WO2015046314A1 - 固体電解質組成物、これを用いた電池用電極シートおよび全固体二次電池 - Google Patents
固体電解質組成物、これを用いた電池用電極シートおよび全固体二次電池 Download PDFInfo
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- WO2015046314A1 WO2015046314A1 PCT/JP2014/075399 JP2014075399W WO2015046314A1 WO 2015046314 A1 WO2015046314 A1 WO 2015046314A1 JP 2014075399 W JP2014075399 W JP 2014075399W WO 2015046314 A1 WO2015046314 A1 WO 2015046314A1
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Images
Classifications
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F12/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F12/02—Monomers containing only one unsaturated aliphatic radical
- C08F12/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F12/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by hetero atoms or groups containing heteroatoms
- C08F12/22—Oxygen
- C08F12/24—Phenols or alcohols
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
- C08F290/12—Polymers provided for in subclasses C08C or C08F
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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
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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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- 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
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
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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
- H01M10/0585—Construction or manufacture of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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- H—ELECTRICITY
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- 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
- 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 a solid electrolyte composition, a battery electrode sheet using the same, and an all-solid secondary battery.
- An electrolyte solution is used for the lithium ion battery. Attempts have been made to replace the electrolytic solution with a solid electrolyte to obtain an all-solid-state secondary battery in which the constituent materials are all solid. Among them, reliability is first mentioned as an advantage of a technique using an inorganic solid electrolyte.
- a flammable material such as a carbonate-based solvent is used as a medium for the electrolytic solution used in the lithium ion secondary battery.
- various safety measures have been taken, it cannot be said that there is no risk of malfunctions during overcharge, and further measures are desired.
- An all-solid-state secondary battery made of an inorganic compound that can make the electrolyte incombustible is positioned as a fundamental solution.
- a further advantage of the all-solid-state secondary battery is that it is suitable for increasing the energy density by stacking electrodes. Specifically, a battery having a structure in which an electrode and an electrolyte are directly arranged in series can be obtained. At this time, since the metal package for sealing the battery cell, the copper wire and the bus bar for connecting the battery cell can be omitted, the energy density of the battery is greatly increased. In addition, good compatibility with the positive electrode material capable of increasing the potential is also mentioned as an advantage.
- Non-patent Document 1 Developed as a next-generation lithium ion secondary battery due to the above-described advantages, it has been vigorously developed (Non-patent Document 1).
- an inorganic all-solid secondary battery has a disadvantage because the electrolyte is a hard solid. For example, the interfacial resistance between the solid particles and between the solid particles and the current collector is increased.
- Patent Document 1 a method of sintering a solid electrolyte at a high temperature (Patent Document 1), a method using a jig for pressurizing a cell (Patent Document 2), and a method of pressing an entire element with a resin (Patent Document) 3)
- Patent Document 4 A method of firing a green sheet containing a solid electrolyte after pressurization (Patent Document 4) has been proposed.
- Patent Document 5 for the purpose of preventing deterioration of the positive electrode material (Patent Document 5), preventing peeling of the electrode material due to volume change of the active material accompanying charge / discharge (Patent Document 6), and improving binding properties (Patent Document 7),
- Patent Document 7 There is an example of selecting a binder to be mixed with an inorganic material.
- the increase in the interfacial resistance in the all-solid-state secondary battery may be improved as a result of the devices of Patent Documents 1 to 4, it is desirable to avoid a method that relies on the physical force of “pressure” in the first place. Further, various properties are expected to be improved by the binders disclosed in Patent Documents 5 to 7, but the improvement effect regarding the interface resistance and the like is not yet sufficient, and further improvement has been desired. Therefore, the present invention can suppress an increase in interfacial resistance between solid particles or between solid particles and a current collector in an all-solid-state secondary battery without applying pressure, and also has good binding properties.
- An object is to provide a solid electrolyte composition that can be realized, a battery electrode sheet using the same, and an all-solid secondary battery.
- the polymer constituting the binder particles includes a repeating unit derived from a monomer selected from (meth) acrylic acid monomer, (meth) acrylic acid ester monomer, and (meth) acrylonitrile [1] to [5]
- Any one of [1] to [7], wherein a ratio of the repeating unit derived from the macromonomer (X) in the polymer constituting the binder particle (B) is 50% by mass or less and 1% by mass or more.
- the macromonomer (X) is represented by any of the monomers represented by the following formulas (b-13a) to (b-13c) or any of (b-14a) to (b-14c): The solid electrolyte composition according to any one of [1] to [10], wherein the monomer has a repeating unit.
- R b2 and R b3 each independently represent a hydrogen atom, a hydroxy group, a cyano group, a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, or an aryl group.
- Ra and Rb each independently represent a linking group. the represented. However, Ra when na is 1 .na a monovalent substituent is .R N represents an integer of 1 to 6 is a hydrogen atom or a substituent.
- the binder particles (B) are contained in an amount of 0.1 to 20 parts by mass with respect to 100 parts by mass of the solid electrolyte (A).
- the dispersion medium (C) is selected from alcohol compound solvents, ether compound solvents, amide compound solvents, ketone compound solvents, ether compound solvents, aromatic compound solvents, aliphatic compound solvents, and nitrile compound solvents [1] ]
- a battery electrode sheet obtained by forming the solid electrolyte composition according to any one of [1] to [14] on a metal foil.
- An all-solid secondary battery comprising a positive electrode active material layer, a negative electrode active material layer, and a solid electrolyte layer, wherein at least one of the positive electrode active material layer, the negative electrode active material layer, and the solid electrolyte layer is [ [1]
- An all-solid secondary battery comprising a layer composed of the solid electrolyte composition according to any one of [14].
- a method for producing an electrode sheet for a battery comprising disposing the solid electrolyte composition according to any one of [1] to [14] on a metal foil and forming a film thereon.
- each substitution may be the same as or different from each other. Further, when a plurality of substituents and the like are close to each other, they may be bonded to each other or condensed to form a ring.
- the solid electrolyte composition of the present invention When used as a material for a solid electrolyte layer or an active material layer of an all-solid-state secondary battery, it does not depend on pressure, between the solid particles or between the solid particles and the current collector, etc. It is possible to suppress an increase in the interfacial resistance, and it is possible to achieve an excellent effect that even better binding properties can be realized.
- the solid electrolyte composition of the present invention includes an inorganic solid electrolyte (A) and binder particles (B) composed of a polymer having a specific side chain.
- A inorganic solid electrolyte
- B binder particles
- FIG. 1 is a cross-sectional view schematically showing an all solid state secondary battery (lithium ion secondary battery) according to a preferred embodiment of the present invention.
- the all-solid-state secondary battery 10 of this embodiment includes a negative electrode current collector 1, a negative electrode active material layer 2, a solid electrolyte layer 3, a positive electrode active material layer 4, and a positive electrode current collector 5 in that order as viewed from the negative electrode side. Have.
- Each layer is in contact with each other and has a laminated structure. By adopting such a structure, at the time of charging, electrons (e ⁇ ) are supplied to the negative electrode side, and lithium ions (Li + ) are accumulated therein.
- the solid electrolyte composition of the present invention is preferably used as a constituent material of the negative electrode active material layer, the positive electrode active material layer, and the solid electrolyte layer. Among them, all of the solid electrolyte layer, the positive electrode active material layer, and the negative electrode active material layer are used. It is preferable to use it as a constituent material.
- the thickness of the positive electrode active material layer 4, the solid electrolyte layer 3, and the negative electrode active material layer 2 is not particularly limited, the positive electrode active material layer and the negative electrode active material layer can be arbitrarily determined according to the intended battery application. .
- the solid electrolyte layer is as thin as possible while preventing a short circuit between the positive and negative electrodes.
- the thickness is preferably 1 to 1000 ⁇ m, and more preferably 3 to 400 ⁇ m.
- a functional layer, a member, or the like is appropriately provided between or outside the negative electrode current collector 1, the negative electrode active material layer 2, the solid electrolyte layer 3, the positive electrode active material layer 4, and the positive electrode current collector 5. It may be interposed or arranged.
- Each layer may be composed of a single layer or a plurality of layers.
- the inorganic solid electrolyte is an inorganic solid electrolyte, and the solid electrolyte is a solid electrolyte capable of moving ions inside. From this point of view, it may be referred to as an ion conductive inorganic solid electrolyte in consideration of distinction from an electrolyte salt (supporting electrolyte) described later. Since it does not contain organic substances (carbon atoms), it is clearly distinguished from organic solid electrolytes (polymer electrolytes typified by PEO and the like, organic electrolyte salts typified by LiTFSI and the like).
- the inorganic solid electrolyte is solid in a steady state, it is not dissociated or released into cations and anions. In this respect, it is also clearly distinguished from inorganic electrolyte salts (LiPF 6 , LiBF 4 , LiFSI, LiCl, etc.) in which cations and anions are dissociated or liberated in the electrolytic solution or polymer.
- the inorganic solid electrolyte is not particularly limited as long as it has conductivity of ions of metals belonging to Group 1 or Group 2 of the periodic table, and generally does not have electron conductivity.
- the inorganic solid electrolyte has ion conductivity of a metal belonging to Group 1 or Group 2 of the periodic table.
- a solid electrolyte material applied to this type of product can be appropriately selected and used.
- Typical examples of inorganic solid electrolytes include (i) sulfide-based inorganic solid electrolytes and (ii) oxide-based inorganic solid electrolytes.
- a sulfide solid electrolyte contains sulfur (S), has ionic conductivity of a metal belonging to Group 1 or Group 2 of the periodic table, and has electronic insulation. Those having properties are preferred.
- a lithium ion conductive inorganic solid electrolyte that satisfies the composition represented by the following formula (1) can be given.
- Li a Mb P c S d (1) (Wherein M represents an element selected from B, Zn, Si, Cu, Ga and Ge. A to d represent the composition ratio of each element, and a: b: c: d represents 1 to 12: 0-0.2: 1: 2-9 are satisfied.)
- the composition ratio of each element can be controlled by adjusting the blending amount of the raw material compound when producing the sulfide-based solid electrolyte as described below.
- the sulfide-based solid electrolyte may be amorphous (glass) or crystallized (glass ceramics), or only part of it may be crystallized.
- the ratio of Li 2 S to P 2 S 5 in the Li—PS system glass and the Li—PS system glass ceramic is a molar ratio of Li 2 S: P 2 S 5 , preferably 65:35 to 85:15, more preferably 68:32 to 75:25.
- the lithium ion conductivity can be increased.
- the lithium ion conductivity can be preferably 1 ⁇ 10 ⁇ 4 S / cm or more, more preferably 1 ⁇ 10 ⁇ 3 S / cm or more.
- the compound include those using a raw material composition containing, for example, Li 2 S and a sulfide of an element belonging to Group 13 to Group 15.
- Li 2 S—P 2 S 5 Li 2 S—GeS 2 , Li 2 S—GeS 2 —ZnS, Li 2 S—Ga 2 S 3 , Li 2 S—GeS 2 —Ga 2 S 3 Li 2 S—GeS 2 —P 2 S 5 , Li 2 S—GeS 2 —Sb 2 S 5 , Li 2 S—GeS 2 —Al 2 S 3 , Li 2 S—SiS 2 , Li 2 S—Al 2 S 3 , Li 2 S—SiS 2 —Al 2 S 3 , Li 2 S—SiS 2 —P 2 S 5 , Li 2 S—SiS 2 —LiI, Li 2 S—SiS 2 —Li 4 SiO 4 , Li 2 Examples thereof include S—SiS 2 —Li 3
- Li 2 S—P 2 S 5 , Li 2 S—GeS 2 —Ga 2 S 3 , Li 2 SGeS 2 —P 2 S 5 , Li 2 S—SiS 2 —P 2 S 5 , Li 2 S— A crystalline and / or amorphous raw material composition made of SiS 2 —Li 4 SiO 4 or Li 2 S—SiS 2 —Li 3 PO 4 is preferable because it has high lithium ion conductivity.
- Examples of a method for synthesizing a sulfide solid electrolyte material using such a raw material composition include an amorphization method.
- the amorphization method include a mechanical milling method and a melt quenching method, and among them, the mechanical milling method is preferable. This is because processing at room temperature is possible, and the manufacturing process can be simplified.
- Oxide-based inorganic solid electrolyte contains oxygen (O), has ion conductivity of a metal belonging to Group 1 or Group 2 of the periodic table, and is an electron What has insulation is preferable.
- Li, P and O Phosphorus compounds containing Li, P and O are also desirable.
- lithium phosphate Li 3 PO 4
- LiPON obtained by substituting part of oxygen of lithium phosphate with nitrogen
- LiPOD LiPOD
- LiAON A is at least one selected from Si, B, Ge, Al, C, Ga, etc.
- the ionic conductivity of the lithium ion conductive oxide-based inorganic solid electrolyte is preferably 1 ⁇ 10 ⁇ 6 S / cm or more, more preferably 1 ⁇ 10 ⁇ 5 S / cm or more.
- X 10 ⁇ 5 S / cm or more is particularly preferable.
- an oxide-based inorganic solid electrolyte it is particularly preferable to use an oxide-based inorganic solid electrolyte. Since the oxide-based inorganic solid electrolyte generally has a higher hardness, the interface resistance is likely to increase in the all-solid secondary battery. By applying the present invention, the effect becomes more prominent.
- the 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. As an upper limit, it is preferable that it is 100 micrometers or less, and it is more preferable that it is 50 micrometers or less.
- the measuring method of the average particle diameter of inorganic solid electrolyte particles shall follow the measuring method of the average particle diameter of the inorganic particle shown in the term of the postscript Example.
- the concentration of the inorganic solid electrolyte (A) in the solid electrolyte composition is preferably 50% by mass or more in 100% by mass of the solid component when considering both the battery performance and the reduction / maintenance effect of the interface resistance. 70 mass% or more is more preferable, and 90 mass% or more is particularly preferable. As an upper limit, it is preferable that it is 99.9 mass% or less from the same viewpoint, It is more preferable that it is 99.5 mass% or less, It is especially preferable that it is 99 mass% or less.
- the solid component refers to a component that does not disappear by volatilization or evaporation when a drying treatment is performed at 100 ° C. Typically, it refers to components other than the dispersion medium described below.
- the said inorganic solid electrolyte may be used individually by 1 type, or may be used in combination of 2 or more type.
- Binder particles (B) The polymer constituting the binder particles used in the present invention incorporates a repeating unit derived from the macromonomer (X) having a number average molecular weight of 1000 or more as a side chain component.
- the main chain of the polymer constituting the binder particle (B) of the present invention is not particularly limited, and a normal polymer component can be applied.
- the monomer constituting the main chain component is preferably a monomer having a polymerizable unsaturated bond, and for example, various vinyl monomers and acrylic monomers can be applied.
- the number of polymerizable groups is not particularly limited, but is preferably 1 to 4.
- the polymer constituting the binder particles according to the present invention preferably has at least one of the following functional group (b).
- This functional group group may be contained in the main chain or may be contained in a side chain described later, but is preferably contained in the main chain.
- the inclusion of a specific functional group in the main chain or the like allows interaction with hydrogen atoms, oxygen atoms, and sulfur atoms that are considered to exist on the surface of the solid electrolyte, active material, and current collector. It can be expected to have an effect of strengthening, improving the binding property, and reducing the interface resistance.
- the carbonyl group-containing group include a carboxyl group, a carbonyloxy group, an amide group, and the like. Is preferable, 1 to 12 is more preferable, and 1 to 6 is particularly preferable.
