CN104272508A - Negative electrode for secondary cell, secondary cell, slurry composition, and manufacturing method - Google Patents

Negative electrode for secondary cell, secondary cell, slurry composition, and manufacturing method Download PDF

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Publication number
CN104272508A
CN104272508A CN201380023021.9A CN201380023021A CN104272508A CN 104272508 A CN104272508 A CN 104272508A CN 201380023021 A CN201380023021 A CN 201380023021A CN 104272508 A CN104272508 A CN 104272508A
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China
Prior art keywords
active material
electrode active
negative electrode
water
monomer
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Chinese (zh)
Inventor
早坂健太郎
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Zeon Corp
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Nippon Zeon Co 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
    • H01M4/13—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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/134—Electrodes based on metals, Si or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
    • 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
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/386—Silicon or alloys based on silicon
    • 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 for a secondary cell containing a negative-electrode active substance, a particulate binder, and a water-soluble polymer, wherein the water-soluble polymer contains 0.1-15 weight percent of a sulfonate-group-containing monomer unit and 0.5-10 weight percent of a fluoride-containing (meth)acrylate monomer unit. The present invention also provides a secondary cell or the like including the negative electrode.

Description

Secondary battery cathode, secondary cell, paste compound and manufacture method
Technical field
The present invention relates to the manufacture method of secondary battery cathode, secondary cell, paste compound and secondary battery cathode.
Background technology
In recent years, the universal highly significant of the portable terminal device such as notebook computer, mobile phone, PDA (Personal Digital Assistant).Can be used as the many uses of secondary cell such as nickel-hydrogen secondary cell, the lithium rechargeable battery etc. of the power supply of these portable terminal devices.Portable terminal device requires more comfortable Portability, and thus its miniaturization, slimming, lighting, high performance are developed rapidly, its result, and portable terminal device has been used to various occasion.In addition, for secondary cell, also require miniaturization, slimming, lighting and high performance in the same manner as portable terminal device.
In order to realize the high performance of secondary cell, have studied the improvement of electrode, electrolyte and other battery components.Wherein, electrode manufactures by operating as follows usually: in water or organic solvent equal solvent, disperse or dissolve the polymer as adhesive (binding agent) and obtain fluid composition, the conductive agent such as mixed electrode active material and conductive carbon as required in this fluid composition, obtain paste compound, this paste compound is coated with on the current collector and carries out drying.About electrode, except the research of electrode active material and collector body itself, also carry out the research (such as with reference to patent documentation 1 ~ 4) for the adhesive and various additive electrode active material etc. being bonded in collector body.
Such as, in patent documentation 1, patent documentation 2, describe the negative pole slurry of non-aqueous secondary batteries, its bonding agent containing material with carbon element active material and be made up of aqueous dispersion emulsion resin and water-soluble high-molecular compound.As water-soluble high-molecular compound, describe polyvinyl alcohol, carboxymethyl cellulose, Sodium Polyacrylate etc.Also describe and make the coating strength of battery thus and be coated with film density to become good.
A kind of binder for secondary battery electrode is described in patent documentation 3, it is made up of copolymer emulsion, and described copolymer emulsion makes to carry out emulsion polymerisation by fluorine-containing unsaturated monomer 0.02 ~ 13 % by weight, aliphatic conjugated diene monomer 10 ~ 38 % by weight, ethylenically unsaturated carboxylic acids monomer 0.1 ~ 10 % by weight and the monomer composition that can form with other monomers 49 ~ 88.88 % by weight of their copolymerization and obtains.Also describe and make fitment stability, resistance to blocking, resistance to dry linting adaptability, cohesive force excellence thus.
In addition, a kind of binder for secondary battery electrode is described in patent documentation 4, it is made up of the polymer had from the monomeric unit of the contain fluorine atoms monomers such as (methyl) fluoroalkyl acrylate, in addition, describe as improving coating or improving charge-discharge characteristic, can cellulosic polymer, polyacrylate etc. be added.Also describe and can obtain thus continuing good electrode with the caking property of active material.
Prior art document
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2003-308841 publication
Patent documentation 2: Japanese Unexamined Patent Publication 2003-217573 publication
Patent documentation 3: Japanese Unexamined Patent Publication 2010-146870 publication
Patent documentation 4: Japanese Unexamined Patent Publication 2002-42819 publication
Summary of the invention
The problem that invention will solve
In the secondary battery, the particle of sometimes contained in negative pole electrode active material can expand with discharge and recharge and shrink.If repeat such expansion and contraction occur, then likely cause negative pole to expand gradually, secondary cell deforms.Therefore, expect to develop the technology that negative pole as above can be suppressed to expand.
In addition, in existing secondary cell, if preserved in such as 60 DEG C such hot environments, then there is the situation that capacity reduces.Therefore, even if expect to develop the technology that the capacity of this secondary cell also can be suppressed to reduce when to preserve secondary cell in hot environment.
In addition, for secondary cell, require that it all has the characteristics such as good cycle characteristics, output characteristic in any environment of hot environment and low temperature environment.
The present invention completes in view of above-mentioned problem, object be to provide a kind of can realize following secondary cell secondary battery cathode, the negative pole paste compound of described secondary battery cathode and the manufacture method of secondary battery cathode can be manufactured and possess the secondary cell of described secondary battery cathode, even if described secondary cell can make the negative pole occurred with discharge and recharge expand, and capacity reduction also not easily occurs when being suppressed to preserve in hot environment, all have good characteristic in any environment of hot environment and low temperature environment.
The method of dealing with problems
The present inventor conducts in-depth research for solving above-mentioned problem, found that, by making in the electrode active material layer of secondary battery cathode containing following water-soluble polymer, the negative pole occurred with discharge and recharge can be suppressed to expand, even and if when preserving in hot environment, also not easily there is the reduction of capacity, described water-soluble polymer contains containing sulfonic group monomeric unit and fluorine-containing (methyl) acrylate monomeric units with special ratios respectively, and then completes the present invention.
That is, according to the present invention, following [1] ~ [11] can be provided.
[1] secondary battery cathode, it contains negative electrode active material, particle-like adhesive and water-soluble polymer, wherein,
Described water-soluble polymer be containing 0.1 % by weight ~ 15 % by weight containing sulfonic group monomeric unit and 0.5 % by weight ~ 10 % by weight the copolymer of fluorine-containing (methyl) acrylate monomeric units.
[2] secondary battery cathode Gen Ju [1], wherein, described water-soluble polymer contains ethylenically unsaturated carboxylic acids monomeric unit.
[3] secondary battery cathode Gen Ju [2], wherein, described ethylenically unsaturated carboxylic acids monomer is olefinic unsaturated monocarboxylic acid monomer.
[4] according to secondary battery cathode according to any one of [1] ~ [3], wherein, described negative electrode active material can occlusion and release lithium, and containing metal.
[5] secondary battery cathode Gen Ju [4], wherein, described metal is silicon.
[6] according to the secondary battery cathode according to any one of [1] ~ [5], wherein, described particle-like adhesive contains the polymer comprising aliphatic conjugated diene monomer unit.
[7] secondary battery cathode Gen Ju [6], wherein, described in comprise aliphatic conjugated diene monomer unit polymer also comprise aromatic vinyl monomer unit.
[8] secondary cell, it possesses positive pole, negative pole, electrolyte and dividing plate, the secondary battery cathode of described negative pole according to any one of [1] ~ [7].
[9] a secondary battery negative pole paste compound, it contains negative electrode active material, particle-like adhesive and water-soluble polymer, wherein,
Described water-soluble polymer be containing 0.1 % by weight ~ 15 % by weight containing sulfonic group monomeric unit and 0.5 % by weight ~ 10 % by weight the copolymer of fluorine-containing (methyl) acrylate monomeric units.
[10] the negative pole paste compound Gen Ju [9], wherein, described water-soluble polymer comprises ethylenically unsaturated carboxylic acids monomeric unit.
[11] manufacture method for secondary battery cathode, it comprises: be coated with [9] or the secondary battery negative pole paste compound described in [10] on the current collector and carry out drying.
The effect of invention
According to secondary battery cathode of the present invention, even if the reduction that can realize suppressing the negative pole occurred with discharge and recharge to expand capacity also not easily occurs when preserving in hot environment and the secondary cell that all characteristic is good in any environment of hot environment and low temperature environment.
Even if the reduction that secondary cell of the present invention can suppress the negative pole occurred with discharge and recharge to expand, and capacity also not easily occurs when preserving in hot environment and all characteristic is good in any environment of hot environment and low temperature environment.
If use negative pole paste compound of the present invention, then can manufacture secondary battery cathode of the present invention.In addition, the stability of negative pole paste compound of the present invention is high, therefore can preserve for a long time, and uses easily.
According to the manufacture method of secondary battery cathode of the present invention, secondary battery cathode of the present invention can be manufactured.
Embodiment
Below, in conjunction with execution mode and illustrative material, the present invention is described in detail, but the present invention is not limited to execution mode shown below and illustrative material etc., at random can changes in the scope not departing from claims of the present invention and equivalency range thereof and implement.
In this manual, " (methyl) acrylic acid " refers to " acrylic acid " and " methacrylic acid ".In this manual, something is water miscible referring to: at 25 DEG C, and when being dissolved in the water of 100g by this material 0.5g, insoluble composition is lower than 0.5 % by weight.In addition, something is non-water-soluble referring to: at 25 DEG C, and when being dissolved in the water of 100g by this material 0.5g, insoluble composition is more than 90 % by weight.
[1. secondary battery cathode]
Secondary battery cathode of the present invention (following, to be suitably called " negative pole of the present invention ") is containing negative electrode active material, particle-like adhesive and water-soluble polymer.Usually, negative pole of the present invention has collector body and is formed at the negative electrode active material layer on surface of above-mentioned collector body, and negative electrode active material layer contains above-mentioned negative electrode active material, particle-like adhesive and water-soluble polymer.
[1-1. negative electrode active material]
Negative electrode active material is negative pole electrode active material, is the material of giving and accepting carrying out electronics in the negative pole of secondary cell.
Such as when secondary cell of the present invention is lithium rechargeable battery, as negative electrode active material, usually using can occlusion and release the material of lithium.
As the example of preferred negative electrode active material, carbon can be enumerated.As carbon, such as, can enumerate: native graphite, Delanium, carbon black etc., wherein preferably use native graphite.
As other examples of preferred negative electrode active material, metallic material can be enumerated.Particularly preferably containing the negative electrode active material of at least a kind that is selected from tin, silicon, germanium and lead.This is because the irreversible capacity of the negative electrode active material containing these elements is little.
Wherein, the negative electrode active material preferably containing silicon.By using the negative electrode active material containing silicon, the capacitance of lithium rechargeable battery can be increased.In addition; usually expansion and the contraction of significantly (such as about 5 times) can be there is with discharge and recharge in the negative electrode active material containing silicon; but in negative pole of the present invention, the reduction of the battery performance caused by the expansion of the negative electrode active material containing silicon and contraction can be suppressed.
As the example of the active material containing silicon, the combination of the active material be made up of metallic silicon, the active material (hereinafter also referred to " silicon class active material ") be made up of the compound of silicon and other elements and the active material be made up of metallic silicon and silicon class active material can be enumerated.
In addition, negative electrode active material can be used alone a kind, also can combinationally use two or more with arbitrary ratio.Therefore, in above-mentioned negative electrode active material, may be combined with and use two or more.Wherein, combination is preferably used to contain the negative electrode active material of carbon and silicon-containing active material.Combination containing carbon and silicon-containing active material as negative electrode active material when, can infer, Li occur under high potential to the insertion of the one or both in metallic silicon and silicon class active material and disengaging, Li occur under electronegative potential to the insertion of carbon and disengaging.Thus, can repression of swelling and contraction, therefore can improve the cycle characteristics of lithium rechargeable battery.
As silicon class active material, such as, can enumerate: SiO, SiO 2, SiO x(0.01≤X<2), SiC, SiOC etc., preferred SiO x, SiC and SiOC.Wherein, from the view point of the expansion that can suppress negative electrode active material self, particularly preferably SiO is used xas silicon class active material.SiO xcan by SiO and SiO 2in one or both and the compound that formed of metallic silicon.This SiO xsuch as by will SiO be heated 2with the mixture of metallic silicon and the silicon monoxide gas cooling that generates and separate out and manufacture.
When combinationally using carbon and silicon-containing active material, preferred silicon-containing active material and conductive carbon Composite.By with conductive carbon Composite, the expansion of negative electrode active material self can be suppressed.
As the method for Composite, such as, can enumerate: carry out the method for Composite by utilizing carbon to apply silicon-containing active material, by the mixture pelleting containing conductive carbon and silicon-containing active material being carried out the method etc. of Composite.
When using combination to contain the negative electrode active material of carbon and silicon-containing active material, in negative electrode active material, preferably relative to amount 100 weight portion of whole carbon atom, the amount of silicon atom is 0.1 weight portion ~ 50 weight portion.Conductive path can be formed well thus, make the conductivity of negative pole good.
When using combination to contain the negative electrode active material of carbon and silicon-containing active material, (" weight of carbon "/" weight of silicon-containing active material " is preferably more than 50/50 to the weight ratio of carbon and silicon-containing active material, be more preferably more than 70/30, be preferably less than 97/3, be more preferably less than 90/10.The cycle characteristics of secondary cell can be improved thus.
(shape of negative electrode active material)
Negative electrode active material is preferably particle shape by whole grain.If the shape of particle is spherical, then, when electrode forming, more highdensity electrode can be formed.
When negative electrode active material is particle, its volume average particle size suitably can be selected according to the balance between other constitutive requirements of secondary cell, be generally more than 0.1 μm, be preferably more than 1 μm, be more preferably more than 5 μm, be generally less than 100 μm, be preferably less than 50 μm, be more preferably less than 30 μm.Here, volume average particle size adopts the particle diameter when the cumulative volume of calculating reaches 50% by small particle diameter side in the particle size distribution measured with laser diffractometry.
Improve from the view point of output density, the specific area of negative electrode active material is generally 2m 2/ more than g, is preferably 3m 2/ more than g, is more preferably 5m 2/ more than g, is generally 20m 2/ below g, is preferably 15m 2/ below g, is more preferably 10m 2/ below g.The specific area of negative electrode active material measures by such as BET method.
