CN108574101A - For the binder aqueous solution of lithium ion battery, slurry, electrode, diaphragm, diaphragm/electrode laminate and lithium ion battery - Google Patents

For the binder aqueous solution of lithium ion battery, slurry, electrode, diaphragm, diaphragm/electrode laminate and lithium ion battery Download PDF

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Publication number
CN108574101A
CN108574101A CN201810166495.3A CN201810166495A CN108574101A CN 108574101 A CN108574101 A CN 108574101A CN 201810166495 A CN201810166495 A CN 201810166495A CN 108574101 A CN108574101 A CN 108574101A
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lithium ion
ion battery
mass
slurry
electrode
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CN108574101B (en
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笹川巨树
尾崎真仁
池谷克彦
合田秀树
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Arakawa Chemical Industries Ltd
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Arakawa Chemical Industries Ltd
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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
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • H—ELECTRICITY
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    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0404—Methods of deposition of the material by coating on electrode collectors
    • H—ELECTRICITY
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    • H01M4/04—Processes of manufacture in general
    • H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
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    • H01M4/00—Electrodes
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    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
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    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/134—Electrodes based on metals, Si or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
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    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
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    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/386—Silicon or alloys based on silicon
    • H—ELECTRICITY
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    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H—ELECTRICITY
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    • 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
    • H01M4/621—Binders
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    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/661—Metal or alloys, e.g. alloy coatings
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    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
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    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
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    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/431—Inorganic material
    • H01M50/434—Ceramics
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    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
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    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/46—Separators, membranes or diaphragms characterised by their combination with electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • H01M50/491—Porosity
    • 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
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A30/00—Adapting or protecting infrastructure or their operation
    • 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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  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Ceramic Engineering (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Composite Materials (AREA)
  • Cell Electrode Carriers And Collectors (AREA)
  • Cell Separators (AREA)

Abstract

The application provides lithium ion battery binder aqueous solution, lithium ion battery slurry and its manufacturing method, lithium ion battery electrode, diaphragm for lithium ion battery, diaphragm for lithium ion battery/electrode laminate and lithium ion battery.The application provides lithium ion battery binder aqueous solution, and the lithium ion battery binder aqueous solution contains：Water-soluble polymer (A) with amide groups；With the silicol based compound (A1) as ortho-siliformic acid based compound and/or tetrahydroxy silane-based compound.

Description

For the binder aqueous solution of lithium ion battery, slurry, electrode, diaphragm, diaphragm/electricity Pole laminate and lithium ion battery
Technical field
This application involves lithium ion battery binder aqueous solution, lithium ion battery slurry and its manufacturing method, lithium from Sub- electrode for cell, diaphragm for lithium ion battery, diaphragm for lithium ion battery/electrode laminate and lithium ion battery.
Background technology
Lithium ion battery is had small-sized, light weight, energy density high and can be used for wide with the characteristic of repeated charge General purposes.Therefore in recent years, for the purpose of the further high performance of lithium ion battery, just in electricity such as Electrode, diaphragms The improvement of pond component.
The anode and cathode of lithium ion battery are all manufactured by following methods：Electrode active material and adhesive resin are existed Disperse the slurry to be formed in solvent and carry out double spread on collector (such as metal foil), solvent seasoning is removed to form electrode After layer, it is used into the compression formings such as roll squeezer.
In recent years, in lithium ion battery electrode, from the viewpoint of improving battery capacity, as electrode active material, Propose various electrode active materials.However, different due to electrode active material, with charge and discharge be easy expansion and It shrinks.Therefore, following problems can occur for lithium ion battery electrode：It (is returned since volume change occurs for the initial stage of repeated charge Elasticity), be easily reduced using electrical characteristics such as the cycle characteristics of lithium ion battery of lithium ion battery electrode.
Then in the art, studying and attempting to solve above-mentioned technical problem by adhesive resin, such as is public Knowing has polyimides (patent document 1) and polyacrylic acid (patent document 2).Meanwhile a kind of slurry is proposed in patent document 3 Composition, the paste compound include：Water-soluble polymer, particulate adhesive, electrode active material containing silicon-containing monomer. Meanwhile in patent document 4, it is proposed that the lithium rechargeable battery silica being surface-treated using silane coupling agent.
About the diaphragm of lithium ion battery, proposes and formed on the surface of polyolefin micro porous polyolefin membrane containing ceramic micro- in recent years The heat resistance diaphragm of the coating (refractory layer) of grain and adhesive.Also may be used if exposed to high temperature it is well known that aforementioned coatings have To inhibit the effect of the contraction of diaphragm.However, there are following technical problems for obtained heat resistance diaphragm：Due in the production line Deformation when bending when transport and in battery unit, the engagement of coating and polyolefin micro porous polyolefin membrane cannot maintain, It is easy to fall off.
Then in the art, studying and attempting to solve above-mentioned technical problem by adhesive resin, for example, Bonding layer (patent document 5) on the surface of polyolefin micro porous polyolefin membrane is well known, which contains selected from heat-resisting porous Layer and at least one of thermoplastic elastomer and rubber constituent.A kind of diaphragm is proposed in patent document 6, it is characterised in that Oxide inorganic particle, the polymer with reactive functional groups and crosslinking agent is set to react.
Existing technical literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2013-089437 bulletins
Patent document 2：Japanese Unexamined Patent Publication 2005-216502 bulletins
Patent document 3：No. 6048070 bulletins of Japanese Patent Publication No.
Patent document 4：Japanese Unexamined Patent Publication 2001-216961 bulletins
Patent document 5：Japanese Unexamined Patent Publication 2012-89346 bulletins
Patent document 6：Japanese Unexamined Patent Publication 2012-69457 bulletins
Invention content
Technical problems to be solved by the inivention
About the electrode of lithium ion battery, the polyimides of patent document 1 is will to be dissolved in as the polyamic acid of precursor Adhesive resin slurry is used as in solvent containing organic solvents such as n-methyl-2-pyrrolidone (NMP), in this case, In the mass production to accompany with increase in demand from now on, the case where compared to water solvent is used, the organic solvents such as NMP It is very big using the carrying capacity of environment in coating-drying.
For the polyacrylic acid recorded in patent document 2, due to the lithium ion quilt received in active material in charging The carboxyl of polyacrylic acid obtains, and there is technical issues that initial stage discharge capacity.Meanwhile it not being recorded about resistance to resilience.
The electrode slurry of the active material containing polyacrylamide and given average grain diameter is proposed in patent document 3, so And the rebound patience about electrode is not recorded.
In patent document 4, it is proposed that lived using being diluted silane coupling agent using water, being added into the aqueous solution Property material powder mixed, filtered, dry obtained from the active material that is surface-treated.In the case, first Phase can inhibit irreversible capacity when charging, however, the problem of rebound patience does not solve still.
Meanwhile patent document 5 be used to form heat-resisting porous layer between bit-type Wholly aromatic polyamide be to contain diformazan Material of the dissolving as adhesive resin slurry in the solvent of the organic solvents such as yl acetamide.Accompany with increase in demand from now on With mass production in, compared with the case where using water solvent, the carrying capacity of environment of the use of organic solvent in coating-drying Greatly.
The diaphragm porous layer using polyacrylic acid or polyvinyl alcohol resin and crosslinking agent is proposed in patent document 6, but Since the reactivity of the two is high, the stability of slurry is poor, has the tendency for being easy gelatine.Therefore particle is aggregated, at any time Between elapse and settle, uneven distribution when causing to coat, it is difficult to manufacture uniform perforated membrane.
Then, technical problem to be solved by the invention is to provide the methods that can manufacture electrode and diaphragm, which can To assign lithium ion battery with excellent resistance to resilience and electrical characteristics, which can assign lithium ion battery with excellent heat-resisting Shrinkage, anti-picking property, base material adherence, multiplying power property, output characteristics.In addition, in this application, anti-picking property refers to ceramics The associativity of particle from each other；Base material adherence refers to base material and is coated with slurry according to the present invention on base material, is dry The zygosity of layer obtained from dry (coating).
Solve the technological means of technical problem
It is in order to solve the above-mentioned technical problem present inventor concentrates on studies as a result, it has been found that, by using there is the water-soluble of amide groups Property polymer and silicol based compound, can to solve the above technical problems, thereby completing the present invention.
Following items are provided by the application.
(project 1)
Lithium ion battery binder aqueous solution, the lithium ion battery binder aqueous solution contain：
Water-soluble polymer (A) with amide groups；With
As ortho-siliformic acid based compound and/or the silicol based compound (A1) of tetrahydroxy silane-based compound.
(project 2)
Lithium ion battery slurry, the lithium ion battery slurry contain：
Water-soluble polymer (A) with amide groups；With
As ortho-siliformic acid based compound and/or the silicol based compound (A1) of tetrahydroxy silane-based compound.
(project 3)
Lithium ion battery slurry as described in project 2, wherein the water-soluble polymer (A) is that have (methyl) third The homopolymer of the compound of acrylamide base or with (methyl) acrylamido compound and unsaturated carboxylic acid copolymer.
(project 4)
Lithium ion battery slurry as described in project 2 or 3, wherein relative to 100 matter of the water-soluble polymer (A) Part is measured, the lithium ion battery slurry contains 1~15 mass parts of silicol based compound (A1).
(project 5)
Lithium ion battery slurry as described in any one of project 2~4, wherein the silicol based compound (A1) contain ortho-siliformic acid base propylamine.
(project 6)
Lithium ion battery slurry as described in any one of project 2~5, wherein the lithium ion battery is contained with slurry There is electrode active material (B).
(project 7)
Lithium ion battery slurry as described in any one of project 2~6, wherein at the electrode active material (B) In, contain silicon or 10 mass % of silica or more.
(project 8)
Lithium ion battery slurry as described in project 6 or 7, wherein relative to 100 matter of the electrode active material (B) Amount part, the water-soluble polymer (A) and the silicol based compound (A1) add up to 2~12 mass parts.
(project 9)
Lithium ion battery slurry as described in any one of project 2~8, wherein the lithium ion battery is contained with slurry There is ceramic particle (C).
(project 10)
Lithium ion battery slurry as described in project 9, wherein relative to 100 mass parts of the ceramic particle (C), institute That states water-soluble polymer (A) and the silicol based compound (A1) adds up to 1~15 mass parts.
(project 11)
The manufacturing method of lithium ion battery slurry described in any one of project 2~10, includes the following steps：
By with amide groups water-soluble polymer (A) with as ortho-siliformic acid based compound and/or tetrahydroxy silane The silicol based compound (A1) of based compound is mixed.
(project 12)
Lithium ion battery electrode, the lithium ion battery electrode contain the lithium described in any one of project 2~10 Poly- (methyl) acrylamide-polysiloxane oligomers obtained from ion battery is coated with slurry and is allowed to dry on the current collector Compound.
(project 13)
Lithium ion battery electrode as described in project 12, wherein the collector is copper foil.
(project 14)
Lithium ion battery containing the electrode described in project 12 or 13.
(project 15)
By the lithium ion battery slurry described in any one of project 2~10 porous polyolefin resin base material or plastics without Diaphragm for lithium ion battery obtained from being coated in woven fabric and being allowed to dry.
(project 16)
Lithium ion battery described in any one of project 2~10 is coated on the electrode with slurry and is allowed to drying and is obtained Diaphragm for lithium ion battery/electrode laminate.
(project 17)
Contain the diaphragm for lithium ion battery described in project 15 and/or diaphragm for lithium ion battery/electricity described in project 16 The lithium ion battery of pole laminate.
In this application, it for above-mentioned one or more features, other than the combination expressed, can also provide into one The combination of step.
Invention effect
By using the lithium ion battery binder aqueous solution and lithium ion battery slurry of the present invention, electricity can be provided The lithium ion battery that the continuation of the journey of tankage and resistance to resilience improve.
By using the lithium ion battery binder aqueous solution and lithium ion battery slurry of the present invention, can provide resistance to The diaphragm for lithium ion battery that heat-shrinkable, anti-picking property, base material adherence, multiplying power property, output characteristics improve.
Specific implementation mode
In the full text of the application, the ranges of the numerical value such as value, content of each physical characteristic can be appropriate (such as from following each Selected in the value of upper and lower bound recorded in project) setting.Specifically, for numerical value α, the upper limit of numerical value α be, for example, A1, A2, A3 etc., the lower limit of numerical value α are, for example, B1, B2, B3 etc., in the case, the range of numerical value α be, for example, A1 or less, A2 with Under, A3 or less, B1 or more, B2 or more, B3 or more, A1~B1, A1~B2, A1~B3, A2~B1, A2~B2, A2~B3, A3~ B1, A3~B2, A3~B3 etc..
[1. lithium ion battery binder aqueous solutions：Also referred to as aqueous solution]
The application provides lithium ion battery binder aqueous solution, and the lithium ion battery binder aqueous solution contains：
Water-soluble polymer (A) with amide groups；And
As ortho-siliformic acid based compound and/or the silicol based compound (A1) of tetrahydroxy silane-based compound.
＜ has the water-soluble polymer (A) of amide groups：Also referred to as (A) ingredient ＞
In this application, " water-soluble polymer with amide groups " refers to amide groups (- C (O) NH2) water solubility Polymer.
In this application, " water solubility " refer to, when compound 0.5g is dissolved in 100g water 25 DEG C, insoluble composition Less than 0.5 mass % (being less than 2.5mg).
(the compound (a) with (methyl) acrylamido：Also referred to as (a) ingredient)
In this application, " compound with (methyl) acrylamido " refers to having (methyl) acrylamide skeleton Compound or its salt.Compound with (methyl) acrylamido can be used alone various well known compounds, also may be used Two or more merging to be used.
[changing 1]
(in formula, R1For hydrogen or methyl)
In this application, " (methyl) acrylic acid " refers to " being selected from the group being made of acrylic acid and methacrylic acid It is at least one ".Similarly, " (methyl) acrylate " refers to " being selected from the group being made of acrylate and methacrylate At least one selected ".Meanwhile " (methyl) acryloyl group " refers to " from the group being made of acryloyl group and methylacryloyl At least one of selection ".