- the amino group preferably has 0 to 12 carbon atoms, more preferably 0 to 6, and particularly preferably 0 to 2.
- the sulfonic acid group may be its ester or salt. In the case of an ester, the number of carbon atoms is preferably 1 to 24, more preferably 1 to 12, and particularly preferably 1 to 6.
- the phosphate group may be its ester or salt.
- the number of carbon atoms is preferably 1 to 24, more preferably 1 to 12, and particularly preferably 1 to 6.
- the said functional group may exist as a substituent or may exist as a coupling group.
- the amino group may exist as a divalent imino group or a trivalent nitrogen atom.
- vinyl monomer constituting the polymer those represented by the following formula (b-1) are preferable.
- R 1 represents a hydrogen atom, a hydroxy group, a cyano group, a halogen atom, an alkyl group (preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, and particularly preferably 1 to 6 carbon atoms), an alkenyl group (2 carbon atoms).
- an alkynyl group preferably having a carbon number of 2 to 24, more preferably 2 to 12, and particularly preferably 2 to 6
- the number of carbon atoms is preferably 6 to 22, and more preferably 6 to 14.
- a hydrogen atom or an alkyl group is preferable, and a hydrogen atom or a methyl group is more preferable.
- R 2 is a hydrogen atom, an alkyl group (preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, particularly preferably 1 to 6 carbon atoms), an alkenyl group (preferably 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms) ), Aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 14 carbon atoms), aralkyl group (preferably having 7 to 23 carbon atoms, more preferably 7 to 15 carbon atoms), cyano group, carboxyl group, hydroxy group, thiol Group, sulfonic acid group, phosphoric acid group, phosphonic acid group, aliphatic heterocyclic group containing oxygen atom (preferably having 2 to 12 carbon atoms, more preferably 2 to 6), or amino group (NR N 2 : R N is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms according to the definition described later.
- R 2 may further have a substituent T described later.
- a carboxyl group, a halogen atom (fluorine atom or the like), a hydroxy group, an alkyl group, or the like may be substituted.
- the carboxyl group, hydroxy group, sulfonic acid group, phosphoric acid group, and phosphonic acid group may be esterified with, for example, an alkyl group having 1 to 6 carbon atoms.
- the aliphatic heterocyclic group containing an oxygen atom is preferably an epoxy group-containing group, an oxetane group-containing group, a tetrahydrofuryl group-containing group, or the like.
- L 1 is an arbitrary linking group, and examples of the linking group L described later are given. Specifically, an alkylene group having 1 to 6 (preferably 1 to 3) carbon atoms, an alkenylene group having 2 to 6 (preferably 2 to 3) carbon atoms, and 6 to 24 (preferably 6 to 10) carbon atoms. Arylene group, oxygen atom, sulfur atom, imino group (NR N ), carbonyl group, phosphate linking group (—O—P (OH) (O) —O—), phosphonic acid linking group (—P (OH) ( And groups relating to O) -O-) or a combination thereof.
- the linking group may have an arbitrary substituent. The preferable number of connecting atoms and the number of connecting atoms are the same as described later. As an arbitrary substituent, the substituent T is mentioned, For example, an alkyl group or a halogen atom is mentioned.
- N is 0 or 1.
- acrylic monomer constituting the above polymer in addition to the above (b-1), those represented by any of the following formulas (b-2) to (b-6) are preferable.
- R 1 and n are as defined in the above formula (b-1).
- R 3 has the same meaning as R 2 .
- preferred examples thereof include a hydrogen atom, an alkyl group, an aryl group, a carboxyl group, a thiol group, a phosphoric acid group, a phosphonic acid group, an aliphatic heterocyclic group containing an oxygen atom, and an amino group (NR N 2 ).
- L 2 is an arbitrary linking group, and is preferably an example of L 1 , an oxygen atom, an alkylene group having 1 to 6 carbon atoms (preferably 1 to 3), or an alkylene group having 2 to 6 carbon atoms (preferably 2 to 3).
- L 3 is a linking group, and an example of L 2 is preferable, and an alkylene group having 1 to 6 (preferably 1 to 3) carbon atoms is more preferable.
- L 4 is synonymous with L 1 .
- R 4 is a hydrogen atom, an alkyl group having 1 to 6 (preferably 1 to 3) carbon atoms, a hydroxy group-containing group having 0 to 6 (preferably 0 to 3) carbon atoms, or 0 to 6 (preferably 0) carbon atoms.
- R 4 may be a linking group for L 1 and may form a dimer at this portion.
- m represents an integer of 1 to 200, preferably an integer of 1 to 100, and more preferably an integer of 1 to 50.
- any group which may take a substituent such as an alkyl group, an aryl group, an alkylene group or an arylene group may be substituted as long as the effects of the present invention are maintained. It may have a group.
- the optional substituent include a substituent T, and specifically include a halogen atom, a hydroxy group, a carboxyl group, a thiol group, an acyl group, an acyloxy group, an alkoxy group, an aryloxy group, an aryloyl group, and an aryl group.
- N in the following formula represents 1 to 1,000,000.
- the macromonomer has a number average molecular weight of 1,000 or more, more preferably 2,000 or more, and particularly preferably 3,000 or more.
- the upper limit is preferably 500,000 or less, more preferably 100,000 or less, and particularly preferably 30,000 or less.
- the above-mentioned side chain component in the binder polymer has a function of improving dispersibility in a solvent.
- a binder is suitably disperse
- an equal interval is maintained between the binder particles and the electrical connection between the particles is not interrupted, so that it is considered that an increase in interfacial resistance between the solid particles and the current collector can be suppressed.
- the binder polymer has side chains, not only the binder particles adhere to the solid electrolyte particles, but also an effect of tangling the side chains can be expected. This is considered to achieve both suppression of the interfacial resistance related to the solid electrolyte and improvement of adhesion. Furthermore, due to its good dispersibility, the step of layer transfer into an organic solvent can be omitted compared to emulsion polymerization in water, and a solvent having a low boiling point can be used as a dispersion medium.
- the molecular weight of the side chain component (X) can be identified by measuring the molecular weight of the polymerizable compound (macromonomer) incorporated when synthesizing the polymer constituting the binder particle (B).
- the molecular weight of the polymer means the number average molecular weight unless otherwise specified, and the number average molecular weight in terms of standard polystyrene is measured by gel permeation chromatography (GPC).
- the measurement method is basically a value measured by the following condition 1 or condition 2 (priority) method.
- an appropriate eluent may be selected and used depending on the polymer type.
- Carrier flow rate 1.0 ml / min Sample concentration: 0.1% by mass Detector: RI (refractive index) detector (Condition 2) Column: TOSOH TSKgel Super HZM-H, TOSOH TSKgel Super HZ4000, TOSOH TSKgel Super HZ2000 connected to column Carrier: Tetrahydrofuran Measurement temperature: 40 ° C Carrier flow rate: 1.0 ml / min Sample concentration: 0.1% by mass Detector: RI (refractive index) detector
- the SP value of the macromonomer (X) is preferably 10 or less, and more preferably 9.5 or less. Although there is no particular lower limit, it is practical that it is 5 or more.
- the SP value is obtained by the Hoy method (HL Hoy Journal of Paining, 1970, Vol. 42, 76-118). The SP value is shown with the unit omitted, but the unit is cal 1/2 cm ⁇ 3/2 . Note that the SP value of the side chain component (X) is not substantially different from the SP value of the raw material monomer forming the side chain, and may be evaluated accordingly.
- the SP value is an index indicating the characteristic of being dispersed in an organic solvent.
- the side chain component is set to a specific molecular weight or more, preferably to the SP value or more, the binding property with the solid electrolyte is improved, thereby improving the affinity with the solvent and stably dispersing. This is preferable.
- the main chain of the side chain component of said macromonomer (X) is not specifically limited, A normal polymer component can be applied.
- the macromonomer (X) preferably has a polymerizable unsaturated bond, and can have, for example, various vinyl groups or (meth) acryloyl groups. In the present invention, it is preferable to have a (meth) acryloyl group.
- the term “acryl” or “acryloyl” refers broadly to those containing not only an acryloyl group but also a derivative structure thereof, and includes a structure having a specific substituent at the ⁇ -position of the acryloyl group.
- the case where the ⁇ -position is a hydrogen atom may be referred to as acryl or acryloyl.
- Those having a methyl group at the ⁇ -position are referred to as methacryl, which means either acryl (the ⁇ -position is a hydrogen atom) or methacryl (the ⁇ -position is a methyl group), and is sometimes referred to as (meth) acryl.
- the macromonomer (X) preferably contains a repeating unit derived from a monomer selected from a (meth) acrylic acid monomer, a (meth) acrylic acid ester monomer, and (meth) acrylonitrile.
- the macromonomer (X) is a polymerizable double bond and a linear hydrocarbon structural unit S having 6 or more carbon atoms (preferably an alkylene group having 6 to 30 carbon atoms, more preferably 8 to 24 carbon atoms). Of the alkylene group).
- the macromonomer (X) preferably has a site represented by the following formula (b-11).
- R 11 has the same meaning as R 1 . * Is a connecting part.
- the macromonomer (X) preferably has a site represented by the following formulas (b-12a) to (b-12c). Hereinafter, these sites may be referred to as “specific polymerizable sites”.
- R b2 has the same meaning as R 1 .
- RN has the same definition as the substituent T described later.
- An arbitrary substituent T may be substituted on the benzene ring of the formulas (b-12c), (b-13c), and (b-14c).
- the structure part present at the end of the bond part of * is not particularly limited as long as the molecular weight as a macromonomer is satisfied, but a structure part composed of a carbon atom, an oxygen atom, and a hydrogen atom is preferable.
- you may have the substituent T for example, you may have a halogen atom (fluorine atom) etc.
- the macromonomer (X) is a compound represented by the following formulas (b-13a) to (b-13c) or a compound having a repeating unit represented by (b-14a) to (b-14c). It is preferable.
- R b2 and R b3 have the same meaning as R 1 .
- n a is not particularly limited, preferably an integer of 1 to 6, more preferably 1 or 2.
- Ra represents a substituent (preferably an organic group) when na is 1, and represents a linking group when na is 2 or more.
- Rb is a divalent linking group.
- examples of the linking group include the following linking group L. Specifically, an alkane linking group having 1 to 30 carbon atoms (an alkylene group in the case of divalent), a cycloalkane linking group having 3 to 12 carbon atoms (a cycloalkylene group in the case of divalent), an aryl having 6 to 24 carbon atoms.
- Linking group (arylene group for divalent), heteroaryl linking group having 3 to 12 carbon atoms (heteroarylene group for divalent), ether group (—O—), sulfide group (—S—), phosphinidene group ( -PR-: R is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms), a silylene group (-SiRR'-: R, R 'is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms), a carbonyl group, an imino group ( -NR N -: according R N is below the defined, here, a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 10 carbon atoms), or is preferably a combination thereof.
- an alkane linking group having 1 to 30 carbon atoms (an alkylene group in the case of divalent), an aryl linking group having 6 to 24 carbon atoms (an arylene group in the case of divalent), an ether group, a carbonyl group, or a combination thereof. It is preferable.
- the linking group constituting Ra and Rb is preferably a linking structure composed of a carbon atom, an oxygen atom, and a hydrogen atom.
- the linking group constituting Ra and Rb is also preferably a structural part having a repeating unit (b-15) described later.
- Ra and Rb are linking groups, the number of atoms constituting the linking group and the number of linking atoms are as defined for the linking group L described later.
- Ra is a monovalent substituent
- examples of the substituent T described below are given, and among them, an alkyl group, an alkenyl group, and an aryl group are preferable.
- the linking group L may be present in the substituent.
- Ra is a monovalent substituent
- a structure of —Rb—Rc or a structure having a repeating unit (b-15) described later is also preferred.
- Rc includes examples of the substituent T described later, and among them, an alkyl group, an alkenyl group, and an aryl group are preferable.
- each of Ra and Rb preferably contains at least a linear hydrocarbon structural unit having 1 to 30 carbon atoms (preferably an alkylene group), and preferably contains the linear hydrocarbon structural unit S. More preferred.
- Each of Ra to Rc may have a linking group or a substituent, and examples thereof include a linking group L and a substituent T described later.
- the macromonomer (X) preferably further has a repeating unit represented by the following formula (b-15).
- R b4 represents a hydrogen atom or a substituent T described later. Of these, a hydrogen atom, an alkyl group, an alkenyl group, and an aryl group are preferable.
- R b4 is an alkyl group, an alkenyl group, or an aryl group, it may further have a substituent T described later, and may have, for example, a halogen atom or a hydroxy group.
- X is a linking group, and examples of the linking group L can be given.
- they are an ether group, a carbonyl group, an imino group, an alkylene group, an arylene group, or a combination thereof.
- the linking group in combination include a linking group composed of a carbonyloxy group, an amide group, an oxygen atom, a carbon atom, and a hydrogen atom.
- R b4 and X contain carbon, the preferred number of carbon atoms is the same as the substituent T and the linking group L described later.
- the preferable number of constituent atoms of the linking group and the number of linking atoms are also synonymous.
- the macromonomer X includes a (meth) acrylate structural unit such as the above formula b-15, and an alkylene which may have a halogen atom (for example, a fluorine atom) Examples include chains (for example, ethylene chains). At this time, an ether group (O) or the like may be present in the alkylene chain.
- Examples of the substituent include a structure in which an arbitrary substituent is arranged at the terminal of the linking group.
- Examples of the terminal substituent include the substituent T described below, and the example of R 1 is preferable.
- it uses for the meaning containing the salt and its ion other than the said compound itself about the display of a compound (For example, when attaching
- it is meant to include derivatives in which a part thereof is changed, such as introduction of a substituent, within a range where a desired effect is exhibited.
- a substituent that does not specify substitution / non-substitution means that the group may have an arbitrary substituent.
- substituents include the following substituent T.
- substituent T include the following.
- An alkyl group preferably an alkyl group having 1 to 20 carbon atoms, such as methyl, ethyl, isopropyl, t-butyl, pentyl, heptyl, 1-ethylpentyl, benzyl, 2-ethoxyethyl, 1-carboxymethyl, etc.
- alkenyl A group preferably an alkenyl group having 2 to 20 carbon atoms such as vinyl, allyl, oleyl and the like
- an alkynyl group preferably an alkynyl group having 2 to 20 carbon atoms such as ethynyl, butadiynyl, phenylethynyl and the like
- a cycloalkyl group preferably a cycloalkyl group having 3 to 20 carbon atoms, such as cycl
- each of the groups listed as the substituent T may be further substituted with the substituent T described above.
- a compound or a substituent / linking group includes an alkyl group / alkylene group, an alkenyl group / alkenylene group, an alkynyl group / alkynylene group, etc., these may be cyclic or linear, and may be linear or branched These may be substituted as described above or may be unsubstituted.
- Each substituent defined in the present specification may be substituted through the following linking group L within the scope of the effects of the present invention, or the linking group L may be present in the structure thereof.
- the alkyl group / alkylene group, alkenyl group / alkenylene group and the like may further have the following hetero-linking group interposed in the structure.
- the linking group L includes a hydrocarbon linking group [an alkylene group having 1 to 10 carbon atoms (more preferably 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms), an alkenylene group having 2 to 10 carbon atoms (more preferably carbon atoms).
- the said hydrocarbon coupling group may form the double bond and the triple bond suitably, and may connect.