[1-2. particle-like adhesive]
Particle-like adhesive is the composition making electrode active material be bonded in collector body surface in negative pole.In negative pole of the present invention, to be bondd negative electrode active material by particle-like adhesive, negative electrode active material can be suppressed to depart from from negative electrode active material layer.In addition, particle-like adhesive also bonds the particle beyond negative electrode active material contained in negative electrode active material layer usually, also plays the effect of the intensity keeping negative electrode active material layer.
As particle-like adhesive, preferably use the excellent performance of maintenance negative electrode active material, for the high adhesive of the adaptation of collector body.Usually, use the adhesive containing polymer as particle-like adhesive, particularly can use the adhesive formed by polymer in fact.The polymer of particle-like adhesive can be homopolymers, also can be copolymer.
The polymer of particle-like adhesive is preferably containing aliphatic conjugated diene monomer unit.Aliphatic conjugated diene monomer unit is the low and repetitive of softness of rigidity.Therefore, by the polymer containing aliphatic conjugated diene monomer unit is used as particle-like adhesive, sufficient adaptation can be obtained between negative electrode active material layer and collector body.
Aliphatic conjugated diene monomer unit is the repetitive being undertaken being polymerized by aliphatic conjugated diene monomer and obtain.As the example of aliphatic conjugated diene monomer, can enumerate: 1,3-butadiene, 2-methyl isophthalic acid, 3-butadiene, 2,3-dimethyl-1,3-butadiene, 2-chloro-1,3-butadiene, substituted straight chain conjugation pentadiene class, replacement and side chain conjugation hexadiene class etc.Wherein, preferred 1,3-butadiene.
Aliphatic conjugated diene monomer can be used alone a kind, also can combinationally use two or more with arbitrary ratio.Therefore, the polymer of particle-like adhesive only can contain a kind of aliphatic conjugated diene monomer unit, also can with arbitrary ratio combination containing aliphatic conjugated diene monomer unit of more than two kinds.
In particle-like adhesive polymer, the ratio of aliphatic conjugated diene monomer unit is preferably more than 20 % by weight, is more preferably more than 30 % by weight, is preferably less than 70 % by weight, is more preferably less than 65 % by weight, is particularly preferably less than 55 % by weight.By more than the lower limit that the ratio of aliphatic conjugated diene monomer unit is located at above-mentioned scope, the flexibility of negative pole can be improved, in addition, by below the higher limit that is located at above-mentioned scope, sufficient adaptation can be obtained between negative electrode active material layer and collector body, or improve the electrolyte resistance of electrode.
Particle-like adhesive polymer is preferably containing aromatic vinyl monomer unit.Aromatic vinyl monomer unit is stablized, and can reduce polymer containing this aromatic vinyl monomer unit dissolubility in the electrolytic solution and negative electrode active material layer is stablized.
Aromatic vinyl monomer unit is the repetitive being undertaken being polymerized by aromatic vinyl monomer and obtain.As the example of aromatic vinyl monomer, can enumerate: styrene, AMS, vinyltoluene, divinylbenzene etc.Wherein, optimization styrene.Particle-like adhesive polymer is preferably containing aromatic vinyl monomer unit, and as mentioned above, the polymer of particle-like adhesive is preferably containing aliphatic conjugated diene monomer unit such as butadiene.Therefore, the polymer of particle-like adhesive is preferably the polymer containing aliphatic conjugated diene monomer unit and aromatic vinyl monomer unit, such as optimization styrene-butadiene copolymer.
Aromatic vinyl monomer can be used alone a kind, also can combinationally use two or more with arbitrary ratio.Therefore, the polymer of particle-like adhesive only can contain a kind of aromatic vinyl monomer unit, also can with arbitrary ratio combination containing aromatic vinyl monomer unit of more than two kinds.
When using aromatic vinyl monomer, in the polymer of particle-like adhesive, sometimes contain the unreacted aliphatic conjugated diene monomer as residual monomer and unreacted aromatic vinyl monomer.Now, the amount of the unreacted aliphatic conjugated diene monomer contained by particle-like adhesive polymer is preferably below 50ppm, be more preferably below 10ppm, the amount of the unreacted aromatic vinyl monomer contained by particle-like adhesive polymer is preferably below 1000ppm, is more preferably below 200ppm.If the amount of the aliphatic conjugated diene monomer contained by particle-like adhesive polymer is in above-mentioned scope, then on surface negative pole paste compound of the present invention being coated collector body and when making it dry and manufacture negative pole, can prevent from producing on the surface of negative pole caused by foaming chap or cause environmental pressure by foul smell.In addition, if the amount of the aromatic vinyl monomer contained by particle-like adhesive polymer is in above-mentioned scope, then can suppress chapping of the environmental pressure that produces corresponding to drying condition and negative terminal surface, and then, the electrolyte resistance of particle-like adhesive polymer can be improved.
In particle-like adhesive polymer, the ratio of aromatic vinyl monomer unit is preferably more than 30 % by weight, is more preferably more than 35 % by weight, is preferably less than 79.5 % by weight, is more preferably less than 69 % by weight.By making the ratio of aromatic vinyl monomer unit more than the lower limit of above-mentioned scope, the electrolyte resistance of secondary battery cathode of the present invention can be improved, in addition, by making its ratio below higher limit, when negative pole paste compound of the present invention is coated collector body, sufficient adaptation can be obtained between negative electrode active material layer and collector body.
The polymer of particle-like adhesive is preferably containing ethylenically unsaturated carboxylic acids monomeric unit.Because ethylenically unsaturated carboxylic acids monomeric unit is comprise the carboxyl (-COOH base) of the adsorptivity improving anticathode active material and collector body and the high repetitive of intensity, therefore, can stably prevent negative electrode active material from departing from from negative electrode active material layer, in addition, the intensity of negative pole can be improved.
Ethylenically unsaturated carboxylic acids monomeric unit is the repetitive being undertaken being polymerized by ethylenically unsaturated carboxylic acids monomer and obtain.As the example of ethylenically unsaturated carboxylic acids monomer, can enumerate: the monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid and dicarboxylic acids and its acid anhydrides etc.Wherein, from the view point of the stability of negative pole paste compound of the present invention, preferably the monomer be selected from acrylic acid, methacrylic acid and itaconic acid is used alone or in combination.
Ethylenically unsaturated carboxylic acids monomer can be used alone a kind, also can combinationally use two or more with arbitrary ratio.Therefore, particle-like adhesive polymer only can contain a kind of ethylenically unsaturated carboxylic acids monomeric unit, also can with arbitrary ratio combination containing ethylenically unsaturated carboxylic acids monomeric unit of more than two kinds.
In the polymer of particle-like adhesive, the ratio of ethylenically unsaturated carboxylic acids monomeric unit is preferably more than 0.5 % by weight, is more preferably more than 1 % by weight, be particularly preferably more than 2 % by weight, be preferably less than 10 % by weight, be more preferably less than 8 % by weight, be particularly preferably less than 7 % by weight.By making the ratio of ethylenically unsaturated carboxylic acids monomeric unit more than the lower limit of above-mentioned scope, the stability of negative pole paste compound of the present invention can be improved, in addition, by making its ratio below higher limit, can prevent the excess stickiness of negative pole slurry of the present invention from uprising, thus be easy to operation.
Significantly not destroying in the scope of effect of the present invention, particle-like adhesive polymer also can comprise any repetitive than that described above.As the example of the monomer corresponding with above-mentioned any repetitive, can enumerate: vinyl cyanide base class monomer, unsaturated carboxylic acid alkyl ester monomer, unsaturated monomer, unsaturated carboxylic acid amide monomer etc. containing hydroxyalkyl.These monomers can be used alone a kind, also can combinationally use two or more with arbitrary ratio.
As vinyl cyanide base class monomer, such as, can enumerate: acrylonitrile, methacrylonitrile, α-chloro-acrylonitrile, α-ethyl acrylonitrile etc.Wherein, preferred acrylonitrile and methacrylonitrile.These monomers can be used alone a kind, also can combinationally use two or more with arbitrary ratio.
As unsaturated carboxylic acid alkyl ester monomer, such as, can enumerate: methyl acrylate, methyl methacrylate, ethyl acrylate, EMA, butyl acrylate, glycidyl methacrylate, dimethyl fumarate, DEF, dimethyl maleate, diethyl maleate, dimethyl itaconate, monomethyl fumarate, monomethyl ester, 2-EHA etc.Wherein, preferable methyl methyl acrylate, ethyl acrylate and butyl acrylate.These monomers can be used alone a kind, also can combinationally use two or more with arbitrary ratio.
As the unsaturated monomer containing hydroxy alkyl, such as, can enumerate: propenoic acid beta-hydroxy base ethyl ester, methacrylic acid beta-hydroxy ethyl ester, hydroxypropyl acrylate, hydroxy propyl methacrylate, hydroxy butyl acrylate, methacrylic acid hydroxyl butyl ester, methacrylic acid 3-chlorine-2-hydroxyl propyl ester, maleic acid two (ethylene glycol) ester, itaconic acid two (ethylene glycol) ester, maleic acid 2-hydroxy methacrylate, maleic acid two (2-hydroxyethyl) ester, fumaric acid 2-hydroxyethyl methyl esters etc.Wherein, preferred propenoic acid beta-hydroxy base ethyl ester.These monomers can be used alone a kind, also can combinationally use two or more with arbitrary ratio.
As unsaturated carboxylic acid amide monomer, such as, can enumerate: acrylamide, Methacrylamide, N hydroxymethyl acrylamide, N-methylol methacrylamide, N,N-DMAA etc.Wherein, preferred acrylamide and Methacrylamide.These monomers can be used alone a kind, also can combinationally use two or more with arbitrary ratio.
In addition, as the monomer of the polymer of constituent particle shape adhesive, the monomer that such as ethene, propylene, vinyl acetate, propionate, vinyl chloride, vinylidene chloride etc. use in common emulsion polymerisation can also be used.These monomers can be used alone a kind, also can combinationally use two or more with arbitrary ratio.
The weight average molecular weight of the polymer of particle-like adhesive is preferably 10, and more than 000, be more preferably 20, more than 000, be preferably 2,000, less than 000, be more preferably 500, less than 000.If the weight average molecular weight of particle-like adhesive polymer is in above-mentioned scope, then easily make the intensity of negative pole of the present invention and the favorable dispersibility of negative electrode active material.The weight average molecular weight of the polymer of particle-like adhesive can utilize gel permeation chromatography (GPC), obtains as using oxolane as the value of the polystyrene conversion of developing solvent.
The glass transition temperature of particle-like adhesive is preferably more than-75 DEG C, is more preferably more than-55 DEG C, is particularly preferably more than-35 DEG C, is preferably less than 40 DEG C, is preferably less than 30 DEG C, is more preferably less than 20 DEG C, is particularly preferably less than 15 DEG C.By making the glass transition temperature of particle-like adhesive in above-mentioned scope, the characteristic such as the flexibility of negative pole, caking property and windability, adaptation between negative electrode active material layer and collector body can obtain high balance, therefore preferably.
Usually, particle-like adhesive is the particle of non-soluble polymer.Therefore, in negative pole paste compound of the present invention, particle-like adhesive is not dissolved in the water as solvent, but disperses in the form of a particle.When particle-like adhesive is for being dissolved in the material in water and organic solvent (such as METHYLPYRROLIDONE), adhesive will be adsorbed in negative electrode active material, its result, and the output characteristic of gained secondary cell can be caused to reduce.And by making particle-like adhesive be non-water-soluble polymer, can prevent above-mentioned bad.In negative pole paste compound, particle-like adhesive is preferably dispersed in water with particle shape.As negative pole paste compound, when adhesive uses and is dissolved in the organic solvents such as NMP (METHYLPYRROLIDONE) and cannot keeps the material of particle shape shape, adhesive will be adsorbed in negative electrode active material surface, output characteristic reduction.
The number average bead diameter of the particle of particle-like adhesive is preferably more than 50nm, is more preferably more than 70nm, is preferably below 500nm, is more preferably below 400nm.By making the number average bead diameter of particle-like adhesive in above-mentioned scope, can make the intensity of gained negative pole and flexibility good.The existence of particle easily can be measured by transmission electron microscopy or coulter counter method, laser diffraction and scattering method etc.
Particle-like adhesive is such as by making the monomer composition containing above-mentioned monomer carry out being polymerized manufacturing in aqueous solvent.
In monomer composition, the ratio of the repetitive (such as, aliphatic conjugated diene monomer unit, aromatic vinyl monomer unit, ethylenically unsaturated carboxylic acids monomeric unit etc.) of ratio usually and in the polymer of particle-like adhesive of each monomer is identical.
As aqueous solvent, as long as the solvent of the particle dispersion of particle-like adhesive can be made just to be not particularly limited.Usually can be generally more than 80 DEG C, be preferably more than 100 DEG C, be generally less than 350 DEG C by the boiling point from normal pressure, be preferably in the aqueous solvent of less than 300 DEG C and select.Below, the example of this aqueous solvent is enumerated.In following illustration, the numeral in the bracket after solvent name is the boiling point (unit DEG C) under normal pressure, and it is that decimal point is later through to round up or by the value cast out.
As aqueous solvent, such as, can enumerate: water (100); The ketones such as diacetone alcohol (169), gamma-butyrolacton (204); The alcohols such as ethanol (78), isopropyl alcohol (82), normal propyl alcohol (97); The glycol ethers such as propylene glycol monomethyl ether (120), methyl cellosolve (124), ethyl cellosolve (136), ethylene glycol tertbutyl ether (152), butyl cellosolve (171), MMB (174), ethylene glycol list propyl ether (150), diethylene glycol monobutyl ether (230), triethylene glycol monobutyl base ether (271), DPGME (188); And the ethers etc. such as DOX (75), Isosorbide-5-Nitrae-dioxolanes (101), oxolane (66).Wherein, never flammable, the viewpoint easily obtaining the dispersion of particle-like adhesive particle is considered, particularly preferably water.Also water can be used as main solvent, the aqueous solvent beyond the water of above-mentioned record used in combination in the scope of dispersity can guaranteeing particle-like adhesive particle.
