WO2021039946A1 - 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、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、並びに、複合ポリマー粒子 - 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、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、並びに、複合ポリマー粒子 Download PDFInfo
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
- H01M4/134—Electrodes based on metals, Si or alloys
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- 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
- H01M4/139—Processes of manufacture
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- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
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- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
- H01M2300/0068—Solid electrolytes inorganic
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- 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
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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Definitions
- the present invention relates to an inorganic solid electrolyte-containing composition, a sheet for an all-solid secondary battery and an all-solid secondary battery, a sheet for an all-solid secondary battery and a method for producing the all-solid secondary battery, and composite polymer particles.
- the negative electrode, the electrolyte, and the positive electrode are all made of solid, and the safety and reliability, which are the problems of the battery using the organic electrolytic solution, can be greatly improved. It is also said that it will be possible to extend the service life. Further, the all-solid-state secondary battery can have a structure in which electrodes and electrolytes are directly arranged side by side and arranged in series. Therefore, it is possible to increase the energy density as compared with a secondary battery using an organic electrolytic solution, and it is expected to be applied to an electric vehicle, a large storage battery, or the like.
- examples of the compound forming a constituent layer include an inorganic solid electrolyte, an active material, and the like.
- this inorganic solid electrolyte particularly a sulfide-based inorganic solid electrolyte, is expected as an electrolyte material having high ionic conductivity approaching that of an organic electrolytic solution.
- a material for forming a constituent layer of an all-solid secondary battery (constituent layer forming material)
- a material containing the above-mentioned inorganic solid electrolyte and the like has been proposed.
- Patent Document 1 contains (A) an inorganic solid electrolyte having ionic conductivity of a metal belonging to Group 1 or Group 2 of the Periodic Table, (B) a polymer, and (C) a dispersion medium.
- the polymer has a hydrocarbon polymer segment in the main chain, and the main chain is the bond group (I): ester bond, amide bond, urethane bond, urea bond, imide bond,
- a solid electrolyte composition comprising at least one bond selected from ether and carbonate bonds has been described. In this solid electrolyte composition, the polymer (B) is used alone.
- Patent Document 2 describes a slurry for an all-solid secondary battery in which a binder composed of an inorganic solid electrolyte and a particulate polymer having an average particle size of 30 to 300 nm is dissolved or dispersed in a specific non-polar solvent. Has been done.
- This Patent Document 2 merely describes a particulate polymer having a core-shell structure made of a (meth) acrylic polymer as the particulate polymer.
- the constituent layer of the all-solid-state secondary battery is usually formed of solid particles such as an inorganic solid electrolyte and an active material, the binding force between the solid particles is not sufficient. As a result, the battery performance (cycle characteristics) deteriorates due to the charging and discharging of the all-solid-state secondary battery. Further, in the sheet for an all-solid-state secondary battery that can be used as a constituent layer of an all-solid-state secondary battery, if the binding force is not sufficient, the constituent layer may be chipped, cracked, cracked or peeled off, and in some cases. The constituent layer is peeled off from the base material.
- the present invention provides an inorganic solid electrolyte-containing composition capable of firmly binding solid particles while suppressing an increase in resistance by being used as a material constituting a constituent layer of an all-solid secondary battery. Is the subject. Further, the present invention provides a method for producing an all-solid-state secondary battery sheet and an all-solid-state secondary battery, and an all-solid-state secondary battery sheet and an all-solid-state secondary battery using this inorganic solid electrolyte-containing composition. The challenge is to provide. Further, the present invention provides composite polymer particles capable of firmly binding solid particles while suppressing an increase in resistance by being used in combination with solid particles forming a constituent layer of an all-solid secondary battery. The task is to do.
- the present inventors have conducted not only a combination of two or more polymers but a combination of two or more polymers as a binder to be used in combination with the inorganic solid electrolyte in the composition containing an inorganic solid electrolyte.
- the solid particles are strengthened while suppressing an increase in resistance. I found that it can be tied to.
- this inorganic solid electrolyte-containing composition as a constituent layer forming material, it is possible to realize an all-solid-state secondary battery sheet in which the occurrence of defects is suppressed, and the all-solid secondary battery has low resistance and excellent cycle characteristics. We found that a battery could be realized.
- the present invention has been further studied based on these findings and has been completed.
- An inorganic solid electrolyte-containing composition containing a binder and an inorganic solid electrolyte having conductivity of metal ions belonging to Group 1 or Group 2 of the periodic table.
- the binder comprises composite polymer particles having at least two polymers.
- X and Y independently represent atoms belonging to Group 15 or Group 16 of the Periodic Table. When Y is an atom belonging to Group 15, this atom has a hydrogen atom, an alkyl group or an aryl group.
- Z indicates an atom belonging to Group 14 or Group 15 of the Periodic Table.
- the structural unit having an SP value of 20.5J 0.5 / cm 1.5 or more and 40J 0.5 / cm 1.5 or less is 20 to 99.5% by mass.
- the structural unit SP value is less than 15 J 0.5 / cm 1.5 or 20.5J 0.5 / cm 1.5 is 0.5 to 80 mass%, according to ⁇ 1> inorganic Solid electrolyte-containing composition.
- ⁇ 4> The inorganic solid electrolyte-containing composition according to any one of ⁇ 1> to ⁇ 3>, which contains an organic solvent having a ClogP value of 1.0 or more.
- ⁇ 5> The inorganic solid electrolyte-containing composition according to any one of ⁇ 1> to ⁇ 4>, wherein the average primary particle size of the composite polymer particles is 0.1 nm to 5.0 ⁇ m.
- At least one polymer is a low polar polymer having a structural unit SP value is less than 15 J 0.5 / cm 1.5 or 20.5J 0.5 / cm 1.5 5 wt% or more, At least one polymer is a highly polar polymer having SP value of 20.5J 0.5 / cm 1.5 or 40 J 0.5 / cm 1.5 to 90 mass% or more of the following constitutional units, ⁇ 1> The inorganic solid electrolyte-containing composition according to any one of ⁇ 5>. ⁇ 7> The inorganic solid electrolyte-containing composition according to ⁇ 6>, wherein the highly polar polymer has a bond represented by the formula (1).
- the content of the low-polarity polymer in the total polymer contained in the composite polymer particles is 1 to 70% by mass, and the content of the high-polarity polymer is 30 to 99% by mass, ⁇ 6> or ⁇ 7>
- the inorganic solid electrolyte-containing composition ⁇ 9>
- the bond represented by the formula (1) forms a urethane bond, a urea bond, an amide bond, an imide bond, an ester bond, a carbonate bond, a thiourea bond, a thiourethane bond, an imidazole bond or a triazole bond.
- the inorganic solid electrolyte-containing composition according to any one of.
- ⁇ 10> The inorganic solid electrolyte-containing composition according to any one of ⁇ 1> to ⁇ 9>, which contains an active material.
- ⁇ 11> The inorganic solid electrolyte-containing composition according to ⁇ 10>, wherein the active material is an active material containing a silicon element or a tin element.
- ⁇ 12> The inorganic solid electrolyte-containing composition according to any one of ⁇ 1> to ⁇ 11>, which contains a conductive auxiliary agent.
- ⁇ 13> The composition containing an inorganic solid electrolyte according to any one of ⁇ 1> to ⁇ 12>, wherein the inorganic solid electrolyte is a sulfide-based inorganic solid electrolyte.
- An all-solid-state secondary battery sheet having a layer composed of the inorganic solid electrolyte-containing composition according to any one of ⁇ 1> to ⁇ 13> above.
- An all-solid-state secondary battery including a positive electrode active material layer, a solid electrolyte layer, and a negative electrode active material layer in this order. At least one layer of the positive electrode active material layer, the solid electrolyte layer, and the negative electrode active material layer is a layer composed of the inorganic solid electrolyte-containing composition according to any one of ⁇ 1> to ⁇ 13> above.
- ⁇ 16> A method for producing a sheet for an all-solid secondary battery, which forms a film of the inorganic solid electrolyte-containing composition according to any one of ⁇ 1> to ⁇ 13> above.
- ⁇ 17> A method for manufacturing an all-solid-state secondary battery, wherein the all-solid-state secondary battery is manufactured through the manufacturing method according to ⁇ 16> above.
- X and Y independently represent atoms belonging to Group 15 or Group 16 of the Periodic Table. When Y is an atom belonging to Group 15, this atom has a hydrogen atom, an alkyl group or an aryl group.
- Z indicates an atom belonging to Group 14 or Group 15 of the Periodic Table.
- the present invention realizes that the increase in resistance is suppressed and solid particles are firmly bound to each other, thereby suppressing the occurrence of defects in the constituent layers, lowering the resistance of the all-solid secondary battery, and further improving the cycle characteristics.
- An inorganic solid electrolyte-containing composition that contributes can be provided.
- the present invention can also provide an all-solid-state secondary battery sheet and an all-solid-state secondary battery having a layer composed of the inorganic solid electrolyte-containing composition.
- the present invention can provide a sheet for an all-solid-state secondary battery and a method for producing an all-solid-state secondary battery using this inorganic solid electrolyte-containing composition.
- the present invention provides composite polymer particles that can be used in combination with solid particles forming a constituent layer of an all-solid secondary battery to firmly bind the solid particles while suppressing an increase in resistance. it can.
- FIG. 2 is a vertical cross-sectional view schematically showing the coin-type all-solid-state secondary battery produced in the examples.
- the numerical range represented by using "-" means a range including the numerical values before and after "-" as the lower limit value and the upper limit value.
- the indication of a compound is used to mean that the compound itself, its salt, and its ion are included.
- it is meant to include a derivative which has been partially changed, such as by introducing a substituent, as long as the effect of the present invention is not impaired.
- (meth) acrylic means one or both of acrylic and methacrylic. The same applies to (meth) acrylate.
- substituents for which substitution or non-substitution is not specified may have an appropriate substituent in the group. Therefore, in the present invention, even if it is simply described as a YYY group, this YYY group includes a mode having a substituent in addition to a mode having no substituent. This is also synonymous with compounds that do not specify substitution or no substitution.
- Preferred substituents include, for example, Substituent Z described later.
- the substituents or the like may be the same or different from each other. Means that.
- the polymer means a polymer, but is synonymous with a so-called polymer compound.
- the inorganic solid electrolyte-containing composition of the present invention contains an inorganic solid electrolyte having ionic conductivity of a metal belonging to Group 1 or Group 2 of the Periodic Table, and composite polymer particles.
- the composite polymer particles contained in the inorganic solid electrolyte-containing composition of the present invention are the inorganic solid electrolyte (furthermore, an active substance, a conductive additive that can coexist) and the like in the layer formed of the inorganic solid electrolyte-containing composition. It functions as a binder that binds the solid particles of the above (for example, inorganic solid electrolytes to each other, inorganic solid electrolytes to active substances, and active substances to each other).
- the composite polymer particles contained in the inorganic solid electrolyte-containing composition of the present invention may or may not have a function of binding the solid particles to each other in the inorganic solid electrolyte-containing composition.
- the composition containing an inorganic solid electrolyte of the present invention is preferably a slurry in which the inorganic solid electrolyte is dispersed in a dispersion medium.
- the composite polymer particles have a function of dispersing the solid particles in the dispersion medium.
- the composite polymer particles are usually dispersed in the dispersion medium (in the solid state), but a part of the composite polymer particles may be dissolved in the dispersion medium as long as the effects of the present invention are not impaired.
- the inorganic solid electrolyte-containing composition of the present invention can firmly bind solid particles while suppressing an increase in resistance.
- this inorganic solid electrolyte-containing composition as a constituent layer forming material, it is possible to realize an all-solid-state secondary battery sheet in which the occurrence of defects is suppressed, and an all-solid-state secondary battery having low resistance and excellent cycle characteristics. ..
- the details of the reason are not yet clear, but it can be considered as follows. That is, at least one of the polymers forming the composite polymer particles is a polymer having a specific bond described later in the main chain. As a result, the polymer exhibits adhesion to the solid particles or the current collector, and the solid particles or the solid particles can be bound to the current collector.
- the inorganic solid electrolyte-containing composition of the present invention is preferably used as a slurry containing a dispersion medium when producing a sheet for an all-solid secondary battery or the like. At this time, it is not necessary to uniformly introduce the chemical structure part (low-polarity structural unit, etc. described later) for adjusting the dispersibility with respect to the dispersion medium into the polymer constituting the composite polymer particles, and the content rate thereof should be arbitrarily set. Can be done.
- the content of the chemical structure portion that contributes to the binding property of the solid particles can be relatively increased without lowering the dispersibility, and the binding force of the solid particles and the like can be strengthened. ..
- the composite polymer particles exhibiting such strong binding properties maintain the particle shape and adhere to a part of the surface of the solid particles instead of the entire surface. Therefore, the electron conduction path and / or the ion conduction path can be secured without blocking the contact between the surfaces of the solid particles. Due to the function of the composite polymer particles, the sheet for an all-solid-state secondary battery produced by using the composition containing the inorganic solid electrolyte of the present invention can suppress the occurrence of defects in the constituent layers and the increase in resistance. .. Further, the all-solid-state secondary battery provided with this constituent layer can achieve excellent cycle characteristics and low resistance of the battery.
- the inorganic solid electrolyte-containing composition of the present invention is a material for forming an all-solid secondary battery sheet (including an electrode sheet for an all-solid secondary battery) or an all-solid secondary battery, such as a solid electrolyte layer and an active material layer. It can be preferably used as (material for forming a constituent layer). In particular, it can be preferably used as a material for forming a negative electrode sheet for an all-solid secondary battery or a negative electrode active material layer containing a negative electrode active material having a large expansion and contraction due to charge and discharge, and also in this embodiment, high binding property and low resistance can be achieved. Can be achieved.
- the inorganic solid electrolyte-containing composition of the present invention is preferably a non-aqueous composition.
- the non-aqueous composition includes not only a water-free aspect but also a form in which the water content (also referred to as water content) is preferably 500 ppm or less.
- the water content is more preferably 200 ppm or less, further preferably 100 ppm or less, and particularly preferably 50 ppm or less.
- the water content indicates the amount of water contained in the inorganic solid electrolyte-containing composition (mass ratio to the inorganic solid electrolyte-containing composition).
- the mixture is filtered through a 0.02 ⁇ m membrane filter and curled fisher.
- the value shall be the value measured using titration.
- the composition containing an inorganic solid electrolyte of the present invention also includes an embodiment containing an active material, a conductive additive, and the like in addition to the inorganic solid electrolyte (the composition of this embodiment is referred to as a composition for an electrode layer).
- the composition of this embodiment is referred to as a composition for an electrode layer.
- the inorganic solid electrolyte-containing composition of the present invention contains an inorganic solid electrolyte.
- the inorganic solid electrolyte is an inorganic solid electrolyte
- the solid electrolyte is a solid electrolyte capable of transferring ions inside the solid electrolyte. Since it does not contain organic substances as the main ionic conductive material, it is an organic solid electrolyte (polymer electrolyte typified by polyethylene oxide (PEO), organic typified by lithium bis (trifluoromethanesulfonyl) imide (LiTFSI), etc. It is clearly distinguished from electrolyte salts).
- PEO polyethylene oxide
- LiTFSI lithium bis (trifluoromethanesulfonyl) imide
- the inorganic solid electrolyte is a solid in a steady state, it is usually not dissociated or liberated into cations and anions. In this respect, it is clearly distinguished from the electrolyte or the inorganic electrolyte salts (LiPF 6 , LiBF 4 , Lithium bis (fluorosulfonyl) imide (LiFSI), LiCl, etc.) that are dissociated or liberated into cations and anions in the polymer. Will be done.
- the inorganic solid electrolyte is not particularly limited as long as it has the conductivity of the ions of the metal belonging to the Group 1 or Group 2 of the periodic table, and is generally one having no electron conductivity.
- the inorganic solid electrolyte preferably has lithium ion ionic conductivity.
- a solid electrolyte material usually used for an all-solid secondary battery can be appropriately selected and used.
- examples of the inorganic solid electrolyte include (i) a sulfide-based inorganic solid electrolyte, (ii) an oxide-based inorganic solid electrolyte, (iii) a halide-based inorganic solid electrolyte, and (iv) a hydride-based inorganic solid electrolyte.
- the sulfide-based inorganic solid electrolyte is preferable from the viewpoint that a better interface can be formed between the active material and the inorganic solid electrolyte.
- the sulfide-based inorganic solid electrolyte contains a sulfur atom, has ionic conductivity of a metal belonging to Group 1 or Group 2 of the Periodic Table, and is electronically insulated. Those having sex are preferable.
- the sulfide-based inorganic solid electrolyte preferably contains at least Li, S and P as elements and has lithium ion conductivity, but other than Li, S and P may be used depending on the purpose or case. It may contain elements.
- Examples of the sulfide-based inorganic solid electrolyte include a lithium ion conductive inorganic solid electrolyte satisfying the composition represented by the following formula (S1).
- L a1 M b1 P c1 S d1 A e1 (S1)
- L represents an element selected from Li, Na and K, with Li being preferred.
- M represents an element selected from B, Zn, Sn, Si, Cu, Ga, Sb, Al and Ge.
- A represents an element selected from I, Br, Cl and F.
- a1 to e1 indicate the composition ratio of each element, and a1: b1: c1: d1: e1 satisfy 1 to 12: 0 to 5: 1: 2 to 12: 0 to 10.
- a1 is preferably 1 to 9, more preferably 1.5 to 7.5.
- b1 is preferably 0 to 3, more preferably 0 to 1.
- the d1 is preferably 2.5 to 10, more preferably 3.0 to 8.5.
- e1 is preferably 0 to 5, more preferably 0 to 3.
- composition ratio of each element can be controlled by adjusting the blending amount of the raw material compound when producing the sulfide-based inorganic solid electrolyte as described below.
- the sulfide-based inorganic solid electrolyte may be non-crystal (glass) or crystallized (glass-ceramic), or only a part thereof may be crystallized.
- Li-PS-based glass containing Li, P and S, or Li-PS-based glass ceramics containing Li, P and S can be used.
- Sulfide-based inorganic solid electrolytes include, for example, lithium sulfide (Li 2 S), phosphorus sulfide (for example, diphosphorus pentasulfide (P 2 S 5 )), simple phosphorus, simple sulfur, sodium sulfide, hydrogen sulfide, and lithium halide (for example). It can be produced by the reaction of at least two or more raw materials in sulfides of LiI, LiBr, LiCl) and the element represented by M (for example, SiS 2 , SnS, GeS 2).
- the ratio of Li 2 S to P 2 S 5 in Li-PS-based glass and Li-PS-based glass ceramics is the molar ratio of Li 2 S: P 2 S 5, preferably 60:40 to It is 90:10, more preferably 68:32 to 78:22.
- the lithium ion conductivity can be made high.
- the lithium ion conductivity can be preferably 1 ⁇ 10 -4 S / cm or more, and more preferably 1 ⁇ 10 -3 S / cm or more. There is no particular upper limit, but it is practical that it is 1 ⁇ 10 -1 S / cm or less.
- Li 2 S-P 2 S 5 Li 2 S-P 2 S 5 -LiCl, Li 2 S-P 2 S 5 -H 2 S, Li 2 S-P 2 S 5 -H 2 S-LiCl, Li 2 S-LiI-P 2 S 5 , Li 2 S-LiI-Li 2 O-P 2 S 5 , Li 2 S-LiBr-P 2 S 5 , Li 2 S-Li 2 O-P 2 S 5 , Li 2 S-Li 3 PO 4- P 2 S 5 , Li 2 S-P 2 S 5- P 2 O 5 , Li 2 S-P 2 S 5- SiS 2 , Li 2 S-P 2 S 5- SiS 2- LiCl, Li 2 S-P 2 S 5- SnS, Li 2 S-P 2 S 5- Al 2 S 3 , Li 2 S-GeS 2 , Li 2 S-GeS 2 , Li 2 S-Ge
- the mixing ratio of each raw material does not matter.
- an amorphization method can be mentioned.
- the amorphization method include a mechanical milling method, a solution method and a melt quenching method. This is because processing at room temperature is possible and the manufacturing process can be simplified.
- the oxide-based inorganic solid electrolyte contains oxygen atoms, has ionic conductivity of a metal belonging to Group 1 or Group 2 of the Periodic Table, and is electronically insulated. Those having sex are preferable.
- the oxide-based inorganic solid electrolyte preferably has an ionic conductivity of 1 ⁇ 10 -6 S / cm or more, more preferably 5 ⁇ 10 -6 S / cm or more, and 1 ⁇ 10 -5 S / cm or more. It is particularly preferable that it is / cm or more.
- the upper limit is not particularly limited, but it is practical that it is 1 ⁇ 10 -1 S / cm or less.
- Li xa La ya TiO 3 [xa satisfies 0.3 ⁇ xa ⁇ 0.7, and ya satisfies 0.3 ⁇ ya ⁇ 0.7.
- LLT Li xb Layb Zr zb M bb mb Onb
- M bb is one or more elements selected from Al, Mg, Ca, Sr, V, Nb, Ta, Ti, Ge, In and Sn.
- Xb satisfies 5 ⁇ xb ⁇ 10, yb satisfies 1 ⁇ yb ⁇ 4, zb satisfies 1 ⁇ zb ⁇ 4, mb satisfies 0 ⁇ mb ⁇ 2, and nb satisfies 5 ⁇ nb ⁇ 20. Satisfies.); Li xc Byc M cc zc Onc (M cc is one or more elements selected from C, S, Al, Si, Ga, Ge, In and Sn.
- Xc is 0 ⁇ xc ⁇ 5 , Yc satisfies 0 ⁇ yc ⁇ 1, zc satisfies 0 ⁇ zc ⁇ 1, nc satisfies 0 ⁇ nc ⁇ 6); Li xd (Al, Ga) yd (Ti, Ge) zd Si.
- Li xf Si yf O zf (xf satisfies 1 ⁇ xf ⁇ 5, yf satisfies 0 ⁇ yf ⁇ 3 , zf satisfies 1 ⁇ zf ⁇ 10);.
- Li xg S yg O zg (xg satisfies 1 ⁇ xg ⁇ 3, yg satisfies 0 ⁇ yg ⁇ 2, zg satisfies 1 ⁇ zg ⁇ 10.
- Li 7 La 3 Zr 2 O 12 (LLZ) having a garnet-type crystal structure.
- Phosphorus compounds containing Li, P and O are also desirable.
- lithium phosphate Li 3 PO 4
- LiPON in which a part of oxygen of lithium phosphate is replaced with nitrogen
- LiPOD 1 (D 1 is preferably Ti, V, Cr, Mn, Fe, Co, Ni, One or more elements selected from Cu, Zr, Nb, Mo, Ru, Ag, Ta, W, Pt and Au) and the like.
- LiA 1 ON (A 1 is one or more elements selected from Si, B, Ge, Al, C and Ga) and the like can also be preferably used.
- the halide-based inorganic solid electrolyte contains a halogen atom, has the conductivity of an ion of a metal belonging to Group 1 or Group 2 of the Periodic Table, and has electrons. A compound having an insulating property is preferable.
- the halide-based inorganic solid electrolyte is not particularly limited, and examples thereof include compounds such as Li 3 YBr 6 and Li 3 YCl 6 described in LiCl, LiBr, LiI, ADVANCED MATERIALS, 2018, 30, 1803075. Of these, Li 3 YBr 6 and Li 3 YCl 6 are preferable.
- the hydride-based inorganic solid electrolyte contains a hydrogen atom, has ionic conductivity of a metal belonging to Group 1 or Group 2 of the Periodic Table, and is electronically insulated. A compound having a property is preferable.
- the hydride-based inorganic solid electrolyte is not particularly limited, and examples thereof include LiBH 4 , Li 4 (BH 4 ) 3 I, and 3 LiBH 4- LiCl.
- the inorganic solid electrolyte is preferably particles.
- the particle size (volume average particle size) of the inorganic solid electrolyte is not particularly limited, but is preferably 0.01 ⁇ m or more, and more preferably 0.1 ⁇ m or more.
- the upper limit is preferably 100 ⁇ m or less, and more preferably 50 ⁇ m or less.
- the particle size of the inorganic solid electrolyte is measured by the following procedure. Inorganic solid electrolyte particles are prepared by diluting 1% by mass of a dispersion in a 20 mL sample bottle with water (heptane in the case of a water-unstable substance).
- the diluted dispersion sample is irradiated with 1 kHz ultrasonic waves for 10 minutes, and immediately after that, it is used for the test.
- data was captured 50 times using a laser diffraction / scattering particle size distribution measuring device LA-920 (trade name, manufactured by HORIBA) using a measuring quartz cell at a temperature of 25 ° C. Obtain the volume average particle size.
- JIS Japanese Industrial Standards
- Z 8828 2013 "Grain size analysis-Dynamic light scattering method" as necessary. Five samples are prepared for each level and the average value is adopted.
- the inorganic solid electrolyte may contain one kind or two or more kinds.
- the mass (mg) (grain amount) of the inorganic solid electrolyte per unit area (cm 2) of the solid electrolyte layer is not particularly limited. It can be appropriately determined according to the designed battery capacity, and can be, for example, 1 to 100 mg / cm 2 .
- the amount of the inorganic solid electrolyte is preferably such that the total amount of the active material and the inorganic solid electrolyte is in the above range.
- the content of the inorganic solid electrolyte in the composition containing the inorganic solid electrolyte is not particularly limited, but is 50% by mass or more at 100% by mass of the solid content in terms of binding property and dispersibility. Is more preferable, 70% by mass or more is more preferable, and 90% by mass or more is particularly preferable. From the same viewpoint, the upper limit is preferably 99.9% by mass or less, more preferably 99.5% by mass or less, and particularly preferably 99% by mass or less.
- the content of the inorganic solid electrolyte in the inorganic solid electrolyte-containing composition is such that the total content of the active material and the inorganic solid electrolyte is in the above range. Is preferable.
- the solid content refers to a component that does not disappear by volatilizing or evaporating when the inorganic solid electrolyte-containing composition is dried at 150 ° C. for 6 hours under an atmospheric pressure of 1 mmHg and a nitrogen atmosphere. .. Typically, it refers to a component other than the dispersion medium described later.
- the inorganic solid electrolyte-containing composition of the present invention contains composite polymer particles as a binder for binding solid particles at least in the constituent layers of an all-solid secondary battery, and further contains various binders usually used as appropriate. You may.
- the composite polymer particles (composite polymer particles of the present invention) contained in the inorganic solid electrolyte-containing composition of the present invention will be described.
- the composite polymer particles of the present invention contain at least two types of polymers, and at least one of these polymers has a bond (sometimes referred to as bond (I)) represented by the formula (1) described later as a main chain.
- the composite polymer particles have a property of dispersing in a dispersion medium containing an organic solvent having a ClogP value of 1.0 or more.
- dispersing in a dispersion medium means dispersing in a dispersion medium as normal particles in a solid state, and includes an embodiment in which a part of the particles is dissolved in the dispersion medium.
- the particle size of the composite polymer particles in the dispersed state is the same as the average primary particle size described later.
- the composite polymer particles of the present invention can be used in combination with solid particles such as an inorganic solid electrolyte in an inorganic solid electrolyte-containing composition for an all-solid secondary battery to improve dispersibility in the inorganic solid electrolyte-containing composition (slurry). Can be enhanced. In addition, it contributes to reducing the resistance and strengthening the binding property of the constituent layer formed of the composition containing the inorganic solid electrolyte, and imparts excellent cycle characteristics and low resistance to the all-solid secondary battery provided with this constituent layer.
- the composite polymer particles of the present invention are composite particles in which at least two types of polymers are mixed.
- the composite polymer particles are not a mere mixture (including coprecipitates, aggregates, and aggregates) of a plurality of polymer particles, but a composite formed by integrating at least two kinds of polymers (or particles).
- a particle which is usually recognizable as one particle.
- the integration of the polymer (or particles) is not particularly limited, and examples thereof include mechanical, physical or chemical interactions or bonds, and structural integration.
- Structural integration includes, for example, a core-shell structure in which a specific polymer is coated (incorporated) with another polymer, a microphase-separated structure, a mutual penetration polymer network (IPN) structure, and the like.
- IPN mutual penetration polymer network
- the polymer (or particles) forming the core and the polymer (or particles) forming the shell may exhibit the above-mentioned interaction or form a bond.
- the polymer (core layer) forming the core may be at least partially coated with the polymer (shell layer) forming the shell, and the coating amount of the core is not particularly limited.
- the layer thickness of the shell layer is not particularly limited.
- the coating amount and the layer thickness of the shell layer can be specified by, for example, the mass ratio of the polymer (or particles) forming the core and the polymer (or particles) forming the shell, and the mass ratio thereof. Is represented by [polymer forming the core: polymer forming the shell], for example, it is preferably 30 to 99: 70 to 1, more preferably 70 to 99: 30 to 1, and 80 to 80 to. It is more preferably 99:20 to 1.
- the polymer forming the composite polymer particles may be at least 2 types, preferably 2 to 5 types, and more preferably 2 or 3 types.
- the combination of at least two kinds of polymers is not particularly limited, and may be a combination of the same kind of polymers or a combination of different kinds of polymers, and a combination of the same kind of polymers is preferable.
- the details of the polymer forming the composite polymer particles will be described later, but at least one, preferably one or two, more preferably two of the plurality of polymers forming the composite polymer particles will be described later in the formula (1). It is a polymer having a bond (I) represented by (I) in the main chain.
- the solid particles and the like can be adhered to the solid particles and the like and firmly bonded to each other.
- the number of bonds (I) incorporated in the main chain may be at least one, and is appropriately set according to the degree of polymerization of the polymer, the mass average molecular weight, and the like.
- the main chain of a polymer means a linear molecular chain in which all other molecular chains constituting the polymer can be regarded as a branched chain or a pendant with respect to the main chain. Although it depends on the mass average molecular weight of the molecular chain regarded as a branched chain or a pendant chain, the longest chain among the molecular chains constituting the polymer is typically the main chain. However, the terminal group of the polymer terminal is not included in the main chain. Further, the side chain of the polymer means a molecular chain other than the main chain, and includes a short molecular chain and a long molecular chain.
- SP value (sometimes referred to as highly polar structural unit.) 20.5J 0.5 / cm 1.5 or 40 J 0.5 / cm 1.5 or less is a constituent unit It is preferable to have it.
- the SP value of the highly polar constituent unit is preferably 21.0 to 35.0J 0.5 / cm 1.5 in terms of binding properties, and is 23.0 to 30.0J 0.5 / cm 1 It is more preferably .5.
- the polymer having a highly polar constituent unit is preferably at least one kind of polymer among the polymers forming the composite polymer particles, preferably one kind or two kinds of polymers, and more preferably all polymers. preferable.
- the highly polar constituent unit of each polymer may be one kind or two or more kinds, and is appropriately set.
- SP value (sometimes referred to as a low polarity structural unit.) 15J 0.5 / cm 1.5 or 20.5J 0.5 / cm 1.5 less than a is a constituent unit It is preferable to have it. Since the polymer forming the composite polymer particles has a low polar constituent unit, the dispersibility of the composite polymer particles with respect to the dispersion medium is increased, and the composite polymer particles can be adhered to the solid particles as a particle shape.
- the SP value of the low-polarity structural unit is preferably 17.0 to 20.5J 0.5 / cm 1.5 , and 18.0 to 20.0J 0.5 / cm 1 in terms of binding properties. It is more preferably .5.
- the polymer having the low polar constituent unit is preferably at least one kind of polymer among the polymers forming the composite polymer particles, and more preferably one kind of polymer.
- the low-polarity structural unit of each polymer may be one type or two or more types, and is appropriately set.
- At least one of the polymers forming the composite polymer particles preferably contains both high-polarity building blocks and low-polarity building blocks, while the remaining polymers have high-polarity building blocks and low-polarity building blocks. It may or may not have units.
- the polymer present on the surface of the composite polymer particles preferably has a low-polarity constitutional unit in terms of dispersibility, and preferably contains both a low-polarity constitutional unit and a high-polarity constitutional unit. More preferred.
- the polymer forming the composite polymer particles preferably contains 20 to 99.5% by mass of highly polar constituent units in the total polymer.
- the highly polar constituent units present in all the polymers contained in the composite polymer particles are preferably 20 to 99.5% by mass with respect to the total mass of all the polymers.
- the composite polymer particles contain the highly polar constituent units in the above-mentioned content, strong adhesion to the solid particles (bonding property of the solid particles and the like) can be realized.
- the content of the highly polar constituent unit in the total polymer is more preferably 70 to 99.5% by mass, further preferably 85 to 99.3% by mass.
- the polymer forming the composite polymer particles preferably contains 0.5 to 80% by mass of low-polarity constituent units in the total polymer.
- the low-polarity constituent units present in all the polymers contained in the composite polymer particles are preferably 0.5 to 80% by mass with respect to the total mass of all the polymers.
- the composite polymer particles exhibit high dispersibility by containing the low-polarity structural unit in the above-mentioned content.
- the composite polymer particles of the present invention which form a complex with a plurality of polymers, can maintain high dispersibility even if the content of low-polarity constituent units is reduced.
- the content of the low-polarity constituent unit in the total polymer is more preferably 0.5 to 30% by mass, and 0.7 to 0.7 to that the binding property of solid particles and the like can be reinforced while maintaining high dispersibility. 15% by mass is more preferable.
- the polymer forming the composite polymer particles preferably contains high-polarity structural units in the above range and low-polarity constitutional units in the above range among all the polymers.
- the content ratio of the high-polarity structural unit to the low-polarity structural unit is not particularly limited, and is preferably 1 to 150, for example, 4 to 150. 150 is more preferable.
- the high-polarity structural unit and the low-polarity structural unit are structural units contained in the chemical structure of the polymer and refer to convenient units for calculating the SP value.
- This structural unit may be the same as or different from the component derived from the raw material compound, such as the component represented by the formula (I-1) described later.
- the SP value when the SP value is calculated, when the polymer (segment) is a chain polymerization polymer (segment), it has the same constituent unit as the constituent component derived from the raw material compound, but the polymer (segment) has the following formula.
- the polymer (segment) has the bond (I) represented by (1), the unit is different from the constituent components derived from the raw material compound.
- the structural unit for specifying the SP value is defined as follows.
- an -O- group is bonded to one -NH-CO- group with respect to the component represented by the following formula (I-1) derived from the polyisocyanate compound.
- the remaining -NH-CO- group is removed (unit having one urethane bond).
- a constituent unit derived from the polyol compound a —CO—NH— group is bonded to one —O— group to the constituent component represented by the following formula (I-3) derived from the polyol compound.
- the remaining —O— group is removed (unit having one urethane bond).
- the constituent unit is determined in the same manner as that of polyurethane.
- the SP measurement method (calculation method) for each structural unit will be described later.
- the polymer contained in the composite polymer particles preferably has the above-mentioned structural units when focusing on the structural units, but preferably contains at least one low-polarity polymer and at least one high-polarity polymer when focusing on the polymer.
