electrolyte
polymer
inorganic solid
secondary battery
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/JP2022/026899
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
浩司 安田
広 磯島
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Fujifilm Corp
Original Assignee
Fujifilm Corp
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 Fujifilm Corp filed Critical Fujifilm Corp
Priority to JP2023533178A priority Critical patent/JPWO2023282312A1/ja
Publication of WO2023282312A1 publication Critical patent/WO2023282312A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

Classifications

    • 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
    • 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
    • H01B1/10—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances sulfides
    • 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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • H01M10/0585—Construction or manufacture of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators
    • 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 secondary battery sheet and an all-solid secondary battery, and a method for producing an all-solid secondary battery sheet and an all-solid secondary battery.
  • An all-solid-state secondary battery consists of a solid negative electrode, electrolyte, and positive electrode, and can greatly improve safety and reliability, which are problems of batteries using organic electrolytes. In addition, it is said that it will be possible to extend the service life. Furthermore, the all-solid secondary battery can have a structure in which the electrodes and the electrolyte are directly arranged in series. Therefore, it is possible to achieve a higher energy density than a secondary battery using an organic electrolyte, and it is expected to be applied to electric vehicles, large storage batteries, and the like.
  • an inorganic solid electrolyte, an active material, a conductive aid, and the like are used as materials for forming constituent layers (a solid electrolyte layer, a negative electrode active material layer, a positive electrode active material layer, etc.).
  • these inorganic solid electrolytes particularly oxide-based inorganic solid electrolytes and sulfide-based inorganic solid electrolytes, have been expected as electrolyte materials having high ionic conductivity approaching that of organic electrolytes.
  • a constituent layer using an inorganic solid electrolyte is usually formed using a material (constituent layer-forming material) containing an inorganic solid electrolyte and a binder in consideration of an improvement in productivity.
  • Patent Document 1 describes an active material layer slurry containing an active material as an essential component and a solid electrolyte material, a graft polymer, a conductive agent, an organic solvent, etc. as optional components.
  • the graft polymer described in Patent Document 1 is a branched polymer composed of two or more segments, one of which constitutes the main chain and the other constitutes the graft portion (side chain). It is considered to be a polymer with no groups.
  • Patent Document 2 a nitrogen-containing polymer having a repeating unit having a specific substituent such as a substituent X having a pKa of 14 or less, a substituent Y having a polymer chain containing a hetero atom, and a periodic table number
  • a nitrogen-containing polymer having a repeating unit having a specific substituent such as a substituent X having a pKa of 14 or less, a substituent Y having a polymer chain containing a hetero atom, and a periodic table number
  • a solid electrolyte composition containing an inorganic solid electrolyte having ionic conductivity of a metal belonging to the first or second group and a conductive aid is described.
  • the constituent layers of all-solid-state secondary batteries are formed of solid particles (inorganic solid electrolyte, active material, conductive aid, etc.), the state of interfacial contact between solid particles and the interfacial contact between solid particles and current collectors The state is restricted, and as a result, the interfacial resistance tends to increase, and solid particles cannot be brought into close contact with each other with strong adhesion.
  • This increase in interfacial resistance causes not only an increase in battery resistance (decrease in ionic conductivity) of the all-solid secondary battery, but also a decrease in cycle characteristics.
  • the adhesion between solid particles is not sufficient, resulting in further degradation of cycle characteristics.
  • the increase in resistance at interfaces, batteries, etc. which is a factor in the deterioration of battery performance, is caused not only by the interfacial contact state of solid particles, but also by the uneven presence (arrangement) of solid particles in the constituent layers. surface flatness is also a factor. Therefore, when the constituent layer is formed from the constituent layer forming material, the constituent layer forming material has a property (dispersion stability) that stably maintains the excellent dispersibility of the solid particles immediately after preparation and an appropriate viscosity. It is also required to have properties (handling properties) capable of forming a good coating film with high fluidity.
  • a conductive aid is sometimes used together with the inorganic solid electrolyte for the purpose of sufficiently constructing an electron conduction path to form a low-resistance constituent layer.
  • Conductive agents generally have poorer dispersibility in a dispersion medium than the inorganic solid electrolyte layer. Therefore, coexistence of a conductive agent reduces not only the dispersibility of the conductive agent but also the dispersibility of the composition. Therefore, sufficient dispersion stability and handleability cannot be achieved.
  • Patent Documents 1 and 2 do not describe this point of view.
  • the present invention provides an inorganic solid electrolyte-containing composition that exhibits excellent dispersion stability and handleability even if it contains a conductive aid, and is used as a constituent layer forming material of an all-solid secondary battery to achieve low resistance.
  • An object of the present invention is to provide an inorganic solid electrolyte-containing composition that enables the realization of an all-solid secondary battery that is excellent in cycle characteristics.
  • the present invention also provides a sheet for an all-solid secondary battery and an all-solid secondary battery, and a method for producing an all-solid secondary battery sheet and an all-solid secondary battery using this inorganic solid electrolyte-containing composition. The task is to provide
  • a polymer having a polymer chain component (X) having a polymer chain containing a polymer chain component having a functional group (b) as an essential component, and further dissolved in the polymer binder in a dispersion medium By simultaneously imparting the property of absorbing and the property of adsorbing 50% or less to the conductive aid, even if the inorganic solid electrolyte-containing composition contains the conductive aid, excellent dispersion stability and handling properties can be achieved. I found what I could do.
  • ⁇ 1> Contains an inorganic solid electrolyte having ion conductivity of a metal belonging to Group 1 or Group 2 of the periodic table, a conductive aid, a polymer binder, and a dispersion medium, An inorganic solid electrolyte-containing composition in which a polymer binder satisfies the following [I] and [II].
  • the polymer binder dissolves in the dispersion medium and has an adsorption rate of 50% or less with respect to the conductive aid.
  • ⁇ 3> The inorganic solid electrolyte-containing composition according to ⁇ 1> or ⁇ 2>, wherein the content of the component (A) in the polymer is 0.1 to 20% by mass.
  • ⁇ 4> The inorganic solid electrolyte-containing composition according to any one of ⁇ 1> to ⁇ 3>, wherein the polymer is a (meth)acrylic polymer.
  • ⁇ 5> The inorganic solid electrolyte-containing composition according to any one of ⁇ 1> to ⁇ 4>, which contains an active material.
  • ⁇ 6> The inorganic solid electrolyte-containing composition according to any one of ⁇ 1> to ⁇ 5>, wherein the inorganic solid electrolyte is a sulfide-based inorganic solid electrolyte.
  • ⁇ 7> A sheet for an all-solid secondary battery, having a layer composed of the inorganic solid electrolyte-containing composition according to any one of ⁇ 1> to ⁇ 6> above.
  • An all-solid secondary battery comprising a positive electrode active material layer, a solid electrolyte layer and a negative electrode active material layer in this order, An all-solid secondary battery, wherein at least one of the positive electrode active material 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 ⁇ 6>.
  • a method for producing a sheet for an all-solid secondary battery comprising forming a film from the inorganic solid electrolyte-containing composition according to any one of ⁇ 1> to ⁇ 6> above.
  • a method for manufacturing an all-solid secondary battery including the manufacturing method according to ⁇ 9> above.
  • the present invention is an inorganic solid electrolyte-containing composition that exhibits excellent dispersion stability and handleability even when containing a conductive aid, and enables the realization of an all-solid secondary battery that has low resistance and excellent cycle characteristics.
  • the present invention can provide a sheet for an all-solid secondary battery and an all-solid secondary battery having a layer composed of this excellent inorganic solid electrolyte-containing composition.
  • the present invention can provide a sheet for an all-solid secondary battery and a method for producing an all-solid secondary battery using this inorganic solid electrolyte-containing composition.
  • FIG. 1 is a vertical cross-sectional view schematically showing an all-solid secondary battery according to a preferred embodiment of the present invention
  • FIG. 2 is a vertical cross-sectional view schematically showing a coin-type all-solid-state secondary battery produced in Examples.
  • a numerical range represented by "to” means a range including the numerical values before and after “to” as lower and upper limits.
  • the upper limit and lower limit forming the numerical range are described before and after "-" as a specific numerical range. It is not limited to the combination of the specific upper limit value and the lower limit value, and can be a numerical range in which the upper limit value and the lower limit value of each numerical range are appropriately combined.
  • the expression of a compound (for example, when it is called with a compound at the end) is used to mean the compound itself, its salt, and its ion.
  • (meth)acryl means one or both of acryl and methacryl.
  • substituents, linking groups, etc. for which substitution or non-substitution is not specified are intended to mean that the group may have an appropriate substituent. Therefore, in the present invention, even when the YYY group is simply described, this YYY group includes not only the embodiment having no substituent but also the embodiment having a substituent.
  • substituents include, for example, substituent Z described later.
  • the respective substituents, etc. may be the same or different from each other. means that Further, even if not otherwise specified, when a plurality of substituents and the like are adjacent to each other, they may be connected to each other or condensed to form a ring.
  • a polymer means a polymer and is synonymous with a so-called high molecular compound.
  • a polymer binder (also referred to simply as a binder) means a binder composed of a polymer, and includes a polymer itself and a binder composed (formed) of a polymer.
  • the main chain of a polymer and a polymer chain means that all other molecular chains constituting the polymer or polymer chain are linear molecular chains that can be regarded as branched chains or pendant groups with respect to the main chain.
  • the longest chain among the molecular chains constituting the polymer or polymer chain is the main chain.
  • the main chain does not include a terminal group possessed by the polymer or the end of the polymer chain.
  • the side chain of a polymer refers to a branched chain other than the main chain, and includes short and long chains.
  • the inorganic solid electrolyte-containing composition of the present invention contains an inorganic solid electrolyte having ion conductivity of a metal belonging to Group 1 or Group 2 of the periodic table, a conductive aid, a polymer binder, and a dispersion medium. do.
  • This polymer binder is formed by containing a polymer having a specific constituent component, dissolves in a dispersion medium, and exhibits an adsorption characteristic of 50% or less adsorption rate to the conductive aid.
  • the inorganic solid electrolyte-containing composition containing the above components exhibits excellent dispersion stability and handleability even when it contains a conductive aid or when the solid content concentration is increased. Therefore, an all-solid secondary battery having a constituent layer made of the inorganic solid electrolyte-containing composition of the present invention has low resistance and excellent cycle characteristics.
  • the binder containing the polymer having each of the constituent components (X) and (A), which will be described later, is dissolved in the dispersion medium and exists in a state in which the molecular chains of the polymer are spread in the inorganic solid electrolyte-containing composition. Moreover, it is considered that the excluded volume effect between the binders due to the constituent component (X) present in the polymer is increased, while the repulsive force between the binders due to the osmotic pressure effect is increased. As a result, the aggregation and adhesion of the binders are suppressed, and the dispersibility is improved.
  • the binder mainly adsorbs the conductive aid in its component (X) and mainly adsorbs the inorganic solid electrolyte etc. in the component (A), and forms solid particles containing the conductive additive in the dispersion medium.
  • (Re)agglomeration and sedimentation can be inhibited and highly dispersed. Therefore, even if a conductive additive is contained or the solid content concentration is increased, excellent dispersibility can be maintained even over time, and even if the solid particles have once aggregated or precipitated, excellent dispersibility immediately after preparation can be maintained. can be reproduced, and it is considered to exhibit moderate fluidity.
  • the binder is adsorbed to the solid particles, the surfaces of the solid particles are partially covered by the repulsive force. Therefore, it is considered that direct contact between the solid particles (contact without a binder intervening) can be maintained without greatly impairing the strong adhesion between the solid particles.
  • the binder since the binder exhibits the adsorption rate as described above with respect to the conductive aid, it is possible to reinforce the direct contact of the conductive aid due to the repulsive force and construct a sufficient electron conduction path by the conductive aid.
  • the inorganic solid electrolyte-containing composition in which the solid particles are highly dispersed moderately flows (levels), suppressing uneven distribution of the solid particles, It is thought that a constituent layer can be formed in which the occurrence of irregular surface roughness caused by insufficient or excessive flow, and surface roughness caused by clogging of the discharge part during coating is also suppressed. Therefore, the composition containing an inorganic solid electrolyte of the present invention maintains contact between solid particles with suppressed uneven distribution while firmly adhering or binding solid particles to each other, and provides sufficient conduction paths (ion conduction paths and electron conduction paths).
  • a constituent layer with reduced interfacial resistance by constructing a conductive path).
  • This constituent layer can suppress the occurrence of overcurrent during charging and discharging of the all-solid secondary battery, and can also prevent deterioration of the solid particles.
  • the inorganic solid electrolyte-containing composition of the present invention exhibiting the above action is used as a constituent layer-forming material, a sheet for an all-solid secondary battery having a constituent layer of low resistance in which solid particles are firmly adhered, and further excellent in low resistance. It is possible to manufacture an all-solid secondary battery that exhibits excellent cycle characteristics.
  • the polymer binder contained in the constituent layers is easily degraded (oxidized) by oxygen (atoms or molecules), etc., and as the degradation progresses, the adhesion of solid particles and the interfacial contact state are gradually reduced, and the cycle characteristics are further improved. cause a further decline.
  • oxygen atoms or molecules
  • the binder containing the above polymer can preferably express oxidative deterioration resistance to oxygen and the like, suppresses oxidative deterioration of the inorganic solid electrolyte-containing composition and further constituent layers, and even in industrial production methods, oxidative deterioration can be suppressed. It is possible to realize a constituent layer capable of suppressing further deterioration of cycle characteristics due to
  • the polymer binder adsorbs to the conductive aid, further adsorbs to the inorganic solid electrolyte and the active material, and intervenes between the solid particles to provide conductivity. It is thought that it has the function of dispersing solid particles such as auxiliary agents in the dispersion medium.
  • the adsorption of the polymer binder to each solid particle is not particularly limited, but includes not only physical adsorption but also chemical adsorption (adsorption due to formation of chemical bonds, adsorption due to transfer of electrons, etc.).
  • the dispersion characteristics (initial dispersibility and dispersion stability) exhibited by the polymer binder can be maintained even in the coexistence of the conductive aid.
  • the solid content concentration at this time is not particularly limited and can be set as appropriate. preferable.
  • the inorganic solid electrolyte-containing composition of the present invention exhibits excellent dispersion characteristics, it can be made into a high-concentration composition in which the solid content concentration is set higher than in the past.
  • the lower limit of the solid content concentration of the high-concentration composition can be set at 25° C. to 50% by mass or more, for example, 60% by mass or more.
  • the upper limit is less than 100% by mass, for example, 90% by mass or less, preferably 85% by mass or less, more preferably 80% by mass or less, and 75% by mass or less. is more preferred.
  • the inorganic solid electrolyte-containing composition of the present invention is preferably a slurry, particularly a high-concentration slurry, in which solid particles are dispersed in a dispersion medium.
  • the polymer binder functions as a binder that firmly binds the solid particles together in the constituent layers formed from the inorganic solid electrolyte-containing composition. Furthermore, it also functions as a binder that firmly binds a substrate such as a current collector and solid particles. In addition, in the inorganic solid electrolyte-containing composition, the polymer binder may or may not have the function of binding the solid particles together.
  • the inorganic solid electrolyte-containing composition of the present invention is preferably a non-aqueous composition.
  • the non-aqueous composition includes not only a form containing no water but also a form having a water content (also referred to as water content) of preferably 500 ppm or less.
  • the water content is more preferably 200 ppm or less, still more 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). It is the value measured using titration.
  • the inorganic solid electrolyte-containing composition of the present invention exhibits the excellent properties described above, it can be preferably used as a material for forming a constituent layer of an all-solid secondary battery sheet and an all-solid secondary battery.
  • the constituent layers it can be preferably used as a material for forming an active material layer, particularly a positive electrode active material layer and a negative electrode active material layer containing a negative electrode active material that expands and contracts significantly due to charging and discharging.
  • the inorganic solid electrolyte-containing composition of the present invention also includes an embodiment containing an active material and the like in addition to the inorganic solid electrolyte (compositions of this embodiment are referred to as electrode compositions). Components contained and components that can be contained in the composition containing an inorganic solid electrolyte of the present invention are described below.
  • the inorganic solid electrolyte-containing composition of the present invention contains an inorganic solid electrolyte.
  • an inorganic solid electrolyte means an inorganic solid electrolyte
  • a solid electrolyte means a solid electrolyte in which ions can move. Since inorganic solid electrolytes do not contain organic substances as main ion-conducting materials, organic solid electrolytes (polymer electrolytes typified by polyethylene oxide (PEO), lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), etc. Organic electrolyte salt represented by) is clearly distinguished.
  • PEO polyethylene oxide
  • LiTFSI lithium bis(trifluoromethanesulfonyl)imide
  • the inorganic solid electrolyte is solid in a steady state, it is not usually dissociated or released into cations and anions. In this respect, it is clearly distinguished from electrolytes or inorganic electrolyte salts that are dissociated or released into cations and anions in polymers (LiPF 6 , LiBF 4 , lithium bis(fluorosulfonyl)imide (LiFSI), LiCl, etc.). be done.
  • the inorganic solid electrolyte is not particularly limited as long as it has ion conductivity of a metal belonging to Group 1 or Group 2 of the periodic table, and generally does not have electronic conductivity.
  • the inorganic solid electrolyte a solid electrolyte material normally used in all-solid secondary batteries can be appropriately selected and used.
  • the inorganic solid electrolyte includes (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.
  • a sulfide-based inorganic solid electrolyte is preferable from the viewpoint of being able to form a better interface between the active material and the inorganic solid electrolyte.
  • the all-solid secondary battery of the present invention is a lithium ion battery
  • the inorganic solid electrolyte preferably has ion conductivity of lithium ions.
  • Sulfide-based inorganic solid electrolyte contains sulfur atoms, has the ion conductivity of a metal belonging to Group 1 or Group 2 of the periodic table, and is electronically insulating. It is preferable to use a material having properties.
  • the sulfide-based inorganic solid electrolyte preferably contains at least Li, S and P as elements and has lithium ion conductivity, but may contain elements other than Li, S and P as appropriate. .
  • Examples of sulfide-based inorganic solid electrolytes include lithium ion conductive inorganic solid electrolytes that satisfy the composition represented by the following formula (S1).
  • L represents an element selected from Li, Na and K, preferably Li.
  • 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 satisfies 1-12:0-5:1:2-12:0-10.
  • a1 is preferably 1 to 9, more preferably 1.5 to 7.5.
  • b1 is preferably 0-3, more preferably 0-1.
  • 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 compounding 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), crystallized (glass-ceramics), or only partially crystallized.
