CN104823308B - Lithium rechargeable battery - Google Patents

Lithium rechargeable battery Download PDF

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Publication number
CN104823308B
CN104823308B CN201380059504.4A CN201380059504A CN104823308B CN 104823308 B CN104823308 B CN 104823308B CN 201380059504 A CN201380059504 A CN 201380059504A CN 104823308 B CN104823308 B CN 104823308B
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active material
nitrile group
acid
positive
rechargeable battery
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CN104823308A (en
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召田郁哉
杉本拓己
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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
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • 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
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • 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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • H01M4/623—Binders being polymers fluorinated polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • H01M10/0587—Construction or manufacture of accumulators having only wound construction elements, i.e. wound positive electrodes, wound negative electrodes and wound separators
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Abstract

It is an object of the invention to provide during soft, bending the high power capacity that active material layer is not cracked, high potential cycle characteristics is excellent lithium rechargeable battery.The lithium rechargeable battery of the present invention possesses positive pole, negative pole and nonaqueous electrolytic solution, and the positive pole contains positive active material, positive pole binding agent and conductive material, and the positive active material is 9～11 (cal/cm by SP value3)1/2Nitrile group-containing acrylate copolymer cladding, the positive pole binding agent contains fluoropolymer.

Description

Lithium rechargeable battery
Technical field
The present invention relates to lithium rechargeable battery, more particularly, to the lithium ion secondary electricity that can realize high capacity Pond.
Background technology
In recent years, the portable terminal device such as notebook computer, mobile phone, PDA (Personal Digital Assistant) Popularization highly significant.Using nickel-hydrogen secondary cell, lithium ion two secondary cell of the power supply that can be used for these portable terminal devices more Primary cell etc..Portable terminal device requires more comfortable Portability, thus its miniaturization, slimming, lighting, high performance obtain urgency Speed development, as a result, portable terminal device has been used for various occasions.
In addition, for battery, also require in the same manner as portable terminal device to minimize, be thinned, lighting and high performance.Separately Outward, in order to increase the use level of the active material in active material layer so as to realize the high capacity of battery, it is desirable to which reducing is used for Binding material that active material is fixed on collector, for guaranteeing the materials such as the conductive material of electric conductivity.
For the purpose of the high capacity of lithium rechargeable battery, have been developed for using the alloy type active material containing Si etc. Lithium ion secondary battery cathode (such as patent document 1).Along with high capacity, voltage during discharge and recharge also constantly becomes Height, the electrolyte being made up of ethylene carbonate, propylene carbonate etc. sometimes cannot tolerating high voltage and decompose, therefore, Being applied in combination for fluorine system electrolysis additive is carried out.
On the other hand, in positive pole, as the binding agent for forming active material layer, Kynoar has been employed (PVdF) fluoropolymer such as.Fluoropolymer can expect stable caking property due to being not dissolved in electrolyte, therefore, but PVdF There is firmly Deng fluoropolymer and be difficult to the property for bending.Therefore, shape according to battery, of different sizes, electrode is through pulleying Around rear it some times happens that crushing, when being configured to give shape, in the case of only using fluoropolymer, sometimes in activity Material layer is cracked.
In addition, in order to realize high capacity, particularly grain refined is carried out to the carbon black etc. as conductive material in positive pole Technology studied.But, in the case of fluoropolymer being used alone as binding agent, through the conduction of grain refined Material is it some times happens that cohesion, dispersed insufficient, electric conductivity cannot be improved, it is impossible to seek the raising of capacity.
Prior art literature
Patent document
Patent document 1：Japanese Patent No. 4025995
Patent document 2：Japanese Patent No. 3598153
Patent document 3：Japanese Patent No. 4929573
Content of the invention
Problems to be solved by the invention
With regard to lithium rechargeable battery, there are the following problems：In order to realize high capacity, fluoropolymer used in positive pole When thing is as binding agent, can crack in active material layer.In addition, as the binding agent used in positive pole, having been for combination Carried out using fluoropolymer and nitrile rubber, the technology for being applied in combination fluoropolymer and cross-linked acrylic acid esters polymer Research.
For example, in patent document 2, as the binding agent for forming the active material layer of lithium rechargeable battery, group Conjunction employs fluoropolymer and nitrile rubber.But, as active material density can be relatively dropped because binder amount increases Low, therefore, sufficient battery capacity cannot be obtained sometimes.Further, since binding agent quantitative change is many, sometimes active material layer with respect to The swellbility of electrolyte also increases, and peel strength when particularly high potential is circulated reduces, and cycle characteristics declines.
In addition, in patent document 3, as binding agent, being applied in combination fluoropolymer and crosslink propylene esters of gallic acid being poly- Compound.But, due to employing cross-linked acrylic acid esters polymer, therefore, although active material layer is molten with respect to electrolyte Swollen be inhibited, but due to cross-linked acrylic acid esters polymer with particle shape exist, therefore, dispersiveness insufficient, as a result, can High potential cycle characteristics can be caused to reduce.
Therefore, it is an object of the invention to provide active material layer is not cracked, high potential is followed during a kind of soft, bending The lithium rechargeable battery of the excellent high power capacity of ring property.
The method of solve problem
The present inventor etc. are had made intensive studies to solve the above problems, and are as a result found：By by positive electrode active material Matter is coated with the acrylate copolymer of the nitrile group-containing with specific physical property, and the acrylate copolymer of nitrile group-containing is dissolved in positive pole slurry The decentralized medium of feed composition, but insoluble in the close electrolyte of solubility parameter (SP value), such that it is able to make which with appropriate Scope occurs swelling.Additionally, the inventors discovered that：By conducting material powder is used for the same of positive pole and pursuing high capacity When, by using fluoropolymer as positive pole binding agent, when can obtain softness, bending, active material layer is not cracked And the high electrode of active material density, and then, the lithium ion secondary electricity of the excellent high power capacity of high potential cycle characteristics can be obtained Pond.The present invention is completed based on these opinions.
The main points of the present invention are as follows.
[1] a kind of lithium rechargeable battery, which possesses positive pole, negative pole and nonaqueous electrolytic solution,
Wherein, the positive pole contains positive active material, positive pole binding agent and conductive material,
The positive active material is 9～11 (cal/cm by SP value3)1/2Nitrile group-containing acrylate copolymer cladding,
The positive pole binding agent contains fluoropolymer.
[2] according to the lithium rechargeable battery described in [1], wherein, the positive active material be containing Li, Mn, Co and The lithium excess lamellar compound of Ni.
[3] lithium rechargeable battery according to [1] or [2], wherein, the negative pole contains alloy type active material.
[4] lithium rechargeable battery according to any one of [1]～[3], wherein, the acrylic acid of the nitrile group-containing gathers Swellbility of the compound in nonaqueous electrolytic solution is less than 3 times, and its THF insoluble component amount is below 30 mass %.
[5] lithium rechargeable battery according to any one of [1]～[4], wherein, the particle diameter of the conductive material is 5～40nm.
[6] lithium rechargeable battery according to any one of [1]～[5], wherein, with respect to the positive electrode active material 100 mass parts of matter, the content of conductive material is 1～3 mass parts, the content of positive pole binding agent is 0.4～2 mass parts.
[7] according to the lithium rechargeable battery any one of [1]～[6], wherein, the fluoropolymer is poly- inclined PVF.
[8] lithium rechargeable battery according to any one of [1]～[7], wherein, the acrylic acid of the nitrile group-containing gathers Compound contains ethylenic unsaturated acid monomeric unit.
[9] according to the lithium rechargeable battery described in [8], wherein, the olefinic in the acrylate copolymer of the nitrile group-containing The content ratio of unsaturated acid monomer unit is 10～30 mass %.
[10] lithium rechargeable battery according to any one of [1]～[9], which is convoluted bag-type battery (pouch cell).
The effect of invention
According to the present invention, by conducting material powder is used for positive pole, by positive active material with specific physical property The acrylate copolymer of nitrile group-containing is coated and uses fluoropolymer as binding agent, it is possible to obtain lived during not only soft, bending Property material layer is not cracked, and the high electrode of active material density.Furthermore it is possible to provide circulate with excellent high potential The lithium rechargeable battery of characteristic.
Specific embodiment
Hereinafter, the present invention is described in more detail.The lithium rechargeable battery of the present invention (is also denoted as " two below Primary cell ") possess positive pole, negative pole and nonaqueous electrolytic solution.Positive pole contains positive active material, positive pole binding agent and conduction material Material.Positive active material is 9～11 (cal/cm by SP value3)1/2Nitrile group-containing acrylate copolymer cladding.Positive pole bonds Agent is fluoropolymer.Hereinafter, respectively more specific detail is carried out to positive pole, negative pole and nonaqueous electrolytic solution.
(positive pole)
Positive pole is comprising collector and the positive electrode active material layer being stacked on the collector.Positive electrode active material layer contains Positive active material (A), positive pole binding agent (B) and conductive material (C), and contain other compositions as desired.In addition, just Pole active material (A) be by SP value be 9～11 (cal/cm3)1/2Nitrile group-containing acrylate copolymer cladding positive pole live Property material.
(A) positive active material
Positive active material use can be embedded in and depart from the active material of lithium ion, and such positive active material substantially divides It is the active material and the active material being made up of organic compound being made up of inorganic compound.
As the positive active material being made up of inorganic compound, can enumerate：Transition metal oxide, Transition Metal Sulfur Lithium-contained composite metal oxide that compound, lithium and transition metal are formed etc..
As above-mentioned transition metal, it is possible to use Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Mo etc..
As transition metal oxide, can enumerate：MnO、MnO2、V2O5、V6O13、TiO2、Cu2V2O3, noncrystalline V2O- P2O5、MoO3、V2O5、V6O13Deng, wherein, from from the aspect of cycle characteristics and capacity, preferably MnO, V2O5、V6O13、TiO2.
As transient metal sulfide, can enumerate：TiS2、TiS3, noncrystalline MoS2, FeS etc..
As lithium-contained composite metal oxide, for example, can enumerate：Lithium-contained composite metal oxide with layer structure, Lithium-contained composite metal oxide with spinel structure, lithium-contained composite metal oxide with olivine-type structure etc..
As the lithium-contained composite metal oxide with layer structure, for example, can enumerate：Cobalt/cobalt oxide containing lithium (LiCoO2), containing lithium nickel oxide (LiNiO2), lithium composite xoide (Li (CoMnNi) O of Co-Ni-Mn2), containing Li, The lithium excess lamellar compound (Li [Ni of Mn, Co and Ni0.17Li0.2Co0.07Mn0.56]O2), the lithium composite xoide of Ni-Mn-Al, Lithium composite xoide of Ni-Co-Al etc..
As the lithium-contained composite metal oxide with spinel structure, for example, can enumerate：LiMn2O4 (LiMn2O4) or By a part of the Mn Li [Mn of other transition metal substitution3/2M1/2]O4(here, M is Cr, Fe, Co, Ni, Cu etc.) Deng.
As the lithium-contained composite metal oxide with olivine-type structure, for example, can enumerate：LixMPO4(in formula, M table Show at least a kind in Mn, Fe, Co, Ni, Cu, Mg, Zn, V, Ca, Sr, Ba, Ti, Al, Si, B and Mo, 0≤x≤2) shown in Olivine-type lithium phosphate compound.
Wherein, from cycle characteristics and initial capacity excellent from the aspect of, preferably containing lithium cobalt/cobalt oxide (LiCoO2), contain lithium Nickel oxide (LiNiO2), lithium composite xoide (Li (CoMnNi) O of Co-Ni-Mn2), the lithium mistake containing Li, Mn, Co and Ni Amount lamellar compound (Li [Ni0.17Li0.2Co0.07Mn0.56]O2), the lithium-contained composite metal oxide with spinel structure, more It is preferred that cobalt/cobalt oxide (the LiCoO containing lithium2), the excess lamellar compound (Li of the lithium containing Li, Mn, Co and Ni [Ni0.17Li0.2Co0.07Mn0.56]O2).
As the positive active material being made up of organic compound, such as polyacetylene can also be used, gathered to conductions such as benzene Property macromolecule.
In addition, for the not enough ferrous oxide of electric conductivity, can be by carrying out reduction burning in the presence of carbon source material Make and use as the electrode active material covered by material with carbon element.
In addition it is also possible to using the material that these compounds are carried out with Partial Elements displacement.
Positive electrode active material for lithium ion secondary battery can also be the mixed of above-mentioned inorganic compound and organic compound Compound.