Polymerization is not particularly limited, and can use any means in such as solution polymerization process, suspension polymerization, mass polymerization, emulsion polymerization etc.As polymerization, any polymerization in such as ionic polymerization, radical polymerization, active free radical polymerization etc. can be used.Be easy to get calmly heavy polymer and polymer can directly obtain with the state being scattered in water, therefore do not need to carry out again decentralized process, can directly manufacture the viewpoint of efficiency for the manufacture in negative pole paste compound of the present invention etc., wherein particularly preferably emulsion polymerization.
Emulsion polymerization can utilize conventional method to carry out usually.Such as by " experimental chemistry lecture " the 28th volume, the method recorded in (publisher: ball is apt to (strain), Japanization association compiles) is carried out.Namely, the method is as follows: in the closed container being with mixer and heater, add additive, water, polymerization initiator and the monomers such as dispersant, emulsifying agent, crosslinking agent with given composition, composition in stirred vessel makes the emulsifications in water such as monomer, stirs and makes temperature increase and initiated polymerization.Or, can be add in closed container after making above-mentioned composition emulsification, and the method for similarly initiation reaction.
As polymerization initiator, can enumerate such as: lauroyl peroxide, di-isopropyl peroxydicarbonate, peroxy dicarbonate two (2-ethylhexyl) ester, tert-Butyl peroxypivalate, peroxidating 3, the organic peroxides such as 3,5-trimethyl acetyl; α, α ' azo-compound such as-azodiisobutyronitrile; Ammonium persulfate; Potassium peroxydisulfate etc.Polymerization initiator can be used alone a kind, also can combinationally use two or more with arbitrary ratio.
Emulsifying agent, dispersant, polymerization initiator etc. are the conventional materials used in these polymerizations, and its use amount is also the conventional amount used usually.In addition, when being polymerized, seed particles also can be adopted to carry out seeding polymerization.
Polymerization temperature and polymerization time at random can be selected according to the kind etc. of polymerization and polymerization initiator, and usually, polymerization temperature is about more than 30 DEG C, and polymerization time is 0.5 hour ~ 30 hours.
In addition, also the additives such as amine can be used as reagent and additive in polymerization.
In addition, also can by the aqueous liquid dispersion of the particle-like adhesive obtained by these methods and the hydroxide, ammonia, Inorganic Ammonium compound (the such as NH that such as comprise alkali metal (such as, Li, Na, K, Rb, Cs) 4cl etc.), the alkaline aqueous solution mixing of organic amine compound (such as monoethanolamine, diethylamine etc.) etc., thus pH is adjusted to the usual scope of 5 ~ 10, preferably 5 ~ 9.Wherein, the pH adjustment utilizing alkali metal hydroxide to carry out can make the caking property (peel strength) between collector body and negative electrode active material improve, therefore preferably.
The particle of above-mentioned particle-like adhesive also can for the composite polymer particle be made up of polymer of more than two kinds.Composite polymer particle also can be obtained by following method (two-stage polymerization method) etc.: utilize conventional method to make at least a kind of polymerizing monomer components, then utilize conventional method to make other at least a kind of polymerizing monomer components.Substep ground polymerization single polymerization monomer as described above, can obtain the particle of the nucleocapsid structure with the stratum nucleare being present in inside particles and the shell covering this stratum nucleare.
Relative to negative electrode active material 100 weight portion, the amount of particle-like adhesive is preferably more than 0.3 weight portion, is more preferably more than 0.5 weight portion, is preferably below 8 weight portions, is more preferably below 4 weight portions, is particularly preferably below 2 weight portions.By making the amount of particle-like adhesive be above-mentioned scope, negative pole paste compound of the present invention can be made to have suitable viscosity, thus can successfully be coated with on the current collector.In addition, the resistance of negative pole of the present invention can not be made to uprise, make between collector body and negative electrode active material layer, to obtain sufficient dhering strength.Its result, can suppress to implement in the operation of pressurized treatments at anticathode active material layer, particle-like adhesive is peeled off from negative electrode active material layer.
[1-3. water-soluble polymer]
In negative pole of the present invention, the water-soluble polymer contained by negative electrode active material layer is the copolymer containing fluorine-containing (methyl) acrylate monomeric units of sulfonic group monomeric unit and regulation ratio containing regulation ratio.By making negative pole of the present invention contain water-soluble polymer, can realize suppressing the negative pole occurred with discharge and recharge to expand, even and if also not easily there is the secondary cell of the reduction of capacity when preserving in hot environment.In addition, by using described water-soluble polymer, coating when being coated with on the current collector by negative pole paste compound of the present invention and the negative electrode active material layer in secondary cell of the present invention become excellent usually to the adaptation of collector body and high-temperature cycle and low temperature output characteristic.
Contain containing sulfonic group monomeric unit by making water-soluble polymer, the dispersion stabilization of negative electrode active material can be improved, prevent negative electrode active material from departing from from negative electrode active material layer, or suppress the chemical change of negative electrode active material self, therefore, High temperature storage characteristic and the low temperature output characteristic of secondary cell can be improved.In addition, fluorine-containing (methyl) acrylate monomeric units is contained by making water-soluble polymer, the swellability of water-soluble polymer to water can be improved (when be impregnated in water by water-soluble polymer, swelling degree is there is) because water-soluble polymer absorbs water, in addition, water-soluble polymer becomes and strain can occur, its result, the proterties of slurry improves, and then the performance of battery improves.Can think, these acting combination create above-mentioned effect together.
Specifically, in negative pole, when negative electrode active material there occurs and expands or shrink, water-soluble polymer can be followed the expansion of negative electrode active material or contraction and strain occurs, and therefore, the negative pole occurred with discharge and recharge can be suppressed to expand.In the past, if negative electrode active material carries out expanding and shrinking repeatedly, then particle-like adhesive can not be closely sealed with negative electrode active material sometimes, produce gap each other or between negative electrode active material and conductive agent at negative electrode active material, the negative electrode active material in negative pole and the electrical connection of conductive agent impaired.If above-mentioned electrical connection is impaired, then the capacitance of secondary cell likely reduces.But, if water-soluble polymer can be followed the expansion of negative electrode active material or contraction and strain occurs, then can suppress the generation in above-mentioned gap, maintain electrical connection, therefore, can cycle characteristics be improved.
In addition, in negative pole, the adsorbable surface in negative electrode active material of water-soluble polymer and cover negative electrode active material, forms protective layer.By this protective layer, the decomposition of the decomposition of the electrolyte under hot environment and the electrolyte with discharge and recharge can be suppressed.If electrolyte decomposes, then generation bubble around negative electrode active material, this bubble can hinder giving and accepting of electronics, likely reduces the capacitance of secondary cell.But, if suppress the decomposition of electrolyte by water-soluble polymer, then can suppress the reduction of capacitance as above, improve High temperature storage characteristic and high-temperature cycle.
In addition, the protective layer formed by water-soluble polymer is compared with the protective layer formed by existing additives such as such as carboxymethyl celluloses (following, to be suitably called " CMC "), and ionic conduction degree is high.Can infer, this is because water-soluble polymer has swellability (when water-soluble polymer be impregnated in electrolyte, water-soluble polymer occurs swelling by Electolyte-absorptive) to electrolyte.Because ionic conduction degree is high, therefore, diffusion resistance (that is, hindering the resistance of ion diffuse) reduces, and therefore, the output characteristic of secondary cell of the present invention is high, and particularly low temperature output characteristic is excellent.So, even if there is swellability relative to electrolyte, described swelling be also that the solvent of electrolyte easily through degree swelling of protective layer, therefore, can not can give full play to the effect suppressing electrolyte decomposition as above.
In addition, the dissolubility of water-soluble polymer in water is high, and easily can be adsorbed in negative electrode active material.Therefore, in the entirety of negative pole paste compound of the present invention, water-soluble polymer covers the particle surface of negative electrode active material, can improve the dispersiveness of the particle of negative electrode active material.Therefore, during coating negative pole paste compound, not easily produce the caking of negative electrode active material, therefore, easily can form thickness and the uniform film of composition.In addition, in the negative electrode active material layer obtained by the film formed as mentioned above, because negative electrode active material disperses well, therefore, the capacitance of secondary cell can be improved.
And then the flexibility due to water-soluble polymer is high and soft, therefore, can be very close to each otherly easily closely sealed between the surface of collector body and the surface of negative electrode active material.Therefore, water-soluble polymer can supplement the bonding between the collector body utilizing particle-like adhesive to realize and negative electrode active material, thus improves closing force.Therefore, the adaptation of negative electrode active material layer to collector body can be improved.
(containing sulfonic group monomeric unit)
Contained by water-soluble polymer is by containing sulfonic group (-SO containing sulfonic group monomeric unit 3h) repetitive that monomer carries out being polymerized and obtains.As the example of the monomer containing sulfonic acid, can enumerate: do not have except sulfonic group functional group containing sulfonic group monomer or its salt, containing amide groups and sulfonic monomer or its salt and containing hydroxyl and sulfonic monomer or its salt.These monomers can be used alone a kind, also can combinationally use two or more with arbitrary ratio.Therefore, water-soluble polymer only can contain sulfonic group monomeric unit containing a kind, also can with arbitrary ratio combination containing two or more.
As do not have except sulfonic group functional group containing sulfonic group monomer, such as can enumerate: by the monomer of the sulfonation of in the conjugated double bond of the diolefin compound such as isoprene and butadiene, vinyl sulfonic acid, styrene sulfonic acid, allyl sulphonic acid, sulfoethyl methacrylate, methacrylic acid sulphur propyl ester, methacrylic acid sulphur butyl ester etc.In addition, as its salt, such as, can enumerate: lithium salts, sodium salt, sylvite etc.These monomers can be used alone a kind, also can combinationally use two or more with arbitrary ratio.
As containing amide groups and sulfonic monomer, such as, can enumerate: 2-acrylamide-2-methyl propane sulfonic (AMPS) etc.In addition, as its salt, such as, can enumerate: lithium salts, sodium salt, sylvite etc.These monomers can be used alone a kind, also can combinationally use two or more with arbitrary ratio.
As containing hydroxyl and sulfonic monomer, such as, can enumerate: 3-allyloxy-2-hydroxy-propanesulfonic acid (HAPS) etc.In addition, as its salt, such as, can enumerate: lithium salts, sodium salt, sylvite etc.These monomers can be used alone a kind, also can combinationally use two or more with arbitrary ratio.
Wherein, optimization styrene sulfonic acid, 2-acrylamide-2-methyl propane sulfonic (AMPS) and other contain amide groups and sulfonic monomer and salt thereof.
The ratio containing sulfonic group monomeric unit in water-soluble polymer is more than 0.1 % by weight, is preferably more than 1 % by weight, is less than 15 % by weight on the other hand, is preferably less than 10 % by weight.If water-soluble polymer have sulfonic exist density increase, then negative pole slurry dispersiveness improve.In addition, due to usually when manufacturing negative pole of the present invention, can there is cross-linking reaction in sulfonic group, therefore, in negative electrode active material layer, form cross-linked structure by sulfonic group.Now, by the sulfonic group making water-soluble polymer have q.s, the quantity of cross-linked structure can be increased, thus strengthen the intensity of negative electrode active material layer, in addition, High temperature storage characteristic and the low temperature output characteristic of secondary cell can be improved.Therefore, preferred water soluble polymer is as described above more containing containing sulfonic group monomeric unit.But, if too much containing sulfonic group monomeric unit, then can relatively make monomeric unit in addition reduce, adsorptivity and the intensity of water-soluble polymer anticathode active material diminish, therefore, the amount preferably containing sulfonic group monomeric unit is below the upper limit of above-mentioned scope.
(fluorine-containing (methyl) acrylate monomeric units)
Fluorine-containing (methyl) acrylate monomeric units contained by water-soluble polymer is except above-mentioned containing the unit except sulfonic group monomeric unit, is the repetitive being undertaken being polymerized by fluorine-containing (methyl) acrylate monomer and obtain.
As fluorine-containing (methyl) acrylate monomer, such as, can enumerate the monomer shown in following formula (I).
[chemical formula 1]
In above-mentioned formula (I), R 1represent hydrogen atom or methyl.
In above-mentioned formula (I), R 2represent the alkyl containing fluorine atom.The carbon number of alkyl is generally more than 1, is generally less than 18.In addition, R 2contained number of fluorine atoms can be 1, also can be more than 2.
As the example of fluorine-containing (methyl) acrylate monomer shown in formula (I), can enumerate: (methyl) fluoroalkyl acrylate, (methyl) acrylic acid fluorinated aryl ester, (methyl) acrylic acid fluoroaralkyl ester etc.Wherein, preferred (methyl) fluoroalkyl acrylate.As the object lesson of such monomer, can enumerate: (methyl) acrylic acid trifluoro methyl esters, (methyl) acrylic acid-2, 2, 2-trifluoro ethyl ester, (methyl) senecioate-(perfluoro capryl) ethyl ester, (methyl) acrylic acid-2, 2, 3, 3-tetrafluoro propyl ester, (methyl) acrylic acid-2, 2, 3, 4, 4, 4-hexafluoro butyl ester, (methyl) acrylic acid-1H, 1H, 9H-perfluor-1-ester in the ninth of the ten Heavenly Stems, (methyl) acrylic acid-1H, 1H, 11H-perfluor undecyl ester, (methyl) perfluoroethyl monooctyl ester, (methyl) acrylic acid-3-[4-[1-trifluoromethyl-2, two [two (trifluoromethyl) methyl fluoride] the second alkynyloxy group of 2-] benzoyloxy] (methyl) perfluoroalkyl acrylate etc. such as-2-hydroxy propyl ester.
Fluorine-containing (methyl) acrylate monomer can be used alone a kind, also can combinationally use two or more with arbitrary ratio.Therefore, water-soluble polymer only can contain a kind of fluorine-containing (methyl) acrylate monomeric units, also can with arbitrary ratio combination containing two or more.