In one embodiment, the compound with (methyl) acrylamido is indicated by following structural formula：
[changing 2]
(in formula, R1It is hydrogen or methyl, R2And R3It is separately hydrogen, substituted or unsubstituted alkyl, acetyl group or sulphur Acidic group or R2And R3For the group of ring structure, R is collectively formed4And R5Separately be hydrogen, substituted or unsubstituted alkyl, Carboxyl, hydroxyl, amino (- NRaRb(RaAnd RbBe separately hydrogen or substituted or unsubstituted alkyl) (the same below)), acetyl Base, sulfonic group.It is, for example, hydroxyl, amino, acetyl group, sulfonic group etc. to replace the substituent group of alkyl.Meanwhile R2And R3It is collectively formed The group of ring structure is, for example, morpholinyl (モ Le ホ リ Le) etc.)
Alkyl is, for example,：Straight chained alkyl, branched alkyl, naphthenic base etc..
Straight chained alkyl is by general formula-CnH2n+1(n is 1 or more integer) indicates.Straight chained alkyl is, for example,：Methyl, ethyl, third Base, normal-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, positive decyl etc..
Branched alkyl is at least one hydrogen of straight chained alkyl by alkyl-substituted group.Branched alkyl is, for example,：Diethyl Amyl, trimethyl butyl, tri-methyl-amyl, trimethyl etc..
Naphthenic base is, for example,：Monocyclic cycloalkyl, bridged ring naphthenic base, condensed ring naphthenic base etc..
In this application, monocycle refer to formed by the covalent bond of carbon, in the internal cyclic structure for not having bridging structure. Meanwhile condensed ring refers to that more than two monocycles share two atoms (that is, each ring only shares (condensed) a line from each other) Cyclic structure.Bridged ring refers to the cyclic structure that more than two monocycles share 3 or more atoms.
Monocyclic cycloalkyl is, for example,：Cyclopenta, cyclohexyl, suberyl, cyclodecyl, 3,5,5- trimethylcyclohexyls etc..
Bridged ring naphthenic base is, for example,：Tricyclodecyl, adamantyl, norborny etc..
Condensed ring naphthenic base is, for example,：Bicyclodecyl etc..
The above-mentioned compound (a) with (methyl) acrylamido is e.g.：With unsubstituted (methyl) acrylamides of N- The monomer of skeleton, the monomer with monosubstituted (methyl) the acrylamide skeletons of N- replace (methyl) acrylamide with N, N- bis- The monomer etc. of skeleton.
Monomer with unsubstituted (methyl) the acrylamide skeletons of N- is, for example,：(methyl) acrylamide, maleic amide etc..
Monomer with monosubstituted (methyl) the acrylamide skeletons of N- is, for example,：N- isopropyls (methyl) acrylamide, N- Methylol (methyl) acrylamide, diacetone (methyl) acrylamide, (methyl) acrylamide tertiary butyl sulfonic acid, ethoxy (first Base) acrylamide etc..
With N- bis- replace (methyl) acrylamide skeleton monomer be, for example,：N, N- dimethyl (methyl) acrylamide, N, N- diethyl (methyl) acrylamide, N, N- dimethylaminopropyls (methyl) acrylamide, (methyl) acryloyl morpholine etc..
Above-mentioned salt is, for example,：The Methochloride quaternary ammonium salt, dimethylamino of dimethylaminopropyl (methyl) acrylamide The benzyl chloride quaternary ammonium salt etc. of base ethyl (methyl) acrylate.
Above-mentioned in the compound (a) of (methyl) acrylamido, if using (methyl) acrylamide, especially Use acrylamide, then water-soluble and slurry dispersibility raising.As a result, electrode active material from each other, ceramic particle Associativity from each other improves.
Come from the compound with (methyl) acrylamido contained in 100 mass % of water-soluble polymer (A) (a) upper limit of the ratio of its structural unit be, for example, 100 mass %, 90 mass %, 80 mass %, 70 mass %, 60 mass %, 50 mass %, 45 mass % etc., lower limit are, for example, 90 mass %, 80 mass %, 70 mass %, 60 mass %, 50 mass %, 45 Quality %, 40 mass % etc..In one embodiment, come from tool contained in 100 mass % of water-soluble polymer (A) It is preferably 40~100 mass % to have its ratio of the structural unit of the compound (a) of (methyl) acrylamido, more preferably for 45~ 100 mass %, particularly preferably 50~100 mass %.Due to coming from the compound (a) with (methyl) acrylamido Structural unit contains (A) ingredient of specific quantity, and electrode active material, filler, ceramic particle isodispersity improve, and can manufacture Even layer (electrode active material layer and ceramic particle layer etc.) shows good charge-discharge characteristic so fault of construction disappears.Into One step, contain the structural unit for coming from the compound with (methyl) acrylamido with specific quantity in (A) ingredient, because The oxidative resistance of this polymer, reducing resistance improve, so deterioration when high pressure is suppressed, show that good charge and discharge are durable Characteristic.
Relative to 100 moles of % of all structural units in water-soluble polymer (A), coming from has (methyl) acryloyl The upper limit of its ratio of the structural unit of the compound (a) of amido is, for example, that 100 moles of %, 90 moles of %, 80 moles of %, 70 are rubbed Your %, 60 moles of % etc., lower limit is, for example, 90 moles of %, 80 moles of %, 70 moles of %, 60 moles of %, 50 moles of % etc..One In a embodiment, relative to 100 moles of % of all structural units in water-soluble polymer (A), coming from has (methyl) Its ratio of the structural unit of the compound (a) of acrylamido is preferably 50~100 moles of %.
(it is not the monomer of (a) ingredient：Also referred to as (b) ingredient)
In water-soluble polymer (A), the structure list for coming from the monomer ((b) ingredient) for not being (a) ingredient can be contained Member.(b) ingredient can be used alone various well known compounds, can also use two or more merging.(b) ingredient is for example It is：Monomer, esters of unsaturated carboxylic acids, α with acid groups such as unsaturated carboxylic acid, unsaturated sulfonic acid, unsaturated phosphoric acid, β-unsaturation Nitrile, conjugated diene, aromatic vinyl compound etc..
Unsaturated carboxylic acid is, for example,：Acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid and it Salt etc..
In 100 moles of % of all structural units of water-soluble polymer (A), the content of unsaturated carboxylic acid is not by special It limits, if it is considered that reacted with above-mentioned silicol based compound (A1), then all knots relative to water-soluble polymer (A) 100 moles of % of structure unit, the content of unsaturated carboxylic acid are preferably less than 40 moles of % and (are, for example, less than 30 moles of %, rub less than 20 That %, it is less than 19 moles of %, is less than 15 moles of %, is less than 10 moles of %, is less than 5 moles of %, less than 1 mole of %, 0 mole of %).
Relative to the 100 mass % of all structural units of water-soluble polymer (A), come from the structure list of unsaturated carboxylic acid The upper limit of its first content is, for example, 60 mass %, 50 mass %, 40 mass %, 30 mass %, 20 mass %, 10 mass %, 5 matter % etc. is measured, lower limit is, for example, 50 mass %, 40 mass %, 30 mass %, 20 mass %, 10 mass %, 5 mass %, 0 mass % Deng.In one embodiment, relative to the 100 mass % of all structural units of water-soluble polymer (A), come from unsaturation The content of the structural unit of carboxylic acid is preferably 0~60 mass %.
Unsaturated sulfonic acid is, for example,：The α such as vinyl sulfonic acid, styrene sulfonic acid, (methyl) propene sulfonic acid, β-ethylene belong to not It is saturated sulfonic acid；(methyl) acrylamide tertiary butyl sulfonic acid, 2- (methyl) acrylamide -2- methyl propane sulfonic acids, 2- (methyl) third Acrylamide -2- hydroxypropanesulfonic acids, 3- sulfonic groups propyl (methyl) acrylate, bis- (3- sulfonic groups propyl) itaconates and Their salt etc..
In 100 moles of % of all structural units of water-soluble polymer (A), the content of unsaturated sulfonic acid is not by special It limits, if it is considered that reacted with above-mentioned silicol based compound (A1), then all knots relative to water-soluble polymer (A) 100 moles of % of structure unit, the upper limit of the content of unsaturated sulfonic acid are, for example, that 40 moles of %, 30 moles of %, 20 moles of %, 19 are rubbed That %, 15 moles of %, 10 moles of %, 5 moles of %, 1 mole of %, 0.5 mole of %, 0.1 mole of %, 0.05 mole of %, 0.02 are rubbed Your % etc., lower limit are, for example, that 30 moles of %, 20 moles of %, 19 moles of %, 15 moles of %, 10 moles of %, 5 moles of %, 1 are rubbed Your %, 0.5 mole of %, 0.1 mole of %, 0.05 mole of %, 0.02 mole of %, 0.01 mole of %, 0 mole of % etc..
Relative to the 100 mass % of all structural units of water-soluble polymer (A), the upper limit example of the content of unsaturated sulfonic acid 70 mass % in this way, 60 mass %, 50 mass %, 40 mass %, 30 mass %, 20 mass %, 10 mass %, 5 mass % etc., Lower limit is, for example, 60 mass %, 50 mass %, 40 mass %, 30 mass %, 20 mass %, 10 mass %, 5 mass %, 0 matter Measure % etc..In one embodiment, relative to the 100 mass % of all structural units of water-soluble polymer (A), come from not The content for being saturated the structural unit of sulfonic acid is preferably 0~70 mass %.
Unsaturated phosphorus acid monomer is, for example,：Vinyl phosphoric acid, vinyl phosphate, bis- ((methyl) acryloyl-oxyethyls) Phosphate, diphenyl -2- (methyl) acryloyl-oxyethyl phosphate, dibutyl -2- (methyl) acryloyl-oxyethyl phosphoric acid Ester, dioctyl -2- (methyl) acryloyl-oxyethyl phosphate, monomethyl -2- (methyl) acryloyl-oxyethyl phosphate, 3- (methyl) acryloxy -2- hydroxy propanes phosphoric acid and their salt etc..
In 100 moles of % of all structural units of soluble polymer (A), there is the monomer of the acid groups such as unsaturated phosphoric acid Content it is not particularly restricted, if it is considered that reacted with above-mentioned (b) ingredient, then institute relative to water-soluble polymer (A) There are 100 moles of % of structural unit, preferably less than 40 moles of % (to be, for example, less than 30 moles of %, less than 20 moles %, rub less than 19 That %, it is less than 15 moles of %, is less than 10 moles of %, is less than 5 moles of %, is less than 1 mole of %, 0 mole of %).
Relative to the 100 mass % of all structural units of water-soluble polymer (A), come from the composition list of unsaturated phosphoric acid The upper limit of its first content is, for example, 60 mass %, 50 mass %, 40 mass %, 30 mass %, 20 mass %, 10 mass %, 5 matter % etc. is measured, lower limit is, for example, 50 mass %, 40 mass %, 30 mass %, 20 mass %, 10 mass %, 5 mass %, 0 mass % Deng.In one embodiment, relative to the 100 mass % of all structural units of water-soluble polymer (A), come from unsaturation The content of the Component units of phosphorus acid monomer is preferably 0~60 mass %.
In one embodiment, water-soluble relative to 100 moles of % of all structural units of water-soluble polymer (A) There are the acidic groups such as unsaturated carboxylic acid, unsaturated sulfonic acid, unsaturated phosphoric acid in 100 moles of % of all structural units of polymer (A) Total content of the monomer of group is preferably less than 40 moles of % and (is, for example, less than 30 moles of %, less than 20 moles %, rubs less than 19 That %, it is less than 15 moles of %, is less than 10 moles of %, is less than 5 moles of %, is less than 1 mole of %, 0 mole of %).
Relative to the 100 mass % of all structural units of water-soluble polymer (A), come from unsaturated carboxylic acid, no It is saturated the upper limit such as 70 mass %, 60 matter of its total content of the Component units of the monomers of acid groups such as sulfonic acid, unsaturated phosphoric acid %, 50 mass %, 40 mass %, 30 mass %, 20 mass %, 10 mass %, 5 mass % etc. are measured, lower limit is, for example, 60 matter Measure %, 50 mass %, 40 mass %, 30 mass %, 20 mass %, 10 mass %, 5 mass %, 0 mass % etc..In a reality It applies in mode, relative to the 100 mass % of all structural units of water-soluble polymer (A), comes from unsaturated carboxylic acid, no Its total content of the Component units of the monomers of acid groups such as saturation sulfonic acid, unsaturated phosphoric acid is preferably 0~70 mass %.
Esters of unsaturated carboxylic acids preferably (methyl) acrylate.(methyl) acrylate is, for example,：Straight chain (methyl) acrylic acid Ester, branch (methyl) acrylate, alicyclic ring (methyl) acrylate, substitution (methyl) acrylate etc..
Straight chain (methyl) acrylate is, for example,：(methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) propylene Sour n-propyl, (methyl) n-butyl acrylate, (methyl) acrylic acid n-pentyl ester, (methyl) Hexyl 2-propenoate, (methyl) acrylic acid N-octyl, (methyl) acrylic acid nonyl ester, (methyl) decyl acrylate etc..
Branch (methyl) acrylate is, for example,：(methyl) isopropyl acrylate, (methyl) isobutyl acrylate, (methyl) Isoamyl acrylate, (methyl) 2-EHA etc..
Alicyclic ring (methyl) acrylate is, for example, (methyl) cyclohexyl acrylate etc..
Substitution (methyl) acrylate be, for example,：(methyl) glycidyl acrylate, (methyl) acrylate, (methyl) hydroxy-ethyl acrylate, (methyl) acrylic acid glycol ester, two (methyl) acrylic acid glycol esters, two (methyl) acrylic acid Propylene glycol ester, three (methyl) acrylic acid trihydroxy methyl propyl ester, four (methyl) acrylate, pentaerythritols, six (methyl) acrylic acid two Pentaerythritol ester, (methyl) allyl acrylate, two (methyl) acrylic acid ethylidene esters etc..
In 100 moles of % of all structural units of water-soluble polymer (A), the content of esters of unsaturated carboxylic acids is not by spy It does not limit, by using esters of unsaturated carboxylic acids, electrode can be assigned with flexibility, especially using wound form, cylinder type electricity It is useful in the case of pond；When manufacturing diaphragm, from the glass transition temperature of all structural units of water-soluble polymer (A) Degree reduces, so as to be useful from the viewpoint of inhibiting the bending of diaphragm.On the other hand, if it is considered that lithium ion battery The water solubility of cycle characteristics and water-soluble polymer (A), it is (such as small that the content of esters of unsaturated carboxylic acids is preferably less than 40 moles of % In 30 moles of %, it is less than 20 moles of %, is less than 19 moles of %, is less than 15 moles of %, is less than 10 moles of %, is less than 5 moles of %, small In 1 mole of %, 0 mole of %).