  • glass glass
  • glass-ceramics glass-ceramics
  • Li--P--S type glass containing Li, P and S, or Li--P--S type 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 (e.g., diphosphorus pentasulfide (P 2 S 5 )), elemental phosphorus, elemental sulfur, sodium sulfide, hydrogen sulfide, lithium halide (e.g., LiI, LiBr, LiCl) and sulfides of the element represented by M above (eg, SiS 2 , SnS, GeS 2 ) can be produced by reacting at least two raw materials.
  • Li 2 S lithium sulfide
  • phosphorus sulfide e.g., diphosphorus pentasulfide (P 2 S 5 )
  • elemental phosphorus e.g., elemental sulfur
  • sodium sulfide sodium sulfide
  • hydrogen sulfide e.g., lithium halide
  • the ratio of Li 2 S and P 2 S 5 in the Li—P—S type glass and Li—P—S type glass ceramics is Li 2 S:P 2 S 5 molar ratio, preferably 60:40 to 90:10, more preferably 68:32 to 78:22.
  • the lithium ion conductivity can be increased.
  • the lithium ion conductivity can be preferably 1 ⁇ 10 ⁇ 4 S/cm or higher, more preferably 1 ⁇ 10 ⁇ 3 S/cm or higher. Although there is no particular upper limit, it is practical to be 1 ⁇ 10 ⁇ 1 S/cm or less.
  • Li 2 SP 2 S 5 Li 2 SP 2 S 5 , Li 2 SP 2 S 5 -LiCl, Li 2 SP 2 S 5 -H 2 S, Li 2 SP 2 S 5 -H 2 S-LiCl, Li 2 S—LiI—P 2 S 5 , Li 2 S—LiI—Li 2 OP 2 S 5 , Li 2 S—LiBr—P 2 S 5 , Li 2 S—Li 2 OP 2 S 5 , Li 2 S—Li 3 PO 4 —P 2 S 5 , Li 2 SP 2 S 5 —P 2 O 5 , Li 2 SP 2 S 5 —SiS 2 , Li 2 SP 2 S 5 —SiS 2 -LiCl, Li2SP2S5 - SnS, Li2SP2S5 - Al2S3 , Li2S - GeS2 , Li2S - GeS2 - ZnS
  • Amorphization method include, for example, a mechanical milling method, a solution method, and a melt quenching method. This is because the process can be performed at room temperature, and the manufacturing process can be simplified.
  • the oxide-based inorganic solid electrolyte contains oxygen atoms, has the ion conductivity of a metal belonging to Group 1 or Group 2 of the periodic table, and is electronically insulating. It is preferable to use a material having properties.
  • the ion conductivity of the oxide-based inorganic solid electrolyte is preferably 1 ⁇ 10 ⁇ 6 S/cm or more, more preferably 5 ⁇ 10 ⁇ 6 S/cm or more, and 1 ⁇ 10 ⁇ 5 S/cm or more. /cm or more is particularly preferable. Although the upper limit is not particularly limited, it is practically 1 ⁇ 10 ⁇ 1 S/cm or less.
  • a specific example of the compound is Li xa La ya TiO 3 [xa satisfies 0.3 ⁇ xa ⁇ 0.7, and ya satisfies 0.3 ⁇ ya ⁇ 0.7. ] (LLT); Li xb La yb Zr zb M bb mb Onb (M bb is one or more elements selected from Al, Mg, Ca, Sr, V, Nb, Ta, Ti, Ge, In and Sn.
  • xb is 5 ⁇ xb ⁇ 10, yb satisfies 1 ⁇ yb ⁇ 4, zb satisfies 1 ⁇ zb ⁇ 4, mb satisfies 0 ⁇ mb ⁇ 2, and nb satisfies 5 ⁇ nb ⁇ 20.); Li xc Byc M cc zc Onc (M cc is one or more elements selected from C, S, Al, Si, Ga, Ge, In and Sn.
  • xc satisfies 0 ⁇ xc ⁇ 5, yc satisfies 0 ⁇ yc ⁇ 1, zc satisfies 0 ⁇ zc ⁇ 1, and nc satisfies 0 ⁇ nc ⁇ 6.); Li xd (Al, Ga) yd (Ti, Ge) zd Si ad P md O nd (xd satisfies 1 ⁇ xd ⁇ 3, yd satisfies 0 ⁇ yd ⁇ 1, zd satisfies 0 ⁇ zd ⁇ 2 , ad satisfies 0 ⁇ ad ⁇ 1, md satisfies 1 ⁇ md ⁇ 7, and nd satisfies 3 ⁇ nd ⁇ 13.); Li (3-2xe) M ee xe D ee O (xe represents a number of 0 or more and 0.1 or less, M ee represents a divalent metal atom.
  • D ee is a halogen atom or two or more halogen atoms represents a combination.
  • Li xf Si yf O zf (xf satisfies 1 ⁇ xf ⁇ 5, yf satisfies 0 ⁇ yf ⁇ 3, and zf satisfies 1 ⁇ zf ⁇ 10)
  • Li xg Syg O zg (xg satisfies 1 ⁇ xg ⁇ 3, yg satisfies 0 ⁇ yg ⁇ 2, and zg satisfies 1 ⁇ zg ⁇ 10)
  • Li, P and O Phosphorus compounds containing Li, P and O are also desirable.
  • lithium phosphate Li3PO4
  • LiPON in which a part of the oxygen element of lithium phosphate is replaced with a nitrogen element
  • LiPOD 1 LiPOD 1
  • LiA 1 ON LiA 1 is one or more elements selected from Si, B, Ge, Al, C and Ga
  • Si, B, Ge, Al, C and Ga can also be preferably used.
  • the halide-based inorganic solid electrolyte contains a halogen atom and has ion conductivity of a metal belonging to Group 1 or Group 2 of the periodic table, and electron Compounds having insulating properties are preferred.
  • the halide-based inorganic solid electrolyte include, but are not limited to, compounds such as LiCl, LiBr, LiI, and Li 3 YBr 6 and Li 3 YCl 6 described in ADVANCED MATERIALS, 2018, 30, 1803075. Among them, Li 3 YBr 6 and Li 3 YCl 6 are preferred.
  • the hydride-based inorganic solid electrolyte contains hydrogen atoms, has the ion conductivity of a metal belonging to Group 1 or Group 2 of the periodic table, and is electronically insulating. A compound having a property is preferred.
  • the hydride-based inorganic solid electrolyte is not particularly limited, but examples thereof include LiBH 4 , Li 4 (BH 4 ) 3 I, 3LiBH 4 --LiCl, and the like.
  • the inorganic solid electrolyte is preferably particulate in the inorganic solid electrolyte-containing composition.
  • the particle size (volume average particle size) of the inorganic solid electrolyte is not particularly limited, but is preferably 0.01 ⁇ m or more, more preferably 0.1 ⁇ m or more.
  • the upper limit is preferably 100 ⁇ m or less, more preferably 50 ⁇ m or less.
  • the particle size of the inorganic solid electrolyte is measured by the following procedure. A 1% by mass dispersion of inorganic solid electrolyte particles is prepared by diluting it in a 20 mL sample bottle with water (heptane for water-labile substances).
  • the diluted dispersion sample is irradiated with ultrasonic waves of 1 kHz for 10 minutes and immediately used for the test.
  • a laser diffraction/scattering particle size distribution analyzer LA-920 (trade name, manufactured by HORIBA)
  • data was taken 50 times using a quartz cell for measurement at a temperature of 25 ° C.
  • JIS Japanese Industrial Standard
  • Z 8828 2013
  • the method for adjusting the particle size is not particularly limited, and a known method can be applied, for example, a method using an ordinary pulverizer or classifier.
  • the pulverizer or classifier for example, a mortar, ball mill, sand mill, vibrating ball mill, satellite ball mill, planetary ball mill, whirling jet mill, sieve, or the like is preferably used.
  • wet pulverization can be performed in which a dispersion medium such as water or methanol is allowed to coexist.
  • Classification is preferably carried out in order to obtain a desired particle size. Classification is not particularly limited, and can be performed using a sieve, an air classifier, or the like. Both dry and wet classification can be used.
  • the inorganic solid electrolyte may contain one type or two or more types.
  • the content of the inorganic solid electrolyte in the inorganic solid electrolyte-containing composition is not particularly limited, but in terms of binding properties and dispersibility, it should be 50% by mass or more based on a solid content of 100% by mass. is preferred, 70% by mass or more is more preferred, and 90% by mass or more is particularly preferred. 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 the total content of the active material and the inorganic solid electrolyte within the above range. is preferred.
  • the solid content refers to a component that does not disappear by volatilization or evaporation when the inorganic solid electrolyte-containing composition is dried at 150° C. for 6 hours under a pressure of 1 mmHg under a nitrogen atmosphere. . Typically, it refers to components other than the dispersion medium described below.
  • the inorganic solid electrolyte-containing composition of the present invention contains a conductive aid.
  • a conductive aid there are no particular restrictions on the conductive aid, and any commonly known conductive aid can be used.
  • electronic conductive materials such as natural graphite and artificial graphite, carbon blacks such as acetylene black, ketjen black and furnace black, amorphous carbon such as needle coke, vapor grown carbon fiber or carbon nanotube.
  • carbon fibers such as carbon fibers such as graphene or fullerene, metal powders such as copper and nickel, metal fibers, and conductive polymers such as polyaniline, polypyrrole, polythiophene, polyacetylene, and polyphenylene derivatives. may be used.
  • ions of metals belonging to Group 1 or Group 2 of the periodic table preferably Li A material that does not insert or release ions
  • those that can function as an active material in the active material layer during charging and discharging of the battery are classified as active materials rather than conductive aids. Whether or not it functions as an active material when the battery is charged/discharged is not univocally determined by the combination with the active material.
  • the conductive aid is preferably particulate in the inorganic solid electrolyte-containing composition.
  • the particle size (volume average particle size) of the conductive aid is not particularly limited, but is preferably 0.02 to 1.0 ⁇ m, more preferably 0.03 to 0.5 ⁇ m. preferable.
  • the particle size of the conductive aid can be adjusted in the same manner as the particle size of the inorganic solid electrolyte, and can be measured in the same manner as the particle size of the inorganic solid electrolyte. 1 type or 2 types or more may be sufficient as the conductive support agent which an inorganic solid electrolyte containing composition contains.
  • the content of the conductive aid in the inorganic solid electrolyte-containing composition is preferably 0 to 10% by mass, and 1 to 5% by mass is more preferred.
  • the inorganic solid electrolyte-containing composition of the present invention is a polymer binder formed by containing a polymer having constituent components described later, and is dissolved in the dispersion medium contained in the inorganic solid electrolyte-containing composition, and an inorganic solid It is a polymer binder that exhibits an adsorption rate of 50% or less with respect to the conductive aid contained in the electrolyte-containing composition.
  • the polymer that is contained in the polymer binder and forms this polymer binder has a constituent component (X) and a constituent component (A) that will be described later, and the polymer binder has a dispersing medium. It develops the solubility and the adsorption rate to the conductive aid.
  • the binder-forming polymer includes a component (X) having a polymer chain, which is composed of a polymer chain component (b) having at least one functional group in the functional group group (b) described later, and a functional group described later. It has a constituent (A) having at least one functional group from group (a) and optionally constituents other than both constituents.
  • the binder-forming polymer is a constituent component (X ) is preferably contained in one or more.
  • the polymer chain is a molecular chain containing the polymer chain component (b) and is incorporated as a side chain in the binder-forming polymer.
  • Component (X) has a polymer chain directly or via a linking group in the partial structure incorporated into the main chain of the binder-forming polymer.
  • the partial structure to be incorporated into the main chain is not uniquely determined according to the type of the binder-forming polymer (main chain) and is appropriately selected.
  • carbon chains carbon-carbon bonds
  • the linking group L P that links the partial structure to be incorporated into the main chain and the polymer chain is not particularly limited. is more preferable), an alkenylene group (having preferably 2 to 6 carbon atoms, more preferably 2 to 3 carbon atoms), an arylene group (having preferably 6 to 24 carbon atoms, more preferably 6 to 10 carbon atoms), an oxygen atom, a sulfur atom , an imino group (-NR N -: R N represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 10 carbon atoms.), a carbonyl group, a phosphoric acid linking group (-O-P ( OH)(O)--O--), phosphonic acid linking group (--P(OH)(O)--O--), or a combination thereof.
  • linking group a group formed by combining an alkylene group, an arylene group, a carbonyl group, an oxygen atom, a sulfur atom and an imino group is preferable. is more preferred, and a group containing a —CO—O— group or —CO—N(R N )— group (R N is as defined above) and an alkylene group is even more preferred.
  • linking group a linking group containing a structural portion derived from a chain transfer agent, a polymerization initiator, or the like used for synthesizing the polymer chain, and a (meth)acryl that reacts with this structural portion and the chain transfer agent
  • a linking group to which a structural moiety derived from compound (M1) is bonded is also preferably exemplified.
  • chain transfer agents include, but are not limited to, 3-mercaptopropionic acid, mercaptoacetic acid, 2-mercaptopropionic acid, 3-mercaptoisobutyric acid, 2-mercaptoethanol, 6-mercapto-1-hexanol, 2-amino ethanethiol, 2-aminoethanethiol hydrochloride and the like.
  • Examples of the linking group consisting of the structural part derived from the chain transfer agent and the structural part derived from the (meth)acrylic compound (M1) include -CO-O-alkylene group -X-CO-(X)n-alkylene —S— groups.
  • X represents an oxygen atom or -NH-
  • n is 0 or 1. More specifically, the linking group in the component (X) contained in the polymer synthesized in Examples can be mentioned.
  • the number of atoms constituting the linking group is preferably 1-36, more preferably 1-30, even more preferably 1-24.
  • the number of connecting atoms in the connecting group is preferably 16 or less, more preferably 12 or less, and even more preferably 10 or less.
  • the lower limit is 1 or more.
  • the polymer chain possessed by the constituent component (X) is not particularly limited as long as it has one or more of the above polymer chain constituent components (b). Chains made of polymers can be applied.
  • a chain composed of a chain polymer is preferable, a polymer chain composed of a (meth)acrylic polymer and a polymer chain composed of a vinyl polymer are more preferable, and a polymer chain composed of a (meth)acrylic polymer and a polymer chain composed of polystyrene are preferable. More preferred.
  • each component can be the same or different.
  • the binding mode is not particularly limited, and may be random, alternating, or block.
  • the polymer chain-constituting component (b) constituting the polymer chain is a component having at least one (one) functional group (b) in the functional group (b), preferably in a side chain portion. has a functional group (b) directly or through a linking group in the partial structure incorporated in the main chain of The partial structure incorporated into the main chain of the polymer chain is as described above.
  • the linking group L Xb that links the partial structure to be incorporated into the main chain and the functional group (b) is not particularly limited and is the same as the above L P , but a -CO-O- group or -CO-N ( More preferred are groups comprising a R N )— group, where R N is as defined above, and a —CO—O— or —CO—N(R N )— group, where R N is defined above. ) and an alkylene group are particularly preferred.
  • the alkylene group constituting the combined group is preferably a short-chain alkyl group having 1 to 3 carbon atoms.
  • the number of atoms constituting the linking group L 2 Xb and the number of linking atoms of the linking group L 2 Xb are as described above, but the number of atoms is particularly preferably 1 to 12, and the number of linking atoms is 8 or less. is particularly preferred.
  • the polymer chain component (b) may have at least one (one) functional group (b), and usually preferably has 1 to 3 functional groups.
  • the functional group (b) is selected from the following functional group group (b) and shows adsorptivity to the conductive aid.
  • ⁇ Functional Group (b)> Sulfonic acid group (sulfo group), phosphoric acid group, phosphonic acid group, carboxy group, hydroxy group, oxetane group, epoxy group, dicarboxylic acid anhydride group, thiol group (sulfanyl group), ether group (-O-), thioether group (-S-), thioester group (-CS-O-, -CO-S-, -CS-S-), thiocarbamate group (-NR-CS-O-, -NRS-CO-S-), imino group ( NR, -NR-), amide group (-CO-NR-), urethane group (-NR-CO-O-),
  • a chemical formula written in brackets after each group name such as an ether group shows the chemical structure of that group (bond).
  • Terminal groups bonded to these groups are not particularly limited, and include groups selected from substituents Z described later, such as alkyl groups.
  • R in each bond represents a hydrogen atom or a substituent, preferably a hydrogen atom.
  • the substituent is not particularly limited, and is selected from substituents Z described later, preferably an alkyl group.
  • Ether groups are included in carboxy groups, hydroxy groups, and the like, but —O— included in these groups is not interpreted as an ether group.
  • a thioether group is also included in the thioester group and the like, but -S- included in these is not interpreted as a thioether group.
  • An ether group, a thioether group, an imino group, etc. are preferably not included as bonds constituting a partial structure incorporated into the main chain of the polymer chain, and are incorporated into the partial structure corresponding to the side chain of the polymer chain. is preferred.
  • a hydroxy group, a thiol group, an amino group, etc. are not bonded to a partial structure (as a terminal group) to be incorporated into the main chain of the polymer chain, and to a partial structure corresponding to a side chain of the polymer chain (terminal as a group).
  • the sulfo group, phosphoric acid group (phosphoryl group), phosphonic acid group, heterocyclic group, amino group and aryl group contained in the functional group group (b) are not particularly limited, but correspond to the substituent Z described later. is synonymous with the group for However, the amino group preferably has 0 to 12 carbon atoms, more preferably 0 to 6 carbon atoms, and particularly preferably 0 to 2 carbon atoms.
  • the ring structure contains an amino group, ether group, thioether group, thioester group, thiocarbamate group, imino group (-NR-), amide group, urethane group, urea group, thiourea group, etc., it is classified as a heterocycle.
  • a hydroxy group, an amino group, a carboxy group, a sulfo group, a phosphate group, a phosphonic acid group, and a sulfanyl group may form a salt.
  • Salts include various metal salts, ammonium or amine salts, and the like.
  • the component having an amide group means a component in which the amide bond is not directly bonded to the atom constituting the main chain of the polymer chain, and does not include, for example, a component derived from (meth)acrylic acid alkylamide. .
  • a dicarboxylic anhydride group and a fluoroalkyl group are synonymous with the dicarboxylic anhydride group and the fluoroalkyl group in the functional group (a).
  • the siloxane group is not particularly limited, and for example, a group having a structure represented by -(SiR 2 -O)n s - is preferred. R is as described above.
  • the number of repetitions n s is preferably an integer of 1-100, more preferably an integer of 5-50, and even more preferably an integer of 10-30.
  • One component (X) may have one or two or more functional groups (b), and when two or more functional groups are present, they may or may not be bonded to each other.
  • a dicarboxylic anhydride group or an addition reaction product group thereof for example, maleic acid monoalkyl ester
  • a carboxy group, an aryl group, and the like are preferable.
  • the polymer chain of the component (X) contains a functional group corresponding to the functional group (a) or (b) as a linking group, these functional groups function as a linking group, Since the functional group (a) or (b) does not exhibit effective adsorption properties to the inorganic solid electrolyte or conductive aid, it is not used as the functional group (a) or (b) possessed by the component (X).
  • the polymer chain component (b) containing the polymer chain can be configured by appropriately combining a partial structure incorporated into the main chain, a linking group and a linking group L Xb .
  • Constituent components that constitute a polymer chain that bonds to the linking group L X1 of formula (X1A) can be mentioned. More specifically, examples of the component in which the functional group (b) is directly bonded to the partial structure incorporated into the main chain include styrene constituents, (meth)acrylic acid constituents, etc., and the partial structure incorporated into the main chain. and the functional group (b) via the linking group L Xb include alkyl ester constituents in which the functional group (b) is substituted for (meth)acrylic acid.
  • the partial structure incorporated into the main chain and the linking group L Xb may each have a substituent other than the functional group included in the functional group group (b) described below.
  • a substituent is not particularly limited, and examples thereof include groups selected from substituents Z described later, and specific examples thereof include an alkoxycarbonyl group and the like.
  • the polymer chain possessed by the component (X) may have one or more polymer chain components (z) other than the polymer chain component (b) in addition to the polymer chain component (b).
  • This polymer chain component (z) is preferably a component having a substituent on the partial structure incorporated into the main chain directly or via a linking group.
  • the partial structure incorporated into the main chain is as described above.
  • the linking group is not particularly limited and is the same as L Xb above, but a -CO-O- group or a -CO-N(R N )- group (R N is as defined above) is particularly preferred. .
  • the substituent is not particularly limited, and a group selected from the substituent Z described later can be mentioned. Among them, an alkyl group or an aryl group is preferred, an alkyl group is more preferred, and a long-chain alkyl group having 8 or more carbon atoms and a cycloalkyl group having 8 or more carbon atoms are even more preferred.
  • the preferred number of carbon atoms in the long-chain alkyl group is the same as the long-chain alkyl group in R X7A described above.
  • the polymer chain component (z) may have further substituents, but does not have the above functional groups (a) and (b).
  • Examples of the polymer chain component (z) include a component derived from the (meth)acrylic compound (M1) described below and a component derived from the vinyl compound (M2) described below.
  • a component derived from an ester compound is preferable, and a component derived from a (meth)acrylic acid alkyl ester compound having 1 to 7 carbon atoms, a component derived from a (meth)acrylic acid long-chain alkyl ester compound, and the like are more preferable.
  • the group that binds to the end of the polymer chain is not particularly limited, and can be an appropriate group depending on the polymerization method, polymerization termination method, and the like. Examples thereof include a hydrogen atom, an alkyl group, an aryl group, a hydroxy group, a chain transfer agent residue, an initiator residue, etc., and preferably an alkyl group (having preferably 1 carbon atom) from the viewpoint of dispersion characteristics. to 20, more preferably 4 to 20). Although this group may further have a substituent, it is preferably unsubstituted.
  • the polymer chain composed of the (meth)acrylic polymer is not particularly limited, but preferably has a constituent component derived from the (meth)acrylic compound (M1) described later and a constituent component derived from the vinyl compound (M2) described later. .
  • a polymer chain having a constituent component derived from one or more (meth)acrylic acid ester compounds is more preferable, and a polymer chain having a constituent component derived from a (meth)acrylic acid alkyl ester compound is even more preferable.
  • the (meth)acrylic acid alkyl ester compound preferably contains an ester compound of an alkyl group having 4 or more carbon atoms (preferably 6 or more carbon atoms), and further contains an ester compound of a short-chain alkyl group having 3 or less carbon atoms.