The volume average particle size of positive active material is usually 1～50 μm, preferably 2～30 μm.By by positive-active The volume average particle size of material is set in above range, it is possible to reduce the amount of the positive pole binding agent in positive electrode active material layer, The reduction of battery capacity can be suppressed.In addition, in order to form positive electrode active material layer, generally will prepare containing positive active material And the slurry (being also denoted as " positive pole paste compound " below) of positive pole binding agent, can be easily by the positive pole slurry group Compound is modulated into the viscosity for being suitable to be coated with, so as to obtain uniform positive electrode active material layer.
The content ratio of the positive active material in positive electrode active material layer is preferably 90～99.9 mass %, more preferably 95～99 mass %.By the content of the positive active material in positive electrode active material layer is set to above range, can be aobvious Flexibility, caking property is shown while high power capacity is shown.
Positive active material (A) in the present invention is coated by the acrylate copolymer of nitrile group-containing.By using by nitrile group-containing Acrylate copolymer cladding positive active material (A), cycle characteristics of the lithium rechargeable battery in high potential can be improved. Hereinafter, the acrylate copolymer to nitrile group-containing is illustrated.
The acrylate copolymer of nitrile group-containing
The acrylate copolymer of nitrile group-containing be containing the poly- of nitrile group-containing monomeric unit and (methyl) acrylate monomeric units Compound.Nitrile group-containing monomeric unit refers to the construction unit formed by the monomer polymerization with itrile group, (methyl) acrylate Monomeric unit refers to the construction unit formed by the polymerization of (methyl) acrylate monomer.The acrylate copolymer of nitrile group-containing contains There are nitrile group-containing monomeric unit and (methyl) acrylate monomeric units, contain ethylenic unsaturated acid monomer list further as needed Unit and the monomeric unit introduced by other monomers such as cross-linkable monomers.These monomeric units are to be formed by corresponding monomer polymerization Construction unit.Here, the content ratio (rate of charge of monomer) of each monomer generally with the acrylate copolymer of nitrile group-containing in each The content ratio of monomeric unit is consistent.
As the specific example of the monomer of nitrile group-containing, acrylonitrile, methacrylonitrile etc. can be enumerated, wherein, from can carry High adaptation with collector, improve pole strength from the viewpoint of, preferred acrylonitrile.
The content ratio of the nitrile group-containing monomeric unit in the acrylate copolymer of nitrile group-containing is preferably 5～35 mass %, enters One step is preferably 10～30 mass %, the particularly preferably scope of 15～25 mass %.If the containing of nitrile group-containing monomeric unit Ratio is the scope, then the excellent adhesion with collector, and the intensity of the electrode obtained is improved.
(methyl) acrylate monomeric units be by coming from formula (1)：CH2=CR1-COOR2(in formula, R1Represent that hydrogen is former Son or methyl, R2Represent alkyl or cycloalkyl) shown in compound monomer polymerization and formed construction unit.
As the specific example of the compound shown in formula (1), can enumerate：Ethyl acrylate, propyl acrylate, propylene Isopropyl propionate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, acrylic acid n-pentyl ester, isoamyl acrylate, third The acrylate such as the just own ester of olefin(e) acid, 2-EHA, lauryl acrylate, stearyl acrylate ester；Methacrylic acid second Ester, propyl methacrylate, isopropyl methacrylate, n-BMA, Isobutyl methacrylate, metering system Tert-butyl acrylate, n-amylmethacrylate, isopentyl methacrylate, the just own ester of methacrylic acid, methacrylic acid 2- ethyl The methacrylates such as own ester, lauryl methacrylate, stearyl methacrylate.Wherein, preferred acrylate, from permissible From the viewpoint of improving the intensity of the electrode obtained, particularly preferred n-butyl acrylate and 2-EHA.
(methyl) acrylate monomer can be used alone a kind, it is also possible to combine two or more with arbitrary ratio.Therefore, contain The acrylate copolymer of itrile group can only contain a kind of (methyl) acrylate monomer, it is also possible to contain 2 kinds with arbitrary ratio combination (methyl) acrylate monomer above.
The content ratio of (methyl) acrylate monomeric units in the acrylate copolymer of nitrile group-containing is preferably 35～85 Quality %, more preferably 45～80 mass %, more preferably 45～75 mass %, particularly preferably 50～70 mass %. If using the content ratio of (methyl) acrylate monomeric units for the acrylate copolymer of the nitrile group-containing of above range, electricity The flexibility of pole is high, can suppress the swellability in nonaqueous electrolytic solution.In addition, heat resistance is high, the internal resistance of the electrode obtained can be reduced.
In addition to above-mentioned nitrile group-containing monomeric unit and (methyl) acrylate monomeric units, the acroleic acid polymerization of nitrile group-containing Thing can also contain ethylenic unsaturated acid monomeric unit.
Ethylenic unsaturated acid monomeric unit is the construction unit for being formed that is polymerized by ethylenic unsaturated acid monomer.Olefinic insatiable hunger It is the ethylenically unsaturated monomer with acidic groups such as carboxyl, sulfonic group, phosphinyls with acid monomers, is not limited to specific monomer.Olefinic The specific example of unsaturated acid monomer is ethylenically unsaturated carboxylic acids monomer, olefinic unsaturated sulfonic acid monomer, olefinic unsaturation phosphoric acid Monomer etc..
As the specific example of ethylenically unsaturated carboxylic acids monomer, can enumerate：Olefinic unsaturated monocarboxylic acid and its derivative Thing, olefinic unsaturated dicarboxylic acid and its acid anhydrides and their derivative.
As the example of olefinic unsaturated monocarboxylic acid, can enumerate：Acrylic acid, methacrylic acid and crotonic acid.
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 and β-diaminourea acrylic acid.
As the example of olefinic unsaturated dicarboxylic acid, can enumerate：Maleic acid, fumaric acid and itaconic acid.
As the example of the acid anhydrides of olefinic unsaturated dicarboxylic acid, can enumerate：Maleic anhydride, acrylic anhydride, methyl horse Come acid anhydrides and dimethyl maleic anhydride.
As the example of the derivative of olefinic unsaturated dicarboxylic acid, can enumerate：Citraconic acid, dimethyl Malaysia The Methyl allyl esters such as acid, phenyl maleic acid, chlorine maleic acid, dichloromaleic acid, fluorine maleic acid；And maleic acid hexichol The horses such as ester, maleic acid nonyl ester, maleic acid decyl ester, maleic acid dodecyl ester, maleic acid stearyl, maleic acid fluoroalkyl ester Carry out acid esters.
As the specific example of olefinic unsaturated sulfonic acid monomer, can enumerate：Vinyl sulfonic acid, methyl ethylene sulfonic acid, Styrene sulfonic acid, (methyl) propene sulfonic acid, (methyl) acrylic acid -2- sulfonic acid, 2- acrylamide -2- hydroxy-propanesulfonic acid, 2- Acrylamide-2-methyl propane sulfonic etc..
As the specific example of olefinic unsaturation phosphorus acid monomer, can enumerate：The chloro- 2- phosphoric acid third of (methyl) acrylic acid -3- Ester, (methyl) acrylic acid -2- etherophosphoric acid, 3- allyloxy -2- hydroxy propane phosphoric acid etc..
Alternatively, it is also possible to the alkali metal salts or ammonium salt using above-mentioned ethylenic unsaturated acid monomer.
Above-mentioned ethylenic unsaturated acid monomer can be used alone a kind, it is also possible to combine two or more with arbitrary ratio.Therefore, The acrylate copolymer of nitrile group-containing can only contain a kind of ethylenic unsaturated acid monomer, it is also possible to contain 2 kinds with arbitrary ratio combination Above ethylenic unsaturated acid monomer.
Wherein, from from the viewpoint of the dispersiveness of acrylate copolymer for improving nitrile group-containing, as ethylenic unsaturated acid list Body, is preferably used alone ethylenically unsaturated carboxylic acids monomer or olefinic unsaturated sulfonic acid monomer, or is applied in combination olefinic unsaturation carboxylic Acid monomers and olefinic unsaturated sulfonic acid monomer.
In ethylenically unsaturated carboxylic acids monomer, the viewpoint of good dispersiveness is shown from the acrylate copolymer for making nitrile group-containing Set out, preferably olefinic unsaturated monocarboxylic acid, more preferably acrylic acid, methacrylic acid, particularly preferably methacrylic acid.
In addition, in olefinic unsaturated sulfonic acid monomer, showing good dispersiveness from the acrylate copolymer for making nitrile group-containing From the viewpoint of, preferably 2- acrylamide -2- hydroxy-propanesulfonic acid, 2- acrylamide-2-methyl propane sulfonic, more preferably 2- third Acrylamide -2- methyl propane sulfonic acid.
The content ratio of the ethylenic unsaturated acid monomeric unit in the acrylate copolymer of nitrile group-containing is preferably 3～30 matter Amount %, more preferably 10～30 mass %, more preferably 12～28 mass %, the particularly preferably model of 14～26 mass % Enclose.Ethylenically unsaturated carboxylic acids monomer and olefinic unsaturated sulfonic acid monomer are applied in combination as the situation of ethylenic unsaturated acid monomer Under, the content ratio of the ethylenically unsaturated carboxylic acids monomer in the acrylate copolymer of nitrile group-containing is preferably 3～30 mass %, enters one Step is preferably 10～30 mass %, and particularly preferably 12～28 mass %, the content ratio of olefinic unsaturated sulfonic acid monomer are preferred For 0.1～10 mass %.
By the content ratio of ethylenic unsaturated acid monomeric unit is set to above range, when can improve slurried, contain nitrile The dispersiveness of the acrylate copolymer of base, clad anode active material, lives such that it is able to form the high positive pole of uniformity well Property material layer, can reduce the resistance of positive pole.
In addition to above-mentioned each monomeric unit, the acrylate copolymer of nitrile group-containing can also be in the propylene for not affecting nitrile group-containing Contain cross-linking monomer units further in the range of the THF insoluble component amount of acid polymer.Cross-linking monomer units are to pass through Cross-linkable monomer is heated or energy exposure and can during being polymerized or polymerization after formed cross-linked structure construction unit. As the example of cross-linkable monomer, can generally enumerate with thermally crosslinkable monomer.More specifically, can enumerate：Have Thermally crosslinkable crosslinkable groups and every 1 molecule have mono-functional's monomer of 1 olefinic double bond and every 1 molecule has 2 The multi-functional monomer of above olefinic double bond.
As the example of contained thermally crosslinkable crosslinkable groups in mono-functional's monomer, can enumerate：Epoxy radicals, N- Methylol amide base, oxetanylmethoxy,Oxazoline base and combinations thereof.Wherein, from easily dimmable crosslinking and crosslink density From the viewpoint of, more preferably epoxy radicals.
As the cross-linkable monomer with epoxy radicals as thermally crosslinkable crosslinkable groups and with olefinic double bond Example, can enumerate：Vinyl glycidyl ether, allyl glycidyl ether, cyclobutenyl glycidol ether, o-allyl base The unsaturated glycidyl ethers such as glycidol ether；Butadiene monoepoxide, chlorobutadiene monoepoxide, 4,5- epoxy -2- The diene such as amylene, 3,4- epoxy -1- VCH, 12 carbon diene of 1,2- epoxy -5,9- ring or the mono-epoxide of polyenoid Thing；The alkenyl epoxides such as 3,4- epoxy-1-butylene, 1,2- epoxy -5- hexene, 1,2- epoxy -9- decene；And acrylic acid contracting Water glyceride, GMA, crotons acid glycidyl ester, 4- heptene acid glycidyl ester, sorbic acid shrink Glyceride, linoleic acid ethylene oxidic ester, pyroterebic acid ethylene oxidic ester, the ethylene oxidic ester of 3- cyclohexene carboxylate, 4- The glycidol esters of the unsaturated carboxylic acids such as the ethylene oxidic ester of methyl -3- cyclohexene carboxylate.
As the crosslinking with N- methylol amide base as thermally crosslinkable crosslinkable groups and with olefinic double bond The example of property monomer, can enumerate (methyl) acrylic amide with methylol such as N- methylol (methyl) acrylamide.
As the bridging property list with oxetanylmethoxy as thermally crosslinkable crosslinkable groups and with olefinic double bond The example of body, can enumerate：3- ((methyl) acryloyloxymethyl) oxetanes, 3- ((methyl) acryloxy first Base) -2- trifluoromethyl oxetanes, 3- ((methyl) acryloyloxymethyl) -2- phenyl oxetanes, 2- ((methyl) Acryloyloxymethyl) oxetanes and 2- ((methyl) acryloyloxymethyl) -4- trifluoromethyl oxetanes.