The ratio of fluorine-containing (methyl) acrylate monomeric units in water-soluble polymer is more than 0.5 % by weight, and be preferably more than 1 % by weight, described ratio is less than 10 % by weight, is preferably less than 5 % by weight.By making the amount of fluorine-containing (methyl) acrylate monomeric units more than the lower limit of above-mentioned scope, the low temperature output characteristic of secondary cell can be improved.In addition, by making the amount of fluorine-containing (methyl) acrylate monomeric units below the higher limit of above-mentioned scope, can prevent water-soluble polymer from becoming excessive softness, thus prevent the durability of negative pole from reducing.
(arbitrary unit)
Water-soluble polymer, significantly not damaging in the scope of effect of the present invention, can contain except above-mentioned containing the repetitive except sulfonic group monomeric unit and fluorine-containing (methyl) acrylate monomeric units.Such repetitive can for the repetitive obtained by carrying out being polymerized with the monomer containing sulfonic group monomer and the copolymerization of fluorine-containing (methyl) acrylate monomer.
(arbitrary unit: ethylenically unsaturated carboxylic acids monomeric unit)
Such as, water-soluble polymer can contain ethylenically unsaturated carboxylic acids monomeric unit.Ethylenically unsaturated carboxylic acids monomeric unit is the repetitive being undertaken being polymerized by ethylenically unsaturated carboxylic acids monomer and obtain.
As ethylenically unsaturated carboxylic acids monomer, such as, can enumerate: olefinic unsaturated monocarboxylic acid and derivative, olefinic unsaturated dicarboxylic acid and acid anhydrides thereof and their derivative etc.Wherein, olefinic unsaturated monocarboxylic acid can improve the dispersiveness of gained water-soluble polymer in water further, therefore preferably.
As the example of olefinic unsaturated monocarboxylic acid, can enumerate: acrylic acid, methacrylic acid, crotonic acid etc.As the example of the derivative of olefinic unsaturated monocarboxylic acid, can enumerate: 2-ethylacrylic acid, iso-crotonic acid, α-acetoxypropen acid, β-trans-aryloxy group acrylic acid, α-chloro-β-E-methoxy acrylic acid, β-diaminourea acrylic acid etc.As the example of olefinic unsaturated dicarboxylic acid, can enumerate: maleic acid, fumaric acid, itaconic acid etc.As the example of the acid anhydrides of olefinic unsaturated dicarboxylic acid, can enumerate: maleic anhydride, acrylic anhydride, methyl maleic anhydride, dimethyl maleic anhydride etc.As the example of the derivative of olefinic unsaturated dicarboxylic acid, can enumerate: the maleic acid that the alkyl such as citraconic acid, dimethyl maleic acid, phenyl maleic acid replace; The halogenated maleic acids such as chloromaleic acid, dichloromaleic acid, fluoro maleic acid; Methyl allyl ester; And the maleate etc. such as maleic acid diphenyl ester, maleic acid ester in the ninth of the ten Heavenly Stems, maleic acid ester in the last of the ten Heavenly stems, maleic acid dodecyl ester, maleic acid stearyl, maleic acid fluoroalkyl.Wherein, the olefinic unsaturated monocarboxylic acid such as preferred acrylic acid, methacrylic acid.This is because the dispersiveness of gained water-soluble polymer in water can be improved further.
Ethylenically unsaturated carboxylic acids monomer can be used alone a kind, also can combinationally use two or more with arbitrary ratio.Therefore, water-soluble polymer only can contain a kind of ethylenically unsaturated carboxylic acids monomeric unit, also can with arbitrary ratio combination containing two or more.
In water-soluble polymer, the ratio of ethylenically unsaturated carboxylic acids monomeric unit is preferably more than 5 % by weight, is more preferably more than 10 % by weight, is preferably less than 35 % by weight, is more preferably less than 30 % by weight.By making the amount of ethylenically unsaturated carboxylic acids monomeric unit more than the lower limit of above-mentioned scope, the adsorptivity of water-soluble polymer anticathode active material can be improved, improve the dispersiveness of negative electrode active material and the adaptation to collector body.In addition, by making the amount of ethylenically unsaturated carboxylic acids monomeric unit below the higher limit of above-mentioned scope, the flexibility of water-soluble polymer can be improved, therefore, the flexibility of negative pole can be improved, prevent negative pole from producing or breaking, improve durability.
(arbitrary unit: (methyl) acrylate monomeric units)
In addition, such as, water-soluble polymer can contain (methyl) acrylate monomeric units.(methyl) acrylate monomeric units is the repetitive being undertaken being polymerized by (methyl) acrylate monomer and obtain.It should be noted that, in (methyl) acrylate monomer, be equivalent to the above-mentioned part containing sulfonic group monomer or fluorine-containing (methyl) acrylate monomer be included in containing in sulfonic group monomer or fluorine-containing (methyl) acrylate monomer than time at calculating content, and be not included in (methyl) acrylate monomer.Such as, the monomer containing fluorine in (methyl) acrylate monomer distinguishes with (methyl) acrylate monomer as fluorine-containing (methyl) acrylate monomer.
As (methyl) acrylate monomer, such as, can enumerate: the alkyl acrylates such as methyl acrylate, ethyl acrylate, n-propyl, isopropyl acrylate, n-butyl acrylate, tert-butyl acrylate, amyl acrylate, Hexyl 2-propenoate, heptylacrylate, 2-ethyl hexyl acrylate, 2-EHA, acrylic acid ester in the ninth of the ten Heavenly Stems, decyl acrylate, lauryl acrylate, n-myristyl base ester, stearyl acrylate ester, methyl methacrylate, EMA, n propyl methacrylate, isopropyl methacrylate, n-BMA, Tert-butyl Methacrylate, pentylmethacrylate, hexyl methacrylate, metering system heptyl heptylate, 2-Propenoic acid, 2-methyl-, octyl ester, 2-Ethylhexyl Methacrylate, nonyl methacrylate, decyl-octyl methacrylate, lauryl methacrylate, methacrylic acid n-tetradecane base ester, the alkyl methacrylates etc. such as stearyl methacrylate.
(methyl) acrylate monomer can be used alone a kind, also can combinationally use two or more with arbitrary ratio.Therefore, water-soluble polymer only can contain a kind of (methyl) acrylate monomeric units, also can with arbitrary ratio combination containing (methyl) of more than two kinds acrylate monomeric units.
In water-soluble polymer, the ratio of (methyl) acrylate monomeric units is preferably more than 30 % by weight, is more preferably more than 35 % by weight, is particularly preferably more than 40 % by weight, in addition, is preferably less than 70 % by weight.By making the amount of (methyl) acrylate monomeric units below the higher limit of above-mentioned scope, the adaptation of negative electrode active material confrontation collector body can be improved, by making the amount of (methyl) acrylate monomeric units more than the lower limit of above-mentioned scope, the flexibility of negative pole can be improved.
(arbitrary unit: cross-linking monomer units)
In addition, such as, water-soluble polymer can contain cross-linking monomer units.Cross-linking monomer units is by heating cross-linkable monomer or energy exposure and form the construction unit of cross-linked structure between polymerization period or after polymerization.By containing cross-linking monomer units, water-soluble polymer can be made to be cross-linked, therefore, can improve by water-soluble polymer formed by film strength and stability.
As cross-linkable monomer, the monomer that can form cross-linked structure when being polymerized can be used.As the example of cross-linkable monomer, the monomer in every 1 molecule with more than 2 reactive groups can be enumerated.More specifically, can enumerate: there is the crosslinkable groups of heat cross-linking and there is in every 1 molecule the multi-functional monomer in mono-functional's monomer of 1 alkene double bond and every 1 molecule with more than 2 alkene double bonds.
As the example of the crosslinkable groups of heat cross-linking contained in mono-functional's monomer, can enumerate: epoxy radicals, N-methylol amide base, oxetanylmethoxy, azoles quinoline base and their combination.Wherein, from the view point of being easily cross-linked and easily regulating crosslink density, more preferably epoxy radicals.
As there is epoxy radicals as the crosslinkable groups of heat cross-linking there is the example of the cross-linkable monomer of alkene double bond, can enumerate: the unsaturated glycidyl ethers such as vinyl glycidyl ether, allyl glycidyl ether, cyclobutenyl glycidyl ether, o-allyl base glycidyl ether; The monoepoxide of the diene such as butadiene monoepoxide, chlorobutadiene monoepoxide, 4,5-epoxy-2-amylenes, 3,4-epoxy-1-VCHs, 1,2-epoxy-5,9-ring 12 carbon diene or polyenoid; The alkenyl epoxides such as 3,4-epoxy-1-butylene, 1,2-epoxy-5-hexene, 1,2-epoxy-9-decene; And the ethylene oxidic ester class etc. of the unsaturated carboxylic acid such as glycidyl acrylate, glycidyl methacrylate, crotonic acid ethylene oxidic ester, 4-heptenoic acid ethylene oxidic ester, sorbic acid ethylene oxidic ester, linoleic acid ethylene oxidic ester, pyroterebic acid ethylene oxidic ester, the glycidyl esters of 3-cyclohexene carboxylate, glycidyl esters of 4-methyl-3-cyclohexene carboxylate.
As there is N-methylol amide base as the crosslinkable groups of heat cross-linking there is the example of the cross-linkable monomer of alkene double bond, can enumerate: N-methylol (methyl) acrylamide etc. has (methyl) acrylic amide etc. of methylol.
As there is oxetanylmethoxy as the crosslinkable groups of heat cross-linking there is the example of the cross-linkable monomer of alkene double bond, can enumerate: 3-((methyl) acryloyloxymethyl) oxetanes, 3-((methyl) acryloyloxymethyl)-2-trifluoromethyl oxetanes, 3-((methyl) acryloyloxymethyl)-2-phenyl oxetanes, 2-((methyl) acryloyloxymethyl) oxetanes and 2-((methyl) acryloyloxymethyl)-4-trifluoromethyl oxetanes etc.
As having azoles quinoline base as heat cross-linking crosslinkable groups and there is the example of the cross-linkable monomer of alkene double bond, can enumerate: 2-vinyl-2- azoles quinoline, 2-vinyl-4-methyl-2- azoles quinoline, 2-vinyl-5-methyl-2- azoles quinoline, 2-isopropenyl-2- azoles quinoline, 2-isopropenyl-4-methyl-2- azoles quinoline, 2-isopropenyl-5-methyl-2- azoles quinoline and 2-isopropenyl-5-ethyl-2- azoles quinoline etc.
As the example of multi-functional monomer with more than 2 alkene double bonds, can enumerate: (methyl) allyl acrylate, ethylene glycol bisthioglycolate (methyl) acrylate, diethylene glycol two (methyl) acrylate, triethylene glycol two (methyl) acrylate, TEG two (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, DPG diallyl ether, polyethylene glycol diallyl ether, triethyleneglycol divinylether, quinhydrones diallyl ether, tetraallyloxyethane, trimethylolpropane allyl ether, the pi-allyl of multi-functional alcohol other than the above or vinyl ethers, triallylamine, methylene-bisacrylamide, and divinylbenzene etc.
Wherein, as cross-linkable monomer, can particularly preferably ethylene glycol dimethacrylate, allyl glycidyl ether and glycidyl methacrylate.
Cross-linking monomer units in water-soluble polymer containing proportional be preferably more than 0.1%, be more preferably more than 0.2 % by weight, be particularly preferably more than 0.5 % by weight, be preferably less than 2 % by weight, be more preferably less than 1.5 % by weight, be particularly preferably less than 1 % by weight.By making containing of cross-linking monomer units proportional in above-mentioned scope, swellbility can be suppressed, improve the durability of electrode.Here, the ratio of the cross-linking monomer units in water-soluble polymer is usually consistent with the ratio (charge ratio) of the cross-linking monomer units in whole monomers of water-soluble polymer.
(arbitrary unit: reactive surfactant monomeric unit)
In addition, such as, water-soluble polymer also can contain reactive surfactant monomeric unit.Reactive surfactant monomeric unit is the construction unit being undertaken being polymerized by reactive surfactant monomer and obtain.Reactive surfactant monomeric unit forms a part for water-soluble polymer, and can be used as surfactant and play a role.
Reactive surfactant monomer is have to have a monomer of surface active groups (hydrophilic radical and hydrophobic group) with the polymerizable group of other monomer copolymerizations.Usually, reactive surfactant monomer has polymerism unsaturated group, and this group also plays a role as hydrophobic group after polymerisation.As the example of the polymerism unsaturated group that reactive surfactant monomer has, can enumerate: vinyl, pi-allyl, ethenylidene, acrylic, isopropenyl and isobutenyl.The kind of such polymerism unsaturated group can be used alone a kind, also can combinationally use two or more with arbitrary ratio.
Reactive surfactant monomer has hydrophilic radical usually as the hydrophilic part of display.Reactive surfactant monomer can be categorized as anionic, cationic, nonionic surface active agent according to the kind of hydrophilic radical.
As the example of the hydrophilic radical of anionic, can enumerate :-SO 3m ,-COOM and-PO (OM) 2.Here, M represents hydrogen atom or cation.As cationic example, can enumerate: the alkali metal ions such as lithium, sodium, potassium; The alkaline-earth metal ions such as calcium, magnesium; Ammonium ion; The ammonium ion of the alkylamines such as monomethyl amine, dimethyl amine, MEA, triethylamine; And the ammonium ion etc. of the alkanolamine such as monoethanolamine, diethanol amine, triethanolamine.
As the example of cationic hydrophilic radical, can enumerate :-NH 2primary amine the salt ,-NHCH such as HX 3the secondary amine salt such as HX ,-N (CH 3) 2the tertiary ammonium salt ,-N such as HX +(CH 3) 3x -deng quaternary ammonium salt etc.Here, X represents halogen group.
As the example of the hydrophilic radical of nonionic, can enumerate :-OH.
As the example of preferred reactive surfactant monomer, can enumerate: the compound shown in following formula (II).
[chemical formula 2]
In formula (II), R represents divalent binding groups.As the example of R, can enumerate :-Si-O-base, methylene and phenylene.
In formula (II), R 3represent hydrophilic radical.As R 3example, can enumerate :-SO 3nH 4.
In formula (II), n represents more than 1 and the integer of less than 100.