- Low polar polymer is preferably a polymer with SP value 15 J 0.5 / cm 1.5 or 20.5J 0.5 / cm structural units is less than 1.5 5 mass% or more, more preferably It has a structural unit having an SP value of 20.5J 0.5 / cm 1.5 or more and 40J 0.5 / cm 1.5 or less.
- the highly polar polymer is preferably a polymer having 90% by mass or more of structural units having an SP value of 20.5J 0.5 / cm 1.5 or more and 40J 0.5 / cm 1.5 or less, and has an SP value of 15J. It may have a structural unit of 0.5 / cm 1.5 or more and 20.5J 0.5 / cm less than 1.5.
- a certain polymer corresponds to both the low-polarity polymer and the high-polarity polymer defined above, they are distinguished by the content of the constituent components described later in each polymer, if necessary, and further described later. It is decided to distinguish by the SP value of each polymer.
- each structural unit corresponds to the above-mentioned low-polarity structural unit and high-polarity structural unit.
- the low-polarity polymer and the high-polarity polymer contained in the composite polymer particles are not particularly limited, but are preferably 1 to 3 types, and more preferably 1 type or 2 types, respectively.
- the content of the low-polarity constituent unit is not particularly limited as long as it is 5% by mass or more in terms of dispersibility, but it is low in all polymers forming composite polymer particles together with the high-polarity polymer. It is preferable to set the range so as to satisfy the content of the polar constituent unit.
- the content of the low polar constituent unit in one kind of low polar polymer is preferably 10 to 99% by mass, more preferably 40 to 90% by mass, still more preferably 70 to 85% by mass in terms of dispersibility. ..
- one type of low-polarity polymer has a high-polarity constituent unit
- its content is not particularly limited, but satisfies the content of the high-polarity constituent unit in all the polymers forming the composite polymer particles together with the high-polarity polymer. It is preferably set in the range.
- the content of the highly polar constituent unit in one kind of low-polarity polymer is more preferably 1 to 90% by mass, further preferably 10 to 60% by mass, and particularly preferably 15 to 30% by mass.
- the content of the highly polar constituent unit is not particularly limited as long as it is 90% by mass or more in terms of binding property, but all the polymers forming composite polymer particles together with the low polar polymer.
- the content of the highly polar constituent unit in one kind of highly polar polymer is more preferably 95% by mass or more.
- the content thereof is not particularly limited, and is a range that satisfies the content of low-polarity structural units in all the polymers forming composite polymer particles together with the low-polarity polymer. Is preferably set to, for example, 10% by mass or less is more preferable, 5% by mass or less is further preferable, and 0% by mass can be set.
- the low-polarity polymer and the high-polarity polymer are determined relative to the plurality of polymers contained in the composite polymer particles.
- the SP value as a low-polarity polymer is, for example, not particularly limited, in terms of dispersibility, and further, in terms of dispersibility, the resistance is reduced or formed by adhesion in the form of particles.
- in terms of enhancement of adhesive strength is preferably from 15.0 ⁇ 23.5J 0.5 / cm 1.5, more preferably from 15.0 ⁇ 20.5J 0.5 / cm 1.5, It is more preferably 17.5 to 20.5J 0.5 / cm 1.5 , and particularly preferably 18.0 to 20.0J 0.5 / cm 1.5.
- the SP value as a high-polarity polymer shows a higher SP value than the low-polarity polymer used in combination.
- 20.6 to 40.0 J 0.5 / cm 1 It is preferably .5 , more preferably 20.6 to 35.0J 0.5 / cm 1.5 , and further preferably 21.0 to 35.0J 0.5 / cm 1.5. It is preferable, and it is particularly preferable that it is 23.0 to 30.0 J 0.5 / cm 1.5.
- the SP value of the structural unit (low-polarity structural unit, high-polarity structural unit, etc.) is obtained as follows. First, for the polymer, as described above, the structural unit for which the SP value is specified is determined. Then, unless otherwise specified, obtaining the SP value of each structural unit by Hoy method (H.L.Hoy JOURNAL OF PAINT TECHNOLOGY Vol.42, No.541,1970,76-118, and POLYMER HANDBOOK 4 th, 59 Chapter , VII, page 686 (see formula below in Table 5, Table 6, and Table 6). The unit is J 1/2 cm -3/2 .
- SP value of polymer It is calculated from the following formula using the structural unit determined as described above and the obtained SP value.
- SP p 2 (SP 1 2 x W 1 ) + (SP 2 2 x W 2 ) + ...
- SP 1 , SP 2 Indicates the SP value of the constituent unit
- W 1 , W 2 Indicates the mass fraction of the constituent unit.
- the mass fraction of the constituent unit is the mass fraction in the polymer of the constituent component (raw material compound that derives this constituent) corresponding to the constituent unit.
- the content thereof is preferably 1 to 70% by mass, and 1 to 50% by mass in terms of low resistance and binding property. Is more preferable, 1 to 20% by mass is further preferable, and 1 to 10% by mass is particularly preferable.
- the content thereof is preferably 30 to 99% by mass, more preferably 50 to 99% by mass in terms of binding properties. 80 to 99% by mass is more preferable, and 90 to 95% by mass is particularly preferable.
- the content of both polymers is preferably set in the above range, but the ratio of the content of the high polar polymer to the content of the low polar polymer (high polarity).
- the polymer content / low polar polymer content) is, for example, preferably 1 to 99, more preferably 9 to 99.
- the polymer present on the surface of the composite polymer particles may be a high-polarity polymer or a low-polarity polymer, but is preferably a low-polarity polymer in terms of dispersibility.
- the polymer forming the shell may be a high-polarity polymer or a low-polarity polymer, but preferably contains a low-polarity polymer.
- the polymer existing inside the composite polymer particles may be a high-polarity polymer or a low-polarity polymer, but preferably contains a high-polarity polymer.
- At least one of the high-polarity polymer and the low-polarity polymer is preferably a polymer having a bond (I) in the main chain, and at least the high-polarity polymer is a polymer having a bond (I) in the main chain. More preferred. It is also one of the preferred embodiments that both the high-polarity polymer and the low-polarity polymer are polymers having a bond (I) in the main chain. Further, the polymer present on the surface of the composite polymer particles may be a polymer having a bond (I) or a polymer having no bond (I).
- the polymer existing inside the composite polymer particles may be a polymer having no bond (I), but a polymer having a bond (I) is preferable. From the viewpoint of further strengthening the binding property, it is preferable that both the polymer present on the surface of the composite polymer particles and the polymer existing inside the composite polymer particles are polymers having a bond (I).
- At least one of the polymers contained in the composite polymer particles has an acidic functional group or a basic functional group.
- These functional groups exhibit adsorptivity (interaction) on the surface of the solid particle and appropriately on the surface of the current collector, and reinforce the binding property of the solid particle.
- the interaction exhibited by the functional group is not particularly limited, but is, for example, hydrogen bond, acid-base ionic bond, covalent bond, ⁇ - ⁇ interaction with aromatic ring, or hydrophobic-hydrophobic interaction. Examples include those due to interaction.
- the functional groups interact, the chemical structure of the functional groups may or may not change. For example, in the above-mentioned ⁇ - ⁇ interaction or the like, the functional group usually does not change and the structure as it is is maintained.
- an active hydrogen such as a carboxylic acid group is usually released as an anion (the functional group is changed) to bond with a solid electrolyte or the like.
- This interaction contributes to the adsorption of the fibrous binder with the solid particles during or during the preparation of the solid electrolyte composition.
- the functional groups also interact with the surface of the current collector.
- the acidic functional group is not particularly limited, a carboxylic acid group (-COOH), a sulfonic acid group (sulfo group: -SO 3 H) and phosphate groups (phospho group: -OPO (OH) 2, etc.) is preferably mentioned Be done.
- the acidic functional group may be a salt thereof or an ester.
- the salt include sodium salt, calcium salt and the like.
- the ester include alkyl esters and aryl esters. In the case of an ester, the number of carbon atoms is preferably 1 to 24, more preferably 1 to 12, and particularly preferably 1 to 6.
- the basic functional group is not particularly limited, and examples thereof include an amino group and a pyridine group, and an amino group is particularly preferable.
- the amino group is not particularly limited, and examples thereof include an amino group having 0 to 20 carbon atoms.
- Amino groups include alkylamino groups and arylamino groups.
- the number of carbon atoms of the amino group is preferably 0 to 12, more preferably 0 to 6, and even more preferably 0 to 2.
- Examples of the amino group include amino, N, N-dimethylamino, N, N-diethylamino, N-ethylamino, anilino and the like.
- the amino group may form a salt.
- the acidic functional group and the basic functional group are preferably an acidic functional group, more preferably a carboxylic acid group, a sulfonic acid group, and a phosphoric acid group, and further preferably a carboxylic acid group, in terms of binding properties.
- the number of the functional groups contained in one molecule of the polymer may be one or more, and preferably has a plurality of functional groups. Further, the number of types of functional groups is not particularly limited as long as it has at least one functional group, and may be one type or two or more types.
- the plurality of polymers contained in the composite polymer particles are not particularly limited, and examples thereof include those usually used as a binder for an all-solid-state secondary battery, and at least one of them is a bond represented by the following formula (1). It is a polymer having (I) in the main chain.
- X and Y independently represent atoms belonging to Group 15 or Group 16 of the Periodic Table.
- Z indicates an atom belonging to Group 14 or Group 15 of the Periodic Table.
- the atoms belonging to Group 14 of the Periodic Table include, for example, carbon, silicon, germanium, tin and the like, and the atoms belonging to Group 15 include, for example, nitrogen, phosphorus and arsenic.
- Etc. examples of the atoms belonging to the 16th group include atoms such as oxygen, sulfur, and selenium.
- the atom that can be taken as X is not particularly limited, but an atom belonging to Group 16 is preferable, and an oxygen atom is more preferable.
- this atom is a hydrogen atom or a substituent depending on its valence (unless otherwise specified, the substituent is preferably a group selected from the substituent Z described later).
- Preferred examples of this substituent include an alkyl group and an aryl group.
- the atom that can be taken as Y is not particularly limited and is appropriately selected according to the type of polymer, and each atom of nitrogen, phosphorus, oxygen or sulfur is preferable, and a nitrogen atom or an oxygen atom is more preferable.
- Y takes an atom belonging to Group 15, this atom has a hydrogen atom, an alkyl group or an aryl group.
- the alkyl group and aryl group that X or Y can have are synonymous with the alkyl group or aryl group of the substituent Z.
- Examples of the atom that can be taken as Z include an atom that can be taken as tetravalent, and an atom belonging to Group 14 is preferable, and a carbon atom is more preferable.
- a phosphorus atom or the like can be taken as an atom belonging to Group 15. In this case, it may have a hydrogen atom or a substituent depending on the valence of the atom.
- the combination of X to Z is not particularly limited, and examples thereof include combinations of the above-mentioned atoms that can be preferably taken by each, and more specifically, combinations that form bonds described later.
- “having a bond (I) in the main chain” is represented by an embodiment in which the bond represented by the formula (1) is held alone (as is) in the main chain and the formula (1). It includes both aspects of having a bond in the main chain (as a bond containing bond (I)) as another bond formed with another atom or group of atoms.
- the other atoms or groups of atoms are not particularly limited, and examples thereof include one or more atoms belonging to groups 14, 15 and 16 of the periodic table, and hydrogen atoms and the like.
- the bond containing the bond (I) may have a linear or branched chain structure, or may have a ring structure.
- the ring structure containing the bond (I) is not particularly limited, and examples thereof include an imide ring, an imidazole ring, and a triazole ring.
- the mode in which the bond including the bond (I) is incorporated into the main chain is not particularly limited, and a mode in which at least one of Y and Z of the bond (I) becomes a bond and is incorporated into the main chain, another atom or Examples thereof include a mode in which the atomic group serves as a bond and is incorporated into the main chain.
- the bond containing the bond (I) is preferably a urethane bond, a urea bond, an amide bond, an imide bond, an ester bond, a carbonate bond, a thiourea bond, a thiourethane bond, or an imidazole bond.
- at least one of the triazole bonds is mentioned, and urethane bonds, urea bonds, amide bonds, ester bonds or carbonate bonds are preferable.
- the thiourethane bond includes three types of bonds in which at least one oxygen atom of the carbonyl group (-CO-) and the oxy group (-O-) in the urethane bond is replaced with a sulfur atom.
- the imidazole bond and the triazole bond mean a divalent cyclic bond (linking group) formed by removing two hydrogen atoms from the imidazole ring or the triazole ring, and the hydrogen atom to be removed is not particularly limited. It is preferably a hydrogen atom bonded to a carbon atom.
- the polymer having the bond (I) in the main chain is not particularly limited.
- the main chain includes a polymer having at least one bond selected from urethane bond, urea bond, amide bond, imide bond, ester bond and carbonate bond.
- the bond (I) contained in the main chain contributes to the improvement of the binding property of solid particles and the like in the constituent layers of the all-solid-state secondary battery and the like by hydrogen-bonding between the polymer molecules or within the molecule.
- these bonds (I) form hydrogen bonds in the polymer, the hydrogen bonds may be formed between the bonds (I) and with the bond (I) and the other bonds (I) of the main chain. May be formed with.
- the bond (I) preferably has a hydrogen atom forming a hydrogen bond (Y of the bond (I) has a hydrogen atom) in that a hydrogen bond can be formed with each other.
- the bond (I) is not particularly limited as long as it is contained in the main chain of the polymer, and is either a mode contained in a component (repeating unit) and / or a mode included as a bond connecting different components. It may be.
- the bond (I) contained in the main chain is not limited to one type, and may be two or more types, preferably 1 to 6 types, and more preferably 1 to 4 types.
- the binding mode of the main chain is not particularly limited, and two or more kinds of bindings (I) may be randomly held, and the segment having a specific binding and the segment having another binding are segmented. It may be a broken main chain.
- the polymer having the bond (I) in the main chain is not particularly limited, but specifically, polyurethane, polyurea, polyamide, polyimide, polyester, polycarbonate, polythiourea, polythiourethane, and imidazole bond or triazole bond in the main chain.
- examples thereof include each polymer having a polymer (for example, polyimidazole), or a copolymer thereof.
- the copolymer may be a block copolymer having each of the above polymers as a segment, or a random copolymer in which each component constituting two or more of the above polymers is randomly bonded.
- the main chain having the bond (I) is not particularly limited, but a main chain having at least one segment of urethane bond, urea bond, amide bond, imide bond, ester bond and polycarbonate is preferable, and polyamide, polyurea or A main chain made of polyurethane is more preferable, and a main chain made of polyurethane is further preferable.
- the main chain forming the polymer having the bond (I) contains two or more kinds of constituents represented by any of the following formulas (I-1) to (I-4) (preferably 2 to 8 kinds, more preferably).
- Is a main chain composed of 2 to 4 types, more preferably 3 or 4 types), or a carboxylic acid dianhydride represented by the following formula (I-5) and a configuration represented by the following formula (I-6).
- a main chain formed by sequentially polymerizing a diamine compound that derives a component is preferable.
- the polymer having such a main chain include polyurethane, polyurea, polyamide, polyimide, polyester and polycarbonate. The combination of each component is appropriately selected according to the polymer species.
- constituents formula (I-3) as a constituent or R P1 is represented by the following formula was introduced oxygen atoms at both ends of R P1 (I-2)
- Examples thereof include a main chain having a constituent component represented by the following formula (I-2) and a constituent component represented by the following formula (I-3).
- Thiourea has a structural unit in which an oxygen atom in a component represented by the following formula (I-1) is changed to a sulfur atom
- thiourethane has the following formula (I-1) and / or formula (I-3). It has a structural unit in which an oxygen atom in a component represented by) is changed to a sulfur atom.
- One kind of constituent component used for the combination of constituent components means a constituent component represented by any one of the following formulas, and even if two kinds of constituent components represented by one of the following formulas are included. It is not interpreted as two kinds of constituents.
- RP1 and RP2 each represent a molecular chain having a (mass average) molecular weight of 20 or more and 200,000 or less.
- the molecular weight of this molecular chain cannot be uniquely determined because it depends on the type and the like, but for example, 30 or more is preferable, 50 or more is more preferable, 100 or more is further preferable, and 150 or more is particularly preferable.
- the upper limit is preferably 100,000 or less, more preferably 10,000 or less.
- the molecular weight of the molecular chain is measured for the starting compound before it is incorporated into the main chain of the polymer.
- the molecular chains that can be taken as RP1 and RP2 are not particularly limited, but hydrocarbon chains, polyalkylene oxide chains, polycarbonate chains or polyester chains are preferable, hydrocarbon chains or polyalkylene oxide chains are more preferable, and hydrocarbon chains. , Polyester oxide chains or polypropylene oxide chains are more preferred.
- the hydrocarbon chain that can be taken as RP1 and RP2 means a chain of hydrocarbons composed of carbon atoms and hydrogen atoms, and more specifically, at least two compounds composed of carbon atoms and hydrogen atoms. It means a structure in which an atom (for example, a hydrogen atom) or a group (for example, a methyl group) is eliminated.
- the hydrocarbon chain also includes a chain having a group containing an oxygen atom, a sulfur atom or a nitrogen atom in the chain, for example, a hydrocarbon group represented by the following formula (M2).
- M2 hydrocarbon group represented by the following formula
- This hydrocarbon chain may have a carbon-carbon unsaturated bond and may have a ring structure of an aliphatic ring and / or an aromatic ring. That is, the hydrocarbon chain may be a hydrocarbon chain composed of a hydrocarbon selected from an aliphatic hydrocarbon and an aromatic hydrocarbon.
- Such a hydrocarbon chain may satisfy the above molecular weight, and both a chain composed of a low molecular weight hydrocarbon group and a hydrocarbon chain composed of a hydrocarbon polymer (also referred to as a hydrocarbon polymer chain).
- hydrocarbon chains A low molecular weight hydrocarbon chain is a chain composed of ordinary (non-polymerizable) hydrocarbon groups, and examples of the hydrocarbon groups include aliphatic or aromatic hydrocarbon groups, and specific examples thereof.
- This hydrocarbon chain may have a polymerized chain (eg, (meth) acrylic polymer) as a substituent.
- the aliphatic hydrocarbon group is not particularly limited, and for example, from a hydrogen-reduced product of an aromatic hydrocarbon group represented by the following formula (M2), or a partial structure of a known aliphatic diisosoane compound (for example, from isophorone). Narumoto) and the like.
- the hydrocarbon group contained in each of the constituent components of each example described later can also be mentioned.
- the aromatic hydrocarbon group include a hydrocarbon group contained in each of the constituent components described below, and an arylene group (for example, one or more hydrogen atoms from the aryl group listed in the substituent Z described later).
- the removed group specifically a phenylene group, a trilene group or a xylylene group) or a hydrocarbon group represented by the following formula (M2) is preferable.
- X represents a single bond, -CH 2- , -C (CH 3 ) 2- , -SO 2- , -S-, -CO- or -O-, and is a viewpoint of binding property. Therefore, -CH 2- or -O- is preferable, and -CH 2- is more preferable.
- the above-mentioned alkylene group and alkylene group exemplified here may be substituted with a substituent Z, preferably a halogen atom (more preferably a fluorine atom).
- RM2 to RM5 each represent a hydrogen atom or a substituent, and a hydrogen atom is preferable.
- the substituents that can be taken as RM2 to RM5 are not particularly limited, and examples thereof include a substituent Z described later.
- a halogen atom e.g., Fluorine atom, chlorine atom, bromine atom
- the ⁇ N ( RM6 ) 2 is an alkylamino group (preferably 1 to 20 carbon atoms, more preferably 1 to 6 carbon atoms) or an arylamino group (preferably 6 to 40 carbon atoms, 6 to 20 carbon atoms). More preferred).
- a hydrocarbon polymer chain may be a polymer chain in which (at least two) polymerizable hydrocarbons are polymerized, and may be a chain composed of a hydrocarbon polymer having a larger number of carbon atoms than the above-mentioned low molecular weight hydrocarbon chain.
- the chain is not particularly limited, but is preferably a chain composed of a hydrocarbon polymer composed of 30 or more, more preferably 50 or more carbon atoms.
- the upper limit of the number of carbon atoms constituting the hydrocarbon polymer is not particularly limited, and can be, for example, 3,000.
- the hydrocarbon polymer chain is preferably a chain composed of an aliphatic hydrocarbon having a main chain satisfying the above number of carbon atoms, and is composed of an aliphatic saturated hydrocarbon or an aliphatic unsaturated hydrocarbon. It is more preferable that the chain is made of a polymer (preferably an elastomer). Specific examples of the polymer include a diene polymer having a double bond in the main chain and a non-diene polymer having no double bond in the main chain.
- diene polymer examples include a styrene-butadiene copolymer, a styrene-ethylene-butadiene copolymer, a copolymer of isobutylene and isoprene (preferably butyl rubber (IIR)), a butadiene polymer, an isoprene polymer, and ethylene.
- IIR butyl rubber
- non-diene polymer include olefin polymers such as ethylene-propylene copolymer and styrene-ethylene-butylene copolymer, and hydrogen-reduced products of the above-mentioned diene polymer.
- the hydrocarbon to be a hydrocarbon chain preferably has a reactive group at its terminal, and more preferably has a polycondensable terminal reactive group.
- the polycondensation or polyaddition-capable terminal reactive group forms a group bonded to RP1 or RP2 of each of the above formulas by polycondensation or polyaddition.
- Examples of such a terminal reactive group include an isocinate group, a hydroxy group, a carboxy group, an amino group and an acid anhydride, and a hydroxy group is preferable.
- hydrocarbon polymers having terminal reactive groups include, under the trade names, NISSO PB series (manufactured by Nippon Soda Co., Ltd.), Claysol series (manufactured by Tomoe Kosan Co., Ltd.), PolyVEST-HT series (manufactured by Ebonic), and the like.
- Poly-bd series manufactured by Idemitsu Kosan Co., Ltd.
- poly-ip series manufactured by Idemitsu Kosan Co., Ltd.
- EPOL manufactured by Idemitsu Kosan Co., Ltd.
- Polytail series manufactured by Mitsubishi Chemical Co., Ltd.
- polyalkylene oxide chain examples include chains composed of known polyalkyleneoxy groups.
- the number of carbon atoms of the alkyleneoxy group in the polyalkyleneoxy chain is preferably 1 to 10, more preferably 1 to 6, and further preferably 2 or 3 (polyethylene oxy chain or polypropylene oxy chain).
- the polyalkyleneoxy chain may be a chain composed of one type of alkyleneoxy group or a chain composed of two or more types of alkyleneoxy groups (for example, a chain composed of an ethyleneoxy group and a propyleneoxy group).
- Examples of the polycarbonate chain or polyester chain include known chains made of polycarbonate or polyester.
- the polyalkyleneoxy chain, the polycarbonate chain, or the polyester chain each preferably has an alkyl group (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms) at the terminal.
- Polyalkyleneoxy chain can be taken as R P1 and R P2, end of the polycarbonate chain and a polyester chain, appropriately changing the constituents as R P1 and R P2 are represented by the formulas above the embeddable ordinary chemical structure be able to.
- polyalkyleneoxy chain terminal oxygen atoms are incorporated as R P1 or R P2 of the removed with the component.
- RN is a hydrogen atom, inside or at the end of the alkyl group contained in the molecular chain. It may have an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 10 carbon atoms).
- RP1 and RP2 are divalent molecular chains, but at least one hydrogen atom is substituted with -NH-CO-, -CO-, -O-, -NH- or -N ⁇ .
- the molecular chain may be trivalent or higher.
- R P1 among the molecular chain is preferably a hydrocarbon is a chain, more preferably a hydrocarbon chain of low molecular weight, more preferably a hydrocarbon chain comprised of hydrocarbon groups aliphatic or aromatic, Hydrocarbon chains consisting of aromatic hydrocarbon groups are particularly preferred.
- RP2 is preferably a low molecular weight hydrocarbon chain (more preferably an aliphatic hydrocarbon group) or a molecular chain other than a low molecular weight hydrocarbon chain, preferably a low molecular weight hydrocarbon chain and a low molecular weight hydrocarbon chain.
- a mode containing each molecular chain other than the hydrocarbon chain having a molecular weight is also one of the preferred modes.
- formula (I-3), component represented by any one of formula (I-4) and formula (I-6) are components R P2 is a hydrocarbon group chain of low molecular weight And, RP2 contains at least two kinds of constituents which are molecular chains other than low molecular weight hydrocarbon chains.
- constituent components represented by the above formula (I-1) are shown below and Examples.
- Examples of the raw material compound (diisocyanate compound) for deriving the constituent component represented by the above formula (I-1) include the diisocyanate compound represented by the formula (M1) described in International Publication No. 2018/20827. Specific examples thereof include Polymeric 4,4'-diphenylmethane diisocyanate and the like.
- the constituent component represented by the formula (I-1) and the raw material compound derived from the constituent component are not limited to those described in the following specific examples and the above documents.
- the raw material compound (carboxylic acid or its acid chloride, etc.) that derives the constituents represented by the above formula (I-2) is not particularly limited, and is described in, for example, paragraph [0074] of International Publication No. 2018/020827. , Carboxylic acid or acid chloride compounds and specific examples thereof.
- the constituents represented by the above formula (I-3) or formula (I-4) are shown below and Examples.
- the raw material compound (diol compound or diamine compound) for deriving the constituent component represented by the above formula (I-3) or formula (I-4) is not particularly limited, and for example, International Publication No. 2018 / Examples of each compound described in 020827 and specific examples thereof are given, and dihydroxyoxamid is also mentioned.
- the constituent components represented by the formula (I-3) or the formula (I-4) and the raw material compounds derived thereto are not limited to those described in the following specific examples, examples and the above documents.
- the number of repetitions is an integer of 1 or more, and is appropriately set within a range satisfying the molecular weight or the number of carbon atoms of the molecular chain.
- R P3 represents an aromatic or aliphatic linking group (tetravalent), preferred linking group represented by any one of the following formulas (i) ⁇ (iix).
- X 1 represents a single bond or a divalent linking group.
- divalent linking group an alkylene group having 1 to 6 carbon atoms (for example, methylene, ethylene, propylene) is preferable.
- propylene 1,3-hexafluoro-2,2-propanediyl is preferable.
- RX and RY represent hydrogen atoms or substituents, respectively.
- * indicates the binding site with the carbonyl group in formula (I-5).
- the substituents can take as R X and R Y, not particularly limited, include later-described substituent Z, an alkyl group (carbon number is preferably from 1 to 12, more preferably 1 to 6, 1-3 More preferably) or an aryl group (the number of carbon atoms is preferably 6 to 22, more preferably 6 to 14, and even more preferably 6 to 10).
- the carboxylic acid dianhydride represented by the above formula (I-5) and the raw material compound (diamine compound) leading to the constituent components represented by the above formula (I-6) are not particularly limited, and for example, Examples thereof include the compounds described in WO2018 / 020827 and WO2015 / 046313 and specific examples thereof.
- R P1 , R P2 and R P3 may each have a substituent.
- substituent group is not particularly limited, for example, include substituents Z to be described later, the substituents which can take as R M2 are preferably exemplified.
- the polymer having the bond (I), particularly the polymer having the urethane bond in the main chain, has the above formula (I-3) or the formula (I-3) or the formula in addition to the constituents represented by the formula (I-1) as shown below. It is preferable to have (I-4), and it is more preferable to have a constituent component represented by the formula (I-3). Component as the component of the formula (I-3), is properly selected in view of SP value, etc.
- R P2 is the above described hydrocarbon polymer chain as a molecular chain as (preferably constituents represented by the following formula (I-3C)), R P2 is a hydrocarbon group of low molecular weight chain (functional groups, preferably a group, or both have an ether group or carbonyl group, and more A constituent component (preferably having a group containing a carboxy group) (preferably a constituent component represented by the following formula (I-3A)) and a constituent component in which RP2 is the polyalkylene oxide chain as a molecular chain (preferably). Is preferably contained at least one of the constituents represented by the following formula (I-3B)).
- a polymer having a urethane bond in the main chain as a low-polarity polymer has a component in which RP2 is the above-mentioned hydrocarbon polymer chain as a molecular chain in addition to the component represented by the formula (I-1). (Preferably, it has a constituent component represented by the following formula (I-3C)).
- the polymer having a urethane bond in the main chain as a highly polar polymer has a component in which RP2 is the polyalkylene oxide chain as a molecular chain in addition to the component represented by the formula (I-1). It is preferable to have a constituent component represented by the following formula (I-3B)).
- RP1 is as described above.
- RP2A represents a chain composed of a low molecular weight hydrocarbon group (preferably an aliphatic hydrocarbon group), and the functional group is preferably from the above-mentioned acidic functional group and basic functional group. It has at least one group of choice, more preferably a group containing an ether group and / or a carbonyl group, and even more preferably a carboxy group. Examples thereof include bis (hydroxymethyl) acetic acid compounds such as 2,2-bis (hydroxymethyl) butyric acid.
- RP2B represents a polyalkyleneoxy chain.
- RP2C represents a hydrocarbon polymer chain.
- R P2A hydrocarbon group of low molecular weight
- R P2C hydrocarbon polymer chain which can be taken as a polyalkyleneoxy chain
- R P2C hydrocarbon polymer chain which can be taken as a polyalkyleneoxy chain
- R P2B are respectively taken as R P2 in the above formula (I-3) It is synonymous with the aliphatic hydrocarbon groups, polyalkyleneoxy chains and hydrocarbon polymer chains, and the preferred ones are also the same.
- the compounds that derive the low polar constituent units are represented by, for example, the above formula (I-3A).
- examples thereof include compounds that lead to constituents (where RP2A has no functional group), constituents represented by the formula (I-3C), and the like.
- the polymer having the bond (I) may have a constituent component other than the constituent components represented by the above formulas.
- a constituent component is not particularly limited as long as it can be sequentially polymerized with the raw material compound that derives the constituent component represented by the above formulas.
- the (total) content of the components represented by the above formulas (1-1) to (I-6) in the polymer having the bond (I) is not particularly limited, but is 5 to 100% by mass. It is more preferable, it is more preferably 10 to 100% by mass, further preferably 50 to 100% by mass, and further preferably 80 to 100% by mass. The upper limit of this content may be, for example, 90% by mass or less regardless of the above 100% by mass.
- the content of the constituent components other than the constituent components represented by the above formulas in the polymer having the bond (I) is not particularly limited, but is preferably 50% by mass or less.
- the content thereof is not particularly limited, and the content of the constituent unit or the polymer is not particularly limited. It is appropriately selected in consideration of the SP value and the like, and can be set in the following range, for example. That is, it is derived from the constituent component represented by the formula (I-1) or the formula (I-2) or the carboxylic acid dianhydride represented by the formula (I-5) in the polymer having the bond (I).
- the content of the constituent component is not particularly limited, and is preferably 0 to 90% by mass, more preferably 0.01 to 70% by mass, and further preferably 0.1 to 40% by mass. ..
- the content of the constituents represented by the formula (I-3), the formula (I-4) or the formula (I-6) in the polymer having the bond (I) is not particularly limited and is 0 to 95 mass. %, More preferably 5 to 75% by mass, and even more preferably 30 to 75% by mass.
- the component in which RP2 is a chain composed of a low molecular weight hydrocarbon group (for example, represented by the above formula (I-3A)).
- the content of the constituent component) in the polymer having the bond (I) is not particularly limited, but is preferably, for example, 0 to 50% by mass, more preferably 0 to 30% by mass, and 0. It is more preferably to 20% by mass.
- the component in which RP2 is the polyalkyleneoxy chain as a molecular chain for example, represented by the above formula (I-3B)).
- the content of the constituent component) in the polymer having the bond (I) is not particularly limited, but is preferably, for example, 0 to 80% by mass, more preferably 0 to 70% by mass, and 0. It is more preferably 1 to 60% by mass, and particularly preferably 10 to 50% by mass.
- the component in which RP2 is the hydrocarbon polymer chain as a molecular chain for example, represented by the above formula (I-3C)
- the content of the constituent component) in the polymer having the bond (I) is not particularly limited, but is preferably, for example, 0 to 90% by mass, more preferably 5 to 85% by mass, and 50 to 50% by mass. It is more preferably 80% by mass.
- the above-mentioned content of each constituent component shall be the total content.
- the polymer having the bond (I) preferably has the above-mentioned acidic functional group or basic functional group.
- the polymer having the bond (I) may have the functional group in any of the constituent components forming the polymer, and may have the functional group in either the main chain or the side chain of the polymer.
- the constituents represented by the formula (I-3A) can be mentioned.
- the content of the functional group in the polymer having the bond (I) is not particularly limited.
- the ratio of the constituent components having the functional groups to the total constituent components constituting the polymer having the bond (I) is preferably 0.01 to 20% by mass, more preferably 0.1 to 15% by mass. 1 to 10% by mass is particularly preferable.
- the polymer having the bond (I) (each constituent component and the raw material compound) may have a substituent.
- the substituent is not particularly limited, but preferably, a group selected from the following substituent Z can be mentioned.
- the polymer having the bond (I) can be synthesized by selecting a raw material compound by a known method according to the type of bond held by the main chain and subjecting the raw material compound to polyaddition or polycondensation.
- a synthesis method for example, International Publication No. 2018/151118 can be referred to.
- Polyurethane, polyurea, polyamide, and polyimide polymers that can be taken as the polymer having the bond (I) include, for example, International Publication No. 2018/020827 and International Publication No. 2015/046313, in addition to those synthesized in Examples. Further, each polymer and the like described in JP-A-2015-08480 can be mentioned.
- -Substituent Z- Alkyl groups preferably alkyl groups having 1 to 20 carbon atoms, such as methyl, ethyl, isopropyl, t-butyl, pentyl, heptyl, 1-ethylpentyl, benzyl, 2-ethoxyethyl, 1-carboxymethyl, etc.
- alkenyl groups preferably alkyl groups having 1 to 20 carbon atoms, such as methyl, ethyl, isopropyl, t-butyl, pentyl, heptyl, 1-ethylpentyl, benzyl, 2-ethoxyethyl, 1-carboxymethyl, etc.
- an alkenyl group having 2 to 20 carbon atoms for example, vinyl, allyl, oleyl, etc.
- an alkynyl group preferably an alkynyl group having 2 to 20 carbon atoms, for example, ethynyl, butadynyl, phenylethynyl, etc.
- a cycloalkyl group having 3 to 20 carbon atoms for example, cyclopropyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, etc., is used in the present specification to mean that an alkyl group usually includes a cycloalkyl group.
- An aryl group (preferably an aryl group having 6 to 26 carbon atoms, for example, phenyl, 1-naphthyl, 4-methoxyphenyl, 2-chlorophenyl, 3-methylphenyl, etc.), an aralkyl group (preferably having 7 carbon atoms).
- ⁇ 23 aralkyl groups eg, benzyl, phenethyl, etc.
- heterocyclic groups preferably heterocyclic groups having 2 to 20 carbon atoms, more preferably 5 or 5 having at least one oxygen atom, sulfur atom, nitrogen atom. It is a 6-membered heterocyclic group.
- the heterocyclic group includes an aromatic heterocyclic group and an aliphatic heterocyclic group.