As havingCross-linkable monomer of the oxazoline base as thermally crosslinkable crosslinkable groups and with olefinic double bond Example, can enumerate：2- vinyl -2-Oxazoline, 2- vinyl -4- methyl -2-Oxazoline, 2- vinyl -5- methyl - 2-Oxazoline, 2- isopropenyl -2-Oxazoline, 2- isopropenyl -4- methyl -2-Oxazoline, 2- isopropenyl -5- methyl - 2-Oxazoline and 2- isopropenyl -5- ethyl -2-Oxazoline.
As the example of the multi-functional monomer with more than 2 olefinic double bonds, can enumerate：(methyl) acrylic acid alkene Propyl ester, ethylene glycol two (methyl) acrylate, diethylene glycol two (methyl) acrylate, triethylene glycol two (methyl) acrylic acid Ester, TEG two (methyl) acrylate, trimethylolpropane-three (methyl) acrylate, DPG diallyl ether, Polyethylene glycol diallyl ether, triethyleneglycol divinylether, hydroquinones diallyl ether, tetraallyl epoxide ethane, three Hydroxymethyl-propane-diallyl ether, the pi-allyl of multi-functional alcohol other than the above or vinyl ethers, triallylamine, methylene Base bisacrylamide and divinylbenzene.
As cross-linkable monomer, (methyl) allyl acrylate, ethylene glycol two (methyl) propylene can be particularly preferably used Acid esters, allyl glycidyl ether and GMA.
Above-mentioned cross-linkable monomer can be used alone a kind, it is also possible to combine two or more with arbitrary ratio.Therefore, nitrile group-containing Acrylate copolymer can only contain a kind of cross-linkable monomer, it is also possible to arbitrary ratio combine containing two or more bridging property list Body.
Containing in the case of cross-linking monomer units in the acrylate copolymer of nitrile group-containing, its content ratio is preferably 0.1 More than quality %, more than more preferably 0.2 mass %, more than particularly preferably 0.5 mass %, below preferably 5 mass %, more Below preferably 4 mass %, below particularly preferably 2 mass %.By the content ratio of cross-linking monomer units is set to More than the lower limit of scope is stated, the degree of cross linking of the acrylate copolymer of nitrile group-containing can be improved, prevent swellbility from excessively rising.Separately On the one hand, the propylene of nitrile group-containing, by the ratio of cross-linking monomer units is set to below the higher limit of above range, can be made The favorable dispersibility of acid polymer.Therefore, by setting within the above range the content ratio of cross-linking monomer units, can obtain Acrylate copolymer to the good nitrile group-containing of swellbility and two aspect of dispersiveness.
In addition, in the acrylate copolymer of nitrile group-containing, in addition to the foregoing, aromatic vinyl monomer list can also be contained Unit, ethylenically unsaturated carboxylic acids amide monomer units etc..
As the example of aromatic vinyl monomer, can enumerate：Styrene, AMS, vinyltoluene, chlorine Styrene, hydroxymethylstyrene etc..
As the example of ethylenically unsaturated carboxylic acids amide monomer, can enumerate：(methyl) acrylamide, N- methoxy (methyl) acrylamide etc..
By containing these monomeric units, when can improve slurried, the acrylate copolymer of nitrile group-containing is dispersed, good Clad anode active material well.These monomeric units can be contained with the ratio below 10 mass %.
Here, the content ratio (rate of charge of monomer) of each monomer generally with the acrylate copolymer of nitrile group-containing in each list The containing of body unit (for example, (methyl) acrylate monomeric units, ethylenic unsaturated acid monomeric unit and cross-linking monomer units) Proportional consistent.
Then the third of SP value, to the acrylate copolymer of nitrile group-containing, the swellbility in nonaqueous electrolytic solution and nitrile group-containing The amount of tetrahydrofuran (THF) insoluble component of olefin(e) acid polymer is illustrated.
The SP value of the acrylate copolymer of nitrile group-containing is 9～11 (cal/cm3)1/2, preferably 9～10.5 (cal/cm3)1/2, More preferably 9.5～10 (cal/cm3)1/2.By the SP value of the acrylate copolymer of nitrile group-containing is set to above range, permissible Maintain and (be also denoted as that " slurry divides below with respect to the decentralized medium used in manufacture positive pole paste compound hereinafter described Dispersion media ") dissolubility, while the swellability of the appropriateness in nonaqueous electrolytic solution can be given.Thus, it is possible to improve further The uniformity of the electrode obtained, and improve the cycle characteristics of secondary cell using which.
SP value refers to solubility parameter.The SP value can be write according to J.Brandrup and E.H.Immergut (John Wiley＆Sons is public for " Polymer Handbook " VII Solubility Paramet Values, pp 519-559 Department, the 3rd edition is issued for 1989) in described method obtain.
In addition, the SP value of the polymer that does not record in above-mentioned document " Polymer Handbook " can be carried according to Small " the molecular attraction constant method " for going out is obtained.The method is divided by the characteristic value of the functional group's (atomic group) for constituting compound molecule The statistics of sub- gravitational constant (G) and molecular weight, the method for obtaining SP value (δ) according to following formula.
δ=Σ G/V=d Σ G/M
In above-mentioned formula, δ represents SP value, and Σ G represents the total of molecular attraction constant G, and V represents specific volume, and M represents molecule Amount, d represent proportion.
Additionally, carrying out the feelings on the surface of clad anode active material in the acrylate copolymer for combining nitrile group-containing of more than two kinds Under condition, the SP value that the acrylate copolymer of nitrile group-containing is overall can be by the SP value of the acrylate copolymer of each nitrile group-containing and mixing Mol ratio, by calculate and obtain.Specifically, the SP value to the acrylate copolymer of each nitrile group-containing is carried out according to mol ratio The weighted average being weighted, the overall SP value of the acrylate copolymer so as to calculate nitrile group-containing.
The acrylate copolymer of nitrile group-containing has SP value as above and refers to, the acrylate copolymer of nitrile group-containing is dissolved in slurry Expect decentralized medium but occur in nonaqueous electrolytic solution swelling.Therefore, in lithium rechargeable battery, the quilt of positive active material The part of the acrylate copolymer cladding of nitrile group-containing will not be contacted with nonaqueous electrolytic solution, thus can suppress positive active material Deterioration, even if repeat the reduction that charge and discharge cycles are also possible to prevent cycle characteristics.
In addition, the acrylate copolymer of nitrile group-containing has SP value as above referring to, the acrylate copolymer of nitrile group-containing Occur in the nonaqueous electrolytic solution of lithium rechargeable battery swelling.Therefore, in the lithium rechargeable battery of the present invention, nitrile group-containing Acrylate copolymer will not hinder the migration of ion, therefore the internal resistance of lithium ion secondary battery positive electrode can be controlled in low water Flat.In addition, generally, not aqueous in lithium rechargeable battery, though aqueous be also a small amount of, therefore, even if the acrylic acid of nitrile group-containing Polymer generation is swelling, and the corrosion of the collector caused by the dissolution of positive active material is not easy to carry out.
In order to avoid the volume of the acrylate copolymer of nitrile group-containing occurs significant changes in nonaqueous electrolytic solution, nitrile group-containing Swellbility of the acrylate copolymer in nonaqueous electrolytic solution is preferably more than 1.0 times and less than 3 times, more preferably more than 1.0 times And less than 2.8 times, more preferably more than 1.0 times and less than 2.6 times.Here, nonaqueous electrolytic solution is the lithium for constituting the present invention The electrolyte of ion secondary battery.It is set to by the swellbility by the acrylate copolymer of nitrile group-containing in nonaqueous electrolytic solution above-mentioned Scope, even if repeat charge and discharge cycles, it is also possible to keeps adaptation of the positive electrode active material layer to collector, improves circulation Characteristic.Swellbility in nonaqueous electrolytic solution for example can be controlled according to the content ratio of above-mentioned each monomeric unit. Specifically, if increasing the content ratio of nitrile group-containing monomeric unit, swellbility increases.In addition, if increasing olefinic insatiable hunger With the content ratio of acid monomer units, then swellbility reduction.
In addition, in order that the acrylate copolymer of nitrile group-containing is moderately dissolved in slurry decentralized medium, the propylene of nitrile group-containing The amount of tetrahydrofuran (THF) insoluble component of acid polymer is preferably below 30 mass %, below more preferably 25 mass %, is entered Scope of one step preferably below 20 mass %.THF insoluble component is the index of gel content, if THF insoluble component amount is many, In the slurry for employing the organic solvents such as 1-METHYLPYRROLIDONE (being also denoted as NMP below), with the possibility that particle shape is present Uprise, damage dispersiveness in the slurry sometimes.THF insoluble component amount as mentioned below, can according to polymeric reaction temperature, The interpolation time of monomer, amount of polymerization initiator etc. are being controlled.Specifically, using raising polymeric reaction temperature, increase The method of polymerization initiator, chain-transferring agent etc. can reduce THF insoluble component amount.In addition, the lower limit of THF insoluble component amount does not have It is particularly limited to, more than preferably 0 mass %, more than more preferably greater than 0 mass %, particularly preferably 5 mass %.
As the solubility parameter (SP value) of nonaqueous electrolytic solution and the organic solvent as slurry decentralized medium is close to, if Swellbility by polymer in nonaqueous electrolytic solution is set in appropriate scope, then the polymer is starched insoluble in conduct sometimes The organic solvent (THF insoluble component amount becomes excessive) of material decentralized medium, if conversely, to be readily soluble in the polymer organic Solvent, then swellbility of the polymer in nonaqueous electrolytic solution can deviate appropriate scope sometimes, in the present invention, above-mentioned swelling Degree and THF insoluble component amount are all in appropriate scope.
The preparation method of the acrylate copolymer of nitrile group-containing is not particularly limited, and can will constitute nitrile group-containing containing as above The monomer mixture of monomer of acrylate copolymer carry out emulsion polymerization and obtain.As the method for emulsion polymerization, there is no spy Do not limit, using currently known emulsion polymerization.Mixed method is not particularly limited, for example, can enumerate to employ and stir The method for mixing formula, oscillatory type and rotary etc. mixing arrangement.Furthermore it is possible to enumerate employ homogenizer, ball mill, sand milling The method of the dispersion kneading device such as machine, roller mill, planetary-type mixer and planetary mixer.
As the polymerization initiator for emulsion polymerization, for example, can enumerate：Sodium peroxydisulfate, potassium peroxydisulfate, ammonium persulfate, The inorganic peroxides such as potassium superphosphate, hydrogen peroxide；Tert-butyl peroxide, cumene hydroperoxide, p-menthane hydroperoxide, two uncles Butylperoxide, cumyl t-butyl peroxide, acetyl peroxide, isobutyryl peroxide, caprylyl peroxide, benzoyl peroxide first The organic peroxides such as acyl, peroxidating 3,5,5- trimethyl acetyl, peroxidating tert-butyl isobutyrate；Azodiisobutyronitrile, azo Azo-compounds such as two -2,4- methyl pentane nitriles, azo bis cyclohexane formonitrile HCN, two methyl isobutyrate of azo etc..
Wherein, preferably using inorganic peroxide.These polymerization initiators can each be used singly or in combination 2 More than kind.In addition, peroxide initiator can also be combined with reducing agents such as sodium hydrogensulfites drawing as redox Type of Collective Send out agent to use.
With respect to 100 mass parts of total amount of the monomer mixture for polymerization, the usage amount of polymerization initiator is preferably 0.05～5 mass parts, more preferably 0.1～2 mass parts.By using polymerization initiator with above range, suitably can adjust The THF insoluble component amount of the acrylate copolymer of section gained nitrile group-containing.
In order to adjust the THF insoluble component amount of the acrylate copolymer of gained nitrile group-containing, it is also possible to make in emulsion polymerization Use chain-transferring agent.As chain-transferring agent, for example, can enumerate：N-hexyl mercaptan, n octylmercaptan, tert octyl mercaptan, positive 12 The alkyl hydrosulfides such as alkyl hydrosulfide, tert-dodecylmercaotan, n-octadecane base mercaptan；Dimethyl disulfide xanthate, curing The xanthogen compound such as diisopropyl xanthate；Terpinolene, tetramethylthiuram disulfide, tetraethyl Ji Qiulan The thiuram compounds such as nurse, tetramethylthiuram monosulfide；2,6 di tert butyl 4 methyl phenol, styrenated phenol etc. Phenolic compound；The allyl compounds such as allyl alcohol；The halogenated hydrocarbon compounds such as dichloromethane, methylene bromide, carbon tetrabromide；Mercapto Guanidine-acetic acid, dimercaptosuccinic acid, 2-ethylhexyl mercaptoacetate, diphenylethlene, α-methylstyrenedimer etc..
Wherein it is possible to alkyl hydrosulfide is preferably used, more preferably using tert-dodecylmercaotan.These chain-transferring agents can be single Solely use or be applied in combination two or more.