Relative to the 100 mass % of all structural units of water-soluble polymer (A), come from the structure of esters of unsaturated carboxylic acids The upper limit of its content of unit be, for example, 80 mass %, 70 mass %, 60 mass %, 50 mass %, 40 mass %, 30 mass %, 20 mass %, 10 mass %, 5 mass % etc., lower limit are, for example, 70 mass %, 60 mass %, 50 mass %, 40 mass %, 30 Quality %, 20 mass %, 10 mass %, 5 mass %, 0 mass % etc..In one embodiment, relative to water-soluble polymeric The 100 mass % of all structural units of object (A), the content for coming from the structural unit of esters of unsaturated carboxylic acids is preferably 0~80 matter Measure %.
For electrode and diaphragm is assigned with the purpose of flexibility, α, alpha, beta-unsaturated nitriles can be properly used.α, β-insatiable hunger It is, for example, with nitrile：(methyl) acrylonitrile, α-chlorine (methyl) acrylonitrile, α-ethyl (methyl) acrylonitrile, vinylidene dinitrile (シ ア Application Change ビ ニ リ デ Application) etc..Wherein, preferred (methyl) acrylonitrile, particularly preferred acrylonitrile.
The content of α, alpha, beta-unsaturated nitriles is not particularly restricted, all structural units relative to water-soluble polymer (A) 100 moles of %, preferably less than 40 moles of % (are, for example, less than 30 moles of %, less than 20 moles %, less than 19 moles %, are less than 15 moles of %, it is less than 10 moles of %, is less than 5 moles of %, is less than 1 mole of %, 0 mole of %).Relative to water-soluble polymer (A) All structural units 100 moles of %, the content of α, alpha, beta-unsaturated nitriles are less than 40 moles of %, thus in holding (A) ingredient to water It is deliquescent simultaneously, the layer (coating) of above-mentioned slurry becomes uniform, plays aforementioned flexibility and becomes easy.
Relative to the 100 mass % of all structural units of water-soluble polymer (A), come from α, the composition of alpha, beta-unsaturated nitriles The upper limit of its content of unit is, for example, 60 mass %, 50 mass %, 40 mass %, 30 mass %, 20 mass %, 10 mass %, 5 Quality % etc., lower limit are, for example, 50 mass %, 40 mass %, 30 mass %, 20 mass %, 10 mass %, 5 mass %, 0 matter Measure % etc..In one embodiment, relative to the 100 mass % of all structural units of water-soluble polymer (A), come from α, The content of the Component units of alpha, beta-unsaturated nitriles is preferably 0~60 mass %.
Conjugated diene is, for example,：1,3- butadiene, 2- methyl-1s, 3- butadiene, 2,3- dimethyl -1,3- butadiene, 2- Chloro- 1,3- butadiene, the conjugation hexadiene etc. for substituted straight chain conjugation pentadiene, replacing and there is side chain.
In 100 moles of % of all structural units of water-soluble polymer (A), the content of conjugated diene is not limited especially It is fixed；From the viewpoint of the cycle characteristics of lithium ion battery, in 100 moles of % of all structural units of water-soluble polymer (A) In, the content of conjugated diene is preferably less than 10 moles of %, is more preferably 0 mole of %.
Relative to the 100 mass % of all structural units of water-soluble polymer (A), come from the Component units of conjugated diene The upper limit of its content is, for example, 30 mass %, 20 mass %, 10 mass %, 5 mass % etc., and lower limit is, for example, 25 mass %, 20 Quality %, 10 mass %, 5 mass %, 0 mass % etc..In one embodiment, the institute relative to water-soluble polymer (A) It is preferably 0~30 mass % to have 100 mass % of structural unit, the content for coming from the Component units of conjugated diene.
Meanwhile aromatic vinyl compound is, for example,：Styrene, α-methylstyrene, p-methylstyrene, vinyl first Benzene, chlorostyrene, divinylbenzene etc..
In 100 moles of % of all structural units of water-soluble polymer (A), the content of aromatic vinyl compound not by To being particularly limited to；From the viewpoint of the cycle characteristics of lithium ion battery, in all structural units of water-soluble polymer (A) In 100 moles of %, the content of aromatic vinyl compound is preferably less than 10 moles of %, is more preferably 0 mole of %.
Relative to the 100 mass % of all structural units of water-soluble polymer (A), come from aromatic vinyl compound The upper limit of its content of structural unit is, for example, 30 mass %, 20 mass %, 10 mass %, 5 mass % etc., and lower limit is, for example, 25 matter Measure %, 20 mass %, 10 mass %, 5 mass %, 0 mass %.In one embodiment, relative to water-soluble polymer (A) 100 mass % of all structural units, the content for coming from the structural unit of aromatic vinyl compound is preferably 0~30 matter Measure %.
Relative to 100 moles of % of all structural units of water-soluble polymer (A), in addition to it is above-mentioned have unsaturated carboxylic acid, The monomer of the acid groups such as unsaturated sulfonic acid, unsaturated phosphoric acid, esters of unsaturated carboxylic acids, 'alpha ', ' bela '-unsaturated nitrile, conjugated diene, aromatics second The content of (b) ingredient other than alkenyl compound is, for example,：Less than 10 moles %, less than 5 moles %, less than 2 moles %, it is less than 1 mole of %, it is less than 0.1 mole of %, less than 0.01 mole of %, 0 mole of % etc.；All knots relative to water-soluble polymer (A) 100 mass % of structure unit, in addition to above-mentioned monomer with acid groups such as unsaturated carboxylic acid, unsaturated sulfonic acid, unsaturated phosphoric acid, no The content of (b) ingredient other than saturated carboxylic acid ester, 'alpha ', ' bela '-unsaturated nitrile, conjugated diene, aromatic vinyl compound is, for example,：It is small In 10 mass %, be less than 5 mass %, be less than 1 mass %, be less than 0.5 mass %, be less than 0.1 mass %, be less than 0.01 matter Measure %, 0 mass % etc..
Relative to 100 mass % of slurry, the upper limit of the content of water-soluble polymer (A) is, for example, 99.9 mass %, 99 matter Measure %, 95 mass %, 90 mass %, 85 mass %, 80 mass %, 75 mass %, 70 mass %, 65 mass %, 60 mass %, 55 mass %, 50 mass %, 45 mass %, 40 mass %, 35 mass %, 30 mass %, 25 mass %, 20 mass %, 15 matter %, 10 mass %, 5 mass %, 1 mass %, 0.9 mass %, 0.5 mass %, 0.2 mass % etc. are measured, lower limit is, for example, 99 matter Measure %, 95 mass %, 90 mass %, 85 mass %, 80 mass %, 75 mass %, 70 mass %, 65 mass %, 60 mass %, 55 mass %, 50 mass %, 45 mass %, 40 mass %, 35 mass %, 30 mass %, 25 mass %, 20 mass %, 15 matter Measure %, 10 mass %, 5 mass %, 1 mass %, 0.9 mass %, 0.5 mass %, 0.2 mass %, 0.1 mass % etc..One In a embodiment, relative to 100 mass % of slurry, the content of water-soluble polymer (A) is preferably 0.1~99.9 mass %.
The manufacturing method ＞ of ＜ (A) ingredient
(A) ingredient can use various well known polymerizations to be synthesized, it is preferable to use radical polymerization is closed At.Specifically, it is preferable that radical polymerization initiator and as needed is added into the monomer mixed solution containing aforesaid ingredients Chain-transferring agent carries out polymerisation at 50~100 DEG C of reaction temperature while stirring.Reaction time is not particularly restricted, excellent It is selected as 1~10 hour.
Radical polymerization initiator is not particularly restricted, and can use various well known radical polymerization initiators.From It is, for example, by base polymerization initiator：The persulfates such as potassium peroxydisulfate and ammonium persulfate；Above-mentioned persulfate and sodium hydrogensulfite etc. The redox system polymerization initiator that reducing agent is combined；The azos systems such as 2,2 '-azo two (2- amidine propanes) dihydrochlorides Initiator etc..The usage amount of radical polymerization initiator is not particularly restricted, relative to the monomer group for being supplied to (A) ingredient 100 mass %, preferably 0.05~5.00 mass % are more preferably 0.1~3.0 mass %.
It is steady for manufacture is improved before Raolical polymerizable and/or when obtained (A) ingredient is carried out water-solubleization Qualitative purpose, the neutralizer that ammonia and organic amine, potassium hydroxide, sodium hydroxide, lithium hydroxide etc. can also be used common carry out The pH of reaction solution is adjusted.In the case, pH is preferably 2~11.It meanwhile for the same purpose, can also be used as The EDTA of metal ion sealant or its salt etc..
In the case where (A) ingredient has acid groups, neutralization ratio appropriate can be adjusted to according to purposes.Herein, in The alkali neutralization of molal quantity identical with the sour component that the expression of ratio 100% is contained in (A) ingredient.Meanwhile 50% table of neutralization ratio Show by the alkali neutralization of the half molal quantity relative to the sour component contained in (A) ingredient.Neutralization ratio when ceramic particle being made to disperse Rate is not particularly restricted, after the formation such as coating, preferred neutralization ratio 70~120%, more preferably neutralization ratio 80~ 120%.Within the above range by the degree of neutralization after making above-mentioned coating manufacture, sour major part becomes the state being neutralized, With the combinations such as Li ions in battery, capacity reduction will not occur, it is advantageous to.Neutralizing salt is, for example,：Li salt, Na salt, K salt, ammonium Salt, Mg salt, Ca salt, Zn salt, Al salt etc..
The physical characteristic ＞ of ＜ (A) ingredient
(A) weight average molecular weight (Mw) of ingredient is not particularly restricted, and the upper limit of weight average molecular weight (Mw) is, for example, 600 Ten thousand, 5,500,000,5,000,000,4,500,000,4,000,000,3,500,000,3,000,000,2,500,000,2,000,000,1,500,000,1,000,000,950,000,900,000,85 Ten thousand, 800,000,750,000,700,000,650,000,600,000,550,000,500,000,450,000,400,000 etc., lower limit is, for example, 5,500,000,5,000,000,450 Ten thousand, 4,000,000,3,500,000,3,000,000,2,900,000,2,500,000,2,000,000,1,500,000,1,000,000,950,000,900,000,850,000,800,000,750,000, 700000,650,000,600,000,550,000,500,000,450,000,400,000,350,000,300,000 etc..In one embodiment, from lithium ion battery From the viewpoint of the dispersion stabilization of slurry, the weight average molecular weight (Mw) of (A) ingredient is preferably 300,000~6,000,000, more preferably It is 350,000~6,000,000.
(A) upper limit of the number-average molecular weight (Mn) of ingredient is, for example, 6,000,000,5,500,000,5,000,000,4,500,000,4,000,000,350 Ten thousand, 3,000,000,2,500,000,2,000,000,1,500,000,1,000,000,950,000,900,000,850,000,800,000,750,000,700,000,650,000,600,000,55 Ten thousand, 500,000,450,000,400,000,300,000,200,000,100,000,50,000 etc., lower limit is, for example, 5,500,000,5,000,000,4,500,000,4,000,000,350 Ten thousand, 3,000,000,2,900,000,2,500,000,2,000,000,1,500,000,1,000,000,950,000,900,000,850,000,800,000,750,000,700,000,650,000,60 Ten thousand, 550,000,500,000,450,000,400,000,350,000,300,000,200,000,100,000,50,000,10,000 etc..In one embodiment, (A) ingredient Number-average molecular weight (Mn) be preferably 10,000 or more.
Weight average molecular weight and number-average molecular weight, which are for example used as, to be measured by gel permeation chromatography (GPC) under appropriate solvent Polyacrylic acid scaled value find out.
(A) the Type B viscosity of ingredient is not particularly restricted, and the upper limit is, for example, 100,000 mPas, 90,000 mPas, 80,000 MPas, 70,000 mPas, 60,000 mPas, 50,000 mPas, 40,000 mPas, 30,000 mPas, 20,000 mPas, 10,000 mPas, 9000mPa·s、8000mPa·s、7000mPa·s、6000mPa·s、5000mPa·s、4000mPa·s、3000mPa·s、 2000mPas etc., lower limit are, for example, 90,000 mPas, 80,000 mPas, 70,000 mPas, 60,000 mPas, 50,000 mPas, 40,000 MPas, 30,000 mPas, 20,000 mPas, 10,000 mPas, 9000mPas, 8000mPas, 7000mPas, 6000mPas, 5000mPas, 4000mPas, 3000mPas, 2000mPas, 1000mPas etc..In a reality It applies in mode, the Type B viscosity of (A) ingredient ranges preferably from 1000~100,000 mPas.In addition, Type B viscosity is produced using eastern machine The Brookfield viscometers such as the manufacture of industry Co., Ltd., trade name " Brookfield viscometer BM types " are measured.
(silicol based compound (A1) (also referred to as (A1) ingredient))
In this application, silicol based compound refers to the structure that there is hydroxyl (- OH) to bind directly on the silicon atoms Compound；Ortho-siliformic acid based compound refers to ortho-siliformic acid base (- Si (OH)3) compound；Tetrahydroxy silane Based compound refers to Si (OH)4The compound of expression.
In one embodiment, ortho-siliformic acid based compound is the compound indicated with the following general formula：
RSi(OH)3
(in formula, R indicates substituted or unsubstituted alkyl, vinyl or (methyl) acryloxy, and above-mentioned substituent group is for example It is：Amino, sulfydryl, glycidoxypropyl, (methyl) acryloxy, epoxy group etc.)
Silane coupling agent and tetraalkoxysilane are preferably hydrolyzed and are carried out by the silicol based compound (A1) of the present invention It prepares.The silicol based compound (B) of the present invention is not being lost in water-soluble range, can also partly polycondensation.Silane Coupling agent can use the silane coupling agent generally used in the technical field of the invention.
Silane coupling agent is not particularly restricted.The silicol based compound (A1) manufactured by silane coupling agent can be single It solely uses, two or more merging can also be used.In one embodiment, silicol based compound (B) includes trihydroxy Propyl.
Trialkoxy silane is, for example,：3- TSL 8330s, 3-aminopropyltriethoxysilane, N-2 (amino-ethyl) 3- TSL 8330s, N-2 (amino-ethyl) 3-aminopropyltriethoxysilane, tri- ethoxies of 3- Base silane base-N- (1,3- dimethyl-butylidene) propylamine, N- phenyl -3- TSL 8330s, 3- mercaptopropyis three Methoxy silane, 3- isocyanatopropyls triethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3- Methacryloxypropyl trimethoxy silane, 3- methacryloxypropyls, 3- acryloxies Propyl trimethoxy silicane, tetrahydroxy silane etc..