- a tetrahydropyran ring group for example, a tetrahydropyran ring group, a tetrahydrofuran ring group, 2-pyridyl, 4-pyridyl, 2-. Imidazolyl, 2-benzoimidazolyl, 2-thiazolyl, 2-oxazolyl, pyrrolidone group, etc.), alkoxy group (preferably an alkoxy group having 1 to 20 carbon atoms, for example, methoxy, ethoxy, isopropyloxy, benzyloxy, etc.), aryloxy group (Preferably, an aryloxy group having 6 to 26 carbon atoms, for example, phenoxy, 1-naphthyloxy, 3-methylphenoxy, 4-methoxyphenoxy, etc., is used in the present specification to include an aryloxy group.
- alkoxy group preferably an alkoxy group having 1 to 20 carbon atoms, for example, methoxy, ethoxy, is
- a heterocyclic oxy group (a group in which an —O— group is bonded to the above heterocyclic group), an alkoxycarbonyl group (preferably an alkoxycarbonyl group having 2 to 20 carbon atoms, for example, ethoxycarbonyl, 2-ethylhexyloxycarbonyl).
- aryloxycarbonyl groups preferably aryloxycarbonyl groups with 6-26 carbon atoms, such as phenoxycarbonyl, 1-naphthyloxycarbonyl, 3-me Chilphenoxycarbonyl, 4-methoxyphenoxycarbonyl, etc.
- heterocyclic oxycarbonyl group group in which -O-CO- group is bonded to the above heterocyclic group
- amino group preferably amino group having 0 to 20 carbon atoms, alkyl It contains an amino group and an arylamino group, and includes, for example, amino (-NH 2 ), N, N-dimethylamino, N, N-diethylamino, N-ethylamino, anirino, etc., and a sulfamoyl group (preferably having 0 to 20 carbon atoms).
- Sulfamoyl group of, for example, N, N-dimethylsulfamoyl, N-phenylsulfamoyl, etc. acyl group (alkylcarbonyl group, alkenylcarbonyl group, alkynylcarbonyl group, arylcarbonyl group, heterocyclic carbonyl group, etc.
- an acyl group having 1 to 20 carbon atoms for example, acetyl, propionyl, butyryl, octanoyl, hexadecanoyl, acryloyl, methacryloyl, crotonoyle, benzoyl, naphthoyl, nicotineol, etc., and an acyloxy group (alkylcarbonyloxy group, alkenylcarbonyloxy).
- heterocyclic thio group group in which -S- group is bonded to the above heterocyclic group
- alkylsulfonyl group preferably alkylsulfonyl group having 1 to 20 carbon atoms.
- RP is a hydrogen atom or a substituent (preferably a group selected from the substituent Z). Further, each of the groups listed in these substituents Z may be further substituted with the above-mentioned substituent Z.
- the alkyl group, alkylene group, alkenyl group, alkenylene group, alkynyl group and / or alkynylene group and the like may be cyclic or chain-like, or may be linear or branched.
- the polymer having no bond (I) in the main chain is not particularly limited, but one or more monomers having a non-aromatic carbon-carbon double bond.
- examples thereof include a polymer obtained by chain polymerization of (chain polymerization polymer).
- a fluoropolymer (fluoropolymer), a hydrocarbon polymer, a vinyl polymer, and a (meth) acrylic polymer are preferable, and a (meth) acrylic polymer is more preferable.
- the fluorine-containing polymer examples include polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVdF), a copolymer of polyvinylidene fluoride and hexafluoropropylene (PVdF-HFP), and polyvinylidene fluoride. And a copolymer of hexafluoropropylene and tetrafluoroethylene (PVdF-HFP-TFE).
- the copolymerization ratio [PVdF: HFP] (mass ratio) of PVdF and HFP is not particularly limited, but is preferably 9: 1 to 5: 5, and more preferably 9: 1 to 7: 3.
- the copolymerization ratio [PVdF: HFP: TFE] (mass ratio) of PVdF, HFP, and TFE is not particularly limited, but may be 20 to 60:10 to 40: 5 to 30. preferable.
- hydrocarbon polymer examples include polyethylene, polypropylene, natural rubber, polybutadiene, polyisoprene, polystyrene, polystyrene butadiene copolymer, styrene-based thermoplastic elastomer, polybutylene, acrylonitrile butadiene copolymer, or hydrogenation thereof (hydrogenation). Chemistry) Polymers can be mentioned.
- the styrene-based thermoplastic elastomer or its hydride is not particularly limited, and for example, styrene-ethylene-butylene-styrene block copolymer (SEBS), styrene-isoprene-styrene block copolymer (SIS), styrene-isobutylene.
- SEBS styrene-ethylene-butylene-styrene block copolymer
- SIS styrene-isoprene-styrene block copolymer
- styrene-isobutylene styrene-isobutylene.
- SIBS -Styrene block copolymer
- SIBS hydrogenated SIS
- SBS styrene-butadiene-styrene block copolymer
- SEEPS hydrogenated SBS
- SEPS styrene-ethylene-ethylene-propylene-styrene block copolymer
- SEEPS hydrogenated SBS
- SEPS styrene-ethylene-ethylene-propylene-styrene block copolymer
- SEEPS styrene-propylene-styrene block copolymer
- SEPS ethylene-propylene-styrene block copolymer
- SBR styrene-butadiene rubber
- HSBR hydride styrene-butadiene rubber
- the hydrocarbon polymer having no unsaturated group for example, 1,2-butadiene constituent
- vinyl-based polymer examples include polymers containing, for example, 50 mol% or more of vinyl-based monomers other than the following (meth) acrylic compound (M1).
- vinyl-based monomer examples include vinyl compounds described later.
- Specific examples of the vinyl polymer include polyvinyl alcohol, polyvinyl acetal, polyvinyl acetate, and a copolymer containing these.
- the (meth) acrylic polymer at least one (meth) acrylic compound (M1) selected from a (meth) acrylic acid compound, a (meth) acrylic acid ester compound, a (meth) acrylamide compound and a (meth) acrylonitrile compound. ) Is (co) polymerized to obtain a polymer. Further, a (meth) acrylic polymer composed of a copolymer of the (meth) acrylic compound (M1) and another polymerizable compound (M2) is also preferable.
- the other polymerizable compound (M2) is not particularly limited, and examples thereof include vinyl compounds such as styrene compounds, vinylnaphthalene compounds, vinylcarbazole compounds, allyl compounds, vinyl ether compounds, vinyl ester compounds, and dialkyl itaconate compounds.
- vinyl compound examples include "vinyl-based monomers" described in JP-A-2015-88886.
- the content of the other polymerizable compound (M2) in the (meth) acrylic polymer is not particularly limited, but can be, for example, less than 50 mol%.
- the compound represented by the following formula (b-1) is preferable.
- R 1 is a hydrogen atom, a hydroxy group, a cyano group, a halogen atom, an alkyl group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, particularly preferably 1 to 6 carbon atoms), and an alkenyl group (2 carbon atoms).
- ⁇ 24 is preferred, 2-12 is more preferred, 2-6 is particularly preferred), an alkynyl group (2-24 carbon atoms is preferred, 2-12 is more preferred, 2-6 is particularly preferred), or an aryl group (preferably 2-6).
- 6 to 22 carbon atoms are preferable, and 6 to 14 carbon atoms are more preferable).
- a hydrogen atom or an alkyl group is preferable, and a hydrogen atom or a methyl group is more preferable.
- R 2 represents a hydrogen atom or a substituent.
- the substituent that can be taken as R 2 is not particularly limited, but an alkyl group (preferably having 1 to 30 carbon atoms, more preferably 1 to 24 carbon atoms, particularly preferably 1 to 12 chains, and preferably a branched chain but a straight chain).
- An alkenyl group preferably 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms
- an aryl group preferably 6 to 22 carbon atoms, more preferably 6 to 14 carbon atoms
- an aralkyl group preferably 7 to 23 carbon atoms, 7).
- an aliphatic heterocyclic group containing a cyano group, a hydroxy group, a sulfanyl group, and an oxygen atom preferably having 2 to 12 carbon atoms, more preferably 2 to 6.
- the aliphatic heterocyclic group containing an oxygen atom is preferably an epoxy group-containing group, an oxetane group-containing group, a tetrahydrofuryl group-containing group, or the like.
- L 1 is a linking group and is not particularly limited, but for example, an alkylene group having 1 to 6 carbon atoms (preferably 1 to 3), an alkenylene group having 2 to 6 carbon atoms (preferably 2 to 3), and a carbon number of carbons.
- 6 to 24 (preferably 6 to 10) arylene groups, oxygen atoms, sulfur atoms, imino groups (-NR N- ), carbonyl groups, phosphate linking groups (-O-P (OH) (O) -O- ), phosphonic acid linking group (-P (OH) (O) -O-), or group, and the like in accordance with a combination thereof, -CO-O-group, -CO-N (R N) - group ( R N is as defined above.) is preferable.
- the linking group may have any substituent. Examples of the optional substituent include the above-mentioned Substituent Z, and examples thereof include an alkyl group and a halogen atom.
- the number of atoms constituting the linking group is preferably 1 to 36, more preferably 1 to 24, further preferably 1 to 12, and preferably 1 to 6. Especially preferable.
- the number of connecting atoms of the linking group is preferably 10 or less, more preferably 8 or less.
- the lower limit is 1 or more.
- n is 0 or 1, preferably 1. However, when ⁇ (L 1 ) n ⁇ R 2 indicates one kind of substituent (for example, an alkyl group), n is set to 0 and R 2 is used as a substituent (alkyl group).
- (meth) acrylic compound (M1) a compound represented by the following formula (b-2) or (b-3) is also preferable.
- R 1, n has the same meaning as the above formula (b-1).
- R 3 is synonymous with R 2.
- L 2 is a linking group and has the same meaning as L 1 described above.
- L 3 is a linking group and is synonymous with L 1 , but an alkylene group having 1 to 6 carbon atoms (preferably 1 to 3) is preferable.
- m is an integer of 1 to 200, preferably an integer of 1 to 100, and more preferably an integer of 1 to 50.
- Examples of the compound represented by the formula (b-3) include nonylphenoxypolyethylene glycol acrylate.
- the substituent is not particularly limited, for example, the groups that can be taken as R 1.
- the substituent is used as long as the effect of the present invention is not impaired. May have.
- substituents examples include the above-mentioned Substituent Z and a group selected from the above-mentioned acidic functional group and basic functional group. Specific examples thereof include a halogen atom, a hydroxy group, a sulfanyl group, an acyl group and an acyloxy group. , Alkoxy group, aryloxy group, allyloyl group, allyloyloxy group and the like.
- examples of the compound that derives a highly polar constituent unit include (meth) acrylic acid, an alkyl (meth) acrylic acid ester having a polar group such as a hydroxyl group, an alkylene oxide group or an amino group, or (meth) acrylic acid ester.
- examples thereof include (meth) acrylamide having an alkyl group on an amide nitrogen such as meta) acrylic acid amide, dimethylacrylamide or isopropylacrylamide, further acrylamide, (meth) acrylonitrile and the like.
- (meth) acrylic compound (M1) As a compound that derives a highly polar constituent unit in the (meth) acrylic compound (M1), it has excellent compatibility with a polymer having a bond represented by the above formula (1) in the main chain, and is suitable for synthesizing composite particles and binding.
- (meth) acrylic acid ester having an alkylene oxide group, (meth) acrylamide having an alkyl group on the amide group nitrogen, and (meth) acrylonitrile are preferable, and (meth) having an alkyl group on the amide group nitrogen.
- Acrylamide and (meth) acrylonitrile are more preferable, and (meth) acrylamide having an alkyl group on the amide group nitrogen is further preferable.
- the (meth) acrylic polymer preferably contains a component derived from a macromonomer (X) having a mass average molecular weight of 1000 or more.
- the macromonomer has a mass average molecular weight of 1,000 or more, more preferably 2,000 or more, and particularly preferably 3,000 or more.
- the upper limit is preferably 500,000 or less, more preferably 100,000 or less, and particularly preferably 30,000 or less.
- the main chain of the side chain component of the macromonomer (X) is not particularly limited, and a normal polymer component can be applied.
- a chain made of a normal polymer can be applied without particular limitation, and examples thereof include a polymerized chain made of a (meth) acrylic polymer.
- the polymerized chain made of the (meth) acrylic polymer preferably has a constituent component derived from the (meth) acrylic compound (M1), a constituent component derived from the vinyl compound (M2), and the like.
- the macromonomer (X) preferably has a polymerizable group at its terminal, and more preferably has a polymerizable group at one end or both ends thereof.
- the polymerizable group is preferably a group having a polymerizable unsaturated bond, and examples thereof include various vinyl groups and (meth) acryloyl groups.
- the macromonomer (X) preferably has a (meth) acryloyl group.
- the macromonomer (X) preferably contains a partial structure (components constituting the polymerized chain) derived from the (meth) acrylic compound (M1). Further, the macromonomer (X) has a polymerizable double bond and a hydrocarbon structural unit S having 6 or more carbon atoms (preferably an alkylene group having 6 or more and 30 or less carbon atoms, and more preferably an alkylene having 8 or more and 24 or less carbon atoms. Group) is preferably included.
- the hydrocarbon structural unit S is dodecyl in a structure derived from dodecyl methacrylate.
- the macromonomer (X) preferably has a moiety represented by the following formula (P) as a polymerizable group or a part thereof.
- R 11 is a hydrogen atom, a hydroxyl group, a cyano group, a halogen atom, a carboxyl group, an alkyl group (preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms), an alkenyl group (1 to 6 carbon atoms are particularly preferable), and an alkenyl group (carbon number).
- 2 to 24 are preferred, 2 to 12 are more preferred, 2 to 6 are particularly preferred), alkynyl groups (2 to 24 carbon atoms are preferred, 2 to 12 are more preferred, 2 to 6 are particularly preferred), or aryl groups.
- a hydrogen atom or an alkyl group is preferable, and a hydrogen atom or a methyl group is more preferable. * Is a joint.
- the content of the constituent components in the (meth) acrylic polymer is not particularly limited, and is appropriately selected in consideration of the constituent unit or the SP value of the polymer, and can be set in the following range, for example.
- the content of the component derived from the (meth) acrylic compound (M1) in the (meth) acrylic polymer is not particularly limited, but is preferably 1 to 99% by mass, and is preferably 5 to 97% by mass. Is more preferable, and 10 to 95% by mass is particularly preferable.
- the content of the component derived from the vinyl compound (M2) in the (meth) acrylic polymer is not particularly limited, but is preferably 0 to 30% by mass, more preferably 0 to 20% by mass. , 0 to 10% by mass is particularly preferable.
- any of the above-mentioned constituent components may have a functional group, and the content of the constituent component having a functional group is as described later, but the above-mentioned content also meet the amount.
- the polymer having no bond (I) in the main chain preferably has the above-mentioned acidic functional group or basic functional group.
- the polymer having no bond (I) may have the functional group in any of the constituent components forming the polymer, and may have the functional group in either the main chain or the side chain of the polymer. ..
- the content of the functional group in the polymer having no bond (I) is not particularly limited.
- the ratio of the component having the functional group to all the components constituting the polymer having no bond (I) is preferably in the same range as that in the polymer having the bond (I) in the main chain. ..
- the polymer (each constituent component and raw material compound) having no bond (I) in the main chain may have a substituent other than the acidic functional group and the basic functional group.
- a substituent is not particularly limited, but preferably includes a group selected from the above-mentioned Substituent Z.
- the polymer having no bond (I) in the main chain can be synthesized by selecting a raw material compound and polymerizing the raw material compound by a known method.
- the composite polymer particles contain a polymer that does not have the bond (I) in the main chain, it is preferably contained as a low-polarity polymer, and the content thereof is the same as the content of the low-polarity polymer.
- the composite polymer particles may contain a polymer other than the above-mentioned low-polarity polymer and high-polarity polymer.
- the polymer forming the composite polymer particles may be a non-crosslinked polymer or a crosslinked polymer. Further, when the cross-linking of the polymer proceeds by heating or application of a voltage, the molecular weight may be larger than the above molecular weight. Preferably, the polymer has a mass average molecular weight in the range described below at the start of use of the all-solid-state secondary battery.
- the shape of the composite polymer particles is not particularly limited and may be flat, amorphous or the like, but spherical or granular is preferable.
- the average primary particle size of the particulate composite polymer particles is not particularly limited, but is preferably 0.1 nm or more, more preferably 1 nm or more, further preferably 5 nm or more, and 10 nm or more. Is particularly preferable, and 50 nm or more is most preferable.
- the upper limit value is preferably 5.0 ⁇ m or less, more preferably 1 ⁇ m or less, further preferably 700 nm or less, and particularly preferably 500 nm or less.
- the average particle size of the composite polymer particles can be measured in the same manner as the particle size of the inorganic solid electrolyte.
- the average primary particle diameter of the composite polymer particles in the constituent layers of the all-solid-state secondary battery is determined in advance by, for example, disassembling the battery to peel off the constituent layers containing the composite polymer particles, and then measuring the constituent layers. The measurement can be performed by excluding the measured value of the particle size of the particles other than the composite polymer particles that have been measured.
- the average primary particle size of the composite polymer particles can be adjusted, for example, by the type of dispersion medium, the content and content of constituents in the polymer, and the like.
- the water concentration of the composite polymer particles is preferably 100 ppm (mass basis) or less.
- the polymer may be crystallized and dried, or the composite polymer particle dispersion may be used as it is.
- the polymer forming the composite polymer particles is preferably amorphous.
- the term "amorphous" as a polymer typically means that no endothermic peak due to crystal melting is observed when measured at the glass transition temperature.
- the mass average molecular weight of the polymer forming the composite polymer particles is not particularly limited. For example, 15,000 or more is preferable, 30,000 or more is more preferable, and 50,000 or more is further preferable. As the upper limit, 5,000,000 or less is practical, but 4,000,000 or less is preferable, and 3,000,000 or less is more preferable.
- the molecular weights of the polymer and the polymer chain refer to the mass average molecular weight and the number average molecular weight in terms of standard polystyrene by gel permeation chromatography (GPC) unless otherwise specified.
- GPC gel permeation chromatography
- the value measured by the method of the following condition 1 or condition 2 (priority) is basically used. However, depending on the type of polymer or the like, an appropriate eluent may be appropriately selected and used.
- Condition 1 Column: Connect two TOSOH TSKgel Super AWM-H (trade name, manufactured by Tosoh Corporation) Carrier: 10 mM LiBr / N-methylpyrrolidone Measurement temperature: 40 ° C.
- Carrier flow rate 1.0 ml / min Sample concentration: 0.1% by mass Detector: RI (refractive index) detector (condition 2) Column: A column in which TOSOH TSKgel Super HZM-H, TOSOH TSKgel Super HZ4000, and TOSOH TSKgel Super HZ2000 (trade names, all manufactured by Tosoh Corporation) are connected is 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
- polymer contained in the composite polymer particles include those synthesized in Examples, but the present invention is not limited thereto.
- the composite polymer particles of the present invention are synthesized (prepared) by a method capable of forming composite particles composed of at least two kinds of polymers.
- a method for synthesizing a polymer in which composite particles can be adjusted a dispersion polymerization method, a suspension polymerization method and the like can be mentioned.
- the method for synthesizing the composite polymer other than the above include a usual method for synthesizing a polymer having a core-shell structure, a so-called seed polymerization method, a coating method, and the like.
- a seed synthesis method for example, a synthesis method under the following methods and conditions can be mentioned.
- a monomer as a constituent component of the second polymer is added to the dispersion liquid of the particles composed of the first polymer, and the monomer is absorbed by the first polymer particles.
- a reaction initiator or a reaction catalyst is added, the reaction vessel is heated, and the monomer is polymerized in the particles to obtain composite polymer particles.
- a method of synthesizing each polymer separately and then combining two or more kinds of polymers for example, a coating method or the like can be adopted.
- the preparation conditions for the above-mentioned composite polymer particles the conditions usually performed according to each method can be appropriately selected. Examples of the sheet polymerization conditions include the synthesis conditions in the examples described later.
- the seed polymerization method is preferable in the following points, especially when preparing composite polymer particles containing the polymer having the above bond (I). That is, the seed polymerization method makes it possible to polymerize the raw material compound in an organic solvent (preferably a dispersion medium described later), and for the polymer, particularly the polymer having the above bond (I), the composition (type of raw material compound).
- the desired composition can be obtained without excessively limiting the amount used). For example, the content of low polar constituents can be reduced to the above range.
- the raw material compound is dispersed and polymerized in an aqueous solvent to prepare composite particles, and then the phase is transferred to an organic solvent. It is usually prepared by Therefore, at the time of polymerization in an aqueous solvent or phase inversion to an organic solvent, the type of the raw material compound, the amount used thereof, and the like are limited, and the desired polymer composition may not be realized.
- the conventional sheet polymerization is generally synthesized by chain polymerization via radicals in an aqueous solvent.
- Composite particles having a core-shell structure can be prepared by the sheet polymerization method.
- the inorganic solid electrolyte-containing composition of the present invention may contain one type of composite polymer particles or a plurality of types.
- the content of the composite polymer particles in the composition containing the inorganic solid electrolyte is preferably 0.001% by mass or more, more preferably 0.05% by mass or more, based on 100% by mass of the solid component, in terms of binding properties. 0.1% by mass or more is more preferable, and 0.2% by mass or more is particularly preferable.
- As the upper limit 10% by mass or less is preferable, 5% by mass or less is more preferable, and 3% by mass or less is further preferable, in terms of low resistance and cycle characteristics.
- the mass ratio of the total mass (total amount) of the inorganic solid electrolyte and the active material to the mass of the composite polymer particles [(mass of the inorganic solid electrolyte + mass of the active material) / (composite polymer).
- the mass of the particles)] is preferably in the range of 1,000 to 1. This ratio is more preferably 1000 to 2, and even more preferably 500 to 10.
- the non-composite polymer particles may appropriately contain other binders as described above.
- the inorganic solid electrolyte-containing composition of the present invention preferably contains a dispersion medium for dispersing each of the above components.
- the dispersion medium may be an organic compound that is liquid in the usage environment, and examples thereof include various organic solvents. Specifically, an alcohol compound, an ether compound, an amide compound, an amine compound, a ketone compound, and an aromatic compound. , Aliper compounds, nitrile compounds, ester compounds and the like.
- the dispersion medium may be a non-polar dispersion medium (hydrophobic dispersion medium) or a polar dispersion medium (hydrophilic dispersion medium), but a non-polar dispersion medium is preferable because it can exhibit excellent dispersibility.
- the non-polar dispersion medium generally has a property of having a low affinity for water, and in the present invention, for example, an ester compound, a ketone compound, an ether compound, a perfume compound, an aliphatic compound and the like can be mentioned.
- 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 can be mentioned.
- ether compound examples include alkylene glycol (diethylene glycol, triethylene glycol, polyethylene glycol, dipropylene glycol, etc.), alkylene glycol monoalkyl ether (ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, diethylene glycol monomethyl ether, etc.).
- alkylene glycol diethylene glycol, triethylene glycol, polyethylene glycol, dipropylene glycol, etc.
- alkylene glycol monoalkyl ether ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, diethylene glycol monomethyl ether, etc.
- amide compound examples include N, N-dimethylformamide, N-methyl-2-pyrrolidone, 2-pyrrolidinone, 1,3-dimethyl-2-imidazolidinone, ⁇ -caprolactam, formamide, N-methylformamide and acetamide. , N-Methylacetamide, N, N-dimethylacetamide, N-methylpropanamide, hexamethylphosphoric triamide and the like.
- Examples of the amine compound include triethylamine, diisopropylethylamine, tributylamine and the like.
- Examples of the ketone compound include acetone, methyl ethyl ketone, methyl isobutyl ketone (MIBK), cyclopentanone, cyclohexanone, cycloheptanone, dipropyl ketone, dibutyl ketone, diisopropyl ketone, diisobutyl ketone (DIBK), isobutyl propyl ketone, sec-. Examples thereof include butyl propyl ketone, pentyl propyl ketone and butyl propyl ketone.
- Examples of the aromatic compound include benzene, toluene, xylene and the like.
- Examples of the aliphatic compound include hexane, heptane, octane, nonane, decane, dodecane, cyclohexane, methylcyclohexane, ethylcyclohexane, cycloheptane, cyclooctane, decalin, paraffin, gasoline, naphtha, kerosene, and light oil.
- Examples of the nitrile compound include acetonitrile, propionitrile, isobutyronitrile and the like.
- ester compound examples include ethyl acetate, butyl acetate, propyl acetate, propyl butyrate, isopropyl butyrate, butyl butyrate, isobutyl butyrate, butyl pentanate, ethyl isobutyrate, propyl isobutyrate, isopropyl isobutyrate, isobutyl isobutyrate, and pivalic acid.
- Examples thereof include propyl, isopropyl pivalate, butyl pivalate, and isobutyl pivalate.
- ether compounds, ketone compounds, aromatic compounds, aliphatic compounds and ester compounds are preferable, and ester compounds, ketone compounds or ether compounds are more preferable.
- the number of carbon atoms of the compound constituting the dispersion medium is not particularly limited, and is preferably 2 to 30, more preferably 4 to 20, further preferably 6 to 15, and particularly preferably 7 to 12.
- the dispersion medium is preferably an organic solvent having a ClogP value of 1.0 or more.
- the composite polymer particles of the present invention can be highly dispersed to further enhance the effect of lowering the resistance and improving the binding property of the composite polymer particles. Further, by using it in the above seed polymerization method, the inorganic solid electrolyte-containing composition of the present invention containing a dispersion medium can be easily prepared.
- the ClogP value of the dispersion medium is preferably 1.0 or more, more preferably 1.5 or more, and further preferably 2.0 or more.
- the upper limit of the ClogP value is not particularly limited, but is actually 8.0, preferably 7.5 or less, and may be 5.0 or less.
- the CLogP value is a value obtained by calculating the common logarithm LogP of 1-octanol and the partition coefficient P to water.
- Known methods and software can be used for calculating the CRogP value, but unless otherwise specified, the structure is drawn using ChemDraw of PerkinElmer, and the calculated value is used.
- the ClogP value of the organic solvent is the sum of the products of the ClogP value of each organic solvent and the mass fraction.
- organic solvents having a ClogP value of 1.0 or more include benzene, toluene, ethylbenzene, xylene, mesitylene, tetraline, ethyl acetate, butyl acetate, propyl acetate, butyl butyrate, butyl pentanate, acetone, methyl ethyl ketone, and methyl isobutyl ketone.
- the dispersion medium one type may be used, or two or more types may be used.
- one kind is preferably the above-mentioned organic solvent having a LogP value of 1.0 or more, and another organic solvent is not particularly limited as long as the dispersion of the composite polymer particles is not impaired, and is appropriately selected.
- examples thereof include the above-mentioned alkylene glycol, alkylene glycol monoalkyl ether, dialkyl ether, cyclic ether and the like.
- the content of the organic solvent having a ClogP value of 1.0 or more is not particularly limited, and examples thereof include 50 to 95% by mass with respect to the total amount of the dispersion medium.
- the ClogP value of the entire two or more types of dispersion media is not particularly limited, but it is preferable that the ClogP range is satisfied.
- the dispersion medium preferably has a boiling point of 50 ° C. or higher at normal pressure (1 atm), and more preferably 70 ° C. or higher.
- the upper limit is preferably 250 ° C. or lower, and more preferably 220 ° C. or lower.
- the content of the dispersion medium in the composition containing the inorganic solid electrolyte is not particularly limited and can be appropriately set.
- the composition containing an inorganic solid electrolyte 20 to 80% by mass is preferable, 30 to 70% by mass is more preferable, and 40 to 60% by mass is particularly preferable.
- the inorganic solid electrolyte-containing composition of the present invention may also contain an active material capable of inserting and releasing ions of a metal belonging to Group 1 or Group 2 of the periodic table.
- the active material include a positive electrode active material and a negative electrode active material, which will be described below.
- an inorganic solid electrolyte-containing composition containing an active material positive electrode active material or negative electrode active material
- an electrode layer composition positive electrode layer composition or negative electrode layer composition
- the positive electrode active material is an active material capable of inserting and releasing ions of a metal belonging to Group 1 or Group 2 of the periodic table, and is preferably one 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, an organic substance, an element that can be composited with Li such as sulfur, or the like by decomposing the battery.
- the 1 (Ia) group elements of the transition metal oxide to elemental M b (Table metal periodic other than lithium, the elements of the 2 (IIa) group, Al, Ga, In, Ge , Sn, Pb, Elements such as Sb, Bi, Si, P and B) may be mixed.
- the mixing amount is preferably 0 to 30 mol% relative to the amount of the transition metal element M a (100 mol%). That the molar ratio of li / M a was synthesized were mixed so that 0.3 to 2.2, more preferably.
- transition metal oxide examples include (MA) a transition metal oxide having a layered rock salt type structure, (MB) a transition metal oxide having a spinel type structure, (MC) a lithium-containing transition metal phosphoric acid compound, and (MD). ) Lithium-containing transition metal halide phosphoric acid compound, (ME) lithium-containing transition metal silicic acid compound, and the like.
- transition metal oxide having a layered rock salt structure examples include LiCoO 2 (lithium cobalt oxide [LCO]), LiNi 2 O 2 (lithium nickel oxide), LiNi 0.85 Co 0.10 Al 0. 05 O 2 (Lithium Nickel Cobalt Oxide [NCA]), LiNi 1/3 Co 1/3 Mn 1/3 O 2 (Lithium Nickel Manganese Cobalt Oxide [NMC]) and LiNi 0.5 Mn 0.5 O 2 ( Lithium manganese nickel oxide).
- LiCoO 2 lithium cobalt oxide [LCO]
- LiNi 2 O 2 lithium nickel oxide
- LiNi 0.85 Co 0.10 Al 0. 05 O 2 Lithium Nickel Cobalt Oxide [NCA]
- LiNi 1/3 Co 1/3 Mn 1/3 O 2 Lithium Nickel Manganese Cobalt Oxide [NMC]
- LiNi 0.5 Mn 0.5 O 2 Lithium manganese nickel oxide
- (MB) Specific examples of the transition metal oxide having a spinel structure, LiMn 2 O 4 (LMO) , LiCoMnO 4, Li 2 FeMn 3 O 8, Li 2 CuMn 3 O 8, Li 2 CrMn 3 O 8 and Li 2 Nimn 3 O 8 can be mentioned.
- Examples of the (MC) lithium-containing transition metal phosphate compound include olivine-type iron phosphate salts such as LiFePO 4 and Li 3 Fe 2 (PO 4 ) 3 , iron pyrophosphates such as LiFeP 2 O 7 , and LiCoPO 4.
- Examples thereof include cobalt phosphates of the above and monoclinic panocycon-type vanadium phosphate salts such as Li 3 V 2 (PO 4 ) 3 (vanadium lithium phosphate).
- (MD) as the lithium-containing transition metal halogenated phosphate compound for example, Li 2 FePO 4 F such fluorinated phosphorus iron salt, Li 2 MnPO 4 hexafluorophosphate manganese salts such as F and Li 2 CoPO 4 F Fluorophosphate cobalts and the like.
- Examples of the (ME) lithium-containing transition metal silicic acid compound include Li 2 FeSiO 4 , Li 2 MnSiO 4 , and Li 2 CoSiO 4 .
- a transition metal oxide having a (MA) layered rock salt type structure is preferable, and LCO or NMC is more preferable.
- the shape of the positive electrode active material is not particularly limited, but is preferably in the form of particles.
- the 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 measured in the same manner as the particle size of the above-mentioned inorganic solid electrolyte.
- a normal crusher or classifier is used to adjust the positive electrode active material to a predetermined particle size. For example, a mortar, a ball mill, a sand mill, a vibrating ball mill, a satellite ball mill, a planetary ball mill, a swirling airflow type jet mill, a sieve, or the like is preferably used.
- wet pulverization in which a dispersion medium such as water or methanol coexists can also be performed. It is preferable to perform classification in order to obtain a desired particle size.
- the classification is not particularly limited, and can be performed using a sieve, a wind power classifier, or the like. Both dry and wet classifications can be used.
- the positive electrode active material obtained by the firing method may be used after being washed with water, an acidic aqueous solution, an alkaline aqueous solution, or an organic solvent.
- the positive electrode active material one type may be used alone, or two or more types may be used in combination.
- the mass (mg) (grain amount) of the positive electrode active material per unit area (cm 2) of the positive electrode active material layer is not particularly limited. It can be appropriately determined according to the designed battery capacity, and can be, for example, 1 to 100 mg / cm 2 .
- the content of the positive electrode active material in the composition containing an inorganic solid electrolyte is not particularly limited, and is preferably 10 to 97% by mass, more preferably 30 to 95% by mass, and 40 to 93% by mass in terms of solid content of 100% by mass. More preferably, 50 to 90% by mass is particularly preferable.
- the negative electrode active material is an active material capable of inserting and releasing ions of a metal belonging to Group 1 or Group 2 of the periodic table, and is preferably one capable of reversibly inserting and releasing lithium ions.
- the material is not particularly limited as long as it has the above characteristics, and is a negative electrode activity capable of forming an alloy with a carbonaceous material, a metal oxide, a metal composite oxide, a single lithium substance, a lithium alloy, or lithium. Examples include substances. Of these, carbonaceous materials, metal composite oxides, or elemental lithium are preferably used from the viewpoint of reliability.
- An active material that can be alloyed with lithium is preferable in that the capacity of the all-solid-state secondary battery can be increased.
- a negative electrode active material capable of forming an alloy with lithium can be used as the negative electrode active material. This makes it possible to increase the capacity of the all-solid-state secondary battery and extend the life of the battery.
- the carbonaceous material used as the negative electrode active material is a material substantially composed of carbon.
- carbon black such as acetylene black (AB), graphite (artificial graphite such as natural graphite and vapor-grown graphite), and PAN (polyacrylonitrile) -based resin or furfuryl alcohol resin.
- a carbonaceous material obtained by firing a resin can be mentioned.
- various carbon fibers such as PAN-based carbon fibers, cellulose-based carbon fibers, pitch-based carbon fibers, vapor-grown carbon fibers, dehydrated PVA (polypoly alcohol) -based carbon fibers, lignin carbon fibers, graphitic carbon fibers and activated carbon fibers.
- carbonaceous materials can also be divided into non-graphitizable carbonaceous materials (also referred to as hard carbon) and graphite-based carbonaceous materials depending on the degree of graphitization. Further, the carbonaceous material preferably has the plane spacing or density and the size of crystallites described in JP-A No. 62-22066, JP-A No. 2-6856, and JP-A-3-45473.
- the carbonaceous material does not have to be a single material, and a mixture of natural graphite and artificial graphite described in JP-A-5-90844, graphite having a coating layer described in JP-A-6-4516, and the like should be used. You can also.
- As the carbonaceous material hard carbon or graphite is preferably used, and graphite is more preferably used.
- the metal or semi-metal element oxide applied as the negative electrode active material is not particularly limited as long as it is an oxide capable of storing and releasing lithium, and is a composite of a metal element oxide (metal oxide) and a metal element.
