CN102187503A - Negative-electrode mix for nonaqueous-electrolyte secondary battery, negative electrode for nonaqueous-electrolyte secondary battery, and nonaqueous-electrolyte secondary battery - Google Patents

Negative-electrode mix for nonaqueous-electrolyte secondary battery, negative electrode for nonaqueous-electrolyte secondary battery, and nonaqueous-electrolyte secondary battery Download PDF

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CN102187503A
CN102187503A CN2009801409164A CN200980140916A CN102187503A CN 102187503 A CN102187503 A CN 102187503A CN 2009801409164 A CN2009801409164 A CN 2009801409164A CN 200980140916 A CN200980140916 A CN 200980140916A CN 102187503 A CN102187503 A CN 102187503A
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vinylidene
electrolyte secondary
base polymer
secondary battery
anode
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五十岚绫香
佐久间充康
阿彦信男
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Kureha Corp
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Kureha Corp
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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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08L27/16—Homopolymers or copolymers or vinylidene fluoride
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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
    • H01M4/623—Binders being polymers fluorinated polymers
    • 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
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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

Abstract

A negative-electrode mix for nonaqueous-electrolyte secondary batteries is provided which, when used in producing a negative electrode for nonaqueous-electrolyte secondary batteries, gives a mix layer having an excellent strength of peeling from the current collector. The negative-electrode mix for nonaqueous-electrolyte secondary batteries is characterized by comprising a vinylidene fluoride polymer having polar groups, a vinylidene fluoride polymer having chlorine atoms, an electrode active material, and an organic solvent, the chlorine-atom-containing vinylidene fluoride polymer containing chlorine atoms in an amount of 0.3-5 wt.% per 100 wt.% the polymer.

Description

Anode for nonaqueous electrolyte secondary battery mixture, anode for nonaqueous electrolyte secondary battery and rechargeable nonaqueous electrolytic battery
Technical field
The present invention relates to anode for nonaqueous electrolyte secondary battery mixture, anode for nonaqueous electrolyte secondary battery and rechargeable nonaqueous electrolytic battery.
Background technology
In recent years, development of electronic technology is remarkable unusually, and various device just is miniaturized, lighting.Adapt with miniaturization, the lighting of above-mentioned electronic equipment, require miniaturization, lighting as the battery of its power supply.As obtaining battery with little volume and weight than macro-energy, the rechargeable nonaqueous electrolytic battery that uses lithium mainly as mobile phone, PC, and family such as video camera in the power supply of the miniaturized electronics that uses use.
The electrode of above-mentioned rechargeable nonaqueous electrolytic battery (positive pole and negative pole) for example can form mixture layer and obtain by electrode mixture being coated on the current-collector and carrying out drying, and described electrode mixture is by forming in the material mixed adhesive (binding agent) at electrode active material and the powdered electrodes such as conductive auxiliary agent that add as required and with its dissolving or be dispersed in the appropriate solvent and obtain.
As adhesive, need have durability to non-aqueous electrolyte, it is good to require the little and film of intrinsic resistance to form property, and described non-aqueous electrolyte is with for example LiPF 6, LiClO 4Obtain in non-water solvents such as ethylene carbonate, propylene carbonate Deng electrolyte dissolution.As adhesive, particularly, can use the vinylidene base polymer usually.
As the vinylidene base polymer, a kind of vinylidene analog copolymer with vinylidene and unsaturated dibasic acid monoesters copolymerization gained is for example disclosed in patent documentation 1.The purpose of patent documentation 1 is to provide the vinylidene base polymer that the adhesiveness of base materials such as a kind of and metal is good, chemical proofing is excellent and can generate by aqueous polymerization, wherein put down in writing the electrode mixture that this polymer is used with adhesive as the electrode manufacturing of battery, but the composition that electrode mixture comprised to except that this polymer is not particularly limited.
Therefore, the peel strength that constitutes the current-collector of electrode and mixture layer hour, in punching press, cut, have the problem that produces be full of cracks and peel off in the electrode in the operation such as winding.The problems referred to above are not only relevant with the reduction of battery performance, and the danger that exists stripping film to connect interlayer, be short-circuited, and are important management project in the electrode manufacturing.
As the method for the electrode for cell of the peel strength excellence of making current-collector and mixture layer, disclose in the patent documentation 2 and added acid in the slurry on coating current-collector.Disclose in the patent documentation 2 as acid preferred organic acid, more preferably carboxylic acid.
Yet the peel strength of current-collector and mixture layer is still insufficient, needs further to improve.
Patent documentation 1: Japanese kokai publication hei 6-172452 communique
Patent documentation 2: Japanese kokai publication hei 2-68855 communique
Summary of the invention
The present invention finishes in view of above-mentioned problems of the prior art, the object of the present invention is to provide a kind of anode for nonaqueous electrolyte secondary battery mixture, anode for nonaqueous electrolyte secondary battery and have the rechargeable nonaqueous electrolytic battery of this negative pole, described anode for nonaqueous electrolyte secondary battery mixture is when making anode for nonaqueous electrolyte secondary battery, the peel strength excellence of mixture layer and current-collector, described anode for nonaqueous electrolyte secondary battery carries out drying and obtains by this mixture is coated on the current-collector.
In order to realize above-mentioned problem, the inventor etc. further investigate, found that in the anode for nonaqueous electrolyte secondary battery that the anode for nonaqueous electrolyte secondary battery mixture of the specific polymer that uses the particular polymers contain chloride atom and polar functionalities makes, peel strength excellence between mixture layer and the current-collector, thus the present invention finished.
Promptly, anode for nonaqueous electrolyte secondary battery mixture of the present invention is characterised in that, the vinylidene base polymer, electrode active material and the organic solvent that contain the vinylidene base polymer of polar functionalities, chloride atom contain the chlorine atom of 0.3～5 weight % in the vinylidene base polymer of the above-mentioned chloride atom of per 100 weight %
The polar group that the vinylidene base polymer of preferred above-mentioned polar functionalities is contained is at least a kind the polar group that is selected among carboxyl and the acid anhydride.In addition, the polar group that is contained at the vinylidene base polymer of above-mentioned polar functionalities is to be selected under the situation of at least a kind of polar group among carboxyl and the acid anhydride, and the absorbance of following formula (1) expression when measuring the infrared absorption spectroscopy of vinylidene base polymer of above-mentioned polar functionalities is than (I R) preferably in 0.10～1.5 scope.
I R＝I 1750/I 3025 …(1)
(in the above-mentioned formula (1), I 1750Be 1750cm -1Absorbance, I 3025Be 3025cm -1Absorbance.)
The vinylidene base polymer of preferred above-mentioned polar functionalities is the vinylidene base polymer that the following substances copolymerization is obtained: the vinylidene of 80～99.9 weight portions, and the monomer of the polar functionalities of 0.1～20 weight portion (wherein, above-mentioned vinylidene, and the monomer of polar functionalities add up to 100 weight portions).More preferably the monomer of above-mentioned polar functionalities is to contain the monomer that is selected from least a kind polar group among carboxyl and the acid anhydride.
The vinylidene base polymer of preferred above-mentioned chloride atom is the vinylidene base polymer that the following substances copolymerization is obtained: the vinylidene of 90～99 weight portions, and the monomer of the chloride atom of 1～10 weight portion (wherein, above-mentioned vinylidene, and the monomer of chloride atom add up to 100 weight portions).