Meanwhile tetraalkoxysilane is, for example,：Tetramethoxy-silicane, tetramethoxy-silicane oligomer, tetraethoxysilane, Tetraethoxysilane oligomer etc..
Wherein, from from the viewpoint of the stability and electrolyte resistance of water-soluble polymer (A), it is preferable to use 3- amino Propyl trimethoxy silicane manufactures silicol based compound.
Mechanism
Alkoxyl silicone alkanes generates multiple silanol groups by hydrolyzing.The silanol group (SiOH) has and siloxanes key (Si-O-Si) balanced reaction, there are siloxanes keys for a part.Lithium ion battery binder aqueous solution or aftermentioned lithium from In sub- battery slurry, because most of exist as silanol group, it is possible to present aqueous solution storage stability or Stability of Slurry.In addition, this mechanism is only a kind of theory, being not intended to makes the present invention be constrained by the theory.
In order to make to stabilize in these silanol groups, preferably by lithium ion battery binder aqueous solution or lithium ion battery It is adjusted in a certain range with the pH of slurry.The range of suitable pH is even because of the silane as silicol based compound raw material Join agent and it is different.
In 3- TSL 8330s, 3-aminopropyltriethoxysilane, N-2- (amino-ethyl) 3- amino Propyl trimethoxy silicane, N-2- (amino-ethyl) 3-aminopropyltriethoxysilane, 3- triethoxysilicane alkyl-N- (1, 3- dimethyl-butylidene) in propylamine, the ranging from pH 9~12 of above-mentioned suitable pH.
In N- phenyl -3- TSL 8330s, 3- mercapto propyl methyl dimethoxy silanes, 3- mercaptopropyis Trimethoxy silane, 3- isocyanatopropyls triethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3- glycidyl ether oxypropyltrimethoxysilanes, 2- (3,4- epoxycyclohexyls) ethyl trimethoxy silane, 3- shrink sweet Oily ether oxygen base propyl-triethoxysilicane, 3- methacryloxypropyl trimethoxy silanes, 3- methacryloxies third Ethyl triethoxy silicane alkane, 3- acryloyloxypropyltrimethoxysilanes, tetramethoxy-silicane, tetramethoxy-silicane oligomer, In tetraethoxysilane, tetraethoxysilane oligomer, the ranging from pH 2~5 of above-mentioned suitable pH.
The manufacturing method of tetrahydroxy silane-based compound (ortho-siliformic acid based compound)
Method as hydrolysis is not particularly restricted, e.g. following methods etc.：Into water or water-alcohol mixed solution, Above-mentioned silane coupling agent is added, be hydrolyzed into muddy disappearance and homogenizes, uses the sol solution for promoting part condensation reaction.
Above-mentioned sol solution can be mixed using following any methods, modulates the lithium ion battery of the present invention Use slurry：
It is mixed in the monomer solutions such as compound with (methyl) acrylamido
It is mixed after the aqueous solution for manufacturing the water-soluble polymer (A) with amide groups
Dispersive electrode active material (B) and ceramics are micro- in the aqueous solution of the water-soluble polymer (A) with amide groups It is mixed after grain (C).
Relative to water-soluble polymer (A), the content of silicol based compound (A1) is not particularly restricted.Relative to The upper limit of 100 mass % of water-soluble polymer (A), the content of silicol based compound (A1) are, for example, 15 mass %, 13 matter %, 10 mass %, 9 mass %, 5 mass %, 3 mass %, 1 mass % etc. are measured, lower limit is, for example, 13 mass %, 10 mass %, 9 Quality %, 5 mass %, 3 mass %, 1 mass %, 0.5 mass % etc..The range of above-mentioned content can be appropriate (such as from above-mentioned Selected in the value of upper and lower bound) setting.In one embodiment, above-mentioned content is preferably 0.5~15 mass %；From hydroxyl The additive effect of silane-based compound (A1) and prevent the agglutination particle shape of electrode active material (B) or ceramic particle (C) at equal sight It is more preferably 1~10 mass % from the point of view of point.
＜ additives ＞
Lithium ion battery binder aqueous solution can contain neither (A) ingredient, nor (A1) ingredient, nor water Ingredient as additive.Additive is, for example,：Dispersant, levelling agent, antioxidant, tackifier, dispersion (lotion), crosslinking Agent etc..Relative to 100 mass % of (A) ingredient, the content of additive is, for example, 0~5 mass %, is less than 1 mass %, is less than 0.1 Quality %, it is less than 0.01 mass %, 0 mass % etc.；Meanwhile relative to 100 mass % of above-mentioned aqueous solution, the content example of additive 0~5 mass % in this way, it is less than 1 mass %, is less than 0.1 mass %, is less than 0.01 mass %, 0 mass % etc..
Dispersant is, for example,：Anionic property compound, cationic compound, nonionic compound, macromolecule chemical combination Object etc..
Levelling agent is, for example,：Alkyl system surfactant, silicon-based surfactant, fluorine system surfactant, metal system table Surfactants such as face activating agent etc..By using surfactant, the shrinkage cavity (は じ I) generated when coating, Ke Yiti are prevented The flatness of the layer (coating) of high above-mentioned slurry.
Antioxidant is, for example,：Phenolic compounds, hydroquinone compound, organic phosphine compound, sulphur compound, phenylenediamine Close object, polymer-type phenolic compounds etc..Polymer-type phenolic compounds is the polymer for having in the molecule phenol structure.Polymer-type The weight average molecular weight of phenolic compounds is preferably 200~1000, is more preferably 600~700.
Tackifier are, for example,：The cellulose-based polymer such as carboxymethyl cellulose, methylcellulose, hydroxypropyl cellulose and Their ammonium salt and alkali metal salt；(modification) poly- (methyl) acrylic acid and their ammonium salt and alkali metal salt；(modification) poly- second The copolymer of vinyl-ethyl alcohol, acrylic acid or acrylates and allylcarbinol, maleic anhydride or maleic acid or fumaric acid and second The polyvinyls ethyl alcohol class such as copolymer of vinyl-ethyl alcohol；Polyethylene glycol, polyvinylpyrrolidone, is modified and gathers polyethylene oxide Acrylic acid, oxidized starch, starch phosphate, casein, various modified starches, acrylonitrile-butadiene copolymer hydride etc..
Dispersion (lotion) is e.g.：Styrene-butadiene system copolymer emulsion, gathers polystyrenic polymer latex Butadiene-based polymer emulsion, acrylonitrile-butadiene based copolymer latex, polyurethane series polymer latex, polymethylacrylic acid Methyl esters based polymer latex, methyl methacrylate-butadiene-based copolymer emulsion, polyacrylate based polymer latex, chlorine Ethylene-based polymer latex, vinyl acetate system polymer emulsion, vinyl based copolymer lotion, polyethylene breast Liquid, carboxy-modified styrenebutadiene copolymer resin emulsion, emulsion acrylic resin, polyethylene, polypropylene, poly terephthalic acid Glycol ester, polyamide (PA), polyimides (PI), polyamidoimide (PAI), aromatic polyamides, alginic acid and its salt gather Vinylidene (PVDF), polytetrafluoroethylene (PTFE) (PTFE), tetrafluoraoethylene-hexafluoropropylene copolymer (FEP), tetrafluoroethylene-perfluoro alkane Base vinyl ether co-polymer (PFA), ethylene-tetrafluoroethylene copolymer (ETFE) etc..
Crosslinking agent is, for example,：Formaldehyde, glyoxal, hexa, urea-formaldehyde resin, melamine methylol tree Fat, carbodiimide compound, multi-group epoxy compound, oxazoline compounds, polyfunctional group hydrazide compound, isocyanic acid Ester compounds, melamine compound, urea compounds and their mixture.
Lithium ion battery uses binder aqueous solution can be as lithium ion cell electrode binder aqueous solution, lithium-ion electric Pond cathode binder aqueous solution, lithium ion cell positive binder aqueous solution, lithium ion battery separator adhesive are water-soluble Liquid uses.
[2. lithium ion battery slurries：Also referred to as slurry]
The application provides lithium ion battery slurry, and the lithium ion battery slurry contains：
Water-soluble polymer (A) with amide groups；With
As ortho-siliformic acid based compound and/or the silicol based compound (A1) of tetrahydroxy silane-based compound.
In this application, " slurry " refers to the suspension of liquid and solid particle.
Above-mentioned lithium ion battery slurry can also contain the adhesive other than (A) ingredient, (A) in all adhesives at Point content be preferably 90 mass % or more (such as 91 mass % or more, 95 mass % or more, the above % of 98 mass, 99 matter Measure % or more, 100 mass %).
In addition, the adhesive other than (A) ingredient can be used alone, two or more merging can also be used；(A) ingredient Adhesive in addition is, for example,：Fluorine resin (Kynoar, polytetrafluoroethylene (PTFE) etc.), polyolefin (polyethylene, polypropylene etc.), Polymer (SBR styrene butadiene rubbers, isoprene rubber, butadiene rubber etc.), acrylic acid series with unsaturated bond are poly- Close object (acrylic copolymer, methacrylic acid copolymer), carboxymethyl cellulose salt, polyvinyl alcohol copolymer, polyethylene Base pyrrolidones etc..
＜ electrode active materials (B)：Also referred to as (B) ingredient ＞
In one embodiment, above-mentioned lithium ion battery slurry contains electrode active material (B).Electrode active material E.g. negative electrode active material, positive active material.
It, can be with as long as the substance that can lithium reversibly received and be discharged, negative electrode active material are not particularly restricted Suitably select suitable material from the type as the lithium ion battery of target, can be used alone, can also by two kinds with Upper merging uses.Negative electrode active material is, for example,：Carbon material and silicon materials, the oxide containing lithium atom, lead compound, tin Close the material etc. that object, arsenic compound, antimonial and aluminium compound etc. carry out alloying with lithium.
Above-mentioned carbon material is, for example,：Graphite (also referred to as blacklead, such as natural graphite, artificial graphite as highly crystalline carbon Deng), low crystalline carbon (soft carbon, hard carbon), carbon black (black, thermal black of Ketjen black, acetylene black, channel black, lampblack, oil oven etc.), fowler Alkene, carbon nanotube, carbon nano-fiber, carbon nanohorn, carbon fiber silk, carbonaceous mesophase spherules (MCMB), pitch-based carbon fiber etc..
Above-mentioned silicon materials are other than silicon, silica, silicon alloy, such as also have：SiC；SiOxCy(0 x≤3 ＜, 0 ＜ y≤ 5)；Si3N4；Si2N2O；With SiOxThe silica composite that (0 x≤2 ＜) indicate is (such as in Japanese Unexamined Patent Publication 2004-185810 public affairs Material etc. described in report and Japanese Unexamined Patent Publication 2005-259697 bulletins)；Remember in Japanese Unexamined Patent Publication 2004-185810 bulletins The silicon materials etc. of load.It is also possible to use described in Japanese Patent Publication No. 5390336, Japanese Patent Publication No. 5903761 Silicon materials.
Above-mentioned silica is preferably with structural formula SiOxThe silica that (0 ＜ x ＜ 2, preferably 0.1≤x≤1) indicates.
Above-mentioned silicon alloy is preferably the alloy of silicon and at least one transition metal, the transition metal be selected from by titanium, zirconium, The group of nickel, copper, iron and molybdenum composition.The silicon alloy of these transition metal is with high electron conductivity and with high intensity, so excellent Choosing.Silicon alloy is more preferably silicon-nickel alloy or silicon-titanium alloy, particularly preferably silicon-titanium alloy.Relative in above-mentioned alloy 100 moles of % of metallic element, the content ratio of silicon is preferably 10 moles of % or more in silicon alloy, is more preferably rubbed for 20~70 You are %.In addition, silicon materials can be any one of monocrystalline, polycrystalline and amorphous.
Meanwhile in the case where using silicon materials as electrode active material, it can merge using the electricity other than silicon materials Pole active material.Such electrode active material is, for example,：Above-mentioned carbon material；The electroconductive polymers such as polyacene；AXBYOZ(A tables Show alkali metal or transition metal；B indicates at least one selected from the transition metal such as cobalt, nickel, aluminium, tin, manganese；O indicates that oxygen is former Son；X, Y and Z is the number of the range of 0.05 ＜ X ＜ 1.10,0.85 ＜ Y ＜ 4.00,1.5 ＜ Z ＜ 5.00 respectively) indicate compound Metal oxide；And other metal oxides etc..In the case where using silicon materials as electrode active material, with lithium The volume change for receiving and discharging and occurring is small, and it is advantageous to merge use with carbon material.
The above-mentioned oxide containing lithium atom is, for example,：Ternary system nickle cobalt lithium manganate, lithium-manganese composite oxide (LiMn2O4 Deng), lithium-ni compound oxide (LiNiO2Deng), lithium-cobalt composite oxide (LiCoO2Deng), lithium-iron composite oxides (LiFeO2 Deng), lithium-nickel-manganese composite oxide (LiNi0.5Mn0.5O2Deng), lithium-nickel-cobalt composite oxides (LiNi0.8Co0.2O2Deng), lithium- Transition metal phosphate compound (LiFePO4Deng) and lithium-transition metal sulphate (LixFe2(SO4)3), lithium-titanium composite oxygen Compound (lithium titanate：Li4Ti5O12) etc. lithiums-compound transition metal oxide and other previously known electrode active material etc..
From the viewpoint of the notable effect for playing the present invention, the material that alloying is carried out with carbon material and/or with lithium exists It is preferably further preferably to contain containing 80 mass % or more containing 50 mass % or more, more preferably in electrode active material There are 90 mass % or more, particularly preferably contains 100 mass %.