- metal oxide metal oxide
- examples thereof include oxides or composite oxides of metal elements and semi-metal elements (collectively referred to as metal composite oxides) and oxides of semi-metal elements (semi-metal oxides).
- metal composite oxides oxides or composite oxides of metal elements and semi-metal elements
- oxides of semi-metal elements semi-metal elements
- amorphous oxides are preferable, and chalcogenides, which are reaction products of metal elements and elements of Group 16 of the periodic table, are also preferable.
- the metalloid element means an element exhibiting properties intermediate between a metalloid element and a non-metalloid element, and usually contains six elements of boron, silicon, germanium, arsenic, antimony and tellurium, and further selenium. , Polonium and Astatine.
- amorphous means an X-ray diffraction method using CuK ⁇ rays, which has a broad scattering band having an apex in a region of 20 ° to 40 ° in 2 ⁇ value, and a crystalline diffraction line is used. You may have.
- the strongest intensity of the crystalline diffraction lines found at the 2 ⁇ value of 40 ° to 70 ° is 100 times or less the diffraction line intensity at the apex of the broad scattering band seen at the 2 ⁇ value of 20 ° to 40 °. It is preferable that it is 5 times or less, and it is particularly preferable that it does not have a crystalline diffraction line.
- the amorphous oxide of the metalloid element or the chalcogenide is more preferable, and the elements of the groups 13 (IIIB) to 15 (VB) of the periodic table (for example).
- Al, Ga, Si, Sn, Ge, Pb, Sb and Bi) alone or a combination of two or more (composite) oxides, or chalcogenides are particularly preferred.
- preferable amorphous oxides and chalcogenides include, for example, Ga 2 O 3 , GeO, PbO, PbO 2 , Pb 2 O 3 , Pb 2 O 4 , Pb 3 O 4 , Sb 2 O 3 , Sb 2.
- Negative electrode active materials that can be used in combination with amorphous oxides such as Sn, Si, and Ge include carbonic materials capable of occluding and / or releasing lithium ions or lithium metals, lithium alone, lithium alloys, and lithium.
- a negative electrode active material that can be alloyed with is preferably mentioned.
- the oxide of a metal or a metalloid element contains at least one of titanium and lithium as constituent components from the viewpoint of high current density charge / discharge characteristics.
- the lithium-containing metal composite oxide include a composite oxide of lithium oxide and the metal (composite) oxide or the chalcogenide, and more specifically, Li 2 SnO 2.
- the negative electrode active material for example, a metal oxide, contains a titanium element (titanium oxide).
- Li 4 Ti 5 O 12 lithium titanate [LTO]
- LTO lithium titanate
- the lithium alloy as the negative electrode active material is not particularly limited as long as it is an alloy usually used as the negative electrode active material of the secondary battery, and examples thereof include a lithium aluminum alloy.
- the negative electrode active material that can be alloyed with lithium is not particularly limited as long as it is usually used as the negative electrode active material of the secondary battery. Such an active material has a large expansion and contraction due to charging and discharging of the all-solid secondary battery and accelerates the deterioration of the cycle characteristics. However, since the inorganic solid electrolyte-containing composition of the present invention contains the above-mentioned composite polymer particles, Deterioration of cycle characteristics can be suppressed.
- Examples of such an active material include a (negative electrode) active material having a silicon element or a tin element (alloy, etc.), and metals such as Al and In, and a negative electrode active material having a silicon element that enables a higher battery capacity.
- a silicon element-containing active material (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 the constituent elements is more preferable.
- a negative electrode containing these negative electrode active materials (for example, a Si negative electrode containing a silicon element-containing active material, a Sn negative electrode containing a tin element active material, etc.) is a carbon negative electrode (graphite, acetylene black, etc.). ), It can occlude more Li ions. That is, the amount of Li ions occluded per unit mass increases. Therefore, the battery capacity (energy density) can be increased. As a result, there is an advantage that the battery drive time can be lengthened.
- silicon element-containing active material examples include silicon materials such as Si and SiOx (0 ⁇ x ⁇ 1), and silicon-containing alloys containing titanium, vanadium, chromium, manganese, nickel, copper, lanthanum, and the like (for example,). LaSi 2 , VSi 2 , La-Si, Gd-Si, Ni-Si) or organized active material (eg LaSi 2 / Si), as well as other silicon and tin elements such as SnSiO 3 , SnSiS 3 Examples include active materials containing.
- SiOx itself can be used as a negative electrode active material (semi-metal oxide), and since Si is generated by the operation of an all-solid-state secondary battery, a negative electrode active material that can be alloyed with lithium (its). It can be used as a precursor substance).
- the negative electrode active material having a tin element include Sn, SnO, SnO 2 , SnS, SnS 2 , and the active material containing the silicon element and the tin element.
- a composite oxide with lithium oxide for example, Li 2 SnO 2 can also be mentioned.
- the above-mentioned negative electrode active material can be used without particular limitation, but in terms of battery capacity, a negative electrode active material that can be alloyed with silicon is a preferable embodiment as the negative electrode active material.
- a negative electrode active material that can be alloyed with silicon is a preferable embodiment as the negative electrode active material.
- the above-mentioned silicon material or silicon-containing alloy (alloy containing a silicon element) is more preferable, and it is further preferable to contain silicon (Si) or a silicon-containing alloy.
- the chemical formula of the compound obtained by the above firing method can be calculated from the inductively coupled plasma (ICP) emission spectroscopic analysis method as a measurement method and the mass difference of the powder before and after firing as a simple method.
- ICP inductively coupled plasma
- the shape of the negative electrode active material is not particularly limited, but it is preferably in the form of particles.
- the volume average particle size of the negative electrode active material is not particularly limited, but is preferably 0.1 to 60 ⁇ m.
- the volume average particle size of the negative electrode active material particles can be measured in the same manner as the particle size of the inorganic solid electrolyte. In order to obtain a predetermined particle size, a normal crusher or classifier is used as in the case of the positive electrode active material.
- the negative electrode active material may be used alone or in combination of two or more.
- the mass (mg) (grain amount) of the negative electrode active material per unit area (cm 2) of the negative electrode active material layer is not particularly limited. It can be appropriately determined according to the designed battery capacity, and can be, for example, 1 to 100 mg / cm 2 .
- the content of the negative electrode active material in the composition containing an inorganic solid electrolyte is not particularly limited, and is preferably 10 to 90% by mass, more preferably 20 to 85% by mass, and 30 to 30% by mass in terms of solid content of 100% by mass. It is more preferably 80% by mass, and even more preferably 40 to 75% by mass.
- the negative electrode active material layer when the negative electrode active material layer is formed by charging the secondary battery, instead of the negative electrode active material, a metal belonging to Group 1 or Group 2 of the periodic table generated in the all-solid-state secondary battery Ions can be used.
- the negative electrode active material layer can be formed by combining these ions with electrons and precipitating them 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.
- the surface coating agent include metal oxides containing Ti, Nb, Ta, W, Zr, Al, Si or Li. Specific examples thereof include spinel titanate, tantalum oxide, niobate oxide, lithium niobate compound and the like.
- 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 positive electrode active material or the particle surface of the negative electrode active material may be surface-treated with active light rays or an active gas (plasma or the like) before and after the surface coating.
- the inorganic solid electrolyte-containing composition of the present invention may appropriately contain a conductive auxiliary agent, and it is particularly preferable that the silicon atom-containing active material as the negative electrode active material is used in combination with the conductive auxiliary agent.
- the conductive auxiliary agent is not particularly limited, and those known as general conductive auxiliary agents can be used. For example, graphites such as natural graphite and artificial graphite, carbon blacks such as acetylene black, ketjen black and furnace black, amorphous carbon such as needle coke, vapor-grown carbon fibers or carbon nanotubes, which are electron conductive materials.
- It may be a carbon fiber such as graphene or fullerene, a metal powder such as copper or nickel, or a metal fiber, and a conductive polymer such as polyaniline, polypyrrole, polythiophene, polyacetylene, or polyphenylene derivative. May be used.
- a conductive auxiliary agent is one that does not insert and release ions) and does not function as an active material.
- conductive auxiliary agents those that can function as active materials in the active material layer when the battery is charged and discharged are classified as active materials instead of conductive auxiliary agents. Whether or not the battery functions as an active material when it is charged and discharged is not unique and is determined by the combination with the active material.
- the conductive auxiliary agent may contain one kind or two or more kinds.
- the shape of the conductive auxiliary agent is not particularly limited, but is preferably in the form of particles.
- the content of the conductive auxiliary agent in the inorganic solid electrolyte-containing composition is preferably 0 to 10% by mass based on the solid content.
- the inorganic solid electrolyte-containing composition of the present invention preferably contains a lithium salt (supporting electrolyte).
- the lithium salt the lithium salt usually used for this kind of product is preferable, and there is no particular limitation.
- the lithium salt described in paragraphs 882 to 985 of JP2015-088486 is preferable.
- the content of the lithium salt is preferably 0.1 part by mass or more, more preferably 5 parts by mass or more, based on 100 parts by mass of the solid electrolyte.
- the upper limit is preferably 50 parts by mass or less, and more preferably 20 parts by mass or less.
- the inorganic solid electrolyte-containing composition of the present invention does not have to contain a dispersant other than the composite polymer particles, but may contain a dispersant. Good.
- the dispersant those usually used for all-solid-state secondary batteries can be appropriately selected and used. In general, compounds intended for particle adsorption, steric repulsion and / or electrostatic repulsion are preferably used.
- the composition containing an inorganic solid electrolyte of the present invention contains an ionic liquid, a thickener, and a cross-linking agent (such as those that undergo a cross-linking reaction by radical polymerization, condensation polymerization, or ring-opening polymerization) as other components other than the above components.
- a cross-linking agent such as those that undergo a cross-linking reaction by radical polymerization, condensation polymerization, or ring-opening polymerization
- Polymerization initiators such as those that generate acids or radicals by heat or light
- defoaming agents leveling agents, dehydrating agents, antioxidants and the like
- the ionic liquid is contained in order to further improve the ionic conductivity, and known ones can be used without particular limitation.
- a polymer other than the polymer contained in the composite polymer particles, a commonly used binder and the like may be contained.
- composition containing inorganic solid electrolyte Preparation of composition containing inorganic solid electrolyte
- the inorganic solid electrolyte, the composite polymer particles, preferably a dispersion medium, and optionally a lithium salt, and any other components are mixed, for example, in various mixers usually used. Thereby, it can be prepared as a mixture, preferably as a slurry.
- the mixing method is not particularly limited, and the mixture may be mixed all at once or sequentially.
- the mixing environment is not particularly limited, and examples thereof include under dry air and under an inert gas.
- the sheet for an all-solid-state secondary battery of the present invention is a sheet-like molded body capable of forming a constituent layer of an all-solid-state secondary battery, and includes various aspects depending on its use.
- a sheet preferably used for a solid electrolyte layer also referred to as a solid electrolyte sheet for an all-solid secondary battery
- an electrode or a sheet preferably used for a laminate of an electrode and a solid electrolyte layer (an electrode for an all-solid secondary battery).
- Sheet and the like.
- these various sheets are collectively referred to as an all-solid-state secondary battery sheet.
- the solid electrolyte sheet for an all-solid secondary battery of the present invention may be a sheet having a solid electrolyte layer, and even a sheet having a solid electrolyte layer formed on a base material does not have a base material and is a solid electrolyte layer. It may be a sheet formed of.
- the solid electrolyte sheet for an all-solid secondary battery may have another layer in addition to the solid electrolyte layer. Examples of other layers include a protective layer (release sheet), a current collector, a coat layer, and the like.
- the solid electrolyte sheet for an all-solid secondary battery of the present invention for example, a sheet having a layer composed of the inorganic solid electrolyte-containing composition of the present invention, a normal solid electrolyte layer, and a protective layer on a substrate in this order.
- the solid electrolyte layer contained in the solid electrolyte sheet for an all-solid secondary battery is preferably formed of the inorganic solid electrolyte-containing composition of the present invention.
- the content of 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-state secondary battery is the same as the layer thickness of each layer described in the all-solid-state 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 a material described in the current collector described later, a sheet body (plate-like body) such as an organic material and an inorganic material.
- a material described in the current collector described later a sheet body (plate-like body) such as an organic material and an inorganic material.
- the organic material include various polymers, and specific examples thereof include polyethylene terephthalate, polypropylene, polyethylene, and cellulose.
- the inorganic material include glass and ceramics.
- the electrode sheet for an all-solid-state 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 base material (current collector).
- the sheet may be a sheet that does not have a base material and is formed from an active material layer.
- This electrode sheet is usually a sheet having a current collector and an active material layer, but an embodiment having a current collector, an active material layer and a solid electrolyte layer in this order, and a current collector, an active material layer and a solid electrolyte. An embodiment having a layer and an active material layer in this order is also included.
- the solid electrolyte layer and the active material layer of the electrode sheet are preferably formed of the inorganic solid electrolyte-containing composition of the present invention.
- the content of each component in the solid electrolyte layer or the active material layer is not particularly limited, but preferably, the content of each component in the solid content of the inorganic solid electrolyte-containing composition (composition for electrode layer) of the present invention. Synonymous with quantity.
- the layer thickness of each layer constituting the electrode sheet of the present invention is the same as the layer thickness of each layer described in the all-solid-state secondary battery described later.
- the electrode sheet of the present invention may have the other layers described above.
- the all-solid-state secondary battery sheet of the present invention at least one layer of the solid electrolyte layer and the active material layer is formed of the inorganic solid electrolyte-containing composition of the present invention, and solid particles are firmly bonded while suppressing an increase in resistance. It has a worn constituent layer. Therefore, it exhibits high resistance to bending (flexibility).
- the sheet for an all-solid-state secondary battery of the present invention can be produced by industrial production, for example, a roll-to-roll method having high productivity, in which defects in the constituent layers are suppressed.
- the sheet for an all-solid-state secondary battery of the present invention is used for the production of an all-solid-state secondary battery having low resistance and excellent cycle characteristics when used as a constituent layer of the all-solid-state secondary battery, particularly for industrial production. , Contribute. Therefore, the sheet for an all-solid-state secondary battery of the present invention is suitably used as a sheet capable of forming a constituent layer of an all-solid-state secondary battery.
- an all-solid-state secondary battery is manufactured using the sheet for an all-solid-state secondary battery of the present invention, it is possible to realize excellent cycle characteristics with low resistance in spite of high productivity.
- the method for producing the sheet for an all-solid secondary battery of the present invention is not particularly limited, and the sheet can be produced by forming each of the above layers using the inorganic solid electrolyte-containing composition of the present invention.
- a film is formed (coating and drying) on a base material or a current collector (which may be via another layer) to form a layer (coating and drying layer) composed of an inorganic solid electrolyte-containing composition.
- the method can be mentioned. Thereby, an all-solid-state secondary battery sheet having a base material or a current collector and a coating dry layer can be produced.
- the coating dry layer is a layer formed by applying the inorganic solid electrolyte-containing composition of the present invention and drying the dispersion medium (that is, the inorganic solid electrolyte-containing composition of the present invention is used.
- the dispersion medium may remain as long as the effects of the present invention are not impaired, and the residual amount may be, for example, 3% by mass or less in each layer.
- each step such as coating and drying will be described in the following method for producing an all-solid-state secondary battery.
- the coating dry layer obtained as described above can also be pressurized.
- the pressurizing conditions and the like will be described later in the method for manufacturing an all-solid-state secondary battery.
- the base material, the protective layer (particularly the release sheet) and the like can be peeled off.
- the all-solid secondary battery of the present invention has a positive electrode active material layer, a negative electrode active material layer facing the positive electrode active material layer, and a solid electrolyte layer arranged between the positive electrode active material layer and the negative electrode active material layer.
- the positive electrode active material layer is preferably formed on the positive electrode current collector to form the positive electrode.
- the negative electrode active material layer is preferably formed on the negative electrode current collector to form the negative electrode.
- At least one layer of the negative electrode active material layer, the positive electrode active material layer and the solid electrolyte layer is preferably formed of the inorganic solid electrolyte-containing composition of the present invention, and at least the negative electrode active material layer contains the inorganic solid electrolyte of the present invention.
- the negative electrode active material layer and the solid electrolyte layer are formed of the inorganic solid electrolyte-containing composition of the present invention, and all the layers are the inorganic solid electrolyte-containing composition of the present invention. It is more preferably formed of an object.
- the active material layer or the solid electrolyte layer formed of the inorganic solid electrolyte-containing composition of the present invention is preferably one in the solid content of the inorganic solid electrolyte-containing composition of the present invention with respect to the component species contained therein and the content ratio thereof. Is the same as.
- the active material layer or the solid electrolyte layer is not formed by the inorganic solid electrolyte-containing composition of the present invention
- a known material can be used.
- the thicknesses of the negative electrode active material layer, the solid electrolyte layer, and the positive electrode active material layer are not particularly limited.
- the thickness of each layer is preferably 10 to 1,000 ⁇ m, more preferably 20 ⁇ m or more and less than 500 ⁇ m, respectively, in consideration of the dimensions of a general all-solid-state secondary battery.
- 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 positive electrode active material layer and the negative electrode active material layer may each have a current collector on the opposite side of the solid electrolyte layer.
- the all-solid-state secondary battery of the present invention may be used as an all-solid-state secondary battery with the above structure, but in order to form a dry battery, it should be further enclosed in a suitable housing.
- the housing may be made of metal or resin (plastic).
- a metallic material for example, one made of aluminum alloy or stainless steel can be mentioned.
- the metallic housing is divided into a positive electrode side housing and a negative electrode side housing, and electrically connected to the positive electrode current collector and the negative electrode current collector, respectively. It is preferable that the housing on the positive electrode side and the housing on the negative electrode side are joined and integrated via a gasket for preventing a short circuit.
- FIG. 1 is a schematic cross-sectional view showing an all-solid-state secondary battery (lithium ion secondary battery) according to a preferred embodiment of the present invention.
- the all-solid-state secondary battery 10 of the present embodiment has a negative electrode current collector 1, a negative electrode active material layer 2, a solid electrolyte layer 3, a positive electrode active material layer 4, and a positive electrode current collector 5 in this order when viewed from the negative electrode side. ..
- Each layer is in contact with each other and has an adjacent structure.
- the lithium ions (Li + ) accumulated in the negative electrode are returned to the positive electrode side, and electrons are supplied to the operating portion 6.
- a light bulb is used as a model for the operating portion 6, and the light bulb is turned on by electric discharge.
- the all-solid-state secondary battery having the layer structure shown in FIG. 1 When the all-solid-state secondary battery having the layer structure shown in FIG. 1 is placed in a 2032-inch coin case, the all-solid-state secondary battery is referred to as an all-solid-state secondary battery laminate, and the all-solid-state secondary battery laminate is referred to as an all-solid-state secondary battery laminate.
- a battery manufactured by putting it in a 2032 type coin case is sometimes called an all-solid-state secondary battery.
- the positive electrode active material layer, the solid electrolyte layer, and the negative electrode active material layer are all formed of the inorganic solid electrolyte-containing composition of the present invention.
- the all-solid-state secondary battery 10 exhibits excellent battery performance.
- the inorganic solid electrolyte and the composite polymer particles contained in the positive electrode active material layer 4, the solid electrolyte layer 3, and the negative electrode active material layer 2 may be of the same type or different from each other.
- either or both of the positive electrode active material layer and the negative electrode active material layer may be simply referred to as an active material layer or an electrode active material layer.
- either or both of the positive electrode active material and the negative electrode active material may be collectively referred to as an active material or an electrode active material.
- the composite polymer particles when used in combination with solid particles such as an inorganic solid electrolyte or an active material for the constituent layer, the solid particles are firmly bound while suppressing an increase in resistance as described above. It is possible to realize an all-solid-state secondary battery with low resistance and excellent cycle characteristics even if it is manufactured by the industrially advantageous roll-to-roll method.
- the negative electrode active material layer can be a lithium metal layer.
- the lithium metal layer include a layer formed by depositing or molding a lithium metal powder, a lithium foil, a lithium vapor deposition film, and the like.
- the thickness of the lithium metal layer can be, for example, 1 to 500 ⁇ m regardless of the thickness of the negative electrode active material layer.
- the positive electrode current collector 5 and the negative electrode current collector 1 are preferably electron conductors.
- either or both of the positive electrode current collector and the negative electrode current collector may be collectively referred to as a current collector.
- a current collector As a material for forming the positive electrode current collector, in addition to aluminum, aluminum alloy, stainless steel, nickel and titanium, the surface of aluminum or stainless steel is treated with carbon, nickel, titanium or silver (a thin film is formed). Of these, aluminum and aluminum alloys are more preferable.
- As a material for forming the negative electrode current collector in addition to aluminum, copper, copper alloy, stainless steel, nickel and titanium, carbon, nickel, titanium or silver is treated on the surface of aluminum, copper, copper alloy or stainless steel.
- aluminum, copper, copper alloy and stainless steel are more preferable.
- the shape of the current collector is usually a film sheet, but a net, a punched body, a lath body, a porous body, a foam body, a molded body of a fiber group, or the like can also be used.
- the thickness of the current collector is not particularly limited, but is preferably 1 to 500 ⁇ m. Further, it is also preferable that the surface of the current collector is made uneven by surface treatment.
- a layer formed of a known constituent layer forming material can be applied to the positive electrode active material layer.
- a functional layer, a member, or the like is appropriately interposed or arranged between or outside each of the negative electrode current collector, the negative electrode active material layer, the solid electrolyte layer, the positive electrode active material layer, and the positive electrode current collector. You may. Further, each layer may be composed of a single layer or a plurality of layers.
- the all-solid-state secondary battery can be manufactured by a conventional method. Specifically, the all-solid-state secondary battery can be manufactured by forming each of the above layers using the inorganic solid electrolyte-containing composition or the like of the present invention. The details will be described below.
- the inorganic solid electrolyte-containing composition of the present invention is appropriately applied onto a base material (for example, a metal foil serving as a current collector) to form a coating film (film formation).
- a method including (via) a step a method for producing a sheet for an all-solid-state secondary battery of the present invention
- an inorganic solid electrolyte-containing composition containing a positive electrode active material is applied as a positive electrode material (composition for a positive electrode layer) on a metal foil which is a positive electrode current collector to form a positive electrode active material layer.
- a positive electrode sheet for a solid secondary battery is produced.
- an inorganic solid electrolyte-containing composition for forming the solid electrolyte layer is applied onto the positive electrode active material layer to form the solid electrolyte layer.
- an inorganic solid electrolyte-containing composition containing a negative electrode active material is applied as a negative electrode material (composition for the negative electrode layer) on the solid electrolyte layer to form a negative electrode active material layer.
- a negative electrode current collector metal foil
- an all-solid secondary battery having a structure in which a solid electrolyte layer is sandwiched between the positive electrode active material layer and the negative electrode active material layer can be obtained. Can be done. This can be enclosed in a housing to obtain a desired all-solid-state secondary battery.
- a negative electrode active material layer, a solid electrolyte layer and a positive electrode active material layer are formed on the negative electrode current collector, and the positive electrode current collectors are superposed to manufacture an all-solid secondary battery. You can also do it.
- a positive electrode sheet for an all-solid-state secondary battery is produced. Further, an inorganic solid electrolyte-containing composition containing a negative electrode active material is applied as a negative electrode material (composition for a negative electrode layer) on a metal foil which is a negative electrode current collector to form a negative electrode active material layer. A negative electrode sheet for a solid secondary battery is manufactured. Next, a solid electrolyte layer is formed on the active material layer of any one of these sheets as described above.
- the other of the positive electrode sheet for the all-solid-state secondary battery and the negative electrode sheet for the all-solid-state secondary battery is laminated on the solid electrolyte layer so that the solid electrolyte layer and the active material layer are in contact with each other.
- an all-solid-state secondary battery can be manufactured.
- the following method can be mentioned. That is, as described above, a positive electrode sheet for an all-solid-state secondary battery and a negative electrode sheet for an all-solid-state secondary battery are 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 composed of a solid electrolyte layer.
- the positive electrode sheet for the all-solid-state secondary battery and the negative electrode sheet for the all-solid-state secondary battery are laminated so as to sandwich the solid electrolyte layer peeled from the base material. In this way, an all-solid-state secondary battery can be manufactured. Further, as described above, a positive electrode sheet for an all-solid-state secondary battery or a negative electrode sheet for an all-solid-state secondary battery, and a solid electrolyte sheet for an all-solid-state secondary battery are produced. Next, the positive electrode sheet for the all-solid secondary battery or the negative electrode sheet for the all-solid secondary battery and the solid electrolyte sheet for the all-solid secondary battery were brought into contact with the positive electrode active material layer or the negative electrode active material layer and the solid electrolyte layer.
- the solid electrolyte layer is transferred to the positive electrode sheet for the all-solid-state secondary battery or the negative electrode sheet for the all-solid-state secondary battery.
- the solid electrolyte layer from which the base material of the solid electrolyte sheet for the all-solid secondary battery is peeled off and the negative electrode sheet for the all-solid secondary battery or the positive electrode sheet for the all-solid secondary battery are separated (the negative electrode active material layer or the negative electrode active material layer on the solid electrolyte layer). (With the positive electrode active material layer in contact), pressurize the layers. In this way, an all-solid-state secondary battery can be manufactured.
- the pressurizing method and pressurizing conditions in this method are not particularly limited, and the methods and pressurizing conditions described later in the pressurization of the applied composition can be applied.
- the solid electrolyte layer or the like can also be formed by, for example, forming an inorganic solid electrolyte-containing composition or the like on a substrate or an active material layer by pressure molding under the pressure conditions described later.
- the inorganic solid electrolyte-containing composition of the present invention may be used as any one of the positive electrode layer composition, the inorganic solid electrolyte-containing composition, and the negative electrode layer composition, and the negative electrode layer composition. It is preferable to use the inorganic solid electrolyte-containing composition of the present invention, and the inorganic solid electrolyte-containing composition of the present invention can be used for any of the compositions.
- the solid electrolyte layer or the active material layer is formed by a composition other than the solid electrolyte composition of the present invention
- examples of the material include commonly used compositions and the like. Further, it belongs to the first group or the second group of the periodic table, which is accumulated in the negative electrode current collector by the initialization or charging during use, which will be described later, without forming the negative electrode active material layer at the time of manufacturing the all-solid secondary battery.
- a negative electrode active material layer can also be formed by combining metal ions with electrons and depositing them as a metal on a negative electrode current collector or the like.
- the solid electrolyte layer or the like can be formed, for example, by pressure-molding the solid electrolyte composition or the like on a substrate or the active material layer under the pressure conditions described later, or a sheet molded body of the solid electrolyte or the active material. It can also be used.
- the method for applying the composition containing an inorganic solid electrolyte is not particularly limited and can be appropriately selected.
- coating preferably wet coating
- spray coating spin coating coating
- dip coating coating dip coating coating
- slit coating stripe coating
- bar coating coating can be mentioned.
- the inorganic solid electrolyte-containing composition may be subjected to a drying treatment after being applied to each of them, or may be subjected to a drying treatment 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.
- the dispersion medium can be removed and a solid state (coating dry layer) can be obtained. Further, it is preferable because the temperature is not raised too high and each member of the all-solid-state secondary battery is not damaged. As a result, in an all-solid-state secondary battery, it is possible to obtain excellent overall performance, good binding properties, and good ionic conductivity even without pressurization.
- the inorganic solid electrolyte-containing composition of the present invention is applied and dried as described above, the solid particles are firmly bound to each other, and a coating and drying layer having a small interfacial resistance between the solid particles can be formed.
- the pressurizing method include a hydraulic cylinder press machine and the like.
- the pressing force is not particularly limited, and is generally preferably in the range of 5 to 1500 MPa.
- the applied inorganic solid electrolyte-containing composition may be heated at the same time as pressurization.
- the heating temperature is not particularly limited, and is generally in the range of 30 to 300 ° C. It can also be pressed at a temperature higher than the glass transition temperature of the inorganic solid electrolyte.
- the pressurization may be performed in a state where the coating solvent or the dispersion medium is dried in advance, or may be performed in a state where the solvent or the dispersion medium remains.
- each composition may be applied at the same time, and the application drying press may be performed simultaneously and / or sequentially. After coating on separate substrates, they may be laminated by transfer.
- the atmosphere during the manufacturing process is not particularly limited, and is in the atmosphere, in dry air (dew point -20 ° C or less), in an inert gas (for example, in argon gas, helium gas, nitrogen gas). And so on.
- the pressing time may be short (for example, within several hours) and high pressure may be applied, or medium pressure may be applied for a long time (1 day or more).
- an all-solid-state secondary battery restraint screw tightening pressure, etc.
- the press pressure may be uniform or different with respect to the pressed portion such as the sheet surface.
- the press pressure can be changed according to the area or film thickness of the pressed portion. It is also possible to change the same part step by step with different pressures.
- the pressed surface may be smooth or roughened.
- each of the above-mentioned layers particularly the coating and drying of the composition containing an inorganic solid electrolyte, can be performed by a so-called batch method using a single-wafer-shaped base material.
- the roll-to-roll method which has high productivity among industrial production methods, can also be used.
- the all-solid-state secondary battery manufactured as described above is preferably initialized after manufacturing or before use.
- the initialization is not particularly limited, and can be performed, for example, by performing initial charging / discharging with the press pressure increased, and then releasing the pressure until the pressure reaches the general working pressure of the all-solid-state secondary battery.
- the all-solid-state secondary battery of the present invention can be applied to various applications.
- the application mode is not particularly limited, but for example, when mounted on an electronic device, a laptop computer, a pen input computer, a mobile computer, an electronic book player, a mobile phone, a cordless phone handset, a pager, a handy terminal, a mobile fax, or a mobile phone. Examples include copying, mobile printers, headphone stereos, video movies, LCD TVs, handy cleaners, portable CDs, mini discs, electric shavers, transceivers, electronic notebooks, calculators, memory cards, portable tape recorders, radios, backup power supplies, etc.
- Other consumer products include automobiles, electric vehicles, motors, lighting equipment, toys, game equipment, road conditioners, watches, strobes, cameras, medical equipment (pacemakers, hearing aids, shoulder massagers, etc.). Furthermore, it can be used for various munitions and space. It can also be combined with a solar cell.
- Composite polymer particles P-1 composed of a low-polarity polymer (P1-1) and a high-polarity polymer (P2-1) were prepared. It is presumed that the composite polymer particles P-1 have a core-shell structure having a core made of a highly polar polymer (P2-1) and a shell made of a low polar polymer (P1-1).
- the obtained dispersion is heated to 40 ° C. and reduced to 40 hPa with an evaporator to distill off a part of the solvent and adjust the solid content concentration to adjust the solid content concentration of the composite polymer particles P-.
- the DIBK dispersion of 1 was obtained.
- Synthesis Examples 2 to 19 Synthesis of composite polymer particles P-2 to 9, 15, 16, 18, 19 and 21 to 24, 33 and 34 (composite polymer particle dispersions P-2 to 9, 15, 16, 18) , 19 and 21-24, 33 and 34)]
- Synthesis Example 1 a compound that guides each component so that the low-polarity polymer (P1) and the high-polarity polymer (P2) have the composition (type and content of the component) and the polymer mass ratio shown in Table 1 is used. If necessary, the composite polymer particles P-2 to P-2 to the same as in Synthesis Example 1 except that the DIBK used for preparing the dispersion liquid of the low polar polymer (P1-1) was changed to the dispersion medium shown in Table 1.
- a composite polymer P-10 was prepared in the same manner as in Synthesis Example 1 except for the above.
- the composite polymer particles are presumed to have a core-shell structure having a core made of a highly polar polymer and a shell made of a low polar polymer.
- Synthesis Examples 21-23 Synthesis of Composite Polymer Particles P-11, 12 and 20 (Preparation of Composite Polymer Particle Dispersions P-11, 12 and 20)] Synthesis Example 20 except that a compound that guides each component so that the highly polar polymer (P2) has the composition (type and content of the component) and the polymer mass ratio shown in Table 1 is used in Synthesis Example 20.
- the composite polymer particles P-11, 12 and 20, respectively were synthesized. It is presumed that all of the obtained composite polymer particles have a core-shell structure having a core made of a high-polarity polymer and a shell made of a low-polarity polymer. Then, using each of the synthesized composite polymer particles, the composite polymer particle dispersions P-11, 12 and 20, respectively, were prepared in the same manner as in the preparation of the composite polymer particle dispersion P-1.
- Composite polymer particles P-13 composed of a low-polarity polymer (P1-9) and two types of high-polarity polymers (P2-9 and P3-13) were prepared. It is presumed that the composite polymer particles P-13 have a core-shell structure having a core made of high-polarity polymers (P2-9 and P3-13) and a shell made of low-polarity polymer (P1-9). ..
- the obtained dispersion is heated to 40 ° C. and reduced to 40 hPa with an evaporator to distill off a part of the solvent and adjust the solid content concentration to adjust the solid content concentration of the composite polymer particles P-. 13 dispersions were obtained.
- a low-polarity polymer (P1-14) of the composite polymer P-14 was obtained. Further, 15 g of the low-polarity polymer (P1-14) was transferred to a 200 mL flask, and 75 g of DIBK was added dropwise over 1 hour with stirring to prepare a dispersion of the low-polarity polymer (P1-14). Next, 500 mL of diisobutyl ketone and 50 g of a 3.0 mass% dispersion of the low-polarity polymer (P1-14) obtained above were placed in a 1000 mL three-necked flask, and the mixture was stirred at 25 ° C. and uniformly dispersed.
- composite polymer particles P-25 of a low-polarity polymer (P1-19) and a high-polarity polymer (P2-25) It is presumed that the composite polymer particles P-25 have a core-shell structure having a core made of a highly polar polymer (P2-25) and a shell made of a low polar polymer (P1-19).
- the obtained dispersion is heated to 40 ° C. and reduced to 40 hPa with an evaporator to distill off a part of the solvent and adjust the solid content concentration to adjust the solid content concentration of the composite polymer particles P-. Twenty-five dispersions were obtained.
- a high-polarity polymer (P2-CP2) polymer by setting a container on Fritsch's planetary ball mill P-7 (trade name, manufactured by Fritsch) and performing mechanical milling at a temperature of 25 ° C. and a rotation speed of 600 rpm for 10 hours.
- a particle dispersion CP-2 was obtained.
- composite polymer particles CP-3 After that, 120 m of azobisisobutyronitrile (molecular weight 164, manufactured by Fujifilm Wako Co., Ltd.) was added, and the mixture was stirred at 90 ° C. for 8 hours to prepare composite polymer particles CP-3. It is presumed that the obtained composite polymer particles CP-3 have a core-shell structure having a core made of a low-polarity polymer (P1-CP3) and a shell made of a high-polarity polymer (P2-CP3).
- P1-CP3 low-polarity polymer
- P2-CP3 high-polarity polymer
- Synthesis Example 33 Synthesis of Composite Polymer Particles P-26 (Preparation of Composite Polymer Particle Dispersion Solution P-26)]
- Synthesis Example 1 the same procedure as in Synthesis Example 1 except that a compound for guiding each component so that the low-polarity polymer (P1) has the composition (type and content of components) shown in Table 1 was used.