With respect to 100 mass parts of monomer mixture, the usage amount of chain-transferring agent is preferably 0.05～2 mass parts, more preferably For 0.1～1 mass parts.
During emulsion polymerization, it is possible to use surfactant.Surfactant can for anionic surfactant, non-from Arbitrary surfaces activating agent in subtype surfactant, cationic surface active agent, amphoteric surfactant.As anion The specific example of type surfactant, can enumerate：Lauryl sulfate ester sodium, lauryl sulfate ester ammonium, laurilsulfate Sodium, laurilsulfate ammonium, octyl sulfate ester sodium, decyl sulfate ester sodium, myristyl sulfate ester sodium, hexadecyl hydrosulfate ester The sulfuric acid of the higher alcohols such as sodium, octadecyl sodium sulfovinate；Neopelex, sodium lauryl benzene sulfonate, hexadecane The alkylbenzenesulfonates such as base benzene sulfonic acid sodium salt；The aliphatic sulphur such as dodecyl sodium sulfate, dodecyl sodium sulfate, myristyl sodium sulfonate Hydrochlorate etc..
With respect to 100 mass parts of monomer mixture, the usage amount of surfactant is preferably 0.5～10 mass parts, more excellent Elect 1～5 mass parts as.
Additionally, in emulsion polymerization, can be suitably using pH adjusting agents such as NaOH, ammonia；Dispersant, chelating agent, oxygen Capturing agent, builder, for adjusting the various additives such as the seed latex of particle diameter.Seed latex refers to become in emulsion polymerization Dispersion liquid for the fine particle of the core of reaction.The particle diameter of fine particle mostly is below 100nm.Fine particle is not especially limited Fixed, it is possible to use the general polymer such as diolefinic polymer, acrylic polymer.Gathered according to the emulsion using seed latex Legal, the more homogeneous polymer particle of particle diameter is obtained.
Polymerization temperature when carrying out polymerisation is not particularly limited, and is typically set to 0～100 DEG C, is preferably set to 40～80 ℃.Emulsion polymerization is carried out in such temperature range, adds polymerization inhibitor in given polymerisation conversion or polymerization system is cooled down, So as to terminate polymerisation.Polymerisation conversion when terminating polymerisation is preferably more than 93 mass %, more preferably 95 matter Amount more than %.In addition, by making polymerization temperature for above range, can suitably adjust the acrylate copolymer of gained nitrile group-containing THF insoluble component amount.
After polymerisation is terminated, according to expecting to remove unreacted monomer, and the concentration of pH, solid constituent is adjusted, with The form (latex) that polymer is scattered in decentralized medium obtains the acrylate copolymer of nitrile group-containing.Thereafter, can also be according to need Decentralized medium to be replaced, alternatively, it is also possible to evaporate decentralized medium, obtains the acrylic acid of emboliform nitrile group-containing with powder shape Polymer.
Can add in the dispersion liquid of the acrylate copolymer of nitrile group-containing as needed known dispersant, tackifier, Age resistor, defoamer, preservative, antiseptic, antifrothing agent, pH adjusting agent etc..
It is not particularly limited using the method for the acrylate copolymer clad anode active material of above-mentioned nitrile group-containing, for example may be used With by the acrylate copolymer of positive active material and nitrile group-containing being mixed and being carried out when positive pole paste compound is prepared Stir to obtain.The method of mixing and stirring is not particularly limited.In addition, with respect to 100 mass parts of positive active material, containing nitrile The amount of the acrylate copolymer of base preferably 0.05～1.95 mass parts, more preferably 0.1～1.0 mass parts, particularly preferably 0.2～0.6 mass parts.If the amount of the acrylate copolymer of nitrile group-containing is in above range, clad anode can live well Property material.In the present invention, the acrylate copolymer of nitrile group-containing not only plays the function of clad anode active material, can also have The function having as binding agent.
(B) positive pole binding agent
Positive pole binding agent (B) contains fluoropolymer.
Fluoropolymer
Fluoropolymer used in positive pole binding agent.Contain fluoropolymer, Ke Yiti by making positive pole binding agent The stability of high slurry, it is additionally possible to suppress binding agent is swelling in nonaqueous electrolytic solution, improves cycle characteristics.
Fluoropolymer is the polymer containing fluorine-containing monomer unit.Fluorine-containing monomer unit is polymerized and shape by fluorochemical monomer The construction unit for becoming.Fluoropolymer can specifically be enumerated：The homopolymers of fluorochemical monomer, fluorochemical monomer and can with its copolymerization its The copolymer of his fluorochemical monomer, fluorochemical monomer and can be with the copolymer of the monomer of its copolymerization, fluorochemical monomer and can be with its copolymerization Other fluorochemical monomers and can be with the copolymer of the monomer of their copolymerization.
As fluorochemical monomer, can enumerate：Vinylidene, tetrafluoroethene, hexafluoropropene, CTFE, PVF, complete Vinyl ethers etc., preferably vinylidene.
The ratio of the fluorine-containing monomer unit in fluoropolymer be usually 70 mass % more than, preferably 80 mass % with On.It should be noted that the upper limit of the ratio of fluorine-containing monomer unit in fluoropolymer is 100 mass %.
As be able to can enumerate with the monomer of fluorochemical monomer copolymerization：The 1- alkene such as ethene, propylene, 1- butylene；Styrene, The aromatic ethenyl compounds such as AMS, p-tert-butylstyrene, vinyltoluene, chlorostyrene；(methyl) third The unsaturated nitrile compounds such as alkene nitrile (acrylonitrile and methacrylonitrile write a Chinese character in simplified form, similarly hereinafter)；(methyl) methyl acrylate, (methyl) third (methyl) acrylate compounds such as olefin(e) acid butyl ester, (methyl) 2-EHA；(methyl) acrylamide, N- methylol (methyl) acrylamide compounds such as (methyl) acrylamide, N- butoxymethyl (methyl) acrylamide；(methyl) acrylic acid, The carboxylic vinyl compound such as itaconic acid, fumaric acid, crotonic acid, maleic acid；Allyl glycidyl ether, (methyl) propylene The unsaturated compound containing epoxy radicals such as acid glycidyl ester；(methyl) acrylate, (methyl) acrylic acid The unsaturated compound containing amino such as diethylamino ethyl ester；Styrene sulfonic acid, vinyl sulfonic acid, (methyl) allyl sulphonic acid etc. Containing sulfonic unsaturated compound；The unsaturated compound of the sulfur-bearing acidic groups such as 3- allyloxy -2- hydroxy propane sulfuric acid；(first Base) the phosphorous acidic group such as the chloro- 2- phosphoric acid propyl ester of acrylic acid -3-, 3- allyloxy -2- hydroxy propane phosphoric acid unsaturated compound Deng.
Can be usually below 30 mass %, preferably with the ratio of the monomeric unit of fluorochemical monomer copolymerization in fluoropolymer Below 20 mass %.
In fluoropolymer, vinylidene is preferably comprised as the polymer of fluorochemical monomer, specifically, preferably inclined fluorine second The homopolymers of alkene, vinylidene and can be with the copolymer of other fluorochemical monomers of its copolymerization, vinylidene and can be with its copolymerization Other fluorochemical monomers and can be with the copolymer of the monomer of their copolymerization, vinylidene and can be with the copolymer of the monomer of its copolymerization.
In fluoropolymer as above, the preferably homopolymers (Kynoar) of vinylidene, vinylidene-hexafluoro Propylene copolymer, polyvinyl fluoride, more preferably Kynoar.
Fluoropolymer can be individually a kind of, in addition can also be applied in combination two or more.It is applied in combination of more than two kinds In the case of, preferably low-molecular-weight thing and HMW thing are applied in combination.Specifically, will be according to ASTM D3835/232 DEG C 100sec-1Fluoropolymer of the melt viscosity of the fluoropolymer of measure less than 35kpoise, will used as low-molecular-weight thing Both are preferably applied in combination by the fluoropolymer of more than 35kpoise as HMW thing.
For example, as the Kynoar of HMW, can enumerate：ARKEMA company system KYNAR HSV900, SOLVAY company system Solef 6020, Solef 6010, Solef 1015, Solef 5130, KUREHA company system KF7208.Separately Outward, as the Kynoar of low-molecular-weight, for example, can enumerate：ARKEMA company system KYNAR 710 720 740 760 760A, SOLVAY company system Solef 6008, KUREHA KF1120.
In the case of HMW thing and low-molecular-weight thing being applied in combination as fluoropolymer, low point of fluoropolymer The weight ratio (low-molecular-weight thing/HMW thing) of son amount thing and HMW thing is preferably 30/70～70/30.
By with the ratio combine of above range using low-molecular-weight thing and HMW thing, just more effectively guaranteeing Caking property, the uniformity of slurry between pole active material caking property each other, collector and positive active material.
The weight average molecular weight of the polystyrene conversion value that the utilization gel permeation chromatography of fluoropolymer is determined is preferably 100,000～2,000,000, more preferably 200,000～1,500,000, particularly preferably 400,000～1,000,000.
By the weight average molecular weight of fluoropolymer is set to above range, just can suppress in positive electrode active material layer The disengaging (dry linting) of pole active material (A), conductive material (C) etc., also, the viscosity regulation of positive pole paste compound becomes appearance Easily.
The glass transition temperature (Tg) of fluoropolymer is preferably less than 0 DEG C, more preferably less than -20 DEG C, especially excellent Elect less than -30 DEG C as.The lower limit of the Tg of fluoropolymer is not particularly limited, preferably more than -50 DEG C, more preferably -40 DEG C More than.By the Tg of fluoropolymer is located above range, the positive active material that can suppress in positive electrode active material layer (A), the disengaging (dry linting) of conductive material (C) etc..In addition, the Tg of fluoropolymer can by combine various monomers come Adjustment.It should be noted that Tg can be using differential scanning calorimetric analysis instrument, based on JIS K 7121；1987 are measured.
The fusing point (Tm) of fluoropolymer is preferably less than 190 DEG C, more preferably 150～180 DEG C, more preferably 160～170 DEG C.By the Tm of fluoropolymer is located above range, flexibility can be obtained and dhering strength is excellent just Pole.In addition, the Tm of fluoropolymer can be adjusted by combining various monomers or control polymerization temperature etc..Tm is permissible Using differential scanning calorimetric analysis instrument, it is based on JIS K7121；1987 are measured.
The manufacture method of fluoropolymer is not particularly limited, it is possible to use solution polymerization process, suspension polymerization, body gather Any means in legal, emulsion polymerization etc..Wherein, preferably suspension polymerization, emulsion polymerization.By using emulsion polymerization Method can improve the productivity of fluoropolymer, while can obtain with desired average grain diameter manufacturing fluoropolymer Fluoropolymer.As polymerisation, it is possible to use appointing in ionic polymerization, radical polymerization, active free radical polymerization etc. Meaning reaction.As the polymerization initiator for polymerization, for example, can enumerate：Lauroyl peroxide, peroxy dicarbonate diisopropyl Ester, peroxy dicarbonate two (2- ethylhexyl) ester, tert-Butyl peroxypivalate, peroxidating 3,3,5- trimethyl acetyl etc. have Machine peroxide, α, the azo-compound such as α '-azodiisobutyronitrile or ammonium persulfate, potassium peroxydisulfate etc..
Fluoropolymer can be made with the state of the dispersion liquid disperseed in decentralized medium or the solution of dissolving With.As decentralized medium, as long as the medium that can be uniformly dispersed or dissolve fluoropolymer is just not particularly limited, and permissible Using water, organic solvent.As organic solvent, can enumerate：The cyclic aliphatic hydrocarbons such as pentamethylene, hexamethylene；Toluene, diformazan Benzene, ethylbenzene etc. are aromatic hydrocarbon；The ketones such as acetone, MEK, diisobutyl acetone, cyclohexanone, methyl cyclohexanone, ethyl cyclohexanone； The chloro fat such as dichloromethane, chloroform, carbon tetrachloride race hydrocarbon；The esters such as ethyl acetate, butyl acetate, gamma-butyrolacton, 6-caprolactone Class；The alkyl nitrile such as acetonitrile, propionitrile；The ethers such as tetrahydrofuran, ethylene glycol Anaesthetie Ether：Methyl alcohol, ethanol, isopropanol, ethylene glycol, The alcohols such as ethylene glycol single methyl ether；The amide-types such as 1-METHYLPYRROLIDONE, N,N-dimethylformamide.
These decentralized media can be used alone, it is also possible to use two or more mixing in them as mixed solvent. Wherein, particularly from when positive pole paste compound is manufactured industrially use, not volatile during fabrication in terms of, by From the aspect of this can suppress the volatilization of positive pole paste compound and improve the flatness of gained positive pole, preferably water or N- first Base pyrrolidones, cyclohexanone, toluene etc..