The monomer of preferred above-mentioned chloride atom is a chlorotrifluoroethylene.
Preferred above-mentioned electrode active material is a material with carbon element.
Anode for nonaqueous electrolyte secondary battery of the present invention is characterised in that, described anode for nonaqueous electrolyte secondary battery carries out drying and obtains by above-mentioned anode for nonaqueous electrolyte secondary battery mixture is coated on the current-collector.
Rechargeable nonaqueous electrolytic battery of the present invention is characterised in that described rechargeable nonaqueous electrolytic battery has the anode for nonaqueous electrolyte secondary battery of above-mentioned record.
Because anode for nonaqueous electrolyte secondary battery mixture of the present invention contains vinylidene base polymer, and the vinylidene base polymer of chloride atom of polar functionalities, so use in the anode for nonaqueous electrolyte secondary battery of this mixture manufacturing the peel strength excellence between mixture layer and the current-collector.
Description of drawings
The figure of the IR spectrum of vinylidene base polymer-(1) of the polar functionalities that [Fig. 1] Fig. 1 uses among the embodiment for expression.
Embodiment
Next, specifically describe the present invention.
Anode for nonaqueous electrolyte secondary battery mixture of the present invention is characterised in that, the vinylidene base polymer, electrode active material, and the organic solvent that contain the vinylidene base polymer of polar functionalities, chloride atom contain the chlorine atom of 0.3～5 weight % in the vinylidene base polymer of the above-mentioned chloride atom of per 100 weight %.
(electrode active material)
Anode for nonaqueous electrolyte secondary battery mixture of the present invention contains electrode active material.As electrode active material, be not particularly limited, can use present known negative pole electrode active material, as concrete example, can enumerate material with carbon element, metal alloy compositions, metal oxide etc., wherein, preferred material with carbon element.
As above-mentioned material with carbon element, can use Delanium, native graphite, difficult graphitized carbon, easy graphitized carbon etc.In addition, above-mentioned material with carbon element can use a kind separately, also can use more than 2 kinds.
When using above-mentioned material with carbon element, can improve the energy density of battery.
As above-mentioned Delanium, for example can at high temperature heat-treat crushing and classification and obtaining by with the organic material carbonization again.As Delanium, can use MAG series (Hitachi changes into the industry system), MCMB (Osaka gas system) etc.
(the vinylidene base polymer of polar functionalities)
Anode for nonaqueous electrolyte secondary battery mixture of the present invention contains the vinylidene base polymer of polar functionalities as adhesive resin.In the present invention, the vinylidene base polymer of polar functionalities is meant in the polymer polar functionalities and uses the polymer of vinylidene as the monomer gained at least.In addition, the vinylidene base polymer of polar functionalities typically uses the polymer that the monomer of vinylidene and polar functionalities obtains, and then also can use other monomers.Need to prove that the monomer of polar functionalities is also referred to as the monomer of polar functionalities in its molecule.
In addition, among the present invention, polar group is meant the atomic group of the atom that electronegativity such as containing nitrogen, oxygen, sulphur, phosphorus is also bigger than carbon.That is, single atom such as fluorine, chlorine is not the polar group among the present invention.
As the polar group that the vinylidene base polymer of the polar functionalities that uses among the present invention contains, can enumerate carboxyl, epoxy radicals, hydroxyl, sulfonic group, acid anhydride, amino etc., wherein, preferred carboxyl, acid anhydride.The vinylidene base polymer of the polar functionalities that uses among the present invention contains a kind of above-mentioned polar group at least, also can contain more than 2 kinds.As the vinylidene base polymer of polar functionalities, consider from the aspect of the bond properties and the situation of purchase, be preferably the vinylidene base polymer that contains at least a kind of polar group that is selected among carboxyl and the acid anhydride.
In addition, the vinylidene base polymer of the polar functionalities that uses among the present invention can use a kind separately, also can use more than 2 kinds.
When the polar group that the vinylidene base polymer of polar functionalities contains is at least a kind of polar group that is selected among carboxyl and the acid anhydride, the vinylidene base polymer of polar functionalities is following polymer, that is, contain construction unit more than 80 weight portions, more than preferred 85 weight portions usually from vinylidene with respect to this polymer of 100 weight portions.
The vinylidene base polymer of the polar functionalities that uses among the present invention usually can be according to the preparation of any method in following (1)～(3): (1) is with the method for the monomer of vinylidene, polar functionalities and other monomer copolymerizations of using as required (below, also note is made method (1)); (2) polymer of use vinylidene base polymer and polar functionalities, with the polymer graft of the polar functionalities method to the vinylidene base polymer, described vinylidene base polymer obtains with the vinylidene polymerization or with vinylidene and other monomer copolymerizations, the polymer of described polar functionalities is with the monomer polymerization of polar functionalities or (below, also note is made method (2)) that the monomer of polar functionalities and other monomer copolymerizations are obtained; (3) obtain the vinylidene base polymer with the vinylidene polymerization or with vinylidene and other monomer copolymerizations after, use contains the monomer of polar functionalities such as maleic acid or maleic anhydride, with the method for this vinylidene base polymer modification (below, also note is made method (3)).
Vinylidene base polymer that use among the present invention, polar functionalities because polar functionalities, so compare with the Kynoar of polar functionalities not, improves with the adhesiveness of current-collector.In addition, the vinylidene base polymer of polar functionalities has and the suitable chemical proofing of Kynoar of polar functionalities not.
As the manufacture method of the vinylidene base polymer of polar functionalities, in said method (1)～(3), consider from the viewpoint of process number and production cost, preferably adopt method (1) preparation.
The vinylidene base polymer of the polar functionalities that uses among the present invention, be generally the vinylidene analog copolymer that monomer (wherein, the monomer of vinylidene and polar functionalities the adds up to 100 weight portions) copolymerization with the polar functionalities of the vinylidene of 80～99.9 weight portions and 0.1～20 weight portion obtains.Need to prove,, can also carry out the polymer that copolymerization obtains for monomer and other monomers with above-mentioned vinylidene, polar functionalities as the vinylidene base polymer of above-mentioned polar functionalities.Need to prove, when using other monomers, when the monomer of above-mentioned vinylidene and polar functionalities adds up to 100 weight portions, can use other monomers of 0.1～20 weight portion usually.
In addition, when preparation contains the vinylidene base polymer of at least a kind of polar group that is selected among carboxyl and the acid anhydride, monomer as polar functionalities, usually can use and contain the monomer that is selected from least a kind of polar group among carboxyl and the acid anhydride, the preferred use is selected from the monomer that contains carboxyl and contains at least a monomer in acid anhydride's the monomer.
When use is selected from the monomer that contains carboxyl and contains at least a kind of monomer in acid anhydride's the monomer, the vinylidene base polymer of polar functionalities, be preferably with the vinylidene of 90～99.9 weight portions and 0.1～10 weight portion be selected from the monomer that contains carboxyl and contain in acid anhydride's the monomer at least a kind of monomer (wherein, vinylidene and be selected from the monomer that contains carboxyl and contain 100 weight portions that add up to of at least a kind of monomer in acid anhydride's the monomer) the vinylidene analog copolymer that obtains of copolymerization, more preferably be being selected from the monomer that contains carboxyl and containing the vinylidene analog copolymer that at least a kind of monomer in acid anhydride's the monomer (wherein, vinylidene and be selected from the monomer that contains carboxyl and contain 100 weight portions that add up to of at least a kind of monomer in acid anhydride's the monomer) copolymerization obtains with 95～99.9 weight portion vinylidenes and 0.1～5 weight portion.