- the ring to be formed is preferably a 5-membered ring or a 6-membered ring.
- a nitrogen-containing five-membered ring is preferable, and examples of the compound forming the ring include pyrrole, imidazole, pyrazole, indazole, indole, benzimidazole, pyrrolidine, imidazolidine, pyrazolidine, indoline, carbazole, or these And derivatives thereof.
- 6-membered ring examples include piperidine, morpholine, piperazine, and derivatives thereof. Moreover, when an aryl group, a heterocyclic group, etc. are included, they may be monocyclic or condensed and may be similarly substituted or unsubstituted.
- RN is a hydrogen atom or a substituent. Examples of the substituent include an alkyl group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, further preferably 1 to 6 carbon atoms, and particularly preferably 1 to 3 carbon atoms), and an alkenyl group (preferably having 2 to 24 carbon atoms and 2 carbon atoms).
- To 12 is more preferable, 2 to 6 is more preferable, and 2 to 3 is particularly preferable, and an alkynyl group (2 to 24 carbon atoms is preferable, 2 to 12 is more preferable, 2 to 6 is more preferable, and 2 to 3 is Particularly preferred), an aralkyl group (preferably 7 to 22 carbon atoms, more preferably 7 to 14 carbon atoms, particularly preferably 7 to 10 carbon atoms), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 14 carbon atoms, 6 to 14 carbon atoms). 10 is particularly preferred).
- RP is a hydrogen atom, a hydroxyl group, or a substituent.
- substituents examples include an alkyl group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, further preferably 1 to 6 carbon atoms, and particularly preferably 1 to 3 carbon atoms), and an alkenyl group (preferably having 2 to 24 carbon atoms and 2 carbon atoms).
- To 12 is more preferable, 2 to 6 is more preferable, and 2 to 3 is particularly preferable, and an alkynyl group (2 to 24 carbon atoms is preferable, 2 to 12 is more preferable, 2 to 6 is more preferable, and 2 to 3 is Particularly preferred), an aralkyl group (preferably 7 to 22 carbon atoms, more preferably 7 to 14 carbon atoms, particularly preferably 7 to 10 carbon atoms), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 14 carbon atoms, 6 to 14 carbon atoms).
- an alkoxy group preferably having 1 to 24 carbon atoms, more preferably 1 to 12, more preferably 1 to 6 and particularly preferably 1 to 3
- an alkenyloxy group having carbon number
- More preferably 2 to 12, more preferably 2 to 6, particularly preferably 2 to 3, and an alkynyloxy group preferably having 2 to 24 carbon atoms, more preferably 2 to 12 and more preferably 2 to 6.
- More preferably, 2 to 3 are particularly preferred
- an aralkyloxy group preferably 7 to 22 carbon atoms, more preferably 7 to 14 carbon atoms, particularly preferably 7 to 10 carbon atoms
- an aryloxy group preferably 6 to 22 carbon atoms, 6 to 14 are more preferable, and 6 to 10 are particularly preferable.
- the number of atoms constituting the linking group is preferably from 1 to 36, more preferably from 1 to 24, still more preferably from 1 to 12, and from 1 to 6 Is particularly preferred.
- the number of linking atoms in the linking group is preferably 10 or less, and more preferably 8 or less.
- the lower limit is 1 or more.
- the number of connected atoms refers to the minimum number of atoms that are located in a path connecting predetermined structural portions and are involved in the connection. For example, in the case of —CH 2 —C ( ⁇ O) —O—, the number of atoms constituting the linking group is 6, but the number of linking atoms is 3. Specific examples of combinations of linking groups include the following.
- x is an integer of 1 or more, preferably 1 to 500, 1 to 100 is more preferable.
- Lr is preferably an alkylene group, an alkenylene group or an alkynylene group.
- the carbon number of Lr is preferably 1 to 12, more preferably 1 to 6, and particularly preferably 1 to 3.
- a plurality of Lr, R N , R P , x, etc. need not be the same.
- the direction of the linking group is not limited by the above description, and may be understood as appropriate according to a predetermined chemical formula.
- the macromonomer a macromonomer having an ethylenically unsaturated bond at the terminal may be used.
- the macromonomer is composed of a polymer chain portion and a polymerizable functional group portion having an ethylenically unsaturated double bond at the terminal thereof.
- the copolymerization ratio of the repeating unit derived from the macromonomer (X) is not particularly limited, but is preferably 1% by mass or more, more preferably 3% by mass or more in the polymer constituting the binder particles. It is particularly preferable that the content is at least mass%. As an upper limit, it is preferable that it is 50 mass% or less, It is more preferable that it is 30 mass% or less, It is especially preferable that it is 20 mass% or less.
- the number average molecular weight of the polymer constituting the binder particles (B) is preferably 5,000 or more, more preferably 10,000 or more, and particularly preferably 30,000 or more. preferable. As an upper limit, it is preferable that it is 1,000,000 or less, and it is more preferable that it is 200,000 or less.
- the blending amount of the binder particles (B) is preferably 0.1 parts by mass or more, and 0.3 parts by mass or more with respect to 100 parts by mass of the solid electrolyte (including this when an active material is used). More preferably, it is more preferably 1 part by mass or more.
- the upper limit is preferably 20 parts by mass or less, more preferably 10 parts by mass or less, and particularly preferably 5 parts by mass or less.
- the binder particles in the solid component are preferably 0.1% by mass or more, more preferably 0.3% by mass or more, and 1% by mass or more. Particularly preferred.
- the upper limit is preferably 20% by mass or less, more preferably 10% by mass or less, and particularly preferably 5% by mass or less.
- the binder particles (B) may be used alone or in combination of a plurality of types. Further, it may be used in combination with other particles.
- the average particle size of the binder particles is important and is set to 1,000 nm or less, preferably 750 nm or less, more preferably 500 nm or less, further preferably 300 nm or less, and 200 nm or less. It is particularly preferred that The lower limit is set to 10 nm or more, preferably 20 nm or more, more preferably 30 nm or more, and particularly preferably 50 nm or more. In the present invention, unless otherwise specified, the average particle size of the binder particles is determined according to the conditions measured by measuring the average particle size of the binder described in the Examples section below.
- the binder particles When the solid electrolyte is in the form of particles, the binder particles preferably have a particle size smaller than the average particle size of the solid electrolyte.
- the measurement from the created all-solid-state secondary battery is, for example, after disassembling the battery and peeling off the electrode, then measuring the electrode material according to the method of particle size measurement of the binder described later, and measuring in advance. This can be done by eliminating the measured value of the particle size of the particles other than the binder.
- the polymer constituting the binder particles is preferably amorphous.
- the polymer being “amorphous” typically means a polymer in which no endothermic peak due to crystal melting is observed when measured by the Tg measurement method described later.
- the glass transition temperature (Tg) of the polymer is preferably 50 ° C. or less, more preferably 30 ° C. or less, further preferably 20 ° C. or less, and particularly preferably 0 ° C. or less.
- the lower limit is preferably ⁇ 80 ° C. or higher, more preferably ⁇ 70 ° C. or higher, and particularly preferably ⁇ 60 ° C. or higher.
- the glass transition temperature of the polymer forming the binder particles is based on the conditions measured at the glass transition temperature of the polymer shown in the Examples section below.
- the measurement from the created all-solid-state secondary battery is, for example, disassembling the battery, placing the electrode in water and dispersing the material, filtering, collecting the remaining solid, and measuring Tg described later
- the glass transition temperature can be measured by the method.
- the binder particles (B) may be composed only of the polymer constituting the binder particles (B), or may be composed in a form containing another kind of material (polymer, low molecular compound, inorganic compound, etc.). Preferably, it is a binder particle which consists only of a constituent polymer.
- a dispersion medium in which the above components are dispersed may be used.
- the dispersion medium include a water-soluble organic solvent.
- a water-soluble organic solvent for example, 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, Alcohol compounds such as 4-pentanediol, 1,3-butanediol, 1,4-butanediol, alkylene glycol alkyl ethers (ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol, dipropylene glycol, propylene glycol monomethyl ether, Diethylene glycol monomethyl ether, triethylene glycol, polyethylene glycol,
- amide compound solvent examples include N, N-dimethylformamide, 1-methyl-2-pyrrolidone, 2-pyrrolidinone, 1,3-dimethyl-2-imidazolidinone, 2-pyrrolidinone, ⁇ -caprolactam, formamide, N -Methylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, N-methylpropanamide, hexamethylphosphoric triamide and the like.
- ketone compound solvent examples include acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone.
- ether compound solvent examples include dimethyl ether, diethyl ether, tetrahydrofuran, and the like.
- aromatic compound solvent examples include benzene and toluene.
- Examples of the aliphatic compound solvent include hexane and heptane.
- nitrile compound solvent examples include acetonitrile.
- the dispersion medium preferably has a boiling point of 50 ° C. or higher, more preferably 80 ° C. or higher at normal pressure (1 atm).
- the upper limit is preferably 250 ° C. or lower, and more preferably 220 ° C. or lower.
- the said dispersion medium may be used individually by 1 type, or may be used in combination of 2 or more type.
- the quantity of the dispersion medium in a solid electrolyte composition can be made into arbitrary quantity with the balance of the viscosity of a solid electrolyte composition, and a dry load. Generally, it is preferably 20 to 99% by mass in the solid electrolyte composition.
- the supporting electrolyte (lithium salt or the like) that can be used in the present invention is preferably a lithium salt that is usually used for this type of product, and is not particularly limited. For example, those described below are preferable.
- Inorganic lithium salts inorganic fluoride salts such as LiPF 6 , LiBF 4 , LiAsF 6 , LiSbF 6 ; perhalogenates such as LiClO 4 , LiBrO 4 , LiIO 4 ; inorganic chloride salts such as LiAlCl 4 etc.
- (L-3) Oxalatoborate salt lithium bis (oxalato) borate, lithium difluorooxalatoborate and the like.
- Rf 1 and Rf 2 each represent a perfluoroalkyl group.
- the electrolyte used for electrolyte solution may be used individually by 1 type, or may combine 2 or more types arbitrarily.
- the content of the lithium salt is preferably 0.1 parts by mass or more, and more preferably 0.5 parts by mass or more with respect to 100 parts by mass of the solid electrolyte (A).
- As an upper limit it is preferable that it is 10 mass parts or less, and it is more preferable that it is 5 mass parts or less.
- the solid electrolyte composition of the present invention may contain a positive electrode active material. Thereby, it can be set as the composition for positive electrode materials. It is preferable to use a transition metal oxide for the positive electrode active material, and it is preferable to have a transition element M a (one or more elements selected from Co, Ni, Fe, Mn, Cu, and V). Further, mixed element M b (elements of the first (Ia) group of the metal periodic table other than lithium, elements of the second (IIa) group, Al, Ga, In, Ge, Sn, Pb, Sb, Bi, Si , P, B, etc.) may be mixed.
- transition metal oxide examples include specific transition metal oxides including those represented by any of the following formulas (MA) to (MC), or other transition metal oxides such as V 2 O 5 and MnO 2. Is mentioned.
- the positive electrode active material a particulate positive electrode active material may be used. Specifically, a transition metal oxide capable of reversibly inserting and releasing lithium ions can be used, but the specific transition metal oxide is preferably used.
- the transition metal oxides, oxides containing the above transition element M a is preferably exemplified.
- a mixed element M b (preferably Al) or the like may be mixed.
- the mixing amount is preferably 0 to 30 mol% with respect to the amount of the transition metal. That the molar ratio of li / M a was synthesized were mixed so that 0.3 to 2.2, more preferably.
- M 1 is as defined above Ma.
- a represents 0 to 1.2 (preferably 0.2 to 1.2), and preferably 0.6 to 1.1.
- b represents 1 to 3 and is preferably 2.
- a part of M 1 may be substituted with the mixed element M b .
- the transition metal oxide represented by the above formula (MA) typically has a layered rock salt structure.
- the transition metal oxide is more preferably one represented by the following formulas.
- g has the same meaning as a.
- j represents 0.1 to 0.9.
- i represents 0 to 1; However, 1-ji is 0 or more.
- k has the same meaning as b above.
- Specific examples of the transition metal compound include LiCoO 2 (lithium cobaltate [LCO]), LiNi 2 O 2 (lithium nickelate) LiNi 0.85 Co 0.01 Al 0.05 O 2 (nickel cobalt aluminum acid Lithium [NCA]), LiNi 0.33 Co 0.33 Mn 0.33 O 2 (lithium nickel manganese cobaltate [NMC]), LiNi 0.5 Mn 0.5 O 2 (lithium manganese nickelate).
- the transition metal oxide represented by the formula (MA) partially overlaps, but when represented by changing the notation, those represented by the following are also preferable examples.
- (I) Li g Ni x Mn y Co z O 2 (x> 0.2, y> 0.2, z ⁇ 0, x + y + z 1) Representative: Li g Ni 1/3 Mn 1/3 Co 1/3 O 2 Li g Ni 1/2 Mn 1/2 O 2
- (Ii) Li g Ni x Co y Al z O 2 (x> 0.7, y>0.1,0.1> z ⁇ 0.05, x + y + z 1) Representative: Li g Ni 0.8 Co 0.15 Al 0.05 O 2
- M 2 is as defined above Ma.
- c represents 0 to 2 (preferably 0.2 to 2), and preferably 0.6 to 1.5.
- d represents 3 to 5 and is preferably 4.
- the transition metal oxide represented by the formula (MB) is more preferably one represented by the following formulas.
- (MB-1) Li m Mn 2 O n
- (MB-2) Li m Mn p Al 2-p O n
- (MB-3) Li m Mn p Ni 2-p O n
- m is synonymous with c.
- n is synonymous with d.
- p represents 0-2.
- Specific examples of the transition metal compound are LiMn 2 O 4 and LiMn 1.5 Ni 0.5 O 4 .
- Preferred examples of the transition metal oxide represented by the formula (MB) include those represented by the following.
- an electrode containing Ni is more preferable from the viewpoint of high capacity and high output.
- Transition metal oxide represented by formula (MC) As the lithium-containing transition metal oxide, it is also preferable to use a lithium-containing transition metal phosphor oxide, and among them, one represented by the following formula (MC) is also preferable. Li e M 3 (PO 4 ) f ... (MC)
- e represents 0 to 2 (preferably 0.2 to 2), and is preferably 0.5 to 1.5.
- f represents 1 to 5, and preferably 0.5 to 2.
- the M 3 represents one or more elements selected from V, Ti, Cr, Mn, Fe, Co, Ni, and Cu.
- the M 3 are, in addition to the mixing element M b above, Ti, Cr, Zn, Zr, may be substituted by other metals such as Nb.
- Specific examples include, for example, olivine-type iron phosphates such as LiFePO 4 and Li 3 Fe 2 (PO 4 ) 3 , iron pyrophosphates such as LiFeP 2 O 7 , cobalt phosphates such as LiCoPO 4 , and Li 3.
- Monoclinic Nasicon type vanadium phosphate salts such as V 2 (PO 4 ) 3 (lithium vanadium phosphate) can be mentioned.
- the a, c, g, m, and e values representing the composition of Li are values that change due to charge and discharge, and are typically evaluated as values in a stable state when Li is contained.
- the composition of Li is shown as a specific value, but this also varies depending on the operation of the battery.
- the average particle diameter of the positive electrode active material used is not particularly limited, but is preferably 0.1 ⁇ m to 50 ⁇ m.
- an ordinary pulverizer or classifier may be used.