In the case that fluoropolymer is scattered in decentralized medium with particle shape, from from the viewpoint of operability, containing containing The solid component concentration of the dispersion liquid of fluoropolymer be usually 1～25 mass %, preferably 3～20 mass %, further preferably For 5～15 mass %.
In addition, make fluoropolymer be dissolved in 1-METHYLPYRROLIDONE in the form of becoming 8% solution (being also denoted as below " NMP ") when viscosity be preferably 10～5000mPa s, more preferably 100～2000mPa s.By by fluoropolymer 8%NMP solution viscosity is set to above range, easily adjusts positive pole with paste compound when positive pole paste compound is manufactured For being easy to the viscosity being coated with.The 8%NMP solution viscosity of fluoropolymer can be by making fluoropolymer to become 8% solution Form be dissolved in NMP, and using Brookfield viscometer (eastern machine industry RB-80L) with 25 DEG C, 60rpm, based on JIS K 7117-1； 1999 are measured.
Positive pole binding agent contains above-mentioned fluoropolymer.Except utilizing the acrylate copolymer cladding of specific nitrile group-containing Beyond positive active material, contain fluoropolymer by making positive pole binding agent, the bendability that can obtain coiling body is excellent Positive electrode, the excellent lithium rechargeable battery of initial capacity, output characteristics, high potential cycle characteristics.
With respect to 100 mass % of total amount of positive pole binding agent, the ratio of fluoropolymer is preferably 50～100 matter Amount %, more preferably 60～90 mass %, more preferably 70～85 mass %.
In addition to above-mentioned fluoropolymer, positive pole binding agent can also as needed containing can be used as binding agent its His polymer.As the other polymers that can be applied in combination, for example, can enumerate：Polyacrylic acid derivative, polyacrylonitrile spread out The resins such as biology, acrylate soft polymer, diene soft polymer, alkene soft polymer, vinyl soft polymer Deng soft polymer.They can be used alone, it is also possible to which they are applied in combination two or more.With respect to positive pole binding agent 100 mass % of total amount, above-mentioned other polymers with 30 mass % below, further with 0.1～20 mass %, particularly with The ratio of 0.2～10 mass % contains.It is 9～11 (cal/cm not contain SP value in the amount of positive pole binding agent described here3 )1/2Nitrile group-containing acrylate copolymer amount.
With respect to 100 mass parts of positive active material, the amount of positive pole binding agent is preferably 0.4～2 mass parts, more preferably For 1～2 mass parts, the particularly preferably scope of 1.5～2 mass parts.If the amount of positive pole binding agent, can in above range So that the adaptation between gained positive electrode active material layer and collector is substantially ensured that, the capacity of lithium rechargeable battery can be improved And reduce internal resistance.
(C) conductive material
Positive pole contains conductive material.In positive pole, the particle diameter of contained conductive material is preferably 5～40nm in terms of number average bead diameter, More preferably 10～38nm, more preferably 15～36nm.If the particle diameter of the conductive material in positive pole is too small, become to hold Easily condense, dispersed become difficult, as a result, exist causing the internal resistance increase of electrode, raisings of capacity to become inclining for difficulty To.However, by using above-mentioned positive pole binding agent, being uniformly dispersed micronized conductive material becomes possibility, Ke Yimou Ask the raising of capacity.In addition, if the particle diameter of conductive material is excessive, then it is difficult to be present between positive active material, positive pole is lived Property material layer internal resistance increase, the raising of capacity becomes difficult.The number average bead diameter of conductive material can pass through by conductive material With 0.01 mass % ultrasonic disperse in the water after, using dynamic light scattering particle diameter/particle size distribution device (for example, day machine dress Co. Ltd. system, particle size distribution device Nanotrac Wave-EX150) it is measured to obtain.
In addition, the specific surface area (BET formula) of the conductive material in positive pole is preferably 1500m2/ below g, more preferably 1000m2/ below g, particularly preferably 400m2/ below g.If the specific surface area of conductive material is excessive, become easily cohesion, Dispersed become difficult, as a result, causing the internal resistance increase of electrode, the raising of capacity to become difficult.It should be noted that making For conductive material, a kind of conductive material with above-mentioned specific surface area is can be used alone, it is also possible to will have not table on year-on-year basis each other The conductive material of more than two kinds of area is so that the BET specific surface area of mixed conductive material reaches the size in above range Mode be applied in combination.
As conductive material, identical with negative pole, it is possible to use acetylene black, Ketjen black, carbon black, graphite, vapor grown carbon are fine The conductive carbon such as dimension and CNT.By containing conductive material, stability when positive pole is manufactured with paste compound is improved, Furthermore it is possible to the electrical contact each other of positive active material in positive electrode active material layer is improved, so as to pursuing high capacity. With respect to 100 mass parts of total amount of positive active material, the content of conductive material is preferably 1～3 mass parts, and more preferably 1.2 ～2.8 mass parts, particularly preferably 1.5～2.5 mass parts.If the content of conductive material is very few, positive electrode active material layer In internal resistance increase, high capacity becomes difficult sometimes.In addition, if the content of conductive material is excessive, then the high density of positive pole Changing becomes difficult, and initial capacity can reduce sometimes.
Other positive pole compositions
In addition, identical with negative pole hereinafter described, can also be containing supporting material, levelling agent, with electrolyte in positive pole Decompose electrolysis additives of function such as suppression etc. as optional member, in addition it is also possible to remain prepare when positive pole is manufactured Slurry in contained tackifier etc..
As supporting material, it is possible to use various inorganic and organically spherical, tabular, bar-shaped or fibrous filler.Logical Cross and supporting material is used, tough and soft positive pole can be obtained, excellent long-term cycle characteristics can be shown.With respect to just 100 mass parts of total amount of pole active material, the content of supporting material are usually 0.01～20 mass parts, preferably 1～10 mass Part.By containing supporting material with above range, high power capacity and high part throttle characteristics can be shown.
As levelling agent, can enumerate：Alkyl-based surfactant, organosilicone surfactants, fluorine class surface-active The surfactants such as agent, metal class surfactant.By mixing levelling agent, can prevent shrinkage cavity is produced in coating or make The flatness of positive pole is improved.With respect to 100 mass parts of total amount of positive active material, the content of levelling agent is preferably 0.01～10 Mass parts.By containing levelling agent with above range, productivity when positive pole makes, flatness and battery behavior are excellent.
As electrolysis additive, it is possible to use can be used for vinylene carbonate of electrolyte etc..With respect to positive-active 100 mass parts of total amount of material, the content of electrolysis additive are preferably 0.01～10 mass parts.By making electrolysis additive Content be above range, the cycle characteristics of gained lithium rechargeable battery and hot properties excellent.Furthermore, it is possible to enumerate gas phase The nanoparticles such as silica, gaseous oxidation aluminium.By mixing nanoparticle, the slurry for preparing when positive pole is manufactured can be controlled The thixotropy of composition, and then the levelability of thus obtained positive pole can be improved.Total amount 100 with respect to positive active material Mass parts, the content of nanoparticle are preferably 0.01～10 mass parts.By with aforementioned proportion in positive pole paste compound Using nanoparticle, Stability of Slurry, productivity are excellent, can show high battery behavior.
The manufacture method of lithium ion secondary battery positive electrode paste compound
Lithium ion secondary battery positive electrode paste compound by mix in decentralized medium above-mentioned positive active material, The acrylate copolymer of nitrile group-containing, positive pole binding agent (B), conductive material (C) and other additives and obtain.By by positive pole The acrylate copolymer of active material and nitrile group-containing mixes in decentralized medium, contained cyanogen in the acrylate copolymer of nitrile group-containing Base and contained in the acrylate copolymer of nitrile group-containing acidic group when containing ethylenic unsaturated acid monomeric unit etc., can with just The functional groups such as the hydroxyl of pole active material surface interact, and the acrylate copolymer Preferential adsorption of nitrile group-containing is lived in positive pole Property material.Then, by the lithium ion secondary battery positive electrode for obtaining paste compound is coated collector hereinafter described And be dried, can be formed by nitrile group-containing acrylate copolymer coat positive active material, i.e. for the present invention just Pole active material (A).
In addition, in paste compound obtained as indicated above, due to above-mentioned cyano group, acidic group etc. and collection hereinafter described The functional groups such as the hydroxyl on the surface of electric body interact and adsorb, and therefore can improve positive electrode active material layer and collector Between adaptation.
As decentralized medium, it is possible to use organic solvent.As organic solvent, can enumerate：The rings such as pentamethylene, hexamethylene Shape aliphatic hydrocarbon；Toluene, dimethylbenzene, ethylbenzene etc. are aromatic hydrocarbon；Acetone, MEK, diisopropyl ketone, cyclohexanone, methyl The ketones such as cyclohexanone, ethyl cyclohexanone；The chlorine such as dichloromethane, chloroform, carbon tetrachloride system aliphatic hydrocarbon；Ethyl acetate, acetic acid fourth The esters such as ester, gamma-butyrolacton, 6-caprolactone；The alkyl nitrile such as acetonitrile, propionitrile；The ethers such as tetrahydrofuran, ethylene glycol Anaesthetie Ether Class；The alcohols such as methyl alcohol, ethanol, isopropanol, ethylene glycol, ethylene glycol single methyl ether；1-METHYLPYRROLIDONE, N, N- dimethyl formyl The amide-types such as amine.
These decentralized media can be used alone, it is also possible to use two or more mixing in them as mixed solvent. Wherein, the decentralized medium that dispersiveness is excellent, low boiling point and volatility are high particularly to positive active material, due to can be short Remove under time and low temperature, thus it is preferred that.Specifically, preferably acetone, toluene, cyclohexanone, pentamethylene, tetrahydrofuran, hexamethylene Alkane, dimethylbenzene or 1-METHYLPYRROLIDONE or their mixed solvent.
Mixed method is not particularly limited, for example, can enumerate：Employ stirring-type, oscillatory type and rotary etc. mixed Attach together the method that puts.Furthermore it is possible to enumerate employ homogenizer, ball mill, sand mill, roller mill and planetary mixer etc. The method of dispersion milling device.
Lithium ion secondary battery positive electrode
Lithium ion secondary battery positive electrode is by coating collection by above-mentioned lithium ion secondary battery positive electrode paste compound Electric body being dried is formed.
The manufacture method of lithium ion secondary battery positive electrode includes for above-mentioned positive pole paste compound to coat collector One or both sides are simultaneously dried, so as to form the operation of positive electrode active material layer.
Above-mentioned positive pole paste compound is coated the method on collector be not particularly limited.Can for example enumerate： The methods such as scraper plate method, infusion process, inverse roller method, direct roller method, intagliotype, extrusion molding and spread coating.
As drying means, for example, can enumerate：Using warm braw, hot blast, the drying of low wet wind, vacuum drying, utilize The seasoning of the irradiation of (remote) infrared ray, electron beam etc..Drying time is usually 5～30 minutes, and baking temperature is usually 40 DEG C ～180 DEG C.
When lithium ion secondary battery positive electrode is manufactured, go forward side by side above-mentioned positive pole paste compound is coated on collector After row dries, preferably having by using moulding press or roll squeezer etc. carries out pressurized treatments to reduce the sky of positive electrode active material layer The operation of gap rate.The voidage of positive electrode active material layer is preferably 5～30%, more preferably 7～20%.If positive electrode active material The voidage of matter layer is too high, then charge efficiency, discharging efficiency may be caused to be deteriorated.On the other hand, if positive electrode active material layer Voidage too low, then be difficult to obtain high volume capacity, in fact it could happen that positive electrode active material layer easily peeled off from collector, easily Produce bad situation.Additionally, in the case of using curable polymer as positive pole binding agent (B), preferably making its solidification.
The thickness of the positive electrode active material layer in lithium ion secondary battery positive electrode is usually 5～300 μm, preferably 30～ 250μm.By the thickness of positive electrode active material layer being made in above range, can obtain part throttle characteristics and cycle characteristics all high by two Primary cell.
The content ratio of the positive active material in positive electrode active material layer preferably 85～99 mass %, more preferably 88 ～97 mass %.It is above range by the content ratio for making the positive active material in positive electrode active material layer, can obtains High power capacity is shown, while showing the secondary cell of flexibility, caking property.
The density of positive electrode active material layer is preferably 3.0～4.0g/cm3, more preferably 3.4～4.0g/cm3.By just making The density of pole active material layer is above range, can obtain the secondary cell of high power capacity.