Positive active material can totally be divided into the active material containing inorganic compound and the activity containing organic compound Substance.The inorganic compound contained in positive active material is, for example,：Transition metal oxide, lithium and transition metal it is compound Oxide, transient metal sulfide etc..Above-mentioned transition metal is, for example,：Fe, Co, Ni, Mn, Al etc..In positive active material The inorganic compound used is, for example,：LiCoO2、LiNiO2、LiMnO2、LiMn2O4、LiFePO4、LiNi1/2Mn3/2O4、LiCo1/ 3Ni1/3Mn1/3O2、Li[Li0.1Al0.1Mn1.9]O4、LiFeVO4Deng the metal composite oxide containing lithium；TiS2、TiS3, amorphous MoS2Equal transient metal sulfides；Cu2V2O3, amorphous V2O-P2O5、MoO3、V2O5、V6O13Equal transition metal oxides etc..These Compound can be the compound of Partial Elements substitution.The organic compound contained in positive active material is, for example,：Poly- second Alkynes gathers to electric conductive polymers such as benzene etc..Since the ferrous oxide of poorly conductive makes carbon source material exist when restoring sintering, It thus can also be used as and used with the electrode active material that carbon material coats.Meanwhile these compounds can also be Partial Elements Substituted compound.Wherein, from practicability, electrical characteristics, long lifespan in terms of, preferably LiCoO2、LiNiO2、LiMnO2、 LiMn2O4、LiFePO4、LiNi1/2Mn3/2O4、LiCo1/3Ni1/3Mn1/3O2、Li[Li0.1Al0.1Mn1.9]O4。
The shape of electrode active material is not particularly restricted, and can be the arbitrary shape such as microgranular, film-form, preferably It is microgranular.The average grain diameter of electrode active material is not particularly restricted, and the upper limit is, for example, 50 μm, 45 μm, 40 μm, 35 μ M, 30 μm, 25 μm, 20 μm, 15 μm, 10 μm, 5 μm, 4 μm, 3 μm, 2.9 μm, 2 μm, 1 μm, 0.5 μm, 0.1 μm etc., lower limit is, for example, 45μm、40μm、35μm、30μm、25μm、20μm、15μm、10μm、5μm、4μm、3μm、2.9μm、2μm、1μm、0.5μm、0.1μm Deng.In one embodiment, from the viewpoint for being formed uniformly thin film specifically, if average grain diameter 0.1 μm with On then operability it is good, if the coating for being easy progress electrode if 50 μm or less, therefore, the average grain diameter of electrode active material Preferably 0.1~50 μm, be more preferably 0.1~45 μm, further preferably 1~10 μm, particularly preferably 5 μm.
In this application, " grain size " refers to the maximum distance in the distance between arbitrary 2 points on the contour line of particle (the same below).In this application simultaneously, if be not specifically stated, " average grain diameter " refers to using scanning electron microscope (SEM) and the Observations Means such as transmission electron microscope (TEM), using the particle observed in several visuals field to dozens of The calculated value (the same below) of mean particle size institute.
Relative to the 100 mass % of electrode active material (B) in above-mentioned slurry, aforementioned water-soluble polymer (A) and aforementioned The upper limit of its total content of silicol based compound (A1) be, for example, 12 mass %, 11 mass %, 10 mass %, 9 mass %, 8 mass %, 7 mass %, 6 mass %, 5 mass %, 4 mass %, 3 mass %, 2.5 mass % etc., lower limit is, for example, 11 matter Measure %, 10 mass %, 9 mass %, 8 mass %, 7 mass %, 6 mass %, 5 mass %, 4 mass %, 3 mass %, 2 mass % Deng.In one embodiment, relative to 100 mass % of electrode active material (B), aforementioned water-soluble polymer (A) and aforementioned Total content of silicol based compound (A1) is preferably 2~12 mass %.
In one embodiment, from the viewpoint of the battery capacity for improving lithium ion battery, relative to electrode activity 100 mass % of substance, in electrode active material the content of silicon or silica be preferably 20 mass % or more (such as 30 mass % with Upper, 40 mass % or more, 50 mass % or more, 60 mass % or more, 70 mass % or more, 80 mass % or more, 90 mass % Above, 100 mass %).
In one embodiment, conductive auxiliary agent can be contained in above-mentioned slurry.Conductive auxiliary agent is, for example,：Vapor grown carbon The fibrous carbons such as fiber (VGCF), carbon nanotube (CNT), carbon nano-fiber (CNF)；Blacklead particle, acetylene black, Ketjen black, stove Black equal carbon blacks；The micropowder etc. formed by average grain diameter 10 μm of Cu, Ni, Al, Si below or their alloy.Relative to electrode The content of active material ingredients, conductive auxiliary agent is not particularly restricted, preferably 0~10 mass %, is more preferably 0.5~6 matter Measure %.
＜ ceramic particles (C)：Also referred to as (C) ingredient ＞
In one embodiment, above-mentioned lithium ion battery slurry contains ceramic particle (C).Ceramic particle is porous The ingredient of the active material side coating of vistanex base material, plastics non-woven fabrics, electrode material, the ceramic particle is from each other Gap can form hole.Because ceramic particle has non-conductive, it is possible to insulating properties is played, accordingly it is possible to prevent lithium Short circuit in ion battery.Meanwhile because ceramic particle usually have high rigidity, it is possible to improve lithium ion battery with every The mechanical strength of film.Therefore, even being answered by what heat generation was shunk on porous polyolefin resin base material, plastics non-woven fabrics In the case of power, diaphragm for lithium ion battery can be resistant to the stress.As a result, it is possible to prevent by porous polyolefin resin base Material, plastics non-woven fabrics contraction caused by short-circuit generation.
By using ceramic particle, dispersion stabilization in water is excellent, and difficulty is settled in lithium ion battery slurry, Uniform slurry form can be maintained for a long time.Meanwhile if using ceramic particle, heat resistance can be improved.In addition, ceramics are micro- Grain can be used alone, and can also use two or more merging.
The material of ceramic particle is preferably electrochemically stable material.From this point of view, ceramic particle is, for example,： Oxide particle, nitride particles, covalent crystal particle, slightly solubility ionic crystals particle, small bits of clay etc..
Oxide particle is, for example,：Hydrate (boehmite (AlOOH), the three water aluminium of aluminium oxide (ア Le ミ Na), aluminium oxide Stone (Al (OH)3), bakelite (ベ ー Network ラ イ ト), iron oxide, silica, magnesia (マ グ ネ シ ア), magnesium hydroxide, oxidation Calcium, titanium oxide (チ タ ニ ア), BaTiO3, ZrO, alumina silica composite oxides etc..
Nitride particles are, for example,：Aluminium nitride, silicon nitride, boron nitride etc..
Covalent crystal particle is, for example,：Silicon, diamond etc..
Slightly solubility ionic crystals particle is, for example,：Barium sulfate, calcirm-fluoride, barium fluoride etc..
Small bits of clay is, for example,：Small bits of clay such as silica, talcum, montmorillonite etc..
Wherein, from the viewpoint of low from water imbibition, excellent heat resistance, preferably boehmite, aluminium oxide, magnesia and sulfuric acid Barium, more preferably boehmite.
The upper limit of the average grain diameter of ceramic particle is, for example, 30 μm, 25 μm, 20 μm, 15 μm, 10 μm, 5 μm, 1 μm, 0.5 μm, 0.1 μm, 0.05 μm etc., lower limit is, for example, 25 μm, 20 μm, 15 μm, 10 μm, 5 μm, 1 μm, 0.5 μm, 0.1 μm, 0.05 μm, 0.01 μ M etc..In one embodiment, the average grain diameter of ceramic particle is preferably 0.01~30 μm.
Relative to 100 mass % of above-mentioned slurry, the upper limit of the content of ceramic particle (C) is, for example, 99.9 mass %, 95 matter Measure %, 90 mass %, 80 mass %, 70 mass %, 60 mass %, 50 mass %, 40 mass %, 30 mass %, 20 mass %, 10 mass %, 5 mass %, 1 mass %, 0.5 mass %, 0.2 mass % etc., lower limit are, for example, 95 mass %, 90 mass %, 80 Quality %, 70 mass %, 60 mass %, 50 mass %, 40 mass %, 30 mass %, 20 mass %, 10 mass %, 5 matter Measure %, 1 mass %, 0.5 mass %, 0.2 mass %, 0.1 mass % etc..In one embodiment, relative to 100 matter of slurry % is measured, 0.1~99.9 mass % of ceramic particle (C) is contained.
In above-mentioned slurry, relative to 100 mass % of ceramic particle (C), aforementioned water-soluble polymer (A) and aforementioned hydroxy silicon The upper limit of total content of alkyl compound (A1) is, for example, 15 mass %, 14 mass %, 13 mass %, 12 mass %, 11 matter Measure %, 10 mass %, 9 mass %, 8 mass %, 7 mass %, 6 mass %, 5 mass %, 4 mass %, 3 mass %, 2 matter %, 1.5 mass % etc. are measured, lower limit is, for example, 14 mass %, 13 mass %, 12 mass %, 11 mass %, 10 mass %, 9 matter Measure %, 8 mass %, 7 mass %, 6 mass %, 5 mass %, 4 mass %, 3 mass %, 2 mass %, 1.5 mass %, 1 matter Measure % etc..In one embodiment, relative to 100 mass % of ceramic particle (C), aforementioned water-soluble polymer (A) and aforementioned Total content of silicol based compound (A1) is preferably 1~15 mass %, is more preferably 1.5~14 mass %, further Preferably 2~12 mass %.By having such content, it can manufacture that adherence is more excellent and resistance is small thus charge and discharge The more excellent lithium ion battery separator of electrical characteristics.
＜ slurry viscosities adjust solvent ＞
Slurry viscosity adjustment solvent is not particularly restricted, as long as including with the non-of 80~350 DEG C of normal boiling point Water-medium.Slurry viscosity adjustment solvent can be used alone, and can also use two or more merging.Slurry viscosity tune Whole solvent is, for example,：The amide solvents such as N-Methyl pyrrolidone, dimethylformamide, DMAC N,N' dimethyl acetamide；Toluene, diformazan The hydrocarbon solvents such as benzene, n-dodecane, naphthane；Methanol, ethyl alcohol, 2- propyl alcohol, isopropanol, 2- ethyl -1- hexanols, 1 nonyl alcohol, bay The alcoholic solvents such as alcohol；The ketone solvents such as acetone, methyl ethyl ketone, cyclohexanone, phorone, acetophenone, isophorone；Dioxane, four The ether solvents such as hydrogen furans (THF)；The ester solvents such as benzyl acetate, isoamyl butyrate, methyl lactate, ethyl lactate, butyl lactate；It is adjacent The amine solvents such as toluidines, meta-aminotoluene, para-totuidine；The lactones such as gamma-butyrolacton, δ-butyrolactone；Dimethyl sulfoxide (DMSO), sulfolane etc. Sulfoxide-sulfoxide solvent；Water etc..Wherein, in terms of coating operations, preferred N-Methyl pyrrolidone.Above-mentioned non-water system matchmaker The content of body is not particularly restricted, relative to 100 mass % of above-mentioned slurry, preferably 0~10 mass %.
Do not lose the present invention effect in the range of, above-mentioned slurry can contain be not belonging to (A) ingredient, (A1) ingredient, (B) any one of ingredient, (C) ingredient, water, conductive auxiliary agent, slurry viscosity adjustment solvent matter are as additive.Additive is for example Be " lithium ion battery binder aqueous solution " project in above-mentioned additive etc..Relative to 100 mass % of (A) ingredient, add Add the content of agent to be, for example, 0~5 mass %, be less than 1 mass %, be less than 0.1 mass %, be less than 0.01 mass %, 0 mass % Deng；Meanwhile relative to 100 mass % of (B) ingredient or (C) ingredient, the content of additive is, for example, 0~5 mass %, is less than 1 matter Measure %, be less than 0.1 mass %, be less than 0.01 mass %, 0 mass % etc..
Above-mentioned lithium ion battery uses slurry that can be starched as pulp for lithium ionic cell electrode, negative electrode of lithium ion battery Material, lithium ion cell positive slurry, lithium ion battery separator are used with slurry.
[manufacturing methods of 3. lithium ion battery slurries]
The application provides the manufacturing method of above-mentioned lithium ion battery slurry, includes the following steps：It will be with amide groups Water-soluble polymer (A) and the silicol base as ortho-siliformic acid based compound and/or tetrahydroxy silane-based compound Object (A1) is closed to be mixed.In addition, (A) ingredient etc. described in this project is, for example, previously described ingredient etc..
The manufacturing method of above-mentioned slurry is for example：By the ingredient (electrode activity other than the aqueous solution of (A) ingredient and (A) ingredient Substance (B) and ceramic particle (C) etc.) method that is mixed；By the ingredient (electrode activity thing other than (A) ingredient, (A) ingredient Matter (B) and ceramic particle (C) etc.), the method that is mixed respectively of water.In addition, the sequence mixed in the above-mentioned methods not by It is particularly limited to.The mixed media of slurry is, for example,：Ball mill, sand mill, pigment dispersion machine, mixing and kneading machine, ultrasonic dispersing machine, Matter machine, planetary stirring machine, Hobart's blender etc..
[4. lithium ion battery electrode]
Above-mentioned lithium ion battery is coated with slurry and is allowed to obtained from drying, is collecting by the application offer on the current collector Electric body surface face has the lithium ion battery electrode of the dried object of above-mentioned lithium ion battery slurry.
Collector uses various well known collectors in which can be not particularly limited.The material of collector is not limited especially It is fixed, e.g.：The metal materials such as copper, iron, aluminium, nickel, stainless steel, nickel-plated steel；And the carbon materials such as carbon cloth, carbon paper.Collector Form is also not particularly limited, in the case of metal material, e.g. metal foil, metal cylinder, wire coil, metallic plate Deng；In the case of carbon material, e.g. carbon plate, C film, carbon cylinder etc..Wherein, electrode active material is being used for cathode In the case of, use copper foil as collector in present industrial product, it is advantageous to.
Coating means are not particularly restricted, e.g.：Comma coating machine, gravure coater, micro gravure coating machine, mould Have the previously known coating units such as coating machine, metering bar coater.
Drying means is also not particularly limited, and temperature is preferably 60~200 DEG C, is more preferably 100~195 DEG C.Atmosphere is Dry air or inert atmosphere.
The thickness of electrode (cured coating film) is not particularly restricted, preferably 5~300 μm, is more preferably 10~250 μm. Within the above range, the function of receiving-discharge of the sufficient Li for highdensity current value can be easy to get.
It is described below using containing the water-soluble polymer (A) and silicol based compound (A1) with amide groups The continuation of the journey for the battery capacity that aqueous solution or slurry are played stably when being manufactured and resistance to elastic mechanism, however be only one kind Theory, being not intended to makes the present invention be constrained by the theory.