- the positive electrode active material obtained by the firing method may be used after being washed with water, an acidic aqueous solution, an alkaline aqueous solution, or an organic solvent.
- the method for measuring the average particle size of the positive electrode active material particles is in accordance with the method for measuring the average particle size of the inorganic particles described in the Examples section below.
- the concentration of the positive electrode active material is not particularly limited, but is preferably 20 to 90% by mass, more preferably 40 to 80% by mass in 100% by mass of the solid component in the solid electrolyte composition.
- the solid electrolyte composition of the present invention may contain a negative electrode active material. Thereby, it can be set as the composition for negative electrode materials.
- a negative electrode active material those capable of reversibly inserting and releasing lithium ions are preferable.
- the material is not particularly limited, and is a carbonaceous material, a metal oxide such as tin oxide or silicon oxide, a metal composite oxide, a lithium alloy such as lithium alone or a lithium aluminum alloy, and an alloy with lithium such as Sn or Si. Examples thereof include metals that can be formed. These may be used individually by 1 type, or may use 2 or more types together by arbitrary combinations and a ratio.
- carbonaceous materials or lithium composite oxides are preferably used from the viewpoint of reliability.
- the metal composite oxide is preferably capable of inserting and extracting lithium.
- the material is not particularly limited, but preferably contains titanium and / or lithium as a constituent component from the viewpoint of high current density charge / discharge characteristics.
- the carbonaceous material used as the negative electrode active material is a material substantially made of carbon.
- Examples thereof include carbonaceous materials obtained by baking various synthetic resins such as artificial pitches such as petroleum pitch, natural graphite, and vapor-grown graphite, and PAN-based resins and furfuryl alcohol resins.
- various carbon fibers such as PAN-based carbon fiber, cellulose-based carbon fiber, pitch-based carbon fiber, vapor-grown carbon fiber, dehydrated PVA-based carbon fiber, lignin carbon fiber, glassy carbon fiber, activated carbon fiber, mesophase micro
- Examples thereof include spheres, graphite whiskers, and flat graphite.
- carbonaceous materials can be divided into non-graphitizable carbon materials and graphite-based carbon materials depending on the degree of graphitization.
- the carbonaceous material preferably has a face spacing, density, and crystallite size described in JP-A-62-222066, JP-A-2-6856, and 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, or the like is used. You can also.
- an amorphous oxide is particularly preferable, and chalcogenite, which is a reaction product of a metal element and an element of Group 16 of the periodic table, is also preferably used. It is done.
- amorphous as used herein means an X-ray diffraction method using CuK ⁇ rays, which has a broad scattering band having a peak in the region of 20 ° to 40 ° in terms of 2 ⁇ , and is a crystalline diffraction line. You may have.
- the strongest intensity of crystalline diffraction lines seen from 2 ° to 40 ° to 70 ° is 100 times the diffraction line intensity at the peak of the broad scattering band seen from 2 ° to 20 °. It is preferable that it is 5 times or less, and it is particularly preferable not to have a crystalline diffraction line.
- amorphous metal oxides and chalcogenides are more preferable, and elements in groups 13 (IIIB) to 15 (VB) of the periodic table are preferable.
- oxides and chalcogenides composed of one kind of Al, Ga, Si, Sn, Ge, Pb, Sb, Bi or a combination of two or more kinds thereof.
- preferable amorphous oxides and chalcogenides include, for example, Ga 2 O 3 , SiO, GeO, SnO, SnO 2 , PbO, PbO 2 , Pb 2 O 3 , Pb 2 O 4 , Pb 3 O 4 , Sb 2 O 3 , Sb 2 O 4 , Sb 2 O 5 , Bi 2 O 3 , Bi 2 O 4 , SnSiO 3 , GeS, SnS, SnS 2 , PbS, PbS 2 , Sb 2 S 3 , Sb 2 S 5 , such as SnSiS 3 may preferably be mentioned. Moreover, these may be a complex oxide with lithium oxide, for example, Li 2 SnO 2 .
- the average particle size of the negative electrode active material is preferably 0.1 ⁇ m to 60 ⁇ m.
- a well-known pulverizer or classifier is used.
- a mortar, a ball mill, a sand mill, a vibrating ball mill, a satellite ball mill, a planetary ball mill, a swirling air flow type jet mill or a sieve is preferably used.
- wet pulverization in the presence of water or an organic solvent such as methanol can be performed as necessary.
- classification is preferably performed.
- the classification method is not particularly limited, and a sieve, an air classifier, or the like can be used as necessary. Classification can be used both dry and wet.
- the method for measuring the average particle size of the negative electrode active material particles is in accordance with the method for measuring the average particle size of the inorganic particles described in the Examples section below.
- the chemical formula of the compound obtained by the above firing method can be calculated from an inductively coupled plasma (ICP) emission spectroscopic analysis method as a measurement method, and from a mass difference between powders before and after firing as a simple method.
- ICP inductively coupled plasma
- Examples of the negative electrode active material that can be used in combination with the amorphous oxide negative electrode active material centering on Sn, Si, and Ge include carbon materials that can occlude and release lithium ions or lithium metal, lithium, lithium alloys, lithium A metal that can be alloyed with is preferable.
- the negative electrode active material preferably contains a titanium atom. More specifically, since Li 4 Ti 5 O 12 has a small volume fluctuation at the time of occlusion and release of lithium ions, it has excellent rapid charge / discharge characteristics, suppresses electrode deterioration, and improves the life of lithium ion secondary batteries. This is preferable. By combining a specific negative electrode and a specific electrolyte, the stability of the secondary battery is improved even under various usage conditions.
- the concentration of the negative electrode active material is not particularly limited, but is preferably 10 to 80% by mass, more preferably 20 to 70% by mass in 100% by mass of the solid component in the solid electrolyte composition.
- the present invention is not construed as being limited thereto.
- a solid electrolyte layer may be formed using the solid electrolyte composition according to the preferred embodiment of the present invention in combination with such a commonly used positive electrode material or negative electrode material.
- As a general conductive assistant graphite, carbon black, acetylene black, ketjen black, carbon fiber, metal powder, metal fiber, polyphenylene derivative, and the like can be included as an electron conductive material.
- the positive / negative current collector an electron conductor that does not cause a chemical change is preferably used.
- the current collector of the positive electrode in addition to aluminum, stainless steel, nickel, titanium, etc., the surface of aluminum or stainless steel is preferably treated with carbon, nickel, titanium, or silver. Among them, aluminum and aluminum alloys are preferable. More preferred.
- the negative electrode current collector aluminum, copper, stainless steel, nickel, and titanium are preferable, and aluminum, copper, and a copper alloy are more preferable.
- a film sheet is usually used, but a net, a punched one, a lath body, a porous body, a foamed body, a molded body of a fiber group, and the like can also be used.
- the thickness of the current collector is not particularly limited, but is preferably 1 ⁇ m to 500 ⁇ m.
- the current collector surface is roughened by surface treatment.
- the all-solid-state secondary battery may be manufactured by a conventional method. Specifically, there is a method in which the solid electrolyte composition is applied onto a metal foil serving as a current collector to form a battery electrode sheet having a coating film formed thereon. For example, a composition serving as a positive electrode material is applied onto a metal foil that is a positive electrode current collector and then dried to form a positive electrode layer. Next, the solid electrolyte composition is applied onto the positive electrode sheet for a battery and then dried to form a solid electrolyte layer. Furthermore, after applying the composition used as a negative electrode material on it, it dries and forms a negative electrode layer.
- a structure of an all-solid-state secondary battery in which a solid electrolyte layer is sandwiched between a positive electrode layer and a negative electrode layer can be obtained by stacking a current collector (metal foil) on the negative electrode side thereon.
- coating method of said each composition should just follow a conventional method.
- a drying treatment may be performed after each application of the composition forming the positive electrode active material layer, the composition forming the inorganic solid electrolyte layer (solid electrolyte composition), and the composition forming the negative electrode active material layer.
- a drying process may be performed.
- drying temperature is not specifically limited, 30 degreeC or more is preferable and 60 degreeC or more is more preferable.
- the upper limit is preferably 300 ° C. or lower, and more preferably 250 ° C. or lower.
- the all solid state secondary battery according to the present invention can be applied to various uses.
- the application mode for example, when installed in an electronic device, a notebook computer, a pen input personal computer, a mobile personal computer, an electronic book player, a mobile phone, a cordless phone, a pager, a handy terminal, a mobile fax machine, a mobile phone Copy, portable printer, headphone stereo, video movie, LCD TV, handy cleaner, portable CD, minidisc, electric shaver, transceiver, electronic notebook, calculator, memory card, portable tape recorder, radio, backup power supply, memory card, etc. It is done.
- Other consumer products include automobiles, electric vehicles, motors, lighting equipment, toys, game equipment, road conditioners, watches, strobes, cameras, medical equipment (such as pacemakers, hearing aids, and shoulder grinders). Furthermore, it can be used for various military use and space use. Moreover, it can also combine with a solar cell.
- a solid electrolyte composition (a composition for a positive electrode or a negative electrode) containing an active material capable of inserting and releasing metal ions belonging to Group 1 or Group 2 of the Periodic Table.
- a battery electrode sheet obtained by forming the solid electrolyte composition on a metal foil.
- An all-solid secondary battery comprising a positive electrode active material layer, a negative electrode active material layer, and a solid electrolyte layer, wherein at least one of the positive electrode active material layer, the negative electrode active material layer, and the solid electrolyte layer is All-solid-state secondary battery made into the layer comprised with the solid electrolyte composition.
- the manufacturing method of the battery electrode sheet which arrange
- the manufacturing method of the all-solid-state secondary battery which manufactures an all-solid-state secondary battery via the manufacturing method of the said battery electrode sheet.
- inhibitor particles such as a side reaction accompanying it, can form binder particle
- the inversion emulsification step can be omitted, which leads to relatively improved production efficiency.
- An all-solid secondary battery refers to a secondary battery in which the positive electrode, the negative electrode, and the electrolyte are all solid. In other words, it is distinguished from an electrolyte type secondary battery using a carbonate-based solvent as an electrolyte.
- this invention presupposes an inorganic all-solid-state secondary battery.
- the all-solid-state secondary battery is classified into an organic (polymer) all-solid-state secondary battery that uses a polymer compound such as polyethylene oxide as an electrolyte, and an inorganic all-solid-state secondary battery that uses the above LLT, LLZ, or the like. .
- the application of the polymer compound to the inorganic all-solid secondary battery is not hindered, and the polymer compound can be applied as a binder for the positive electrode active material, the negative electrode active material, and the inorganic solid electrolyte particles.
- the inorganic solid electrolyte is distinguished from an electrolyte (polymer electrolyte) using the above-described polymer compound as an ion conductive medium, and the inorganic compound serves as an ion conductive medium. Specific examples include the above LLT and LLZ.
- the inorganic solid electrolyte itself does not release cations (Li ions) but exhibits an ion transport function.
- a material that is added to the electrolytic solution or the solid electrolyte layer and serves as a source of ions that release cations is sometimes called an electrolyte, but it is distinguished from the electrolyte as the ion transport material.
- electrolyte salt or “supporting electrolyte”.
- the electrolyte salt include LiTFSI (lithium bistrifluoromethanesulfonimide).
- composition means a mixture in which two or more components are uniformly mixed. However, as long as the uniformity is substantially maintained, aggregation or uneven distribution may partially occur within a range in which a desired effect is achieved.
- Example 1 and Comparative Example 1> (Resin synthesis example) In a 2 L three-necked flask equipped with a reflux condenser and a gas introduction cock, 7.2 g of a 40 mass% heptane solution of macromonomer M-1, 12.4 g of methyl acrylate (manufactured by Wako Pure Chemical Industries, Ltd.), methacrylic acid 6.7 g of methyl (manufactured by Wako Pure Chemical Industries, Ltd.), 207 g of heptane (manufactured by Wako Pure Chemical Industries, Ltd.) and 1.4 g of azoisobutyronitrile are added, and nitrogen gas is added at a flow rate of 200 mL / min.
- Macromonomer obtained by reacting acrylic acid (manufactured by Wako Pure Chemical Industries, Ltd.) with a polymer polymerized at a ratio of 1: 0.99: 0.01 (molar ratio) with methyl acrylate and glycidyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) M-1 was obtained.
- the macromonomer M-1 had an SP value of 9.3 and a number average molecular weight of 11,000.
- the estimated structural formulas of the synthesized macromonomer and polymer are shown below.
- Example of production of solid electrolyte sheet The solid electrolyte composition obtained above was applied onto an aluminum foil having a thickness of 20 ⁇ m with an applicator having an arbitrary clearance, and heated at 80 ° C. for 1 hour and further at 110 ° C. for 1 hour to dry the coating solvent. Then, 20-micrometer-thick copper foil was match
- Example of producing a positive electrode sheet for a secondary battery The composition for the positive electrode of the secondary battery obtained above was applied onto an aluminum foil having a thickness of 20 ⁇ m with an applicator having an arbitrary clearance, heated at 80 ° C. for 1 hour and further at 110 ° C. for 1 hour, and dried. Then, it heated and pressurized so that it might become arbitrary density using the heat press machine, and the positive electrode sheet for secondary batteries was obtained.
- a negative electrode sheet for a secondary battery excluding Comparative Example c12 can be prepared in the same manner.
- the solid electrolyte composition obtained above is applied with an applicator having an arbitrary clearance, heated at 80 ° C. for 1 hour and further at 110 ° C. for 1 hour and dried. It was. Thereafter, the composition for a secondary battery negative electrode obtained above (not applied when a solid electrolyte sheet is prepared) was further applied, and heated and dried at 80 ° C. for 1 hour and further at 110 ° C. for 1 hour. A copper foil having a thickness of 20 ⁇ m was combined on the negative electrode layer, and heated and pressurized to a desired density using a heat press machine, to obtain an electrode sheet for a secondary battery. At this time, each composition may be applied simultaneously, or application / drying presses may be applied simultaneously / sequentially. You may laminate
- the solid electrolyte sheet or secondary battery electrode sheet obtained above is cut into a disk shape having a diameter of 14.5 mm and placed in a stainless steel 2032 type coin case incorporating a spacer and a washer (when using a solid electrolyte sheet) Further, an aluminum foil cut into a disk shape having a diameter of 14.5 mm was put in a coin case so as to be in contact with the solid electrolyte layer), and a coin battery was produced. From the outside of the coin battery, it was sandwiched between jigs capable of applying pressure between the electrodes, and used for various electrochemical measurements. The pressure between the electrodes was 500 kgf / cm 2 .
- the resistance in the film thickness direction of the sample was measured in a constant temperature bath at 30 ° C. using a 1255B FREQUENCY RESPONSE ANALYZER manufactured by SOLARTRON to measure the AC impedance to a voltage amplitude of 5 mV and a frequency of 1 MHz to 1 Hz. And calculated by the following formula (1).
- the test body shown in FIG. 2 was used for pressurization of the battery.
- 11 is an upper support plate
- 12 is a lower support plate
- 13 is a coin battery
- 14 is a coin case
- 15 is an electrode sheet (solid electrolyte sheet or secondary battery electrode sheet)
- S is a screw.
- Ionic conductivity (mS / cm) 1000 ⁇ sample film thickness (cm) / (resistance ( ⁇ ) ⁇ sample area (cm 2 )) (1)
- ⁇ Measurement of particle size> (Measurement of average particle size of binder)
- the average particle diameter of the binder particles was measured according to the following procedure. A 1% by mass dispersion was prepared using the above-prepared binder with any solvent (dispersion medium used for preparing the solid electrolyte composition; in the case of binder B-1, heptane). Using this dispersion liquid sample, the volume average particle diameter of the resin particles was measured using a laser diffraction / scattering particle size distribution analyzer LA-920 (manufactured by HORIBA).