As long as material of the collector with electric conductivity and with electrochemistry durability, is just not particularly limited, but in order to With heat resistance, preferred metal materials, for example, can enumerate：Iron, copper, aluminium, nickel, stainless steel, titanium, tantalum, gold, platinum etc..Wherein, make It is the collector for lithium ion secondary battery positive electrode, particularly preferred aluminium.The shape of collector is not particularly limited, preferred thickness The sheet collector of 0.001mm～0.5mm or so.For collector, bonding strong with positive electrode active material layer in order to improve which Degree, can reuse after being roughened to surface in advance.As roughening method, can enumerate：Mechanical polishing method, electrolysis Polishing processes, chemical polishing etc..In mechanical polishing method, can there are the sand paper of polishing agent particle, grinding stone, Buddha's warrior attendant sand milling using cementation Ray machine (emery buff), possesses line brush of steel wire etc. etc..In addition, in order to improve the adhesive strength of positive electrode active material layer, lead Electrically, it is also possible to form priming coat etc. on collector surface.
(negative pole)
Negative pole is made up of collector and the negative electrode active material layer being stacked on the collector.Negative electrode active material layer contains There is negative electrode active material (a), and negative pole binding agent (b), conductive material (c) etc. is usually contained, as negative electrode active material A (), preferably comprises alloy type active material (a1) and as desired containing other carbons active materials (a2).
(a) negative electrode active material
Negative electrode active material is the material that gives and accepts for carrying out electronics (lithium ion) in negative pole.As negative electrode active material, Alloy type active material (a1) can be used, or can be as needed using carbons active material (a2).Negative electrode active material is of fine quality Select containing alloy type active material and carbons active material, by being applied in combination alloy type active material and carbons active material, The secondary cell bigger with the negative pole phase specific capacity that only obtains using alloy type active material can be obtained, and can also solve to bear The problems such as reduction of the dhering strength of pole, reduction of cycle characteristics.
(a1) alloy type active material
Alloy type active material is referred in the structure containing the element that can be embedded in lithium and per single in the case of it embedded in lithium The theoretical capacity of position weight is that (upper limit of the theoretical capacity is not particularly limited more than 500mAh/g, for example, can be set to Below 5000mAh/g) active material, can specifically use：Form elemental metals and its alloy and their oxygen of lithium alloy Compound, sulfide, nitride, silicide, carbide, phosphide etc..
As the elemental metals for forming lithium alloy and alloy, can enumerate：Ag、Al、Ba、Bi、Cu、Ga、Ge、In、Ni、P、 The metals such as Pb, Sb, Si, Sn, Sr, Zn, the compound containing the metal.Wherein, the list of preferably silicon (Si), tin (Sn) or lead (Pb) Matter metal or the compound of the alloy containing these atoms or these metals.Further, wherein more preferably can enter in electronegative potential The elemental metals of the Si of the embedded disengaging of row lithium.
Alloy type active material can also the nonmetalloid containing more than one.Specifically, can for example enumerate： SiC、SiOxCy(hereinafter referred to as " SiOC ") (0 ＜ x≤3,0 ＜ y≤5), Si3N4、Si2N2O、SiOx(x=0.01 less than 2)、SnOx(0 ＜ x≤2), LiSiO, LiSnO etc., wherein, be preferably able to electronegative potential carry out the embedded disengaging of lithium SiOC, SiOxAnd SiC, more preferably SiOC, SiOx.
For example, SiOC can be obtained by being fired to the macromolecular material containing silicon.In SiOC, from take into account capacity and From the aspect of cycle characteristics, 0.8≤x≤3, the scope of 2≤y≤4 is preferably adopted.
As formed the oxide of the elemental metals of lithium alloy and its alloy, sulfide, nitride, silicide, carbide, Phosphide, can enumerate：The oxide of the element of lithium, sulfide, nitride, silicide, carbide, phosphide can be embedded in Deng, wherein, particularly preferred oxide.Specifically, the preferably oxidation such as tin oxide, manganese oxide, titanium oxide, niobium oxide, vanadium oxide Thing, contain metallic element in Si, Sn, Pb and Ti atom containing lithium-metal composite oxides.
As lithium-metal composite oxides are contained, can also enumerate：LixTiyMzO4Shown lithium-titanium composite oxide (0.7≤ X≤1.5,1.5≤y≤2.3,0≤z≤1.6, M are Na, K, Co, Al, Fe, Ti, Mg, Cr, Ga, Cu, Zn and Nb), wherein, excellent Select Li4/3Ti5/3O4、Li1Ti2O4、Li4/5Ti11/5O4.
In these alloy type active materials, the active material of silicon is preferably comprised.By using the active material containing silicon, can To increase the capacitance of secondary cell.Further, in the active material containing silicon, more preferably SiOxCy、SiOxAnd SiC.Due to Can speculate in active material of the combination containing silicon and carbon, Li can occur under high potential to the embedded disengaging of Si (silicon), low Embedded disengaging of the Li to C (carbon) can occur under current potential, compared with other alloy type active materials, expand, shrink and can be suppressed, Therefore it is easier to obtain the effect of the present invention.
The preferred granulation of alloy type active material is particle shape.If being shaped as particle is spherical, in electrode moulding The higher electrode of density can be formed.In the case that alloy type active material is particle, its volume average particle size is preferably 0.1 ～50 μm, more preferably 0.5～20 μm, particularly preferably 1～10 μm.If the volume average particle size of alloy type active material exists In the range of being somebody's turn to do, then the making of the paste compound for manufacturing negative pole becomes easy.It should be noted that the volume in the present invention Average grain diameter can be obtained by using determination of laser diffraction particle diameter distribution.
The tap density of alloy type active material is not particularly limited, it may be preferred to using 0.6g/cm3Above alloy type Active material.
The specific surface area (BET formula) of alloy type active material is preferably 3.0～20.0m2/ g, more preferably 3.5～ 15.0m2/ g, particularly preferably 4.0～10.0m2/g.By making the specific surface area of alloy type active material in above range, alloy The active site of class active material surface increases, and therefore, the output characteristics of lithium rechargeable battery is excellent.In the present invention, " BET Specific surface area " refers to the BET specific surface area using determination of nitrogen adsorption, is the value determined based on ASTM D3037-81.
(a2) carbons active material
The carbons active material refers to, can be embedded in the active material of the carbon of lithium as main framing, can specifically enumerate carbon Material and graphite material.The carbonaceous material be usually by carbon precursor 2000 DEG C of heat treated below what carbonization became The material with carbon element of degree of graphitization low (i.e. crystallinity is low).The lower limit of the temperature of the heat treatment is not particularly limited, for example permissible It is set to more than 500 DEG C.Graphite material is that have obtained from by being heat-treated to easily graphitic carbon more than 2000 DEG C The graphite material of the high crystalline being close to graphite.The upper limit of the treatment temperature is not particularly limited, for example, can be set to Less than 5000 DEG C.
As carbonaceous material, for example, can enumerate：It is easy to be graphitic that the structure of carbon easily changes according to heat treatment temperature Carbon or the graphitic carbon of the difficulty with the structure close to non crystalline structure with glassy carbon as representative etc..
As easily graphitic carbon, for example, can enumerate the material with carbon element with the tar asphalt obtained by oil, coal as raw material.Make For specific example, can enumerate：Coke, carbonaceous mesophase spherules (MCMB), mesophase pitch based carbon fiber, thermal decomposition vapor phase growth Carbon fiber etc..The MCMB is to carry out carbon particulate obtained from separation and Extraction, the mesophasespherule to mesophasespherule Be 400 DEG C or so pitch class is heated during generate.The mesophase pitch based carbon fiber be with by upper It is the carbon fiber of raw material mesophasespherule to be stated through growth, mesophase pitch obtained from zoarium.The thermal decomposition vapor phase growth Carbon fiber is the carbon fiber obtained by following methods：(1) by the method for the thermal decompositions such as acroleic acid macromolecular fiber；(2) will drip Blue or green spinning the method for being thermally decomposed；(3) use the nano-particles such as iron, as catalyst, hydrocarbon is carried out urging for gas phase thermal decomposition Agent vapor phase growth (catalyst CVD) method.
As difficult graphitic carbon, can enumerate：Phenolic resin fired body, polyacrylonitrile based carbon fiber, quasi-isotropic carbon, Furfuryl alcohol resin fired body (PFA), hard carbon etc..
As graphite material, for example, can enumerate：Native graphite, Delanium etc..As Delanium, Ke Yiju Go out：The main Delanium for carrying out more than 2800 DEG C being heat-treated, MCMB is carried out more than 2000 DEG C heat treatment form Graphitization MCMB, mesophase pitch based carbon fiber is carried out more than 2000 DEG C the graphitized intermediate-phase pitch that is heat-treated Based carbon fiber etc..
In above-mentioned carbons active material, preferred graphite material.By using graphite material, negative electrode active is easily improved The density of material layer, the density for easily making negative electrode active material layer are 1.6g/cm3(upper limit of the density is not especially above Limit, 2.2g/cm can be set to3Negative pole below).If the density with negative electrode active material layer is the negative of above range The negative pole of pole active material layer, then can significantly embody the effect of the present invention.
Carbons active material is particle shape preferably by whole grain.If being shaped as particle is spherical, in electrode moulding, can The electrode higher to form density.In the case that carbons active material is particle, the volume average particle size of carbons active material is excellent Elect 0.1～100 μm as, more preferably 0.5～50 μm, particularly preferably 1～30 μm.If the volume of carbons active material is average Within the range, the making for manufacturing the paste compound of negative pole becomes easy to particle diameter.
The tap density of carbons active material is not particularly limited, and can preferably use 0.6g/cm3Above carbons activity Material.
The specific surface area of carbons active material is preferably 3.0～20.0m2/ g, more preferably 3.5～15.0m2/ g, especially excellent Elect 4.0～10.0m as2/g.By making the specific surface area of carbons active material in above range, the work of carbons active material surface Property point increase, therefore, the output characteristics of lithium rechargeable battery is excellent.Specific surface area for example can be determined by BET method.
Negative electrode active material can be used alone a kind of alloy type active material, it is also possible to be applied in combination 2 kinds with arbitrary ratio More than.In addition, as the preferred embodiment of negative electrode active material, can enumerate alloy type active material and carbons active matter The active material that matter is combined.Alloy type active material (a1) and carbons active material (a2) are applied in combination as negative electrode active In the case of material (a), as its mixed method, it is not particularly limited, currently known dry type mixing, wet type can be enumerated and mixed Close.
In negative electrode active material (a), the feelings of alloy type active material (a1) and carbons active material (a2) are applied in combination Under condition, with respect to 100 mass parts of carbons active material (a2), 1～50 mass parts of alloy type active material (a1) are preferably comprised.Logical Cross with above range hybrid alloys class active material and carbons active material, can obtain with existing only using carbons active matter The bigger battery of negative pole phase specific capacity obtained from matter, and the reduction of the dhering strength of negative pole and the drop of cycle characteristics can be prevented Low.If with above-mentioned range combinations using alloy type active material (a1) and the negative electrode active of carbons active material (a2) The negative pole of material layer, then can significantly embody the effect of the present invention.
(b) negative pole binding agent
Negative pole binding agent is in negative pole, make negative electrode active material be bonded in collector surface composition, preferably uses guarantor Hold the excellent performance of negative electrode active material, for the high binding agent of the adaptation of collector.Generally, polymer is used as bonding The material of agent.Polymer as the material of binding agent can be homopolymers, or copolymer.As negative pole binding agent Polymer, be not particularly limited, for example, can enumerate：Fluoropolymer, diene polymer, acrylate polymer, polyamides are sub- The macromolecular compounds such as amine, polyamide, polyurethane, wherein, preferably fluoropolymer, diene polymer or acrylate polymer, From from the viewpoint of can improve proof voltage and improve the energy density of secondary cell, more preferably diene polymer or acrylic acid Ester polymer, from from the viewpoint of improve pole strength, particularly preferred diene polymer.
Diene polymer is (to be also denoted as " conjugation two below containing the construction unit formed by conjugate diene monomer polymerization Alkene monomer unit ") polymer, can specifically enumerate：The homopolymers of conjugated diene；By different types of conjugated diene shape each other The copolymer for becoming；Copolymer or their hydride etc. obtained from the polymerization of the monomer mixture containing conjugated diene.As Above-mentioned conjugated diene, for example, can enumerate：1,3- butadiene, 2- methyl isophthalic acid, 3- butadiene, 2,3- dimethyl -1,3- butadiene, 2- ethyl -1,3- butadiene, the chloro- 1,3- butadiene of 2-, 1,3- pentadiene, 1,3- hexadiene and 2,4- hexadiene etc..Wherein, It is preferred that 1,3- butadiene, 2- methyl isophthalic acid, 3- butadiene.It should be noted that conjugated diene can be used alone a kind, it is also possible to Two or more is applied in combination with arbitrary ratio.The ratio of the conjugated diene monomeric unit in diene polymer is preferably 20 mass % Above and below 60 mass %, more than preferably 30 mass % and below 55 mass %.