  • an ester compound of an alkyl group having 4 or more carbon atoms preferably 6 or more carbon atoms
  • an ester compound of a short-chain alkyl group having 3 or less carbon atoms can also As the component derived from the vinyl compound (M2), a component derived from a polymerizable cyclic dicarboxylic acid anhydride or an addition reaction product thereof is preferable.
  • the functional group (b) may be introduced into any of the above components, and is introduced into the component derived from the (meth)acrylic compound (M1).
  • the functional group (b) may be introduced as a component different from the above components, for example, a component derived from a (meth)acrylic acid compound, a component derived from a styrene compound, a dicarboxylic acid Constituents derived from polymerizable compounds constituting polymer chains, such as addition reaction products of anhydride groups or dicarboxylic acid anhydride groups, can be mentioned.
  • More specific examples include constituents derived from (meth)acrylic acid, styrene, maleic acid monomethyl ester, and the like.
  • the content of each component in the polymer chain is not particularly limited and is set as appropriate.
  • the content of the polymer chain component having a functional group (b) is not particularly limited, but can be 0.1 to 100% by mass, and 1 to 100 % by mass is preferred.
  • Component (X) is preferably a component represented by the following formula (X1).
  • R X1 to R X3 each represent a hydrogen atom or a substituent.
  • Substituents that can be used as R X1 to R X3 are not particularly limited, and include groups selected from substituents Z described later. Among them, an alkyl group or a halogen atom is preferable.
  • Each of R 1 X1 and R 1 X3 is preferably a hydrogen atom, and R 1 X2 is preferably a hydrogen atom or a methyl group.
  • L X1 represents a linking group.
  • the linking group that can be used as L X1 the linking group LP described above, which links the partial structure to be incorporated into the main chain of the binder-forming polymer and the polymer chain, can be applied without particular limitation.
  • L X1 is more preferably a group containing a -CO-O- group and an alkylene group.
  • Particularly preferred is a linking group in which a --CO--O-- group, the above-mentioned structural moiety, and a structural moiety derived from a (meth)acrylic compound (M1) that reacts with a chain transfer agent or the like are bonded together.
  • the structure in which the partial structure to be incorporated into the main chain in formula (X1) and L X1 are combined includes the linking groups exemplified for the linking group LP described above, and more specifically, glycidyl (meta ) groups consisting of reactants of acrylates with chain transfer agents such as 3-mercaptopropionic acid or 2-mercaptoethanol.
  • R X4 to R X6 each represent a hydrogen atom or a substituent.
  • the substituents that can be taken as R X4 to R X6 are not particularly limited, and have the same meanings as the substituents that can be taken as R X1 to R X3 .
  • R 1 X4 is preferably a hydrogen atom
  • R 1 X5 is preferably a hydrogen atom or an alkyl group
  • R 1 X6 is preferably a hydrogen atom or an alkoxycarbonyl group.
  • L X2 represents a single bond or a linking group.
  • the linking group that can be used as L X2 the above linking group L Xb can be applied without particular limitation.
  • the linking group that can be used as L X2 is more preferably a group containing a --CO--O-- group, particularly preferably a --CO--O-- group.
  • the number of atoms constituting the connecting group and the number of connecting atoms are as described above, but the number of atoms constituting L X2 is particularly preferably 1 to 6, and the number of connecting atoms is 1 to 3. is most preferred.
  • R X7 represents a hydrogen atom or a substituent. Substituents that can be taken as R 1 X7 are not particularly limited, and groups selected from substituents Z described later can be mentioned. Among them, an alkyl group or an aryl group is preferable, and an alkyl group is more preferable.
  • the alkyl group is not particularly limited .
  • An alkyl group that can be taken as X7B is preferred.
  • R X6 and L X2 -R X7 may combine or react to form a ring containing an ethylene chain.
  • R X6 and L X2 -R X7 are carboxy groups, they may undergo a dehydration reaction to form -CO-O-CO- groups (dicarboxylic anhydride groups containing ethylene chains). .
  • At least one of R X4 to R X7 and L X2 has at least one functional group (b).
  • Two or more of R X4 to R X7 and L X2 may have a functional group (b), or may constitute the functional group itself.
  • the ring itself formed by R X6 and L X2 -R X7 may serve as the functional group (b), or -L X2 -R X7 may serve as the functional group (b).
  • all R 1 X4 etc. contained in the polymer chain may have the functional group (b) (for example, polystyrene chain), and even if some R 1 X4 etc. have the functional group (b) good.
  • the ratio of having the functional group (b) is the same as the content of the polymer chain component having the functional group (b) in the polymer chain described above.
  • R X7 preferably has a functional group (b), or -L X2 -R X7 is a functional group (b).
  • the polymer chain constituents in the above formula (X1) include polymer chain constituents derived from (meth)acrylic acid, styrene, maleic acid monomethyl ester, and the like.
  • mX indicates the average degree of polymerization, is a number of 2 or more, and is preferably set to a degree of polymerization that satisfies the number-average molecular weight of polymer chains described later.
  • the polymer chain that binds to L X1 preferably includes, for example, a chain composed of a chain-polymerized polymer described later, a polymer chain composed of a (meth)acrylic polymer, Particular preference is given to polymeric chains made of polystyrene.
  • the terminus of the polymer chain in formula (X1) is as described above.
  • the component represented by the above formula (X1) may have one component that binds to L X1 , or may have two or more components in one component. Although the upper limit is not particularly limited, it can be five. When the component (X) represented by the above formula (X1) has two types of components, the component (X) is more preferably represented by the following formula (X1A).
  • R X1 to R X3 and L X1 have the same definitions as R X1 to R X3 and L X1 in formula (X1).
  • the polymer chain component having an average degree of polymerization m XA is the polymer chain component (z) having no functional group (b), and the average degree of polymerization is m
  • a polymer chain component having XB is a polymer chain component (b) having a functional group (b).
  • R X4A to R X6A each represent a hydrogen atom or a substituent, and have the same meaning as R X4 to R X6 in Formula (X1).
  • R 1 X4A and R 1 X6A are each preferably a hydrogen atom
  • R 1 X5A is preferably a hydrogen atom or a methyl group.
  • LX2A represents a single bond or linking group.
  • the linking group that can be used as L X2A has the same meaning as the linking group L X2 .
  • L X2A -R X7A is not the above functional group (b).
  • R X7A represents a hydrogen atom or a substituent.
  • Substituents that can be taken as R 1 X7 are not particularly limited, and groups selected from substituents Z described later can be mentioned. Among them, an alkyl group or an aryl group is preferable, an alkyl group is more preferable, a long-chain alkyl group (chain alkyl group) having 8 or more carbon atoms, or a cycloalkyl group having 8 or more carbon atoms is more preferable, and 8 or more carbon atoms are more preferable. is even more preferable.
  • the number of carbon atoms in the long-chain alkyl group may be 8 or more, preferably 10 or more, and more preferably 12 or more.
  • the upper limit is not particularly limited, and is preferably 24 or less, more preferably 20 or less, and even more preferably 16 or less.
  • the number of carbon atoms of a substituent indicates the number of carbon atoms constituting this substituent, and when this substituent further has a substituent, the number of carbon atoms constituting the further substituent is included.
  • R X4A to R X6A , L X2A and R X7A may have substituents, but in this case, they are substituents other than the functional group (b).
  • R X4B to R X6B are synonymous with R X4 to R X6 in formula (X1), respectively.
  • L X2B has the same meaning as L X2 in formula (X1).
  • R X7B has the same definition as R X7 in formula (X1).
  • the alkyl group that can be taken as R 1 X7B may be an alkyl group having 4 or more carbon atoms, but is preferably a short-chain alkyl group (chain alkyl group) having 3 or less carbon atoms.
  • At least one of R X4B to R X7B and L X2B has at least one functional group (b).
  • R X4B to R X7B and L X2B have the functional group (b) is the same as the embodiment in which at least one of R X4 to R X7 and L X2 in formula (X1) above has the functional group (b). and preferred polymer chain constituents are also the same.
  • mXA and mXB indicate the average degree of polymerization
  • mXA is 0 or more and mXB is 1 or more.
  • m XA and m XB are a total number of 2 or more and have the same meaning as m X in formula (X1).
  • mXA and mXB preferably satisfy the number average molecular weight of the polymer chain described later, and mXB is the content of the polymer chain constituent having the functional group (b) in the polymer chain described above. It is set to the degree of polymerization that satisfies.
  • the terminus of the polymer chain in formula (X1) is as described above.
  • the polymer chain that binds to L X1 in the component (X) represented by the formula (X1A) is as described above, and a polymer chain made of (meth)acrylic polymer and a polymer chain made of polystyrene are particularly preferred. .
  • the constituent components represented by formula (X1) or formula (X1A) may be the same or different.
  • the constituent component (X) may have an average degree of polymerization of 2 or more, but is preferably a constituent component derived from a macromonomer having a number average molecular weight of 200 or more in the measurement method described later.
  • the number average molecular weight of the macromonomer is preferably from 1,000 to 100,000, more preferably from 1,000 to 50,000, still more preferably from 2,000 to 25,000, and from 2,000 to 20,000 is particularly preferred.
  • the component (X) is not particularly limited, but may be a component derived from the (meth)acrylic compound (M1) described below or a component derived from the vinyl compound (M2) described below, or a functional group (b) added thereto.
  • a component having a polymer chain containing two or more components derived from a compound into which the ) A constituent component derived from a compound having a polymer chain of an acrylic acid ester compound or a styrene compound is preferred.
  • the component (X) may have a functional group selected from the functional group group (a) described later, but in that it has a polymer chain having a functional group selected from the functional group group (b) , is different from the component (A) described later.
  • the functional group selected from the functional group group (a) possessed by the component (A) and the functional group selected from the functional group group (b) possessed by the component (X) may be the same.
  • the component (X) has a functional group selected from the functional group (b) in the above-described macromonomer, and the component (A) has a functional group selected from the functional group (a) in the main part of the polymer.
  • a mode in which the partial structure incorporated into the chain is directly or via a linking group is also one of the preferred modes.
  • the component (X) may contain a nitrogen atom, but preferably does not contain it, and particularly preferably does not contain it in the partial structure incorporated into the main chain.
  • component (X) examples include those possessed by the polymers synthesized in Examples, but the present invention is not limited to these.
  • the binder-forming polymer has one or more constituent components (A) having at least one (one) functional group from the following functional group group (a). By including the component (A) in the binder-forming polymer, it is possible to enhance the adsorption or adhesion to the inorganic solid electrolyte.
  • Component (A) may have at least one (one) functional group, and preferably has 1 to 3 functional groups.
  • Component (A) has a functional group (a) directly or via a linking group in the partial structure incorporated into the main chain of the binder-forming polymer.
  • the partial structure incorporated into the main chain of the polymer chain is as described above.
  • the linking group linking the partial structure to be incorporated into the main chain and the functional group (a) is not particularly limited, and has the same definition as LXb above.
  • the sulfonic acid group, phosphoric acid group (phosphoryl group), phosphonic acid group, and the like included in the functional group (a) are not particularly limited, but are synonymous with the corresponding groups of the substituent Z described later.
  • the dicarboxylic anhydride group is not particularly limited, but a group obtained by removing one or more hydrogen atoms from a dicarboxylic anhydride (for example, a group represented by the following formula (2a)), further copolymerizable
  • the component itself for example, the component represented by the following formula (2b) obtained by copolymerizing a polymerizable dicarboxylic anhydride as a compound is included.
  • the group obtained by removing one or more hydrogen atoms from a dicarboxylic anhydride is preferably a group obtained by removing one or more hydrogen atoms from a cyclic dicarboxylic anhydride.
  • Dicarboxylic anhydrides include, for example, non-cyclic dicarboxylic anhydrides such as acetic anhydride, propionic anhydride and benzoic anhydride, and cyclic anhydrides such as maleic anhydride, phthalic anhydride, fumaric anhydride, succinic anhydride and itaconic anhydride. dicarboxylic anhydrides and the like.
  • the polymerizable dicarboxylic acid anhydride is not particularly limited, but includes a dicarboxylic acid anhydride having an unsaturated bond in the molecule, preferably a polymerizable cyclic dicarboxylic acid anhydride. Specific examples include maleic anhydride and itaconic anhydride.
  • An example of the dicarboxylic anhydride group includes a group represented by the following formula (2a) or a constituent represented by the formula (2b), but the present invention is not limited thereto. In each formula, * indicates a bonding position.
  • An ether group (--O--), a thioether group (--S--), and a thioester group (--CO--S--, --CS--O--, --CS--S--) mean the bond shown in parentheses.
  • the terminal group bonded to this group is not particularly limited, and may be a group selected from substituents Z described later, for example, an alkyl group.
  • Ether groups are included in carboxy groups, hydroxy groups, oxetane groups, epoxy groups, dicarboxylic acid anhydride groups and the like, but -O- included in these groups is not an ether group. The same applies to thioether groups.
  • the fluoroalkyl group is a group in which at least one hydrogen atom of an alkyl group or a cycloalkyl group is substituted with a fluorine atom, and the number of carbon atoms thereof is preferably 1 to 20, more preferably 2 to 15, and further preferably 3 to 10. preferable.
  • the number of fluorine atoms on the carbon atoms may be one in which some of the hydrogen atoms are replaced, or one in which all of the hydrogen atoms are replaced (perfluoroalkyl group).
  • a group capable of forming a salt such as a sulfonic acid group (sulfo group), a phosphoric acid group, a phosphonic acid group, a carboxyl group, etc. may form a salt. Salts include various metal salts, ammonium or amine salts, and the like.
  • the functional group (a) of the component (A) is a sulfonic acid group, a phosphoric acid group, a phosphonic acid group, a carboxyl group, a hydroxy group, an oxetane group, an epoxy group, a dicarboxylic anhydride group, a thiol group, an ether group, A thioether group, a thioester group, a fluoroalkyl group, and salts thereof are preferred, and a sulfonic acid group, a phosphoric acid group, a phosphonic acid group, a carboxy group, a hydroxy group, a dicarboxylic acid anhydride group, a thiol group, a thioether group, a thioester group, A fluoroalkyl group and salts thereof are more preferable, and a hydroxy group, a carboxy group, a dicarboxylic acid anhydride group and salts thereof are particularly preferable in terms of
  • One component (A) may have one or two or more functional groups (a).
  • the compound (also referred to as a compound having a functional group (a)) leading to the component (A) is not particularly limited, but for example, has at least one carbon-carbon unsaturated bond and at least one functional group (a) compound.
  • a compound in which the carbon-carbon unsaturated bond and the functional group (a) are directly bonded a compound in which the carbon-carbon unsaturated bond and the functional group (a) are bonded via the linking group L Xb , furthermore, a functional It includes compounds in which the group itself contains a carbon-carbon unsaturated bond (eg, the polymerizable cyclic dicarboxylic acid anhydrides described above).
  • a compound capable of introducing a functional group by various reactions into the polymer constituent after polymerization for example, a constituent derived from carboxylic anhydride, a structure having a carbon-carbon unsaturated bond It includes alcohol, amino, mercapto or epoxy compounds (including polymers) capable of addition reaction or condensation reaction with components.
  • the component (A) may have a functional group (a), and examples thereof include components derived from polymerizable compounds having at least one functional group (a).
  • the polymerizable compound is not particularly limited as long as it has the functional group (a), but is preferably a compound having a polymerizable group and a substituent having the functional group (a).
  • the polymerizable compound that leads to the component (A) is not particularly limited as long as it has the functional group (a), and examples thereof include compounds obtained by introducing the functional group into the raw material compound that constitutes the binder-forming polymer.
  • a (meth)acrylic compound (M1) or a vinyl compound (M2) which will be described later, or a compound obtained by introducing the functional group (a) into these compounds (M1) or (M2).
  • the compound having a functional group (a) is not particularly limited. ) into which a functional group (a) is introduced.
  • the compound obtained by introducing the functional group (a) into the polymerizable cyclic carboxylic acid anhydride is, for example, a dicarboxylic acid monoester compound obtained by addition reaction (ring-opening reaction) of a maleic anhydride compound and an alcohol or the like. mentioned.
  • Component (A) preferably does not have a polymer chain.
  • the constituent component (A) may contain a nitrogen atom, but preferably does not contain it, and particularly preferably does not contain it in the partial structure incorporated into the main chain.
  • component (A) examples include those possessed by the polymers synthesized in Examples, but the present invention is not limited to these.
  • the binder-forming polymer may have one or more constituent components (N) containing nitrogen atoms.
  • the component (N) it is preferable to contain the component (N) in a content of less than 10 mol % in all the components of the binder-forming polymer in order to suppress deterioration in cycle characteristics.
  • This constituent component (N) may contain a nitrogen atom in any of the constituent components, and has a nitrogen atom in a partial structure incorporated into the main chain of the binder-forming polymer or in a side chain.
  • component (N) examples include polyalkyleneimine, polyalkylamine, poly(meth)acrylalkylamine, poly(meth)acrylamide, poly(meth)acrylonitrile, polyamide, polyimide, polyurea, polyurethane, and the like. Constituents constituting the polymer, further constituents having an amino group as a substituent, and the like can be mentioned.
  • the binder-forming polymer has one or more constituent components (referred to as other constituent components (Z)) that do not correspond to any of the constituent component (X), the constituent component (A), and the constituent component (N).
  • the other component (Z) is preferably a component having a substituent directly or via a linking group on the partial structure incorporated into the main chain of the binder-forming polymer.
  • the partial structure incorporated into the main chain is as described above.
  • the linking group is not particularly limited and is the same as L Xb above, but a --CO--O-- group is particularly preferred.
  • the substituent is not particularly limited, and a group selected from the substituent Z described later can be mentioned.
  • an alkyl group or an aryl group is preferred, an alkyl group is more preferred, and a long-chain alkyl group having 8 or more carbon atoms and a cycloalkyl group having 8 or more carbon atoms are even more preferred.
  • the preferred number of carbon atoms in the long-chain alkyl group is the same as the long-chain alkyl group in R X7A described above.
  • Other constituents may have further substituents, but do not have the above functional groups (a) and (b).
  • Other constituents include constituents derived from the (meth)acrylic compound (M1) described later and constituents derived from the vinyl compound (M2) described later.
  • Components derived from are preferable, such as components derived from (meth)acrylic acid C 1-7 alkyl ester compounds, components derived from (meth)acrylic acid long-chain alkyl ester compounds, components derived from styrene, etc. is mentioned.
  • Binder-forming polymer is not particularly limited as long as it has the above constituent components and can impart the above properties to the polymer binder, and various known polymers can be used.
  • the primary structure (binding pattern of constituent components) of the binder-forming polymer is not particularly limited, and may have any binding structure such as random structure, block structure, alternating structure, graft structure, and the like.
  • the binder-forming polymer for example, a polymer having at least one bond selected from a urethane bond, a urea bond, an amide bond, an imide bond and an ester bond, or a carbon-carbon double bond polymer chain in the main chain is preferable. be done.
  • the above bond is not particularly limited as long as it is contained in the main chain of the polymer, and may be contained in a constituent component (repeating unit) and/or contained as a bond connecting different constituent components. .
  • the number of the bonds contained in the main chain is not limited to 1, and may be 2 or more, preferably 1 to 6, more preferably 1 to 4.
  • the binding mode of the main chain is not particularly limited, and may have two or more types of bonds at random.
  • polymers having urethane bonds, urea bonds, amide bonds, imide bonds or ester bonds in the main chain among the above bonds include sequential polymerization (polycondensation, polymerization) of polyurethane, polyurea, polyamide, polyimide, polyester, polysiloxane, etc. addition or addition condensation) polymers, or copolymers thereof.
  • polymers having a polymer chain of carbon-carbon double bonds in the main chain include chain polymerization polymers such as fluorine-based polymers (fluoropolymers), hydrocarbon-based polymers, vinyl polymers, and (meth)acrylic polymers. Polymers or (meth)acrylic polymers are preferred.
  • the (meth)acrylic polymer suitable as the binder-forming polymer includes a copolymer of each of the constituent components described above, and a copolymer with an appropriate (meth)acrylic compound (M1), which is derived from the (meth)acrylic compound. and a polymer comprising a copolymer containing 50% by mass or more of the constituent component of.