- the average particle size of the inorganic particles was measured according to the following procedure. A 1 mass% dispersion was prepared using inorganic particles as water (heptane in the case of a substance unstable to water). Using this dispersion sample, the volume average particle size of the inorganic particles was measured using a laser diffraction / scattering particle size distribution analyzer LA-920 (manufactured by HORIBA).
- Tg is the intermediate temperature between the descent start point and descent end point of the DSC chart
- LMO LiMn 2 O 4 lithium manganate LTO; Li 4 Ti 5 O 12 lithium titanate (trade name “Enamite LT-106”, manufactured by Ishihara Sangyo Co., Ltd.) 100 parts (average particle size 6 ⁇ m) LCO; LiCoO 2 lithium cobaltate NMC; Li (Ni 1/3 Mn 1/3 Co 1/3 ) O 2 nickel, manganese, lithium cobaltate
- a macromonomer is obtained by reacting 4-hydroxystyrene (Wako Pure Chemical Industries, Ltd.) with a self-condensate (GPC polystyrene standard number average molecular weight: 2,000) of 12-hydroxystearic acid (manufactured by Wako Pure Chemical Industries, Ltd.). M-3 was obtained. The ratio of 12-hydroxystearic acid to 4-hydroxystyrene was 99: 1 (molar ratio).
- the macromonomer M-3 had an SP value of 9.2 and a number average molecular weight of 13,000.
- Macromonomer M-4 (GPC polystyrene standard number average molecular weight: 100) by reacting glycidyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) with a functional group-containing fluoroethylene / vinyl ether copolymer (Fluon PFA adhesive grade: manufactured by Asahi Glass Co., Ltd.) , 000).
- the ratio of the fluoroethylene / vinyl ether copolymer (Asahi Glass Co., Ltd.) to glycidyl methacrylate was 99: 1 (molar ratio).
- the SP value of this macromonomer M-4 was 7.3.
- Example 3 ⁇ Example 3 and Comparative Example 2> Each of the above evaluations was performed on Example 101 in the same manner except that the particle size of the binder was changed. The results showed good performance as shown in Table 5 below. At this time, the particle size was changed by changing the dropping speed at the time of binder synthesis.
- MM Macromonomer Molecular weight: Number average molecular weight (x1000)
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Abstract
Description
全固体二次電池のさらなる利点としては、電極のスタックによる高エネルギー密度化に適していることが挙げられる。具体的には、電極と電解質を直接並べて直列化した構造を持つ電池にすることができる。このとき、電池セルを封止する金属パッケージ、電池セルをつなぐ銅線やバスバーを省略することができるので、電池のエネルギー密度が大幅に高められる。また、高電位化が可能な正極材料との相性の良さなども利点として挙げられる。
そこで本発明は、全固体二次電池において、加圧によらずに、固体粒子間または固体粒子と集電体間等の界面抵抗の上昇を抑えることができ、かつ良好な結着性をも実現できる固体電解質組成物、これを用いた電池用電極シートおよび全固体二次電池の提供を目的とする。
〔1〕周期律表第1族または第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(A)と、側鎖成分として数平均分子量1,000以上のマクロモノマー(X)を組み込んだポリマーで構成された平均粒径が10nm以上1,000nm以下のバインダー粒子(B)と、分散媒(C)とを含む固体電解質組成物。
〔2〕上記バインダー粒子(B)を構成するポリマーが非晶性である〔1〕に記載の固体電解質組成物。
〔3〕上記バインダー粒子を構成するポリマーのガラス転移温度(Tg)が30℃以下である〔1〕または〔2〕に記載の固体電解質組成物。
〔4〕上記バインダー粒子を構成するポリマーが下記官能基群(b)のうち少なくとも1つを有している〔1〕~〔3〕のいずれか1項に記載の固体電解質組成物。
官能基群(b)
カルボニル基、アミノ基、スルホン酸基、リン酸基、ヒドロキシ基、エーテル基、シアノ基、チオール基
〔5〕上記バインダー粒子を構成するポリマーにカルボニル基が含まれている〔1〕~〔4〕のいずれか1項に記載の固体電解質組成物。
〔6〕上記バインダー粒子を構成するポリマーが、(メタ)アクリル酸モノマー、(メタ)アクリル酸エステルモノマー、および(メタ)アクリロニトリルから選ばれるモノマーに由来する繰り返し単位を含む〔1〕~〔5〕のいずれか1項に記載の固体電解質組成物。
〔7〕上記バインダー粒子(B)の平均粒径が200nm以下である〔1〕~〔6〕のいずれか1項に記載の固体電解質組成物。
〔8〕上記バインダー粒子(B)を構成するポリマー中の上記マクロモノマー(X)由来の繰り返し単位の割合が50質量%以下1質量%以上である〔1〕~〔7〕のいずれか1項に記載の固体電解質組成物。
〔9〕上記マクロモノマー(X)のSP値が10以下である〔1〕~〔8〕のいずれか1項に記載の固体電解質組成物。
〔10〕上記マクロモノマー(X)が、重合性二重結合と炭素数6以上の直鎖炭化水素構造単位を含む〔1〕~〔9〕のいずれか1項に記載の固体電解質組成物。
〔11〕上記マクロモノマー(X)が、下記式(b-13a)~(b-13c)のいずれかで表されるモノマーまたは(b-14a)~(b-14c)のいずれかで表される繰り返し単位を有するモノマーである〔1〕~〔10〕のいずれか1項に記載の固体電解質組成物。
〔12〕さらに周期律表第1族または第2族に属する金属のイオンの挿入放出が可能な活物質とを含む〔1〕~〔11〕のいずれか1項に記載の固体電解質組成物。
〔13〕上記バインダー粒子(B)を上記固体電解質(A)100質量部に対して、0.1質量部以上20質量部以下で含有させた〔1〕~〔12〕のいずれか1項に記載の固体電解質組成物。
〔14〕上記分散媒(C)が、アルコール化合物溶媒、エーテル化合物溶媒、アミド化合物溶媒、ケトン化合物溶媒、エーテル化合物溶媒、芳香族化合物溶媒、脂肪族化合物溶媒、およびニトリル化合物溶媒から選ばれる〔1〕~〔13〕のいずれか1項に記載の固体電解質組成物。
〔15〕〔1〕~〔14〕のいずれか1項に記載の固体電解質組成物を金属箔上に製膜した電池用電極シート。
〔16〕正極活物質層と負極活物質層と固体電解質層とを具備する全固体二次電池であって、上記正極活物質層、負極活物質層、および固体電解質層の少なくともいずれかを〔1〕~〔14〕のいずれか1項に記載の固体電解質組成物で構成した層とした全固体二次電池。
〔17〕〔1〕~〔14〕のいずれか1項に記載の固体電解質組成物を金属箔上に配置し、これを製膜する電池用電極シートの製造方法。
〔18〕〔17〕に記載の製造方法を介して、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、下記の記載および添付の図面からより明らかになるであろう。
なお、上記負極集電体1、負極活物質層2、固体電解質層3、正極活物質層4、正極集電体5の各層の間あるいはその外側には、機能性の層や部材等を適宜介在ないし配設してもよい。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。
(無機固体電解質(A))
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。この観点から、後記電解質塩(支持電解質)との区別を考慮し、イオン伝導性の無機固体電解質と呼ぶことがある。
有機物(炭素原子)を含まないことから、有機固体電解質(PEOなどに代表される高分子電解質、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、カチオンおよびアニオンに解離または遊離していない。この点で、電解液やポリマー中でカチオンおよびアニオンが解離または遊離している無機電解質塩(LiPF6、LiBF4,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族または第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。
硫化物固体電解質は、硫黄(S)を含有し、かつ、周期律表第1族または第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。例えば下記式(1)で示される組成を満たすリチウムイオン伝導性無機固体電解質が挙げられる。
LiaMbPcSd (1)
(式中、Mは、B、Zn、Si、Cu、Ga及びGeから選択される元素を示す。a~dは各元素の組成比を示し、a:b:c:dは1~12:0~0.2:1:2~9を満たす。)
酸化物系固体電解質は、酸素(O)を含有し、かつ、周期律表第1族または第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。
その中でも、LixLayTiO3〔x=0.3~0.7、y=0.3~0.7〕(LLT)、Li7La3Zr2O12(LLZ)は、高いリチウムイオン伝導性を有し、化学的に安定して取り扱いが容易であり好ましい。これらは単独で用いてもよく、2種以上を組み合わせて用いてもよい。
なお、本明細書において固形成分とは、100℃で乾燥処理を行ったときに、揮発ないし蒸発して消失しない成分を言う。典型的には、後記分散媒体以外の成分を指す。
上記無機固体電解質は、1種を単独で用いても、2種以上を組み合わせて用いてもよい。
本発明に用いられるバインダー粒子を構成するポリマーは、側鎖成分として数平均分子量1000以上のマクロモノマー(X)に由来する繰り返し単位が組み込まれている。
本発明のバインダー粒子(B)をなすポリマーの主鎖は特に限定されず、通常のポリマー成分を適用することができる。主鎖成分を構成するモノマーとしては、重合性不飽和結合を有するモノマーであることが好ましく、例えば各種のビニル系モノマーやアクリル系モノマーを適用することができる。本発明においては、中でも、アクリル系モノマーを用いることが好ましい。さらに好ましくは、(メタ)アクリル酸モノマー、(メタ)アクリル酸エステルモノマー、および(メタ)アクリロニトリルから選ばれるモノマーを用いることが好ましい。重合性基の数は特に限定されないが、1~4個であることが好ましい。
本発明に係るバインダー粒子を構成するポリマーは、下記官能基群(b)のうち少なくとも1つを有していることが好ましい。この官能基群は、主鎖に含まれていても、後述する側鎖に含まれていてもよいが、主鎖に含まれることが好ましい。このように、主鎖等に特定の官能基が含まれることで、固体電解質、活物質、集電体の表面に存在していると考えられる水素原子、酸素原子、硫黄原子との相互作用が強くなり、結着性が向上し、界面の抵抗が下げられるという作用が期待できる。
官能基群(b)
カルボニル基、アミノ基、スルホン酸基、リン酸基、ヒドロキシ基、エーテル基、シアノ基、チオール基
カルボニル基含有基としてはカルボキシル基、カルボニルオキシ基、アミド基等が挙げられ、炭素数1~24が好ましく、1~12がより好ましく、1~6が特に好ましい。
アミノ基は炭素数0~12が好ましく、0~6がより好ましく、0~2が特に好ましい。
スルホン酸基はそのエステルや塩でもよい。エステルの場合、炭素数1~24が好ましく、1~12がより好ましく、1~6が特に好ましい。
リン酸基はそのエステルや塩でもよい。エステルの場合、炭素数1~24が好ましく、1~12がより好ましく、1~6が特に好ましい。
なお、上記官能基は、置換基として存在しても、連結基として存在していてもよい。例えば、アミノ基は2価のイミノ基または3価の窒素原子として存在してもよい。
R2はさらに後記置換基Tを有していてもよい。なかでも、カルボキシル基、ハロゲン原子(フッ素原子等)、ヒドロキシ基、アルキル基などが置換していてもよい。
カルボキシル基、ヒドロキシ基、スルホン酸基、リン酸基、ホスホン酸基は例えば炭素数1~6のアルキル基を伴ってエステル化されていてもよい。
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。ただし、その好ましいものとしては、水素原子、アルキル基、アリール基、カルボキシル基、チオール基、リン酸基、ホスホン酸基、酸素原子を含有する脂肪族複素環基、アミノ基(NRN 2)などが挙げられる。
L2は、任意の連結基であり、L1の例が好ましく、酸素原子、炭素数1~6(好ましくは1~3)のアルキレン基、炭素数2~6(好ましくは2~3)のアルケニレン基、カルボニル基、イミノ基(NRN)、またはそれらの組合せに係る基等がより好ましい。
L3は連結基であり、L2の例が好ましく、炭素数1~6(好ましくは1~3)のアルキレン基がより好ましい。
L4は、L1と同義である。
R4は、水素原子、炭素数1~6(好ましくは1~3)のアルキル基、炭素数0~6(好ましくは0~3)のヒドロキシ基含有基、炭素数0~6(好ましくは0~3)のカルボキシル基含有基、または(メタ)アクリロイルオキシ基である。なお、R4は上記L1の連結基になって、この部分で二量体を構成していてもよい。
mは1~200の整数を表し、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。
マクロモノマーは、数平均分子量が1,000以上であり、2,000以上であることがより好ましく、3,000以上であることが特に好ましい。上限としては、500,000以下であることが好ましく、100,000以下であることがより好ましく、30,000以下であることが特に好ましい。上記バインダー粒子を構成するポリマーが上記の範囲の分子量をもつ側鎖を有することで、より良好に有機溶剤中に均一に分散でき固体電解質粒子と混合して塗布できるようになる。
本発明においてポリマーの分子量については、特に断らない限り、数平均分子量をいい、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数平均分子量を計測する。測定法としては、基本として下記条件1または条件2(優先)の方法により測定した値とする。ただし、ポリマー種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
本明細書においてSP値は、特に断らない限り、Hoy法によって求める(H.L.Hoy Journal of Painting,1970,Vol.42,76-118)。また、SP値については単位を省略して示しているが、その単位はcal1/2cm-3/2である。なお、側鎖成分(X)のSP値は、上記側鎖をなす原料モノマーのSP値とほぼ変わらず、それにより評価してもよい。
なお、本明細書において、「アクリル」ないし「アクリロイル」と称するときには、アクリロイル基のみならずその誘導構造を含むものを広く指し、アクリロイル基のα位に特定の置換基を有する構造を含むものとする。ただし、狭義には、α位が水素原子の場合をアクリルないしアクリロイルと称することがある。α位にメチル基を有するものをメタクリルと呼び、アクリル(α位が水素原子)とメタクリル(α位がメチル基)のいずれかのものを意味して(メタ)クリルなどと称することがある。
*の結合部の先に存在する構造部としては、マクロモノマーとしての分子量を満たせば特に限定されないが、炭素原子、酸素原子、水素原子から構成される構造部位であることが好ましい。このとき、置換基Tを有していてもよく、例えば、ハロゲン原子(フッ素原子)などを有していてもよい。
Rbは二価の連結基である。