In addition to conjugated diene monomeric unit, above-mentioned diene polymer can also contain nitrile group-containing monomeric unit.As The specific example of the monomer of the nitrile group-containing of nitrile group-containing monomeric unit is constituted, can be enumerated：Acrylonitrile, methacrylonitrile, alpha-chloro The α such as acrylonitrile, α-ethyl acrylonitrile, alpha, beta-unsaturated nitriles compound etc., wherein preferred acrylonitrile.Nitrile group-containing in diene polymer The ratio of monomeric unit is preferably 5～40 mass %, the more preferably scope of 5～30 mass %.By by nitrile group-containing monomer list The ratio of unit is set to above range, can improve the pole strength for obtaining further.It should be noted that the monomer of nitrile group-containing can To be used alone a kind, it is also possible to be applied in combination two or more with arbitrary ratio.
In addition, in above-mentioned diene polymer in addition to above-mentioned monomeric unit, can also be containing by other monomers polymerization The construction unit of formation.As the other monomers for constituting other monomers unit, can enumerate：Acrylic acid, methacrylic acid, clothing health The unsaturated carboxylic acid class such as acid, fumaric acid；Styrene, chlorostyrene, vinyltoluene, t-butyl styrene, vinyl benzoic acid, Vinylbenzoate, vinyl naphthalene, 1-chloro-4-methyl-benzene, hydroxymethylstyrene, AMS, divinylbenzene etc. Styrene monomer；The olefines such as ethene, propylene；Vinyl acetate, propionate, vinyl butyrate, vinyl benzoate Deng vinyl ester；The amide-type monomer such as acrylamide, N hydroxymethyl acrylamide, acrylamide-2-methyl propane sulfonic；Methyl The vinyl ethers such as vinyl ethers, ethyl vinyl ether, butyl vinyl ether；Methyl vinyl ketone, ethyl vinyl ketone, butyl The vinyl ketones such as vinyl ketone, hexyl vinyl ketone, isopropenyl vinyl ketone；NVP, vinylpyridine The vinyl compound containing heterocycle such as pyridine, vinyl imidazole.Above-mentioned other monomers can each be used alone a kind, it is also possible to Arbitrary ratio is applied in combination two or more.
Acrylate polymer be containing origin self-drifting (1)：CH2=CR1-COOR2(in formula, R1Represent hydrogen atom or first Base, R2Represent alkyl or cycloalkyl) shown in compound monomer polymerization and formed monomeric unit ((methyl) acrylate list Body unit) polymer.As the specific example of the monomer for constituting (methyl) acrylate monomeric units, can enumerate：Propylene Acetoacetic ester, propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, acrylic acid N-pentyl ester, isoamyl acrylate, the just own ester of acrylic acid, 2-EHA, lauryl acrylate, stearyl acrylate ester etc. Acrylate；EMA, propyl methacrylate, isopropyl methacrylate, n-BMA, methyl Isobutyl acrylate, Tert-butyl Methacrylate, n-amylmethacrylate, isopentyl methacrylate, methacrylic acid are just Methacrylates such as own ester, 2-Ethylhexyl Methacrylate, lauryl methacrylate, stearyl methacrylate etc.. Wherein, preferred acrylate, from from the viewpoint of the intensity that can improve the electrode obtained, particularly preferred n-butyl acrylate and third Olefin(e) acid 2- Octyl Nitrite.The ratio of (methyl) acrylate monomeric units in acrylate polymer be usually 50 mass % with On, more than preferably 70 mass %.If the use of the ratio of above-mentioned (methyl) acrylate monomeric units being the third of above range Olefine acid ester polymer, then heat resistance is high, and can reduce the internal resistance of the electrode obtained.
In addition to (methyl) acrylate monomeric units, aforesaid propylene acid ester polymer preferably comprises nitrile group-containing monomer list Unit.As nitrile group-containing monomer, acrylonitrile, methacrylonitrile etc. can be enumerated, wherein, from collector and negative electrode active can be improved Caking property between material layer, improve pole strength from the viewpoint of, preferred acrylonitrile.Nitrile group-containing in acrylate polymer The ratio of monomeric unit is preferably 5～35 mass %, the more preferably scope of 10～30 mass %.By by nitrile group-containing monomer list The amount of unit is set to above range, can improve the pole strength for obtaining further.
In addition to above-mentioned monomeric unit, can also use by copolymerizable containing carboxylic acid group in aforesaid propylene acid ester polymer The construction unit (being also denoted as " monomeric unit containing carboxylic acid group " below) that monomer is polymerized and is formed.As containing the concrete of carboxylic acid group's monomer Example, can enumerate：The acid monomers containing unitary such as acrylic acid, methacrylic acid；Maleic acid, fumaric acid, itaconic acid etc. contain binary acid Monomer.Wherein, preferably contain dicarboxylic acid monomer, from can improve with the caking property of collector, improve pole strength from the viewpoint of, Particularly preferred itaconic acid.These acid monomers containing unitary, each can be used singly or in combination containing dicarboxylic acid monomer 2 kinds with On.The ratio containing carboxylic acid group's monomeric unit in acrylate polymer is preferably 1～50 mass %, more preferably 1～20 matter Amount %, the particularly preferably scope of 1～10 mass %.By the amount containing carboxylic acid group's monomeric unit is set to above range, permissible The intensity of the electrode obtained is improved further.
Additionally, in addition to above-mentioned monomeric unit, can also contain by copolymerizable list in aforesaid propylene acid ester polymer Construction unit obtained from body polymerization, as the specific example of above-mentioned other monomers, can enumerate：Ethyleneglycol dimethacrylate The carboxylic acid with more than 2 carbon-to-carbon double bonds such as ester, dimethacrylate, trimethylolpropane trimethacrylate Esters；The side chains such as perfluoroethyl octyl group ethyl ester, perfluoroalkylethyl methacrylate contain the unsaturated esters of fluorine；Benzene second Alkene, chlorostyrene, vinyltoluene, t-butyl styrene, vinyl benzoic acid, vinylbenzoate, vinyl naphthalene, The styrene monomers such as 1-chloro-4-methyl-benzene, hydroxymethylstyrene, AMS, divinylbenzene；Acrylamide, N- hydroxyl first The amide monomers such as base acrylamide, acrylamide-2-methyl propane sulfonic；The olefines such as ethene, propylene；Butadiene, isoprene Deng diene monomers；The halogen atom monomer such as vinyl chloride, vinylidene chloride；Vinyl acetate, propionate, vinyl butyrate, benzene The vinyl esters such as vinyl formate；The vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether；First The vinyl ketones such as base vinyl ketone, ethyl vinyl ketone, butyl vinyl ketone, hexyl vinyl ketone, isopropenyl vinyl ketone Class；The vinyl compound containing heterocycle such as NVP, vinylpyridine, vinyl imidazole；Allyl glycidyl is sweet The glycidol ethers such as oily ether；Glycidol esters such as glycidyl acrylate, GMA etc..Propylene The ratio of these the copolymerizable other monomers units in acid ester polymer can be suitably adjusted according to using purpose.
In addition, as negative pole binding agent than that described above, can enumerate：Polyethylene, polypropylene, polyisobutene, poly- Vinyl chloride, Vingon, Kynoar, polytetrafluoroethylene (PTFE), polyvinyl acetate, polyvinyl alcohol, polyvinyl isobutyl base Ether, polyacrylonitrile, polymethacrylonitrile, polymethyl methacrylate, PMA, polyethyl methacrylate, poly- second The polyvinyls such as allyl propionate, polystyrene；Polyformaldehyde, polyoxyethylene, poly- cyclic thioether, dimethyl silicone polymer etc. are main Chain contains heteroatomic ether polymer；Polylactone, poly- cyclic acid anhydride, polyethylene terephthalate, Merlon etc. are condensed ester Polymer；Nylon 6, nylon66 fiber, poly, PPTA, four formyl of poly- equal benzene are sub- The condensation acylamide polymer such as amine, tackifier hereinafter described etc..
The shape of negative pole binding agent is not particularly limited, and as the adaptation with collector is good, and can suppress system The reduction of the capacity of the electrode of work and repeat the deterioration caused by discharge and recharge, therefore preferably particle shape.Particle shape bonds As long as the material that agent is kept/existed with shape of particle in the state of decentralized medium is scattered in, preferably in negative electrode active Also can be to keep the binding agent of the state presence of shape of particle in material layer.In the present invention, described " shape of particle is kept State " need not be the state of holding shape of particle completely, as long as keep the state of its shape of particle in a way. As particle shape binding agent, for example, can enumerate：The bonding of the state that the particle of binding agent as latex is dispersed in water Agent, such dispersion liquid is dried obtained from powder binding agent.
The glass transition temperature (Tg) of negative pole binding agent is preferably less than 50 DEG C, more preferably -40～0 DEG C. If the glass transition temperature of binding agent (Tg) is in the scope, with a small amount of usage amount can achieve excellent adaptation, High electrode intensity is simultaneously rich in flexibility, and pressurization operation when can be formed by electrode easily improves electrode density.
In the case that negative pole binding agent is particle shape binding agent, its number average bead diameter is not particularly limited, and usually 0.01 ～1 μm, preferably 0.03～0.8 μm, more preferably 0.05～0.5 μm.When the number average bead diameter of binding agent is the scope, even if few Amount is used, it is also possible to give negative electrode active material layer with excellent closing force.Here, number average bead diameter is to determine transmission electron microscopy The particle diameter of randomly selected 100 binding agent particles in mirror photo, and the number average bead diameter calculated as its arithmetic mean of instantaneous value. The shape of particle can be the arbitrary shape in spherical, special-shaped.
These binding agents can be used alone or be applied in combination two or more.
With respect to 100 mass parts of negative electrode active material, the amount of negative pole binding agent is usually 0.1～50 mass parts, preferably For 0.5～20 mass parts, the more preferably scope of 1～10 mass parts.If the amount of binding agent is in the scope, can be fully true The adaptation that protects between gained negative electrode active material layer and collector, improves the capacity of secondary cell, and reduces internal resistance.
(c) conductive material
Negative electrode active material layer can contain conductive material.In negative pole, the particle diameter of contained conductive material is in terms of number average bead diameter For 5～40nm, more preferably preferably 10～38nm, 15～36nm.As conductive material, it is possible to use acetylene black, Ketjen black, The conductive carbon such as carbon black, graphite, gas-phase growth of carbon fibre and CNT.By containing conductive material, negative pole work can be improved Property material electrical contact each other, for discharging-rate performance can be improved in the case of lithium rechargeable battery.Relative In 100 mass parts of total amount of negative electrode active material, the content of conductive material is preferably 1～20 mass parts, more preferably 1～10 matter Amount part.
Other negative pole compositions
In addition, identical with above-mentioned positive pole, can also be containing supporting material, levelling agent, with electrolyte decomposition in negative pole The electrolysis additives of function etc. such as suppression as optional member, in addition it is also possible to remain the slurry prepared when negative pole is manufactured Contained tackifier etc. in material.
The manufacture method of lithium ion secondary battery negative pole paste compound
Lithium ion secondary battery negative pole paste compound passes through above-mentioned negative electrode active material (a), negative pole bond Agent (b), conductive material (c), other additives are obtained by mixing in decentralized medium.As decentralized medium, it is possible to use water and Arbitrary substance in organic solvent.As organic solvent, can enumerate：The cyclic aliphatic hydrocarbons such as pentamethylene, hexamethylene；First Benzene, dimethylbenzene, ethylbenzene etc. are aromatic hydrocarbon；Acetone, MEK, diisobutyl acetone, cyclohexanone, methyl cyclohexanone, ethyl cyclohexanone Deng ketone；The chlorine such as dichloromethane, chloroform, carbon tetrachloride system aliphatic hydrocarbon；Ethyl acetate, butyl acetate, gamma-butyrolacton, ε-oneself The esters such as lactone；The alkyl nitrile such as acetonitrile, propionitrile；The ethers such as tetrahydrofuran, ethylene glycol Anaesthetie Ether：Methyl alcohol, ethanol, isopropyl The alcohols such as alcohol, ethylene glycol, ethylene glycol single methyl ether；The amide-types such as 1-METHYLPYRROLIDONE, N,N-dimethylformamide.
These decentralized media can be used alone, and also mixes two or more and uses as mixed solvent.Wherein, particularly right The decentralized medium that dispersiveness is excellent, boiling point low volatility is high of each composition can be removed in the short time and under low temperature, therefore preferably.Tool For body, preferably acetone, toluene, cyclohexanone, pentamethylene, tetrahydrofuran, cyclohexanone, dimethylbenzene, water or 1-METHYLPYRROLIDONE, Or their mixed solvent.