As the above-mentioned monomer that contains carboxyl, the monoesters of preferred unsaturated monoacid, unsaturated dibasic acid, unsaturated dibasic acid etc., the more preferably monoesters of unsaturated dibasic acid, unsaturated dibasic acid.
As above-mentioned unsaturated monoacid, can enumerate acrylic acid etc.As above-mentioned unsaturated dibasic acid, can enumerate maleic acid, citraconic acid etc.In addition, as the monoesters of above-mentioned unsaturated dibasic acid, preferred carbon number is 5～8, for example, can enumerate monomethyl maleate, ethyl maleate, citraconic acid mono-methyl, citraconic acid mono ethyl ester etc.
Wherein, as the monomer that contains carboxyl, preferred maleic acid, citraconic acid, monomethyl maleate, citraconic acid mono-methyl.
As the above-mentioned monomer that contains the acid anhydride, can enumerate the acid anhydrides of unsaturated dibasic acid, as the acid anhydrides of unsaturated dibasic acid, can enumerate maleic anhydride, citraconic anhydride etc.
The vinylidene base polymer of the polar functionalities that uses among the present invention normally contains the polymer from the polar group of the monomer of polar functionalities.For example, when using the monomer contain carboxyl,, can obtain containing the vinylidene base polymer of carboxyl usually as the vinylidene base polymer of polar functionalities as the monomer of polar functionalities.In addition, when using the monomer contain the acid anhydride as the monomer of polar functionalities, the vinylidene base polymer as polar functionalities can contain the carboxyl that is obtained by acid anhydride's hydrolysis, also can contain the acid anhydride.
Operable other monomers are meant the monomer except that the monomer of vinylidene and polar functionalities among the present invention, as other monomers, for example can enumerate can with the fluorine class monomer or the hydro carbons monomers such as ethene, propylene of vinylidene copolymerization.As can with the fluorine class monomer of vinylidene copolymerization, can enumerate PVF, trifluoro-ethylene, tetrafluoroethene, hexafluoropropylene etc.
Need to prove that above-mentioned other monomers can use a kind separately, also can use more than 2 kinds.
In addition,, can adopt methods such as suspension polymerisation, emulsion polymerisation, polymerisation in solution, but consider, suspension polymerisation, the emulsion polymerisation of preferred water system, the suspension polymerisation of preferred especially water system from the aspects such as easiness of reprocessing as method (1).
Be in the suspension polymerisation of decentralized medium with water, with respect to the whole monomers that use in the 100 weight portion copolymerization (monomer of vinylidene, polar functionalities and other monomers that carry out copolymerization as required), at 0.005～1.0 weight portion, preferably in the scope of 0.01～0.4 weight portion, add following suspending agent and use, that is, methylcellulose, methoxylation methylcellulose, propoxylation methylcellulose, hydroxyethylcellulose, hydroxypropyl cellulose, polyvinyl alcohol, poly(ethylene oxide), gelatin etc.
As polymerization initiator, can use di-isopropyl peroxydicarbonate, peroxy dicarbonate di-n-propyl ester, peroxy dicarbonate two positive seven fluorine propyl ester, di-isopropyl peroxydicarbonate, peroxidating isobutyryl, two (chlorine fluoro acyl group) peroxide, two (perfluoro acyl group) peroxide etc.When being 100 weight portions, its use amount is 0.1～5 weight portion to the whole monomers that use in the copolymerization (monomer of vinylidene, polar functionalities and other monomers that carry out copolymerization as required), is preferably 0.3～2 weight portion.
In addition, also can add chain-transferring agent and regulate the degree of polymerization of vinylidene base polymer of the polar functionalities of gained, described chain-transferring agent is ethyl acetate, methyl acetate, diethyl carbonate, acetone, ethanol, normal propyl alcohol, acetaldehyde, propionic aldehyde, ethyl propionate, carbon tetrachloride etc.When being 100 weight portions, its use amount is generally 0.1～5 weight portion to the whole monomers that use in the copolymerization (monomer of vinylidene, polar functionalities and other monomers that carry out copolymerization as required), is preferably 0.5～3 weight portion.
In addition, the input amount of the whole monomers that use in the copolymerization (monomer of vinylidene, polar functionalities and other monomers that carry out copolymerization as required), total amount with monomer: the weight ratio of water counts 1: 1～and 1: 10, be preferably 1: 2～1: 5, polymerization temperature is 10～80 ℃, polymerization time is 10～100 hours, pressure during polymerization carries out adding to depress usually, is preferably 2.0～8.0MPa-G.
By carrying out the suspension polymerisation of water system under these conditions, can be easily with the monomer of vinylidene, polar functionalities and other monomer copolymerizations that carry out copolymerization as required, can access the vinylidene base polymer of the polar functionalities that uses among the present invention.
In addition, when preparing the vinylidene base polymer of polar functionalities, for example can adopt following method to carry out according to method (2).
When preparing the vinylidene base polymer of polar functionalities, at first, obtain the vinylidene base polymer by with the vinylidene polymerization or with vinylidene and other monomer copolymerizations according to method (2).This polymerization or copolymerization can utilize suspension polymerisation or emulsion polymerisation to carry out usually.In addition, different with above-mentioned vinylidene base polymer, by with the monomer polymerization of polar functionalities or with monomer and other monomer copolymerizations of polar functionalities, obtain the polymer of polar functionalities in addition.The polymer of this polar functionalities can utilize emulsion polymerisation or suspension polymerisation to obtain usually.And then, use the polymer of above-mentioned vinylidene base polymer and polar functionalities, the polymer graft of polar functionalities to the vinylidene base polymer, can be obtained the vinylidene base polymer of polar functionalities thus.This grafting can use peroxide to carry out, and also can use radioactive ray to carry out, and carry out but be preferably as follows: the mixture of polymers to vinylidene base polymer and polar functionalities in the presence of peroxide is carried out heat treated.
The logarithmic viscosity number of the vinylidene base polymer of the polar functionalities that uses among the present invention (with the 4g resin dissolves at 1 liter of N, the logarithm viscosity of the solution that forms in the dinethylformamide under 30 ℃.Below identical) be preferably the value in the scope of 0.5～5.0dl/g, more preferably be the value in the scope of 1.1～4.0dl/g.During for the viscosity in the above-mentioned scope, can be preferred for the anode for nonaqueous electrolyte secondary battery mixture.
Logarithmic viscosity number η iCalculating can followingly carry out: the vinylidene base polymer of 80mg polar functionalities is dissolved in 20ml N, in the dinethylformamide, in 30 ℃ thermostat, uses Ubbelohde viscometer (Ubbelohde viscometer) to calculate according to following formula.
η i＝(1/C)·ln(η/η 0)
Herein, η is the viscosity of polymer solution, η 0For solvent is N, the viscosity that dinethylformamide is independent, C is 0.4g/dl.
In addition, the vinylidene base polymer of polar functionalities uses GPC (gel permeation chromatography) to measure the weight average molecular weight of trying to achieve, usually in 50,000～1,500,000 scope.