RaおよびRbが連結基であるとき、その連結基としては、下記連結基Lが挙げられる。具体的には、炭素数1~30のアルカン連結基(2価の場合アルキレン基)、炭素数3~12のシクロアルカン連結基(2価の場合シクロアルキレン基)、炭素数6~24のアリール連結基(2価の場合アリーレン基)、炭素数3~12のヘテロアリール連結基(2価の場合ヘテロアリーレン基)、エーテル基(-O-)、スルフィド基(-S-)、ホスフィニデン基(-PR-:Rは水素原子もしくは炭素数1~6のアルキル基)、シリレン基(-SiRR’-:R、R’は水素原子もしくは炭素数1~6のアルキル基)カルボニル基、イミノ基(-NRN-:RNは後記の定義に従い、ここでは、水素原子もしくは炭素数1~6のアルキル基、炭素数6~10のアリール基)、またはその組み合わせであることが好ましい。なかでも、炭素数1~30のアルカン連結基(2価の場合アルキレン基)、炭素数6~24のアリール連結基(2価の場合アリーレン基)、エーテル基、カルボニル基、またはその組み合わせであることが好ましい。
RaおよびRbを構成する連結基は、炭素原子、酸素原子、水素原子から構成される連結構造であることが好ましい。あるいは、RaおよびRbを構成する連結基が、後記繰り返し単位(b-15)を有する構造部であることも好ましい。RaおよびRbが連結基であるときの連結基を構成する原子の数や連結原子数は後記連結基Lと同義である。
あるいは、Raが一価の置換基であるときは、-Rb-Rcの構造や、後記繰り返し単位(b-15)を有する構造部であることも好ましい。ここでRcは、後記置換基Tの例が挙げられ、なかでもアルキル基、アルケニル基、アリール基であることが好ましい。
Xは連結基であり、連結基Lの例が挙げられる。好ましくは、エーテル基、カルボニル基、イミノ基、アルキレン基、アリーレン基、またはその組合せである。組合せに係る連結基としては、具体的には、カルボニルオキシ基、アミド基、酸素原子、炭素原子、および水素原子で構成された連結基が挙げられる。Rb4およびXが炭素を含むときその好ましい炭素数は、後記置換基Tおよび連結基Lと同義である。連結基の好ましい構成原子数や連結原子数も同義である。
その他、マクロモノマーXには、上述した重合性基を有する繰り返し単位のほか、上記式b-15のような(メタ)アクリレート構成単位、ハロゲン原子(例えばフッ素原子)を有していてもよいアルキレン鎖(例えばエチレン鎖)が挙げられる。このとき、アルキレン鎖には、エーテル基(O)等が介在していてもよい。
なお、本明細書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、上記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、所望の効果を奏する範囲で、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。
本明細書において置換・無置換を明記していない置換基(連結基についても同様)については、その基に任意の置換基を有していてもよい意味である。これは置換・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、下記置換基Tが挙げられる。
置換基Tとしては、下記のものが挙げられる。
アルキル基(好ましくは炭素原子数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(好ましくは炭素原子数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(好ましくは炭素原子数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(好ましくは炭素原子数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)、アリール基(好ましくは炭素原子数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)、ヘテロ環基(好ましくは炭素原子数2~20のヘテロ環基、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または6員環のヘテロ環基が好ましく、例えば、テトラヒドロピラン、テトラヒドロフラン、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-オキサゾリル等)、アルコキシ基(好ましくは炭素原子数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(好ましくは炭素原子数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)、アルコキシカルボニル基(好ましくは炭素原子数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等)、アリールオキシカルボニル基(好ましくは炭素原子数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)、アミノ基(好ましくは炭素原子数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、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(好ましくは炭素原子数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(好ましくは炭素原子数1~20のアシル基、例えば、アセチル、プロピオニル、ブチリル等)、アリーロイル基(好ましくは炭素原子数7~23のアリーロイル基、例えば、ベンゾイル等)、アシルオキシ基(好ましくは炭素原子数1~20のアシルオキシ基、例えば、アセチルオキシ等)、アリーロイルオキシ基(好ましくは炭素原子数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(好ましくは炭素原子数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(好ましくは炭素原子数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(好ましくは炭素原子数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(好ましくは炭素原子数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)、アルキルスルホニル基(好ましくは炭素原子数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(好ましくは炭素原子数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(好ましくは炭素原子数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(好ましくは炭素原子数6~42のアリールシリル基、例えば、トリフェニルシリル等)、ホスホリル基(好ましくは炭素原子数0~20のリン酸基、例えば、-OP(=O)(RP)2)、ホスホニル基(好ましくは炭素原子数0~20のホスホニル基、例えば、-P(=O)(RP)2)、ホスフィニル基(好ましくは炭素原子数0~20のホスフィニル基、例えば、-P(RP)2)、(メタ)アクリロイル基、(メタ)アクリロイルオキシ基、ヒドロキシル基、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。
また、これらの置換基Tで挙げた各基は、上記の置換基Tがさらに置換していてもよい。
化合物ないし置換基・連結基等がアルキル基・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・アルキニレン基等を含むとき、これら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く、上記のように置換されていても無置換でもよい。
本明細書で規定される各置換基は、本発明の効果を奏する範囲で下記の連結基Lを介在して置換されていても、その構造中に連結基Lが介在していてもよい。たとえば、アルキル基・アルキレン基、アルケニル基・アルケニレン基等はさらに構造中に下記のヘテロ連結基を介在していてもよい。
連結基Lとしては、炭化水素連結基〔炭素数1~10のアルキレン基(より好ましくは炭素数1~6、さらに好ましくは1~3)、炭素数2~10のアルケニレン基(より好ましくは炭素数2~6、さらに好ましくは2~4)、炭素数2~10のアルキニレン基(より好ましくは炭素数2~6、さらに好ましくは2~4)、炭素数6~22のアリーレン基(より好ましくは炭素数6~10)〕、ヘテロ連結基〔カルボニル基(-CO-)、チオカルボニル基(-CS-)、エーテル基(-O-)、チオエーテル基(-S-)、イミノ基(-NRN-)、イミン連結基(RN-N=C<,-N=C(RN)-)、スルホニル基(-SO2-)、スルフィニル基(-SO-)、リン酸連結基(-O-P(OH)(O)-O-)、ホスホン酸連結基(-P(OH)(O)-O-)〕、またはこれらを組み合せた連結基が好ましい。なお、縮合して環を形成する場合には、上記炭化水素連結基が、二重結合や三重結合を適宜形成して連結していてもよい。形成される環として好ましくは、5員環または6員環が好ましい。5員環としては含窒素の5員環が好ましく、その環をなす化合物として例示すれば、ピロール、イミダゾール、ピラゾール、インダゾール、インドール、ベンゾイミダゾール、ピロリジン、イミダゾリジン、ピラゾリジン、インドリン、カルバゾール、またはこれらの誘導体などが挙げられる。6員環としては、ピペリジン、モルホリン、ピペラジン、またはこれらの誘導体などが挙げられる。またアリール基、ヘテロ環基等を含むとき、それらは単環でも縮環でもよく、同様に置換されていても無置換でもよい。
RNは水素原子または置換基である。置換基としては、アルキル基(炭素数1~24が好ましく、1~12がより好ましく、1~6がさらに好ましく、1~3が特に好ましい)、アルケニル基(炭素数2~24が好ましく、2~12がより好ましく、2~6がさらに好ましく、2~3が特に好ましい)、アルキニル基(炭素数2~24が好ましく、2~12がより好ましく、2~6がさらに好ましく、2~3が特に好ましい)、アラルキル基(炭素数7~22が好ましく、7~14がより好ましく、7~10が特に好ましい)、アリール基(炭素数6~22が好ましく、6~14がより好ましく、6~10が特に好ましい)が好ましい。
RPは水素原子、ヒドロキシル基、または置換基である。置換基としては、アルキル基(炭素数1~24が好ましく、1~12がより好ましく、1~6がさらに好ましく、1~3が特に好ましい)、アルケニル基(炭素数2~24が好ましく、2~12がより好ましく、2~6がさらに好ましく、2~3が特に好ましい)、アルキニル基(炭素数2~24が好ましく、2~12がより好ましく、2~6がさらに好ましく、2~3が特に好ましい)、アラルキル基(炭素数7~22が好ましく、7~14がより好ましく、7~10が特に好ましい)、アリール基(炭素数6~22が好ましく、6~14がより好ましく、6~10が特に好ましい)、アルコキシ基(炭素数1~24が好ましく、1~12がより好ましく、1~6がさらに好ましく、1~3が特に好ましい)、アルケニルオキシ基(炭素数2~24が好ましく、2~12がより好ましく、2~6がさらに好ましく、2~3が特に好ましい)、アルキニルオキシ基(炭素数2~24が好ましく、2~12がより好ましく、2~6がさらに好ましく、2~3が特に好ましい)、アラルキルオキシ基(炭素数7~22が好ましく、7~14がより好ましく、7~10が特に好ましい)、アリールオキシ基(炭素数6~22が好ましく、6~14がより好ましく、6~10が特に好ましい)、が好ましい。
本明細書において、連結基を構成する原子の数は、1~36であることが好ましく、1~24であることがより好ましく、1~12であることがさらに好ましく、1~6であることが特に好ましい。連結基の連結原子数は10以下であることが好ましく、8以下であることがより好ましい。下限としては、1以上である。上記連結原子数とは所定の構造部間を結ぶ経路に位置し連結に関与する最少の原子数を言う。たとえば、-CH2-C(=O)-O-の場合、連結基を構成する原子の数は6となるが、連結原子数は3となる。
具体的に連結基の組合せとしては、以下のものが挙げられる。オキシカルボニル基(-OCO-)、カーボネート基(-OCOO-)、アミド基(-CONH-)、ウレタン基(-NHCOO-)、ウレア基(-NHCONH-)、(ポリ)アルキレンオキシ基(-(Lr-O)x-)、カルボニル(ポリ)オキシアルキレン基(-CO-(O-Lr)x-、カルボニル(ポリ)アルキレンオキシ基(-CO-(Lr-O)x-)、カルボニルオキシ(ポリ)アルキレンオキシ基(-COO-(Lr-O)x-)、(ポリ)アルキレンイミノ基(-(Lr-NRN)x)、アルキレン(ポリ)イミノアルキレン基(-Lr-(NRN-Lr)x-)、カルボニル(ポリ)イミノアルキレン基(-CO-(NRN-Lr)x-)、カルボニル(ポリ)アルキレンイミノ基(-CO-(Lr-NRN)x-)、(ポリ)エステル基(-(CO-O-Lr)x-、-(O-CO-Lr)x-、-(O-Lr-CO)x-、-(Lr-CO-O)x-、-(Lr-O-CO)x-)、(ポリ)アミド基(-(CO-NRN-Lr)x-、-(NRN-CO-Lr)x-、-(NRN-Lr-CO)x-、-(Lr-CO-NRN)x-、-(Lr-NRN-CO)x-)などである。xは1以上の整数であり、1~500が好ましく、1~100がより好ましい。
Lrはアルキレン基、アルケニレン基、アルキニレン基が好ましい。Lrの炭素数は、1~12が好ましく、1~6がより好ましく、1~3が特に好ましい。複数のLrやRN、RP、x等は同じである必要はない。連結基の向きは上記の記載により限定されず、適宜所定の化学式に合わせた向きで理解すればよい。
バインダー粒子(B)を構成するポリマーの数平均分子量は5,000以上であることが好ましく、10,000以上であることがより好ましく、30,000以上であることが特に好ましい。上限としては、1,000,000以下であることが好ましく、200,000以下であることがより好ましい。
固体電解質組成物に対しては、その固形成分中、バインダー粒子が0.1質量%以上であることが好ましく、0.3質量%以上であることがより好ましく、1質量%以上であることが特に好ましい。上限としては、20質量%以下であることが好ましく、10質量%以下であることがより好ましく、5質量%以下であることが特に好ましい。
バインダー粒子を上記の範囲で用いることにより、一層効果的に固体電解質の固着性と界面抵抗の抑制性とを両立して実現することができる。
固体電解質が粒子状であるときには、固体電解質の平均粒径より、上記バインダー粒子の粒径が小さいことが好ましい。
バインダー粒子の大きさを上記の範囲とすることにより、良好な密着性と界面抵抗の抑制とを実現することができる。
なお、作成された全固体二次電池からの測定は、例えば、電池を分解し電極を剥がした後、その電極材料について後述のバインダーの粒径測定の方法に準じてその測定を行い、あらかじめ測定していたバインダー以外の粒子の粒径の測定値を排除することにより行うことができる。
なお、作成された全固体二次電池からの測定は、例えば、電池を分解し電極を水に入れてその材料を分散させた後、ろ過を行い、残った固体を収集し後述するTgの測定法でガラス転移温度を測定することにより行うことができる。
本発明の固体電解質組成物においては、上記の各成分を分散させる分散媒体を用いてもよい。分散媒体としては、例えば、水溶性有機溶媒が挙げられる。例えば、メチルアルコール、エチルアルコール、1-プロピルアルコール、2-プロピルアルコール、2-ブタノール、エチレングリコール、プロピレングリコール、グリセリン、1,6-ヘキサンジオール、シクロヘキサンジオール、ソルビトール、キシリトール、2-メチル-2,4-ペンタンジオール、1,3-ブタンジオール、1,4-ブタンジオール等のアルコール化合物溶媒、アルキレングリコールアルキルエーテル(エチレングリコールモノメチルエーテル、エチレングリコールモノブチルエーテル、ジエチレングリコール、ジプロピレングリコール、プロピレングリコールモノメチルエーテル、ジエチレングリコールモノメチルエーテル、トリエチレングリコール、ポリエチレングリコール、プロピレングリコールモノメチルエーテル、ジプロピレングリコールモノメチルエーテル、トリプロピレングリコールモノメチルエーテル、ジエチレングリコールモノブチルエーテル、ジエチレングリコールモノブチルエーテル等)を含むエーテル化合物溶媒が挙げられる。
本発明において、固体電解質組成物における分散媒体の量は、固体電解質組成物の粘度と乾燥負荷とのバランスで任意の量とすることができる。一般的に、固体電解質組成物中、20~99質量%であることが好ましい。
本発明に用いることができる支持電解質(リチウム塩等)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、特に制限はないが、例えば、以下に述べるものが好ましい。
これらのなかで、LiPF6、LiBF4、LiAsF6、LiSbF6、LiClO4、Li(Rf1SO3)、LiN(Rf1SO2)2、LiN(FSO2)2、及びLiN(Rf1SO2)(Rf2SO2)が好ましく、LiPF6、LiBF4、LiN(Rf1SO2)2、LiN(FSO2)2、及びLiN(Rf1SO2)(Rf2SO2)などのリチウムイミド塩がさらに好ましい。ここで、Rf1、Rf2はそれぞれパーフルオロアルキル基を示す。
なお、電解液に用いる電解質は、1種を単独で使用しても、2種以上を任意に組み合わせてもよい。
本発明の固体電解質組成物には、正極活物質を含有させてもよい。それにより、正極材料用の組成物とすることができる。正極活物質には遷移金属酸化物を用いることが好ましく、中でも、遷移元素Ma(Co、Ni、Fe、Mn、Cu、Vから選択される1種以上の元素)を有することが好ましい。また、混合元素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、Bなど)を混合してもよい。この、遷移金属酸化物として例えば、下記式(MA)~(MC)のいずれかで表されるものを含む特定遷移金属酸化物、あるいはその他の遷移金属酸化物としてV2O5、MnO2等が挙げられる。正極活物質には、粒子状の正極活物質を用いてもよい。具体的に、可逆的にリチウムイオンを挿入・放出できる遷移金属酸化物を用いることができるが、上記特定遷移金属酸化物を用いるのが好ましい。