- a dispersion of a low polar polymer (P26-1) was obtained.
- 50 g of the 3.0 mass% dispersion of the low-polarity polymer (P26-1) obtained above was placed in a 300 mL three-necked flask, stirred at 25 ° C., and uniformly dispersed.
- D-400 trade name JEFFAMINE (registered trademark) D-400, manufactured by HUNTSMAN
- 4.5 g of triethylamine were added dropwise over 30 minutes and stirred for 1 hour. Accompanied. After that, the mixture was heated to 60 ° C., 4.5 g of terephthalic acid dichloride (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) dissolved in 20 g of THF was added dropwise over 2 hours, and stirring was continued at 60 ° C. for 7 hours for filtration.
- composite polymer particles P-26 composed of a low-polarity polymer (P26-1) and a high-polarity polymer (P26-2) were prepared. It is presumed that the composite polymer particles P-26 have a core-shell structure having a core made of a high-polarity polymer (P26-2) and a shell made of a low-polarity polymer (P26-1).
- the obtained dispersion is heated to 40 ° C. and reduced to 40 hPa with an evaporator to distill off a part of the solvent and adjust the solid content concentration to adjust the solid content concentration of the composite polymer particles P-. Twenty-six DIBK dispersions were obtained.
- Synthesis Examples 34 and 35 Synthesis of Composite Polymer Particles P-27 and P-28 (Preparation of Composite Polymer Particle Dispersions P-27 and P-28)]
- Synthesis Example 33 a compound that guides each component so that the low-polarity polymer (P1) and the high-polarity polymer (P2) have the composition (type and content of the component) and the polymer mass ratio shown in Table 1 was used. Except for the above, the composite polymer particles P-27 and P-28 were synthesized in the same manner as in Synthesis Example 33, respectively. It is presumed that all of the obtained composite polymer particles have a core-shell structure having a core made of a high-polarity polymer and a shell made of a low-polarity polymer. Then, using each of the synthesized composite polymer particles, the composite polymer particle dispersions P-27 and P-28 were prepared in the same manner as in the preparation of the composite polymer particle dispersion P-33.
- the highly polar polymer (P30-2) constituting the composite polymer particles P-30 was synthesized. Further, 15 g of the P30-2 solution was transferred to a 200 mL flask, and 75 g of DIBK was added dropwise over 1 hour with stirring to obtain a dispersion of a highly polar polymer (P30-2). Next, 136 g of DIBK was added to a 500 mL three-necked flask, and the mixture was stirred at 80 ° C. under a nitrogen stream.
- the composite polymer particles P-30 have a core-shell structure having a core made of a high-polarity polymer (P30-2) and a shell made of a low-polarity polymer (P30-1).
- the obtained dispersion is heated to 40 ° C. and reduced to 40 hPa with an evaporator to distill off a part of the solvent and adjust the solid content concentration to adjust the solid content concentration of the composite polymer particles P-.
- Thirty DIBK dispersions were obtained.
- Synthesis Example 37 Synthesis of Composite Polymer Particles P-29 (Preparation of Composite Polymer Particle Dispersion Solution P-29)]
- Synthesis Example 36 a compound that guides each component so that the low-polarity polymer (P1) and the high-polarity polymer (P2) have the composition (type and content of the component) and the polymer mass ratio shown in Table 1 was used. Except for the above, the composite polymer particles P-29 were synthesized in the same manner as in Synthesis Example 36. It is presumed that the obtained composite polymer particles have a core-shell structure having a core made of a highly polar polymer and a shell made of a low polar polymer. Then, each of the synthesized composite polymer particles was used to prepare a composite polymer particle dispersion P-29 in the same manner as in the preparation of the composite polymer particle dispersion P-30.
- Toluene (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) (465.5 g) was added to a 2 L 3-neck flask, and the monomer solution was added dropwise over 2 hours to a place where the mixture was stirred at 80 ° C. After completion of the dropping, the mixture was stirred at 80 ° C. for 2 hours, then heated to 90 ° C. and stirred for 2 hours.
- Diisobutyl ketone was added thereto, and methanol was distilled off under reduced pressure to obtain a diisobutyl ketone solution of macromonomer 1.
- the solid content concentration was 48.9% by mass.
- Macromonomer 1 30.7 g solid 15 g was added to a 300 mL three-necked flask and dissolved in 51.7 g of diisobutyl ketone. This solution was stirred at 80 ° C. and dissolved in 210 g of diisobutyl ketone.
- AEHS Mono oxalate (2-acryloyloxyethyl) 10 g (manufactured by Tokyo Chemical Industry Co., Ltd.), Dimethylacrylamide 25 g (manufactured by Tokyo Chemical Industry Co., Ltd.), V-601 (Product name, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) 0.5 g of the low polar polymer (P31-1) constituting the composite polymer particles P-31 by dropping 0.5 g over 4 hours and continuing heating and stirring for another 4 hours. A dispersion was obtained.
- the high-polarity polymer (P31-2) had the composition (type and content of component) and polymer mass ratio shown in Table 1. Except for this, the composite polymer P-31 was prepared in the same manner as in Synthesis Example 1.
- the composite polymer particles are presumed to have a core-shell structure having a core made of a highly polar polymer and a shell made of a low polar polymer.
- Synthesis Example 39 Synthesis of Composite Polymer Particles P-32 (Preparation of Composite Polymer Particle Dispersion Solution P-32)]
- Synthesis Example 38 a compound that guides each component so that the low-polarity polymer (P1) and the high-polarity polymer (P2) have the composition (type and content of the component) and the polymer mass ratio shown in Table 1 was used. Except for the above, the composite polymer particles P-39 were synthesized in the same manner as in Synthesis Example 38. It is presumed that the obtained composite polymer particles have a core-shell structure having a core made of a highly polar polymer and a shell made of a low polar polymer. Then, each of the synthesized composite polymer particles was used to prepare a composite polymer particle dispersion P-39 in the same manner as in the preparation of the composite polymer particle dispersion P-38.
- the composition of each polymer synthesized, the SP value, and the average primary particle size of each composite polymer particle (referred to as "average particle size” in Table 1), and the total polymer of low polar constituent units in the prepared composite polymer particles.
- the content in the polymer and the content ratio (mass ratio) of the polymer contained in the composite polymer particles are shown in Table 1, respectively.
- the ClogP value of the dispersion medium is also described in the "dispersion medium” column, and the bond (I) that each polymer has in the main chain is described in each polymer column of Table 1.
- the SP value of the polymer and the particle size of the composite polymer particles were measured by the above method.
- those having a basic functional group are the low-polarity polymer (P1-8) of the composite polymer particles P-8, the low-polarity polymer (P1-17) of the composite polymer particles P-17, and the composite polymer.
- those having an acidic functional group are the low-polar polymers (P1) of the composite polymer particles P-9, P-13 and P-14, the high-polar polymers (P2-18) of the composite polymer particles P-18, and the composite.
- -Components represented by formula (I-3B)- PEG200 Polyethylene glycol (number average molecular weight 200, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., SP value: 24.0 (urethane bond), 22.4 (carbonate bond), 21.8 (ester bond))
- PEG600 Polyethylene glycol (number average molecular weight 600, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., SP value: 22.3)
- PPG700 Polypropylene glycol (number average molecular weight 700, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., SP value: 20.1)
- PTMG250 Polytetramethylene glycol (number average molecular weight 250, manufactured by SIGMA-Aldrich, SP value: 21.1)
- NISSO PB-GI1000 Hydrogenated liquid polybutadiene diol (trade name, number average molecular weight 1400, manufactured by Nippon Soda Co., Ltd., SP value: 17.5 (urethane bond), 17.3 (carbonate bond)), the structure is as follows. Shown. NISSO PB-GI3000: Hydrogenated liquid polybutadienediol (trade name, number average molecular weight 3000, manufactured by Nippon Soda Corporation, SP value: 17.4), the structure of which is shown below. NISSO PB-G1000: Liquid polybutadiene diol (trade name, number average molecular weight 1500, manufactured by Nippon Soda Corporation, SP value: 17.8), the structure of which is shown below.
- KF-8021 (manufactured by Shin-Etsu Chemical Co., Ltd., SP value: 16.3 (Okizu method), both-terminal amino-modified silicone)
- Li 2 S lithium sulfide
- Aldrich Corp. purity> 99.98%
- P 2 S 5. diphosphorus pentasulfide 3.90 g was weighed, placed in an agate mortar, and mixed for 5 minutes using an agate mortar.
- Example 1 In Example 1, the prepared composite polymer particle dispersions P-1 to P-34 and CP-1 to CP-6 were used to prepare an inorganic solid electrolyte-containing composition and a sheet for an all-solid secondary battery. Its characteristics were evaluated.
- composition containing inorganic solid electrolyte 60 g of zirconia beads having a diameter of 5 mm were put into a 45 mL container made of zirconia (manufactured by Fritsch), 4.85 g of LPS or LLZ synthesized in the above synthesis example A, and 0.05 g of the composite polymer particle dispersion liquid shown in Table 2 (solid content mass). ) And 16.0 g of the dispersion medium shown in Table 2 were added. After that, this container was set in a planetary ball mill P-7 (trade name) manufactured by Fritsch. Inorganic solid electrolyte-containing compositions S-1 to C-15 and SS-1 to SS-6 were prepared by mixing at a temperature of 25 ° C. and a rotation speed of 150 rpm for 10 minutes, respectively.
- Li-PS LPS synthesized in Synthesis Example A LLZ: Li 7 La 3 Zr 2 O 12 DIBK: Diisobutyl Ketone
- composition for positive electrode In a 45 mL container made of zirconia (manufactured by Fritsch), 60 g of zirconia beads having a diameter of 5 mm was put, 1.7 g of LPS or LLZ synthesized in Synthesis Example A, and 12.3 g (total amount) of heptane as a dispersion medium were put. ..
- This container was set on a planetary ball mill P-7 (trade name) manufactured by Fritsch, and stirred at 25 ° C. at a rotation speed of 200 pm for 30 minutes.
- LiNi 1/3 Co 1/3 Mn 1/3 O 2 (NMC, manufactured by Aldrich) or LiCoO 2 (LCO, manufactured by Aldrich) was added to this container as a conductive auxiliary agent.
- Add 0.2 g of acetylene black (AB) and 0.1 g of the composite polymer particle dispersion shown in Table 3 in terms of solid content set the container on the planetary ball mill P-7, and set the container at a temperature of 25 ° C. and a rotation speed of 200 rpm for 30. Mixing was continued for 1 minute to prepare positive electrode compositions (slurries) C-1 to C-41, respectively.
- composition for negative electrode 60 g of zirconia beads having a diameter of 5 mm were put into a 45 mL container made of zirconia (manufactured by Fritsch), 4.0 g of LPS or LLZ synthesized in Synthesis Example A, and 0.09 g (solid content) of the composite polymer particle dispersion shown in Table 3. (Mass) and 22 g (total amount) of heptane as a dispersion medium were added. This container was set on a planetary ball mill P-7 (trade name) manufactured by Fritsch, and mixed at a temperature of 25 ° C. and a rotation speed of 300 pm for 60 minutes.
- Si Silicon (manufactured by Aldrich)
- Sn Tin (manufactured by Aldrich)
- SiO Silicon oxide (manufactured by Aldrich)
- NMC LiNi 1/3 Co 1/3 Mn 1/3 O 2 (manufactured by Aldrich)
- LCO LiCoO 2 (manufactured by Aldrich)
- Li-PS LPS synthesized in Synthesis Example A LLZ: Li 7 La 3 Zr 2 O 12 AB: Acetylene Black (manufactured by Denka)
- the prepared negative electrode sheet for all-solid-state secondary battery having the solid-state electrolyte layer (the aluminum foil of the solid-state electrolyte sheet for all-solid-state secondary battery has been peeled off) was cut out into a disk shape having a diameter of 14.5 mm, and is shown in FIG. As shown, it was placed in a 2032 type coin case 11 made of stainless steel incorporating a spacer and a washer (not shown in FIG. 2).
- a positive electrode sheet piece for an all-solid secondary battery punched out from the positive electrode sheet for an all-solid secondary battery shown in the “Positive electrode active material layer” column of Table 4 with a diameter of 14.0 mm is laminated.
- a laminate 12 for a solid secondary battery (a laminate composed of a copper foil-negative electrode active material layer-solid electrolyte layer-positive electrode active material layer-aluminum foil) was formed. After that, by closing the 2032 type coin case 11, the coin type all-solid-state secondary battery No. 2 shown in FIG. 1 to 28 were produced respectively.
- the final film thicknesses of the negative electrode active material layer, the solid electrolyte layer and the positive electrode active material layer are shown in Tables 4-1 and 4-2.
- the coin-type all-solid-state secondary battery 13 manufactured in this manner has the layer structure shown in FIG.
- ⁇ Evaluation 1 Battery performance (resistance)> All-solid-state secondary battery No. The resistance was measured and evaluated as the battery performance (battery voltage) of 1 to 47. The resistance of each all-solid-state secondary battery was evaluated by a charge / discharge evaluation device: TOSCAT-3000 (trade name, manufactured by Toyo System Co., Ltd.). Specifically, each all-solid-state secondary battery was charged in an environment of 25 ° C. at a current density of 0.1 mA / cm 2 until the battery voltage reached 4.2 V. Then, the battery was discharged at a current density of 0.2 mA / cm 2 until the battery voltage reached 2.5 V.
- This one charge and one discharge were repeated as one charge / discharge cycle, and two cycles were charged / discharged, and the battery voltage after 5 mAh / g (electricity per 1 g of active material mass) was discharged in the second cycle was read.
- the resistance of the all-solid-state secondary battery was evaluated based on which of the following evaluation ranks the battery voltage was included in. The higher the battery voltage, the lower the resistance. In this test, the higher the evaluation rank, the better the battery performance.
- -Evaluation rank- 8 4.1V or more 7: 4.0V or more and less than 4.1V 6: 3.9V or more and less than 4.0V 5: 3.7V or more and less than 3.9V 4: 3.5V or more and less than 3.7V 3: 3.2V or more and less than 3.5V 2: 2.5V or more and less than 3.2V 1: Cannot charge / discharge
- the test piece was set with its solid electrolyte layer on the opposite side of the mandrel (base material on the mandrel side) and in the width direction parallel to the axis of the mandrel.
- the state of occurrence of defects was investigated by visually observing a range of 3 cm in width and 8 cm in length including the bent portion (a region up to 4 cm toward each end side centering on the bent portion). Defects are considered to occur when the solid electrolyte layer is chipped, cracked or cracked, or peeled off from the aluminum foil of the solid electrolyte layer, and the area of the generated defect is converted to the surface area of the solid electrolyte layer (projected area). Asked as.
- the battery was discharged at a current density of 0.1 mA / cm 2 until the battery voltage reached 2.5 V.
- This one charge and one discharge were set as one charge / discharge cycle, and charging / discharging was repeated for three cycles under the same conditions for initialization. After that, the above charge / discharge cycle was repeated, and the discharge capacity of each all-solid-state secondary battery was measured by a charge / discharge evaluation device: TOSCAT-3000 (trade name) each time the charge / discharge cycle was performed.
- -Evaluation rank- 8 500 cycles or more 7: 300 cycles or more, less than 500 cycles 6: 200 cycles or more, less than 300 cycles 5: 150 cycles or more, less than 200 cycles 4: 80 cycles or more, less than 150 cycles 3: 40 cycles or more, less than 80 cycles 2: 20 cycles or more, less than 40 cycles 1: Less than 20 cycles
- the inorganic solid electrolyte-containing composition that does not contain the composite polymer particles specified in the present invention is inferior in the binding property of the solid particles in the constituent layer.
- the all-solid-state secondary battery in which all the constituent layers were formed of such an inorganic solid electrolyte-containing composition did not have sufficient resistance and cycle characteristics.
- the composition containing an inorganic solid electrolyte containing the composite polymer particles specified in the present invention is used to form a constituent layer of an all-solid-state secondary battery, thereby forming a sheet for an all-solid-state secondary battery. The occurrence of defects in the layer can be suppressed.