In addition, the vinylidene base polymer of above-mentioned polar functionalities is when containing the vinylidene base polymer of at least a kind of polar group that is selected among carboxyl and the acid anhydride, and the absorbance of following formula (1) expression when measuring the infrared absorption spectroscopy of this polymer is than (I R) preferably in 0.10～1.5 scope.Need to prove that the mensuration of the infrared absorption spectroscopy of this polymer is following carries out: this polymer is implemented hot pressing, measure the infrared absorption spectroscopy of making the film that obtains thus.
I R＝I 1750/I 3025 …(1)
(in above-mentioned formula (1), I 1750Be 1750cm -1Absorbance, I 3025Be 3025cm -1Absorbance.)
In infrared absorption spectroscopy, carbonyl is at 1650～1800cm -1Absorption band is arranged.
Therefore, in above-mentioned formula (1), I 1750From carbonyl, I 3025From the C-H structure.Therefore, I RIndex for the amount of carbonyl in the vinylidene base polymer of expression polar functionalities.(the vinylidene base polymer of chloride atom)
Anode for nonaqueous electrolyte secondary battery mixture of the present invention contains the vinylidene base polymer of chloride atom as adhesive resin.In the present invention, the vinylidene base polymer of chloride atom is meant in the polymer chloride atom and uses the polymer of vinylidene as the monomer gained at least.In addition, the chlorine atom that contains 0.3～5 weight % in the vinylidene base polymer of the chloride atom that in the present invention of per 100 weight %, uses.
In addition, the vinylidene base polymer of chloride atom typically uses the polymer that the monomer of vinylidene and chloride atom obtains, and then also can use other monomers, and need to prove, also the monomer note of chloride atom in its molecule is made the monomer of chloride atom.
The vinylidene base polymer of the chloride atom that uses among the present invention can use a kind separately, also can use more than 2 kinds.
The vinylidene base polymer of that use among the present invention, chloride atom because chloride atom, so compare with the Kynoar of chloride atom not, improves with the adhesiveness of current-collector.In addition, the vinylidene base polymer of chloride atom has and the suitable chemical proofing of Kynoar of chloride atom not.
The vinylidene base polymer of the polar functionalities that uses among the present invention, be generally the vinylidene analog copolymer that monomer (wherein, the monomer of vinylidene and chloride atom the adds up to 100 weight portions) copolymerization with the chloride atom of the vinylidene of 90～99 weight portions and 1～10 weight portion obtains.Need to prove,, also can be monomer above-mentioned vinylidene and chloride atom as the vinylidene base polymer of above-mentioned chloride atom, and the polymer that obtains of other monomer copolymerizations.In addition, when using other monomers, when the monomer of above-mentioned vinylidene and chloride atom adds up to 100 weight portions, use other monomers of 0.1～20 weight portion usually.
As the monomer of above-mentioned chloride atom, can use chlorotrifluoroethylene usually.
Operable other monomers are meant the monomer except that the monomer of vinylidene and polar functionalities among the present invention, as other monomers, for example can enumerate can with the fluorine class monomer or the hydro carbons monomers such as ethene, propylene of vinylidene copolymerization.As can with the fluorine class monomer of vinylidene copolymerization, can enumerate PVF, trifluoro-ethylene, tetrafluoroethene, hexafluoropropylene etc.
Need to prove that above-mentioned other monomers can use a kind separately, also can use more than 2 kinds.
The vinylidene base polymer of the chloride atom that uses among the present invention prepares by the method for the monomer of vinylidene, chloride atom and other monomers of using as required being carried out copolymerization usually.
In addition,, can adopt methods such as suspension polymerisation, emulsion polymerisation, polymerisation in solution, but consider, suspension polymerisation, the emulsion polymerisation of preferred water system, the suspension polymerisation of preferred especially water system from the aspects such as easiness of reprocessing as the method for this copolymerization.
Be in the suspension polymerisation of decentralized medium with water, with respect to the whole monomers that use in the 100 weight portion copolymerization (monomer of vinylidene, chloride atom and other monomers that carry out copolymerization as required), at 0.005～1.0 weight portion, preferably in the scope of 0.01～0.4 weight portion, add following suspending agent and use, that is, methylcellulose, methoxylation methylcellulose, propoxylation methylcellulose, hydroxyethylcellulose, hydroxypropyl cellulose, polyvinyl alcohol, poly(ethylene oxide), gelatin etc.
As polymerization initiator, can use di-isopropyl peroxydicarbonate, peroxy dicarbonate di-n-propyl ester, peroxy dicarbonate two positive seven fluorine propyl ester, di-isopropyl peroxydicarbonate, peroxidating isobutyryl, two (chlorine fluoro acyl group) peroxide, two (perfluoro acyl group) peroxide etc.When being 100 weight portions, its use amount is 0.1～5 weight portion to the whole monomers that use in the copolymerization (monomer of vinylidene, chloride atom and other monomers that carry out copolymerization as required), is preferably 0.3～2 weight portion.
In addition, also can add chain-transferring agent and regulate the degree of polymerization of vinylidene base polymer of the polar functionalities of gained, described chain-transferring agent is ethyl acetate, methyl acetate, diethyl carbonate, acetone, ethanol, normal propyl alcohol, acetaldehyde, propionic aldehyde, ethyl propionate, carbon tetrachloride etc.When being 100 weight portions, its use amount is generally 0.1～5 weight portion to the whole monomers that use in the copolymerization (monomer of vinylidene, chloride atom and other monomers that carry out copolymerization as required), is preferably 0.5～3 weight portion.
In addition, the input amount of the whole monomers that use in the copolymerization (monomer of vinylidene, chloride atom and other monomers that carry out copolymerization as required), with whole monomers: the weight ratio of water counts 1: 1～and 1: 10, be preferably 1: 2～1: 5, polymerization temperature is 10～80 ℃, polymerization time is 10～100 hours, pressure during polymerization carries out adding to depress usually, is preferably 2.0～8.0MPa-G.
By carrying out the suspension polymerisation of water system under these conditions, can be easily with the monomer of vinylidene, chloride atom and other monomer copolymerizations that carry out copolymerization as required, can access the vinylidene base polymer of the chloride atom that uses among the present invention.
As mentioned above, the chlorine atom that contains 0.3～5 weight % in the vinylidene base polymer of the chloride atom that uses among the present invention of per 100 weight %, the chlorine atom that preferably contains 0.7～3 weight %, the chlorine atom content of the vinylidene base polymer of chloride atom can followingly be obtained, promptly, according to flask combustion method (JIS K7229), obtain experimental liquid by vinylidene base polymer burning with chloride atom, with above-mentioned experimental liquid ion chromatography analysis, obtain the chromatographic peak area of chloride ion in the gained chromatogram, obtain the chlorine atom content by the absolute standard curve method.
The logarithmic viscosity number of the vinylidene base polymer of the chloride atom that uses among the present invention (with the 4g resin dissolves at 1 liter of N, the logarithm viscosity of the solution that forms in the dinethylformamide under 30 ℃.Below identical) be preferably the value in the scope of 0.5～5.0dl/g, more preferably be the value in the scope of 1.1～4.0dl/g.During for the viscosity in the above-mentioned scope, can be preferred for the anode for nonaqueous electrolyte secondary battery mixture.
Logarithmic viscosity number η iCalculating can followingly carry out: the vinylidene base polymer of the chloride atom of 80mg is dissolved in 20ml N, in the dinethylformamide, in 30 ℃ thermostat, uses Ubbelohde viscometer to calculate according to following formula.