  • the components (X), (A), (N) and (Z) are components derived from a (meth)acrylic compound
  • the content of the component derived from the (meth)acrylic compound is Calculate the content of the ingredients.
  • the content of the component derived from the (meth)acrylic compound is more preferably 60% by mass or more, and even more preferably 70% by mass or more.
  • the upper limit content can be 100% by mass, but can also be 97% by mass or less.
  • a copolymer with a vinyl compound (M2) other than the (meth)acrylic compound (M1) is also preferable.
  • the content of the component derived from the vinyl compound (M2) is 50% by mass or less, preferably 3 to 40% by mass, more preferably 3 to 30% by mass.
  • a vinyl polymer suitable as a binder-forming polymer includes a copolymer of each of the constituent components described above, and further a copolymer with an appropriate vinyl compound (M2), which contains 50% by mass or more of a constituent component derived from the vinyl compound.
  • the components (X), (A), (N) and (Z) are components derived from a vinyl compound
  • the content of each component is included in the content of the components derived from the vinyl compound. do.
  • the content of the constituent component derived from the vinyl compound is more preferably 60% by mass or more, and even more preferably 65% by mass or more. Although the upper limit content can be 100% by mass, it is preferably 95% by mass or less, more preferably 90% by mass or less.
  • a copolymer with a (meth)acrylic compound (M1) is also preferred. In this case, the content of the component derived from the (meth)acrylic compound (M1) may be less than 50% by mass, for example, preferably 0 to 40% by mass, and 0 to 30% by mass. is more preferred.
  • (Meth)acrylic compounds (M1) include (meth)acrylic acid ester compounds, (meth)acrylamide compounds, (meth)acrylonitrile compounds, and the like. Among them, (meth)acrylic acid ester compounds are preferred. Examples of (meth)acrylic acid ester compounds include (meth)acrylic acid alkyl ester compounds, (meth)acrylic acid aryl ester compounds, etc., and (meth)acrylic acid alkyl ester compounds are preferred.
  • the number of carbon atoms in the alkyl group constituting the (meth)acrylic acid alkyl ester compound is not particularly limited. It is preferably 4 to 16, and even more preferably 6 to 14.
  • the number of carbon atoms in the aryl group constituting the aryl ester is not particularly limited, but can be, for example, 6 to 24, preferably 6 to 10, and preferably 6.
  • the nitrogen atom of the amide group may be substituted with an alkyl group or an aryl group.
  • the vinyl compound (M2) is not particularly limited, but is preferably a vinyl compound copolymerizable with the (meth)acrylic compound (M1).
  • examples include styrene compounds, vinylnaphthalene compounds, vinylcarbazole compounds, vinylimidazole compounds, and vinylpyridine.
  • aromatic vinyl compounds such as compounds, furthermore, allyl compounds, vinyl ether compounds, vinyl ester compounds (for example, vinyl acetate compounds), dialkyl itaconate compounds, the above polymerizable cyclic dicarboxylic acid anhydrides, and the like.
  • the vinyl compound include "vinyl-based monomers" described in JP-A-2015-88486.
  • the (meth)acrylic compound (M1) and the vinyl compound (M2) may have a substituent, but it is one of preferred embodiments that they are unsubstituted.
  • the substituent is not particularly limited, and includes groups selected from the substituent Z described below.
  • the (meth)acrylic compound (M1) and vinyl compound (M2) are preferably compounds represented by the following formula (b-1).
  • R 1 is a hydrogen atom, a hydroxy group, a cyano group, a halogen atom, an alkyl group (preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, particularly preferably 1 to 6 carbon atoms), an alkenyl group (2 carbon atoms to 24 are preferred, 2 to 12 are more preferred, and 2 to 6 are particularly preferred), an alkynyl group (having preferably 2 to 24 carbon atoms, more preferably 2 to 12, and particularly preferably 2 to 6), or an aryl group ( preferably 6 to 22 carbon atoms, more preferably 6 to 14 carbon atoms).
  • a hydrogen atom or an alkyl group is preferable, and a hydrogen atom or a methyl group is more preferable.
  • R2 represents a hydrogen atom or a substituent.
  • Substituents that can be taken as R 2 are not particularly limited. particularly preferred), aryl groups (preferably 6 to 22 carbon atoms, more preferably 6 to 14 carbon atoms), aralkyl groups (preferably 7 to 23 carbon atoms, more preferably 7 to 15 carbon atoms), and cyano groups.
  • the carbon number of the alkyl group is synonymous with the carbon number of the alkyl group constituting the (meth)acrylic acid alkyl ester compound, and the preferred range is also the same.
  • L 1 is a linking group, which is not particularly limited and has the same definition as the linking group L P or L Xb , but is particularly preferably a -CO-O- group.
  • L 1 is a -CO-O- group or a -CO-N(R N )- group (R N is as defined above)
  • the compound represented by the above formula (b-1) is (meta ) corresponds to the acrylic compound (M1), and otherwise corresponds to the vinyl compound (M2).
  • n is 0 or 1, preferably 1; However, when —(L 1 ) n —R 2 represents one type of substituent (for example, an alkyl group), n is 0 and R 2 is a substituent (alkyl group).
  • groups that may have a substituent such as an alkyl group, an aryl group, an alkylene group, and an arylene group may have a substituent within a range that does not impair the effects of the present invention.
  • the substituent is not particularly limited, and includes, for example, a group selected from the substituent Z described later, and specifically includes a halogen atom.
  • the binder-forming polymer may have one type of the (meth)acrylic compound (M1) or the vinyl compound (M2), or may have two or more types.
  • the content of each constituent component in the binder-forming polymer is not particularly limited, and is determined by appropriately considering the physical properties of the entire polymer, and is set, for example, within the following ranges.
  • the content of each component in the binder-forming polymer is set within the following range, for example, so that the total content of all components is 100% by mass.
  • the binder-forming polymer has a plurality of specific components, the content of these components is the total content.
  • the content of the component (X) is not particularly limited, but can be appropriately adjusted in consideration of dispersion characteristics and the like.
  • the content of the constituent component (X) is, for example, preferably 5 to 99% by mass, more preferably 10 to 80% by mass, more preferably 20 to 70% by mass, based on the total content of all constituent components. % by mass is more preferred.
  • the content of the constituent component (A) is not particularly limited, but from the point of view of dispersion characteristics and solid particle binding properties, for example, 0.1 to 50% by mass relative to the total content of all constituent components. is preferably 0.1 to 20 mass %, more preferably 0.3 to 10 mass %, particularly preferably 0.5 to 8 mol %, and 0.1 to 20 mass %.
  • the content of the constituent component (A) is, for example, preferably 0.1 to 50 mol%, more preferably 0.1 to 15 mol%, relative to the total number of moles of all constituent components. More preferably 0.3 to 10 mol %, particularly preferably 0.5 to 8 mol %, most preferably 0.5 to 4 mol %.
  • the content of the component (N) may be less than 10 mol% relative to the total number of moles of all the components, for example, 5 mol% or less in terms of oxidation resistance. preferably 3 mol % or less.
  • the lower limit is preferably 0 mol % from the viewpoint of cycle characteristics, but practically it can be 2 mol %.
  • the content of the component (N) is preferably 5% by mass or less, more preferably 0 to 3% by mass, more preferably 0 to 2% by mass, based on the total content of all the components.
  • the content of the other component (Z) is not particularly limited, but is preferably 1 to 97% by mass, more preferably 15 to 95% by mass, based on the total content of all components. , more preferably 30 to 90% by mass, particularly preferably 30 to 75% by mass.
  • the binder-forming polymer may have a substituent.
  • the substituent is not particularly limited, but preferably includes a group selected from the following substituents Z, and substituents that do not correspond to the above functional groups (a) and (b) are preferred.
  • 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 alkenyl groups having 2 to 20 carbon atoms, such as vinyl, allyl, oleyl, etc.
  • alkynyl groups preferably alkynyl groups having 2 to 20 carbon atoms, such as ethynyl, butadiynyl, phenylethynyl, etc.
  • cycloalkyl groups Preferably a cycloalkyl group having 3 to 20 carbon atoms, for example, cyclopropyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, etc.
  • alkyl group usually means including a cycloalkyl group, but here it is described separately.
  • an aryl group preferably an aryl group having 6 to 26 carbon atoms, such as phenyl, 1-naphthyl, 4-methoxyphenyl, 2-chlorophenyl, 3-methylphenyl, etc.
  • an aralkyl group preferably having 7 carbon atoms to 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 or nitrogen atom
  • It is a 6-membered heterocyclic group including aromatic heterocyclic groups and aliphatic heterocyclic groups, such as tetrahydropyran ring group, tetrahydrofuran ring group, 2-pyridyl, 4-pyridyl, 2- imidazolyl, 2-benzimi
  • R P is a hydrogen atom or a substituent (preferably a group selected from substituent Z). Further, each of the groups exemplified for the substituent Z may be further substituted with the substituent Z described above.
  • the alkyl group, alkylene group, alkenyl group, alkenylene group, alkynyl group and/or alkynylene group, etc. may be cyclic or chain, and may be linear or branched.
  • the binder-forming polymer can be synthesized by selecting raw material compounds and polymerizing the raw material compounds by a known method.
  • the method of incorporating each functional group is not particularly limited. A method to be used, an ene reaction to a double bond, an ene-thiol reaction, or ATRP (Atom Transfer Radical Polymerization) polymerization using a copper catalyst can be mentioned.
  • a functional group can be introduced using a functional group present in the main chain, side chain or end of the polymer as a reaction point.
  • a compound having a functional group can be used to introduce a functional group through various reactions with dicarboxylic anhydride groups in the polymer chain.
  • binder-forming polymers include the polymers synthesized in Examples, but the present invention is not limited to these.
  • the polymer binder has a property of dissolving (soluble) in the dispersion medium contained in the inorganic solid electrolyte-containing composition of the present invention.
  • the polymer binder in the inorganic solid electrolyte-containing composition usually exists dissolved in the dispersion medium in the inorganic solid electrolyte-containing composition, depending on the content thereof.
  • the polymer binder stably exerts the adsorption property for the solid particles containing the conductive aid and the function of dispersing the solid particles in the dispersion medium, and the solid particles in the inorganic solid electrolyte-containing composition are excellent. Dispersibility can be maintained.
  • the polymer binder is dissolved in the dispersion medium means that the polymer binder is dissolved in the dispersion medium in the inorganic solid electrolyte-containing composition. It means that it is more than
  • the polymer binder is not limited to the embodiment in which all the polymer binder is dissolved in the dispersion medium in the inorganic solid electrolyte-containing composition, and includes the embodiment in which a part of the polymer binder is insoluble.
  • solubility when the polymer binder is not dissolved in the dispersion medium (insoluble), it means that the solubility is less than 50% by mass in the solubility measurement.
  • the method for measuring solubility is as follows. That is, about 0.1 g of polymer binder (solid) was accurately weighed, and the accurately weighed mass was defined as W0. Next, 10 g of the same type of dispersion medium as the dispersion medium contained in the polymer binder and the inorganic solid electrolyte-containing composition was placed in a container, and mixed with a mix rotor (model number VMR-5, manufactured by AS ONE) at a temperature of 25°C and a rotation speed of 100 rpm.
  • a mix rotor model number VMR-5, manufactured by AS ONE
  • solubility (%) (W0-W1)/W0 x 100
  • the solubility of the polymer binder in the dispersion medium depends on the type of the binder-forming polymer, the composition of the binder-forming polymer (type and content of constituent components), the weight average molecular weight of the binder-forming polymer, and the functional group (a) described above. and (b) can be appropriately imparted depending on the type or content thereof, further, the combination with the dispersion medium, and the like.
  • the polymer binder has an adsorption rate [A CA ] to the conductive aid of more than 0% and 50% or less. This suppresses excessive adsorption of the polymer binder to the conductive aid, improves the dispersion characteristics of the conductive aid, and enables the construction of sufficient electron conduction paths.
  • the adsorption rate [A CA ] is preferably 2% or more, more preferably 5% or more, and even more preferably 10% or more.
  • the upper limit of the adsorption rate [A CA ] is preferably 45% or less, more preferably 40% or less, and more preferably 40%, in terms of achieving both high levels of dispersion characteristics and electron conduction path construction.
  • the adsorption rate [A CA ] to the conductive aid depends on the type of the binder-forming polymer (structure and composition of the polymer chain), the weight average molecular weight of the binder-forming polymer, the type or content of the functional group (b), and the like. can be set appropriately.
  • the adsorption rate [A CA ] is a value measured using the conductive aid, polymer binder and dispersion medium contained in the inorganic solid electrolyte-containing composition. is an index showing the extent to which is adsorbed.
  • the adsorption of the polymer binder to the conductive aid includes not only physical adsorption but also chemical adsorption (adsorption due to chemical bond formation, adsorption due to transfer of electrons, etc.).
  • the inorganic solid electrolyte-containing composition contains a plurality of types of conductive aids, the adsorption rate for the conductive aids having the same composition as the conductive aids (kind and content) in the inorganic solid electrolyte-containing composition.
  • the inorganic solid electrolyte-containing composition contains a plurality of types of dispersion media
  • the adsorption rate of the dispersion medium having the same composition as the dispersion medium (kind and content) in the inorganic solid electrolyte-containing composition is used.
  • the inorganic solid electrolyte-containing composition contains a plurality of types of polymer binders (B)
  • the adsorption rate for the plurality of types of polymer binders is also used.
  • the adsorption rate [A CA ] (%) is a value measured as follows. That is, a binder solution having a concentration of 1% by mass is prepared by dissolving a polymer binder in a dispersion medium. The binder solution and the conductive aid are placed in a 15 mL vial bottle at a ratio of 3:1 by mass between the polymer binder and the conductive aid in the binder solution, and a mix rotor is used at room temperature (25 ° C.). After stirring for 1 hour at a rotation speed of 80 rpm, the mixture is allowed to stand still.
  • the supernatant liquid obtained by solid-liquid separation is filtered through a filter with a pore size of 1 ⁇ m, and the total amount of the obtained filtrate is dried to determine the mass of the polymer binder remaining in the filtrate (not adsorbed to the conductive aid).
  • the adsorption ratio of the polymer binder to the conductive aid is calculated by the following formula. Let the average value of the adsorption rates obtained by performing this operation twice be the adsorption rate [A CA ] (%).
  • Adsorption rate (%) [(W PB ⁇ W PA )/W PB ] ⁇ 100
  • the polymer binder or binder-forming polymer used in the present invention preferably has the following physical properties or characteristics.
  • the polymer binder preferably exhibits an adsorption rate [A SE ] of 45% or less with respect to the inorganic solid electrolyte in the dispersion medium contained in the inorganic solid electrolyte-containing composition.
  • a SE adsorption rate
  • the adsorption rate [A SE ] is preferably 35% or less, more preferably 25% or less, It is more preferably 15% or less.
  • the lower limit of the adsorption rate [A SE ] is practically 0% or more, for example, preferably 3% or more, more preferably 5% or more.
  • the adsorption rate [A SE ] to the inorganic solid electrolyte depends on the type of the binder-forming polymer (structure and composition of the polymer chain), the weight-average molecular weight of the binder-forming polymer, the type or content of the functional group (a), and the like. can be set appropriately.
  • the adsorption rate [A SE ] is the adsorption rate of the polymer binder to the inorganic solid electrolyte in the dispersant, and was measured using the inorganic solid electrolyte, the polymer binder, and the dispersion medium contained in the inorganic solid electrolyte-containing composition. It is an index showing the degree of adsorption of the polymer binder to the inorganic solid electrolyte in the dispersion medium.
  • the adsorption of the polymer binder to the inorganic solid electrolyte includes not only physical adsorption but also chemical adsorption (adsorption due to chemical bond formation, adsorption due to transfer of electrons, etc.).
  • the inorganic solid electrolyte-containing composition contains a plurality of types of inorganic solid electrolytes
  • the adsorption rate to the inorganic solid electrolyte having the same composition as the inorganic solid electrolyte composition (type and content) in the inorganic solid electrolyte-containing composition is used.
  • the inorganic solid electrolyte-containing composition uses a plurality of types of polymer binders
  • the adsorption rate of the plurality of types of polymer binders is used.
  • the adsorption rate [A SE ] (%) is measured as follows using the inorganic solid electrolyte, polymer binder and dispersion medium used for preparing the inorganic solid electrolyte-containing composition. That is, a binder solution having a concentration of 1% by mass is prepared by dissolving a polymer binder in a dispersion medium. The binder solution and the inorganic solid electrolyte are placed in a 15 mL vial bottle at a ratio of 42:1 by mass between the polymer binder and the inorganic solid electrolyte in the binder solution, and a mix rotor is used at room temperature (25 ° C.). After stirring for 1 hour at a rotation speed of 80 rpm, the mixture is allowed to stand still.
  • the supernatant obtained by solid-liquid separation is filtered through a filter with a pore size of 1 ⁇ m, and the total amount of the obtained filtrate is dried to determine the mass of the polymer binder remaining in the filtrate (not adsorbed to the inorganic solid electrolyte).
  • Measure the weight of the polymer binder) W A. From this mass W A and the mass W B of the polymer binder contained in the binder solution used for measurement, the adsorption ratio of the polymer binder to the inorganic solid electrolyte is calculated according to the following formula. Let the average value of the adsorption rates obtained by performing this operation twice be the adsorption rate [A SE ] (%). Adsorption rate (%) [(W B ⁇ W A )/W B ] ⁇ 100
  • the weight average molecular weight of the binder-forming polymer is not particularly limited. For example, 5,000 or more is preferable, 30,000 or more is more preferable, and 100,000 or more is still more preferable.
  • the upper limit is substantially 5,000,000 or less, preferably 2,000,000 or less, more preferably 1,000,000 or less, and even more preferably 600,000 or less.
  • the weight average molecular weight of the binder-forming polymer can be appropriately adjusted by changing the type and content of the polymerization initiator, polymerization time, polymerization temperature, and the like.
  • the molecular weights of polymers, polymer chains and macromonomers refer to mass average molecular weights or number average molecular weights converted to standard polystyrene by gel permeation chromatography (GPC).
  • GPC gel permeation chromatography
  • condition 1 or condition 2 is basically used, but condition 2 is preferentially adopted.
  • an appropriate eluent may be selected and used.
  • Carrier flow rate 1.0 ml/min Sample concentration: 0.1% by mass Detector: RI (refractive index) detector (Condition 2) Column: TOSOH TSKgel Super HZM-H, TOSOH TSKgel Super HZ4000, and TOSOH TSKgel Super HZ2000 (all trade names, manufactured by Tosoh Corporation) are used.
  • Carrier Tetrahydrofuran Measurement temperature: 40°C
  • Carrier flow rate 1.0 ml/min Sample concentration: 0.1% by mass Detector: RI (refractive index) detector
  • the water concentration of the binder is preferably 100 ppm (by mass) or less. Moreover, this binder may be obtained by drying the polymer by crystallizing it, or by using the binder dispersion as it is.
  • the binder-forming polymer is preferably amorphous. In the present invention, a polymer being "amorphous" typically means that no endothermic peak due to crystalline melting is observed when measured at the glass transition temperature.
  • the binder-forming polymer may be a non-crosslinked polymer or a crosslinked polymer. Further, when the polymer is crosslinked by heating or voltage application, the molecular weight may be larger than the above molecular weight. Preferably, the binder-forming polymer has a weight-average molecular weight within the above range at the start of use of the all-solid secondary battery.
  • the binder-forming polymer and the polymer binder do not react with the inorganic solid electrolyte during the preparation of the inorganic solid electrolyte-containing composition, the production of the all-solid secondary battery sheet, or the heating step in the production of the all-solid secondary battery. Specifically, it preferably does not have an ethylenic double bond in the molecule.
  • a polymer having no intramolecular ethylenic double bonds means that the polymer has an intramolecular abundance within a range that does not impair the effects of the present invention, for example, the amount present in the molecule (according to a nuclear magnetic resonance spectroscopy (NMR) method) of 0.5.
  • NMR nuclear magnetic resonance spectroscopy
  • the binder-forming polymer contained in the polymer binder may be of one type or two or more types.
  • the polymer binder may contain other polymers and the like as long as the action of the binder-forming polymer described above is not impaired.
  • polymers that are commonly used as binders for all-solid secondary batteries can be used without particular limitations.
  • One or two or more polymer binders may be contained in the inorganic solid electrolyte-containing composition.
  • the content of the polymer binder in the inorganic solid electrolyte-containing composition is not particularly limited, but is preferably 0.1 to 5.0% by mass in terms of dispersion characteristics, ionic conductivity, and binding properties. It is preferably 0.2 to 4.0% by mass, and even more preferably 0.3 to 2.0% by mass.
  • the content of the polymer binder in 100% by mass of the solid content of the inorganic solid electrolyte-containing composition is preferably 0.1 to 6.0% by mass, and 0.3 to 5.0% by mass. It is more preferably 0% by mass, and even more preferably 0.4 to 2.5% by mass.