- this inorganic solid electrolyte-containing composition for forming at least one layer, preferably all three layers of the constituent layers, it is possible to reduce the resistance and improve the cycle characteristics of the obtained all-solid secondary battery. In particular, it can be seen that even if the content of the low-polarity structural unit is less than 20% by mass, the desired effect is obtained.
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Abstract
Description
全固体二次電池の構成層を形成する材料(構成層形成材料)として、上述の無機固体電解質等を含有する材料が提案されている。
例えば、特許文献1には、(A)周期律表第1族又は第2族に属する金属のイオンの伝導性を有する無機固体電解質と、(B)ポリマーと、(C)分散媒とを含有する固体電解質組成物であって、(B)ポリマーが炭化水素ポリマーセグメントを主鎖に有し、この主鎖が結合群(I):エステル結合、アミド結合、ウレタン結合、ウレア結合、イミド結合、エーテル結合およびカーボネート結合から選択される結合を少なくとも1つ含む、固体電解質組成物が記載されている。この固体電解質組成物では(B)ポリマーを単独で用いている。また、特許文献2は、無機固体電解質と、平均粒径30~300nmの粒子状ポリマーからなる結着剤を特定の非極性溶媒に溶解又は分散してなる全固体二次電池用のスラリーが記載されている。この特許文献2には、粒子状ポリマーとして、(メタ)アクリルポリマーからなるコアシェル構造を有する粒子状ポリマーが記載されているに過ぎない。
このような問題を解決すべく、固体粒子に対してバインダーの併用が検討されている。しかし、バインダーは、一般的にイオン伝導性を有さないため、バインダーを用いた全固体二次電池は抵抗が増大して電池性能(電池電圧)の低下を来す。特に、固体粒子の結着力を強化するためにその使用量を増大させると、抵抗の増大は顕著になる。このように、固体粒子にバインダーを併用する場合、固体粒子の結着性と抵抗とはトレードオフの関係にあり、改善が望まれている。
<1>周期律表第1族若しくは第2族に属する金属のイオンの伝導性を有する無機固体電解質と、バインダーとを含有する無機固体電解質含有組成物であって、
バインダーが、少なくとも2種のポリマーを有する複合ポリマー粒子を含み、
ポリマーのうちの少なくとも1種が下記式(1)で表される結合を主鎖に有する、無機固体電解質含有組成物。
<3>複合ポリマー粒子に含まれるポリマーが、酸性官能基又は塩基性官能基を有する、<1>又は<2>に記載の無機固体電解質含有組成物。
<4>ClogP値が1.0以上の有機溶媒を含有する、<1>~<3>のいずれか1つに記載の無機固体電解質含有組成物。
<5>複合ポリマー粒子の平均一次粒子径が0.1nm~5.0μmである、<1>~<4>のいずれか1つに記載の無機固体電解質含有組成物。
<6>少なくとも2種のポリマーの内、
少なくとも1種のポリマーが、SP値が15J0.5/cm1.5以上20.5J0.5/cm1.5未満である構成単位を5質量%以上有する低極性ポリマーであり、
少なくとも1種のポリマーが、SP値が20.5J0.5/cm1.5以上40J0.5/cm1.5以下の構成単位を90質量%以上有する高極性ポリマーである、<1>~<5>のいずれか1つに記載の無機固体電解質含有組成物。
<7>高極性のポリマーが式(1)で表される結合を有する、<6>に記載の無機固体電解質含有組成物。
<8>複合ポリマー粒子に含まれる全ポリマー中の、低極性ポリマーの含有率が1~70質量%であり、高極性のポリマーの含有率が30~99質量%である、<6>又は<7>に記載の無機固体電解質含有組成物。
<9>式(1)で表される結合が、ウレタン結合、ウレア結合、アミド結合、イミド結合、エステル結合、カーボネート結合、チオウレア結合、チオウレタン結合、イミダゾール結合又はトリアゾール結合を形成する、<1>~<8>のいずれか1つに記載の無機固体電解質含有組成物。
<10>活物質を含有する、<1>~<9>のいずれか1つに記載の無機固体電解質含有組成物。
<11>活物質が、ケイ素元素又はスズ元素を含有する活物質である、<10>に記載の無機固体電解質含有組成物。
<12>導電助剤を含有する、<1>~<11>のいずれか1つに記載の無機固体電解質含有組成物。
<13>無機固体電解質が硫化物系無機固体電解質である、<1>~<12>のいずれか1つに記載の無機固体電解質含有組成物。
<14>上記<1>~<13>のいずれか1つに記載の無機固体電解質含有組成物で構成した層を有する全固体二次電池用シート。
<15>正極活物質層と固体電解質層と負極活物質層とをこの順で具備する全固体二次電池であって、
正極活物質層、固体電解質層及び負極活物質層の少なくとも1つの層が、上記<1>~<13>のいずれか1つに記載の無機固体電解質含有組成物で構成した層である、全固体二次電池。
<16>上記<1>~<13>のいずれか1つに記載の無機固体電解質含有組成物を製膜する、全固体二次電池用シートの製造方法。
<17>上記<16>に記載の製造方法を経て全固体二次電池を製造する、全固体二次電池の製造方法。
本発明の上記及び他の特徴及び利点は、適宜添付の図面を参照して、下記の記載からより明らかになるであろう。
本発明において化合物の表示(例えば、化合物と末尾に付して呼ぶとき)については、この化合物そのもののほか、その塩、そのイオンを含む意味に用いる。また、本発明の効果を損なわない範囲で、置換基を導入するなど一部を変化させた誘導体を含む意味である。
本発明において、(メタ)アクリルとは、アクリル及びメタアクリルの一方又は両方を意味する。(メタ)アクリレートについても同様である。
本発明において、置換又は無置換を明記していない置換基、連結基等(以下、置換基等という。)については、その基に適宜の置換基を有していてもよい意味である。よって、本発明において、単に、YYY基と記載されている場合であっても、このYYY基は、置換基を有しない態様に加えて、更に置換基を有する態様も包含する。これは置換又は無置換を明記していない化合物についても同義である。好ましい置換基としては、例えば後述する置換基Zが挙げられる。
本発明において、特定の符号で示された置換基等が複数あるとき、又は複数の置換基等を同時若しくは択一的に規定するときには、それぞれの置換基等は互いに同一でも異なっていてもよいことを意味する。また、特に断らない場合であっても、複数の置換基等が隣接するときにはそれらが互いに連結したり縮環したりして環を形成していてもよい意味である。
本発明において、ポリマーは、重合体を意味するが、いわゆる高分子化合物と同義である。
本発明の無機固体電解質含有組成物は、周期律表第1族若しくは第2族に属する金属のイオンの伝導性を有する無機固体電解質と、複合ポリマー粒子とを含有する。
本発明の無機固体電解質含有組成物が含有する複合ポリマー粒子は、少なくとも無機固体電解質含有組成物で形成した層中において、無機固体電解質(更には、共存しうる、活物質、導電助剤)等の固体粒子同士(例えば、無機固体電解質同士、無機固体電解質と活物物質、活物質同士)を結着させる結着剤として、機能する。更には、集電体と固体粒子とを結着させる結着剤として機能することもある。なお、本発明の無機固体電解質含有組成物が含有する複合ポリマー粒子は、無機固体電解質含有組成物中において、固体粒子同士を結着させる機能を有していてもいなくてもよい。
本発明の無機固体電解質含有組成物は、無機固体電解質が分散媒中に分散したスラリーであることが好ましい。この場合、複合ポリマー粒子は、固体粒子を分散媒中に分散させる機能を有する。また、複合ポリマー粒子は、通常、分散媒中に(固体状態で)分散しているが、本発明の効果を損なわない範囲でその一部が分散媒に溶解していてもよい。
その理由の詳細はまだ明らかではないが、次のように考えられる。すなわち、複合ポリマー粒子を形成するポリマーのうち少なくとも1つのポリマーを、後述する特定の結合を主鎖に有するポリマーとする。これにより、このポリマーが固体粒子又は集電体に対する密着性を発現して、固体粒子同士又は固体粒子と集電体とを結着させることができる。しかも、この複合ポリマー粒子は、2種以上のポリマーを一体化して複合体に形成されているから、固体粒子等を更に強固に結着させることができる。
また、本発明の無機固体電解質含有組成物は、全固体二次電池用シート等の作製時に好ましくは分散媒を含有するスラリーとして用いられる。このとき、分散媒に対する分散性を調整する化学構造部(後述する低極性構成単位等)を、複合ポリマー粒子を構成するポリマーに一律に導入する必要はなく、その含有率を任意に設定することができる。そのため、分散性を低下させることなく、固体粒子の結着性等に寄与する化学構造部の含有率を相対的に高めることができ、固体粒子等の結着力を強固なものとすることができる。
このような強固な結着性を示す複合ポリマー粒子は、固体粒子等を結着させる際に、粒子形状を維持して固体粒子の表面全体ではなく一部に密着する。そのため、固体粒子の表面同士の接触を遮断することなく、電子伝導パス及び/又はイオン伝導パスを確保できる。
このような複合ポリマー粒子の作用機能により、本発明の無機固体電解質含有組成物を用いて作製した全固体二次電池用シートは、構成層について欠陥発生、更には抵抗上昇の抑制が可能となる。また、この構成層を備えた全固体二次電池は優れたサイクル特性と電池の低抵抗化とを達成できる。
以下、本発明の無機固体電解質含有組成物が含有する成分及び含有しうる成分について説明する。
本発明の無機固体電解質含有組成物は、無機固体電解質を含有する。
本発明において、無機固体電解質とは、無機の固体電解質のことであり、固体電解質とは、その内部においてイオンを移動させることができる固体状の電解質のことである。主たるイオン伝導性材料として有機物を含むものではないことから、有機固体電解質(ポリエチレンオキシド(PEO)などに代表される高分子電解質、リチウムビス(トリフルオロメタンスルホニル)イミド(LiTFSI)などに代表される有機電解質塩)とは明確に区別される。また、無機固体電解質は定常状態では固体であるため、通常カチオン及びアニオンに解離又は遊離していない。この点で、電解液、又は、ポリマー中でカチオン及びアニオンに解離若しくは遊離している無機電解質塩(LiPF6、LiBF4、リチウムビス(フルオロスルホニル)イミド(LiFSI)、LiClなど)とも明確に区別される。無機固体電解質は周期律表第1族若しくは第2族に属する金属のイオンの伝導性を有するものであれば、特に限定されず、電子伝導性を有さないものが一般的である。本発明の全固体二次電池がリチウムイオン電池の場合、無機固体電解質は、リチウムイオンのイオン伝導性を有することが好ましい。
上記無機固体電解質は、全固体二次電池に通常使用される固体電解質材料を適宜選定して用いることができる。例えば、無機固体電解質としては、(i)硫化物系無機固体電解質、(ii)酸化物系無機固体電解質、(iii)ハロゲン化物系無機固体電解質、及び、(iv)水素化物系無機固体電解質が挙げられ、活物質と無機固体電解質との間により良好な界面を形成することができる観点から、硫化物系無機固体電解質が好ましい。
硫化物系無機固体電解質は、硫黄原子を含有し、かつ、周期律表第1族若しくは第2族に属する金属のイオン伝導性を有し、かつ、電子絶縁性を有するものが好ましい。硫化物系無機固体電解質は、元素として少なくともLi、S及びPを含有し、リチウムイオン伝導性を有しているものが好ましいが、目的又は場合に応じて、Li、S及びP以外の他の元素を含んでもよい。
La1Mb1Pc1Sd1Ae1 (S1)
式中、LはLi、Na及びKから選択される元素を示し、Liが好ましい。Mは、B、Zn、Sn、Si、Cu、Ga、Sb、Al及びGeから選択される元素を示す。Aは、I、Br、Cl及びFから選択される元素を示す。a1~e1は各元素の組成比を示し、a1:b1:c1:d1:e1は1~12:0~5:1:2~12:0~10を満たす。a1は1~9が好ましく、1.5~7.5がより好ましい。b1は0~3が好ましく、0~1がより好ましい。d1は2.5~10が好ましく、3.0~8.5がより好ましい。e1は0~5が好ましく、0~3がより好ましい。
硫化物系無機固体電解質は、例えば硫化リチウム(Li2S)、硫化リン(例えば五硫化二燐(P2S5))、単体燐、単体硫黄、硫化ナトリウム、硫化水素、ハロゲン化リチウム(例えばLiI、LiBr、LiCl)及び上記Mで表される元素の硫化物(例えばSiS2、SnS、GeS2)の中の少なくとも2つ以上の原料の反応により製造することができる。
酸化物系無機固体電解質は、酸素原子を含有し、かつ、周期律表第1族若しくは第2族に属する金属のイオン伝導性を有し、かつ、電子絶縁性を有するものが好ましい。
酸化物系無機固体電解質は、イオン伝導度として、1×10-6S/cm以上であることが好ましく、5×10-6S/cm以上であることがより好ましく、1×10-5S/cm以上であることが特に好ましい。上限は特に制限されないが、1×10-1S/cm以下であることが実際的である。
またLi、P及びOを含むリン化合物も望ましい。例えばリン酸リチウム(Li3PO4); リン酸リチウムの酸素の一部を窒素で置換したLiPON; LiPOD1(D1は、好ましくは、Ti、V、Cr、Mn、Fe、Co、Ni、Cu、Zr、Nb、Mo、Ru、Ag、Ta、W、Pt及びAuから選ばれる1種以上の元素である。)等が挙げられる。
更に、LiA1ON(A1は、Si、B、Ge、Al、C及びGaから選ばれる1種以上の元素である。)等も好ましく用いることができる。
ハロゲン化物系無機固体電解質は、ハロゲン原子を含有し、かつ、周期律表第1族若しくは第2族に属する金属のイオンの伝導性を有し、かつ、電子絶縁性を有する化合物が好ましい。
ハロゲン化物系無機固体電解質としては、特に制限されないが、例えば、LiCl、LiBr、LiI、ADVANCED MATERIALS,2018,30,1803075に記載のLi3YBr6、Li3YCl6等の化合物が挙げられる。中でも、Li3YBr6、Li3YCl6を好ましい。
水素化物系無機固体電解質は、水素原子を含有し、かつ、周期律表第1族若しくは第2族に属する金属のイオン伝導性を有し、かつ、電子絶縁性を有する化合物が好ましい。
水素化物系無機固体電解質としては、特に制限されないが、例えば、LiBH4、Li4(BH4)3I、3LiBH4-LiCl等が挙げられる。
無機固体電解質の粒子径の測定は、以下の手順で行う。無機固体電解質粒子を、水(水に不安定な物質の場合はヘプタン)を用いて20mLサンプル瓶中で1質量%の分散液を希釈調製する。希釈後の分散液試料は、1kHzの超音波を10分間照射し、その直後に試験に使用する。この分散液試料を用い、レーザ回折/散乱式粒度分布測定装置LA-920(商品名、HORIBA社製)を用いて、温度25℃で測定用石英セルを使用してデータ取り込みを50回行い、体積平均粒子径を得る。その他の詳細な条件等は必要により日本産業規格(JIS) Z 8828:2013「粒子径解析-動的光散乱法」の記載を参照する。1水準につき5つの試料を作製しその平均値を採用する。
固体電解質層を形成する場合、固体電解質層の単位面積(cm2)当たりの無機固体電解質の質量(mg)(目付量)は特に制限されるものではない。設計された電池容量に応じて、適宜に決めることができ、例えば、1~100mg/cm2とすることができる。
ただし、無機固体電解質含有組成物が後述する活物質を含有する場合、無機固体電解質の目付量は、活物質と無機固体電解質との合計量が上記範囲であることが好ましい。
ただし、無機固体電解質含有組成物が後述する活物質を含有する場合、無機固体電解質含有組成物中の無機固体電解質の含有量は、活物質と無機固体電解質との合計含有量が上記範囲であることが好ましい。
本発明において、固形分(固形成分)とは、無機固体電解質含有組成物を、1mmHgの気圧下、窒素雰囲気下150℃で6時間乾燥処理したときに、揮発若しくは蒸発して消失しない成分をいう。典型的には、後述の分散媒以外の成分を指す。
本発明の無機固体電解質含有組成物は、少なくとも全固体二次電池の構成層中において固体粒子を結着させるバインダーとして、複合ポリマー粒子を含有し、更には適宜に通常用いられる各種バインダーを含有してもよい。
本発明の無機固体電解質含有組成物が含有する複合ポリマー粒子(本発明の複合ポリマー粒子)について説明する。
本発明の複合ポリマー粒子は、少なくとも2種のポリマーを含み、これらポリマーのうちの少なくとも1種が後述する式(1)で表される結合(結合(I)ということがある。)を主鎖に有する複合ポリマー粒子であって、好ましくは平均一次粒子径が0.1nm~5.0μmである複合ポリマー粒子である。この複合ポリマー粒子は、ClogP値が1.0以上である有機溶媒を含む分散媒に分散する特性を有している。本発明において、「分散媒に分散する」とは、分散媒中に、固体状態で、通常粒子として、分散することをいい、一部が分散媒に溶解している態様を包含する。分散状態での複合ポリマー粒子の粒径は後述する平均一次粒子径と同じである。
本発明の複合ポリマー粒子は、全固体二次電池用の無機固体電解質含有組成物において無機固体電解質等の固体粒子と併用することにより、無機固体電解質含有組成物(スラリー)中での分散性を高めることができる。また、無機固体電解質含有組成物で形成される構成層の抵抗低減及び結着性の強化に寄与し、この構成層を備えた全固体二次電池に優れたサイクル特性と低抵抗を付与する。
本発明において、複合ポリマー粒子とは、複数のポリマー粒子の単なる混合物(共沈物、集合物、凝集物を含む。)ではなく、少なくとも2種のポリマー(若しくは粒子)を一体化させてなる複合粒子、通常1つの粒子として認識可能なものをいう。ポリマー(若しくは粒子)の一体化は、特に制限されないが、例えば、機械的、物理的若しくは化学的な相互作用若しくは結合、更には構造的一体化等が挙げられる。構造的一体化としては、例えば、特定のポリマーを別のポリマーが被覆(内蔵)しているコアシェル構造、ミクロ相分離構造、相互貫入高分子網目(IPN)構造等が挙げられる。
コアシェル構造による複合化において、コアを形成するポリマー(若しくは粒子)とシェルを形成するポリマー(若しくは粒子)とは、上述の相互作用を示し、若しくは結合を形成していてもよい。コアを形成するポリマー(コア層)はその少なくとも一部がシェルを形成するポリマー(シェル層)で被覆されていればよく、コアの被覆量は特に限定されない。また、シェル層の層厚も特に限定されない。本発明においては、被覆量、シェル層の層厚は、例えば、コアを形成するポリマー(若しくは粒子)とシェルを形成するポリマー(若しくは粒子)との質量比で特定することができ、その質量比を、[コアを形成するポリマー:シェルを形成するポリマー]で示すと、例えば、30~99:70~1であることが好ましく、70~99:30~1であることがより好ましく、80~99:20~1であることが更に好ましい。
複合ポリマー粒子を形成するポリマーの詳細は後述するが、複合ポリマー粒子を形成する複数のポリマーのうち少なくとも1種、好ましくは1種若しくは2種、より好ましくは2種が、後述する式(1)で表される結合(I)を主鎖に有するポリマーである。複合ポリマー粒子がこの結合(I)を有するポリマーを含むことにより、固体粒子等に密着して固体粒子同士等を強固に結着させることができる。主鎖中に組み込まれる結合(I)の数は、少なくとも1つであればよく、ポリマーの重合度、質量平均分子量等に応じて、適宜に設定される。
高極性構成単位を有するポリマーは、複合ポリマー粒子を形成するポリマーのうち、少なくとも1種のポリマーであることが好ましく、1種若しくは2種のポリマーであることが好ましく、全ポリマーであることがより好ましい。各ポリマーが有する高極性構成単位は、1種でも2種以上でもよく、適宜に設定される。
低極性構成単位を有するポリマーは、複合ポリマー粒子を形成するポリマーのうち、少なくとも1種のポリマーであることが好ましく、1種のポリマーであることがより好ましい。各ポリマーが有する低極性構成単位は、1種でも2種以上でもよく、適宜に設定される。
複合ポリマー粒子の表面に存在するポリマーは、分散性の点で、低極性構成単位を有していることが好ましく、低極性構成単位及び高極性構成単位の両構成単位を含有していることがより好ましい。
本発明においては、SP値を算出するに際して、ポリマー(セグメント)が連鎖重合系ポリマー(セグメント)である場合、原料化合物に由来する構成成分と同じ構成単位とするが、ポリマー(セグメント)が下記式(1)で表される結合(I)を有するポリマー(セグメント)である場合、原料化合物に由来する構成成分と異なる単位とする。
例えば、結合(I)を有するポリマーとしてポリウレタンを例に挙げると、SP値を特定する構成単位は次のように規定される。ポリイソシアネート化合物に由来する構成単位としては、ポリイソシアネート化合物に由来する後記式(I-1)で表される構成成分に対して、1つの-NH-CO-基に-O-基を結合させ、かつ残りの-NH-CO-基を除去した単位(1つのウレタン結合を有する単位)とする。一方、ポリオール化合物に由来する構成単位としては、ポリオール化合物に由来する後記式(I-3)で表される構成成分に対して、1つの-O-基に-CO-NH-基を結合させ、かつ残りの-O-基を除去した単位(1つのウレタン結合を有する単位)とする。
なお、結合(I)を有するポリマーとしてその他の逐次重合系ポリマーの場合もポリウレタンと同様に構成単位を決定する。
低極性ポリマーは、好ましくは、SP値が15J0.5/cm1.5以上20.5J0.5/cm1.5未満である構成単位を5質量%以上有するポリマーであり、より好ましくはSP値が20.5J0.5/cm1.5以上40J0.5/cm1.5以下である構成単位を有する。高極性ポリマーは、好ましくは、SP値が20.5J0.5/cm1.5以上40J0.5/cm1.5以下の構成単位を90質量%以上有するポリマーであり、SP値が15J0.5/cm1.5以上20.5J0.5/cm1.5未満である構成単位を有していてもよい。
本発明において、あるポリマーが上記で規定する低極性ポリマー及び上記高極性ポリマーの両ポリマーに相当するときは、必要に応じて、各ポリマーにおける後述する構成成分の含有量で区別し、更には後述する各ポリマーのSP値で区別することとする。
ここで、各構成単位は上述の低極性構成単位及び高極性構成単位に対応する。
複合ポリマー粒子に含まれる低極性ポリマー及び高極性ポリマーは、それぞれ、特に制限されないが、1~3種であることが好ましく、1種又は2種であることがより好ましい。
一方、1種の高極性ポリマーにおいて、高極性構成単位の含有量は、結着性の点で、90質量%以上であれば特に制限されないが、低極性ポリマーとともに複合ポリマー粒子を形成する全ポリマー中の高極性構成単位の含有量を満たす範囲に設定されることが好ましい。例えば、1種の高極性ポリマー中の高極性構成単位の含有量は、95質量%以上がより好ましい。1種の高極性ポリマーが低極性構成単位を含有する場合、その含有量は、特に制限されず、低極性ポリマーとともに複合ポリマー粒子を形成する全ポリマー中の低極性構成単位の含有量を満たす範囲に設定されることが好ましく、例えば、10質量%以下がより好ましく、5質量%以下が更に好ましく、0質量%とすることもできる。
(1)構成単位のSP値
上記構成単位(低極性構成単位及び高極性構成単位等)のSP値は、次のようにして求める。
まず、ポリマーについて、上述の通り、SP値を特定する構成単位を決定する。
次いで、特に断らない限り、構成単位毎のSP値をHoy法によって求める(H.L.Hoy JOURNAL OF PAINT TECHNOLOGY Vol.42,No.541,1970,76-118、及びPOLYMER HANDBOOK 4th、59章、VII 686ページ Table5、Table6及びTable6中の下記式参照)。また、その単位はJ1/2cm-3/2である。
上記のようにして決定した構成単位と求めたSP値を用いて、下記式から算出する。
SPp 2=(SP1 2×W1)+(SP2 2×W2)+・・・
式中、SP1、SP2・・・は構成単位のSP値を示し、W1、W2・・・は構成単位の質量分率を示す。
本発明において、構成単位の質量分率は、当該構成単位に対応する構成成分(この構成分分を導く原料化合物)のポリマー中の質量分率とする。
複合ポリマー粒子が低極性ポリマー及び高極性ポリマーを含有する場合、両ポリマーの含有率は好ましくは上記範囲に設定されるが、低極性ポリマーの含有率に対する高極性ポリマーの含有率の比(高極性ポリマーの含有率/低極性ポリマーの含有率)は、例えば、1~99が好ましく、9~99がより好ましい。
また、複合ポリマー粒子の表面に存在するポリマーは、結合(I)を有するポリマーでも、この結合(I)を有さないポリマーでもよい。一方、複合ポリマー粒子の内部に存在するポリマーは、結合(I)を有さないポリマーでもよいが、結合(I)を有するポリマーが好ましい。結着性の更なる強化の点で、複合ポリマー粒子の表面に存在するポリマー及び複合ポリマー粒子の内部に存在するポリマーがいずれも結合(I)を有するポリマーであることが好ましい。
塩基性官能基としては、特に制限されないが、アミノ基、ピリジン基が挙げられ、特にアミノ基が好ましい。アミノ基としては、特に限定されず、例えば、炭素数0~20のアミノ基が挙げられる。アミノ基は、アルキルアミノ基及びアリールアミノ基を含む。アミノ基の炭素数は、0~12が好ましく、0~6がより好ましく、0~2が更に好ましい。アミノ基としては、例えば、アミノ、N,N-ジメチルアミノ、N,N-ジエチルアミノ、N-エチルアミノ、アニリノ等が挙げられる。アミノ基は塩を形成していてもよい。
ポリマーが1分子中に有する上記官能基の数は、1つ以上であればよく、複数を有することが好ましい。また、官能基を少なくとも1つ有していれば、官能基の種類数も、特に制限されず、1種でも2種以上でもよい。
本発明において、周期律表第14族に属する原子としては、例えば、炭素、ケイ素、ゲルマニウム、スズ等の各原子が挙げられ、同第15族に属する原子としては、例えば、窒素、リン、ヒ素等の各原子が挙げられ、同第16族に属する原子としては、例えば、酸素、硫黄、セレン等の各原子が挙げられる。
Xとして採りうる原子としては、特に制限されないが、第16族に属する原子が好ましく、酸素原子がより好ましい。Xとして第15族に属する原子を採る場合、この原子はその価数に応じて水素原子若しくは置換基(特に断らない限り、置換基は好ましくは後述する置換基Zから選択れる基である。)を有する。この置換基としてはアルキル基又はアリール基が好ましく挙げられる。
Yとして採りうる原子としては、特に制限されず、ポリマーの種類に応じて適宜に選択され、窒素、リン、酸素又は硫黄の各原子が好ましく、窒素原子又は酸素原子がより好ましい。なお、Yが第15族に属する原子を採る場合、この原子は水素原子、アルキル基又はアリール基を有する。X又はYが有しうるアルキル基及びアリール基は置換基Zのアルキル基又はアリール基と同義である。
Zとして採りうる原子としては、4価を採りうる原子が挙げられ、第14族に属する原子が好ましく、炭素原子がより好ましい。なお、Zは、第15族に属する原子としてリン原子等を採ることもできる。この場合、原子の価数に応じて水素原子若しくは置換基を有していてもよい。
X~Zの組み合わせは、特に制限されず、例えば、それぞれが好ましくとりうる上記各原子同士の組み合わせが挙げられ、より具体的には後述する結合を形成する組み合わせが挙げられる。
上記結合(I)を含む結合は直鎖若しくは分岐鎖構造を有していてもよく、環構造を有していてもよい。結合(I)を含む環構造としては、特に制限されないが、イミド環、イミダゾール環、トリアゾール環等が挙げられる。この結合(I)を含む結合が主鎖に組み込まれる態様は、特に制限されず、結合(I)のY及びZの少なくとも一方が結合部となって主鎖に組み込まれる態様、他の原子若しくは原子群が結合部となって主鎖に組み込まれる態様等が挙げられる。
結合(I)を含む結合(結合(I)が形成する結合)としては、好ましくは、ウレタン結合、ウレア結合、アミド結合、イミド結合、エステル結合、カーボネート結合、チオウレア結合、チオウレタン結合、イミダゾール結合又はトリアゾール結合の少なくとも1つが挙げられ、ウレタン結合、ウレア結合、アミド結合、エステル結合又はカーボネート結合が好ましい。本発明において、チオウレタン結合には、ウレタン結合中のカルボニル基(-CO-)及びオキシ基(-O-)の少なくとも1つの酸素原子が硫黄原子に置換された3種の結合を包含する。また、イミダゾール結合及びトリアゾール結合とは、イミダゾール環又はトリアゾール環から2つの水素原子を除去してなる2価の環状結合(連結基)を意味し、除去される水素原子は、特に制限されないが、炭素原子に結合する水素原子であることが好ましい。
主鎖が含む結合(I)は、ポリマー分子間又は分子内で水素結合することにより、全固体二次電池等の構成層中の固体粒子等の結着性向上に寄与する。これらの結合(I)がポリマー内で水素結合を形成する場合、水素結合は、結合(I)同士で形成されてもよく、結合(I)と主鎖が有するそれ以外の結合(I)とで形成されてもよい。結合(I)は、互いに水素結合を形成可能な点で、水素結合を形成する水素原子を有していること(結合(I)のYが水素原子を有していること)が好ましい。
結合(I)は、ポリマーの主鎖中に含まれる限り特に制限されるものでなく、構成成分(繰り返し単位)中に含まれる態様及び/又は異なる構成成分同士を繋ぐ結合として含まれる態様のいずれでもよい。また、主鎖に含まれる結合(I)は、1種に限定されず、2種以上であってもよく、1~6種が好ましく、1~4種がより好ましい。この場合、主鎖の結合様式は、特に制限されず、2種以上の結合(I)をランダムに有していてもよく、特定の結合を有するセグメントと他の結合を有するセグメントとのセグメント化された主鎖でもよい。
RP1及びRP2としてとりうる上記分子鎖は、特に制限されないが、炭化水素鎖、ポリアルキレンオキシド鎖、ポリカーボネート鎖又はポリエステル鎖が好ましく、炭化水素鎖又はポリアルキレンオキシド鎖がより好ましく、炭化水素鎖、ポリエチレンオキシド鎖又はポリプロピレンオキシド鎖が更に好ましい。
低分子量の炭化水素鎖は、通常の(非重合性の)炭化水素基からなる鎖であり、この炭化水素基としては、例えば、脂肪族若しくは芳香族の炭化水素基が挙げられ、具体的には、アルキレン基(炭素数は1~12が好ましく、1~6がより好ましく、1~3が更に好ましい)、アリーレン基(炭素数は6~22が好ましく、6~14が好ましく、6~10がより好ましい)、又はこれらの組み合わせからなる基が好ましい。RP2としてとりうる低分子量の炭化水素鎖を形成する炭化水素基としては、アルキレン基がより好ましく、炭素数2~6のアルキレン基が更に好ましく、炭素数2又は3のアルキレン基が特に好ましい。この炭化水素鎖は置換基として重合鎖(例えば(メタ)アクリルポリマー)を有していてもよい。
芳香族の炭化水素基は、例えば、後掲する各例示の構成成分が有する炭化水素基が挙げられ、アリーレン基(例えば、後述する置換基Zで挙げたアリール基から更に水素原子を1つ以上除去した基、具体的にはフェニレン基、トリレン基若しくはキシリレン基)又は下記式(M2)で表される炭化水素基が好ましい。
RM2~RM5は、それぞれ、水素原子又は置換基を示し、水素原子が好ましい。RM2~RM5としてとりうる置換基としては、特に制限されず、後述する置換基Zが挙げられ、例えば、炭素数1~20のアルキル基、炭素数1~20のアルケニル基、-ORM6、―N(RM6)2、-SRM6(RM6は置換基を示し、好ましくは炭素数1~20のアルキル基又は炭素数6~10のアリール基を示す。)、ハロゲン原子(例えば、フッ素原子、塩素原子、臭素原子)が好ましく挙げられる。-N(RM6)2としては、アルキルアミノ基(炭素数は、1~20が好ましく、1~6がより好ましい)又はアリールアミノ基(炭素数は、6~40が好ましく、6~20がより好ましい)が挙げられる。
末端反応性基を有する炭化水素ポリマーとしては、例えば、いずれも商品名で、NISSO PBシリーズ(日本曹達社製)、クレイソールシリーズ(巴工業社製)、PolyVEST-HTシリーズ(エボニック社製)、poly-bdシリーズ(出光興産社製)、poly-ipシリーズ(出光興産社製)、EPOL(出光興産社製)及びポリテールシリーズ(三菱化学社製)等が好適に用いられる。
ポリカーボネート鎖又はポリエステル鎖としては、公知のポリカーボネート又はポリエステルからなる鎖が挙げられる。
ポリアルキレンオキシ鎖、ポリカーボネート鎖又はポリエステル鎖は、それぞれ、末端にアルキル基(炭素数は1~12が好ましく、1~6がより好ましい)を有することが好ましい。
RP1及びRP2としてとりうるポリアルキレンオキシ鎖、ポリカーボネート鎖及びポリエステル鎖の末端は、RP1及びRP2として上記各式で表される構成成分に組み込み可能な通常の化学構造に適宜に変更することができる。例えば、ポリアルキレンオキシ鎖は末端酸素原子が取り除かれて上記構成成分のRP1又はRP2として組み込まれる。
上記各式において、RP1及びRP2は2価の分子鎖であるが、少なくとも1つの水素原子が-NH-CO-、-CO-、-O-、-NH-又は-N<で置換されて、3価以上の分子鎖となっていてもよい。
RP2は、上記分子鎖の中でも、低分子量の炭化水素鎖(より好ましくは脂肪族の炭化水素基)、又は低分子量の炭化水素鎖以外の分子鎖が好ましく、低分子量の炭化水素鎖及び低分子量の炭化水素鎖以外の分子鎖をそれぞれ含む態様も好ましい態様の1つである。この態様においては、式(I-3)、式(I-4)及び式(I-6)のいずれかで表される構成成分は、RP2が低分子量の炭化水素基鎖である構成成分と、RP2が低分子量の炭化水素鎖以外の分子鎖である構成成分の少なくとも2種を含む。
なお、下記具体例において、構成成分中に繰り返し構造を有する場合、その繰り返し数は1以上の整数であり、上記分子鎖の分子量又は炭素原子数を満たす範囲で適宜に設定される。
特に、低極性ポリマーとしての、ウレタン結合を主鎖に有するポリマーは、式(I-1)で表される構成成分に加えて、RP2が分子鎖として上記の炭化水素ポリマー鎖である構成成分(好ましくは下記式(I-3C)で表される構成成分)を有することが好ましい。一方、高極性ポリマーとしての、ウレタン結合を主鎖に有するポリマーは、式(I-1)で表される構成成分に加えて、RP2が分子鎖として上記ポリアルキレンオキシド鎖である構成成分(好ましくは下記式(I-3B)で表される構成成分)を有することが好ましい。
結合(I)を有するポリマー中の、上記各式で表される構成成分以外の構成成分の含有量は、特に限定されないが、50質量%以下であることが好ましい。
すなわち、結合(I)を有するポリマー中の、式(I-1)若しくは式(I-2)で表される構成成分、又は式(I-5)で表されるカルボン酸二無水物由来の構成成分の含有量は、特に制限されず、0~90質量%であることが好ましく、0.01~70質量%であることがより好ましく、0.1~40質量%であることが更に好ましい。
結合(I)を有するポリマー中の、式(I-3)、式(I-4)又は式(I-6)で表される構成成分の含有量は、特に制限されず、0~95質量%であることが好ましく、5~75質量%であることがより好ましく、30~75質量%であることが更に好ましい。
式(I-3)又は式(I-4)で表される構成成分のうち、RP2が分子鎖として上記ポリアルキレンオキシ鎖である構成成分(例えば上記式(I-3B)で表される構成成分)の、結合(I)を有するポリマー中の含有量は、特に制限されないが、例えば、0~80質量%であることが好ましく、0~70質量%であることがより好ましく、0.1~60質量%であることが更に好ましく、10~50質量%であることが特に好ましい。
式(I-3)又は式(I-4)で表される構成成分のうち、RP2が分子鎖として上記炭化水素ポリマー鎖である構成成分(例えば上記式(I-3C)で表される構成成分)の、結合(I)を有するポリマー中の含有量は、特に制限されないが、例えば、0~90質量%であることが好ましく、5~85質量%であることがより好ましく、50~80質量%であることが更に好ましい。
結合(I)を有するポリマーは、上述の酸性官能基又は塩基性官能基を有することが好ましい。結合(I)を有するポリマーは、上記官能基を、ポリマーを形成するいずれの構成成分に有していてもよく、またポリマーの主鎖又は側鎖のいずれに有していてもよい。例えば、式(I-3A)で表される構成成分が挙げられる。
結合(I)を有するポリマー中における官能基の含有量は、特に制限されない。例えば、上記官能基を有する構成成分の、結合(I)を有するポリマーを構成する全構成成分中の割合は、0.01~20質量%が好ましく、0.1~15質量%がより好ましく、1~10質量%が特に好ましい。
アルキル基(好ましくは炭素数1~20のアルキル基、例えばメチル、エチル、イソプロピル、t-ブチル、ペンチル、ヘプチル、1-エチルペンチル、ベンジル、2-エトキシエチル、1-カルボキシメチル等)、アルケニル基(好ましくは炭素数2~20のアルケニル基、例えば、ビニル、アリル、オレイル等)、アルキニル基(好ましくは炭素数2~20のアルキニル基、例えば、エチニル、ブタジイニル、フェニルエチニル等)、シクロアルキル基(好ましくは炭素数3~20のシクロアルキル基、例えば、シクロプロピル、シクロペンチル、シクロヘキシル、4-メチルシクロヘキシル等、本明細書においてアルキル基というときには通常シクロアルキル基を含む意味であるが、ここでは別記する。)、アリール基(好ましくは炭素数6~26のアリール基、例えば、フェニル、1-ナフチル、4-メトキシフェニル、2-クロロフェニル、3-メチルフェニル等)、アラルキル基(好ましくは炭素数7~23のアラルキル基、例えば、ベンジル、フェネチル等)、ヘテロ環基(好ましくは炭素数2~20のヘテロ環基で、より好ましくは、少なくとも1つの酸素原子、硫黄原子、窒素原子を有する5又は6員環のヘテロ環基である。ヘテロ環基には芳香族ヘテロ環基及び脂肪族ヘテロ環基を含む。例えば、テトラヒドロピラン環基、テトラヒドロフラン環基、2-ピリジル、4-ピリジル、2-イミダゾリル、2-ベンゾイミダゾリル、2-チアゾリル、2-オキサゾリル、ピロリドン基等)、アルコキシ基(好ましくは炭素数1~20のアルコキシ基、例えば、メトキシ、エトキシ、イソプロピルオキシ、ベンジルオキシ等)、アリールオキシ基(好ましくは炭素数6~26のアリールオキシ基、例えば、フェノキシ、1-ナフチルオキシ、3-メチルフェノキシ、4-メトキシフェノキシ等、本明細書においてアリールオキシ基というときにはアリーロイルオキシ基を含む意味である。)、ヘテロ環オキシ基(上記ヘテロ環基に-O-基が結合した基)、アルコキシカルボニル基(好ましくは炭素数2~20のアルコキシカルボニル基、例えば、エトキシカルボニル、2-エチルヘキシルオキシカルボニル、ドデシルオキシカルボニル等)、アリールオキシカルボニル基(好ましくは炭素数6~26のアリールオキシカルボニル基、例えば、フェノキシカルボニル、1-ナフチルオキシカルボニル、3-メチルフェノキシカルボニル、4-メトキシフェノキシカルボニル等)、ヘテロ環オキシカルボニル基(上記ヘテロ環基に-O-CO-基が結合した基)、アミノ基(好ましくは炭素数0~20のアミノ基、アルキルアミノ基、アリールアミノ基を含み、例えば、アミノ(-NH2)、N,N-ジメチルアミノ、N,N-ジエチルアミノ、N-エチルアミノ、アニリノ等)、スルファモイル基(好ましくは炭素数0~20のスルファモイル基、例えば、N,N-ジメチルスルファモイル、N-フェニルスルファモイル等)、アシル基(アルキルカルボニル基、アルケニルカルボニル基、アルキニルカルボニル基、アリールカルボニル基、ヘテロ環カルボニル基を含み、好ましくは炭素数1~20のアシル基、例えば、アセチル、プロピオニル、ブチリル、オクタノイル、ヘキサデカノイル、アクリロイル、メタクリロイル、クロトノイル、ベンゾイル、ナフトイル、ニコチノイル等)、アシルオキシ基(アルキルカルボニルオキシ基、アルケニルカルボニルオキシ基、アルキニルカルボニルオキシ基、アリールカルボニルオキシ基、ヘテロ環カルボニルオキシ基を含み、好ましくは炭素数1~20のアシルオキシ基、例えば、アセチルオキシ、プロピオニルオキシ、ブチリルオキシ、オクタノイルオキシ、ヘキサデカノイルオキシ、アクリロイルオキシ、メタクリロイルオキシ、クロトノイルオキシ、ベンゾイルオキシ、ナフトイルオキシ、ニコチノイルオキシ等)、アリーロイルオキシ基(好ましくは炭素数7~23のアリーロイルオキシ基、例えば、ベンゾイルオキシ等)、カルバモイル基(好ましくは炭素数1~20のカルバモイル基、例えば、N,N-ジメチルカルバモイル、N-フェニルカルバモイル等)、アシルアミノ基(好ましくは炭素数1~20のアシルアミノ基、例えば、アセチルアミノ、ベンゾイルアミノ等)、アルキルチオ基(好ましくは炭素数1~20のアルキルチオ基、例えば、メチルチオ、エチルチオ、イソプロピルチオ、ベンジルチオ等)、アリールチオ基(好ましくは炭素数6~26のアリールチオ基、例えば、フェニルチオ、1-ナフチルチオ、3-メチルフェニルチオ、4-メトキシフェニルチオ等)、ヘテロ環チオ基(上記ヘテロ環基に-S-基が結合した基)、アルキルスルホニル基(好ましくは炭素数1~20のアルキルスルホニル基、例えば、メチルスルホニル、エチルスルホニル等)、アリールスルホニル基(好ましくは炭素数6~22のアリールスルホニル基、例えば、ベンゼンスルホニル等)、アルキルシリル基(好ましくは炭素数1~20のアルキルシリル基、例えば、モノメチルシリル、ジメチルシリル、トリメチルシリル、トリエチルシリル等)、アリールシリル基(好ましくは炭素数6~42のアリールシリル基、例えば、トリフェニルシリル等)、アルコキシシリル基(好ましくは炭素数1~20のアルコキシシリル基、例えば、モノメトキシシリル、ジメトキシシリル、トリメトキシシリル、トリエトキシシリル等)、アリールオキシシリル基(好ましくは炭素数6~42のアリールオキシシリル基、例えば、トリフェニルオキシシリル等)、ホスホリル基(好ましくは炭素数0~20のリン酸基、例えば、-OP(=O)(RP)2)、ホスホニル基(好ましくは炭素数0~20のホスホニル基、例えば、-P(=O)(RP)2)、ホスフィニル基(好ましくは炭素数0~20のホスフィニル基、例えば、-P(RP)2)、ホスホン酸基(好ましくは炭素数0~20のホスホン酸基、例えば、-PO(ORP)2)スルホ基(スルホン酸基)、カルボキシ基、ヒドロキシ基、スルファニル基、シアノ基、ハロゲン原子(例えばフッ素原子、塩素原子、臭素原子、ヨウ素原子等)が挙げられる。RPは、水素原子又は置換基(好ましくは置換基Zから選択される基)である。