As other example of preferred reactive surfactant, can enumerate: have and undertaken being polymerized by oxirane and the construction unit of the structure formed and the construction unit of structure that undertaken being polymerized by epoxy butane and formed, and at end, there is thiazolinyl containing terminal double bond and-SO 3nH 4compound (such as, trade name " Latemul PD-104 " and " Latemul PD-105 ", Kao Corp's system).
Reactive surfactant monomer can be used alone a kind, also can combinationally use two or more with arbitrary ratio.
Reactive surfactant unit in water-soluble polymer containing proportional be preferably more than 0.1 % by weight, be more preferably more than 0.2 % by weight, be particularly preferably more than 0.5 % by weight, be preferably less than 5 % by weight, be more preferably less than 4 % by weight, be particularly preferably less than 2 % by weight.By making containing of reactive surfactant unit proportional more than the lower limit of above-mentioned scope, the dispersiveness of paste compound can be improved.In addition, by making containing of reactive surfactant unit proportional below the higher limit of above-mentioned scope, the durability of electrode can be improved.
(arbitrary unit: other unit)
The example of any unit that water-soluble polymer can contain is not limited to the above unit enumerated, and also can enumerate and be undertaken being polymerized by various arbitrary copolymerisable monomer and the repetitive obtained.As the example of such copolymerisable monomer, can enumerate: ethylene glycol dimethacrylate, dimethacrylate, trimethylolpropane triacrylate etc. have the carboxylic acid ester monomer of more than 2 carbon-to-carbon double bonds; The styrene monomers such as styrene, chlorostyrene, vinyltoluene, t-butyl styrene, vinyl benzoic acid, vinylbenzoate, vinyl naphthalene, 1-chloro-4-methyl-benzene, hydroxymethylstyrene, AMS, divinylbenzene; The amide-type such as acrylamide, N hydroxymethyl acrylamide monomer; The α such as acrylonitrile, methacrylonitrile, alpha, beta-unsaturated nitriles compound monomer; The olefin monomer such as ethene, propylene; Vinyl chloride, vinylidene chloride etc. (except fluorine-containing (methyl) acrylate monomer) halogen atom monomer; The vinyl ester monomers such as vinyl acetate, propionate, vinyl butyrate, vinyl benzoate; The vinyl ethers monomers such as methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether; The vinyl ketones monomers such as methyl vinyl ketone, ethyl vinyl ketone, butyl vinyl ketone, hexyl vinyl ketone, isopropenyl vinyl ketone; NVP, vinylpyridine, vinyl imidazole etc. are containing heterocyclic vinyl compounds monomer etc.
Above-mentioned copolymerisable monomer can be used alone a kind, also can combinationally use two or more with arbitrary ratio.Therefore, water-soluble polymer only can contain a kind of unit based on above-mentioned copolymerisable monomer, also can with arbitrary ratio combination containing two or more unit based on above-mentioned copolymerisable monomer.In water-soluble polymer, the ratio based on the unit of above-mentioned copolymerisable monomer is preferably 0 quality % ~ 10 quality %, is more preferably 0 quality % ~ 5 quality %.
(characteristic of water-soluble polymer)
The weight average molecular weight of water-soluble polymer is usually little than the polymer of constituent particle shape adhesive, is preferably more than 500, is more preferably more than 700, be particularly preferably more than 1000, be preferably less than 500000, be more preferably less than 250000, be particularly preferably less than 100000.Be more than the lower limit of above-mentioned scope by making the weight average molecular weight of water-soluble polymer; the intensity of water-soluble polymer can be improved; thus form the stable protective layer covering negative electrode active material; therefore, the dispersiveness of negative electrode active material and the High temperature storage characteristic etc. of secondary cell can such as be improved.In addition, by making the weight average molecular weight of water-soluble polymer be below the higher limit of above-mentioned scope, water-soluble polymer can be made to become soft, therefore, such as, can suppress the expansion of negative pole, improve the adaptation etc. of negative electrode active material layer to collector body.The weight average molecular weight of water-soluble polymer, by GPC, is obtained using the solution dissolving the sodium nitrate of 0.85g/ml in the 10 volume % aqueous solution of dimethyl formamide as the value of the polystyrene conversion of developing solvent.
The glass transition temperature of water-soluble polymer is preferably more than 0 DEG C, is more preferably more than 5 DEG C, is preferably less than 100 DEG C, is more preferably less than 50 DEG C.By making the glass transition temperature of water-soluble polymer in above-mentioned scope, adaptation and the flexibility of negative pole can be had concurrently.The glass transition temperature of water-soluble polymer is by combining various monomer to adjust.
Viscosity when water-soluble polymer makes 1 % by weight aqueous solution is generally more than 0.1mPas, is preferably more than 1mPas, is more preferably more than 10mPas, is generally below 20000mPas, is preferably below 10000mPas, is more preferably below 5000mPas.By making above-mentioned viscosity more than the lower limit of above-mentioned scope, the intensity of water-soluble polymer can be improved, thus improve the durability of negative pole, in addition, by making above-mentioned viscosity below the higher limit of above-mentioned scope, the dhering strength that the coating of negative pole paste compound is good, improve collector body and negative electrode active material layer can be made.Above-mentioned viscosity such as can adjust according to the molecular weight of water-soluble polymer.Above-mentioned viscosity be use Brookfield viscometer 25 DEG C, measure under rotating speed 60rpm time value.
(manufacture method of water-soluble polymer)
As the manufacture method of water-soluble polymer, such as, can be polymerized to manufacture in aqueous solvent by containing the above-mentioned monomer composition containing sulfonic group monomer, fluorine-containing (methyl) acrylate monomer and arbitrary monomer as required.Aqueous solvent and polymerization are such as identical with the manufacture of particle-like adhesive.Thus, the aqueous solution of water-soluble polymer dissolves in aqueous solvent can usually be obtained.Water-soluble polymer can be taken out from the aqueous solution as above obtained, but usually use the water-soluble polymer being dissolved in the state of aqueous solvent to manufacture negative pole paste compound, use this negative pole paste compound to manufacture negative pole.
Because the above-mentioned aqueous solution containing water-soluble polymer in aqueous solvent is generally acid, therefore, can alkalizes to pH7 ~ pH13 as required, the operability of the aqueous solution can be improved thus, in addition, the coating of negative pole paste compound can be improved.As alkalization to the method for pH7 ~ pH13, such as, can enumerate the alkali metal aqueous solution such as mixing lithium hydroxide aqueous solution, sodium hydrate aqueous solution, potassium hydroxide aqueous solution; The alkaline-earth metal such as calcium hydroxide aqueous solution, the magnesium hydroxide aqueous solution aqueous solution; The method of the aqueous alkalis such as ammonia spirit.Above-mentioned aqueous alkali can be used alone a kind, also can combinationally use two or more with arbitrary ratio.
(amount of water-soluble polymer)
Relative to negative electrode active material 100 weight portion, the amount of water-soluble polymer is preferably more than 0.1 weight portion, is more preferably more than 0.5 weight portion, is particularly preferably more than 1 weight portion, is preferably below 10 weight portions, is more preferably below 5 weight portions.By making the amount of water-soluble polymer be above-mentioned scope, Absorbable organic halogens ground plays following effect: suppress the negative pole occurred with discharge and recharge to expand; Improve the High temperature storage characteristic of secondary cell, high-temperature cycle and low temperature output characteristic; Negative pole paste compound is coated coating during collector body by improvement; And improve the adaptation etc. of negative electrode active material layer to collector body.
[any composition of 1-4. negative electrode active material layer]
In negative pole of the present invention, except containing except above-mentioned negative electrode active material, particle-like adhesive and water-soluble polymer in negative electrode active material layer, any composition can also be contained.As the example of any composition, can enumerate: viscosity modifier, conductive agent, supporting material, levelling agent, electrolysis additive etc.These compositions only otherwise impact cell reaction and be just not particularly limited.In addition, these compositions can be used alone a kind, also can combinationally use two or more with arbitrary ratio.
Viscosity modifier is that viscosity for adjusting negative pole paste compound of the present invention is to the composition of the dispersiveness and coating of improving negative pole paste compound.Usually, contained in negative pole paste compound viscosity modifier can remain in negative electrode active material layer.
As viscosity modifier, preferably use water miscible polysaccharide.As polysaccharide, such as, can enumerate: natural family macromolecule compound, cellulose family narrow shaping macromolecular compound etc.In addition, viscosity modifier can be used alone a kind, also can combinationally use two or more with arbitrary ratio.
As natural family macromolecule compound, such as, can enumerate: the polysaccharide of plant or animal origin and protein etc.In addition, also can enumerate and according to circumstances carried out the fermentation process utilizing microbe etc., utilize the process etc. of heat and the natural family macromolecule compound that obtains.These natural family macromolecule compounds can be divided into plant type natural family macromolecule compound, animal-type natural family macromolecule compound and the natural family macromolecule compound of microbiocidal etc.
As the natural family macromolecule compound of plant type, such as, can enumerate: Arabic gum, bassora gum, galactan, guar gum, tragon, karaya, carragheen, pectin, Qiong Zhi, Quinces Quince seed (Quinces Quince), phycocolloid (brown alga extract), starch (being derived from the starch of rice, corn, potato, wheat etc.), Radix Glycyrrhizae etc.In addition, as the natural family macromolecule compound of animal-type, such as, can enumerate: collagen, casein, albumin, gelatin etc.In addition, as the natural family macromolecule compound of microbiocidal, can enumerate: xanthans, glucan, succinoglycan, amylopectin (pullulan) etc.
The cellulose family shaping macromolecular compound that narrows can be categorized as nonionic, anionic property and cationic.
To narrow shaping macromolecular compound as non-ionic cellulose element class, such as, can enumerate: the alkylcelluloses such as methylcellulose, methylethylcellulose, ethyl cellulose, microcrystalline cellulose; The hydroxy alkyl celluloses etc. such as hydroxyethylcellulose, hydroxy butyl methyl cellulose, hydroxypropyl cellulose, hydroxypropyl methylcellulose, HEMC, hydroxypropyl methylcellulose stearic oxygen ether, carboxymethyl hydroxyethyl cellulose, alkyl hydroxyethylcellulose, nonyl phenol polyether-based hydroxyethylcellulose.
To narrow shaping macromolecular compound as anionic cellulose element class, can enumerate: the alkylcellulose that the shaping macromolecular compound that above-mentioned non-ionic cellulose element class narrowed utilizes various deriveding group to carry out replacing and obtains and sodium salt and ammonium salt etc.As its object lesson, can enumerate: cellulose sodium sulfate, methylcellulose, methylethylcellulose, ethyl cellulose, carboxymethyl cellulose (CMC) and their salt etc.
To narrow shaping macromolecular compound as cationic cellulose family, such as, can enumerate: low nitrogen hydroxyethylcellulose dimethyl diallyl ammonium chloride (polyquaternium-4), chlorination O-[2-hydroxyl-3-(trimethyl ammonium) propyl group] hydroxyethylcellulose (Polyquaternium-10), chlorination O-[2-hydroxyl-3-(lauryl dimethyl ammonium) propyl group] hydroxyethylcellulose (polyquaternium-24) etc.
Wherein, from the viewpoint of the characteristic that can obtain cationic, anionic property or both sexes, preferred cellulose class narrows shaping macromolecular compound, its sodium salt and ammonium salt thereof.And then from the view point of the dispersiveness of negative electrode active material, wherein particularly preferably the cellulose family of anionic property narrows shaping macromolecular compound.
In addition, the narrow degree of etherification falling of shaping macromolecular compound of cellulose family is preferably more than 0.5, is more preferably more than 0.6, is preferably less than 1.0, is more preferably less than 0.8.Here, described degree of etherification falling refers to the substitution value that the hydroxyl (3) of every 1 the anhydrous grape sugar unit in cellulose is replaced by substituting groups such as carboxymethyls.Degree of etherification falling in theory desirable 0 ~ 3 value.When degree of etherification falling is above-mentioned scope, the cellulose family shaping macromolecular compound that narrows is adsorbed in the surface of negative electrode active material, also shows the compatibility to water, therefore simultaneously, excellent dispersion, can be dissipated to primary particle level by negative electrode active material differential.
In addition, when using macromolecular compound as viscosity modifier, the average degree of polymerization of the viscosity modifier that the inherent viscosity obtained by utilizing Ubbelohde viscometer calculates is preferably more than 500, be more preferably more than 1000, be preferably less than 2500, be more preferably less than 2000, be particularly preferably less than 1500.The average degree of polymerization of viscosity modifier affects the technique in the mobility of negative pole paste compound of the present invention and the film uniformity of negative electrode active material layer and operation sometimes.By making average degree of polymerization in above-mentioned scope, the ageing stability of negative pole paste compound of the present invention can be improved, can not condensation product be there is and there is not the coating of uneven thickness.
Relative to amount 100 weight portion of negative electrode active material, the amount of viscosity modifier is preferably more than 0 weight portion, is preferably below 0.5 weight portion.By making the amount of viscosity modifier be above-mentioned scope, the viscosity of paste compound of the present invention can be made to reach maneuverable proper range.
Conductive agent is the composition improving negative electrode active material electrical contact each other.By containing conductive agent, the discharging-rate performance of secondary cell of the present invention can be improved.
As conductive agent, such as, can use the conductive carbon etc. such as acetylene black, Ketjen black, carbon black, graphite, gas-phase growth of carbon fibre and carbon nano-tube.In addition, conductive agent can be used alone a kind, also can combinationally use two or more with arbitrary ratio.
Relative to amount 100 weight portion of negative electrode active material, the amount of conductive agent is preferably 1 ~ 20 weight portion, is more preferably 1 ~ 10 weight portion.
As supporting material, such as, can use various inorganic and organically spherical, tabular, bar-shaped or fibrous filler.Supporting material can be used alone a kind, also can combinationally use two or more with arbitrary ratio.By using supporting material, the tough and tensile and negative pole of softness can be obtained, the secondary cell showing excellent long-term cycle characteristics can be realized.
Relative to amount 100 weight portion of negative electrode active material, the amount of supporting material is generally more than 0.01 weight portion, is preferably more than 1 weight portion, is generally below 20 weight portions, is preferably below 10 weight portions.By making the amount of reinforcing agent in above-mentioned scope, secondary cell can be made to demonstrate high power capacity and high load characteristics.