  • the mass ratio of the total mass (total mass) of the inorganic solid electrolyte and the active material to the mass of the polymer binder is preferably in the range of 1,000 to 1. This ratio is more preferably 500-2, even more preferably 100-10.
  • the inorganic solid electrolyte-containing composition of the present invention may contain one or more polymer binders (also referred to as other polymer binders) other than the above polymer binders.
  • polymer binders include, for example, polymer binders (particulate binders) that exist (disperse) in the form of particles in the inorganic solid electrolyte-containing composition without dissolving in the dispersion medium, and the adsorption rate [A CA ] to the conductive aid. is more than 50% (high adsorption binder).
  • the particle size of the particulate binder is preferably 1 to 1,000 nm.
  • the particle size can be measured in the same manner as the particle size of the inorganic solid electrolyte.
  • various polymer binders used for production of all-solid secondary batteries can be used without particular limitation.
  • the content of the other polymer binder in the inorganic solid electrolyte-containing composition is not particularly limited, but is preferably, for example, 0.01 to 4% by mass based on 100% by mass of the solid content.
  • the inorganic solid electrolyte-containing composition of the present invention contains a dispersion medium for dispersing or dissolving the above components.
  • a dispersion medium may be an organic compound that exhibits a liquid state in the usage environment, and examples thereof include various organic solvents. Specific examples include alcohol compounds, ether compounds, amide compounds, amine compounds, ketone compounds, Aromatic compounds, aliphatic compounds, nitrile compounds, ester compounds and the like can be mentioned.
  • the dispersion medium may be either a non-polar dispersion medium (hydrophobic dispersion medium) or a polar dispersion medium (hydrophilic dispersion medium), but a non-polar dispersion medium is preferable in that excellent dispersion characteristics can be exhibited.
  • a non-polar dispersion medium generally means a property with low affinity for water, and in the present invention, examples thereof include ester compounds, ketone compounds, ether compounds, aromatic compounds, and aliphatic compounds.
  • alcohol compounds include methyl alcohol, ethyl alcohol, 1-propyl alcohol, 2-propyl alcohol, 2-butanol, ethylene glycol, propylene glycol, glycerin, 1,6-hexanediol, cyclohexanediol, sorbitol, xylitol, 2 -methyl-2,4-pentanediol, 1,3-butanediol, 1,4-butanediol.
  • ether compounds 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, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, diethylene glycol monobutyl ether, etc.), alkylene glycol dialkyl ethers (ethylene glycol dimethyl ether, etc.), dialkyl ethers (dimethyl ether, diethyl ether, diisopropyl ether, dibutyl ether, etc.), cyclic ethers (tetrahydrofuran, dioxane (including 1,2-, 1,3- and 1,4-isomers), etc.).
  • alkylene glycol diethylene glycol, triethylene glycol, polyethylene glycol, dipropylene glycol, etc.
  • amide compounds 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-methylpropanamide, hexamethylphosphoric triamide and the like.
  • amine compounds include triethylamine, diisopropylethylamine, and tributylamine.
  • Ketone compounds include, for example, acetone, methyl ethyl ketone, methyl isobutyl ketone (MIBK), cyclopentanone, cyclohexanone, cycloheptanone, dipropyl ketone, dibutyl ketone, diisopropyl ketone, diisobutyl ketone (DIBK), isobutyl propyl ketone, sec- Butyl propyl ketone, pentyl propyl ketone, butyl propyl ketone and the like.
  • aromatic compounds include benzene, toluene, xylene, and perfluorotoluene.
  • aliphatic compounds include hexane, heptane, octane, nonane, decane, dodecane, cyclohexane, methylcyclohexane, ethylcyclohexane, cycloheptane, cyclooctane, decalin, paraffin, gasoline, naphtha, kerosene, and light oil.
  • nitrile compounds include acetonitrile, propionitrile, isobutyronitrile and the like.
  • Ester compounds include, for example, ethyl acetate, propyl acetate, butyl acetate, ethyl butyrate, propyl butyrate, isopropyl butyrate, butyl butyrate, isobutyl butyrate, butyl pentanoate, pentyl pentanoate, ethyl isobutyrate, propyl isobutyrate, and isopropyl isobutyrate.
  • ether compounds, ketone compounds, aromatic compounds, aliphatic compounds, and ester compounds are preferred, and ester compounds, ketone compounds, aromatic compounds, and ether compounds are more preferred.
  • the number of carbon atoms in the compound constituting the dispersion medium is not particularly limited, preferably 2 to 30, more preferably 4 to 20, even more preferably 6 to 15, and particularly preferably 7 to 12.
  • the dispersion medium has a low polarity in terms of the dispersion characteristics of the solid particles and, in the case of using a sulfide-based inorganic solid electrolyte as the inorganic solid electrolyte, preventing deterioration (decomposition) of the sulfide-based inorganic solid electrolyte ( A low-polarity dispersion medium) is preferred.
  • the boiling point of the dispersion medium at normal pressure (1 atm) is not particularly limited, it is preferably 50°C or higher, more preferably 70°C or higher.
  • the upper limit is preferably 250°C or lower, more preferably 220°C or lower.
  • 1 type or 2 types or more may be sufficient as the dispersion medium which an inorganic solid electrolyte containing composition contains.
  • the content of the dispersion medium in the inorganic solid electrolyte-containing composition is not particularly limited, and is set within a range that satisfies the above solid content concentration.
  • the inorganic solid electrolyte-containing composition of the present invention preferably contains an active material capable of inserting and releasing metal ions 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 metal ions belonging to Group 1 or Group 2 of the periodic table, and preferably capable of reversibly inserting and releasing lithium ions.
  • the material is not particularly limited as long as it has the above characteristics, and may be a transition metal oxide or an element such as sulfur that can be combined with Li by decomposing the battery. Among them, it is preferable to use a transition metal oxide as the positive electrode active material. things are more preferred.
  • the transition metal oxide may contain an element M b (an element of group 1 (Ia) of the periodic table of metals other than lithium, an element of group 2 (IIa) of the periodic table, 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 % with respect to the amount (100 mol %) of the transition metal element Ma. More preferred is one synthesized by mixing so that the Li/M a molar ratio is 0.3 to 2.2.
  • transition metal oxide examples include (MA) a transition metal oxide having a layered rock salt structure, (MB) a transition metal oxide having a spinel structure, (MC) a lithium-containing transition metal phosphate compound, (MD ) lithium-containing transition metal halide phosphate compounds and (ME) lithium-containing transition metal silicate compounds.
  • transition metal oxides having a layered rocksalt structure include LiCoO 2 (lithium cobaltate [LCO]), LiNi 2 O 2 (lithium nickelate), LiNi 0.85 Co 0.10 Al 0.85 . 05O2 ( lithium nickel cobalt aluminum oxide [NCA]), LiNi1 / 3Co1 / 3Mn1 / 3O2 ( lithium nickel manganese cobaltate [NMC]) and LiNi0.5Mn0.5O2 ( lithium manganese nickelate).
  • LiCoO 2 lithium cobaltate [LCO]
  • LiNi 2 O 2 lithium nickelate
  • 05O2 lithium nickel cobalt aluminum oxide [NCA]
  • LiNi1 / 3Co1 / 3Mn1 / 3O2 lithium nickel manganese cobaltate [NMC]
  • LiNi0.5Mn0.5O2 lithium manganese nickelate
  • transition metal oxides having a spinel structure include 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 2NiMn3O8 .
  • Examples of (MC) lithium-containing transition metal phosphate compounds include olivine-type iron phosphates such as LiFePO 4 and Li 3 Fe 2 (PO 4 ) 3 , iron pyrophosphates such as LiFeP 2 O 7 , and LiCoPO 4 . and monoclinic Nasicon-type vanadium phosphates such as Li 3 V 2 (PO 4 ) 3 (lithium vanadium phosphate).
  • lithium-containing transition metal halogenated phosphate compounds include iron fluorophosphates such as Li 2 FePO 4 F, manganese fluorophosphates such as Li 2 MnPO 4 F, and Li 2 CoPO 4 F. and cobalt fluoride phosphates.
  • Lithium-containing transition metal silicate compounds include, for example, Li 2 FeSiO 4 , Li 2 MnSiO 4 , Li 2 CoSiO 4 and the like. In the present invention, transition metal oxides having a (MA) layered rocksalt structure are preferred, and LCO or NMC is more preferred.
  • the shape of the positive electrode active material is not particularly limited, it is preferably particulate in the inorganic solid electrolyte-containing composition.
  • the 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 particle size of the positive electrode active material particles can be prepared in the same manner as the particle size of the inorganic solid electrolyte, and can be measured in the same manner as the particle size of the inorganic solid electrolyte.
  • the positive electrode active material obtained by the calcination method may be washed with water, an acidic aqueous solution, an alkaline aqueous solution, or an organic solvent before use.
  • the positive electrode active material contained in the inorganic solid electrolyte-containing composition of the present invention may be one or two or more.
  • the content of the positive electrode active material in the inorganic solid electrolyte-containing composition 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 based on a solid content of 100% by mass. % is more preferred, and 50 to 90% by mass is particularly preferred.
  • the negative electrode active material is an active material capable of inserting and releasing metal ions belonging to Group 1 or Group 2 of the periodic table, and preferably capable of reversibly inserting and releasing lithium ions.
  • the material is not particularly limited as long as it has the above properties, and carbonaceous materials, metal oxides, metal composite oxides, elemental lithium, lithium alloys, negative electrode active materials that can be alloyed with lithium (alloyable). substances and the like.
  • a carbonaceous material, a metal composite oxide, or lithium simple substance is preferably used from the viewpoint of reliability.
  • An active material that can be alloyed with lithium is preferable from the viewpoint that the capacity of an all-solid secondary battery can be increased.
  • a carbonaceous material used as a negative electrode active material is a material substantially composed of carbon.
  • petroleum pitch carbon black such as acetylene black (AB), graphite (natural graphite, artificial graphite such as vapor-grown graphite, etc.), and various synthetics such as PAN (polyacrylonitrile)-based resin or furfuryl alcohol resin
  • PAN polyacrylonitrile
  • various carbon fibers such as PAN-based carbon fiber, cellulose-based carbon fiber, pitch-based carbon fiber, vapor growth carbon fiber, dehydrated PVA (polyvinyl alcohol)-based carbon fiber, lignin carbon fiber, vitreous carbon fiber and activated carbon fiber.
  • carbonaceous materials can be classified into non-graphitizable carbonaceous materials (also referred to as hard carbon) and graphitic carbonaceous materials according to the degree of graphitization.
  • the carbonaceous material preferably has the interplanar spacing or density and crystallite size described in JP-A-62-22066, JP-A-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, etc. can be used.
  • hard carbon or graphite is preferably used, and graphite is more preferably used.
  • the oxide of a metal or metalloid element that is applied as a negative electrode active material is not particularly limited as long as it is an oxide that can occlude and release lithium.
  • examples include oxides, composite oxides of metal elements and metalloid elements (collectively referred to as metal composite oxides), and oxides of metalloid elements (semimetal oxides).
  • metal composite oxides composite oxides of metal elements and metalloid elements
  • oxides of metalloid elements oxides of metalloid elements (semimetal oxides).
  • amorphous oxides are preferred, and chalcogenides, which are reaction products of metal elements and Group 16 elements of the periodic table, are also preferred.
  • the metalloid element refers to an element that exhibits intermediate properties between metal elements and non-metalloid elements, and usually includes the six elements boron, silicon, germanium, arsenic, antimony and tellurium, and further selenium.
  • amorphous means one having a broad scattering band with an apex in the region of 20° to 40° in 2 ⁇ value in an X-ray diffraction method using CuK ⁇ rays, and a crystalline diffraction line. may have.
  • the strongest intensity among the crystalline diffraction lines seen at 2 ⁇ values of 40° to 70° is 100 times or less than the diffraction line intensity at the top of the broad scattering band seen at 2 ⁇ values of 20° to 40°. is preferable, more preferably 5 times or less, and it is particularly preferable not to have a crystalline diffraction line.
  • amorphous oxides of metalloid elements or chalcogenides are more preferable, and elements of groups 13 (IIIB) to 15 (VB) of the periodic table (for example, , Al, Ga, Si, Sn, Ge, Pb, Sb and Bi) are particularly preferable.
  • elements of groups 13 (IIIB) to 15 (VB) of the periodic table for example, , Al, Ga, Si, Sn, Ge, Pb, Sb and Bi
  • preferred amorphous oxides and chalcogenides include Ga 2 O 3 , GeO, PbO, PbO 2 , Pb 2 O 3 , Pb 2 O 4 , Pb 3 O 4 , Sb 2 O 3 and Sb 2 .
  • Examples of negative electrode active materials that can be used together with amorphous oxides mainly composed of Sn, Si, and Ge include carbonaceous materials capable of absorbing and/or releasing lithium ions or lithium metal, elemental lithium, lithium alloys, and lithium. and a negative electrode active material that can be alloyed with.
  • the oxides of metals or semimetals especially metal (composite) oxides and chalcogenides, preferably contain at least one of titanium and lithium as a constituent component.
  • lithium-containing metal composite oxides include composite oxides of lithium oxide and the above metal (composite) oxides or chalcogenides, more specifically Li 2 SnO 2 . mentioned.
  • the negative electrode active material such as a metal oxide, contain a titanium element (titanium oxide).
  • Li 4 Ti 5 O 12 (lithium titanate [LTO]) is excellent in rapid charge-discharge characteristics due to its small volume fluctuation during lithium ion absorption and release, suppressing deterioration of the electrode, and is a lithium ion secondary battery. It is preferable in that it is possible to improve the service life of
  • the lithium alloy as the negative electrode active material is not particularly limited as long as it is an alloy normally used as a negative electrode active material for secondary batteries. % added lithium aluminum alloy.
  • the negative electrode active material capable of forming an alloy with lithium is not particularly limited as long as it is commonly used as a negative electrode active material for secondary batteries. Such an active material expands and contracts greatly upon charging and discharging of an all-solid secondary battery, and accelerates deterioration of cycle characteristics. A decrease in characteristics can be suppressed.
  • active materials include (negative electrode) active materials (alloys, etc.) containing silicon element or tin element, metals such as Al and In, and negative electrode active materials containing silicon element that enable higher battery capacity.
  • (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.
  • negative electrodes containing these negative electrode active materials are carbon negative electrodes (graphite, acetylene black, etc. ), more Li ions can be occluded. That is, the amount of Li ions stored per unit mass increases. Therefore, the battery capacity (energy density) can be increased. As a result, there is an advantage that the battery driving time can be lengthened.
  • Silicon element-containing active materials include, for example, silicon materials such as Si and SiOx (0 ⁇ x ⁇ 1), and silicon-containing alloys containing titanium, vanadium, chromium, manganese, nickel, copper, lanthanum, etc.
  • SiOx itself can be used as a negative electrode active material (semimetal oxide), and since Si is generated by the operation of the all-solid secondary battery, the negative electrode active material that can be alloyed with lithium (the can be used as a precursor substance).
  • negative electrode active materials containing tin examples include Sn, SnO, SnO 2 , SnS, SnS 2 , active materials containing silicon and tin, and the like.
  • composite oxides with lithium oxide, such as Li 2 SnO 2 can also be mentioned.
  • the above-described negative electrode active material can be used without any particular limitation.
  • the above silicon materials or silicon-containing alloys are more preferred, and silicon (Si) or silicon-containing alloys are even more preferred.
  • the chemical formula of the compound obtained by the above firing method can be calculated by inductively coupled plasma (ICP) emission spectrometry as a measurement method and from the difference in mass 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, it is preferably particulate in the inorganic solid electrolyte-containing composition.
  • the particle size of the negative electrode active material is not particularly limited, but is preferably 0.1 to 60 ⁇ m.
  • the particle size of the negative electrode active material particles can be prepared in the same manner as the particle size of the inorganic solid electrolyte, and can be measured in the same manner as the particle size of the inorganic solid electrolyte.
  • the negative electrode active material contained in the inorganic solid electrolyte-containing composition of the present invention may be one or two or more.
  • the content of the negative electrode active material in the inorganic solid electrolyte-containing composition is not particularly limited, and is preferably 10 to 90% by mass, more preferably 20 to 85% by mass, more preferably 30% by mass, based on a 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 Ions can be used.
  • a negative electrode active material layer can be formed by combining this ion with an electron and depositing it as a metal.
  • the surfaces of the positive electrode active material and the negative electrode active material may be surface-coated with another metal oxide.
  • surface coating agents include metal oxides containing Ti, Nb, Ta, W, Zr, Al, Si or Li. Specific examples include titanate spinel, tantalum-based oxides, niobium-based oxides, lithium niobate-based compounds, and specific examples 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 surface of the particles of the positive electrode active material or the negative electrode active material may be surface-treated with actinic rays or an active gas (such as plasma) before and after the surface coating.
  • the inorganic solid electrolyte-containing composition of the present invention also preferably contains a lithium salt (supporting electrolyte).
  • a lithium salt that is usually used in this type of product is preferable, and there is no particular limitation.
  • the content of the lithium salt is preferably 0.1 parts by mass or more, more preferably 5 parts by mass or more, relative to 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 may contain no dispersant other than the polymer binder, since the polymer binder also functions as a dispersant, but may contain a dispersant.
  • the dispersing agent those commonly used in all-solid secondary batteries can be appropriately selected and used. Generally compounds intended for particle adsorption and steric and/or electrostatic repulsion are preferably used.
  • an ionic liquid inorganic solid electrolyte-containing composition of the present invention, as other components other than the above components, an ionic liquid, a thickener, a cross-linking agent (such as those that undergo a cross-linking reaction by radical polymerization, condensation polymerization, or ring-opening polymerization). , a polymerization initiator (such as one that generates an acid or radical by heat or light), an antifoaming agent, a leveling agent, a dehydrating agent, an antioxidant, and the like.
  • the ionic liquid is contained in order to further improve the ionic conductivity, and known liquids can be used without particular limitation.
  • polymers other than the binder-forming polymer described above, and commonly used binders and the like may be contained.
  • the inorganic solid electrolyte-containing composition of the present invention contains an inorganic solid electrolyte, a conductive aid, the above-mentioned polymer binder, a dispersion medium, and optionally, a lithium salt and any other components, for example, in various commonly used mixers. By mixing, a mixture, preferably a slurry, can be prepared. In the case of an electrode composition, an active material is further mixed.
  • the mixing method is not particularly limited, and can be carried out using known mixers such as ball mills, bead mills, planetary mixers, blade mixers, roll mills, kneaders, disc mills, rotation-revolution mixers, and narrow-gap dispersers. can.
  • Mixing conditions are also not particularly limited.
  • the above components may be mixed all at once, or may be mixed sequentially.
  • the mixing temperature can be 15 to 50°C.
  • the rotation speed of the rotation/revolution mixer can be set to 200 to 3,000 rpm.
  • the mixed atmosphere may be air, dry air (dew point of -20°C or less), inert gas (eg, argon gas, helium gas, nitrogen gas), or the like.
  • the inorganic solid electrolyte readily reacts with moisture, mixing is preferably carried out under dry air or in an inert gas. Since the inorganic solid electrolyte-containing composition of the present invention has excellent solid particle dispersion properties and excellent suppression of oxidative deterioration, it can be stored after preparation and does not need to be prepared each time it is used.
  • the sheet for an all-solid secondary battery of the present invention is a sheet-shaped molded article that can form a constituent layer of an all-solid secondary battery, and includes various aspects according to 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 (electrode for an all-solid secondary battery sheet) and the like.
  • these various sheets are collectively referred to as a sheet for an all-solid secondary battery.
  • each layer constituting the sheet for an all-solid secondary battery may have a single layer structure or a multilayer structure.
  • the active material layer on the substrate is formed of the inorganic solid electrolyte-containing composition of the present invention.
  • the layer formed of the inorganic solid electrolyte-containing composition of the present invention is formed of components (excluding the dispersion medium) derived from the inorganic solid electrolyte-containing composition, and usually solid particles (inorganic solid electrolyte and conductive aid Furthermore, the active material) and the polymer binder are tightly adhered (bonded) in a mixed state.
  • This all-solid secondary battery sheet can be used as an active material layer of an all-solid secondary battery by appropriately peeling off the base material, or used as it is as an electrode (a laminate of a current collector and an active material layer). Cycle characteristics and conductivity (reduction of resistance) of solid secondary batteries can be improved.
  • the solid electrolyte sheet for an all-solid secondary battery of the present invention may be a sheet having a solid electrolyte layer. It may be a sheet (a sheet from which the base material has been removed) formed from The solid electrolyte sheet for an all-solid secondary battery may have other layers in addition to the solid electrolyte layer. Other layers include, for example, a protective layer (release sheet), a current collector, a coat layer, and the like.