また、これらの置換基Zで挙げた各基は、上記置換基Zが更に置換していてもよい。
上記アルキル基、アルキレン基、アルケニル基、アルケニレン基、アルキニル基及び/又はアルキニレン基等は、環状でも鎖状でもよく、また直鎖でも分岐していてもよい。
複合ポリマー粒子を形成するポリマーのうち結合(I)を主鎖に有さないポリマーとしては、特に制限されないが、非芳香族性の炭素-炭素二重結合を有する1種又は2種以上のモノマーが連鎖重合してなるポリマー(連鎖重合系ポリマー)等が挙げられる。例えば、フッ素系ポリマー(含フッ素ポリマー)、炭化水素系ポリマー、ビニル系ポリマー、(メタ)アクリルポリマーが好ましく、(メタ)アクリルポリマーがより好ましい。
(メタ)アクリルポリマー中におけるその他の重合性化合物(M2)の含有量は、特に制限されないが、例えば50モル%未満とすることができる。
酸素原子を含有する脂肪族複素環基は、エポキシ基含有基、オキセタン基含有基、テトラヒドロフリル基含有基などが好ましい。
R3は、R2と同義である。
L2は、連結基であり、上記L1と同義である。
L3は、連結基であり、上記L1と同義であるが、炭素数1~6(好ましくは1~3)のアルキレン基が好ましい。
mは1~200の整数であり、1~100の整数であることが好ましく、1~50の整数であることがより好ましい。
式(b-3)で表される化合物として、例えばノニルフェノキシポリエチレングリコールアクリレートが挙げられる。
また、式(b-1)~(b-3)において、アルキル基、アリール基、アルキレン基、アリーレン基など置換基を取ることがある基については、本発明の効果を損なわない範囲で置換基を有していてもよい。置換基としては、例えば上述の置換基Z並びに上述の酸性官能基及び塩基性官能基から選択される基が挙げられ、具体的には、ハロゲン原子、ヒドロキシ基、スルファニル基、アシル基、アシルオキシ基、アルコキシ基、アリールオキシ基、アリーロイル基、アリーロイルオキシ基等が挙げられる。
(メタ)アクリル化合物(M1)に由来する構成成分の、(メタ)アクリルポリマー中の含有量は、特に限定されないが、1~99質量%であることが好ましく、5~97質量%であることがより好ましく、10~95質量%であることが特に好ましい。
ビニル化合物(M2)に由来する構成成分の、(メタ)アクリルポリマー中の含有量は、特に限定されないが、0~30質量%であることが好ましく、0~20質量%であることがより好ましく、0~10質量%であることが特に好ましい。
(メタ)アクリルポリマーが後述する官能基を有する場合、上記構成成分のいずれが官能基を有していてもよく、官能基を有する構成成分の含有量は、後述する通りであるが、上記含有量も満たす。
結合(I)を主鎖に有さないポリマーは、上述の酸性官能基又は塩基性官能基を有することが好ましい。上記結合(I)を有さないポリマーは、上記官能基を、ポリマーを形成するいずれの構成成分に有していてもよく、またポリマーの主鎖又は側鎖のいずれに有していてもよい。
上記結合(I)を有さないポリマー中における官能基の含有量は、特に制限されない。例えば、上記官能基を有する構成成分の、上記結合(I)を有さないポリマーを構成する全構成成分中の割合は、上記結合(I)を主鎖に有するポリマーにおけるものと同じ範囲が好ましい。
上記結合(I)を主鎖に有さないポリマー(各構成成分及び原料化合物)は、上記酸性官能基及び塩基性官能基以外の置換基を有していてもよい。このような置換基としては、特に制限されないが、好ましくは上述の置換基Zから選択される基が挙げられる。
複合ポリマー粒子を形成するポリマーは、非架橋ポリマーであっても架橋ポリマーであってもよい。また、加熱又は電圧の印加によってポリマーの架橋が進行した場合には、上記分子量より大きな分子量となっていてもよい。好ましくは、全固体二次電池の使用開始時にポリマーが後述する範囲の質量平均分子量であることである。
複合ポリマー粒子の平均粒径は、上記無機固体電解質の粒子径と同様にして測定できる。
なお、全固体二次電池の構成層における複合ポリマー粒子の平均一次粒子径は、例えば、電池を分解して複合ポリマー粒子を含有する構成層を剥がした後、その構成層について測定を行い、予め測定していた複合ポリマー粒子以外の粒子の粒子径の測定値を排除することにより、測定することができる。
複合ポリマー粒子の平均一次粒子径は、例えば、分散媒の種類、ポリマー中の構成成分の含有量及び含有量等により、調整できる。
複合ポリマー粒子を形成するポリマーは、非晶質であることが好ましい。本発明において、ポリマーが「非晶質」であるとは、典型的には、ガラス転移温度で測定したときに結晶融解に起因する吸熱ピークが見られないことをいう。
本発明において、ポリマー、ポリマー鎖の分子量については、特に断らない限り、ゲルパーミエーションクロマトグラフィー(GPC)によって標準ポリスチレン換算の質量平均分子量及び数平均分子量をいう。その測定法としては、基本として下記条件1又は条件2(優先)の方法により測定した値とする。ただし、ポリマー等の種類によっては適宜適切な溶離液を選定して用いればよい。
(条件1)
カラム:TOSOH TSKgel Super AWM-H(商品名、東ソー社製)を2本つなげる
キャリア:10mMLiBr/N-メチルピロリドン
測定温度:40℃
キャリア流量:1.0ml/min
試料濃度:0.1質量%
検出器:RI(屈折率)検出器
(条件2)
カラム:TOSOH TSKgel Super HZM-H、TOSOH TSKgel Super HZ4000、TOSOH TSKgel Super HZ2000(いずれも商品名、東ソー社製)をつないだカラムを用いる。
キャリア:テトラヒドロフラン
測定温度:40℃
キャリア流量:1.0ml/min
試料濃度:0.1質量%
検出器:RI(屈折率)検出器
上記の複合ポリマー粒子の調製条件は、各方法に応じて通常行われる条件を適宜に選択することができる。シート重合条件としては、例えば後述する実施例での合成条件が挙げられる。
これに対して、上記結合(I)を有するポリマー等の逐次重合系ポリマーを含む複合ポリマーラテックスは、水系溶媒中で原料化合物を分散重合して複合粒子を調製した後に、有機溶剤へ転相させて調製することが通常である。そのため、水系溶媒中での重合又は有機溶剤への転相に際して、原料化合物の種類、その使用量等が制限され、目的とするポリマー組成を実現できないことがある。また、従来のシート重合は、水系溶媒中での、ラジカルを経由した連鎖重合による合成が一般的である。
シート重合法により、コアシェル構造を有する複合粒子を調製できる。
複合ポリマー粒子の、無機固体電解質含有組成物中の含有量は、結着性の点で、固形成分100質量%において、0.001質量%以上が好ましく、0.05質量%以上がより好ましく、0.1質量%以上が更に好ましく、0.2質量%以上が特に好ましい。上限としては、低抵抗化及びサイクル特性の点で、10質量%以下が好ましく、5質量%以下がより好ましく、3質量%以下が更に好ましい。
本発明の無機固体電解質含有組成物において、複合ポリマー粒子の質量に対する、無機固体電解質と活物質の合計質量(総量)の質量比[(無機固体電解質の質量+活物質の質量)/(複合ポリマー粒子の質量)]は、1,000~1の範囲が好ましい。この比率は1000~2がより好ましく、500~10が更に好ましい。
本発明の無機固体電解質含有組成物は、上記の各成分を分散させる分散媒を含有することが好ましい。
分散媒としては、使用環境において液状を示す有機化合物であればよく、例えば、各種有機溶媒が挙げられ、具体的には、アルコール化合物、エーテル化合物、アミド化合物、アミン化合物、ケトン化合物、芳香族化合物、脂肪族化合物、ニトリル化合物、エステル化合物等が挙げられる。
分散媒としては、非極性分散媒(疎水性の分散媒)でも極性分散媒(親水性の分散媒)でもよいが、優れた分散性を発現できる点で、非極性分散媒が好ましい。非極性分散媒とは、一般に水に対する親和性が低い性質をいうが、本発明においては、例えば、エステル化合物、ケトン化合物、エーテル化合物、香族化合物、脂肪族化合物等が挙げられる。
ケトン化合物としては、例えば、アセトン、メチルエチルケトン、メチルイソブチルケトン(MIBK)、シクロペンタノン、シクロヘキサノン、シクロヘプタノン、ジプロピルケトン、ジブチルケトン、ジイソプロピルケトン、ジイソブチルケトン(DIBK)、イソブチルプロピルケトン、sec-ブチルプロピルケトン、ペンチルプロピルケトン、ブチルプロピルケトンなどが挙げられる。
芳香族化合物としては、例えば、ベンゼン、トルエン、キシレン等が挙げられる。
脂肪族化合物としては、例えば、ヘキサン、ヘプタン、オクタン、ノナン、デカン、ドデカン、シクロヘキサン、メチルシクロヘキサン、エチルシクロヘキサン、シクロヘプタン、シクロオクタン、デカリン、パラフィン、ガソリン、ナフサ、灯油、軽油等が挙げられる。
ニトリル化合物としては、例えば、アセトニトリル、プロピオニトリル、イソブチロニトリルなどが挙げられる。
エステル化合物としては、例えば、酢酸エチル、酢酸ブチル、酢酸プロピル、酪酸プロピル、酪酸イソプロピル、酪酸ブチル、酪酸イソブチル、ペンタン酸ブチル、イソ酪酸エチル、イソ酪酸プロピル、イソ酪酸イソプロピル、イソ酪酸イソブチル、ピバル酸プロピル、ピバル酸イソプロピル、ピバル酸ブチル、ピバル酸イソブチルなどが挙げられる。
本発明において、CLogP値とは、1-オクタノールと水への分配係数Pの常用対数LogPを計算によって求めた値である。CLogP値の計算に用いる方法及びソフトウェアについては公知のものを用いることができるが、特に断らない限り、PerkinElmer社のChemDrawを用いて構造を描画し、算出した値とする。
有機溶媒を2種以上含有する場合、有機溶媒のClogP値は、各有機溶媒のClogP値と質量分率との積の和とする。
分散媒としては、1種用いてもよく、2種以上用いてもよい。2種以上用いる場合、1種はClogP値が1.0以上の上記有機溶媒が好ましく、別の有機溶媒は、複合ポリマー粒子の分散を損なわない限り特に限定されず、適宜に選択され、例えば、上述の、アルキレングリコール、アルキレングリコールモノアルキルエーテル、ジアルキルエーテル、環状エーテル等が挙げられる。
2種以上の分散媒を用いる場合、ClogP値が1.0以上の上記有機溶媒の含有量は、特に制限されず、例えば、分散媒全量に対して50~95質量%が挙げられる。2種以上の分散媒全体のClogP値は、特に制限されないが、上記ClogPの範囲を満たすことが好ましい。
本発明の無機固体電解質含有組成物には、周期律表第1族若しくは第2族に属する金属のイオンの挿入放出が可能な活物質を含有することもできる。活物質としては、以下に説明するが、正極活物質及び負極活物質が挙げられる。
本発明において、活物質(正極活物質又は負極活物質)を含有する無機固体電解質含有組成物を電極層用組成物(正極層用組成物又は負極層用組成物)ということがある。
正極活物質は、周期律表第1族若しくは第2族に属する金属のイオンの挿入放出が可能な活物質であり、可逆的にリチウムイオンを挿入及び放出できるものが好ましい。その材料は、上記特性を有するものであれば、特に制限はなく電池を分解して、遷移金属酸化物、又は、有機物、硫黄などのLiと複合化できる元素などでもよい。
中でも、正極活物質としては、遷移金属酸化物を用いることが好ましく、遷移金属元素Ma(Co、Ni、Fe、Mn、Cu及びVから選択される1種以上の元素)を有する遷移金属酸化物がより好ましい。また、この遷移金属酸化物に元素Mb(リチウム以外の金属周期律表の第1(Ia)族の元素、第2(IIa)族の元素、Al、Ga、In、Ge、Sn、Pb、Sb、Bi、Si、P及びBなどの元素)を混合してもよい。混合量としては、遷移金属元素Maの量(100モル%)に対して0~30モル%が好ましい。Li/Maのモル比が0.3~2.2になるように混合して合成されたものが、より好ましい。
遷移金属酸化物の具体例としては、(MA)層状岩塩型構造を有する遷移金属酸化物、(MB)スピネル型構造を有する遷移金属酸化物、(MC)リチウム含有遷移金属リン酸化合物、(MD)リチウム含有遷移金属ハロゲン化リン酸化合物及び(ME)リチウム含有遷移金属ケイ酸化合物等が挙げられる。
(MB)スピネル型構造を有する遷移金属酸化物の具体例として、LiMn2O4(LMO)、LiCoMnO4、Li2FeMn3O8、Li2CuMn3O8、Li2CrMn3O8及びLi2NiMn3O8が挙げられる。
(MC)リチウム含有遷移金属リン酸化合物としては、例えば、LiFePO4及びLi3Fe2(PO4)3等のオリビン型リン酸鉄塩、LiFeP2O7等のピロリン酸鉄類、LiCoPO4等のリン酸コバルト類並びにLi3V2(PO4)3(リン酸バナジウムリチウム)等の単斜晶ナシコン型リン酸バナジウム塩が挙げられる。
(MD)リチウム含有遷移金属ハロゲン化リン酸化合物としては、例えば、Li2FePO4F等のフッ化リン酸鉄塩、Li2MnPO4F等のフッ化リン酸マンガン塩及びLi2CoPO4F等のフッ化リン酸コバルト類が挙げられる。
(ME)リチウム含有遷移金属ケイ酸化合物としては、例えば、Li2FeSiO4、Li2MnSiO4、Li2CoSiO4等が挙げられる。
本発明では、(MA)層状岩塩型構造を有する遷移金属酸化物が好ましく、LCO又はNMCがより好ましい。
焼成法によって得られた正極活物質は、水、酸性水溶液、アルカリ性水溶液、有機溶剤にて洗浄した後使用してもよい。
正極活物質層を形成する場合、正極活物質層の単位面積(cm2)当たりの正極活物質の質量(mg)(目付量)は特に制限されるものではない。設計された電池容量に応じて、適宜に決めることができ、例えば、1~100mg/cm2とすることができる。
負極活物質は、周期律表第1族若しくは第2族に属する金属のイオンの挿入放出が可能な活物質であり、可逆的にリチウムイオンを挿入及び放出できるものが好ましい。その材料は、上記特性を有するものであれば、特に制限はなく、炭素質材料、金属酸化物、金属複合酸化物、リチウム単体、リチウム合金、リチウムと合金形成可能(合金化可能)な負極活物質等が挙げられる。中でも、炭素質材料、金属複合酸化物又はリチウム単体が信頼性の点から好ましく用いられる。全固体二次電池の大容量化が可能となる点では、リチウムと合金化可能な活物質が好ましい。本発明の固体電解質組成物で形成した構成層は固体粒子同士が強固に結着しているため、負極活物質としてリチウムと合金形成可能な負極活物質を用いることができる。これにより、全固体二次電池の大容量化と電池の長寿命化とが可能となる。
これらの炭素質材料は、黒鉛化の程度により難黒鉛化炭素質材料(ハードカーボンともいう。)と黒鉛系炭素質材料に分けることもできる。また炭素質材料は、特開昭62-22066号公報、特開平2-6856号公報、同3-45473号公報に記載される面間隔又は密度、結晶子の大きさを有することが好ましい。炭素質材料は、単一の材料である必要はなく、特開平5-90844号公報記載の天然黒鉛と人造黒鉛の混合物、特開平6-4516号公報記載の被覆層を有する黒鉛等を用いることもできる。
炭素質材料としては、ハードカーボン又は黒鉛が好ましく用いられ、黒鉛がより好ましく用いられる。
Sn、Si、Geを中心とする非晶質酸化物に併せて用いることができる負極活物質としては、リチウムイオン又はリチウム金属を吸蔵及び/又は放出できる炭素質材料、リチウム単体、リチウム合金、リチウムと合金化可能な負極活物質が好適に挙げられる。
負極活物質、例えば金属酸化物は、チタン元素を含有すること(チタン酸化物)も好ましい。具体的にはLi4Ti5O12(チタン酸リチウム[LTO])がリチウムイオンの吸蔵放出時の体積変動が小さいことから急速充放電特性に優れ、電極の劣化が抑制されリチウムイオン二次電池の寿命向上が可能となる点で好ましい。
一般的に、これらの負極活物質を含有する負極(例えば、ケイ素元素含有活物質を含有するSi負極、スズ元素を有する活物質を含有するSn負極等)は、炭素負極(黒鉛及びアセチレンブラックなど)に比べて、より多くのLiイオンを吸蔵できる。すなわち、単位質量あたりのLiイオンの吸蔵量が増加する。そのため、電池容量(エネルギー密度)を大きくすることができる。その結果、バッテリー駆動時間を長くすることができるという利点がある。
ケイ素元素含有活物質としては、例えば、Si、SiOx(0<x≦1)等のケイ素材料、更には、チタン、バナジウム、クロム、マンガン、ニッケル、銅、ランタン等を含むケイ素含有合金(例えば、LaSi2、VSi2、La-Si、Gd-Si、Ni-Si)、又は組織化した活物質(例えば、LaSi2/Si)、他にも、SnSiO3、SnSiS3等のケイ素元素及びスズ元素を含有する活物質等が挙げられる。なお、SiOxは、それ自体を負極活物質(半金属酸化物)として用いることができ、また、全固体二次電池の稼働によりSiを生成するため、リチウムと合金化可能な負極活物質(その前駆体物質)として用いることができる。
スズ元素を有する負極活物質としては、例えば、Sn、SnO、SnO2、SnS、SnS2、更には上記ケイ素元素及びスズ元素を含有する活物質等が挙げられる。また、酸化リチウムとの複合酸化物、例えば、Li2SnO2を挙げることもできる。
負極活物質層を形成する場合、負極活物質層の単位面積(cm2)当たりの負極活物質の質量(mg)(目付量)は特に制限されるものではない。設計された電池容量に応じて、適宜に決めることができ、例えば、1~100mg/cm2とすることができる。
正極活物質及び負極活物質の表面は別の金属酸化物で表面被覆されていてもよい。表面被覆剤としてはTi、Nb、Ta、W、Zr、Al、Si又はLiを含有する金属酸化物等が挙げられる。具体的には、チタン酸スピネル、タンタル系酸化物、ニオブ系酸化物、ニオブ酸リチウム系化合物等が挙げられ、具体的には、Li4Ti5O12、Li2Ti2O5、LiTaO3、LiNbO3、LiAlO2、Li2ZrO3、Li2WO4、Li2TiO3、Li2B4O7、Li3PO4、Li2MoO4、Li3BO3、LiBO2、Li2CO3、Li2SiO3、SiO2、TiO2、ZrO2、Al2O3、B2O3等が挙げられる。
また、正極活物質又は負極活物質を含む電極表面は硫黄又はリンで表面処理されていてもよい。
更に、正極活物質又は負極活物質の粒子表面は、上記表面被覆の前後において活性光線又は活性気体(プラズマ等)により表面処理を施されていてもよい。
本発明の無機固体電解質含有組成物は、導電助剤を適宜含有してもよく、特に負極活物質としてのケイ素原子含有活物質は導電助剤と併用されることが好ましい。
導電助剤としては、特に制限はなく、一般的な導電助剤として知られているものを用いることができる。例えば、電子伝導性材料である、天然黒鉛、人造黒鉛などの黒鉛類、アセチレンブラック、ケッチェンブラック、ファーネスブラックなどのカーボンブラック類、ニードルコークスなどの無定形炭素、気相成長炭素繊維若しくはカーボンナノチューブなどの炭素繊維類、グラフェン若しくはフラーレンなどの炭素質材料であってもよいし、銅、ニッケルなどの金属粉、金属繊維でもよく、ポリアニリン、ポリピロール、ポリチオフェン、ポリアセチレン、ポリフェニレン誘導体などの導電性高分子を用いてもよい。
本発明において、活物質と導電助剤とを併用する場合、上記の導電助剤のうち、電池を充放電した際に周期律表第一族若しくは第二族に属する金属のイオン(好ましくはLiイオン)の挿入と放出が起きず、活物質として機能しないものを導電助剤とする。したがって、導電助剤の中でも、電池を充放電した際に活物質層中において活物質として機能しうるものは、導電助剤ではなく活物質に分類する。電池を充放電した際に活物質として機能するか否かは、一義的ではなく、活物質との組み合わせにより決定される。
導電助剤の形状は、特に制限されないが、粒子状が好ましい。
本発明の無機固体電解質含有組成物が導電助剤を含む場合、無機固体電解質含有組成物中の導電助剤の含有量は、固形分中、0~10質量%が好ましい。
本発明の無機固体電解質含有組成物は、リチウム塩(支持電解質)を含有することも好ましい。
リチウム塩としては、通常この種の製品に用いられるリチウム塩が好ましく、特に制限はなく、例えば、特開2015-088486の段落0082~0085記載のリチウム塩が好ましい。
本発明の無機固体電解質含有組成物がリチウム塩を含む場合、リチウム塩の含有量は、固体電解質100質量部に対して、0.1質量部以上が好ましく、5質量部以上がより好ましい。上限としては、50質量部以下が好ましく、20質量部以下がより好ましい。
本発明の無機固体電解質含有組成物は、上述の複合ポリマー粒子が分散剤としても機能するため、この複合ポリマー粒子以外の分散剤を含有していなくてもよいが、分散剤を含有してもよい。分散剤としては、全固体二次電池に通常使用されるものを適宜選定して用いることができる。一般的には粒子吸着と立体反発及び/又は静電反発を意図した化合物が好適に使用される。
本発明の無機固体電解質含有組成物は、上記各成分以外の他の成分として、適宜に、イオン液体、増粘剤、架橋剤(ラジカル重合、縮合重合又は開環重合により架橋反応するもの等)、重合開始剤(酸又はラジカルを熱又は光によって発生させるものなど)、消泡剤、レベリング剤、脱水剤、酸化防止剤等を含有することができる。イオン液体は、イオン伝導度をより向上させるため含有されるものであり、公知のものを特に制限されることなく用いることができる。また、複合ポリマー粒子に含まれるポリマー以外のポリマー、通常用いられる結着剤等を含有していてもよい。
本発明の無機固体電解質含有組成物は、無機固体電解質、上記複合ポリマー粒子、好ましくは分散媒、更には適宜に、リチウム塩、任意の他の成分を、例えば通常用いる各種の混合機で混合することにより、混合物として、好ましくはスラリーとして、調製することができる。
混合方法は特に制限されず、一括して混合してもよく、順次混合してもよい。混合する環境は特に制限されないが、乾燥空気下又は不活性ガス下等が挙げられる。
本発明の全固体二次電池用シートは、全固体二次電池の構成層を形成しうるシート状成形体であって、その用途に応じて種々の態様を含む。例えば、固体電解質層に好ましく用いられるシート(全固体二次電池用固体電解質シートともいう。)、電極、又は電極と固体電解質層との積層体に好ましく用いられるシート(全固体二次電池用電極シート)等が挙げられる。本発明において、これら各種のシートをまとめて全固体二次電池用シートという。
本発明の全固体二次電池用固体電解質シートとして、例えば、基材上に、本発明の無機固体電解質含有組成物で構成した層、通常固体電解質層と、保護層とをこの順で有するシートが挙げられる。全固体二次電池用固体電解質シートが有する固体電解質層は、本発明の無機固体電解質含有組成物で形成されることが好ましい。この固体電解質層中の各成分の含有量は、特に限定されないが、好ましくは、本発明の無機固体電解質含有組成物の固形分中における各成分の含有量と同義である。全固体二次電池用固体電解質シートを構成する各層の層厚は、後述する全固体二次電池において説明する各層の層厚と同じである。
本発明の全固体二次電池用シートは、工業的製造、例えば生産性が高いロール トゥ ロール法によっても、構成層の欠陥発生が抑制されたシートを作製できる。そのため、本発明の全固体二次電池用シートは、全固体二次電池の構成層として用いた際に、低抵抗でサイクル特性にも優れた全固体二次電池の製造、特に工業的製造に、寄与する。したがって、本発明の全固体二次電池用シートは、全固体二次電池の構成層を形成しうるシートとして好適に用いられる。本発明の全固体二次電池用シートを用いて全固体二次電池を製造すると、生産性が高いにもかかわらず、低抵抗で優れたサイクル特性をも実現できる。
本発明の全固体二次電池用シートの製造方法は、特に制限されず、本発明の無機固体電解質含有組成物を用いて、上記の各層を形成することにより、製造できる。例えば、好ましくは基材若しくは集電体上(他の層を介していてもよい。)に、製膜(塗布乾燥)して無機固体電解質含有組成物からなる層(塗布乾燥層)を形成する方法が挙げられる。これにより、基材若しくは集電体と、塗布乾燥層とを有する全固体二次電池用シートを作製することができる。ここで、塗布乾燥層とは、本発明の無機固体電解質含有組成物を塗布し、分散媒を乾燥させることにより形成される層(すなわち、本発明の無機固体電解質含有組成物を用いてなり、本発明の無機固体電解質含有組成物から分散媒を除去した組成からなる層)をいう。活物質層及び塗布乾燥層は、本発明の効果を損なわない範囲であれば分散媒が残存していてもよく、残存量としては、例えば、各層中、3質量%以下とすることができる。
本発明の全固体二次電池用シートの製造方法において、塗布、乾燥等の各工程については、下記全固体二次電池の製造方法において説明する。
また、本発明の全固体二次電池用シートの製造方法においては、基材、保護層(特に剥離シート)等を剥離することもできる。
本発明の全固体二次電池は、正極活物質層と、この正極活物質層に対向する負極活物質層と、正極活物質層及び負極活物質層の間に配置された固体電解質層とを有する。正極活物質層は、好ましくは正極集電体上に形成され、正極を構成する。負極活物質層は、好ましくは負極集電体上に形成され、負極を構成する。
負極活物質層、正極活物質層及び固体電解質層の少なくとも1つの層は、本発明の無機固体電解質含有組成物で形成されることが好ましく、少なくとも負極活物質層が本発明の無機固体電解質含有組成物で形成されることがより好ましく、負極活物質層及び固体電解質層が本発明の無機固体電解質含有組成物で形成されることがより好ましく、全ての層が本発明の無機固体電解質含有組成物で形成されることが更に好ましい。本発明の無機固体電解質含有組成物で形成された活物質層又は固体電解質層は、好ましくは、含有する成分種及びその含有量比について、本発明の無機固体電解質含有組成物の固形分におけるものと同じである。なお、活物質層又は固体電解質層が本発明の無機固体電解質含有組成物で形成されない場合、公知の材料を用いることができる。
負極活物質層、固体電解質層及び正極活物質層の厚さは、それぞれ、特に制限されない。各層の厚さは、一般的な全固体二次電池の寸法を考慮すると、それぞれ、10~1,000μmが好ましく、20μm以上500μm未満がより好ましい。本発明の全固体二次電池においては、正極活物質層及び負極活物質層の少なくとも1層の厚さが、50μm以上500μm未満であることが更に好ましい。
正極活物質層及び負極活物質層は、それぞれ、固体電解質層とは反対側に集電体を備えていてもよい。
本発明の全固体二次電池は、用途によっては、上記構造のまま全固体二次電池として使用してもよいが、乾電池の形態とするためには更に適当な筐体に封入して用いることが好ましい。筐体は、金属性のものであっても、樹脂(プラスチック)製のものであってもよい。金属性のものを用いる場合には、例えば、アルミニウム合金又は、ステンレス鋼製のものを挙げることができる。金属性の筐体は、正極側の筐体と負極側の筐体に分けて、それぞれ正極集電体及び負極集電体と電気的に接続させることが好ましい。正極側の筐体と負極側の筐体とは、短絡防止用のガスケットを介して接合され、一体化されることが好ましい。
全固体二次電池10においては、正極活物質層、固体電解質層及び負極活物質層のいずれも本発明の無機固体電解質含有組成物で形成されている。この全固体二次電池10は優れた電池性能を示す。正極活物質層4、固体電解質層3及び負極活物質層2が含有する無機固体電解質及び複合ポリマー粒子は、それぞれ、互いに同種であっても異種であってもよい。
本発明において、正極活物質層及び負極活物質層のいずれか、又は、両方を合わせて、単に、活物質層又は電極活物質層と称することがある。また、正極活物質及び負極活物質のいずれか、又は両方を合わせて、単に、活物質又は電極活物質と称することがある。
本発明において、正極集電体及び負極集電体のいずれか、又は、両方を合わせて、単に、集電体と称することがある。
正極集電体を形成する材料としては、アルミニウム、アルミニウム合金、ステンレス鋼、ニッケル及びチタンなどの他に、アルミニウム又はステンレス鋼の表面にカーボン、ニッケル、チタンあるいは銀を処理させたもの(薄膜を形成したもの)が好ましく、その中でも、アルミニウム及びアルミニウム合金がより好ましい。
負極集電体を形成する材料としては、アルミニウム、銅、銅合金、ステンレス鋼、ニッケル及びチタンなどの他に、アルミニウム、銅、銅合金又はステンレス鋼の表面にカーボン、ニッケル、チタンあるいは銀を処理させたものが好ましく、アルミニウム、銅、銅合金及びステンレス鋼がより好ましい。
集電体の厚みは、特に制限されないが、1~500μmが好ましい。また、集電体表面は、表面処理により凹凸を付けることも好ましい。
本発明において、負極集電体、負極活物質層、固体電解質層、正極活物質層及び正極集電体の各層の間又はその外側には、機能性の層、部材等を適宜介在若しくは配設してもよい。また、各層は単層で構成されていても、複層で構成されていてもよい。
全固体二次電池は、常法によって、製造できる。具体的には、全固体二次電池は、本発明の無機固体電解質含有組成物等を用いて、上記の各層を形成することにより、製造できる。以下、詳述する。
例えば、正極集電体である金属箔上に、正極用材料(正極層用組成物)として、正極活物質を含有する無機固体電解質含有組成物を塗布して正極活物質層を形成し、全固体二次電池用正極シートを作製する。次いで、この正極活物質層の上に、固体電解質層を形成するための無機固体電解質含有組成物を塗布して、固体電解質層を形成する。更に、固体電解質層の上に、負極用材料(負極層用組成物)として、負極活物質を含有する無機固体電解質含有組成物を塗布して、負極活物質層を形成する。負極活物質層の上に、負極集電体(金属箔)を重ねることにより、正極活物質層と負極活物質層の間に固体電解質層が挟まれた構造の全固体二次電池を得ることができる。これを筐体に封入して所望の全固体二次電池とすることもできる。
また、各層の形成方法を逆にして、負極集電体上に、負極活物質層、固体電解質層及び正極活物質層を形成し、正極集電体を重ねて、全固体二次電池を製造することもできる。
また別の方法として、次の方法が挙げられる。すなわち、上記のようにして、全固体二次電池用正極シート及び全固体二次電池用負極シートを作製する。また、これとは別に、無機固体電解質含有組成物を基材上に塗布して、固体電解質層からなる全固体二次電池用固体電解質シートを作製する。更に、全固体二次電池用正極シート及び全固体二次電池用負極シートで、基材から剥がした固体電解質層を挟むように積層する。このようにして、全固体二次電池を製造することができる。
更に、上記のようにして、全固体二次電池用正極シート又は全固体二次電池用負極シート、及び全固体二次電池用固体電解質シートを作製する。次いで、全固体二次電池用正極シート又は全固体二次電池用負極シートと全固体二次電池用固体電解質シートとを、正極活物質層又は負極活物質層と固体電解質層とを接触させた状態に、重ねて、加圧する。こうして、全固体二次電池用正極シート又は全固体二次電池用負極シートに固体電解質層を転写する。その後、全固体二次電池用固体電解質シートの基材を剥離した固体電解質層と全固体二次電池用負極シート又は全固体二次電池用正極シートとを(固体電解質層に負極活物質層又は正極活物質層を接触させた状態に)重ねて加圧する。こうして、全固体二次電池を製造することができる。この方法における加圧方法及び加圧条件等は、特に制限されず、後述する、塗布した組成物の加圧において説明する方法及び加圧条件等を適用できる。
上記の製造方法においては、正極層用組成物、無機固体電解質含有組成物及び負極層用組成物のいずれか1つに本発明の無機固体電解質含有組成物を用いればよく、負極層用組成物に本発明の無機固体電解質含有組成物を用いることが好ましく、いずれの組成物に本発明の無機固体電解質含有組成物を用いることもできる。
本発明の固体電解質組成物以外の組成物で固体電解質層又は活物質層を形成する場合、その材料としては、通常用いられる組成物等が挙げられる。また、全固体二次電池の製造時に負極活物質層を形成せずに、後述する初期化若しくは使用時の充電で負極集電体に蓄積した、周期律表第一族若しくは第二族に属する金属のイオンを電子と結合させて、金属として負極集電体等の上に析出させることにより、負極活物質層を形成することもできる。
固体電解質層等は、例えば基板若しくは活物質層上で、固体電解質組成物等を後述する加圧条件下で加圧成形して形成することもできるし、固体電解質又は活物質のシート成形体を用いることもできる。
無機固体電解質含有組成物の塗布方法は特に制限されず、適宜に選択できる。例えば、塗布(好ましくは湿式塗布)、スプレー塗布、スピンコート塗布、ディップコート塗布、スリット塗布、ストライプ塗布、バーコート塗布が挙げられる。
このとき、無機固体電解質含有組成物は、それぞれ塗布した後に乾燥処理を施してもよいし、重層塗布した後に乾燥処理をしてもよい。乾燥温度は特に制限されない。下限は30℃以上が好ましく、60℃以上がより好ましく、80℃以上が更に好ましい。上限は、300℃以下が好ましく、250℃以下がより好ましく、200℃以下が更に好ましい。このような温度範囲で加熱することで、分散媒を除去し、固体状態(塗布乾燥層)にすることができる。また、温度を高くしすぎず、全固体二次電池の各部材を損傷せずに済むため好ましい。これにより、全固体二次電池において、優れた総合性能を示し、かつ良好な結着性と、非加圧でも良好なイオン伝導度を得ることができる。
上記のようにして本発明の無機固体電解質含有組成物を塗布乾燥すると、固体粒子が強固に結着し、更に固体粒子間の界面抵抗が小さな、塗布乾燥層を形成することができる。
また、塗布した無機固体電解質含有組成物は、加圧と同時に加熱してもよい。加熱温度としては特に制限されず、一般的には30~300℃の範囲である。無機固体電解質のガラス転移温度よりも高い温度でプレスすることもできる。なお、複合ポリマー粒子に含まれるポリマーのガラス転移温度よりも高い温度でプレスすることもできる。ただし、一般的にはこのポリマーの融点を越えない温度である。
加圧は塗布溶媒又は分散媒を予め乾燥させた状態で行ってもよいし、溶媒又は分散媒が残存している状態で行ってもよい。
なお、各組成物は同時に塗布してもよいし、塗布乾燥プレスを同時及び/又は逐次行ってもよい。別々の基材に塗布した後に、転写により積層してもよい。
プレス時間は短時間(例えば数時間以内)で高い圧力をかけてもよいし、長時間(1日以上)かけて中程度の圧力をかけてもよい。全固体二次電池用シート以外、例えば全固体二次電池の場合には、中程度の圧力をかけ続けるために、全固体二次電池の拘束具(ネジ締め圧等)を用いることもできる。
プレス圧はシート面等の被圧部に対して均一であっても異なる圧であってもよい。
プレス圧は被圧部の面積又は膜厚に応じて変化させることができる。また同一部位を段階的に異なる圧力で変えることもできる。
プレス面は平滑であっても粗面化されていてもよい。
上記のようにして製造した全固体二次電池は、製造後又は使用前に初期化を行うことが好ましい。初期化は特に制限されず、例えば、プレス圧を高めた状態で初充放電を行い、その後、全固体二次電池の一般使用圧力になるまで圧力を解放することにより、行うことができる。
本発明の全固体二次電池は種々の用途に適用することができる。適用態様には特に制限はないが、例えば、電子機器に搭載する場合、ノートパソコン、ペン入力パソコン、モバイルパソコン、電子ブックプレーヤー、携帯電話、コードレスフォン子機、ページャー、ハンディーターミナル、携帯ファックス、携帯コピー、携帯プリンター、ヘッドフォンステレオ、ビデオムービー、液晶テレビ、ハンディークリーナー、ポータブルCD、ミニディスク、電気シェーバー、トランシーバー、電子手帳、電卓、メモリーカード、携帯テープレコーダー、ラジオ、バックアップ電源などが挙げられる。その他民生用として、自動車、電動車両、モーター、照明器具、玩具、ゲーム機器、ロードコンディショナー、時計、ストロボ、カメラ、医療機器(ペースメーカー、補聴器、肩もみ機など)などが挙げられる。更に、各種軍需用、宇宙用として用いることができる。また、太陽電池と組み合わせることもできる。
以下、表1-1~1-3を纏めて表1ということがある。
[合成例1:複合ポリマー粒子P-1の合成(複合ポリマー粒子分散液P-1の調製)]
以下のように、シード重合法により、複合ポリマー粒子P-1を合成して、この複合ポリマー粒子の分散液P-1を調製した。
3000mL3つ口フラスコに、NISSO PB-GI1000(商品名、日本曹達社製)170gを加え、THF(テトラヒドロフラン)1000gに溶解した。この溶液に、ジフェニルメタンジイソシアネート(富士フイルム和光純薬工業社製)30gを加えて60℃で撹拌し、均一に溶解させた。得られた溶液に、ネオスタンU-600(商品名、日東化成社製)100mgを添加して60℃で5時間攪伴し、粘性ポリマー溶液を得た。こうして、複合ポリマー粒子P-1を構成する低極性ポリマー(P1-1)を合成した。更に、15gのP1-1溶液を200mLフラスコに移し、攪拌しながら75gのDIBKを1時間かけて滴下することで低極性ポリマー(P1-1)の分散液を得た。
次いで、300mL3つ口フラスコに、上記で得られた低極性ポリマー(P1-1)の3.0質量%分散液50gを入れ、25℃で攪拌し、均一に分散させた。これに、1.5gのTHFに溶解させたポリエチレングリコール(数平均分子量600、富士フイルム和光純薬工業社製)2.5gを30分かけて滴下し、ネオスタンU-600(商品名、日東化成社製)90mgを添加して1時間攪伴した。この後、60℃まで加温し、10gのTHFに溶解したジフェニルメタンジイソシアネート(富士フイルム和光純薬工業社製)1.0gを1時間かけて滴下し、60℃で7時間攪拌を続けることで、低極性ポリマー(P1-1)及び高極性ポリマー(P2-1)からなる複合ポリマー粒子P-1を調製した。この複合ポリマー粒子P-1は、高極性ポリマー(P2-1)からなるコアと低極性ポリマー(P1-1)からなるシェルとを有するコアシェル構造を有していると推定される。