Mechanism
When slurry to be coated and dry, water volatilization, the chemical balance of silanol group and siloxanes key is to siloxanes Key generates side and substantially moves.It interacts at this point, generating strong hydrogen bond between polyacrylamide and the silanol group of remaining, Occur between polyacrylamide and polysiloxane chain it is intermolecular interpenetrate (Interpenetration), formed intensity it is high Polyacrylamide-silicone composites.And at the same time the silanol group of polysiloxanes acts on collector surface, show Strong binding force.As a result, due to the volume change generation into active material of sening as an envoy to of lithium ion in charge and discharge cycles Under environment, the continuation of the journey of stable battery capacity and resistance to resilience can be obtained.
Above-mentioned lithium ion battery uses electrode that can be used as lithium ion battery anode, negative electrode for lithium ion battery.
[5. diaphragm for lithium ion battery]
Above-mentioned pulp of lithium ion battery is coated with by the application offer on porous polyolefin resin base material or plastics non-woven fabrics And it is starched with above-mentioned lithium ion battery obtained from being allowed to dry, on the surface of porous polyolefin resin base material or plastics non-woven fabrics Expect the diaphragm for lithium ion battery of dried object.Above-mentioned lithium ion battery both can be only coated on the face of base material side with slurry, It can also be coated on the face of both sides.
Above-mentioned diaphragm for lithium ion battery by with by with amide groups water-soluble polymer (A), be used as trihydroxy The silicol based compound (A1) and ceramic particle (C) of silane-based compound and/or tetrahydroxy silane-based compound are handed over The cross-linked structure that connection reaction is formed, thermal shrinkage, anti-picking property, base material adherence, multiplying power property, output characteristics are carried It is high.
(porous polyolefin resin base material)
In one embodiment, base material is preferably to have ionic conductivity, organic solvent without electronic conductivity The perforated membrane that patience is high, aperture is fine.The perforated membrane can be porous polyolefin resin base material.Porous polyolefin resin base material is Contain the microporous membrane of polyolefin and the resins such as their mixture or copolymer as principal component.Porous polyolefin resin base The coating of material coating liquid in the case where obtaining polymeric layer by coating step is excellent, and the film thickness of diaphragm is thinner, from raising Active material ratio in lithium ion battery is preferred from the viewpoint of increasing the capacity of unit volume.In addition, " as it is main at Divide and contain " refer to containing and being more than 50 mass %, preferably 75 mass % or more, be more preferably 85 mass % or more, it is further excellent 90 mass % or more are selected as, are still more preferably 95 mass % or more, particularly preferably contain 98 mass % or more, it can also It is 100 mass %.
In one embodiment, the content of vistanex is not limited especially in porous polyolefin resin base material It is fixed, from the point of view of the viewpoints such as power-off performance in the case where being used as diaphragm for lithium ion battery, in porous polyolefin resin In base material the content of vistanex be preferably constitute the base material all the components 50 mass % or more and 100 mass % with Under, more preferably for 60 mass % or more and 100 mass % hereinafter, further preferably 70 mass % or more and 100 mass % with Under.
Vistanex is not particularly restricted, the polyolefin used in extrusion, injection, inflation and blow molding etc. Resin can be used alone, and can also use two or more merging.Vistanex is, for example,：Ethylene, propylene, 1- Homopolymer, copolymer, the multi-stage polymers etc. of butylene, 4-methyl-1-pentene, 1- hexenes and 1- octenes etc..It is poly- manufacturing these The polymerization catalyst used when olefin resin is it is not also specifically limited, be, for example,：Ziegler-nata series catalysts, Philips system Catalyst and metallocene series catalysts etc..
The vistanex of materials'use as porous polyolefin resin base material, due to low melting point and high intensity, especially It is preferred that using high density polyethylene (HDPE) as the resin of principal component.Further, from the heat resistance for improving polyolefin porous base material From the point of view of viewpoint, will more preferably merge with the porous polyolefin resin base material of the vistanex other than polypropylene containing polypropylene makes With.
Herein, polyacrylic stereochemical structure is not limited, and can be isotactic polypropylene, syndiotactic polypropylene and random poly- third Any one of alkene.
Relative to the polyolefin total amount contained in polyolefine resin composition, polyacrylic ratio is not limited especially Fixed, from the viewpoint of taking into account heat resistance and good power down function, preferably 1~35 mass % is more preferably 3~20 matter Measure %, further preferably 4~10 mass %.
In the case, the vistanex other than polypropylene is not limited, and is for example, for example,：Ethylene, 1- fourths The homopolymer or copolymer of the alkene such as alkene, 4-methyl-1-pentene, 1- hexenes, 1- octenes.Specifically, poly- other than polypropylene Olefin resin is, for example,：Polyethylene, polybutene, ethylene-propylene randomcopolymer etc..
From the viewpoint of the power-off characteristic that the hole of polyolefin porous base material is occluded by heat fusing, as polypropylene Vistanex in addition is, it is preferable to use low density polyethylene (LDPE), linear low density polyethylene (LLDPE), medium density polyethylene, high density are poly- The polyethylene such as ethylene, ultra-high molecular weight polyethylene.Wherein, it from the viewpoint of intensity, is more preferably measured according to JIS K 7112 Density in 0.93g/cm3Above polyethylene.
For control intensity and hardness, the purpose of percent thermal shrinkage, porous polyolefin resin base material can also contain filler and Compound.Meanwhile for the purpose improved with the adherence of bonding layer, or for the surface of reduction and electrolyte Power, the immersion purpose for improving liquid can use low molecular compound and high-molecular compound to porous polyolefin in advance The surface of resin base material carries out at the plasma of the processing of the electromagnetic wires such as cladding processing, ultraviolet light, corona discharge-plasma (orifice) gas etc. Reason.From electrolyte it is immersion it is high, be easy to get with above-mentioned slurry be coated on base material after it is dry obtained from coating glue From the point of view of in terms of the property, particularly preferably wrapped by the high-molecular compound containing carboxylic acid group, hydroxyl and sulfonic group isopolarity group Cover the porous polyolefin resin base material of processing.
The thickness of porous polyolefin resin base material is not particularly restricted, preferably 2 μm or more, is more preferably 5 μm or more； Preferably 100 μm hereinafter, more preferably for 60 μm hereinafter, further preferably 50 μm or less.Its thickness is adjusted to 2 μm or more, It is preferred from the viewpoint of improving mechanical strength.On the other hand, its thickness is adjusted to 100 μm hereinafter, because reducing electricity The possessive volume of pond septation has the advantageous tendency in terms of the high capacity of battery, it is advantageous to.
(plastics non-woven fabrics)
In one embodiment, from the viewpoint of the adherence and membrane thicknesses with non-woven fabrics, in above-mentioned lithium ion The average fiber footpath of the plastics non-woven fabrics used in battery separator is preferably 1~15 μm, is more preferably 1~10 μm.
In one embodiment, the average pore size of above-mentioned plastics non-woven fabrics is preferably 1~20 μm, more preferably for 3~ 20 μm, further preferably 5~20 μm.If average pore size is less than 1 μm, internal resistance becomes larger, and output characteristics is deteriorated.Another party Face, if average pore size is at 20 μm or more, when generating internal short-circuit occurs sometimes for Li dendrite.
In this application, aperture refers to forming the gap of the synthetic fibers of plastics non-woven fabrics from each other.Meanwhile it is flat Equal fiber footpath refers to the fiber footpath for 20 fibers arbitrarily chosen when measuring fiberoptic fiber diameter from electron scanning micrograph Average value.Similarly, average pore size refer to from electron scanning micrograph measure fiber aperture when, arbitrarily choose 20 The average value in the aperture of root fiber.
In addition, non-woven fabrics preferably only by the average fiber footpath for constituting fiber is 1~10 μm, average pore size is 1~20 μm Synthetic fibers are constituted, and the necessity in the thin and thick of diaphragm is less high, as needed can by average fiber footpath and Aperture merges from aforementioned different synthetic fibers to be used.It, can be by the fibre other than synthetic fibers meanwhile from the viewpoint of equally Dimension is appropriate to merge use.By these fiber (the synthesis trees of average fiber footpath and average pore size outside the range that the application specifies Fiber other than fat fiber and synthetic fibers) merge use in the case of, from the point of view of the viewpoints such as the intensity for ensuring non-woven fabrics, contain Amount be preferably 30 mass % hereinafter, more preferably be 20 mass % hereinafter, further preferably 10 mass % or less.
Synthetic resin as synthetic resin fiber material is, for example,：Polyolefin (polyolefin) is resin, polyester (polyester) be resin, polyvinyl acetate (polyvinyl acetate) it is resin, vinyl-vinyl acetate copolymer (ethylene-vinyl acetate copolymer) resin, polyamide (polyamide) are resin, acrylic acid (acrylic) be resin, polyvinyl chloride (polyvinyl chloride) it is resin, Vingon (polyvinylidene Chloride be resin, polyvingl ether (polyvinyl ether) it is) resin, polyvinyl ketone (polyvinylketone) Be resin, polyether system resin, polyvinyl alcohol (polyvinyl alcohol) be resin, diene (diene) it is resin, polyurethane (polyurethane) be resin, phenol (phenol) be resin, melamine (melamine) it is resin, furans (furan) system Resin, Urea Series resin, aniline (aniline) be resin, unsaturated polyester (UP) (Unsaturated polyester) be resin, Alkyd (alkyd) resin, fluorine (carbon fluorine (fluorocarbon)) are that resin, silicone (silicone) are that resin, polyamide acyl are sub- It is resin, polyimides that amine (polyamide imide), which is resin, polyphenylene sulfide (polyphenylene sulfide), (polyimide) be resin, makrolon (polycarbonate) it is resin, poly methylene imine (polyazomethine) system tree Fat, polyesteramide (polyesteramide) resin, polyether-ether-ketone (polyetheretherketone) are resin, polyparaphenylene Benzo-dioxazole (poly-p-phenylenebenzobisoxazole) resin, polybenzimidazoles (polybenzimidazole) Be resin, ethylene-vinyl alcohol copolymer (ethylene-vinylalcohol copolymer) it is resin etc..Wherein, in order to In the case of improving with the adherence of ceramic particle, preferably polyester based resin, Chelate resin, polyolefin-based resins.Meanwhile If using polyester based resin, acrylic resin, polyamide series resin, the heat resistance of diaphragm can be improved.
Polyester based resin is, for example,：Polyethylene terephthalate (polyethylene terephthalate, PET) System, polybutylene terephthalate (PBT) (polybuthylene terephthalate, PBT) system, poly terephthalic acid propylene glycol Ester (polytrimethylene terephthalate, PPT) system, polyethylene naphthalate (polyethylene Naphthalate, PEN system), polybutylene naphthalate (polybuthylene naphthalate), it is poly- between naphthalenedicarboxylic acid Glycol ester (polyethylene isonaphthalate) system, full-aromatic polyester (fully aromatic polyester) The resins such as system.It is also possible to use the derivative of these resins.In these resins, in order to improve heat resistance, electrolyte Patience, with the zygosity of ceramic particle in the case of, preferred PET series resin.
Chelate resin is, for example,：Resin, the propylene corresponding to acrylonitrile formed by the polymer of acrylonitrile 100% The copolymerization of (methyl) acrylic acid derivative of acid, methacrylic acid, acrylate, methacrylate etc., vinyl acetate etc. Object etc..
Polyolefin-based resins are, for example,：Polypropylene, polyethylene, polymethylpentene, ethylene-vinyl alcohol copolymer, olefin-based Copolymer etc..From the viewpoint of heat resistance, the preferred polypropylene of polyolefin-based resins, polymethylpentene, ethylene vinyl alcohol copolymer Object, olefin copolymer etc..
Polyamide series resin is, for example,：The fatty polyamides such as nylon, poly(p-phenylene terephthalamide), poly- terephthaldehyde Acyl p-phenylenediamine -3,4- diphenyl ether terephthalamide (Port リ-p- Off ェ ニ レ Application テ レ Off タ Le ア ミ De -3,4- ジ Off ェ ニ ル エ ー テ Le テ レ Off タ Le ア ミ De), the Wholly aromatic polyamides such as poly；Aromatics polyamides The partially aromatic polyamide etc. with aliphatic chain in a part for main chain in amine.Wholly aromatic polyamide can be paratype, Any one of bit-type.
Synthetic resin fiber can be the fiber (Single Fiber) formed by single resin, can also be by two or more tree The fiber (composite fibre) that fat is formed.Composite fibre is, for example, core-sheath-type, core shift type, parallel type, fabric of island-in-sea type, orange petal type, double gold Belong to lamination-type (multiple バ イ メ タ Le type).
Meanwhile the fiber that can merge with synthetic resin fiber other than the synthetic resin fiber used is, for example,：Solvent is spun The slurry of the staple fiber and fibril compound, native cellulose fibre, native cellulose fibre of silk fiber element and regenerated cellulose With fibril compound, inorfil etc..
From the viewpoint of obtaining the diaphragm that thickness is thin, internal resistance is small, the thickness of plastics non-woven fabrics is preferably 5~25 μm, it is more preferably 5~15 μm.
The method for coating lithium ion battery with slurry on base material is not particularly restricted, e.g.：Scraper, The various coating methods such as stick, reverse roll, lip (リ ッ プ), mould, curtain, air knife；Soft version, silk screen, hectograph, intaglio plate, ink-jet etc. are various Mode of printing；The transfer modes such as roller transfer, film transfer；Using the mode being pulled upwardly such as dipping by the masking liquid of non-coated face side The mode etc. of peeling.
In the layer (coating) of lithium ion battery slurry, by making the lithium ion battery containing (A) ingredient He (C) ingredient Cross-linking reaction is carried out with slurry, the layer of above-mentioned lithium ion battery slurry can be formed.Cross-linking reaction can be by lithium-ion electric It is carried out when pond is dried with slurry etc..Specifically drying means is, for example,：It is air-dried by warm air, hot wind, low wet wind etc. dry；Vacuum is dry It is dry；Pass through the seasoning etc. of the irradiations such as infrared ray, far infrared and electron beam.
Just from the viewpoint of efficiently removing solvent and low molecular compound in porous film composition, temperature when dry Lower limit be preferably 40 DEG C or more, be more preferably 45 DEG C or more, particularly preferably 50 DEG C or more；From the sight for inhibiting base material thermal deformation From the point of view of point, the upper limit of temperature when dry is preferably 90 DEG C hereinafter, being more preferably 80 DEG C or less.