  • the solid electrolyte layer of the solid electrolyte sheet for an all-solid secondary battery is preferably formed from the inorganic solid electrolyte-containing composition of the present invention.
  • each component in the solid electrolyte 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 layer thickness of each layer constituting the solid electrolyte sheet for an all-solid secondary battery is the same as the layer thickness of each layer described in the all-solid secondary battery described later.
  • the base material is not particularly limited as long as it can support the solid electrolyte layer, and examples thereof include sheet bodies (plate-shaped bodies) such as materials described later in the current collector, organic materials, inorganic materials, and the like.
  • sheet bodies plate-shaped bodies
  • organic materials include various polymers, and specific examples include polyethylene terephthalate, polypropylene, polyethylene, cellulose, and the like.
  • inorganic materials include glass and ceramics.
  • the electrode sheet for an all-solid secondary battery of the present invention may be an electrode sheet having an active material layer, and the active material layer is formed on a substrate (current collector). It may be a sheet that does not have a substrate and is formed from an active material layer (a sheet from which the substrate has been removed). This electrode sheet is usually a sheet having a current collector and an active material layer. A mode having a layer and an active material layer in this order is also included.
  • the solid electrolyte layer and active material layer of the electrode sheet are preferably formed from the inorganic solid electrolyte-containing composition of the present invention.
  • each component in the solid electrolyte layer or active material layer is not particularly limited, but is preferably the content of each component in the solid content of the inorganic solid electrolyte-containing composition (electrode composition) of the present invention. Synonymous.
  • 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 secondary battery described later.
  • the electroded sheet may have other layers as described above.
  • the sheet for an all-solid secondary battery of the present invention is an active material layer having a flat surface in which uniformly arranged solid particles are firmly bound while suppressing an increase in the interfacial resistance of solid particles, and furthermore, It has an active material layer in which a polymer binder suppresses oxidative deterioration. Therefore, by using this active material layer as an active material layer of an all-solid secondary battery, excellent cycle characteristics and low resistance (high conductivity) of the all-solid secondary battery can be realized.
  • the electrode sheet for an all-solid secondary battery in which the active material layer is formed on the current collector can firmly adhere the active material layer and the current collector.
  • the sheet for an all-solid-state secondary battery of the present invention is suitably used as a sheet-like member (to be incorporated as an active-material layer or an electrode) forming an active material layer, preferably an electrode, of an all-solid-state secondary battery. .
  • the method for producing the all-solid secondary battery sheet of the present invention is not particularly limited, and the sheet can be produced by forming the above active material layer using the inorganic solid electrolyte-containing composition of the present invention.
  • a method of forming a film (coating and drying) to form a layer (coating and drying layer) comprising the inorganic solid electrolyte-containing composition on a substrate or a current collector (may be via another layer) is preferable. mentioned.
  • an all-solid secondary battery sheet having a base material or current collector and a coated dry layer can be produced.
  • the adhesion between the current collector and the active material layer can be strengthened.
  • the coated 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, using the inorganic solid electrolyte-containing composition of the present invention, Layer) composed of a composition obtained by removing the dispersion medium from the inorganic solid electrolyte-containing composition of the present invention.
  • the constituent layers and the dry coating layer may contain a dispersion medium as long as it does not impair the effects of the present invention.
  • the applied dry layer obtained as described above can also be pressurized. Pressurization conditions and the like will be described later in the manufacturing method of the all-solid secondary battery.
  • a base material, a protective layer (especially a peeling sheet), etc. can also be peeled off.
  • the all-solid secondary battery of the present invention includes a positive electrode active material layer, a negative electrode active material layer facing the positive electrode active material layer, and a solid electrolyte layer disposed between the positive electrode active material layer and the negative electrode active material layer. have.
  • the all-solid secondary battery of the present invention is not particularly limited as long as it has a solid electrolyte layer between the positive electrode active material layer and the negative electrode active material layer. configuration can be adopted.
  • 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 constitute the negative electrode.
  • each constituent layer (including a current collector and the like) that constitutes the all-solid secondary battery may have a single-layer structure or a multi-layer structure.
  • At least one of the negative electrode active material layer and the positive electrode active material layer is preferably formed from the inorganic solid electrolyte-containing composition of the present invention.
  • both the negative electrode active material layer and the positive electrode active material layer are formed from the inorganic solid electrolyte-containing composition of the present invention.
  • the negative electrode laminate of a negative electrode current collector and a negative electrode current collector
  • the positive electrode laminate of a positive electrode current collector and a positive electrode current collector
  • each constituent layer (including a current collector and the like) that constitutes the all-solid secondary battery may have a single-layer structure or a multi-layer structure.
  • the active material layer formed of the composition containing an inorganic solid electrolyte of the present invention preferably has the same component types and contents as those in the solid content of the composition containing an inorganic solid electrolyte of the present invention.
  • the thicknesses of the negative electrode active material layer, the solid electrolyte layer, and the positive electrode active material layer are not particularly limited.
  • the thickness of each layer is preferably 10 to 1,000 ⁇ m, more preferably 20 ⁇ m or more and less than 500 ⁇ m, considering the dimensions of a general all-solid secondary battery.
  • the thickness of at least one of the positive electrode active material layer and the negative electrode active material layer is more preferably 50 ⁇ m or more and less than 500 ⁇ m.
  • the constituent layer having the above thickness may be a single layer (one application of the inorganic solid electrolyte-containing composition) or a multilayer (multiple applications of the inorganic solid electrolyte-containing composition), but the layer can be thickened by increasing the concentration. From the standpoint of resistance reduction and productivity, it is preferable to form a single layer having a large thickness using the composition containing an inorganic solid electrolyte of the present invention.
  • the layer thickness of the thick single-layer active material that can be preferably formed by the composition containing an inorganic solid electrolyte of the present invention can be, for example, 70 ⁇ m or more, and can also be 100 ⁇ m or more.
  • Each of the positive electrode active material layer and the negative electrode active material layer may have a current collector on the side opposite to the solid electrolyte layer. Electron conductors are preferred as the positive electrode current collector and the negative electrode current collector. In the present invention, either one of the positive electrode current collector and the negative electrode current collector, or both of them may simply be referred to as the current collector. Examples of materials for forming the positive electrode current collector include aluminum, aluminum alloys, stainless steel, nickel and titanium, as well as materials obtained by treating the surface of aluminum or stainless steel with carbon, nickel, titanium or silver (thin films are formed). ) are preferred, and among them, aluminum and aluminum alloys are more preferred.
  • Materials for forming the negative electrode current collector include aluminum, copper, copper alloys, stainless steel, nickel and titanium, and the surface of aluminum, copper, copper alloys or stainless steel is treated with carbon, nickel, titanium or silver. and more preferably aluminum, copper, copper alloys and stainless steel.
  • a film sheet is usually used, but a net, a punched one, a lath, a porous body, a foam, a molded body of fibers, and the like can also be used.
  • the thickness of the current collector is not particularly limited, it is preferably 1 to 500 ⁇ m. It is also preferable that the surface of the current collector is roughened by surface treatment.
  • a functional layer or member is appropriately interposed or disposed between or outside each layer of the negative electrode current collector, the negative electrode active material layer, the solid electrolyte layer, the positive electrode active material layer, and the positive electrode current collector.
  • the all-solid secondary battery of the present invention may be used as an all-solid secondary battery with the above structure.
  • the housing may be made of metal or resin (plastic). When using a metallic one, for example, an aluminum alloy or a stainless steel one can be used. It is preferable that the metal casing be divided into a positive electrode side casing and a negative electrode side casing 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 short-circuit prevention.
  • FIG. 1 is a cross-sectional view schematically showing an all-solid 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. By adopting such a structure, during charging, electrons (e ⁇ ) are supplied to the negative electrode side, and lithium ions (Li + ) are accumulated there.
  • a light bulb is used as a model for the operating portion 6, and is lit by discharge.
  • a battery fabricated by placing the body 12 in a 2032-type coin case 11 is sometimes called a (coin-type) all-solid-state secondary battery 13 .
  • both the positive electrode active material layer and the negative electrode active material layer are formed of the inorganic solid electrolyte-containing composition of the present invention.
  • the solid electrolyte layer is formed of a solid electrolyte composition containing the polymer binder used in the present invention and an inorganic solid electrolyte.
  • the inorganic solid electrolyte and 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 types.
  • the conductive aids contained in the positive electrode active material layer 4 and the negative electrode active material layer 2 may be the same or different.
  • either one of the positive electrode active material layer and the negative electrode active material layer, or both of them 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 simply referred to as an active material or an electrode active material.
  • the solid electrolyte layer contains an inorganic solid electrolyte having ion conductivity of a metal belonging to Group 1 or Group 2 of the periodic table, and any of the above-described components within a range that does not impair the effects of the present invention, Usually, it does not contain a positive electrode active material and/or a negative electrode active material.
  • the positive electrode active material layer includes an inorganic solid electrolyte having ion conductivity of a metal belonging to Group 1 or Group 2 of the periodic table, a positive electrode active material, a conductive aid, and a conductive additive within a range that does not impair the effects of the present invention. and any of the components described above.
  • the negative electrode active material layer includes an inorganic solid electrolyte having ion conductivity of a metal belonging to Group 1 or Group 2 of the periodic table, a negative electrode active material, a conductive aid, and the above-described materials as long as the effects of the present invention are not impaired.
  • the negative electrode active material layer can be a lithium metal layer.
  • the lithium metal layer include a layer formed by depositing or molding lithium metal powder, a lithium foil, a lithium 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 constituent layers are formed from the inorganic solid electrolyte-containing composition of the present invention, it is possible to realize an all-solid secondary battery with excellent cycle characteristics and low resistance.
  • the positive electrode current collector 5 and the negative electrode current collector 1 are respectively as described above.
  • layers formed from known constituent layer-forming materials can also be applied. Further, each layer may be composed of a single layer or may be composed of multiple layers.
  • An all-solid secondary battery can be manufactured by a conventional method. Specifically, an all-solid secondary battery can be produced by forming each of the above layers using the inorganic solid electrolyte-containing composition of the present invention. Specifically, in the all-solid secondary battery of the present invention, the inorganic solid electrolyte-containing composition of the present invention is applied onto a suitable base material (for example, a metal foil serving as a current collector) to form a coating film. It can be produced by performing a method (method for producing a sheet for an all-solid secondary battery of the present invention) including (forming) a step of forming a film.
  • a suitable base material for example, a metal foil serving as a current collector
  • an inorganic solid electrolyte-containing composition containing a positive electrode active material is applied and dried to form a positive electrode active material layer.
  • a positive electrode sheet for the next battery is produced.
  • an inorganic solid electrolyte-containing composition for forming a solid electrolyte layer is applied and dried to form a solid electrolyte layer.
  • an inorganic solid electrolyte-containing composition containing a negative electrode active material is applied and dried to form a negative electrode active material layer.
  • an all-solid secondary battery having a structure in which a solid electrolyte layer is sandwiched between a positive electrode active material layer and a negative electrode active material layer by stacking a negative electrode current collector (metal foil) on a negative electrode active material layer.
  • a desired all-solid secondary battery can also be obtained by enclosing this in a housing.
  • a negative electrode active material layer, a solid electrolyte layer, and a positive electrode active material layer are formed on the negative electrode current collector, and the positive electrode current collector is stacked to manufacture an all-solid secondary battery. You can also
  • Another method is the following method. That is, a positive electrode sheet for an all-solid secondary battery is produced as described above.
  • a negative electrode material negative electrode composition
  • an inorganic solid electrolyte-containing composition containing a negative electrode active material is applied and dried to form a negative electrode active material layer on a metal foil that is a negative electrode current collector.
  • a negative electrode sheet for the next battery is produced.
  • a solid electrolyte layer is formed on the active material layer of one of these sheets as described above.
  • the other of the all-solid secondary battery positive electrode sheet and the all-solid secondary battery negative electrode sheet 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 secondary battery can be manufactured.
  • Another method is the following method. That is, as described above, a positive electrode sheet for an all-solid secondary battery and a negative electrode sheet for an all-solid secondary battery are produced. Separately from this, an inorganic solid electrolyte-containing composition is applied onto a substrate to prepare a solid electrolyte sheet for an all-solid secondary battery comprising a solid electrolyte layer. Further, the all-solid secondary battery positive electrode sheet and the all-solid secondary battery negative electrode sheet are laminated so as to sandwich the solid electrolyte layer peeled from the substrate. Thus, an all-solid secondary battery can be manufactured.
  • a positive electrode sheet for an all-solid secondary battery, a negative electrode sheet for an all-solid secondary battery, and a solid electrolyte sheet for an all-solid secondary battery are produced as described above.
  • the all-solid secondary battery positive electrode sheet or the all-solid secondary battery negative electrode sheet and the all-solid secondary battery solid electrolyte sheet were brought into contact with the positive electrode active material layer or the negative electrode active material layer and the solid electrolyte layer. Repeatedly and pressurized. In this way, the solid electrolyte layer is transferred to the all-solid secondary battery positive electrode sheet or all-solid secondary battery negative electrode sheet.
  • the solid electrolyte layer obtained by peeling the base material of the solid electrolyte sheet for all-solid secondary batteries and the negative electrode sheet for all-solid secondary batteries or the positive electrode sheet for all-solid secondary batteries (the solid electrolyte layer and the negative electrode active material layer or (with the positive electrode active material layer in contact) and pressurized.
  • an all-solid secondary battery can be manufactured.
  • the pressurization method, pressurization conditions, and the like in this method are not particularly limited, and the method, pressurization conditions, and the like described in the pressurization step described later can be applied.
  • the solid electrolyte layer or the like can also be formed, for example, by pressure-molding a composition containing an inorganic solid electrolyte or the like on a substrate or an active material layer under pressure conditions described below.
  • the inorganic solid electrolyte-containing composition of the present invention may be used for either the positive electrode composition or the negative electrode composition, and the inorganic solid electrolyte-containing composition of the present invention may be used for both.
  • the method of applying the inorganic solid electrolyte-containing composition is not particularly limited and can be selected as appropriate. Examples thereof include coating (preferably wet coating), spray coating, spin coating, dip coating, slit coating, stripe coating, and bar coating.
  • the application temperature is not particularly limited, and includes, for example, a temperature range of about room temperature (for example, 15 to 30° C.) without heating.
  • the inorganic solid electrolyte-containing composition may be dried after each application, or may be dried after being applied in multiple layers.
  • the drying temperature is not particularly limited.
  • the lower limit is preferably 30°C or higher, more preferably 60°C or higher, and even 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 can be removed and a solid state (coated dry layer) can be obtained.
  • the inorganic solid electrolyte-containing composition After applying the inorganic solid electrolyte-containing composition, after laminating the constituent layers, or after producing the all-solid secondary battery, it is preferable to pressurize each layer or the all-solid secondary battery. It is also preferable to apply pressure while laminating each layer.
  • a hydraulic cylinder press machine etc. are mentioned as a pressurization method.
  • the applied pressure 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 being pressurized.
  • the heating temperature is not particularly limited, and generally ranges from 30 to 300.degree. It is also possible to press at a temperature higher than the glass transition temperature of the inorganic solid electrolyte.
  • pressing can also be performed at a temperature higher than the glass transition temperature of the polymer contained in the polymer binder. However, generally the temperature does not exceed the melting point of the polymer. Pressurization may be performed after drying the coating solvent or dispersion medium in advance, or may be performed while the solvent or dispersion medium remains. Each composition may be applied at the same time, or the application and drying presses may be performed simultaneously and/or sequentially. After coating on separate substrates, they may be laminated by transfer.
  • the atmosphere in the film forming method is not particularly limited, and can be air, dry air (dew point ⁇ 20° C. or less), inert gas (for example, argon gas, in helium gas, in nitrogen gas, etc.).
  • inert gas for example, argon gas, in helium gas, in nitrogen gas, etc.
  • high pressure may be applied for a short period of time (for example, within several hours), or moderate pressure may be applied for a long period of time (one day or more).
  • a restraining tool such as screw tightening pressure
  • the all-solid secondary battery can be used in order to keep applying moderate pressure.
  • the press pressure may be uniform or different with respect to the pressed portion such as the seat surface.
  • the press pressure can be changed according to the area or film thickness of the portion to be pressed. Also, the same part can be changed step by step with different pressures.
  • the pressing surface may be smooth or roughened.
  • the inorganic solid electrolyte-containing composition of the present invention can maintain excellent dispersibility and handleability even when it contains a conductive aid or when the solid content concentration is increased. Therefore, the inorganic solid electrolyte-containing composition can be applied by setting the solid content to a high concentration.
  • the formation of each layer (film formation) described above, particularly the application and drying of the inorganic solid electrolyte-containing composition of the present invention can be carried out in a so-called batch system using a sheet-shaped base material. It can also be carried out by a roll-to-roll method, which is highly productive among industrial production methods.
  • the all-solid 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 charge/discharge while press pressure is increased, and then releasing the pressure to the general working pressure of all-solid secondary batteries.
  • the all-solid secondary battery of the present invention can be applied to various uses. There are no particular restrictions on the mode of application, but for example, when installed in electronic equipment, notebook computers, pen-input computers, mobile computers, e-book players, mobile phones, cordless phone slaves, pagers, handy terminals, mobile faxes, mobile phones, etc. Copiers, portable printers, headphone stereos, video movies, liquid crystal televisions, handy cleaners, portable CDs, minidiscs, electric shavers, transceivers, electronic notebooks, calculators, memory cards, portable tape recorders, radios, backup power sources, etc.