As levelling agent, such as, can enumerate: the surfactants such as alkyl-based surfactant, organosilicone surfactants, fluorine class surfactant, metal species surfactant.Levelling agent can be used alone a kind, also can combinationally use two or more with arbitrary ratio.By using levelling agent, can prevent from producing depression when being coated with negative pole paste compound, or improving the flatness of negative pole.
Relative to amount 100 weight portion of negative electrode active material, the amount of levelling agent is preferably 0.01 weight portion ~ 10 weight portion.By making levelling agent in above-mentioned scope, productivity, flatness and battery behavior when negative pole makes are excellent.In addition, by containing surfactant, the dispersiveness in secondary battery negative pole paste compound such as negative electrode active material can be improved, and then the flatness of the negative pole obtained thus can be improved.
As electrolysis additive, such as, can enumerate: vinylene carbonate etc.Electrolysis additive can be used alone a kind, also can combinationally use two or more with arbitrary ratio.By using electrolysis additive, the decomposition of such as electrolyte can be suppressed.
Relative to amount 100 weight portion of negative electrode active material, the amount of electrolysis additive is preferably 0.01 weight portion ~ 10 weight portion.By making the amount of electrolysis additive be above-mentioned scope, the secondary cell of cycle characteristics and hot properties excellence can be realized.
In addition, negative electrode active material layer such as can contain the nanoparticle such as aerosil and gaseous oxidation aluminium.Nanoparticle can be used alone a kind, also can combinationally use two or more with arbitrary ratio.When containing nanoparticle, the thixotropy of negative pole paste compound can be adjusted, therefore, the levelability of the negative pole of the present invention obtained thus can be improved.
Relative to amount 100 weight portion of negative electrode active material, the amount of nanoparticle is preferably 0.01 weight portion ~ 10 weight portion.By making nanoparticle be above-mentioned scope, stability and the productivity of negative pole paste compound can be improved, high battery behavior can be realized.
[1-5. collector body and negative electrode active material layer]
Negative pole of the present invention is usually containing collector body and the negative electrode active material layer being arranged at collector body surface, and this negative electrode active material layer contains negative electrode active material, particle-like adhesive and water-soluble polymer.Collector body is generally the shape of sheet, and negative electrode active material layer can be arranged at least one side of such sheet collector body, but is preferably disposed on two sides.
As long as negative pole collector body is for having conductivity and the material with electrochemistry durability is just not particularly limited, but in order to have thermal endurance, preferred metal materials.As the material of negative pole collector body, such as, can enumerate: iron, copper, aluminium, nickel, stainless steel, titanium, tantalum, gold, platinum etc.Wherein, as the collector body for secondary battery negative pole, particularly preferably copper.Above-mentioned material can be used alone a kind, also can combinationally use two or more with arbitrary ratio.
The shape of collector body is not particularly limited, the sheet collector body of preferred thickness 0.001mm ~ about 0.5mm.
For collector body, in order to improve the adhesive strength with negative electrode active material layer, can re-use after roughening process be carried out by effects on surface in advance.As roughening method, such as, can enumerate: mechanical polishing method, electrobrightening method, chemical polishing etc.In mechanical polishing method, adhesion usually can be used to have the sand paper of polishing agent particle, grinding stone, emery buff (emery buff), possess the line brush etc. of steel wire etc.In addition, in order to improve adhesive strength and the conductivity of negative electrode active material layer, also can in the formation intermediate layer, surface of collector body.
The thickness being arranged at the negative electrode active material layer on the surface of collector body is generally more than 5 μm, is preferably more than 30 μm, is generally less than 300 μm, is preferably less than 250 μm.By making the thickness of negative electrode active material layer be above-mentioned scope, can make part throttle characteristics and cycle characteristics good.
Negative electrode active material in negative electrode active material layer containing proportional be preferably more than 85 % by weight, be more preferably more than 88 % by weight, be preferably less than 99 % by weight, be more preferably less than 97 % by weight.By making containing of negative electrode active material proportional in above-mentioned scope, while display high power capacity can be realized, show flexibility, close-burning negative pole.
[2. the manufacture method of negative pole paste compound and negative pole]
Secondary battery cathode of the present invention manufactures by arbitrary manufacture method, but secondary battery negative pole paste compound of the present invention as described below preferably can be used (following, suitably be called " negative pole paste compound of the present invention "), manufactured by the manufacture method of secondary battery cathode of the present invention as described below (following, to be suitably called " manufacture method of negative pole of the present invention ").
[2-1. negative pole paste compound]
Negative pole paste compound of the present invention is the pulp-like composition containing negative electrode active material, particle-like adhesive and water-soluble polymer.
Negative pole paste compound of the present invention is usually also containing solvent.As solvent, from the view point of minimizing environmental pressure, the mixture of the liquid beyond preferred water or water and water.
Water plays a role as solvent or decentralized medium in negative pole paste compound, and negative electrode active material can be made to disperse, make particle-like adhesive be separated into particle shape or make water-soluble polymer dissolves.If combinationally use the liquid dissolving particle-like adhesive and water-soluble polymer, then particle-like adhesive and water-soluble polymer are adsorbed in the surface of negative electrode active material, thus, and the decentralized stabilization of negative electrode active material, therefore preferably.
Preferably select from kind to the liquid combined with water of the viewpoint of rate of drying and environment aspect.As preferred example, can enumerate: the annular aliphatic such as pentamethylene, cyclohexane hydro carbons; Toluene, dimethylbenzene etc. are aromatic hydrocarbon based; The ketone such as methylethylketone, cyclohexanone; The ester classes such as ethyl acetate, butyl acetate, gamma-butyrolacton, 6-caprolactone; The nitrile such as acetonitrile, propionitrile; The ethers such as oxolane, ethylene glycol bisthioglycolate ethylether: the alcohols such as methyl alcohol, ethanol, isopropyl alcohol, ethylene glycol, ethylene glycol monomethyl ether; The amide-type such as 1-METHYLPYRROLIDONE, DMF etc., wherein, preferred 1-METHYLPYRROLIDONE (NMP).These liquid can be used alone a kind, also can combinationally use two or more with arbitrary ratio.
For the amount of the solvent in negative pole paste compound, the mode being preferably suitable for the viscosity be coated with to make the viscosity of negative pole paste compound of the present invention become adjusts.Specifically, can tune to make the concentration of the solid constituent of negative pole paste compound of the present invention be preferably more than 30 % by weight, be more preferably more than 40 % by weight, the amount of less than 90 % by weight, more preferably less than 80 % by weight that is preferably uses.
Negative pole paste compound also can as required containing any composition except negative electrode active material, particle-like adhesive, water-soluble polymer and solvent.The amount of any composition is usually identical with the amount of any composition contained in negative electrode active material layer.In such negative pole paste compound of the present invention, usually, part water-soluble polymer dissolves is in water, another part water-soluble polymer is adsorbed in the surface of negative electrode active material, thus, negative electrode active material cover by the stable layer of water-soluble polymer, negative electrode active material dispersiveness in a solvent improves.Therefore, the coating of negative pole paste compound of the present invention when coating collector body is good.
The manufacture method of negative pole paste compound of the present invention is not particularly limited, can by negative electrode active material, particle-like adhesive, water-soluble polymer, solvent and as required and any composition mixing used manufactures.Mixed method is not particularly limited, such as, can enumerate: the method employing stirring-type, oscillatory type and rotary etc. mixing arrangement.In addition, the method employing the dispersion kneading devices such as homogenizer, ball mill, sand mill, roller mill, planetary-type mixer and planetary mixer can be enumerated.
[manufacture method of 2-2. negative pole]
By negative pole paste compound of the present invention being coated the surface of collector body and making it dry as required, negative electrode active material layer can be formed on the surface of collector body, manufacture negative pole of the present invention.
The method that negative pole paste compound of the present invention coats the surface of collector body is not particularly limited.Such as can enumerate: scrape the method such as the skill in using a kitchen knife in cookery, infusion process, inverse roller method, directly roller method, intagliotype, extrusion molding and spread coating.
As the example of drying means, such as, can enumerate: the seasoning etc. of irradiation utilizing warm braw, hot blast, the drying of low wet wind, vacuumize, utilization (far) infrared ray and electron beam etc.Be generally 1 minute ~ 40 minutes drying time, baking temperature is generally 40 DEG C ~ 180 DEG C.
In addition, be preferably coated with negative pole paste compound on the surface of collector body and after drying, use the such as anticathode such as moulding press or roll squeezer active material layer to implement pressurized treatments as required.By pressurized treatments, the voidage of negative electrode active material layer can be reduced.Voidage is preferably more than 5%, is more preferably more than 7%, is preferably less than 30%, is more preferably less than 20%.By making voidage more than the lower limit of above-mentioned scope, easily obtaining high volume capacity, negative electrode active material layer can being made not easily to peel off from collector body, in addition, by making voidage below higher limit, high recharge efficiency and discharging efficiency can be obtained.
In addition, when negative electrode active material layer contains curable polymer, preferably after formation negative electrode active material layer, above-mentioned polymer cure is made.
[3. secondary cell]
Secondary cell of the present invention possesses positive pole, negative pole, electrolyte and dividing plate, and above-mentioned negative pole is negative pole of the present invention.
Owing to possessing negative pole of the present invention, therefore, in secondary cell of the present invention, even if also not easily there is the reduction of capacity when the negative pole occurred with discharge and recharge can be suppressed to expand or preserve in hot environment.In addition, usually can also improve high-temperature cycle and the low temperature output characteristic of secondary cell of the present invention or improve negative electrode active material layer to the adaptation of collector body.
[3-1. positive pole]
Positive pole usually possesses collector body and is formed at the positive electrode active material layer containing positive active material and positive pole adhesive on collector body surface.
As long as the collector body of positive pole has conductivity and the material with electrochemistry durability is just not particularly limited.As the collector body of positive pole, such as, can use the collector body used in negative pole of the present invention.Wherein, particularly preferably aluminium.
As positive active material, such as, when secondary cell of the present invention is lithium rechargeable battery, the material that can insert and depart from lithium ion can be used.Such positive active material is roughly divided into the material be made up of inorganic compound and the material be made up of organic compound.
As the positive active material be made up of inorganic compound, such as, can enumerate: the lithium-contained composite metal oxide etc. that transition metal oxide, transient metal sulfide, lithium and transition metal are formed.
As above-mentioned transition metal, such as, can enumerate: Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Mo etc.
As transition metal oxide, such as, can enumerate: MnO, MnO 2, V 2o 5, V 6o 13, TiO 2, Cu 2v 2o 3, noncrystalline V 2o-P 2o 5, MoO 3, V 2o 5, V 6o 13deng, wherein, from the viewpoint of cyclical stability and capacity, preferred MnO, V 2o 5, V 6o 13, TiO 2.
As transient metal sulfide, such as, can enumerate: TiS 2, TiS 3, noncrystalline MoS 2, FeS etc.
As lithium-contained composite metal oxide, such as, can enumerate: the lithium-contained composite metal oxide with layer structure, the lithium-contained composite metal oxide with spinel structure, there is the lithium-contained composite metal oxide etc. of olivine-type structure.
As the lithium-contained composite metal oxide with layer structure, such as, can enumerate: containing lithium and cobalt oxides (LiCoO 2), containing lithium nickel oxide (LiNiO 2), the lithium composite xoide of Co-Ni-Mn, the lithium composite xoide of Ni-Mn-Al, the lithium composite xoide etc. of Ni-Co-Al.
As the lithium-contained composite metal oxide with spinel structure, such as, can enumerate: LiMn2O4 (LiMn 2o 4) or by the Li [Mn of a part of Mn with other transition metal substitution 3/2m 1/2] O 4(at this, M is Cr, Fe, Co, Ni, Cu etc.) etc.
As the lithium-contained composite metal oxide with olivine-type structure, such as, can enumerate: LiXMPO 4olivine-type lithium phosphate compound shown in (in formula, M represents at least a kind of being selected from Mn, Fe, Co, Ni, Cu, Mg, Zn, V, Ca, Sr, Ba, Ti, Al, Si, B and Mo, and X represents the number of satisfied 0≤X≤2).
As the positive active material be made up of organic compound, such as, can enumerate: polyacetylene, poly-to electroconductive polymers such as benzene.
In addition, also can use by the positive active material that the composite material of inorganic compound and combination of organic compounds is formed.Such as, by ferrous oxide is carried out reducing the composite material fired and make and covered by material with carbon element under the existence of carbon source material, and this composite material can be used as positive active material.There is the tendency of conductivity deficiency in ferrous oxide, but by forming composite material as above, also can use as high performance positive active material.
In addition, also material above-claimed cpd being carried out to Partial Elements displacement can be used as positive active material.In addition, also the mixture of above-mentioned inorganic compound and organic compound can be used as positive active material.
Positive active material can be used alone a kind, also can combinationally use two or more with arbitrary ratio.
The volume average particle size of the particle of positive active material is generally more than 1 μm, is preferably more than 2 μm, is generally less than 50 μm, is preferably less than 30 μm.By making the volume average particle size of the particle of positive active material be above-mentioned scope, the amount of adhesive when preparing positive electrode active material layer can be reduced, the reduction of the capacity of secondary cell can be suppressed.In addition, in order to form positive electrode active material layer, usually to prepare the positive pole paste compound containing positive active material and adhesive, easily the viscosity of this positive pole paste compound can be adjusted to the proper viscosity being easy to be coated with, uniform positive pole can be obtained.
Positive active material in positive electrode active material layer containing proportional be preferably more than 90 % by weight, be more preferably more than 95 % by weight, be preferably less than 99.9 % by weight, be more preferably less than 99 % by weight.By the content of positive active material is set to above-mentioned scope, the capacity of secondary cell can be improved, in addition, the flexibility of positive pole and the caking property between collector body and positive electrode active material layer can be improved.