The lower limit of drying time is preferably 5 seconds or more, is more preferably 10 seconds or more, particularly preferably 15 seconds or more；The upper limit Preferably 3 minutes hereinafter, be more preferably 2 minutes or less.It, can be from more by making drying time more than the lower limit of aforementioned range Solvent is fully removed in the film composition of hole, it is thus possible to improve the output characteristics of battery.Meanwhile by making drying time exist Upper limit value is hereinafter, manufacture efficiency can be improved.
The manufacturing method of above-mentioned diaphragm for lithium ion battery may include arbitrary steps other than the above.Above-mentioned lithium-ion electric The manufacturing method of pond diaphragm may include (being applied to the layer of lithium ion battery slurry with suppressions such as roll-ins by being molded Layer) carry out pressurized treatments the step of.By implementing pressurized treatments, the knot of base material and the layer of lithium ion battery slurry can be improved Conjunction property.But for ensuring in the viewpoint of preferred range by the voidage of the layer of lithium ion battery slurry, preferably suitably Control makes pressure and pressing time be unlikely to excessive.Meanwhile in order to remove residual moisture, the system of above-mentioned diaphragm for lithium ion battery The step of method of making may include by being dried in vacuo and being dried in hothouse etc..
[6. diaphragm for lithium ion battery/electrode laminate]
Lithium-ion electric obtained from above-mentioned pulp of lithium ion battery is coated with and is allowed to dry by the application offer on the electrode Pond diaphragm/electrode laminate.
It is described below using containing water-soluble polymer (A), silicol based compound (A1), pottery with amide groups When the lithium ion battery of porcelain particle (C) and water is manufactured with slurry improve thermal shrinkage, anti-picking property, base material adherence, Multiplying power property, the mechanism of output characteristics, however a kind of only theory, being not intended to makes the present invention be constrained by the theory.
Mechanism
When slurry to be coated and dry, water volatilization, the chemical balance of silanol group and siloxanes key is to siloxanes Key generates side and substantially moves.It interacts at this point, generating strong hydrogen bond between polyacrylamide and the silanol group of remaining, Occur between polyacrylamide and polysiloxane chain it is intermolecular interpenetrate (Interpenetration), formed intensity it is high Polyacrylamide-silicone composites.Cross-linked structure in this way brings thermal shrinkage, anti-picking property, base material adhesion Property, multiplying power property, output characteristics improve effect.It is understood that inhibiting ceramic particle in lithium ion battery to fall off While, the cross-linking reaction with ingredient (A), ingredient (A1) makes the heat resistance of adhesive itself improve.And at the same time ingredient (A1) silanol group acts on ceramic particle surface or acts on the micro- porous polyolefin resin base material being surface-treated And/or the surface of plastics non-woven fabrics, show strong binding force.
The manufacturing method of diaphragm for lithium ion battery/electrode laminate is, for example, the method etc. included the following steps：
The slurry containing electrode materials such as above-mentioned lithium ion battery slurries is coated on the current collector, dry, is pressed The step of processed；
(that is, not being collector side but electrode active material on the dried object of the slurry containing above-mentioned electrode material Side), above-mentioned lithium ion battery is coated with slurry and is allowed to dry step.
In addition, coating method, drying means, condition etc. are, for example, above-mentioned coating method, drying means, condition etc..
[7. lithium ion battery]
The application provides the lithium ion battery containing above-mentioned lithium ion battery electrode.Meanwhile the application is provided containing upper State the lithium ion battery of diaphragm for lithium ion battery and/or above-mentioned diaphragm for lithium ion battery/electrode laminate.In above-mentioned battery In also include electrolyte and packaging material, electrolyte and packaging material be not particularly restricted.
(electrolyte)
Electrolyte is, for example, the non-aqueous electrolyte etc. that supporting electrolyte is dissolved in non-aqueous solvent.Meanwhile upper It states in non-aqueous electrolyte, overlay film forming agent can be contained.
Non-aqueous solvent can use various well known non-aqueous solvents without restriction, can be used alone, can also Two or more merging are used.Non-aqueous solvent is, for example,：The chains carbon such as diethyl carbonate, dimethyl carbonate, methyl ethyl carbonate Acid esters solvent；The cyclic carbonate solvents such as ethylene carbonate ester, propylene glycol carbonate, carbonic acid butanediol ester；1,2- dimethoxys The chains ether solvents such as ethane；The ring-type ether solvents such as tetrahydrofuran, 2- methyltetrahydrofurans, sulfolane, 1,3- dioxolanes；Formic acid The chains ester solvent such as methyl esters, methyl acetate, methyl propionate；The ring-type ester solvent such as gamma-butyrolacton, gamma-valerolactone；Acetonitrile etc..Its In, preferably comprise the combination of cyclic carbonate and the mixed solvent of linear carbonate.
Supporting electrolyte can use lithium salts.Lithium salts can use various well known lithium salts without restriction, can be independent It uses, two or more merging can also be used.Supporting electrolyte is, for example,：LiPF6、LiAsF6、LiBF4、LiSbF6、 LiAlCl4、LiClO4、CF3SO3Li、C4F9SO3Li、CF3COOLi、(CF3CO)2NLi、(CF3SO2)2NLi、(C2F5SO2)NLi Deng.Wherein, it is preferably easy dissolving in a solvent and shows the LiPF of high dissociation degree6、LiClO4、CF3SO3Li.It is got over using degree of dissociation High supporting electrolyte, lithium ion conduction degree is higher, therefore, can adjust lithium ion conduction by the type of supporting electrolyte Degree.
Overlay film forming agent can use various well known overlay film forming agents without restriction, can be used alone, can also Two or more merging are used.Overlay film forming agent is, for example,：Vinylene carbonate base ester, ethylene carbonate base ethylidene ester, carbonic acid second The carbonate products such as alkenyl ethyl ester, methyl phenylester, carbonic acid fluoroethylene ester, two fluoroethylene ester of carbonic acid；Ring The epithios alkane such as sulphur ethane, epithio propane；The sultone compounds such as 1,3- propane sultones, 1,4- butane sultones；Maleic acid Acid anhydrides such as acid anhydride, succinic anhydride etc..The content of overlay film forming agent is not particularly restricted in electrolyte solution, according to 10 mass % with Under, 8 mass % or less, 5 mass % or less and 2 mass % sequences below it is preferred.By making content in 10 mass % hereinafter, covering The advantages of film forming agent, is：The inhibition of initial stage irreversible capacity, the raising of low-temperature characteristics and multiplying power property can be easy to get Deng.
The form of above-mentioned lithium ion battery is not particularly limited.The form of lithium ion battery is, for example,：Make electrode slice (シ ー ト Electricity Very) and diaphragm become spiral helicine cylinder；The inside-out that plate electrode (ペ レ ッ ト Electricity Very) and diaphragm are combined The cylinder of structure；Plate electrode and diaphragm are carried out button-shaped (the U イ Application タ イ プ) etc. of lamination.Meanwhile by by these In the battery outer unexpected packing box in office of form, the arbitrary shape such as coin shape, cylinder type, square can be made and used.
The manufacturing method of above-mentioned lithium ion battery is not particularly restricted, and program groups appropriate is taken according to the structure of battery Dress.The manufacturing method of lithium ion battery is, for example, the method etc. recorded in Japanese Unexamined Patent Publication 2013-089437 bulletins.It can be with Cathode is loaded onto on external packing box, and electrolyte and diaphragm are set on cathode, is loaded on anode, keeps positive electrode and negative electrode opposite, by Gasket (ガ ス ケ ッ ト), hush panel are fixed to manufacture battery.
Embodiment
The present invention is more specifically illustrated hereinafter, enumerating embodiment and comparative example.The present invention is not by following implementation Example limits.In addition, without special instruction, hereinafter " part " and " % " indicates mass parts and quality % respectively.
The manufacture ＞ of ＜ (A) ingredient
Production Example 1
In the reaction unit for having blender, thermometer, reflux condensing tube, nitrogen ingress pipe, ion exchange water is added 3380g, 50% acrylamide aqueous solution 1200g (8.44mol), Sodium methallyl sulfonate (メ タ リ Le ス Le ホ Application acid Na ト リ ウ system) 1.34g (0.0082mol), leads to after the oxygen that nitrogen removes in reaction system, is warming up to 50 DEG C.Herein, input 2,2 '-is even Nitrogen two (2- amidine propanes) dihydrochloride (Nippoh Chemicals Co., Ltd manufactures, trade name " NC-32 ") 6.0g, ion exchange water 60g is warming up to 80 DEG C and carries out reaction 3 hours, obtains the aqueous solution containing the water-soluble polymer with amide groups.
Production Example 2~13
Other than by substance shown in the quantitative change of monomer composition and initiator in above-mentioned Production Example 1 more table 1 and numerical value, The aqueous solution containing the water-soluble polymer with amide groups is modulated in a manner of same as Production Example 1.
[table 1]
·AM：Acrylamide (ケ ミ カ Le Co., Ltd. of Mitsubishi manufactures, " 50% acrylamide ")
·ATBS：Acrylamide tertiary butyl sulfonic acid (Toagosei Co., Ltd manufactures, " ATBS ")
·NMAM：N hydroxymethyl acrylamide (Tokyo Chemical Industry Co., Ltd's manufacture)
·AA：Acrylic acid (Osaka Organic Chemical Industry Co., Ltd. manufactures, " 80% acrylic acid ")
·AN：Acrylonitrile (ケ ミ カ Le Co., Ltd. of Mitsubishi manufactures, " acrylonitrile ")
·HEMA：2-Hydroxyethyl methacrylate (Tokyo Chemical Industry Co., Ltd's manufacture)
·HEA：Acrylic acid -2- hydroxyl ethyl esters (Osaka Organic Chemical Industry Co., Ltd. manufactures, " hydroxy-ethyl acrylate ")
·SMAS：Sodium methallyl sulfonate
Type B viscosity
Using Brookfield viscometer, (Toki Sangyo Co., Ltd. manufactures the viscosity of each binder aqueous solution, trade name " Type B viscosity Meter BM types ") it is measured according to the following conditions at 25 DEG C.
In the case of 100,000~20,000mPas of viscosity：Use No.4 rotors, revolution 6rpm；It is less than in viscosity In the case of 20,000mPas：Use No.3 rotors, revolution 6rpm.
Weight average molecular weight
Weight average molecular weight by gel permeation chromatography (GPC) be used as 0.2M phosphate buffers/acetonitrile solution (90/10, PH8.0 the polyacrylic acid scaled value measured under) is found out.GPC devices are manufactured using HLC-8220 (East ソ ー (Co., Ltd.)), column It uses SB-806M-HQ (SHODEX manufactures).
Embodiment 1-1
(1) manufacture of lithium ion battery binder aqueous solution
In the reaction unit for having blender, thermometer, reflux condensing tube, nitrogen ingress pipe, ion exchange water is added 100g, methanol 100g, 3- TSL 8330 (SHIN-ETSU HANTOTAI's Chemical Co., Ltd. manufacture, trade name " KBM-903 ") 200g carries out reaction 0.5 hour at 25 DEG C, obtains the uniform aqueous solution containing silicol based compound (A1).
Relative to the water-soluble polymer (A) obtained by Production Example 1-1, above-mentioned silicol based compound (A1) 5 is added Mass parts (are converted) with solid constituent, and reaction 0.5 hour is carried out at 25 DEG C, it is water-soluble to obtain uniform lithium ion battery adhesive Liquid.
Embodiment 1-2~1-19, comparative example 1-1~1-13
In addition to by the type of the raw material of silicol based compound (A1) in previous embodiment 1-1 and quantitative change more 2 institute of table Other than the substance and numerical value that show, lithium ion battery binder aqueous solution is obtained in a manner of same as embodiment 1-1.
[table 2]
By obtained water-soluble binder using the glue spreader of 200 μm of thickness to coating glass sheets, it is allowed to do at 120 DEG C Dry 30 minutes, the pencil hardness of obtained resin film is measured according to the method for the ordinary test method for meeting JIS K-5401.
Embodiment 2-1
(2) manufacture of lithium ion battery slurry
Using commercially available rotation-revolution blender, (trade name " あ わ と り Practice Taros ", シ ン キ ー (Co., Ltd.) make Make), it is 5 μm by 7 parts of the aqueous solution (being converted with solid constituent) of embodiment 1-1, D50 in the dedicated container of above-mentioned blender 46.5 mass parts of silicon particle and natural graphite (her vine black plumbing Co., Ltd. manufacture, trade name " Z-5F ") 46.5 mass parts It is mixed.Herein, ion exchange water is added, it is 40% to make solid component concentration, which is placed in aforementioned blender.It connects It, is kneaded after ten minutes in 2000rpm, carries out de-bubble in 1 minute, obtain lithium ion battery slurry.
(3) manufacture of lithium ion battery electrode
On the surface of the collector formed by copper foil, using scraper method by above-mentioned lithium ion battery slurry even spread, It is 25 μm to make the film thickness after drying, after 30 minutes dry at 60 DEG C, handled 120 minutes in 150 DEG C/heating under vacuum and obtains electricity Pole.Thereafter, press process is carried out by using roll squeezer, it is 1.5g/cm to make the density of film (electrode active material layer)3, obtain Electrode.
(4) manufacture of lithium half-cell
In the glove box replaced by argon, the material that above-mentioned electrode punching shaping is diameter 16mm will be loaded into two plate On button battery (precious Izumi Ltd.'s manufacture, trade name " HS Off ラ ッ ト セ Le ").Then, by be punched into diameter 24mm by The diaphragm (CS TECH CO., LTD manufactures, trade name " Selion P2010 ") that polypropylene perforated membrane is formed is loaded, into One step injection 500 μ L of electrolyte prevent air from entering after, load commercially available metallic lithium foil punching shaping be 16mm material, Using screw by the external packing body close encapsulation of aforementioned two plate button battery, to be assembled into lithium half-cell.It is used herein as Electrolyte be in the solvent of ethylene carbonate ester/methyl ethyl carbonate=1/1 (mass ratio), by LiPF6With the dense of 1mol/L Spend the solution of dissolving.
Embodiment 2-2~2-23, comparative example 2-1~2-17
Except silicon particle, natural graphite, the water-soluble binder in embodiment 2-1 are changed according to numerical value shown in table 3 In addition, lithium half-cell is manufactured with operation identical with embodiment 2-1, after carrying out charge and discharge electrometric determination, calculates rebound degree and electric discharge Capacity maintenance rate.