得られた分散液を40℃に加熱し、エバポレーターで、40hPaに減圧することで、溶媒の一部を留去し、固形分濃度を調整することで、濃度10質量%の複合ポリマー粒子P-1のDIBK分散液を得た。
合成例1において、低極性ポリマー(P1)及び高極性ポリマー(P2)が表1に示す組成(構成成分の種類及び含有量)及びポリマー質量比となるように各構成成分を導く化合物を用い、必要であれば低極性ポリマー(P1-1)の分散液の調製に用いたDIBKを表1に示す分散媒に変更したこと以外は、合成例1と同様にして、複合ポリマー粒子P-2~9、15、16、18、19及び21~24、33~34をそれぞれ合成した。得られた複合ポリマー粒子は、いずれも、高極性ポリマーからなるコアと低極性ポリマーからなるシェルとを有するコアシェル構造を有していると推定される。
次いで、合成した各複合ポリマー粒子を用いて、複合ポリマー粒子分散液P-1の調製と同様にして、複合ポリマー粒子分散液P-2~9、15、16、18、19及び21~24、33~34をそれぞれ調製した。
300mL三口フラスコにメタクリル酸トリデシル16g(分子量268、東京化成工業社製)を加え、ジイソブチルケトン30gに溶解した。この溶液を80℃で攪拌し、ジイソブチルケトン25gに溶解したメタクリル酸2-ヒドロキシエチル16g(分子量130、東京化成工業社製)、メタクリル酸メチル21g(分子量100、東京化成工業社製)、V-601(商品名、富士フイルム和光純薬社製)0.9gを4時間かけて滴下し、更に4時間加熱攪拌を続けることで複合ポリマー粒子P-10を構成する低極性ポリマー(P1-10)の分散液を得た。上記低極性ポリマー分散液を用いて、高極性ポリマー(P2-10)が表1に示す組成(構成成分の種類及び含有量)及びポリマー質量比となるように各構成成分を導く化合物を用いたこと以外は、合成例1と同様にして、複合ポリマーP-10を調製した。この複合ポリマー粒子は、高極性ポリマーからなるコアと低極性ポリマーからなるシェルとを有するコアシェル構造を有していると推定される。
合成例20において、高極性ポリマー(P2)が表1に示す組成(構成成分の種類、含有量)及びポリマー質量比となるように各構成成分を導く化合物を用いたこと以外は、合成例20と同様にして、複合ポリマー粒子P-11、12及び20をそれぞれ合成した。得られた複合ポリマー粒子は、いずれも、高極性ポリマーからなるコアと低極性ポリマーからなるシェルとを有するコアシェル構造を有していると推定される。
次いで、合成した各複合ポリマー粒子を用いて、複合ポリマー粒子分散液P-1の調製と同様にして、複合ポリマー粒子分散液P-11、12及び20をそれぞれ調製した。
300mL三口フラスコに上記で調製した複合ポリマーP-9の3.0%分散液P-9を50g入れ、25℃で攪拌し、均一に分散させた。これに、1.5gのTHFに溶解させたポリテトラメチレングリコール(数平均分子量250、富士フイルム和光純薬工業社製)0.8gを15分かけて滴下し、ネオスタンU-600(商品名、日東化成社製)60mgを添加して1時間攪伴した。この後、60℃まで加温し、5gのTHFに溶解したジフェニルメタンジイソシアネート(富士フイルム和光純薬工業社製)0.75gを一時間かけて滴下し、60℃で7時間攪拌を続けることで、低極性ポリマー(P1-9)と二種の高極性ポリマー(P2-9とP3-13)からなる複合ポリマー粒子P-13を調製した。この複合ポリマー粒子P-13は、高極性ポリマー(P2-9とP3-13)からなるコアと低極性ポリマー(P1-9)からなるシェルとを有するコアシェル構造を有していると推定される。
得られた分散液を40℃に加熱し、エバポレーターで、40hPaに減圧することで、溶媒の一部を留去し、固形分濃度を調整することで、濃度10質量%の複合ポリマー粒子P-13の分散液を得た。
2000mL三口フラスコにNISSO PB-GI1000(商品名、日本曹達社製)150gと2,2-ビスヒドロキシ酢酸(分子量148、富士フイルム和光純薬)12.5gを加え、THF900gに溶解した。この溶液にトリホスゲン(分子量296、東京化成工業社製)16gを1時間かけて滴下した後、60℃に加温して7時間攪拌することで、粘性ポリマー溶液を得た。このように、複合ポリマーP-14の低極性ポリマー(P1-14)を得た。更に15gの低極性ポリマー(P1-14)を200mLフラスコに移し、攪拌しながら75gのDIBKを1時間かけて滴下することで低極性ポリマー(P1-14)の分散液を調製した。
次いで、1000mL3つ口フラスコに、ジイソブチルケトン500mLと、上記で得られた低極性ポリマー(P1-14)の3.0質量%分散液50gを入れ、25℃で攪拌し、均一に分散させた。これに、30gのTHFに溶解させた、ポリエチレングリコール(数平均分子量200、富士フイルム和光純薬工業社製)33gを滴下し、1時間攪拌した。この後、15gのTHFに溶解したトリホスゲン(分子量296、東京化成工業社製)16gを1時間かけて滴下した後、60℃に加熱し7時間攪拌することで複合ポリマー粒子P-14を得た。得られた複合ポリマー粒子は、高極性ポリマー(P2-14)からなるコアと低極性ポリマー(P1-14)からなるシェルとを有するコアシェル構造を有していると推定される。
次いで、合成した複合ポリマー粒子を用いて、複合ポリマー粒子分散液P-1の調製と同様にして、複合ポリマー粒子分散液P-14を調製した。
合成例20において、低極性ポリマー(P1-17)及び高極性ポリマー(P2-17)が表1に示す組成(構成成分の種類、含有量)及びポリマー質量比となるように各構成成分を導く化合物を用いたこと以外は、合成例20と同様にして、複合ポリマー粒子P-17を合成した。得られた複合ポリマー粒子は、高極性ポリマーからなるコアと低極性ポリマーからなるシェルとを有するコアシェル構造を有していると推定される。
次いで、合成した複合ポリマー粒子を用いて、複合ポリマー粒子分散液P-1の調製と同様にして、複合ポリマー粒子分散液P-17を調製した。
300mLの三つ口フラスコに、複合ポリマー粒子分散液P-19の調製時に得られる低極性ポリマー(P1-19)の3%分散液50gを入れ、25℃で攪拌し、均一に分散させた。これに、10gのジイソブチルケトンに分散させたアクリル酸2-ヒドロキシエチル(数平均分子量116、富士フイルム和光純薬工業社製)15gを1時間かけて滴下し、1時間攪伴した。この後、90℃まで加温し、8時間攪拌を続けることで、低極性ポリマー(P1-19)と高極性ポリマー(P2-25)の複合ポリマー粒子P-25を得た。この複合ポリマー粒子P-25は高極性ポリマー(P2-25)からなるコアと低極性ポリマー(P1-19)からなるシェルとを有するコアシェル構造を有していると推定される。
得られた分散液を40℃に加熱し、エバポレーターで、40hPaに減圧することで、溶媒の一部を留去し、固形分濃度を調整することで、濃度10質量%の複合ポリマー粒子P-25の分散液を得た。
合成例9で合成した低極性ポリマー(P1-9)の分散液をそのまま分散液CP-1とした。
合成例1の低極性ポリマー(P-1)の分散液の調製において、高極性ポリマー(P2-CP2)が表1-3に示す組成(構成成分の種類及び含有量)となるように各構成成分を導く化合物を用いたこと以外は、合成例1の低極性ポリマー(P-1)の分散液の調製と同様にして、高極性ポリマー(P2-CP2)の粘性ポリマー溶液を得た。
この粘性ポリマー溶液300gを3L容器に入れ攪拌棒で攪拌しながら、エタノール2000gを滴下した後、デカンテーションにすることで高極性ポリマー(P2-CP2)の固形ポリマーを得た。次いで、ジルコニア製45mL容器(フリッチュ社製)に、直径5mmのジルコニアビーズを30g投入し、上記固形ポリマー10gとジイソブチルケトン20gを投入し、容器を完全に密閉した。フリッチュ社製遊星ボールミルP-7(商品名、フリッチュ社製)に容器をセットし、温度25℃で、回転数600rpmで10時間メカニカルミリングを行うことで、高極性ポリマー(P2-CP2)のポリマー粒子分散液CP-2を得た。
500mL三口フラスコにアクリル酸ドデシル25g(分子量240、東京化成工業社製)を加え、DIBK150gに溶解した。この溶液を80℃で攪拌し、アクリル酸2-ヒドロキシエチル12.5g(分子量116、東京化成工業社製)、アクリル酸メチル25g(分子量86、東京化成工業社製)、V-601(商品名、富士フイルム和光純薬社製)1.0gを4時間かけて滴下し、更に4時間加熱攪拌を続けることで複合ポリマー粒子CP-3を構成する低極性ポリマー(P1-CP3)の分散液を得た。
次いで、500mL三口フラスコに上記で得られた低極性ポリマー(P1-CP3)の3.0質量%分散液50gを入れ、25℃で攪拌し、均一に分散させた。この分散液に、アクリル酸2-ヒドロキシエチル30g(分子量116、東京化成工業社製)を添加して、2時間攪拌した。この後、アゾビスイソブチロニトリル(分子量164、富士フイルム和光社製)を120m添加し、90℃で8時間攪拌することで複合ポリマー粒子CP-3を調製した。
得られた複合ポリマー粒子CP-3は、低極性ポリマー(P1-CP3)からなるコアと高極性ポリマー(P2-CP3)からなるシェルとを有するコアシェル構造を有していると推定される。
1000mL3つ口フラスコに、ポリプロピレングリコール(数平均分子量700、富士フイルム和光純薬工業社製)42gと、1,4-ブタンジオール(分子量90、東京化成工業社製)7.0gと、NISSO PB-GI1000(商品名、日本曹達社製)14.0gとを加え、THF(テトラヒドロフラン)450.0gに溶解した。この溶液に、ジフェニルメタンジイソシアネート(富士フイルム和光純薬工業社製)37.0gを加えて60℃で撹拌し、均一に溶解させた。得られた溶液に、ネオスタンU-600(商品名、日東化成社製)300mgを添加して60℃で5時間攪伴し、粘性ポリマー溶液を得た。得られたポリマー溶液30gを300mLの容器に入れ、攪拌しながらオクタン70gを滴下し、CP-4の分散液を得た。
上記特許文献1の実施例1に記載の方法に準拠して、表1に示す組成(構成成分の種類、含有量)及びポリマー質量比となるように各構成成分を導く化合物を用いて、複合ポリマーCP-5を合成して、複合ポリマー粒子CP-5のデカリン分散液CP-5を得た。
得られた複合ポリマー粒子CP-5は、高極性ポリマー(P1-CP5)からなるコアと低極性ポリマー(P2-CP5)からなるシェルとを有するコアシェル構造を有していると推定される。
300mLフラスコにポリマー粒子CP-1の10%分散液1gとポリマー粒子CP-2の10%分散液99gを入れ、攪拌することで低極性ポリマー(CP-1)と高極性ポリマー(CP-2)との混合ポリマー粒子分散液CP-6を得た。
合成例1において、低極性ポリマー(P1)が表1に示す組成(構成成分の種類及び含有量)となるように各構成成分を導く化合物を用いたこと以外は、合成例1と同様にして、低極性ポリマー(P26-1)の分散液を得た。
次いで、300mL3つ口フラスコに、上記で得られた低極性ポリマー(P26-1)の3.0質量%分散液50gを入れ、25℃で攪拌し、均一に分散させた。これに、19.2gのTHFに溶解させたD-400(商品名JEFFAMINE(登録商標)D-400、HUNTSMAN社製)9.2g、トリエチルアミン4.5gを30分かけて滴下して1時間攪伴した。この後、60℃まで加温し、20gのTHFに溶解したテレフタル酸ジクロリド(富士フイルム和光純薬工業社製)4.5gを2時間かけて滴下し、60℃で7時間攪拌を続け、ろ過することで、低極性ポリマー(P26-1)及び高極性ポリマー(P26-2)からなる複合ポリマー粒子P-26を調製した。この複合ポリマー粒子P-26は、高極性ポリマー(P26-2)からなるコアと低極性ポリマー(P26-1)からなるシェルとを有するコアシェル構造を有していると推定される。
得られた分散液を40℃に加熱し、エバポレーターで、40hPaに減圧することで、溶媒の一部を留去し、固形分濃度を調整することで、濃度10質量%の複合ポリマー粒子P-26のDIBK分散液を得た。
合成例33において、低極性ポリマー(P1)及び高極性ポリマー(P2)が表1に示す組成(構成成分の種類及び含有量)及びポリマー質量比となるように各構成成分を導く化合物を用いたこと以外は、合成例33と同様にして、複合ポリマー粒子P-27及びP-28をそれぞれ合成した。得られた複合ポリマー粒子は、いずれも、高極性ポリマーからなるコアと低極性ポリマーからなるシェルとを有するコアシェル構造を有していると推定される。
次いで、合成した各複合ポリマー粒子を用いて、複合ポリマー粒子分散液P-33の調製と同様にして、複合ポリマー粒子分散液P-27及びP-28をそれぞれ調製した。
以下のように、ポリマー粒子の表面へ別のポリマーを酸・塩基相互作用により吸着させるにより、複合ポリマー粒子P-30を合成して、この複合ポリマー粒子の分散液P-30を調製した。
500mL3つ口フラスコに、NISSO PB-GI1000(商品名、日本曹達社製)10.5g、ポリエチレングリコール(数平均分子量200、富士フイルム和光純薬工業社製)13.6g、2,2-ビス(ヒドロキシメチル)酪酸(東京化成工業社製)3.3gを加え、THF(テトラヒドロフラン)210gに溶解した。この溶液に、ジフェニルメタンジイソシアネート(富士フイルム和光純薬工業社製)25.0gを加えて60℃で撹拌し、均一に溶解させた。得られた溶液に、ネオスタンU-600(商品名、日東化成社製)200mgを添加して60℃で5時間攪伴し、粘性ポリマー溶液を得た。こうして、複合ポリマー粒子P-30を構成する高極性ポリマー(P30-2)を合成した。更に、15gのP30-2溶液を200mLフラスコに移し、攪拌しながら75gのDIBKを1時間かけて滴下することで高極性ポリマー(P30-2)の分散液を得た。
次いで、500mL三口フラスコにDIBK136gを加え、窒素気流下、80℃で攪拌した。そこへ、メタクリル酸メチル25g(富士フイルム和光純薬工業社製)、メタクリル酸ドデシル22.5g(富士フイルム和光純薬工業社製)、ジメチルアミノエチルアクリレート2.5g(富士フイルム和光純薬工業社製)、V-601(商品名、富士フイルム和光純薬社製)0.5g、DIBK30gを4時間かけて滴下し、更に4時間加熱攪拌を続けることで、複合ポリマー粒子P-30を構成する低極性ポリマー(P30-1)を合成した。
次いで、300mL3つ口フラスコに、上記で得られた高極性ポリマー(P30-2)の3.0質量%分散液133gを入れ、25℃で攪拌し、均一に分散させた。これに、低極性ポリマー(P30-1)の30.0質量%溶液3.3g及びDIBK30gを2時間かけて滴下し、更に1時間攪拌を続けることで、低極性ポリマー(P30-1)及び高極性ポリマー(P30-2)からなる複合ポリマー粒子P-30を調製した。この複合ポリマー粒子P-30は、高極性ポリマー(P30-2)からなるコアと低極性ポリマー(P30-1)からなるシェルとを有するコアシェル構造を有していると推定される。
得られた分散液を40℃に加熱し、エバポレーターで、40hPaに減圧することで、溶媒の一部を留去し、固形分濃度を調整することで、濃度10質量%の複合ポリマー粒子P-30のDIBK分散液を得た。
合成例36において、低極性ポリマー(P1)及び高極性ポリマー(P2)が表1に示す組成(構成成分の種類及び含有量)及びポリマー質量比となるように各構成成分を導く化合物を用いたこと以外は、合成例36と同様にして、複合ポリマー粒子P-29を合成した。得られた複合ポリマー粒子は、高極性ポリマーからなるコアと低極性ポリマーからなるシェルとを有するコアシェル構造を有していると推定される。
次いで、合成した各複合ポリマー粒子を用いて、複合ポリマー粒子分散液P-30の調製と同様にして、複合ポリマー粒子分散液P-29を調製した。
(マクロモノマー1の合成)
1Lメスシリンダーに、メタクリル酸メチル(東京化成工業社製)130.2g、メタクリル酸ドデシル(東京化成工業社製)330.7g、3-メルカプトプロピオン酸4.5g及び重合開始剤V-601(富士フイルム和光純薬社製)4.61gを加え、撹拌して均一に溶解してモノマー溶液を調製した。2L3口フラスコに、トルエン(富士フイルム和光純薬社製)465.5gを加え、80℃で攪拌したところへ、上記モノマー溶液を2時間かけて滴下した。滴下終了後、80℃で2時間撹拌した後、90℃に昇温して2時間撹拌した。2,2,6,6-テトラメチルピペリジン 1-オキシル(富士フイルム和光純薬社製)275mg、メタクリル酸グリシジル(東京化成工業社製)27.5g、テトラブチルアンモニウムブロミド(富士フイルム和光純薬社製)5.5gを加え、120℃で3時間撹拌した。溶液を室温で静置した後、1800gのメタノールに流し込み、上澄みを除いた。そこへジイソブチルケトンを加え、メタノールを減圧留去することでマクロモノマー1のジイソブチルケトン溶液を得た。固形分濃度は48.9質量%であった。
300mL三口フラスコにマクロモノマー1 30.7g(固形15g)を加え、ジイソブチルケトン51.7gに溶解した。この溶液を80℃で攪拌し、ジイソブチルケトン210gに溶解したAEHS:こはく酸モノ(2-アクリロイルオキシエチル)10g(東京化成工業社製)、ジメチルアクリルアミド25g(東京化成工業社製)、V-601(商品名、富士フイルム和光純薬社製)0.5gを4時間かけて滴下し、更に4時間加熱攪拌を続けることで複合ポリマー粒子P-31を構成する低極性ポリマー(P31-1)の分散液を得た。上記低極性ポリマー分散液を用いて、高極性ポリマー(P31-2)が表1に示す組成(構成成分の種類及び含有量)及びポリマー質量比となるように各構成成分を導く化合物を用いたこと以外は、合成例1と同様にして、複合ポリマーP-31を調製した。この複合ポリマー粒子は、高極性ポリマーからなるコアと低極性ポリマーからなるシェルとを有するコアシェル構造を有していると推定される。
合成例38において、低極性ポリマー(P1)及び高極性ポリマー(P2)が表1に示す組成(構成成分の種類及び含有量)及びポリマー質量比となるように各構成成分を導く化合物を用いたこと以外は、合成例38と同様にして、複合ポリマー粒子P-39を合成した。得られた複合ポリマー粒子は、高極性ポリマーからなるコアと低極性ポリマーからなるシェルとを有するコアシェル構造を有していると推定される。
次いで、合成した各複合ポリマー粒子を用いて、複合ポリマー粒子分散液P-38の調製と同様にして、複合ポリマー粒子分散液P-39を調製した。
ポリマーのSP値及び複合ポリマー粒子の粒径は上記方法により測定した。
合成した各ポリマーのうち、塩基性官能基を有するものは、複合ポリマー粒子P-8の低極性ポリマー(P1-8)、複合ポリマー粒子P-17の低極性ポリマー(P1-17)、複合ポリマー粒子P-19の高極性ポリマー(P2-19)、複合ポリマー粒子P-30の低極性ポリマー(P1-30)である。一方、酸性官能基を有するものは、複合ポリマー粒子P-9、P-13及びP-14の各低極性ポリマー(P1)、複合ポリマー粒子P-18の高極性ポリマー(P2-18)、複合ポリマー粒子P-29~P-32の各高極性ポリマー(P2-29~P1-32)、複合ポリマー粒子P-34の低極性ポリマー(P1-34)である。
表中、構成成分欄中の「-」は該当する構成成分を有していないことを示す。
表中において各構成成分を導く化合物を以下に示す。
- 式(I-1)で表される構成成分 -
MDI:ジフェニルメタンジイソシアネート(富士フイルム和光純薬社製、SP値:24.6)
2,6-TDI:2,6-トリレンジイソシアネート(シグマアルドリッチ社製、SP値:25.4)
Hex-MDI:ジシクロヘキシルメタン-4,4’-ジイソシアナート(東京化成工業社製、SP値:21.0)
m-XDI:m-キシリレンジイソシアナート(東京化成工業社製、SP値:24.7)
トリホスゲン:東京化成工業社製(単分子としてのSP値:30.3)
TPDC:テレフタル酸ジクロリド(東京化成工業社製、SP値:27.7(アミド結合)、23.6(エステル結合))
N-DiEt-Bu:N-ブチル-ジエタノールアミン(東京化成工業社製、SP値:20.9)
DMBA:2,2-ビス(ヒドロキシメチル)酪酸(東京化成工業社製、SP値:23.7(ウレタン結合)、21.4(カーボネート結合))
1,18-ODO:1,18-オクタデカンジオール(東京化成工業社製、SP値:20.2)
1,6-HDT:1,6-ヘキサンジチオール(東京化成工業社製、SP値:23.6)
1,4-BD:1,4-ブタンジオール(富士フイルム和光純薬社製、SP値:25.1)
PEG200:ポリエチレングリコール(数平均分子量200、富士フイルム和光純薬社製、SP値:24.0(ウレタン結合)、22.4(カーボネート結合)、21.8(エステル結合))
PEG600:ポリエチレングリコール(数平均分子量600、富士フイルム和光純薬社製、SP値:22.3)
PPG700:ポリプロピレングリコール(数平均分子量700、富士フイルム和光純薬社製、SP値:20.1)
PTMG250:ポリテトラメチレングリコール(数平均分子量250、SIGMA-Aldrich社製、SP値:21.1)
NISSO PB-GI1000:水素化液状ポリブタジエンジオール(商品名、数平均分子量1400、日本曹達社製、SP値:17.5(ウレタン結合)、17.3(カーボネート結合))で、その構造を下記に示す。
NISSO PB-GI3000:水素化液状ポリブタジエンジオール(商品名、数平均分子量3000、日本曹達社製、SP値:17.4)で、その構造を下記に示す。
NISSO PB-G1000:液状ポリブタジエンジオール(商品名、数平均分子量1500、日本曹達社製、SP値:17.8)で、その構造を下記に示す。
ポリオールP510:ポリエステルジオール(数平均分子量510、クレハ社製、SP値:20.0)
DURANOL-G3450J:ポリカーボネートジオール(数平均分子量800、旭化成社製、SP値:22.8)
- 式(I-5)で表されるカルボン酸二無水物 -
PMDA:ベンゼン-1,2,4,5-テトラカルボン酸無水物(東京化成工業社製、SP値:31.6(イミド結合))
- 式(I-4)で表される構成成分 -
1,6-DAH:1,6-ヘキサンジアミン(東京化成工業社製、SP値:22.7(ウレア結合))
D-400:商品名JEFFAMINE(登録商標)D-400(HUNTSMAN社製、SP値:20.6(アミド結合)プロピレングリコールジアミン)
- 式(I-6)で表される構成成分を導くジアミン化合物 -
1,6-DAH:1,6-ヘキサンジアミン(東京化成工業社製、SP値:25.4(イミド結合))
MMA:メタクリル酸メチル(富士フイルム和光純薬社製、SP値:19.4)
HEMA:メタクリル酸2-ヒドロキシエチル(富士フイルム和光純薬社製、SP値:24.2)
TDMA:メタクリル酸トリデシル(東京化成工業社製、SP値:18.5)
LMA:メタクリル酸ドデシル(東京化成工業社製、SP値:18.5)
アクリル酸ジメチルアミノエチル(富士フイルム和光社製、SP値:18.1)
HEA:アクリル酸2-ヒドロキシエチル(富士フイルム和光純薬社製、SP値:25.9)
LA:アクリル酸ドデシル(東京化成工業社製、SP値:18.8)
ノニルフェノキシポリエチレングリコールアクリレート:(数平均分子量462、日立化成社製、SP値:20.6)
MA:メタクリル酸(富士フイルム和光純薬社製、SP値:19.6)
AEHS:こはく酸モノ(2-アクリロイルオキシエチル)(東京化成工業社製、SP値:21.8)
ジメチルアクリルアミド:(富士フイルム和光社製、SP値:24.2)
アクリロニトリル:(富士フイルム和光社製、SP値:25.3)
マクロモノマー1:合成例38、メタクリル酸メチル/メタクリル酸ドデシル=28/72質量%共重合体の末端メタクリロイル基含有マクロモノマー(SP値:18.7)
スチレン:(富士フイルム和光純薬社製、SP値:19.3)
ジビニルベンゼン:(富士フイルム和光純薬社製、SP値:20.5)
DIBK:ジイソブチルケトン、MEK:メチルエチルケトン
[合成例A]
硫化物系無機固体電解質は、T.Ohtomo,A.Hayashi,M.Tatsumisago,Y.Tsuchida,S.Hama,K.Kawamoto,Journal of Power Sources,233,(2013),pp231-235、及び、A.Hayashi,S.Hama,H.Morimoto,M.Tatsumisago,T.Minami,Chem.Lett.,(2001),pp872-873の非特許文献を参考にして合成した。
具体的には、アルゴン雰囲気下(露点-70℃)のグローブボックス内で、硫化リチウム(Li2S、Aldrich社製、純度>99.98%)2.42g及び五硫化二リン(P2S5、Aldrich社製、純度>99%)3.90gをそれぞれ秤量し、メノウ製乳鉢に投入し、メノウ製乳棒を用いて、5分間混合した。Li2S及びP2S5の混合比は、モル比でLi2S:P2S5=75:25とした。
次いで、ジルコニア製45mL容器(フリッチュ社製)に、直径5mmのジルコニアビーズを66g投入し、上記の硫化リチウムと五硫化二リンの混合物全量を投入し、アルゴン雰囲気下で容器を完全に密閉した。フリッチュ社製遊星ボールミルP-7(商品名、フリッチュ社製)に容器をセットし、温度25℃で、回転数510rpmで20時間メカニカルミリングを行うことで、黄色粉体の硫化物系無機固体電解質(Li-P-S系ガラス、以下、LPSと表記することがある。)6.20gを得た。Li-P-S系ガラスの粒子径は15μmであった。
実施例1では、調製した複合ポリマー粒子分散液P-1~P-34及びCP-1~CP-6を用いて、無機固体電解質含有組成物及び全固体二次電池用シートを作製して、その特性を評価した。
ジルコニア製45mL容器(フリッチュ社製)に、直径5mmのジルコニアビーズを60g投入し、上記合成例Aで合成したLPS又はLLZ4.85g、表2に示す複合ポリマー粒子分散液0.05g(固形分質量)、及び表2に示す分散媒を16.0g投入した。その後に、この容器をフリッチュ社製遊星ボールミルP-7(商品名)にセットした。温度25℃、回転数150rpmで10分間混合して、無機固体電解質含有組成物S-1~C-15及びSS-1~SS-6をそれぞれ調製した。
Li-P-S:合成例Aで合成したLPS
LLZ:Li7La3Zr2O12
DIBK:ジイソブチルケトン
ジルコニア製45mL容器(フリッチュ社製)に、直径5mmのジルコニアビーズを60g投入し、合成例Aで合成したLPS又はLLZを1.7g、及び、分散媒としてヘプタン12.3g(総量)を投入した。フリッチュ社製遊星ボールミルP-7(商品名)にこの容器をセットし、25℃で、回転数200pmで30分間攪拌した。その後、この容器に、正極活物質としてLiNi1/3Co1/3Mn1/3O2(NMC、Aldrich社製)又はLiCoO2(LCO、Aldrich社製)を8.0g、導電助剤としてアセチレンブラック(AB)を0.2g、表3に示す複合ポリマー粒子分散液を固形分相当で0.1g投入し、遊星ボールミルP-7に容器をセットし、温度25℃、回転数200rpmで30分間混合を続け、正極用組成物(スラリー)C-1~C-41をそれぞれ調製した。
ジルコニア製45mL容器(フリッチュ社製)に、直径5mmのジルコニアビーズを60g投入し、合成例Aで合成したLPS又はLLZを4.0g、表3に示す複合ポリマー粒子分散液0.09g(固形分質量)、及び分散媒としてヘプタンを22g(総量)投入した。フリッチュ社製遊星ボールミルP-7(商品名)にこの容器をセットし、温度25℃、回転数300pmで60分間混合した。その後、表3に示す活物質4.0g、導電助剤としてアセチレンブラック(デンカ社製)0.6gを投入し、同様に、遊星ボールミルP-7に容器をセットして、温度25℃、回転数100rpmで10分間混合して、負極用組成物A-1~A-43をそれぞれ調製した。
Si:ケイ素(Aldrich社製)
Sn:スズ(Aldrich社製)
SiO:酸化ケイ素(Aldrich社製)
NMC:LiNi1/3Co1/3Mn1/3O2(Aldrich社製)
LCO:LiCoO2(Aldrich社製)
Li-P-S:合成例Aで合成したLPS
LLZ:Li7La3Zr2O12
AB:アセチレンブラック(デンカ社製)
上記で得られた各無機固体電解質含有組成物を厚み20μmのアルミニウム箔上にベーカー式アプリケーター(商品名:SA-201、テスター産業社製)を用いて塗布し(目付量を表4-1に示す)、80℃で2時間加熱して、無機固体電解質含有組成物を乾燥(分散媒を除去)させた。その後、ヒートプレス機を用いて、120℃の温度及び40MPaの圧力で10秒間、乾燥させた無機固体電解質含有組成物を加熱及び加圧して、全固体二次電池用固体電解質シートS-1~S-15及びSS-1~SS-6をそれぞれ作製した。固体電解質層の膜厚は50μmであった。
上記で得られた各正極用組成物を厚み20μmのアルミニウム箔上にベーカー式アプリケーター(商品名:SA-201)を用いて塗布し(目付量を表4-1及び表4-2に示す)、80℃で1時間加熱し、更に110℃で1時間加熱して、正極用組成物を乾燥(分散媒を除去)した。その後、ヒートプレス機を用いて、乾燥させた正極用組成物を25℃で加圧(10MPa、1分)して、膜厚80μmの正極活物質層を有する全固体二次電池用正極シートC-1~C-41をそれぞれ作製した。
上記で得られた各負極用組成物を厚み20μmの銅箔上にベーカー式アプリケーター(商品名:SA-201)を用いて塗布し(目付量を表4-1及び表4-2に示す)、80℃で1時間加熱し、更に110℃で1時間加熱して、負極用組成物を乾燥(分散媒を除去)させた。その後、ヒートプレス機を用いて、乾燥させた負極用組成物を25℃で加圧(10MPa、1分)して、膜厚70μmの負極活物質層を有する全固体二次電池用負極シートA-1~A-43をそれぞれ作製した。
次いで、表4-1及び表4-2(合わせて表4という)に示す各全固体二次電池用負極シートの負極活物質層上に、表4-1及び表4-2の「固体電解質層」欄に示す全固体二次電池用固体電解質シートを、固体電解質層が負極活物質層に接するように重ね、プレス機を用いて温度120℃、加圧力40MPaで1分間加圧することにより、膜厚50μmの固体電解質層を備えた全固体二次電池用負極シートをそれぞれ作製した。負極活物質層の膜厚は60μmであった。
作製した、固体電解質層を備えた各全固体二次電池用負極シート(全固体二次電池用固体電解質シートのアルミニウム箔は剥離済み)を直径14.5mmの円板状に切り出し、図2に示すように、スペーサーとワッシャー(図2において図示せず)を組み込んだステンレス製の2032型コインケース11に入れた。次いで、この固体電解質層上に、表4の「正極活物質層」欄に示す全固体二次電池用正極シートから直径14.0mmで打ち抜いた全固体二次電池用正極シート片を重ねて全固体二次電池用積層体12(銅箔-負極活物質層-固体電解質層-正極活物質層-アルミニウム箔からなる積層体)を形成した。その後、2032型コインケース11をしめることで、図2に示すコイン型全固体二次電池No.1~28をそれぞれ製造した。負極活物質層、固体電解質層及び正極活物質層の最終的な膜厚を表4-1及び表4-2に示す。このようにして製造したコイン型全固体二次電池13は図1に示す層構成を有する。
全固体二次電池No.1~47の電池性能(電池電圧)として、その抵抗を測定して、評価した。
各全固体二次電池の抵抗を、充放電評価装置:TOSCAT-3000(商品名、東洋システム社製)により評価した。具体的には、各全固体二次電池を、それぞれ、25℃の環境下で、電流密度0.1mA/cm2で電池電圧が4.2Vに達するまで充電した。その後、電流密度0.2mA/cm2で電池電圧が2.5Vに達するまで放電した。この充電1回と放電1回とを充放電1サイクルとして繰り返して2サイクル充放電して、2サイクル目の5mAh/g(活物質質量1g当たりの電気量)放電後の電池電圧を読み取った。この電池電圧が下記評価ランクのいずれに含まれるかにより、全固体二次電池の抵抗を評価した。電池電圧が高いほど低抵抗であることを示す。本試験において、評価ランクが高いほど電池性能に優れる。
- 評価ランク -
8: 4.1V以上
7: 4.0V以上、4.1V未満
6: 3.9V以上、4.0V未満
5: 3.7V以上、3.9V未満
4: 3.5V以上、3.7V未満
3: 3.2V以上、3.5V未満
2: 2.5V以上、3.2V未満
1: 充放電できず
作製した各全固体二次電池用固体電解質シートS-1~S-15及びSS-1~SS-6を幅3cm×長さ14cmの長方形に切り出した。切り出したシートを、円筒形マンドレル試験機(商品コード056、マンドレル直径10mm、Allgood社製)を用いて、日本産業規格(JIS) K5600-5-1(耐屈曲性(円筒形マンドレル:タイプ2の試験装置を用いた試験)、国際標準規格(ISO)1519と同試験。)に従って、屈曲させた。なお、試験片はその固体電解質層をマンドレルとは逆側(基材をマンドレル側)に、幅方向をマンドレルの軸線と平行に、セットした。
屈曲後、屈曲部分を含む幅3cm×長さ8cm(屈曲部分を中心にして各端部側に向かって4cmまでの領域)の範囲を目視にて観察して欠陥の発生状態を調べた。固体電解質層に欠け、割れ若しくはヒビ、又は固体電解質層のアルミニウム箔からの剥がれが確認できた場合を欠陥発生とし、発生した欠陥部分の面積を固体電解質層の表面積に換算した面積(投影面積)として求めた。観測対象とした面積(幅3cm×長さ8cm)に対する、得られた欠陥部分の総面積の割合を求めて、この割合(欠陥の発生状態)を下記評価ランクに当てはめて、固体電解質層の結着性を評価した。本試験において、評価ランクが高いほど電池性能に優れる。
- 評価ランク -
8: 0%(欠陥が全く確認できない)
7: 0%越え、10%以下
6:10%越え、20%以下
5:20%越え、30%以下
4:30%越え、40%以下
3:40%越え、50%以下
2:50%越え、60%以下
1:60%超える
上記評価2「結着性試験」に準拠して上述のマンドレル試験を行った各全固体二次電池用固体電解質シートを用いて、実施例1と同様にして製造した全固体二次電池について、放電容量維持率を充放電評価装置TOSCAT-3000(商品名、東洋システム社製)により測定した。
具体的には、各全固体二次電池を、それぞれ、25℃の環境下で、電流密度0.1mA/cm2で電池電圧が3.6Vに達するまで充電した。その後、電流密度0.1mA/cm2で電池電圧が2.5Vに達するまで放電した。この充電1回と放電1回とを充放電1サイクルとして、同じ条件で充放電を3サイクル繰り返して、初期化した。その後、上記充放電サイクルを繰り返して行い、充放電サイクルを行う毎に各全固体二次電池の放電容量を、充放電評価装置:TOSCAT-3000(商品名)により、測定した。
初期化後の充放電1サイクル目の放電容量(初期放電容量)を100%としたときに、放電容量維持率(初期放電容量に対する放電容量)が80%に達した際の充放電サイクル数が、下記評価ランクのいずれに含まれるかにより、電池性能(サイクル特性)を評価した。本試験において、評価ランクが高いほど、電池性能(サイクル特性)に優れ、充放電を複数回繰り返しても(長期の使用においても)初期の電池性能を維持できる。
なお、全固体二次電池No.1~22、29~47の初期放電容量は、いずれも、全固体二次電池として機能するのに十分な値を示した。
- 評価ランク -
8:500サイクル以上
7:300サイクル以上、500サイクル未満
6:200サイクル以上、300サイクル未満
5:150サイクル以上、200サイクル未満
4: 80サイクル以上、150サイクル未満
3: 40サイクル以上、80サイクル未満
2: 20サイクル以上、40サイクル未満
1: 20サイクル未満
すなわち、本発明で規定する複合ポリマー粒子を含有しない無機固体電解質含有組成物は、構成層中の固体粒子の結着性が劣る。このような無機固体電解質含有組成物ですべての構成層を形成した全固体二次電池は抵抗及びサイクル特性が十分ではなかった。
これに対して、本発明で規定する複合ポリマー粒子を含有する無機固体電解質含有組成物は、全固体二次電池の構成層の形成に用いることにより、得られる全固体二次電池用シートの構成層について欠陥の発生を抑制できる。この無機固体電解質含有組成物を構成層の少なくとも1層、好ましくは3層すべての形成に用いることにより、得られる全固体二次電池について抵抗の低減とサイクル特性の向上を実現できることが分かる。特に、低極性構成単位の含有量を20質量%未満としても、所期の効果を奏することが分かる。
2 負極活物質層
3 固体電解質層
4 正極活物質層
5 正極集電体
6 作動部位
10 全固体二次電池
11 2032型コインケース
12 全固体二次電池用積層体
13 コイン型全固体二次電池
Claims (18)
- 前記複合ポリマー粒子に含まれる全ポリマー中、SP値が20.5J0.5/cm1.5以上40J0.5/cm1.5以下である構成単位が20~99.5質量%であり、SP値が15J0.5/cm1.5以上20.5J0.5/cm1.5未満である構成単位が0.5~80質量%である、請求項1に記載の無機固体電解質含有組成物。
- 前記複合ポリマー粒子に含まれるポリマーが、酸性官能基又は塩基性官能基を有する、請求項1又は2に記載の無機固体電解質含有組成物。
- ClogP値が1.0以上の有機溶媒を含有する、請求項1~3のいずれか1項に記載の無機固体電解質含有組成物。
- 前記複合ポリマー粒子の平均一次粒子径が0.1nm~5.0μmである、請求項1~4のいずれか1項に記載の無機固体電解質含有組成物。
- 前記少なくとも2種のポリマーの内、
少なくとも1種のポリマーが、SP値が15J0.5/cm1.5以上20.5J0.5/cm1.5未満である構成単位を5質量%以上有する低極性ポリマーであり、
少なくとも1種のポリマーが、SP値が20.5J0.5/cm1.5以上40J0.5/cm1.5以下の構成単位を90質量%以上有する高極性ポリマーである、請求項1~5のいずれか1項に記載の無機固体電解質含有組成物。 - 前記高極性のポリマーが前記式(1)で表される結合を有する、請求項6に記載の無機固体電解質含有組成物。
- 前記複合ポリマー粒子に含まれる全ポリマー中の、前記低極性ポリマーの含有率が1~70質量%であり、前記高極性のポリマーの含有率が30~99質量%である、請求項6又は7に記載の無機固体電解質含有組成物。
- 前記式(1)で表される結合が、ウレタン結合、ウレア結合、アミド結合、イミド結合、エステル結合、カーボネート結合、チオウレア結合、チオウレタン結合、イミダゾール結合又はトリアゾール結合を形成する、請求項1~8のいずれか1項に記載の無機固体電解質含有組成物。
- 活物質を含有する、請求項1~9のいずれか1項に記載の無機固体電解質含有組成物。
- 前記活物質が、ケイ素元素又はスズ元素を含有する活物質である、請求項10に記載の無機固体電解質含有組成物。
- 導電助剤を含有する、請求項1~11のいずれか1項に記載の無機固体電解質含有組成物。
- 前記無機固体電解質が硫化物系無機固体電解質である、請求項1~12のいずれか1項に記載の無機固体電解質含有組成物。
- 請求項1~13のいずれか1項に記載の無機固体電解質含有組成物で構成した層を有する全固体二次電池用シート。
- 正極活物質層と固体電解質層と負極活物質層とをこの順で具備する全固体二次電池であって、
前記正極活物質層、前記固体電解質層及び前記負極活物質層の少なくとも1つの層が、請求項1~13のいずれか1項に記載の無機固体電解質含有組成物で構成した層である、全固体二次電池。 - 請求項1~13のいずれか1項に記載の無機固体電解質含有組成物を製膜する、全固体二次電池用シートの製造方法。
- 請求項16に記載の製造方法を経て全固体二次電池を製造する、全固体二次電池の製造方法。
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