As positive pole adhesive, such as, can use the resins such as polyethylene, polytetrafluoroethylene (PTFE), Kynoar (PVDF), tetrafluoraoethylene-hexafluoropropylene copolymer (FEP), polyacrylic acid derivative, HPAM Degraded Bacteria; The soft polymers such as acrylic compounds soft polymer, dienes soft polymer, olefines soft polymer, vinyl-based soft polymer.It should be noted that, adhesive can be used alone a kind, also can combinationally use two or more with arbitrary ratio.
In addition, in positive electrode active material layer, also can as required containing the composition beyond positive active material and adhesive.As its example, such as, can enumerate: viscosity modifier, conductive agent, supporting material, levelling agent, electrolysis additive etc.In addition, these compositions can be used alone a kind, also can combinationally use two or more with arbitrary ratio.
The thickness of positive electrode active material layer is generally more than 5 μm, is preferably more than 10 μm, is generally less than 300 μm, is preferably less than 250 μm.By making the thickness of positive electrode active material layer be above-mentioned scope, high characteristic can be realized in both part throttle characteristics and energy density.
Positive pole such as manufactures by the manufacture method same with above-mentioned negative pole.
[3-2. electrolyte]
As electrolyte, such as, can be used in non-aqueous solvent the electrolyte of the lithium salts dissolved as supporting electrolyte.As lithium salts, such as, can enumerate: LiPF 6, LiAsF 6, LiBF 4, LiSbF 6, LiAlCl 4, LiClO 4, CF 3sO 3li, C 4f 9sO 3li, CF 3cOOLi, (CF 3cO) 2nLi, (CF 3sO 2) 2nLi, (C 2f 5sO 2) lithium salts such as NLi.Particularly, preferably can use and be easily dissolved in solvent and the LiPF showing high degree of dissociation 6, LiClO 4, CF 3sO 3li.These electrolyte can be used alone a kind, also can combinationally use two or more with arbitrary ratio.
The amount of supporting electrolyte is generally more than 1 % by weight relative to electrolyte, is preferably more than 5 % by weight, in addition, is generally less than 30 % by weight, is preferably less than 20 % by weight.The amount of supporting electrolyte is very few or too much, and ionic conduction degree all reduces, and charge characteristic and the flash-over characteristic of secondary cell likely reduce.
As the solvent for electrolyte, as long as solubilized supporting electrolyte is just not particularly limited.As solvent, such as, can use: the alkyl carbonate classes such as dimethyl carbonate (DMC), ethylene carbonate (EC), diethyl carbonate (DEC), propylene carbonate (PC), butylene carbonate (BC) and methyl ethyl carbonate (MEC); The ester such as gamma-butyrolacton, methyl formate class; The ethers such as 1,2-dimethoxy-ethane, oxolane; The sulfur-containing compound such as sulfolane, methyl-sulfoxide class etc.Owing to easily obtaining extra high ionic conductivity, serviceability temperature wide ranges, therefore, preferred dimethyl carbonate, ethylene carbonate, propylene carbonate, diethyl carbonate and methyl ethyl carbonate.It should be noted that, solvent can be used alone a kind, also can combinationally use two or more with arbitrary ratio.
In addition, additive can be contained as required in the electrolytic solution.As additive, preference is as carbonats compounds such as vinylene carbonates (VC).It should be noted that, additive can be used alone a kind, also can combinationally use two or more with arbitrary ratio.
In addition, as electrolyte other than the above, such as, can enumerate: the gel-polymer electrolyte matter of impregnation electrolyte in the polymer dielectric such as polyoxyethylene, polyacrylonitrile; Lithium sulfide, LiI, Li 3the inorganic solid electrolytes etc. such as N.
[3-3. dividing plate]
As dividing plate, usually use the porous substrate with pore portion.As the example of dividing plate, can enumerate: (a) has the porous separator in pore portion, (b) is formed with the porous separator of polymeric coating layer in one or two sides, (c) is formed with the porous separator etc. of the porous resin coating comprising inorganic ceramic powder.As their example, can enumerate: solid macromolecule electrolyte polymeric membrane or the gel polyelectrolyte polymeric membranes such as polypropylene type, polyethylene kind, TPO or aromatic polyamide porous separator, Kynoar, polyoxyethylene, polyacrylonitrile or Kynoar hexafluoropropylene copolymer; Be coated with the dividing plate of gelation polymeric coating layer; Be coated with the dividing plate etc. of the porous membrane layer be made up of inorganic filler and inorganic filler dispersant.
[manufacture method of 3-4. secondary cell]
The manufacture method of secondary cell of the present invention is not particularly limited.Such as, secondary cell can be manufactured by following method: carry out superimposed by above-mentioned negative pole and positive pole across dividing plate, and carried out curling, bending etc. according to cell shapes and put into battery case, inject electrolyte to battery case and seal.In addition, also expansion alloy can be put into as required; The overcurrent such as fuse, PTC element prevent element; Lead plates etc., prevent the pressure increase of inside battery, cross discharge and recharge.The shape of battery can be such as the arbitrary shape in laminated units type, Coin shape, coin shape, flap-type, cylinder type, square, platypelloid type etc.
Embodiment
Below, the present invention is specifically described, but the present invention is not limited to embodiment shown below in conjunction with the embodiments, can at random carries out changing implementing in the scope not departing from claims of the present invention and equivalency range thereof.
In the explanation of following embodiment, " % " and " part " of expression amount unless otherwise specified, is then weight basis.In addition, the operation below illustrated unless otherwise specified, is then carried out under the condition of normal temperature and pressure.Particularly, the operation that battery is evaluated then is carried out unless otherwise specified at 25 DEG C.
[evaluation method]
The evaluation of the characteristic in embodiment and comparative example is carried out as follows.
1. dhering strength
The negative pole manufactured in embodiment and comparative example is cut into length 100mm, width 10mm rectangle as test film.For this test film, the surface making negative electrode active material layer down, at the surface mount cellophane tape of negative electrode active material layer.Now, as cellophane tape, use the cellophane tape of defined in JIS Z1522.In addition, cellophane tape is fixed on the testing stand of level in advance.Then, stress when being carried out stretching with draw speed 50mm/ minute in one end of collector body above vertical and peel off is measured.Carry out 3 these mensuration, obtain its mean value, using this mean value as peel strength (N/m).Peel strength is larger, and represent that the cohesive force of negative electrode active material layer to collector body is larger, namely dhering strength is larger.
2. Stability of Slurry
For the negative pole paste compound manufactured in embodiment and comparative example, Brookfield viscometer is utilized to measure 25 DEG C, viscosities il 0 under rotating speed 60rpm.
Then, negative pole paste compound is left standstill 72 hours at 5 DEG C, returns back to 25 DEG C afterwards, again measure viscosities il 1 as described above.Relatively leave standstill before and after viscosity, if the increase of viscosity B coefficent rate (=(η 1-η 0)/η 0 × 100) is lower than 10%, then be A, if increase by more than 10% ~ increase lower than 30%, be then B, if increase by more than 30%, be then C.
3. coating
The negative pole paste compound manufactured in embodiment and comparative example to be coated on the Copper Foil of the thickness 20 μm of collector body in the mode that dried thickness is about 150 μm and to make it dry.This drying is carried out by being carried in the baking oven of 60 DEG C with the speed of 0.5m/ minute by Copper Foil for 2 minutes.Then, at 120 DEG C, heat treated 2 minutes, obtains negative pole.Gained negative pole is cut into the size of 10 × 10cm, by the number of the pin hole of visual mensuration more than diameter 0.1mm.The number of pin hole is fewer, represents that coating is more excellent.
4. durability
(1) High temperature storage characteristic
After the lithium rechargeable battery of the laminated units type manufactured in embodiment and comparative example is left standstill 24 hours in the environment of 25 DEG C, carry out utilizing the constant current anodizing process of 0.1C to charge to 4.2V in the environment of 25 DEG C and be discharged to the discharge and recharge operation of 3.0V, measuring initial capacity C 0.And then, charge to 4.2V, and preserve after 7 days at 60 DEG C, carry out utilizing the constant current anodizing process of 0.1C to charge to 4.2V in the environment of 25 DEG C and be discharged to the discharge and recharge operation of 3.0V, measuring the capacity C after High temperature storage 1.Utilize Δ C s=C 1/ C 0capacitance Shift Rate Δ C shown in × 100 (%) shigh temperature storage characteristic is evaluated.This Capacitance Shift Rate Δ C svalue higher, represent that High temperature storage characteristic is more excellent.
(2) high-temperature cycle
After the lithium rechargeable battery of the laminated units type manufactured in embodiment and comparative example is left standstill 24 hours in the environment of 25 DEG C, in the environment of 25 DEG C, carry out utilizing the constant current anodizing process of 0.1C to charge to 4.2V and be discharged to the discharge and recharge operation of 3.0V, measuring initial capacity C 0.And then, repeat in the environment of 60 DEG C, utilize the constant current anodizing process of 1C to charge to 4.2V and be discharged to 3.0V discharge and recharge operation, determine the capacity C after 100 circulations 2.Utilize Δ C c=C 2/ C 0capacitance Shift Rate Δ C shown in × 100 (%) chigh-temperature cycle is evaluated.This Capacitance Shift Rate Δ C cvalue higher, represent high-temperature cycle more excellent.
(3) pole plate expansion characteristics
After the evaluation of above-mentioned " (1) High temperature storage characteristic ", the unit of lithium rechargeable battery is disintegrated, measure the electrode thickness d1 of negative pole.Negative plates thickness before making lithium rechargeable battery unit is set to d0, calculates pole plate expansion rate (d1-d0)/d0 × 100 (%) of negative pole.This value is lower, represents that pole plate expansion characteristics is more excellent.
5. low temperature output characteristic
After the lithium rechargeable battery of the laminated units type manufactured in embodiment and comparative example is left standstill 24 hours in the environment of 25 DEG C, the charge rate of 4.2V, 1C is utilized to carry out the operation of charging.Then, in the environment of-10 DEG C, utilize the discharge rate of 1C to carry out discharge operation, measure the voltage V of electric discharge beginning after 15 seconds 15.Utilize Δ V=4.2V-V 15(mV) the change in voltage Δ V shown in evaluates low temperature output characteristic.The value of this change in voltage Δ V is less, represents that low temperature output characteristic is more excellent.
6. the viscosity of 1% aqueous solution of water-soluble polymer
Utilized by the water-soluble polymer manufactured in embodiment and comparative example 10% ammoniacal liquor and ion exchange water to carry out diluting and make pH be 8, having prepared 1% aqueous solution of water-soluble polymer.Brookfield viscometer is utilized to measure the viscosity of this aqueous solution.
[embodiment 1]
(manufacture of 1-1. water-soluble polymer)
Band mixer 5MPa pressure vessel in add the ethyl acrylate 65.5 parts as (methyl) acrylate monomer, the methacrylic acid 30 parts as ethylenically unsaturated carboxylic acids monomer, as fluorine-containing (methyl) acrylate monomer methacrylic acid trifluoro methyl esters 2.5 parts, as contain the 2-acrylamide-2-methyl propane sulfonic 2 parts of sulfonic group monomer, neopelex 1.0 parts, ion exchange water 150 parts and the potassium peroxydisulfate 0.5 part as polymerization initiator as emulsifying agent, after abundant stirring, heat to 60 DEG C with initiated polymerization.The moment reaching 96% at polymerisation conversion carries out cooling and cessation reaction, obtains the aqueous solution containing water-soluble polymer.Containing, for example on add 10% ammoniacal liquor in the aqueous solution of water-soluble polymer that obtains, be adjusted to pH8, obtain the aqueous solution containing the water-soluble polymer expected.Determine the weight average molecular weight of gained water-soluble polymer, result is 12800.
Using the aqueous solution containing gained water-soluble polymer as sample, determine the viscosity of 1% aqueous solution of water-soluble polymer, result is 1500mPas.
(manufacture of 1-2. particle-like adhesive)
1 as aliphatic conjugated diene monomer is added in the 5MPa pressure vessel of band mixer, 3-butadiene 33 parts, the methacrylic acid 1.5 parts as ethylenically unsaturated carboxylic acids monomer, the styrene 65.5 parts as aromatic vinyl base class monomer, neopelex 4 parts, ion exchange water 150 parts and the potassium peroxydisulfate 0.5 part as polymerization initiator as emulsifying agent, after abundant stirring, heat to 50 DEG C with initiated polymerization.The moment reaching 96% at polymerisation conversion carries out cooling and cessation reaction, obtains the aqueous liquid dispersion containing the particle-like adhesive be made up of styrene-butadiene-copolymer (following, to be suitably called " SBR ").Containing, for example on add 5% sodium hydrate aqueous solution in the aqueous liquid dispersion of particle-like adhesive that obtains, after being adjusted to pH8, carried out the removing of unreacted monomer by heating decompression distillation.Then, be cooled to less than 30 DEG C, obtain the aqueous liquid dispersion containing the particle-like adhesive expected.Determine the weight average molecular weight of gained particle-like adhesive, result is 1500000.In addition, the number average bead diameter of particle-like adhesive measured by laser diffraction and scattering mode particle size distribution device is 150nm.
(manufacture of 1-3. negative pole paste compound)
By the aqueous solution dilute with water containing the water-soluble polymer obtained in operation (1-1), concentration is adjusted to 5%.
Add respectively in the planetary-type mixer of band disperser above-mentioned water-soluble polymer 5% aqueous solution 1 part (using solid component meter) and as the SiOC (volume average particle size: 12 μm) 50 parts of negative electrode active material and specific area 4m 2the Delanium (volume average particle size: 24.5 μm) 50 parts of/g, after being adjusted to solid component concentration 55%, mixes 60 minutes with ion exchange water at 25 DEG C.Then, after being adjusted to solid component concentration 52% with ion exchange water, then mix 15 minutes at 25 DEG C, obtain mixed liquor.
The aqueous dispersions 1 part (with solid component meter) containing the particle-like adhesive obtained in operation (1-2) and ion exchange water is added in above-mentioned mixed liquor, with make final solid component concentration be 42% mode adjust, then mix 10 minutes.It is under reduced pressure carried out deaeration process, obtains the negative pole paste compound of good fluidity.
The evaluation of stability and coating has been carried out to gained negative pole paste compound.Result is as shown in table 1.