リチウム含有遷移金属酸化物としては中でも下式で表されるものが好ましい。
LiaM1Ob ・・・ (MA)
(MA-1) LigCoOk
(MA-2) LigNiOk
(MA-3) LigMnOk
(MA-4) LigCojNi1-jOk
(MA-5) LigNijMn1-jOk
(MA-6) LigCojNiiAl1-j-iOk
(MA-7) LigCojNiiMn1-j-iOk
(i)LigNixMnyCozO2(x>0.2,y>0.2,z≧0,x+y+z=1)
代表的なもの:
LigNi1/3Mn1/3Co1/3O2
LigNi1/2Mn1/2O2
(ii)LigNixCoyAlzO2(x>0.7,y>0.1,0.1>z≧0.05,x+y+z=1)
代表的なもの:
LigNi0.8Co0.15Al0.05O2
リチウム含有遷移金属酸化物としては中でも下記式(MB)で表されるものも好ましい。
LicM2 2Od ・・・ (MB)
(MB-1) LimMn2On
(MB-2) LimMnpAl2-pOn
(MB-3) LimMnpNi2-pOn
(a) LiCoMnO4
(b) Li2FeMn3O8
(c) Li2CuMn3O8
(d) Li2CrMn3O8
(e) Li2NiMn3O8
高容量、高出力の観点で上記のうちNiを含む電極が更に好ましい。
リチウム含有遷移金属酸化物としてはリチウム含有遷移金属リン酸化物を用いることも好ましく、中でも下記式(MC)で表されるものも好ましい。
LieM3(PO4)f ・・・ (MC)
なお、Liの組成を表す上記a,c,g,m,e値は、充放電により変化する値であり、典型的には、Liを含有したときの安定な状態の値で評価される。上記式(a)~(e)では特定値としてLiの組成を示しているが、これも同様に電池の動作により変化するものである。
本発明の固体電解質組成物には、負極活物質を含有させてもよい。それにより、負極材料用の組成物とすることができる。負極活物質としては、可逆的にリチウムイオンを挿入・放出できるものが好ましい。その材料は、特に制限はなく、炭素質材料、酸化錫や酸化ケイ素等の金属酸化物、金属複合酸化物、リチウム単体やリチウムアルミニウム合金等のリチウム合金、及び、SnやSi等のリチウムと合金形成可能な金属等が挙げられる。これらは、1種を単独で用いても、2種以上を任意の組み合わせ及び比率で併用しても良い。なかでも炭素質材料又はリチウム複合酸化物が信頼性の点から好ましく用いられる。また、金属複合酸化物としては、リチウムを吸蔵、放出可能であることが好ましい。その材料は、特には制限されないが、構成成分としてチタン及び/又はリチウムを含有していることが、高電流密度充放電特性の観点で好ましい。
正・負極の集電体としては、化学変化を起こさない電子伝導体が用いられることが好ましい。正極の集電体としては、アルミニウム、ステンレス鋼、ニッケル、チタンなどの他にアルミニウムや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、その中でも、アルミニウム、アルミニウム合金がより好ましい。負極の集電体としては、アルミニウム、銅、ステンレス鋼、ニッケル、チタンが好ましく、アルミニウム、銅、銅合金がより好ましい。
全固体二次電池の作製は常法によればよい。具体的には、上記固体電解質組成物を集電体となる金属箔上に塗布し、塗膜を形成した電池用電極シートとする方法が挙げられる。例えば、正極集電体である金属箔上に正極材料となる組成物を塗布後、乾燥し、正極層を形成する。次いでその電池用正極シート上に、固体電解質組成物を塗布後、乾燥し、固体電解質層を形成する。さらに、その上に、負極材料となる組成物を塗布後、乾燥し、負極層を形成する。その上に、負極側の集電体(金属箔)を重ねることで、正極層と負極層の間に、固体電解質層が挟まれた全固体二次電池の構造を得ることができる。なお、上記の各組成物の塗布方法は常法によればよい。このとき、正極活物質層をなす組成物、無機固体電解質層をなす組成物(固体電解質組成物)、及び負極活物質層をなす組成物のそれぞれの塗布の後に、乾燥処理を施しても良いし、重層塗布した後に乾燥処理をしても良い。乾燥温度は特に限定されないが、30℃以上が好ましく、60℃以上がより好ましい。上限は、300℃以下が好ましく、250℃以下がより好ましい。このような温度範囲で加熱することで、分散媒体を除去し、固体状態とさせることができる。これにより、全固体二次電池において、良好な結着性と非加圧でのイオン伝導性を得ることができる。
本発明に係る全固体二次電池は種々の用途に適用することができる。適用態様には特に限定はないが、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、メモリーカードなどが挙げられる。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。
(1)周期律表第1族または第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んでいる固体電解質組成物(正極または負極の電極用組成物)。
(2)上記固体電解質組成物を金属箔上に製膜した電池用電極シート。
(3)正極活物質層と負極活物質層と固体電解質層とを具備する全固体二次電池であって、上記正極活物質層、負極活物質層、および固体電解質層の少なくともいずれかを上記固体電解質組成物で構成した層とした全固体二次電池。
(4)上記固体電解質組成物を金属箔上に配置し、これを製膜する電池用電極シートの製造方法。
(5)上記電池用電極シートの製造方法を介して、全固体二次電池を製造する全固体二次電池の製造方法。
また、本発明の好ましい実施形態においては、界面活性剤を入れずにバインダー粒子を形成することができ、それに伴う副反応等の阻害因子を低減することができるという利点を有する。また、それに伴い、転層乳化工程を省略できることができ、相対的に製造効率の向上にもつながる。
無機固体電解質とは、上述した高分子化合物をイオン伝導媒体とする電解質(高分子電解質)とは区別されるものであり、無機化合物がイオン伝導媒体となるものである。具体例としては、上記のLLTやLLZが挙げられる。無機固体電解質は、それ自体が陽イオン(Liイオン)を放出するものではなく、イオンの輸送機能を示すものである。これに対して、電解液ないし固体電解質層に添加して陽イオン(Liイオン)を放出するイオンの供給源となる材料を電解質と呼ぶことがあるが、上記のイオン輸送材料としての電解質と区別するときにはこれを「電解質塩」または「支持電解質」と呼ぶ。電解質塩としては例えばLiTFSI(リチウムビストリフルオロメタンスルホンイミド)が挙げられる。
本発明において「組成物」というときには、2種以上の成分が均一に混合された混合物を意味する。ただし、実質的に均一性が維持されていればよく、所望の効果を奏する範囲で、一部において凝集や偏在が生じていてもよい。
(樹脂の合成例)
還流冷却管、ガス導入コックを付した2L三口フラスコに、マクロモノマーM-1の40質量% ヘプタン溶液を7.2g、アクリル酸メチル(和光純薬工業株式会社製)を12.4g、メタクリル酸メチル(和光純薬工業株式会社製)を6.7g、ヘプタン(和光純薬工業株式会社製)を207g、アゾイソブチロニトリル1.4gを添加し、流速200mL/minにて窒素ガスを10分間導入した後に、100℃に昇温した。別容器にて調製した液(マクロモノマーM-1の40質量%ヘプタン溶液を93.1g、アクリル酸メチルを222.8g、メタクリル酸メチルを120.0g、ヘプタン300.0g、アゾイソブチロニトリル2.1gを混合した液)を4時間かけて滴下した。滴下完了後、アゾイソブチロニトリル0.5gを添加した。その後100℃で2時間攪拌したあと室温まで冷却し、ろ過することで樹脂B-1の分散液を得た。固形成分濃度は39.2%、粒径は198nmであった。
他の例示バインダーも同様の方法で調製できる(下記表1参照)。
12-ヒドロキシステアリン酸(和光純薬工業株式会社製)の自己縮合体(GPCポリスチレンスタンダード数平均分子量:2,000)にグリシジルメタクリレート(東京化成工業株式会社製)を反応させマクロモノマーとしてそれをメタクリル酸メチルとグリシジルメタクリレート(東京化成工業株式会社製)と1:0.99:0.01(モル比)の割合で重合したポリマーにアクリル酸(和光純薬株式会社製)を反応させたマクロモノマーM-1を得た。このマクロモノマー M-1のSP値は9.3、数平均分子量は11000であった。
下記に合成されたマクロモノマーおよびポリマーの推定構造式を示す。
表中数字は質量部(主鎖成分が100部となるように記載した)
化合物の番号は上記例示化合物の例示を参照
MC:主鎖を構成するモノマー
MM:側鎖を構成するモノマー(マクロモノマー)
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180個投入し、無機固体電解質LLT(豊島製作所製)9.5g、バインダーB-1を0.5g(固形成分重量)、分散媒として、ヘプタン15.0gを投入した後に、フリッチュ社製遊星ボールミルに容器をセットし、回転数300rpmで2時間混合を続け、固体電解質組成物S-2を得た。調製された固体電解質粒子の平均粒径は、50μmであった。組成物T-2を除く他の例示固体電解質組成物も同様の方法で調製した。
表中数字は質量比(%)
化合物の番号は上記例示化合物の例示を参照
LLT :Li0.33La0.55TiO3
LLZ :Li7La3Zr2O12
PTFE :ポリテトラフルオロエチレン
MEK :メチルエチルケトン
HSBR:水素添加スチレン-ブタジエンゴム
PEO :下記の合成方法で得たポリマー粒子
オートクレーブに、アクリル酸n-ブチル700部、スチレン200部、メタクリル酸5部、ジビニルベンゼン10部、乳化剤としてのポリオキシエチレンラウリルエーテル(花王社製、エマルゲン108、非イオン性界面活性剤、アルキル基の炭素数12、HLB値12.1)25部、イオン交換水1500部、重合開始剤としてのアゾビスブチロニトリル15部を仕込み、十分攪拌した。その後、80℃に加温して重合を行なった。そして、重合開始後、冷却して重合反応を停止することで、ポリマー粒子のラテックスを得た。平均粒径は120nmであった。
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180個投入し、無機固体電解質LLT(豊島製作所製)9.5g、バインダーとしてPTFE粒子を0.5gを投入した後に、フリッチュ社製遊星ボールミルに容器をセットし、回転数300rpmで2時間混合を続け、固体電解質組成物T-2を得た。
上記で得られた固体電解質組成物を厚み20μmのアルミ箔上に、任意のクリアランスを有するアプリケーターにより塗布し、80℃1時間とさらに110℃1時間加熱し、塗布溶媒を乾燥させた。その後、厚み20μmの銅箔を合わせ、ヒートプレス機を用いて、任意の密度になるように加熱および加圧し、固体電解質シートを得た。電解質層の膜厚は30μmであった。他の固体電解質シートも同様の方法で調製した。
プラネタリーミキサー(TKハイビスミックス、PRIMIX社製)に、表3に記載の正極活物質100部(平均粒径 10μm)、アセチレンブラック5部、上記により得られた固体電解質組成物S-1 75部、MEK270部を加え、40rpmで一時間撹拌をおこなった。
プラネタリーミキサー(TKハイビスミックス、PRIMIX社製)に、表3に記載の負極活物質、アセチレンブラック5部、上記で得られた固体電解質組成物S-1 75部、MEK270部を加え、40rpmで一時間撹拌をおこなった。
上記で得られた二次電池正極用組成物を厚み20μmのアルミ箔上に、任意のクリアランスを有するアプリケーターにより塗布し、80℃1時間とさらに110℃1時間加熱し、乾燥させた。その後、ヒートプレス機を用いて、任意の密度になるように加熱および加圧し、二次電池用正極シートを得た。
比較例c12を除く二次電池用負極シートも同様の方法で調製できる。
上記で得られた二次電池用正極シート上に、上記で得られた固体電解質組成物を、任意のクリアランスを有するアプリケーターにより塗布し、80℃1時間とさらに110℃1時間加熱し、乾燥させた。
その後、上記で得られた二次電池負極用組成物(固体電解質シートを作成する場合は塗布しない)をさらに塗布し、80℃1時間とさらに110℃1時間加熱し、乾燥させた。負極層上に厚み20μmの銅箔を合わせ、ヒートプレス機を用いて、任意の密度になるように加熱および加圧し、二次電池用電極シートを得た。このとき、各組成物は同時に塗布しても良いし、塗布乾燥プレスを同時/逐次でも良い。別々の基材に塗布した後に、転写により積層してもよい。
上記で得られた固体電解質組成物T-2を任意の密度になるように加圧成型することでシート状の固体電解質シートを得た。作製したシートを直径14.5mmの円板状に切り出し20μmのアルミ箔で挟みコイン電池部材を用いることで電気化学測定用セルを作製した。
固体電解質シートまたは二次電池用正極シートに幅12mm、長さ60mmのセロテープ(登録商標)(商品名、ニチバン社製)を貼り、10mm/minの速度で50mm引き剥がした際に、剥離した部分の面積の比率で評価した。測定は、10回行い、最大値および最小値を除いた、8回の平均を採用した。試験用のサンプルは各水準について5つのものを用いてその平均値を採用した。なお電解質シートの結着性評価の値は二次電池用正極シートにおける上記評価結果を用いた。
5: 0%
4: 0%超5%未満
3: 5%以上20%未満
2: 20%以上50%未満
1: 50%以上
上記で得られた固体電解質シートまたは二次電池電極シートを直径14.5mmの円板状に切り出し、スペーサーとワッシャーを組み込んだステンレス製の2032型コインケースに入れて(固体電解質シートを用いる場合はさらに直径14.5mmの円板状に切り出したアルミ箔を固体電解質層と接触するようにコインケースに入れた)、コイン電池を作製した。コイン電池の外部より、電極間に圧力をかけることができるジグに挟み、各種電気化学的測定に用いた。電極間の圧力は500kgf/cm2とした。
上記で得られたコイン電池を用いて、30℃の恒温槽中、SOLARTRON社製 1255B FREQUENCY RESPONSE ANALYZERを用いて電圧振幅5mV、周波数1MHz~1Hzまで交流インピーダンス測定することで試料の膜厚方向の抵抗を求め、下記式(1)により計算して求めた。このとき、電池の加圧には図2に示した試験体を用いた。11が上部支持板、12が下部支持板、13がコイン電池、14がコインケース、15が電極シート(固体電解質シートまたは二次電池電極シート)、Sがネジである。
イオン伝導度(mS/cm)=
1000×試料膜厚(cm)/(抵抗(Ω)×試料面積(cm2))・・・式(1)
(バインダーの平均粒径の測定)
バインダー粒子の平均粒径の測定は、以下の手順で行った。上記にて調製したバインダーを任意の溶媒(固体電解質組成物の調製に用いる分散媒。バインダーB-1の場合はヘプタン)を用いて1質量%の分散液を調製した。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(HORIBA社製)を用いて、樹脂粒子の体積平均粒径を測定した。
無機粒子の平均粒径の測定は、以下の手順で行った。無機粒子を水(水に不安定な物質の場合はヘプタン)を用いて1質量%の分散液を調製した。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(HORIBA社製)を用いて、無機粒子の体積平均粒径を測定した。
ガラス転移点は、上記の乾燥試料を用いて、示差走査熱量計(SIIテクノロジー社製、DSC7000)を用いて下記の条件で測定した。測定は同一の試料で二回実施し、二回目の測定結果を採用した。
・測定室内の雰囲気:窒素(50mL/min)
・昇温速度:5℃/min
・測定開始温度:-100℃
・測定終了温度:200℃(c12は250℃)
・試料パン:アルミニウム製パン
・測定試料の質量:5mg
・Tgの算定:DSCチャートの下降開始点と下降終了点の中間温度をTgとした
LMO;LiMn2O4 マンガン酸リチウム
LTO;Li4Ti5O12 チタン酸リチウム(商品名「エナマイトLT-106」、石原産業株式会社製)100部(平均粒径 6μm)
LCO;LiCoO2 コバルト酸リチウム
NMC;Li(Ni1/3Mn1/3Co1/3)O2 ニッケル、マンガン、コバルト酸リチウム
上記樹脂組成物B-1に対して、マクロモノマーをM-2~M-5に変えた以外同様にして、上記の各評価を行った。結果は下表4のとおりに、良好な性能を示した。
12-ヒドロキシステアリン酸(和光純薬工業株式会社製)の自己縮合体(GPCポリスチレンスタンダード数平均分子量:2,000)にグリシジルメタクリレート(東京化成工業株式会社製)を反応させることでマクロモノマーM-2を得た。12-ヒドロキシステアリン酸とグリシジルメタクリレートの比率は、99:1とした(モル比)。このマクロモノマーM-2のSP値は9.2、数平均分子量は9000であった。
マクロモノマーM-2の推定構造は下記のとおりである。
12-ヒドロキシステアリン酸(和光純薬工業株式会社製)の自己縮合体(GPCポリスチレンスタンダード数平均分子量:2,000)に4-ヒドロキシスチレン(和光純薬工業株式会社)を反応させることでマクロモノマーM-3を得た。12-ヒドロキシステアリン酸と4-ヒドロキシスチレンの比率は、99:1とした(モル比)。このマクロモノマーM-3のSP値は9.2、数平均分子量13000であった。
官能基含有フルオロエチレン・ビニルエーテル共重合体(Fluon PFA 接着グレード:旭硝子社製)にグリシジルメタクリレート(東京化成工業株式会社製)を反応させることでマクロモノマーM-4(GPCポリスチレンスタンダード数平均分子量:100,000)を得た。フルオロエチレン・ビニルエーテル共重合体(旭硝子社製)とグリシジルメタクリレートの比率は、99:1とした(モル比)。このマクロモノマーM-4のSP値は、7.3であった。
片末端メタクリロイル化ポリ-n-ブチルアクリレートオリゴマー(Mn=6,000、商品名:AB-6、東亜合成化学工業(株)製)をマクロモノマーM-5として用いた。このマクロモノマーM-5のSP値は、9.1であった。