  • Other consumer products include automobiles (electric vehicles, etc.), electric vehicles, motors, lighting equipment, toys, game devices, road conditioners, clocks, strobes, cameras, and medical devices (pacemakers, hearing aids, shoulder massagers, etc.). . Furthermore, it can be used for various military applications and space applications. It can also be combined with a solar cell.
  • a polymer S-1 was synthesized as follows. 24.8 g of dodecyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.), 27 g of macromonomer M-1 solution (solid 10.8 g), 0.4 g of acrylic acid (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), and polymerization initiation 0.36 g of agent V-601 (trade name, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was added and dissolved in 27.0 g of butyl butyrate to prepare a monomer solution.
  • Synthesis Example S-1 using a compound that leads to each constituent component so that the polymer S-2 has the following chemical formula and the composition shown in Table 1 (type and content of constituent component), polymerization concentration and polymerization initiator A polymer S-2 was synthesized in the same manner as in Synthesis Example S-1, except that the amount was appropriately adjusted so as to have a weight average molecular weight shown in Table 1, and a binder solution S-2 composed of this polymer was prepared (concentration 30% by mass) was obtained.
  • Synthesis Example S-1 using a compound that leads each component so that the polymer S-3 has the following chemical formula and the composition (type and content of the component) shown in Table 1, the polymerization concentration and the polymerization initiator Polymer S-3 was synthesized in the same manner as in Synthesis Example S-1, except that the amount was appropriately adjusted so as to have the mass average molecular weight shown in Table 1, and a binder solution S-3 composed of this polymer was prepared (concentration 30% by mass) was obtained.
  • the solid content concentration was 40% by mass and the number average molecular weight was 6,000.
  • Synthesis Example S-1 using a compound that leads to each constituent component so that the polymer S-4 has the following chemical formula and the composition shown in Table 1 (type and content of constituent component), polymerization concentration and polymerization initiator A polymer S-4 was synthesized in the same manner as in Synthesis Example S-1, except that the amount was appropriately adjusted so as to have a weight average molecular weight shown in Table 1, and a binder solution S-4 composed of this polymer was prepared (concentration 30% by mass) was obtained.
  • Synthesis Example S-1 using a compound that leads each component so that the polymer S-5 has the following chemical formula and the composition (type and content of the component) shown in Table 1, the polymerization concentration and the polymerization initiator A polymer S-5 was synthesized in the same manner as in Synthesis Example S-1, except that the amount was appropriately adjusted so as to have a weight average molecular weight shown in Table 1, and a binder solution S-5 composed of this polymer was prepared (concentration 30% by mass) was obtained.
  • Synthesis Example S-1 using a compound that leads to each constituent component so that the polymer S-6 has the following chemical formula and the composition shown in Table 1 (type and content of constituent component), polymerization concentration and polymerization initiator A polymer S-6 was synthesized in the same manner as in Synthesis Example S-1, except that the amount was appropriately adjusted so as to have a mass average molecular weight shown in Table 1, and a binder solution S-6 composed of this polymer was prepared (concentration 30% by mass) was obtained.
  • Synthesis Example S-1 using a compound that leads to each constituent component so that the polymer S-7 has the following chemical formula and the composition shown in Table 1 (types and contents of constituent components), polymerization concentration and polymerization initiator Polymer S-7 was synthesized in the same manner as in Synthesis Example S-1, except that the amount was appropriately adjusted so that the weight average molecular weight shown in Table 1, and a binder solution S-7 made of this polymer was prepared (concentration 30% by mass) was obtained.
  • Synthesis Example S-1 using a compound that leads each constituent component so that the polymer S-8 has the following chemical formula and the composition (type and content of the constituent component) shown in Table 1, the polymerization concentration and the polymerization initiator Polymer S-8 was synthesized in the same manner as in Synthesis Example S-1, except that the amount was appropriately adjusted so as to have the weight average molecular weight shown in Table 1, and a binder solution S-8 composed of this polymer was prepared (concentration 30% by mass) was obtained.
  • Synthesis Example S-10 Synthesis of Polymer S-10 and Preparation of Binder Solution S-10
  • Polymer S-10 has the following chemical formula and the composition shown in Table 1 (types and contents of constituent components).
  • the polymer S-10 was synthesized to obtain a binder solution S-10 (concentration: 30% by mass) composed of this polymer.
  • Synthesis Example S-11 Synthesis of Polymer S-11 and Preparation of Binder Solution S-11
  • Polymer S-11 has the following chemical formula and the composition shown in Table 1 (types and contents of constituent components).
  • the polymer S-11 was synthesized to obtain a binder solution S-11 (concentration: 30% by mass) composed of this polymer.
  • Synthesis Example S-12 Synthesis of Polymer S-12 and Preparation of Binder Solution S-12
  • Polymer S-12 has the following chemical formula and the composition shown in Table 1 (types and contents of constituent components).
  • the polymer S-12 was synthesized to obtain a binder solution S-12 (concentration: 30% by mass) composed of this polymer.
  • Synthesis Example S-1 using a compound that leads to each constituent component so that the polymer T-1 has the following chemical formula and the composition shown in Table 1 (type and content of constituent component), polymerization concentration and polymerization initiator A polymer T-1 was synthesized in the same manner as in Synthesis Example S-1, except that the amount was appropriately adjusted so as to have a weight average molecular weight shown in Table 1, and a binder solution T-1 composed of this polymer was prepared (concentration 30% by mass) was obtained.
  • polymer T-3 was synthesized as follows using macromonomer M-11. Add 28.8 g of methoxyethyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) and 1.40 g of polymerization initiator V-601 (trade name, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) to a 100 mL graduated cylinder and dissolve in 28.8 g of xylene. to prepare a monomer solution. 18 g of macromonomer M-11 solution (7.2 g of solid) and 36.0 g of xylene were added to a 300 mL three-necked flask and stirred at 80° C., and the above monomer solution was added dropwise over 2 hours.
  • macromonomer M-11 Add 28.8 g of methoxyethyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) and 1.40 g of polymerization initiator V-601 (trade name, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd
  • a binder dispersion liquid T-3 (concentration: 40% by mass) was obtained by dispersing the polymer T-3 in xylene.
  • the average particle size of the binder in this dispersion was 250 nm.
  • Synthesis Example T-4 Synthesis of Polymers T-4 and T-5 and Preparation of Binder Solutions T-4 and T-5
  • polymers T-4 and T-5 have the following chemical formulas and Using a compound that leads to each component so that the composition (type and content of the component) is shown in Table 1, the polymerization concentration and the amount of polymerization initiator are adjusted appropriately so that the weight average molecular weight is shown in Table 1.
  • Polymers T-4 and T-5 were synthesized in the same manner as in Synthesis Example S-1 to obtain binder solutions T-4 and T-5 (concentration: 30% by mass) comprising these polymers.
  • Table 1 shows the composition and mass average molecular weight of each synthesized polymer, and the number average molecular weight of the constituent component (X). The mass average molecular weight and number average molecular weight were each measured by the above method.
  • the state of the binder in each composition which will be described later, is shown as the result of evaluation by the above solubility measurement. Specifically, in Table 1, “dissolved” indicates that the binder is dissolved, and “particulate” indicates that the binder is insoluble and dispersed in the form of particles.
  • the content is also indicated using "/".
  • Li 2 S lithium sulfide
  • P 2 S 5 diphosphorus pentasulfide
  • Example 1 Each composition shown in Tables 2-1 to 2-4 (collectively referred to as Table 2) was prepared as follows. ⁇ Preparation of Inorganic Solid Electrolyte-Containing Composition> 2.8 g of the inorganic solid electrolyte LPS synthesized in Synthesis Example A, 0.08 g (solid content mass) of the binder solution or binder dispersion, and Butyl butyrate was added as the following dispersion medium so that the content of the dispersion medium in the composition was 48% by mass. After that, this container was set in a revolutionary mixer ARE-310 (trade name). The mixture was mixed for 5 minutes at 25° C.
  • ARE-310 trade name
  • inorganic solid electrolyte-containing compositions (slurries) K-1 to K-15 were prepared in the same manner except for the setting.
  • ARE-310 rotation-revolution mixer
  • LiNi 1/3 Co 1/3 Mn 1/3 O 2 (NMC, manufactured by Aldrich Co.) as a positive electrode active material and acetylene as a conductive aid were added to this container at a content ratio shown in Table 2-2.
  • Compositions (slurries) PK-1 to PK-15 were respectively prepared.
  • the binder solution or dispersion liquid was changed to the binder solution or dispersion medium shown in Table 2-4, and the content of each component was set to the content shown in the same table.
  • Positive electrode compositions (slurries) PKc21 to PKc25 were prepared in the same manner except for the above.
  • ARE-310 (trade name) manufactured by Thinky
  • Table 2-1 shows the adsorption rate [A CA ] and the adsorption rate [A SE ] for the inorganic solid electrolyte of the polymer binder used in the preparation of each composition measured by the above-described measurement method.
  • Table 2-4 (collectively referred to as Table 2).
  • the composition content is the content (% by mass) relative to the total mass of the composition
  • the solid content is the content (% by mass) relative to 100% by mass of the solid content of the composition. Omit units. Also, the unit (%) of the adsorption rate is omitted.
  • LPS LPS synthesized in Synthesis Example A
  • NMC LiNi1 / 3Co1 / 3Mn1 / 3O2 Si: Silicon (APS 1 to 5 ⁇ m, manufactured by Alfa Aesar)
  • AB acetylene black
  • VGCF carbon nanotube
  • each prepared electrode composition was allowed to stand at 25°C for 24 hours, and then mixed again at a temperature of 25°C using a planetary ball mill P-7 (trade name).
  • the number of revolutions and time for remixing were the same as those for preparing each electrode composition.
  • the remixed electrode composition was checked for the occurrence (presence or absence) of aggregates of solid particles using the grindometer described above.
  • the size of the aggregate at this time was defined as Y ( ⁇ m) and used as an index of redispersibility after storage.
  • the size of the agglomerate was defined as the point at which conspicuous spots appeared in the material applied to the grindometer (see JIS K-5600-2-5 (1999) 6.6).
  • the storage stability of the electrode composition is the easiness of generation of aggregates (aggregation or sedimentation). evaluated.
  • the smaller the size X of the aggregates the better the initial dispersibility, and the smaller the size Y, the better the storage stability. Since the electrode composition can effectively suppress (re)aggregation or precipitation of solid particles even under aging conditions (excellent in dispersion stability), even solid particles that have once aggregated or precipitated can be treated immediately after preparation. Excellent dispersibility can be reproduced and exhibits excellent storage stability.
  • the size Y of aggregates was evaluated according to the following evaluation criteria, and evaluation criteria "C” or higher were taken as a pass level.
  • evaluation criteria "C” or higher were taken as a pass level.
  • the size Y of the aggregate was 8 ⁇ m or less (the evaluation criterion is “C” or more)
  • the size X of the aggregate was also evaluated according to the following evaluation criteria.
  • Tables 3-2 to 3-4 Hereinafter, Tables 3-1 to 3-4 are collectively referred to as Table 3.
  • the tare (self weight) of the poly dropper was W 0 , it was judged that the dropper could not be sucked up when the slurry mass W ⁇ W 0 was less than 0.1 g. If it is determined that the slurry with a solid content concentration of 75% by mass cannot be sucked with a dropper, the dispersion medium is gradually added to the slurry to readjust the slurry with a reduced solid content concentration, and the same procedure as described above is performed again. The readjusted slurry was sucked with a poly dropper, and the solid content concentration of the slurry when the dropper could be sucked for the first time was grasped as the upper limit solid content concentration.
  • the handling property of the electrode composition (whether it has an appropriate viscosity for forming a flat constituent layer with good surface properties) evaluated.
  • the upper limit solid content concentration was calculated by placing 0.30 g of the prepared slurry on an aluminum cup and heating it at 120° C. for 2 hours to distill off the dispersion medium. In this test, the larger the upper limit solid content concentration, the more excellent the handleability, and the evaluation standard "C" or higher was regarded as a passing level. Table 3 shows the results.
  • Adhesion test> The adhesion of the solid particles in the active material layer of each electrode sheet obtained and the adhesion between the active material layer and the current collector were evaluated.
  • Each of the produced electrode sheets was cut into a rectangle having a width of 3 cm and a length of 14 cm. Using a cylindrical mandrel tester (product code 056, mandrel diameter 10 mm, manufactured by Allgood), one end of the cut out sheet test piece in the length direction is fixed to the tester, and the mandrel is attached to the central portion of the sheet test piece.
  • the sheet test piece was set so that the active material layer was on the opposite side of the mandrel (the substrate or current collector was on the mandrel side) and the width direction was parallel to the axis of the mandrel. The test was conducted by gradually reducing the diameter of the mandrel from 32 mm.
  • the evaluation is based on the occurrence of defects (cracks, splits, chips, etc.) in the active material layer due to the collapse of binding of solid particles in the state of being wrapped around the mandrel and the state of being unwound and restored to a sheet form, or the active material layer If either separation from the current collector was confirmed, it was discontinued.
  • Minimum diameter As such, the minimum diameter corresponds to any of the following evaluation criteria. In this test, the smaller the minimum diameter, the stronger the binding force of the solid particles constituting the active material layer, and the stronger the adhesion force between the active material layer and the current collector. C” or higher was defined as a passing level.
  • This test is a test for evaluating the cycle characteristics test of the all-solid secondary battery from the viewpoint of resistance to oxidation deterioration of the polymer binder, and is used as a reference test in the present invention.
  • the pass level is not limited as long as it passes the cycle characteristics test, but the evaluation standard "D" or higher is a preferable level. The results are shown in Tables 3-1 and 3-4.
  • All-solid secondary battery No. 1 having the layer structure shown in FIG. 101 was made.
  • All-solid secondary battery positive electrode sheet No. having a solid electrolyte layer obtained above. 116 (the aluminum foil of the solid electrolyte-containing sheet has already been peeled off) was cut into a disk shape with a diameter of 14.5 mm, and as shown in FIG. I put it in the type coin case 11.
  • a disc-shaped lithium foil with a diameter of 15 mm was placed on the solid electrolyte layer.
  • the 2032 type coin case 11 is crimped to form the No. 2032 coin case shown in FIG. 101 all-solid secondary batteries 13 were manufactured.
  • the all-solid secondary battery manufactured in this manner has the layer structure shown in FIG. 1 (wherein the lithium foil corresponds to the negative electrode active material layer 2 and the negative electrode current collector 1).
  • All-solid secondary battery No. 101 positive electrode sheet for all-solid secondary battery provided with a solid electrolyte layer No. No. 116 shown in the "Electrode Active Material Layer (Sheet No.)" column of Table 4. All-solid secondary battery No. 1 except that the positive electrode sheet for an all-solid secondary battery having a solid electrolyte layer was used. 101, all-solid secondary battery No. 102-115 and c101-c105 were prepared respectively.
  • All-solid secondary battery No. 1 having the layer structure shown in FIG. 116 was made.
  • 131 the aluminum foil of the solid electrolyte-containing sheet has already been peeled off
  • a positive electrode sheet punched out with a diameter of 14.0 mm from a positive electrode sheet for an all-solid secondary battery prepared as described below was placed on the solid electrolyte layer.
  • a stainless steel foil (positive electrode current collector) is further stacked on it, and the all-solid secondary battery laminate 12 (stainless steel foil-aluminum foil-positive electrode active material layer-solid electrolyte layer-negative electrode active material layer-copper foil A laminate) was formed. After that, by crimping the 2032 type coin case 11, the all-solid secondary battery No. 2 shown in FIG. 116 was produced.
  • All-solid-state secondary battery No. 1 was fabricated as follows.
  • a positive electrode sheet for a solid secondary battery used in the production of No. 116 was prepared.
  • - Preparation of positive electrode composition - 180 g of zirconia beads with a diameter of 5 mm were added to a zirconia 45 mL container (manufactured by Fritsch), 2.7 g of LPS synthesized in Synthesis Example A above, KYNAR FLEX 2500-20 (trade name, PVdF-HFP: polyvinylidene fluoride 0.3 g of hexafluoropropylene copolymer (manufactured by Arkema) as a solid mass and 22 g of butyl butyrate were added.
  • This container was set in a planetary ball mill P-7 (trade name) manufactured by Fritsch, and stirred at 25° C. and 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 a positive electrode active material, and similarly, the container was set in a planetary ball mill P-7 and heated at 25° C. Mixing was continued at 100 rpm for 5 minutes to prepare a positive electrode composition.
  • - Production of positive electrode sheet for solid secondary battery The positive electrode composition obtained above was applied onto a 20 ⁇ m thick aluminum foil (positive electrode current collector) using a baker applicator (trade name: SA-201, manufactured by Tester Sangyo Co., Ltd.) and heated at 100° C.
  • the positive electrode composition was dried (the dispersion medium was removed). Then, using a heat press, 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 with a thickness of 80 ⁇ m. .
  • All-solid secondary battery No. 116 a negative electrode sheet for an all-solid secondary battery provided with a solid electrolyte layer No. No. 131 shown in the "electrode active material layer (sheet No.)" column of Table 4. All-solid secondary battery No. 1 except for using a negative electrode sheet for an all-solid secondary battery having a solid electrolyte layer represented by 116, all-solid secondary battery No. 117-130 and c106-c110 were prepared respectively.
  • Ionic conductivity measurement (resistance measurement)> The ionic conductivity of each manufactured all-solid secondary battery was measured. Specifically, for each all-solid secondary battery, AC impedance was measured in a constant temperature bath at 25° C. using a 1255B FREQUENCY RESPONSE ANALYZER (trade name, manufactured by SOLARTRON) at a voltage amplitude of 5 mV and a frequency of 1 MHz to 1 Hz. From this, the resistance in the layer thickness direction of the sample for ion conductivity measurement was obtained, and the ion conductivity was obtained by calculation using the following formula (C1). Table 4 shows the results.
  • ionic conductivity ⁇ (mS/cm) 1000 x sample layer thickness (cm)/[resistance ( ⁇ ) x sample area (cm 2 )]
  • the thickness of the sample layer is the value obtained by subtracting the thickness of the current collector (total thickness of the solid electrolyte layer and the electrode active material layer), which is measured before putting the laminate 12 into the 2032 type coin case 11. is.
  • the sample area is the area of a disk-shaped sheet with 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 was considered to be a passing level when it was equal to or higher than the evaluation standard "C".
  • - Evaluation criteria - A: 0.30 ⁇ B: 0.25 ⁇ 0.30 C: 0.20 ⁇ 0.25 D: 0.15 ⁇ 0.20 E: 0.10 ⁇ 0.15 F: ⁇ 0.10
  • Cycle characteristics in this test were regarded as a pass level of the evaluation standard "C" or higher. Table 4 shows the results. All-solid secondary battery No. All of the initial discharge capacities of 101 to 130 showed values sufficient to function as all-solid secondary batteries.
  • - Evaluation criteria - A: 600 cycles or more B: 450 cycles or more and less than 600 cycles C: 300 cycles or more and less than 450 cycles D: 150 cycles or more and less than 300 cycles E: 80 cycles or more and less than 150 cycles F: 40 cycles or more and less than 80 cycles
  • Comparative inorganic solid electrolyte-containing compositions that do not contain the polymer binder defined in the present invention are inferior in dispersibility (storage stability and handleability) or adhesion. It can be seen that the all-solid secondary batteries of Comparative Examples having active material layers formed from these compositions do not sufficiently reduce the resistance or improve the cycle characteristics.
  • the inorganic solid electrolyte-containing composition (electrode composition) containing the polymer binder defined in the present invention has excellent dispersion characteristics even if it contains a conductive aid and has a high concentration. , the adhesion of solid particles can be strengthened. It also has excellent oxidation resistance.
  • the all-solid secondary battery of the present invention having an active material layer formed of these compositions exhibits high ionic conductivity (low resistance) and can also achieve excellent cycle characteristics.
  • the all-solid secondary battery sheet which is most likely to come into contact with oxygen in the actual manufacturing process, was evaluated. As long as the all-solid secondary battery sheet exhibits an oxidation-inhibiting effect, the same effect can be expected in the inorganic solid electrolyte-containing composition and also in the constituent layers incorporated in the all-solid secondary battery.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
  • Secondary Cells (AREA)
  • Conductive Materials (AREA)
PCT/JP2022/026899 2021-07-07 2022-07-07 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 Ceased WO2023282312A1 (ja)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2023533178A JPWO2023282312A1 (https=) 2021-07-07 2022-07-07