(manufacture of 1-4. negative pole)
Utilized by the negative pole paste compound obtained in operation (1-3) unfilled corner to take turns coating machine to be coated on the Copper Foil of the thickness 20 μm of collector body in the mode that dried thickness is about 150 μm and to make it dry.This drying is carried out by being carried in the baking oven of 60 DEG C with the speed of 0.5m/ minute by Copper Foil for 2 minutes.Then, heat treatment 2 minutes at 120 DEG C, obtains the former film of negative pole (former anti-).Rolled by former for this negative pole film roll squeezer, the thickness obtaining negative electrode active material layer is the negative pole of 80 μm.
The evaluation of dhering strength has been carried out to gained negative pole.Show the result in table 1.
(manufacture of 1-5. positive pole)
As positive pole adhesive, prepare glass transition temperature Tg and be-40 DEG C and number average bead diameter is 40% aqueous dispersion of the acrylate polymer of 0.20 μm.Above-mentioned acrylate polymer is the monomer mixture containing 2-EHA 78 % by weight, acrylonitrile 20 % by weight and methacrylic acid 2 % by weight is carried out the copolymer that emulsion polymerisation obtains.
Using as positive active material volume average particle size 0.5 μm and there is the LiFePO of olivine crystalline texture 4100 parts, 1% aqueous solution (Di-ichi Kogyo Seiyaku Co., Ltd.'s system " BSH-12 ") 1 part (using solid component meter) as the carboxymethyl cellulose of dispersant, 40% aqueous dispersion 5 parts (with solid component meter) as the aforesaid propylene acid ester polymer of adhesive mix, and wherein with make total solid constituent concentration be 40% mode add ion exchange water.Utilize planetary-type mixer to mix, prepare positive pole paste compound.
Utilized by above-mentioned positive pole paste compound unfilled corner to take turns coating machine to be coated on the Copper Foil of the thickness 20 μm of collector body in the mode that dried thickness is about 200 μm and to make it dry.This drying is carried out by being carried in the baking oven of 60 DEG C with the speed of 0.5m/ minute by Copper Foil for 2 minutes.Then, heat treatment 2 minutes at 120 DEG C, obtains the former film of positive pole.Utilize roll squeezer to roll former for this positive pole film, the thickness having manufactured positive electrode active material layer is the positive pole of 70 μm.
(preparation of 1-6. dividing plate)
Prepare the polypropylene dividing plate (width 65mm, length 500mm, thickness 25 μm, utilize dry process manufacture, the porosity 55%) of individual layer.
(1-7. lithium rechargeable battery)
Exterior as battery, prepares aluminium packaging material exterior.The negative pole obtained in operation (1-4) is cut into the square of 4.2mm × 4.2mm.The positive pole obtained in operation (1-5) is cut into the square of 4mm × 4mm.The dividing plate of operation (1-6) is cut into the square of 5mm × 5mm.
Above-mentioned foursquare positive pole is configured to make the exterior mode connected of the surface of collector body and aluminium packaging material.The face of the positive electrode active material layer of foursquare positive pole configures foursquare dividing plate.Then, above-mentioned foursquare negative pole is configured on foursquare dividing plate in the mode of the surface of negative electrode active material layer towards dividing plate.The LiPF of the concentration 1.0M as electrolyte is injected in aluminium packaging material 6the mixed solvent of solution (solvent: EC/DEC=1/2 (volume ratio)).And then in order to be sealed by the opening of aluminium packaging material, the heat-sealing carrying out 150 DEG C, by exterior for aluminium sealing, has manufactured lithium rechargeable battery.
To the cell evaluation High temperature storage characteristic, high-temperature cycle and the pole plate expansion characteristics that obtain.And then evaluate low temperature output characteristic.Show the result in table 1.
In addition, the capacity (initial capacity) when gained lithium rechargeable battery being carried out first discharge and recharge with the charge-discharge velocity of 4.2V, 0.1C is for 50mAH.
[embodiment 2 and 3]
In the manufacture of the water-soluble polymer of operation (1-1), as containing sulfonic group monomer, styrene sulfonic acid (embodiment 2) or vinyl sulfonic acid (embodiment 3) is used to replace 2-acrylamide-2-methyl propane sulfonic, in addition, implement similarly to Example 1, manufacture lithium rechargeable battery and inscape thereof and evaluate.Show the result in table 1.
[embodiment 4 and 5]
In the manufacture of the water-soluble polymer of operation (1-1), as fluorine-containing (methyl) acrylate monomer, acrylic acid trifluoro methyl esters (embodiment 4) or methacrylic acid perfluor monooctyl ester (embodiment 5) is used to replace methacrylic acid trifluoro methyl esters, in addition, implement similarly to Example 1, manufacture lithium rechargeable battery and inscape thereof and evaluate.Show the result in table 1.
[embodiment 6 ~ 12]
In the manufacture of the water-soluble polymer of operation (1-1), the ratio of ethyl acrylate, methacrylic acid, methacrylic acid trifluoro methyl esters and 2-acrylamide-2-methyl propane sulfonic is changed as shown in table 1 and table 2, in addition, implement similarly to Example 1, manufacture lithium rechargeable battery and inscape thereof and evaluate.Show the result in table 1 and table 2.
[embodiment 13]
In the manufacture of the negative pole paste compound of operation (1-3), as negative electrode active material, SiOC 100 parts is used to replace SiOC 50 parts and Delanium 50 parts, in addition, implement similarly to Example 1, made each inscape of lithium rechargeable battery and lithium rechargeable battery and evaluated.Show the result in table 2.
[embodiment 14]
In the manufacture of the negative pole paste compound of operation (1-3), as negative electrode active material, Delanium 100 parts is used to replace SiOC 50 parts and Delanium 50 parts, in addition, implement similarly to Example 1, made each inscape of lithium rechargeable battery and lithium rechargeable battery and evaluated.Show the result in table 2.
[embodiment 15]
(manufacture of 15-1. nano silicon oxide active material A)
By average grain diameter 3 μm, BET specific surface area 12m 2silicon oxide powder (the SiO of/g x: x=1.02) 200g joins after in silicon nitride pallet, is statically placed in and can keeps in the process stove of atmosphere.Then, pass into argon gas, to after having carried out argon replaces in process stove, argon gas has been passed into 2NL/min, is simultaneously warming up to 1200 DEG C with the programming rate of 300 DEG C/hr, keeps 3 hours.After maintenance terminates, start cooling, after reaching room temperature, reclaim powder, obtain Si class active material A.The Si class active material A of gained is average grain diameter 3.5 μm, BET specific surface area 11m 2the powder of/g, confirming it based on the Alpha-ray X-ray diffraction pattern of Cu-K and there is the diffracted ray belonging to Si (111) be positioned near 2 θ=28.4 ° by this powder, and be 40nm by the half-peak breadth of this diffracted ray by the size being scattered in the crystal of the silicon in silicon dioxide that Scherrer method is obtained, this powder is silicon complex powder.
(manufacture of 15-2. lithium rechargeable battery and inscape thereof and evaluation)
In the manufacture of the negative pole paste compound of operation (1-3), as negative electrode active material, the Si class active material A 5 parts obtained in use operation (15-1) and Delanium 95 parts replace SiOC 50 parts and Delanium 50 parts, in addition, implement similarly to Example 1, manufactured lithium rechargeable battery and inscape thereof and evaluated.Show the result in table 2.
[embodiment 16]
(manufacture of 16-1. nano silicon oxide active material B)
Polysilicon grains is imported and after the granular polycrystalline silicon sent into monosilane and manufacture in the fluid bed pulverizing by inside temperature 800 DEG C utilizing jet mill, grader is utilized to carry out classification, obtain the pSi powder of D50=10.2 μm, it can be used as Si class active material B.Be 44nm by the half-peak breadth of X-ray diffraction curve, the crystallite size that confirmed Si class active material B by Scherrer method.
(manufacture of 16-2. lithium rechargeable battery and inscape thereof and evaluation)
In the manufacture of the negative pole paste compound of operation (1-3), as negative electrode active material, the Si class active material B 5 parts obtained in use operation (16-1) and Delanium 95 parts replace SiOC 50 parts and Delanium 50 parts, in addition, implement similarly to Example 1, manufactured lithium rechargeable battery and inscape thereof and evaluated.Show the result in table 2.
[comparative example 1 ~ 4]
In the manufacture of the water-soluble polymer of operation (1-1), change as shown in table 3 for the ratio of ethyl acrylate, methacrylic acid, methacrylic acid trifluoro methyl esters and 2-acrylamide-2-methyl propane sulfonic like that, in addition, implement similarly to Example 1, manufactured lithium rechargeable battery and each inscape thereof and evaluated.Show the result in table 3.
[table 1]
[table 2]
[table 3]
? Comparative example 1 Comparative example 2 Comparative example 3 Comparative example 4
Adhesive Particle shape Particle shape Particle shape Particle shape
EA measures 67.5 35 67.7 53
Fluorine monomer kind TFMMA TFMMA TFMMA TFMMA
Fluorine monomer amount 2.5 0 0.3 15
Sulfonic acid monomer kind - AMPS AMPS AMPS
Sulfonic acid monomer amount 0 35 2 2
MAA measures 30 30 30 30
1% solution viscosity 800 2600 900 2400
Water-soluble Polymer Molecules amount 8000 20000 9000 18000
Negative electrode active material SiOC/C SiOC/C SiOC/C SiOC/C
Active material ratio 50/50 50/50 50/50 50/50
Dhering strength 8 9 10 8
Stability of Slurry C C C C
Coating 25 18 18 15
High temperature storage characteristic 55 55 60 65
High-temperature cycle 45 50 60 55
Pole plate expansion characteristics 20 25 20 25
Low temperature output characteristic 550 520 550 510
The implication be called for short in table is as follows.
TFMMA: methacrylic acid trifluoro methyl esters
TFMA: acrylic acid trifluoro methyl esters
PFOMA: methacrylic acid perfluor monooctyl ester
AMPS:2-acrylamide-2-methyl propane sulfonic
SS: styrene sulfonic acid
VS: vinyl sulfonic acid
Si class A: the nano silicon active material A manufactured in embodiment 15
Si class B: the nano silicon active material B manufactured in embodiment 16
Adhesive: adhesive classification
EA measures: ethyl acrylate addition (part)
Fluorine monomer kind: fluorine-containing (methyl) acrylate monomer kind
Fluorine monomer amount: fluorine-containing (methyl) acrylate monomer addition (part)
Sulfonic acid monomer kind: containing sulfonic group monomeric species
Sulfonic acid monomer amount: containing sulfonic group monomer addition (part)
MAA measures: methacrylic acid addition (part)
1% solution viscosity: the viscosity (mPas) of 1% aqueous solution of water-soluble polymer
Water-soluble Polymer Molecules amount: the weight average molecular weight of water-soluble polymer
Negative electrode active material: negative electrode active material kind
Active material ratio: the addition (part) of each active material
Dhering strength: negative pole peel strength mean value (N/m)
Stability of Slurry: the evaluation result of viscosity B coefficent rate
A: the increase of rate of change lower than 10%,
B: be increased in more than 10% and lower than 30%,
C: be increased in more than 30%
Coating: the pin hole number (individual) after the coating of negative pole slurry
High temperature storage characteristic: the Capacitance Shift Rate Δ C of battery s(%)
High-temperature cycle: the Capacitance Shift Rate Δ C of battery c(%)
Pole plate expansion characteristics: the pole plate expansion rate (%) of the negative pole after High temperature storage evaluating characteristics
Low temperature output characteristic: the change in voltage Δ V (mV) under low temperature
[discussion]
From the result of table 1 ~ table 3, with do not meet the present application any important document comparative example compared with, in the embodiment of the present application 1 ~ 16, can suppress with discharge and recharge occur negative pole expand, and any characteristic in various any characteristic is all good, and can obtain well balanced.In addition, in the embodiment except the embodiment 8 that the addition except water-soluble polymer is less, the stability of slurry is also excellent.

Claims (11)

1. a secondary battery cathode, it comprises negative electrode active material, particle-like adhesive and water-soluble polymer, wherein,
Described water-soluble polymer be comprise 0.1 % by weight ~ 15 % by weight containing sulfonic group monomeric unit and 0.5 % by weight ~ 10 % by weight the copolymer of fluorine-containing (methyl) acrylate monomeric units.
2. secondary battery cathode according to claim 1, wherein, described water-soluble polymer comprises ethylenically unsaturated carboxylic acids monomeric unit.
3. secondary battery cathode according to claim 2, wherein, described ethylenically unsaturated carboxylic acids monomer is olefinic unsaturated monocarboxylic acid monomer.
4. the secondary battery cathode according to any one of claims 1 to 3, wherein, described negative electrode active material can occlusion and release lithium, and containing metal.
5. secondary battery cathode according to claim 4, wherein, described metal is silicon.
6. the secondary battery cathode according to any one of Claims 1 to 5, wherein, described particle-like adhesive contains the polymer comprising aliphatic conjugated diene monomer unit.
7. secondary battery cathode according to claim 6, wherein, described in comprise aliphatic conjugated diene monomer unit polymer also comprise aromatic vinyl monomer unit.
8. a secondary cell, it possesses positive pole, negative pole, electrolyte and dividing plate, the secondary battery cathode of described negative pole according to any one of claim 1 ~ 7.
9. a secondary battery negative pole paste compound, it comprises negative electrode active material, particle-like adhesive and water-soluble polymer, wherein,
Described water-soluble polymer be comprise 0.1 % by weight ~ 15 % by weight containing sulfonic group monomeric unit and 0.5 % by weight ~ 10 % by weight the copolymer of fluorine-containing (methyl) acrylate monomeric units.
10. negative pole paste compound according to claim 9, wherein, described water-soluble polymer comprises ethylenically unsaturated carboxylic acids monomeric unit.
The manufacture method of 11. 1 kinds of secondary battery cathodes, it comprises: be coated with the secondary battery negative pole paste compound described in claim 9 or 10 on the current collector and carry out drying.
CN201380023021.9A 2012-08-09 2013-08-07 Negative electrode for secondary cell, secondary cell, slurry composition, and manufacturing method Pending CN104272508A (en)

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