上記実施例101に対して、バインダーの粒径を変えた以外同様にして、上記の各評価を行った。結果は下表5のとおりに、良好な性能を示した。このとき、粒径の変更はバインダー合成時の滴下スピードを変えることで行った。
分子量:数平均分子量(x1000)
試験101の条件において、バインダーB-1のA-3を、A-19,A-44、バインダーB-2のA-27をA-26,A-56(平均粒径はいずれも約200nm)にそれぞれ代えた以外同様にして上記の試験を行った。その結果、いずれの固体電解質シートまたは二次電池電極シートにおいても良好な非加圧時のイオン伝導度が得られることを確認した。
本願は、2013年9月25日に日本国で特許出願された特願2013-198397に基づく優先権を主張するものであり、これらはここに参照してその内容を本明細書の記載の一部として取り込む。
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 上部支持板
12 下部支持板
13 コイン電池
S ネジ
Claims (18)
- 周期律表第1族または第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(A)と、側鎖成分として数平均分子量1,000以上のマクロモノマー(X)を組み込んだポリマーで構成された平均粒径が10nm以上1,000nm以下のバインダー粒子(B)と、分散媒(C)とを含む固体電解質組成物。
- 上記バインダー粒子(B)を構成するポリマーが非晶性である請求項1に記載の固体電解質組成物。
- 上記バインダー粒子を構成するポリマーのガラス転移温度(Tg)が30℃以下である請求項1または2に記載の固体電解質組成物。
- 上記バインダー粒子を構成するポリマーが下記官能基群(b)のうち少なくとも1つを有している請求項1~3のいずれか1項に記載の固体電解質組成物。
官能基群(b)
カルボニル基、アミノ基、スルホン酸基、リン酸基、ヒドロキシ基、エーテル基、シアノ基、チオール基 - 上記バインダー粒子を構成するポリマーにカルボニル基が含まれている請求項1~4のいずれか1項に記載の固体電解質組成物。
- 上記バインダー粒子を構成するポリマーが、(メタ)アクリル酸モノマー、(メタ)アクリル酸エステルモノマー、および(メタ)アクリロニトリルから選ばれるモノマーに由来する繰り返し単位を含む請求項1~5のいずれか1項に記載の固体電解質組成物。
- 上記バインダー粒子(B)の平均粒径が200nm以下である請求項1~6のいずれか1項に記載の固体電解質組成物。
- 上記バインダー粒子(B)を構成するポリマー中の上記マクロモノマー(X)由来の繰り返し単位の割合が50質量%以下1質量%以上である請求項1~7のいずれか1項に記載の固体電解質組成物。
- 上記マクロモノマー(X)のSP値が10以下である請求項1~8のいずれか1項に記載の固体電解質組成物。
- 上記マクロモノマー(X)が、重合性二重結合と炭素数6以上の直鎖炭化水素構造単位を含む請求項1~9のいずれか1項に記載の固体電解質組成物。
- さらに周期律表第1族または第2族に属する金属のイオンの挿入放出が可能な活物質とを含む請求項1~11のいずれか1項に記載の固体電解質組成物。
- 上記バインダー粒子(B)を上記固体電解質(A)100質量部に対して、0.1質量部以上20質量部以下で含有させた請求項1~12のいずれか1項に記載の固体電解質組成物。
- 上記分散媒(C)が、アルコール化合物溶媒、エーテル化合物溶媒、アミド化合物溶媒、ケトン化合物溶媒、エーテル化合物溶媒、芳香族化合物溶媒、脂肪族化合物溶媒、およびニトリル化合物溶媒から選ばれる請求項1~13のいずれか1項に記載の固体電解質組成物。
- 請求項1~14のいずれか1項に記載の固体電解質組成物を金属箔上に製膜した電池用電極シート。
- 正極活物質層と負極活物質層と固体電解質層とを具備する全固体二次電池であって、上記正極活物質層、負極活物質層、および固体電解質層の少なくともいずれかを請求項1~14のいずれか1項に記載の固体電解質組成物で構成した層とした全固体二次電池。
- 請求項1~14のいずれか1項に記載の固体電解質組成物を金属箔上に配置し、これを製膜する電池用電極シートの製造方法。
- 請求項17に記載の製造方法を介して、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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KR1020187017065A KR20180069137A (ko) | 2013-09-25 | 2014-09-25 | 고체 전해질 조성물, 이를 이용한 전지용 전극 시트 및 전고체 이차전지 |
DE112014004451.2T DE112014004451T5 (de) | 2013-09-25 | 2014-09-25 | Feste Elektrolytzusammensetzung, Elektrodenlage für Batterien und deren Verwendung und Sekundärbatterie mit festem Zustand |
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US15/075,589 US20160204465A1 (en) | 2013-09-25 | 2016-03-21 | Solid electrolyte composition, electrode sheet for batteries using same and all-solid-state secondary battery |
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CN117525575B (zh) * | 2024-01-08 | 2024-04-02 | 潮州三环(集团)股份有限公司 | 一种固态电解质及其制备方法和应用 |
Citations (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2009176484A (ja) * | 2008-01-22 | 2009-08-06 | Idemitsu Kosan Co Ltd | 全固体リチウム二次電池用正極及び負極、並びに全固体リチウム二次電池 |
JP2010113820A (ja) * | 2008-11-04 | 2010-05-20 | Idemitsu Kosan Co Ltd | リチウムイオン伝導性固体電解質組成物及びそれを用いた電池 |
WO2010089891A1 (ja) * | 2009-02-09 | 2010-08-12 | トヨタ自動車株式会社 | 固体電解質材料含有シートの製造方法 |
JP2010186682A (ja) * | 2009-02-13 | 2010-08-26 | Toyota Motor Corp | 固体電解質層の製造方法 |
JP2010205449A (ja) * | 2009-02-27 | 2010-09-16 | Nippon Zeon Co Ltd | 全固体二次電池用固体電解質層、全固体二次電池用積層体および全固体二次電池 |
JP2011134675A (ja) * | 2009-12-25 | 2011-07-07 | Toyota Motor Corp | 電極層、固体電解質層および全固体二次電池 |
JP2011233422A (ja) * | 2010-04-28 | 2011-11-17 | Nippon Zeon Co Ltd | リチウムイオン伝導性固体電解質組成物および全固体二次電池 |
WO2012073678A1 (ja) * | 2010-11-29 | 2012-06-07 | Jsr株式会社 | 電池用バインダー組成物、電池電極用スラリー、固体電解質組成物、電極及び全固体型電池 |
JP2012227107A (ja) * | 2011-04-05 | 2012-11-15 | Sumitomo Electric Ind Ltd | 非水電解質電池用電極体及び非水電解質電池 |
WO2012173089A1 (ja) * | 2011-06-17 | 2012-12-20 | 日本ゼオン株式会社 | 全固体二次電池 |
WO2013001623A1 (ja) * | 2011-06-29 | 2013-01-03 | トヨタ自動車株式会社 | 固体電解質層、二次電池用電極層および全固体二次電池 |
JP2013008611A (ja) * | 2011-06-27 | 2013-01-10 | Nippon Zeon Co Ltd | 全固体二次電池 |
WO2013065738A2 (ja) * | 2011-10-31 | 2013-05-10 | 日本ゼオン株式会社 | 全固体二次電池 |
Family Cites Families (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3268382D1 (en) * | 1981-06-12 | 1986-02-20 | Sound Attenuators Ltd | Method and apparatus for reducing repetitive noise entering the ear |
CN1178313A (zh) * | 1997-10-27 | 1998-04-08 | 天然国际新科学技术研究院 | 无热制冷方法及其循环系统 |
JP2000106154A (ja) | 1998-09-28 | 2000-04-11 | Matsushita Electric Ind Co Ltd | 全固体電池およびその製造法 |
JP4458213B2 (ja) * | 1999-01-29 | 2010-04-28 | 信越化学工業株式会社 | 架橋型高分子固体電解質の製造方法 |
US6645675B1 (en) * | 1999-09-02 | 2003-11-11 | Lithium Power Technologies, Inc. | Solid polymer electrolytes |
WO2001020698A1 (en) * | 1999-09-16 | 2001-03-22 | Matsushita Electric Industrial Co., Ltd. | Electrochemical capacitor |
US20040101758A1 (en) * | 2002-11-21 | 2004-05-27 | Takefumi Okumura | Lithium secondary battery |
WO2005112180A1 (ja) * | 2004-05-14 | 2005-11-24 | Matsushita Electric Industrial Co., Ltd. | リチウムイオン二次電池 |
US9580320B2 (en) | 2005-10-13 | 2017-02-28 | Ohara Inc. | Lithium ion conductive solid electrolyte and method for manufacturing the same |
JP2008059843A (ja) | 2006-08-30 | 2008-03-13 | Kyoto Univ | 固体電解質層及びその製造方法 |
JP2008103284A (ja) | 2006-10-20 | 2008-05-01 | Idemitsu Kosan Co Ltd | 全固体電池 |
JP5397049B2 (ja) * | 2009-07-02 | 2014-01-22 | 日本ゼオン株式会社 | 全固体二次電池 |
JP5638232B2 (ja) * | 2009-12-02 | 2014-12-10 | 住友金属鉱山株式会社 | 非水系電解質二次電池正極活物質用ニッケルコバルトマンガン複合水酸化物粒子とその製造方法、非水系電解質二次電池用正極活物質とその製造方法、および非水系電解質二次電池 |
JP2012099315A (ja) | 2010-11-01 | 2012-05-24 | Sumitomo Electric Ind Ltd | 全固体リチウム電池用正極とその製造方法および全固体リチウム電池 |
-
2014
- 2014-09-25 WO PCT/JP2014/075399 patent/WO2015046314A1/ja active Application Filing
- 2014-09-25 CN CN201480053192.0A patent/CN105580187B/zh active Active
- 2014-09-25 KR KR1020187017065A patent/KR20180069137A/ko not_active Application Discontinuation
- 2014-09-25 DE DE112014004451.2T patent/DE112014004451T5/de active Pending
- 2014-09-25 KR KR1020167007794A patent/KR102013487B1/ko active IP Right Grant
- 2014-09-25 JP JP2014195048A patent/JP6253155B2/ja active Active
-
2016
- 2016-03-21 US US15/075,589 patent/US20160204465A1/en not_active Abandoned
Patent Citations (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2009176484A (ja) * | 2008-01-22 | 2009-08-06 | Idemitsu Kosan Co Ltd | 全固体リチウム二次電池用正極及び負極、並びに全固体リチウム二次電池 |
JP2010113820A (ja) * | 2008-11-04 | 2010-05-20 | Idemitsu Kosan Co Ltd | リチウムイオン伝導性固体電解質組成物及びそれを用いた電池 |
WO2010089891A1 (ja) * | 2009-02-09 | 2010-08-12 | トヨタ自動車株式会社 | 固体電解質材料含有シートの製造方法 |
JP2010186682A (ja) * | 2009-02-13 | 2010-08-26 | Toyota Motor Corp | 固体電解質層の製造方法 |
JP2010205449A (ja) * | 2009-02-27 | 2010-09-16 | Nippon Zeon Co Ltd | 全固体二次電池用固体電解質層、全固体二次電池用積層体および全固体二次電池 |
JP2011134675A (ja) * | 2009-12-25 | 2011-07-07 | Toyota Motor Corp | 電極層、固体電解質層および全固体二次電池 |
JP2011233422A (ja) * | 2010-04-28 | 2011-11-17 | Nippon Zeon Co Ltd | リチウムイオン伝導性固体電解質組成物および全固体二次電池 |
WO2012073678A1 (ja) * | 2010-11-29 | 2012-06-07 | Jsr株式会社 | 電池用バインダー組成物、電池電極用スラリー、固体電解質組成物、電極及び全固体型電池 |
JP2012227107A (ja) * | 2011-04-05 | 2012-11-15 | Sumitomo Electric Ind Ltd | 非水電解質電池用電極体及び非水電解質電池 |
WO2012173089A1 (ja) * | 2011-06-17 | 2012-12-20 | 日本ゼオン株式会社 | 全固体二次電池 |
JP2013008611A (ja) * | 2011-06-27 | 2013-01-10 | Nippon Zeon Co Ltd | 全固体二次電池 |
WO2013001623A1 (ja) * | 2011-06-29 | 2013-01-03 | トヨタ自動車株式会社 | 固体電解質層、二次電池用電極層および全固体二次電池 |
WO2013065738A2 (ja) * | 2011-10-31 | 2013-05-10 | 日本ゼオン株式会社 | 全固体二次電池 |
Cited By (36)
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JP2016212991A (ja) * | 2015-04-30 | 2016-12-15 | 富士フイルム株式会社 | 全固体二次電池、全固体二次電池用電極シート、および全固体二次電池の製造方法 |
JP2016212990A (ja) * | 2015-04-30 | 2016-12-15 | 富士フイルム株式会社 | 全固体二次電池、電極活物質層用組成物および全固体二次電池用電極シートならびに全固体二次電池用電極シートおよび全固体二次電池の製造方法 |
JP2017027657A (ja) * | 2015-07-15 | 2017-02-02 | 三星電子株式会社Samsung Electronics Co.,Ltd. | 二次電池用電解液及び二次電池 |
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Also Published As
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CN105580187A (zh) | 2016-05-11 |
JP6253155B2 (ja) | 2017-12-27 |
KR20160046882A (ko) | 2016-04-29 |
KR20180069137A (ko) | 2018-06-22 |
JP2015088486A (ja) | 2015-05-07 |
US20160204465A1 (en) | 2016-07-14 |
DE112014004451T5 (de) | 2016-06-23 |
CN105580187B (zh) | 2019-03-01 |
KR102013487B1 (ko) | 2019-08-22 |
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