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2021-113029 2021-07-07
JP2021113029 2021-07-07

Publications (1)

Publication Number Publication Date
WO2023282312A1 true WO2023282312A1 (ja) 2023-01-12

Family

ID=84800750

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2022/026899 Ceased WO2023282312A1 (ja) 2021-07-07 2022-07-07 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

Country Status (2)

Country Link
JP (1) JPWO2023282312A1 (https=)
WO (1) WO2023282312A1 (https=)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN118899540A (zh) * 2024-07-15 2024-11-05 新源芯安科技(北京)有限公司 一种高倍率的钠离子电池电解液及其制备方法
CN119735818A (zh) * 2024-12-27 2025-04-01 上海三瑞高分子材料股份有限公司 一种支化分散剂及其制备方法和应用

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020080261A1 (ja) * 2018-10-15 2020-04-23 富士フイルム株式会社 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 (ja) * 2019-08-30 2021-03-04 富士フイルム株式会社 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
WO2021039948A1 (ja) * 2019-08-30 2021-03-04 富士フイルム株式会社 電極用組成物の製造方法、全固体二次電池用電極シートの製造方法及び全固体二次電池の製造方法
WO2021066060A1 (ja) * 2019-09-30 2021-04-08 富士フイルム株式会社 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、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の製造方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020080261A1 (ja) * 2018-10-15 2020-04-23 富士フイルム株式会社 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 (ja) * 2019-08-30 2021-03-04 富士フイルム株式会社 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
WO2021039948A1 (ja) * 2019-08-30 2021-03-04 富士フイルム株式会社 電極用組成物の製造方法、全固体二次電池用電極シートの製造方法及び全固体二次電池の製造方法
WO2021066060A1 (ja) * 2019-09-30 2021-04-08 富士フイルム株式会社 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、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の製造方法

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN118899540A (zh) * 2024-07-15 2024-11-05 新源芯安科技(北京)有限公司 一种高倍率的钠离子电池电解液及其制备方法
CN119735818A (zh) * 2024-12-27 2025-04-01 上海三瑞高分子材料股份有限公司 一种支化分散剂及其制备方法和应用
CN119735818B (zh) * 2024-12-27 2025-08-22 上海三瑞高分子材料股份有限公司 一种支化分散剂及其制备方法和应用

Also Published As

Publication number Publication date
JPWO2023282312A1 (https=) 2023-01-12

Similar Documents

Publication Publication Date Title
JP7234400B2 (ja) 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、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の製造方法
JP7554316B2 (ja) 全固体二次電池及び全固体二次電池用シート
JP7263525B2 (ja) 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
JP7218440B2 (ja) 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
JP7320062B2 (ja) 無機固体電解質含有組成物、全固体二次電池用シート、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、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
JP7514944B2 (ja) 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
JP7292498B2 (ja) 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
JP7796662B2 (ja) 電極組成物、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、全固体二次電池用電極シート及び全固体二次電池の製造方法
US20230275259A1 (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
WO2020138122A1 (ja) 固体電解質組成物、固体電解質含有シート及び全固体二次電池、並びに、固体電解質含有シート及び全固体二次電池の製造方法
WO2023282312A1 (ja) 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
JP7295336B2 (ja) 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
JP7263536B2 (ja) 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
JP7357144B2 (ja) 電極組成物、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、全固体二次電池用電極シート及び全固体二次電池の製造方法
JP7769685B2 (ja) 電極組成物、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、全固体二次電池用電極シート及び全固体二次電池の製造方法
JP7266152B2 (ja) 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
JP7427106B2 (ja) 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
WO2023282333A1 (ja) 電極組成物、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、全固体二次電池用電極シート及び全固体二次電池の製造方法
WO2023249014A1 (ja) 二次電池用バインダー組成物、二次電池用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
WO2023054455A1 (ja) 電極用シート及び全固体二次電池、並びに、電極用シート、電極シート及び全固体二次電池の製造方法
WO2023054425A1 (ja) 電極組成物、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製造方法
JP7791170B2 (ja) 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
US20250183358A1 (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
EP4503196A1 (en) Secondary battery binder composition, nonaqueous secondary battery composition, sheet for all-solid-state secondary battery and all-solid-state secondary battery, and sheet for all-solid-state secondary battery and method for producing all-solid-state secondary battery
JP7373674B2 (ja) 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

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: 22837726

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 2023533178

Country of ref document: JP

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 22837726

Country of ref document: EP

Kind code of ref document: A1