η i＝(1/C)·ln(η/η 0)
Herein, η is the viscosity of polymer solution, η 0For solvent is N, the viscosity that dinethylformamide is independent, C is 0.4g/dl.
In addition, the vinylidene base polymer of chloride atom uses GPC (gel permeation chromatography) to measure the weight average molecular weight of trying to achieve, usually in 50,000～1,500,000 scope.
When using anode for nonaqueous electrolyte secondary battery mixture of the present invention to make anode for nonaqueous electrolyte secondary battery, the peel strength excellence of the mixture layer of this negative pole and current-collector.Though it be unclear that the reason of peel strength excellence, but the inventor etc. infer the reason of peel strength excellence and are, the a part of chlorine atom that is contained in the vinylidene base polymer of chloride atom breaks away from, surface reaction with current-collector, the carboxyl of the vinylidene base polymer of this reflecting point and polar functionalities or acid anhydride's isopolarity radical reaction, so peel strength excellence.
Promptly, in the anode for nonaqueous electrolyte secondary battery mixture of the present invention, need use the vinylidene base polymer of chloride atom and the vinylidene base polymer of polar functionalities simultaneously, monomer as above-mentioned chloride atom, when using chlorotrifluoroethylene, the mixture layer of above-mentioned negative pole and the peel strength of current-collector are excellent especially, so preferred.
The anode for nonaqueous electrolyte secondary battery mixture of the application of the invention can improve the peel strength of mixture layer and current-collector in anode for nonaqueous electrolyte secondary battery.Therefore, compare with existing negative pole mixture, electrode be full of cracks and the problem peeled off are effective when solve making electrode.
(organic solvent)
Anode for nonaqueous electrolyte secondary battery mixture of the present invention contains organic solvent.As organic solvent, can use the solvent of the effect of vinylidene base polymer, the solvent that preferably has polarity with the dissolving vinylidene base polymer of above-mentioned polar functionalities and chloride atom.Concrete example as organic solvent, can enumerate N-N-methyl-2-2-pyrrolidone N-, N, dinethylformamide, N, N-dimethylacetylamide, N, N-dimethyl sulfoxide (DMSO), hexamethyl phosphoramide, dioxane, oxolane, tetramethylurea, triethyl phosphate, trimethyl phosphate etc., preferred N-N-methyl-2-2-pyrrolidone N-, N, dinethylformamide, N, N-dimethylacetylamide, N, the N-dimethyl sulfoxide (DMSO).In addition, organic solvent can use a kind separately, also can be mixed with two or more.
Anode for nonaqueous electrolyte secondary battery mixture of the present invention contains vinylidene base polymer, electrode active material, and the organic solvent of the vinylidene base polymer of above-mentioned polar functionalities, chloride atom.
The content of each composition of anode for nonaqueous electrolyte secondary battery mixture of the present invention, usually with respect to 100 weight portion electrode active materials, the vinylidene base polymer of polar functionalities and the vinylidene base polymer of chloride atom add up to 1～25 weight portion, organic solvent is 20～300 weight portions, the vinylidene base polymer of preferred polar functionalities and the vinylidene base polymer of chloride atom add up to 1～20 weight portion, organic solvent is 70～200 weight portions.In addition, the weight ratio of the vinylidene base polymer of polar functionalities and the vinylidene base polymer of chloride atom is generally 5: 95～95: 5, is preferably 20: 80～80: 20.
When above-mentioned scope contains each composition, when using anode for nonaqueous electrolyte secondary battery mixture of the present invention to make anode for nonaqueous electrolyte secondary battery, can further improve the mixture layer of this electrode and the peel strength between current-collector, in addition, when making anode for nonaqueous electrolyte secondary battery, the coating when being coated with the anode for nonaqueous electrolyte secondary battery mixture on current-collector is also excellent.
In addition, anode for nonaqueous electrolyte secondary battery mixture of the present invention also can contain other compositions except that vinylidene base polymer, electrode active material and the organic solvent of the vinylidene base polymer of above-mentioned polar functionalities, chloride atom.As other compositions, also can contain pigment dispersing agents such as conductive auxiliary agents such as carbon black and polyvinylpyrrolidone.As above-mentioned other compositions, can contain other polymer except that the vinylidene base polymer of the vinylidene base polymer of polar functionalities and chloride atom.As above-mentioned other polymer, for example can enumerate Kynoar, vinylidene fluoride-hexafluoropropylene copolymer, vinylidene-trifluoro-ethylene copolymer, vinylidene-vinylidene base polymers such as perfluoro methyl vinyl ether copolymer.When in anode for nonaqueous electrolyte secondary battery mixture of the present invention, containing other polymer, usually with respect to total 100 weight portions of the vinylidene base polymer of the vinylidene base polymer of polar functionalities and chloride atom, contain above-mentioned other polymer with the amount below 25 weight portions.
The use E type viscosimeter of anode for nonaqueous electrolyte secondary battery mixture of the present invention is at 25 ℃, shear rate 2s -1Viscosity when measuring down is generally 2000～50000mPas, is preferably 5000～30000mPas.
Manufacture method as anode for nonaqueous electrolyte secondary battery mixture of the present invention, as long as vinylidene base polymer with above-mentioned polar functionalities, the vinylidene base polymer of chloride atom, electrode active material and organic solvent are mixed into uniform slurry and get final product, order when mixing is not particularly limited, for example can enumerate following method: the vinylidene base polymer of above-mentioned polar functionalities and the vinylidene base polymer of chloride atom are mixed with the part of organic solvent, the preparation binder solution, in this binder solution, add electrode active material and remaining organic solvent, mix, obtain the method for anode for nonaqueous electrolyte secondary battery mixture; After the vinylidene base polymer of the vinylidene base polymer of above-mentioned polar functionalities, chloride atom being dissolved in the part of organic solvent respectively, 2 kinds of binder solutions are mixed, in this binder solution, add electrode active material and remaining organic solvent, mix, obtain the method for anode for nonaqueous electrolyte secondary battery mixture.
(anode for nonaqueous electrolyte secondary battery)
Anode for nonaqueous electrolyte secondary battery of the present invention can have the layer that is formed by current-collector and anode for nonaqueous electrolyte secondary battery mixture by above-mentioned anode for nonaqueous electrolyte secondary battery mixture being coated on the current-collector and dry obtaining.
Need to prove, in the present invention, will make mixture layer by the layer note that the anode for nonaqueous electrolyte secondary battery mixture is coated on the current-collector and drying forms.
As the current-collector that uses among the present invention, for example can enumerate copper, as its shape, for example can enumerate metal forming or wire netting etc.As current-collector, preferred Copper Foil.
The thickness of current-collector is generally 5～100 μ m, is preferably 5～20 μ m.
When making anode for nonaqueous electrolyte secondary battery of the present invention, the one side at least that above-mentioned anode for nonaqueous electrolyte secondary battery mixture is coated on above-mentioned current-collector goes up, preferably is coated on the two sides.Method during as coating is not particularly limited, and can enumerate the methods such as excellent coating machine, mould coating machine, comma scraper coating machine (Comma coater) are coated with that adopt.
In addition, as the drying of carrying out after the coating, under 50～150 ℃ temperature, carried out 1～300 minute usually.In addition, the pressure when dry is not particularly limited, but under atmospheric pressure or under the decompression carries out usually.