Comparative example 2-18~2-19
Using with the same amount of silicol based compounds of embodiment 2-1, with reference to Japanese Unexamined Patent Publication 2001-216961 public affairs Report, obtains the silicon particle handled through silicol based compound.In addition to by this surface treated silicon particle, natural graphite, Other than water-soluble polymer is changed according to numerical value shown in table 3, similarly to operate manufacture lithium half-cell with embodiment 2-1, After carrying out charge and discharge electrometric determination, rebound degree and discharge capacity sustainment rate are calculated.
[table 3]
＜ electrical characteristics are evaluated：Rebound degree and discharge capacity sustainment rate ＞
(1) charge and discharge electrometric determination
Lithium half-cell through above-mentioned manufacture is placed in 25 DEG C of thermostat, is started to charge up with constant current (0.1C), in voltage As 0.01V time point at charging (cut-off).Then, start to discharge with constant current (0.1C), when voltage becomes 1.0V Between point complete electric discharge (cut-off), electricity repeated 30 times of such charge and discharge.
(2) with the electrode rebound degree of repeated charge
By charge and discharge cycles experiment after (25 DEG C) of the room temperature cycle of progress 30 times, lithium half-cell is decomposed, electrode is measured Thickness.The rebound degree of electrode is found out by following formula.
Rebound degree={ (thickness of electrode-current collection body thickness after 30 cycles)/(thickness of electrode-current collection before charge and discharge Body thickness) } × 100-100 (%)
(3) discharge capacity sustainment rate
Discharge capacity sustainment rate is found out by following formula.
Discharge capacity sustainment rate={ (discharge capacity of the 30th cycle)/(discharge capacity of the 1st cycle) } × 100 (%)
In addition, " 1C " refers in said determination condition, constant-current discharge 1 hour will be carried out with the battery of certain capacitance Afterwards, discharge the current value of end.For example, " 0.1C " refers to the current value for spending electric discharge in 10 hours to terminate, " 10C " refers to spending The current value that electric discharge in 0.1 hour is completed.
Table 3 shows that in the lithium half-cell evaluation made using the binder aqueous solution of embodiment, rebound degree and electric discharge are held The evaluation for measuring sustainment rate is all good.
Meanwhile being compared by table 3 by embodiment 2-1 and comparative example 2-18 or by embodiment 2-2 and comparative example 2-19, Compared with using in the material that active material surface handles silicol based compound, its rebound degree of the material of this formula It is good with the evaluation of discharge capacity sustainment rate.
Embodiment 3-1：The evaluation of diaphragm
(1) manufacture of slurry
37.6 mass parts of aqueous solution (5 mass parts of solid constituent) and 113 mass parts of water that embodiment 1-1 is obtained are stirred Mixing is mixed, boehmite (0.8 μm of average grain diameter) 100 mass parts are added, (IKA societies manufacture, T25digital using homogenizer ULTRA-TURRAX) 15000rpm dispersions stirring 60 minutes.It is viscous that ion exchange water adjustment is further added into obtained slurries Degree manufactures slurry.
(2) manufacture of diaphragm：The lamination of the layer (coating) of diaphragm slurry
Prepare wide 250mm, long 200mm, thick 6 μm of the monolayer polyethylene barrier film base material (PE base materials) manufactured by wet method. The slurries obtained as described above are coated on the face of the side of diaphragm using gravure coater and are dried, makes the thickness after drying It is 3.0 μm, obtains diaphragm for lithium ion battery.
Embodiment 3-2~3-20,3-23, comparative example 3-1~3-13
Other than ceramic particle, binder solution, base material are changed according to numerical value shown in table 4, with embodiment The same modes of 3-1 obtain diaphragm for lithium ion battery.
Embodiment 3-21
The water solubility of glyoxal 1wt% (relative to water-soluble polymer in previous embodiment 3-3) is added in addition to using Other than polymer (A), is equally operated with embodiment 3-3, obtain diaphragm for lithium ion battery.
Embodiment 3-22
Other than slurries are coated in positive side in previous embodiment 3-3, by similarly being grasped with embodiment 3-3 Obtain diaphragm for lithium ion battery.
[table 4]
Thermal shrinkage, anti-picking property, adherence, multiplying power patience and output patience in table are measured by following methods.
＜ thermal shrinkages ＞
The diaphragm obtained by embodiment and comparative example is cut into the square of wide 12cm × long 12cm, is drawn in square interior Go out the length of side be 10cm square as test film.Thermostat by the way that test film to be placed in 150 DEG C, which is placed 1 hour, to be heated Processing.After heat treatment, the area of the square drawn in inside is measured, the change of the front and back area of heat treatment is turned to make It is found out for percent thermal shrinkage, according to following benchmark evaluation heat resistances.Percent thermal shrinkage is smaller to indicate that the thermal shrinkage of diaphragm is better.
○：Percentage reduction of area is less than 1%
△：Percentage reduction of area is 1% less than 3%
×：Percentage reduction of area is 3% or more
The anti-picking property ＞ of ＜
It is rectangular that the diaphragm obtained by embodiment and comparative example is cut into 10cm × 10cm, quality (X0) is correctly weighed, by one Side is pasted onto on ground paper after fixation, the counterweight of diameter 5cm, 900g for being coated using cotton is placed in ceramic layer side, by them With the revolution phase mutual friction 10 minutes of 50rpm.Thereafter, correct quality measurement (X1) once again, by calculating picking according to the following formula (quality %) evaluates the anti-picking of diaphragm according to following benchmark.
Picking property={ (X0-X1)/X0 } × 100
A：Anti- picking property is less than 2 mass %
B：Anti- picking property is in 2 mass % less than 5 mass %
C：Anti- picking property is more than 5 mass %
Adherence (peel strength) ＞ of ＜ diaphragms
The test film that wide 2cm × long 10cm is cut from the diaphragm obtained by embodiment and comparative example, make coating upwardly into Row is fixed.Then, on the surface ceramii layer of the test film, adhesive tape (" the セ ロ テ ー プ (registrars of width 15mm are pressed on one side Mark) " ニ チ バ Application (Co., Ltd.) manufacture)) (according to JIS Z1522 specifications) on one side paste after, under the conditions of 25 DEG C using draw Stretching testing machine, ((" the テ Application シ ロ Application RTM-100 " of Co., Ltd.) エ ー-ア Application De-デ イ manufactures), measures from test film Stress of the one end by the adhesive tape with 30mm/ points of speed when being removed on 180 ° of directions.It measures and carries out 5 times, be scaled each width The value for spending 15mm is calculated its average value as peel strength.Peel strength is bigger, indicates the adhesion strength of base material and ceramic layer The adhesiveness of higher or ceramic layer from each other is higher, is more difficult to from barrier film base material stripped ceramic layer or ceramic layer is shelled from each other From being more difficult to.
＜ multiplying powers patience, output characteristics ＞
(1) manufacture of lamination-type lithium ion battery
Operation is manufactured lamination-type lithium ion battery for measuring multiplying power patience, output characteristics as follows.
The manufacture of (1-1A) cathode
Use commercially available rotation-revolution blender (trade name " あ わ と り Practice Taros ", シ ン キ ー (Co., Ltd.) systems Make), in the dedicated container of above-mentioned blender, by SBR styrene butadiene rubbers (SBR)/carboxymethyl cellulose (CMC) (quality According to solid constituent being scaled 2 parts and natural graphite than 1/1) aqueous solution, (her vine black plumbing Co., Ltd. manufactures, trade name " Z-5F ") 98 parts mixed.Herein, ion exchange water is added, it is 40% to make solid component concentration, which is placed in aforementioned In blender.Then, it is kneaded after ten minutes in 2000rpm, carries out de-bubble in 1 minute, obtain lithium ion battery slurry.By copper Lithium ion battery electrode sizing agent is loaded on the collector that foil is formed, uses blade coating film-like.It will be coated with lithium on the current collector After the material of ion battery electrode slurry makes water volatilization remove in dry 20 minutes at 80 DEG C, adhesion engagement is carried out using roll squeezer. At this point, the density of electrode active material layer is made to be 1.0g/cm3.Binding element is heated 2 hours at 120 DEG C using vacuum drier, It is cut into given shape (rectangle of 26mm × 31mm), obtains the cathode that the thickness of electrode active material layer is 15 μm.
The manufacture of (1-1B) anode
By LiNi as a positive electrode active material0.5Co0.2Mn0.3O288 mass parts and the acetylene black 6 as conductive auxiliary agent Mass parts are mixed as 6 mass parts of Kynoar (PVDF) of adhesive, which is scattered in suitable N- first In base -2-Pyrrolidone (NMP), lithium ion cell positive slurry is manufactured.Then, collector of the aluminium foil as anode is prepared, Lithium ion cell positive slurry is loaded on aluminium foil, becomes membranaceous using blade coating.Coating lithium ion anode is used After aluminium foil after slurry makes NMP volatilizations remove for dry 20 minutes at 80 DEG C, adhesion engagement is allowed to using roll squeezer.At this point, making just The density of pole active material layer is 3.2g/cm2.Binding element is heated 6 hours at 120 DEG C using vacuum drier, be cut into Fixed shape (rectangle of 25mm × 30mm) obtains the anode that the thickness of positive electrode active material layer is 45 μm or so.
The manufacture of (1-2) lamination-type lithium ion battery
Using above-mentioned cathode and above-mentioned anode, lamination-type lithium rechargeable battery is manufactured.Specifically, in anode and cathode Between, by the diaphragm obtained by embodiment and comparative example using rectangular sheet (27 × 32mm, 25 μm of thickness) clamping as pole plate group. The pole plate group is coated using two one group of stack membrane, after three bandings are closed, to as injection electrolysis in bag-shaped composite membrane Liquid.By LiPF in the solvent of ethylene carbonate ester/methyl ethyl carbonate=1/1 (mass ratio)6It is dissolved, is made with the concentration of 1mol/L Use the solution as electrolyte.Thereafter, by being closed remaining on one side, four sides is made airtightly to be closed, obtain pole plate group and Electrolyte is by closed lamination-type lithium rechargeable battery.In addition, anode and cathode with can with the lug of external electrical connections, A part for the lug extends to the outside of lamination-type lithium rechargeable battery.By the lamination-type lithium manufactured according to above step from When sub- battery is powered, do not lead to the problem of in work.
(2) multiplying power patience, the measurement of output characteristics
Using the lithium rechargeable battery of above-mentioned manufacture, charged with 0.1C, 2.5~4.2V voltages at 25 DEG C, in electricity The time point for pressing to 4.2V continues persistently to charge with constant voltage (4.2V), completes to fill as the time point of 0.01C in current value Electric (cut-off).Then, 2.5V being discharged to 0.1C, electric discharge is only changed to 1C by electricity repeated 5 times of charge and discharge after being recycled at the 6th time, Further carry out 50 cycles of charge and discharge.The 1C discharge capacities that 6th time recycles are accounted for the ratio in the charging capacity of the 6th cycle Using the value that percentage calculates as initial stage multiplying power sustainment rate.The value is bigger, and multiplying power patience is better.Further, the 50th time is followed The 1C discharge capacities of ring account for the ratio in the 1C discharge capacities of the 5th cycle using the value that percentage calculates as capacity maintenance rate. The value is bigger, and output characteristics is better.

Claims (17)

1. lithium ion battery binder aqueous solution, the lithium ion battery binder aqueous solution contains：
Water-soluble polymer (A) with amide groups；With
As ortho-siliformic acid based compound and/or the silicol based compound (A1) of tetrahydroxy silane-based compound.
2. lithium ion battery slurry, the lithium ion battery slurry contains：
Water-soluble polymer (A) with amide groups；With
As ortho-siliformic acid based compound and/or the silicol based compound (A1) of tetrahydroxy silane-based compound.
3. lithium ion battery slurry as claimed in claim 2, wherein the water-soluble polymer (A) is that have (methyl) The homopolymer of the compound of acrylamido or with (methyl) acrylamido compound and unsaturated carboxylic acid copolymer.
4. lithium ion battery slurry as claimed in claim 2 or claim 3, wherein relative to the water-soluble polymer (A) 100 Mass parts, the lithium ion battery slurry contain 1~15 mass parts of silicol based compound (A1).
5. the lithium ion battery slurry as described in any one of claim 2~4, wherein the silicol based compound (A1) contain ortho-siliformic acid base propylamine.
6. the lithium ion battery slurry as described in any one of claim 2~5, wherein the lithium ion battery slurry Contain electrode active material (B).
7. lithium ion battery slurry as claimed in claim 6, wherein in the electrode active material (B), containing silicon or 10 mass % of silica or more.
8. lithium ion battery slurry as claimed in claims 6 or 7, wherein relative to the electrode active material (B) 100 Mass parts, the water-soluble polymer (A) and the silicol based compound (A1) add up to 2~12 mass parts.
9. the lithium ion battery slurry as described in any one of claim 2~5, wherein the lithium ion battery slurry Contain ceramic particle (C).
10. lithium ion battery slurry as claimed in claim 9, wherein relative to 100 mass parts of the ceramic particle (C), The water-soluble polymer (A) and the silicol based compound (A1) add up to 1~15 mass parts.
11. the manufacturing method of the lithium ion battery slurry described in any one of claim 2~10, includes the following steps：
By with amide groups water-soluble polymer (A) with as ortho-siliformic acid based compound and/or tetrahydroxy silylation The silicol based compound (A1) for closing object is mixed.
12. lithium ion battery electrode, the lithium ion battery electrode contains will be described in any one of claim 2~8 Poly- (methyl) acrylamide-polysiloxanes is oligomeric obtained from lithium ion battery is coated with slurry and is allowed to dry on the current collector Object compound.
13. lithium ion battery electrode as claimed in claim 12, wherein the collector is copper foil.
14. the lithium ion battery containing the electrode described in claim 12 or 13.
15. by the lithium ion battery slurry described in claim 2~5,9, any one of 10 in porous polyolefin resin base material Or diaphragm for lithium ion battery obtained from being coated on plastics non-woven fabrics and being allowed to dry.
16. the lithium ion battery described in claim 2~5,9, any one of 10 is coated on the electrode with slurry and is allowed to dry Diaphragm for lithium ion battery obtained from dry/electrode laminate.
17. being used containing the lithium ion battery described in the diaphragm for lithium ion battery and/or claim 16 described in claim 15 The lithium ion battery of diaphragm/electrode laminate.
CN201810166495.3A 2017-02-28 2018-02-28 Binder aqueous solution for lithium ion battery, slurry, electrode, separator/electrode laminate, and lithium ion battery Active CN108574101B (en)

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