Adopt above method can make anode for nonaqueous electrolyte secondary battery of the present invention.Need to prove, layer structure as anode for nonaqueous electrolyte secondary battery, when on the one side of current-collector, being coated with the anode for nonaqueous electrolyte secondary battery mixture, two-layer structure for mixture layer/current-collector, when on the two sides of current-collector, being coated with the anode for nonaqueous electrolyte secondary battery mixture, be the three-decker of mixture layer/current-collector/mixture layer.
Anode for nonaqueous electrolyte secondary battery of the present invention, by using above-mentioned anode for nonaqueous electrolyte secondary battery mixture, peel strength excellence between current-collector and the mixture layer, therefore, in punching press, cut, electrode is difficult for producing be full of cracks and peeling off in the operation such as winding, productivity ratio is improved, so preferred.
As mentioned above, the current-collector of anode for nonaqueous electrolyte secondary battery of the present invention and the peel strength excellence between the mixture layer, particularly, according to JIS K6854, when adopting 180 ° of disbonded tests to measure, peel strength between current-collector and the mixture layer is generally 0.5～20gf/mm, is preferably 1～10gf/mm.
(rechargeable nonaqueous electrolytic battery)
Rechargeable nonaqueous electrolytic battery of the present invention is characterised in that to have above-mentioned anode for nonaqueous electrolyte secondary battery.
As rechargeable nonaqueous electrolytic battery of the present invention, as long as have above-mentioned anode for nonaqueous electrolyte secondary battery, be not particularly limited, the position beyond the negative pole, for example positive pole, interlayer etc. can use present known material.
Embodiment
Next, provide embodiment the present invention is described in further detail, but the present invention is not limited thereto.
(preparation of the vinylidene base polymer of polar functionalities-(1))
In the autoclave of 2 liters of inner capacitiess, drop into 1036g ion exchange water, 0.8g methylcellulose, 1.8g di-isopropyl peroxydicarbonate, 396g vinylidene and 4g monomethyl maleate, under 29 ℃, carried out suspension polymerisation 56 hours.Maximum pressure during this period reaches 4.3MPa.After polymerization is finished,, after the washing, under 80 ℃, carried out drying 20 hours, obtain containing carboxyl as vinylidene base polymer-(1) polar group, pulverous polar functionalities with the polymer paste dehydration.
The polymerization yield is 85 weight %, and the logarithmic viscosity number of the vinylidene base polymer of the polar functionalities of gained-(1) is 2.1dl/g.
(preparation of the vinylidene base polymer of chloride atom-(1))
In the autoclave of 2 liters of inner capacitiess, drop into 1040g ion exchange water, 0.4g methylcellulose, 1.6g di-isopropyl peroxydicarbonate, 2g ethyl acetate, 372g vinylidene, reach the 28g chlorotrifluoroethylene, under 28 ℃, carried out suspension polymerisation 43 hours.Maximum pressure during this period reaches 4.2MPa.After polymerization is finished,, after the washing, under 80 ℃, carried out drying 20 hours, obtain vinylidene base polymer-(1) of pulverous chloride atom the polymer paste dehydration.
The polymerization yield is 90 amount %, and the logarithmic viscosity number of the vinylidene base polymer of the chloride atom of gained-(1) is 2.0dl/g.
(preparation of Kynoar-(1))
In the autoclave of 2 liters of inner capacitiess, drop into 1100g ion exchange water, 0.2g methylcellulose, 2.2g di-isopropyl peroxydicarbonate, 3.7g ethyl acetate, 430g vinylidene, under 26 ℃, carried out suspension polymerisation 18.5 hours.Maximum pressure during this period reaches 4.1MPa.After polymerization is finished,, after the washing, under 80 ℃, carried out drying 20 hours, obtain pulverous vinylidene base polymer-(1) the polymer paste dehydration.
The polymerization yield is 90 amount %, and the logarithmic viscosity number of the Kynoar of gained-(1) is 2.0dl/g.
(preparation of vinylidene fluoride-hexafluoropropylene copolymer-(1))
In the autoclave of 2 liters of inner capacitiess, drop into 1075g ion exchange water, 0.2g methylcellulose, 0.8g di-isopropyl peroxydicarbonate, 3.2g ethyl acetate, 386g vinylidene and 34g hexafluoropropylene, under 29 ℃, carried out suspension polymerisation 22 hours.Maximum pressure during this period reaches 4.1MPa.After polymerization is finished,, after the washing, under 80 ℃, carried out drying 20 hours, obtain pulverous vinylidene fluoride-hexafluoropropylene copolymer-(1) the polymer paste dehydration.
The polymerization yield is 90 amount %, and the logarithmic viscosity number of the vinylidene fluoride-hexafluoropropylene copolymer of gained-(1) is 2.1dl/g.
(preparation of vinylidene-trifluoro-ethylene copolymer-(1))
In the autoclave of 2 liters of inner capacitiess, drop into 1024g ion exchange water, 0.4g methylcellulose, 1.2g peroxy dicarbonate di-n-propyl ester, 379.6g vinylidene and 20.4g trifluoro-ethylene, under 26 ℃, carried out suspension polymerisation 22 hours.Maximum pressure during this period reaches 4.0MPa.After polymerization is finished,, after the washing, under 80 ℃, carried out drying 20 hours, obtain pulverous vinylidene-trifluoro-ethylene copolymer-(1) the polymer paste dehydration.
The polymerization yield is 85 amount %, and the logarithmic viscosity number of the vinylidene-trifluoro-ethylene copolymer of gained-(1) is 1.8dl/g.
(chlorinity)
Measure the chlorinity of vinylidene base polymer-(1) of above-mentioned chloride atom in accordance with the following methods.
According to flask combustion method (JIS K7229), obtain experimental liquid by vinylidene base polymer-(1) burning with chloride atom, with above-mentioned experimental liquid ion chromatography analysis, in the gained chromatogram, obtain the chromatographic peak area of chloride ion, obtain the chlorinity of vinylidene base polymer-(1) of above-mentioned chloride atom according to the absolute standard curve method.
The chlorine atom content of vinylidene base polymer-(1) of that obtain as mentioned above, chloride atom is 2.1 weight % with respect to 100 these polymer of weight %.
The chlorine atom content of vinylidene base polymer-(1) of the polar functionalities obtained of using the same method is 0 weight % with respect to 100 these polymer of weight %.
The chlorine atom content of Kynoar-(1) obtained of using the same method is 0 weight % with respect to 100 these polymer of weight %.
The chlorine atom content of vinylidene fluoride-hexafluoropropylene copolymer-(1) obtained of using the same method is 0 weight % with respect to 100 these polymer of weight %.
The chlorine atom content of vinylidene-trifluoro-ethylene copolymer-(1) obtained of using the same method is 0 weight % with respect to 100 these polymer of weight %.
[absorbance is than (I R)]
Measure the IR spectrum of vinylidene base polymer-(1) of above-mentioned polar functionalities with following method.
With the powder of vinylidene base polymer-(1) of above-mentioned polar functionalities respectively at the pressing plate of 200 ℃ of following hot-pressing 30mm * 30mm.
Use infrared spectrophotometer FT-IR4100 (Japanese beam split Co., Ltd. system), at 1500cm -1～4000cm -1Scope measure the IR spectrum of above-mentioned pressing plate.
Obtain the absorbance of following formula (1) expression than (I by the IR spectrum that obtains R).
I R＝I 1750/I 3025 …(1)
(in above-mentioned formula (1), I 1750Be 1750cm -1Absorbance, I 3025Be 3025cm -1Absorbance.)
Need to prove I 1750And I 3025Can try to achieve by subtracting background absorbance the apparent absorbance under above-mentioned wave number.That is, set I 20Be wave number 1750cm -1Apparent absorbance, I 21Be I 20Wave number under the background absorbance time, I then 1750=I 20-I 21
In addition, set I 10Be wave number 3025cm -1Apparent absorbance, I 11Be I 10Wave number under the background absorbance time, I then 3025=I 10-I 11
Need to prove that the background absorbance is meant the absorbance when the terminal and high wave number side of the lower wave number side that links the peak is terminal.That is, at I 21In, it is lower wave number side (1653cm that expression links the zone that absorbs end -1～1662cm -1) and high wave number side (1897cm -1～1907cm -1) straight line when being baseline, 1750cm -1Absorbance, at I 11In, expression links lower wave number side (2859cm -1～2866cm -1) and high wave number side (3306cm -1～3317cm -1) the 3025cm of straight line when being baseline -1Absorbance.
Particularly, for vinylidene base polymer-(1) of polar functionalities,, can as described belowly obtain absorbance than (I according to the IR spectrum (Fig. 1) that said method is measured R).
According to Fig. 1, I 20Be wave number 1750cm -1Apparent absorbance 0.24, I 21For linking wave number 1660cm -1End and 1900cm -1Terminal the time, wave number 1750cm -1Absorbance 0.06, by I 20And I 21The I that obtains 1750Be 0.18.In addition, I 10Be wave number 3025cm -1Apparent absorbance 0.53, I 11For linking wave number 2863cm -1End and 3310cm -1Terminal the time, wave number 3025cm -1Absorbance 0.05, by I 10And I 11The I that obtains 3025Be 0.48.
Therefore, the absorbance of the vinylidene base polymer of polar functionalities-(1) is than (I R) be 0.38.
Use the same method the absorbance of vinylidene base polymer-(1) of obtaining chloride atom than (I R).The absorbance of the vinylidene base polymer of chloride atom-(1) is than (I R) be 0.07.
Use the same method obtain Kynoar-(1) absorbance than (I R).The absorbance of Kynoar-(1) is than (I R) be 0.05.
Use the same method obtain vinylidene fluoride-hexafluoropropylene copolymer-(1) absorbance than (I R).The absorbance of vinylidene fluoride-hexafluoropropylene copolymer-(1) is than (I R) be 0.06.
Use the same method obtain vinylidene-trifluoro-ethylene copolymer-(1) absorbance than (I R).The absorbance of vinylidene-trifluoro-ethylene copolymer-(1) is than (I R) be 0.06.
(embodiment 1)
Vinylidene base polymer-(1) of the chloride atom of 2.0g and vinylidene base polymer-(1) of 6.0g polar functionalities are dissolved in the 92g N-N-methyl-2-2-pyrrolidone N-equably, obtain binder solution.
(Hitachi changes into the industry system to add 9.0g MAG in the binder solution of 12.5g gained, Delanium, average grain diameter 20 μ m) and 3.5g dilution N-N-methyl-2-2-pyrrolidone N-, make to spend bubble and stir too youth's (new base system) and mix, obtain anode for nonaqueous electrolyte secondary battery mixture (A1).
Use excellent coating machine, above-mentioned anode for nonaqueous electrolyte secondary battery mixture (A1) is coated on the rolled copper foil as the thickness 10 μ m of current-collector equably, the weight that makes dried mixture layer is 150g/m 2, dry under 110 ℃ in Geer-Evans-oven (gear oven), after heat-treating under 130 ℃, to pressurize at 40MPa, the bulk density that obtains mixture layer is 1.7g/cm 3Electrode (A1).
(comparative example 1)
Vinylidene base polymer-(1) of 8.0g polar functionalities is dissolved in the 92g N-N-methyl-2-2-pyrrolidone N-equably, obtains binder solution.
(Hitachi changes into the industry system to add 9.0g MAG in the binder solution of 12.5g gained, Delanium, average grain diameter 20 μ m) and 3.5g dilution N-N-methyl-2-2-pyrrolidone N-, make to spend bubble and stir too youth's (new base system) and mix, obtain anode for nonaqueous electrolyte secondary battery mixture (B1).
Use excellent coating machine, above-mentioned anode for nonaqueous electrolyte secondary battery mixture (B1) is coated on the rolled copper foil as the thickness 10 μ m of current-collector equably, the weight that makes dried mixture layer is 150g/m 2, dry under 110 ℃ in Geer-Evans-oven, after heat-treating under 130 ℃, to pressurize at 40MPa, the bulk density that obtains mixture layer is 1.7g/cm 3Electrode (B1).
(comparative example 2)
Except that using 2.0g Kynoar-(1) to replace carrying out similarly to Example 1 vinylidene base polymer-(1) of the chloride atom of 2.0g, obtain anode for nonaqueous electrolyte secondary battery mixture (B2) and electrode (B2).
(comparative example 3)
Except that using 2.0g vinylidene fluoride-hexafluoropropylene copolymer-(1) to replace carrying out similarly to Example 1 vinylidene base polymer-(1) of the chloride atom of 2.0g, obtain anode for nonaqueous electrolyte secondary battery mixture (B3) and electrode (B3).
(comparative example 4)
Except that using 2.0g vinylidene-trifluoro-ethylene copolymer-(1) to replace carrying out similarly to Example 1 vinylidene base polymer-(1) of the chloride atom of 2.0g, obtain anode for nonaqueous electrolyte secondary battery mixture (B4) and electrode (B4).
(embodiment 2)
Vinylidene base polymer-(1) of the chloride atom of 6.0g and vinylidene base polymer-(1) of 2.0g polar functionalities are dissolved in the 92g N-N-methyl-2-2-pyrrolidone N-equably, obtain binder solution.
(Hitachi changes into the industry system to add 9.0g MAG in the binder solution of 12.5g gained, Delanium, average grain diameter 20 μ m) and 3.5g dilution N-N-methyl-2-2-pyrrolidone N-, make to spend bubble and stir too youth's (new base system) and mix, obtain anode for nonaqueous electrolyte secondary battery mixture (A2).
Use excellent coating machine, above-mentioned anode for nonaqueous electrolyte secondary battery mixture (A2) is coated on the rolled copper foil as the thickness 10 μ m of current-collector equably, the weight that makes dried mixture layer is 150g/m 2, dry under 110 ℃ in Geer-Evans-oven, after heat-treating under 130 ℃, to pressurize at 40MPa, the bulk density that obtains mixture layer is 1.7g/cm 3Electrode (A2).
(embodiment 3)
Vinylidene base polymer-(1) of the chloride atom of 4.0g and vinylidene base polymer-(1) of 4.0g polar functionalities are dissolved in the 92g N-N-methyl-2-2-pyrrolidone N-equably, obtain binder solution.
(Hitachi changes into the industry system to add 9.0g MAG in the binder solution of 12.5g gained, Delanium, average grain diameter 20 μ m) and 3.5g dilution N-N-methyl-2-2-pyrrolidone N-, make to spend bubble and stir too youth's (new base system) and mix, obtain anode for nonaqueous electrolyte secondary battery mixture (A3).
Use excellent coating machine, above-mentioned anode for nonaqueous electrolyte secondary battery mixture (A3) is coated on the rolled copper foil as the thickness 10 μ m of current-collector equably, the weight that makes dried mixture layer is 150g/m 2, dry under 110 ℃ in Geer-Evans-oven, after heat-treating under 130 ℃, to pressurize at 40MPa, the bulk density that obtains mixture layer is 1.7g/cm 3Electrode (A3).
(comparative example 5)
Vinylidene base polymer-(1) of the chloride atom of 8.0g is dissolved in the 92gN-N-methyl-2-2-pyrrolidone N-equably, obtains binder solution.
(Hitachi changes into the industry system to add 9.0g MAG in the binder solution of 12.5g gained, Delanium, average grain diameter 20 μ m) and 3.5g dilution N-N-methyl-2-2-pyrrolidone N-, make to spend bubble and stir too youth's (new base system) and mix, obtain anode for nonaqueous electrolyte secondary battery mixture (B5).
Use excellent coating machine, above-mentioned anode for nonaqueous electrolyte secondary battery mixture (B5) is coated on the rolled copper foil as the thickness 10 μ m of current-collector equably, the weight that makes dried mixture layer is 150g/m 2, dry under 110 ℃ in Geer-Evans-oven, after heat-treating under 130 ℃, to pressurize at 40MPa, the bulk density that obtains mixture layer is 1.7g/cm 3Electrode (B5).
(comparative example 6)
Vinylidene base polymer-(1) and 2.0g Kynoar-(1) of the chloride atom of 6.0g are dissolved in the 92g N-N-methyl-2-2-pyrrolidone N-equably, obtain binder solution.
(Hitachi changes into the industry system to add 9.0g MAG in the binder solution of 12.5g gained, Delanium, average grain diameter 20 μ m) and 3.5g dilution N-N-methyl-2-2-pyrrolidone N-, make to spend bubble and stir too youth's (new base system) and mix, obtain anode for nonaqueous electrolyte secondary battery mixture (B6).
Use excellent coating machine, above-mentioned anode for nonaqueous electrolyte secondary battery mixture (B6) is coated on the rolled copper foil as the thickness 10 μ m of current-collector equably, the weight that makes dried mixture layer is 150g/m 2, dry under 110 ℃ in Geer-Evans-oven, after heat-treating under 130 ℃, to pressurize at 40MPa, the bulk density that obtains mixture layer is 1.7g/cm 3Electrode (B6).
(peel strength)
The peel strength of current-collector and mixture layer in the electrode that obtains in embodiment and comparative example is according to JIS K6854, utilize 180 ° of disbonded tests to measure.The results are shown in table 1,2.
Figure BPA00001348260800241
Figure BPA00001348260800251
By above-mentioned table 1 and 2 as can be known, use in the negative pole of anode for nonaqueous electrolyte secondary battery mixture manufacturing of the present invention peel strength excellence between mixture layer and the current-collector.
Specifically, when embodiment 1 compares with comparative example 1～4, the anode for nonaqueous electrolyte secondary battery mixture that contains the vinylidene base polymer of chloride atom, with the situation (comparative example 1) of the vinylidene base polymer that only uses polar functionalities, and use not that the vinylidene base polymer of chloride atom replaces the situation (comparative example 2～4) of the vinylidene base polymer of chloride atom to compare the peel strength excellence.That is, because the vinylidene base polymer that anode for nonaqueous electrolyte secondary battery mixture of the present invention contains chloride atom is as neccessary composition, so use in the negative pole of this mixture manufacturing the peel strength excellence between mixture layer and the current-collector.
In addition, when embodiment 2,3 compares with comparative example 5 and 6, the anode for nonaqueous electrolyte secondary battery mixture that contains the vinylidene base polymer of polar functionalities, with the situation (comparative example 5) of the vinylidene base polymer that only uses chloride atom and use not that the vinylidene base polymer of polar functionalities replaces the situation (comparative example 6) of the vinylidene base polymer of polar functionalities to compare the peel strength excellence.That is, because the vinylidene base polymer that anode for nonaqueous electrolyte secondary battery mixture of the present invention contains polar functionalities is as neccessary composition, so use in the negative pole of this mixture manufacturing the peel strength excellence between mixture layer and the current-collector.

Claims (10)

1. an anode for nonaqueous electrolyte secondary battery mixture is characterized in that, contains vinylidene base polymer, electrode active material, and the organic solvent of the vinylidene base polymer of polar functionalities, chloride atom,
The chlorine atom that contains 0.3～5 weight % in the vinylidene base polymer of the described chloride atom of per 100 weight %.
2. anode for nonaqueous electrolyte secondary battery mixture as claimed in claim 1 is characterized in that, the polar group that the vinylidene base polymer of described polar functionalities contains is at least a kind of polar group that is selected among carboxyl and the acid anhydride.
3. anode for nonaqueous electrolyte secondary battery mixture as claimed in claim 2 is characterized in that, the absorbance of following formula (1) expression when measuring the infrared absorption spectroscopy of vinylidene base polymer of described polar functionalities is than (I R) in 0.10～1.5 scope,
I R＝I 1750/I 3025 …(1)
In described formula (1), I 1750Be 1750cm -1Absorbance, I 3025Be 3025cm -1Absorbance.
4. anode for nonaqueous electrolyte secondary battery mixture as claimed in claim 1, it is characterized in that, the vinylidene base polymer of described polar functionalities is the vinylidene base polymer that the following substances copolymerization is obtained: the monomer of the polar functionalities of the vinylidene of 80～99.9 weight portions, 0.1～20 weight portion, wherein, the monomer of described vinylidene and polar functionalities adds up to 100 weight portions.
5. anode for nonaqueous electrolyte secondary battery mixture as claimed in claim 4 is characterized in that, the monomer of described polar functionalities is to contain the monomer that is selected from least a kind of polar group among carboxyl and the acid anhydride.
6. anode for nonaqueous electrolyte secondary battery mixture as claimed in claim 1, it is characterized in that, the vinylidene base polymer of described chloride atom is the vinylidene base polymer that the following substances copolymerization is obtained: the monomer of the chloride atom of the vinylidene of 90～99 weight portions, 1～10 weight portion, wherein, the monomer of described vinylidene and chloride atom adds up to 100 weight portions.
7. anode for nonaqueous electrolyte secondary battery mixture as claimed in claim 6 is characterized in that, the monomer of described chloride atom is a chlorotrifluoroethylene.
8. as each described anode for nonaqueous electrolyte secondary battery mixture in the claim 1～7, it is characterized in that described electrode active material is a material with carbon element.
9. an anode for nonaqueous electrolyte secondary battery is characterized in that, by each described anode for nonaqueous electrolyte secondary battery mixture in the claim 1～8 being coated on the current-collector and dry obtaining.
10. a rechargeable nonaqueous electrolytic battery is characterized in that, described rechargeable nonaqueous electrolytic battery has the described anode for nonaqueous electrolyte secondary battery of claim 9.
CN2009801409164A 2008-12-26 2009-12-21 Negative-electrode mix for nonaqueous-electrolyte secondary battery, negative electrode for nonaqueous-electrolyte secondary battery, and nonaqueous-electrolyte secondary battery Pending CN102187503A (en)

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