Mixed method is not particularly limited, for example, can enumerate：Employ stirring-type, oscillatory type and rotary etc. mixed Attach together the method that puts.Furthermore it is possible to enumerate employ homogenizer, ball mill, sand mill, roller mill and planetary mixer etc. The method of dispersion milling device.
Lithium ion secondary battery negative pole
Lithium ion secondary battery negative pole is by coating collection by above-mentioned lithium ion secondary battery negative pole paste compound Electric body being dried is formed.
The manufacture method of lithium ion secondary battery negative pole includes for above-mentioned negative electrode slurry composition to coat collector One or both sides are simultaneously dried, so as to form the operation of negative electrode active material layer.
The method that negative electrode slurry composition is coated on collector is not particularly limited.Can for example enumerate：Scraper plate The methods such as method, infusion process, inverse roller method, direct roller method, intagliotype, extrusion molding and spread coating.
As drying means, for example, can enumerate：Using warm braw, hot blast, the drying of low wet wind, vacuum drying, utilize The seasoning of the irradiation of (remote) infrared ray, electron beam etc..Drying time is usually 5～30 minutes, and baking temperature is usually 40 DEG C ～180 DEG C.
When lithium ion secondary battery negative pole is manufactured, preferably above-mentioned negative electrode slurry composition is being coated on collector And after drying, reduce the voidage of negative electrode active material layer with pressurized treatments being carried out by using moulding press, roll squeezer etc. Operation.The voidage of negative electrode active material layer is preferably 5～30%, more preferably 7～20%.If negative electrode active material layer Voidage too high, then may cause charge efficiency, discharging efficiency be deteriorated.If voidage is too low, it is difficult to obtain high body Product capacity, negative electrode active material layer are easy to peel off from collector, are sometimes prone to produce bad.Additionally, using curable polymer In the case of negative pole binding agent, its solidification is preferably made.
The thickness of the negative electrode active material layer in lithium ion secondary battery negative pole is usually 5～300 μm, preferably 30～ 250μm.By making the thickness of negative electrode active material layer in above range, can obtain showing part throttle characteristics and cycle characteristics equal The secondary cell of high characteristic.
The content ratio of the negative electrode active material in negative electrode active material layer preferably 85～99 mass %, more preferably 88 ～97 mass %.It is above range by the content ratio for making the negative electrode active material in negative electrode active material layer, can obtains High power capacity is shown, while showing the secondary cell of flexibility, caking property.
The density of negative electrode active material layer is preferably 1.6～1.9g/cm3, more preferably 1.65～1.85g/cm3.By making The density of negative electrode active material layer is above range, can obtain the secondary cell of high power capacity.
As long as material of the collector with electric conductivity and with electrochemistry durability, is just not particularly limited, but in order to With heat resistance, preferred metal materials, for example, can enumerate：Iron, copper, aluminium, nickel, stainless steel, titanium, tantalum, gold, platinum etc..Wherein, make It is the collector for lithium ion secondary battery negative pole, particularly preferred copper.
The shape of collector is not particularly limited, the sheet collector of preferred thickness 0.001mm～0.5mm or so.
For collector, in order to improve the adhesive strength with negative electrode active material layer, in advance surface can be roughened Reuse after process.As roughening method, can enumerate：Mechanical polishing method, electrobrightening method, chemical polishing etc..In machine In tool polishing processes, can there are the sand paper of polishing agent particle, grinding stone, emery buff (emery buff), possess steel using cementation Line brush of silk etc. etc..In addition, for the adhesive strength, the electric conductivity that improve negative electrode active material layer, it is also possible in the table of collector Face forms priming coat etc..
(lithium rechargeable battery)
The lithium rechargeable battery of the present invention possesses above-mentioned positive pole and negative pole, with nonaqueous electrolytic solution, and usually contains Dividing plate.
Nonaqueous electrolytic solution
Nonaqueous electrolytic solution is not particularly limited, it is possible to use dissolve the lithium salts as supporting electrolyte in non-aqueous solvent Electrolyte.As lithium salts, for example, can enumerate：LiPF6、LiAsF6、LiBF4、LiSbF6、LiAlCl4、LiClO4、 CF3SO3Li、C4F9SO3Li、CF3COOLi、(CF3CO)2NLi、(CF3SO2)2NLi、(C2F5SO2) lithium salts such as NLi.Particularly can be excellent Choosing is used and is easily dissolved in solvent and display high dissociation degree LiPF6、LiClO4、CF3SO3Li.These electrolyte individually can make With, it is also possible to it is mixed with two or more.With respect to nonaqueous electrolytic solution, the amount of supporting electrolyte is usually more than 1 mass %, excellent Elect more than 5 mass % as, in addition, usually below 30 mass %, below preferably 20 mass %.The amount of supporting electrolyte is very few Or excessive, ion conductivity all reduces, and the charge characteristic of secondary cell, flash-over characteristic reduce.
As the solvent for nonaqueous electrolytic solution, as long as the solvent of dissolving supporting electrolyte is just not particularly limited, lead to Can often use：Dimethyl carbonate (DMC), ethylene carbonate (EC), diethyl carbonate (DEC), propylene carbonate (PC), carbonic acid The alkyl carbonate esters such as butylene (BC) and methyl ethyl carbonate (MEC)；The esters such as gamma-butyrolacton, methyl formate, 1,2- diformazan The ethers such as epoxide ethane and tetrahydrofuran；The sulfur-containing compound class such as sulfolane and dimethyl sulfoxide.Extra high due to being readily available Ionic conductivity, use temperature range width, preferably dimethyl carbonate, ethylene carbonate, propylene carbonate, diethyl carbonate, carbon Sour methyl ethyl ester.These solvents can be used alone, it is also possible to be mixed with two or more.
As nonaqueous electrolytic solution other than the above, can enumerate：In the polymer dielectrics such as polyoxyethylene, polyacrylonitrile The gel-polymer electrolyte matter of impregnation nonaqueous electrolytic solution, lithium sulfide, LiI, Li3The inorganic solid electrolytes such as N.
Alternatively, it is also possible to make to reuse containing additive in nonaqueous electrolytic solution.As additive, except vinylene carbonate Etc. (VC) beyond carbonats compound, the preferably fluorine-containing carbonic ester such as fluoroethylene carbonate, ethyl-methyl sulfone.Wherein, fluorine-containing The proof voltage of the such fluorine system electrolyte added material of carbonic ester is high.Along with high capacity, voltage during discharge and recharge is not yet Break and uprise, the electrolyte being made up of ethylene carbonate, propylene carbonate etc. is unable to tolerating high voltage, it some times happens that decompose, because This, preferably coordinates above-mentioned fluorine system electrolyte added material in nonaqueous electrolytic solution.
Dividing plate
Dividing plate is porous substrate having pores portion, as spendable dividing plate, can enumerate：A () is with pore portion Porous separator, (b) is formed with the porous separator of polymeric coating layer in one or both sides or (c) is formed with comprising inorganic The porous separator of the porous resin coating of the non-conductive particles such as ceramic powders and binding agent.As the non-limiting of them Example, can enumerate：PP type, polyethylene kind, TPO or aromatic polyamide porous separator, Kynoar, The solid macromolecule electrolytes such as polyoxyethylene, polyacrylonitrile or Kynoar hexafluoropropylene copolymer are used or gel macromolecule Electrolyte polymeric membrane, it is coated with the dividing plate of gelation polymeric coating layer or is coated with and use comprising inorganic filler, inorganic filler Dividing plate of the porous membrane layer of dispersant etc..
The manufacture method of lithium rechargeable battery
The manufacture method of the lithium rechargeable battery of the present invention is not particularly limited.For example, it is possible to by above-mentioned positive pole and Negative pole is overlapped across dividing plate, and is put into after being crimped, bend etc. according to cell shapes in battery case, is injected to battery case Electrolyte is simultaneously sealed.Unit is prevented alternatively, it is also possible to be put into the overcurrent such as expansion alloy or fuse, PTC-element as needed Part, lead plate etc., prevent the pressure of inside battery from rising, cross discharge and recharge.The shape of battery can be laminated units type, coin Arbitrary shape in type, coin shape, piece type, cylinder type, square, platypelloid type, convoluted bag-type battery etc..Especially, according to this Invention, as active material layer is soft, during bending, active material layer is not cracked, thus, it may be preferable to be used for convoluted pocket type The manufacture of battery.
Embodiment
Hereinafter, the present invention will be described in conjunction with the embodiments, but the present invention is not limited to these embodiments.Need explanation , " part " and " % " in the present embodiment unless otherwise specified, is then quality criteria.In embodiment and comparative example, Various physical property are evaluated as follows.
(SP value)
The SP value refers to solubility parameter." the molecular attraction constant method " that the SP value is proposed by Small is obtained.The party Method be by statistics and the molecule of the molecular attraction constant (G) of the characteristic value as the functional group's (atomic group) for constituting compound molecule Amount, the method that is obtained according to following formula.
δ=Σ G/V=d Σ G/M
In above-mentioned formula, δ represents SP value, and Σ G represents the total of molecular attraction constant G, and V represents specific volume, and M represents molecule Amount, d represent proportion.
Additionally, in the case of two or more polymer is combined, being counted by the SP value and mixing mol ratio of each polymer Calculate and use above-mentioned calculating formula to obtain as the overall SP value of polymer.
(cladding of positive active material confirms)
The mixing ratio of the acrylate copolymer of positive active material, positive pole binding agent and nitrile group-containing is set to 100:1.6: 0.4 making slurry, and it is upper and be dried to coat collector (aluminium foil), makes electrode.
Electrode surface is observed with SEM (Hitachi S-3400N).Observation condition is for again Rate be set as 2000 times, accelerating potential be set as 15kV, 100 μ m, 100 μm of square-shaped image is observed.Additionally, using The subsidiary energy dispersion type x-ray analysis equipment of SEM (Bruker Quantax) carries out nickle atom and nitrogen Element mapping (mapping) of atom and carbon atom, has made respective mapping graph.5 positions on electrode are randomly selected, will Aforesaid operations have carried out 5 times.
10 positive active material particles, wherein, the length of these positive active material particles are randomly choosed on this image Side and minor face are more than 10 μm, and the surface of particle is observed that more than 90% and not Chong Die with other particles.
In the element mapping positive active material particle picture of above-mentioned selection, the part that there is nitrogen has been will confirm that Area is judged as the active material surface coated by the acrylate copolymer of nitrile group-containing.Additionally, cladding ratio is more than 60% Situation be considered as the acrylate copolymer of nitrile group-containing and coated positive active material particle surface, and be evaluated as " qualified ".
(measure of nonaqueous electrolytic solution swellbility)
1-METHYLPYRROLIDONE (NMP) solution by the 8% of the acrylate copolymer of nitrile group-containing with dried thickness is 100 μm of mode is poured in Teflon (registration mark) culture dish, makes polymer film.The film for obtaining is struck out 16mm φ, Weight (is designated as " A ") by gravimetry.It is 3 to the weight ratio of ethylene carbonate and methyl ethyl carbonate:Mix in 7 mixture 5% fluoroethylene carbonate, and make lithium hexafluoro phosphate (LiPF6) solution has been prepared with the concentration dissolving of 1mol/L, should Solution is used as nonaqueous electrolytic solution.Make the film immersion of 16mm φ to be struck out in 20g nonaqueous electrolytic solution, impregnate 72 hours in 60 DEG C. Then, the film through dipping is taken out, the nonaqueous electrolytic solution on surface is gently wiped, weight (is designated as " B ") by gravimetry.By these Value obtains nonaqueous electrolytic solution swellbility (=B/A).Nonaqueous electrolytic solution swellbility is bigger, represents that the deformation in nonaqueous electrolytic solution is got over Greatly.
(measure of THF insoluble component amount)
The 8% of the acrylate copolymer of nitrile group-containing nmp solution is poured in the way of dried thickness is 100 μm In Teflon (registration mark) culture dish, polymer film is made.The film for obtaining is struck out 16mm φ, gravimetry is (by weight It is designated as " C ").Make the film immersion of 16mm φ to be struck out in 20g tetrahydrofuran, made soluble ingredient completely molten in 25 DEG C through 24 hours Solution.Then, the residual solid as insoluble component is taken out, after so that tetrahydrofuran is volatilized completely with infrared drier, is determined Weight (is designated as " D ") by weight.THF insoluble component amount (=D/C × 100) is obtained by these values.THF insoluble component amount is less, Represent that the crosslinking between polymer molecule is fewer.
(flexural property of coiling body)
Sheet-like anode and sheet-like cathode are wound across dividing plate using the core of diameter 20mm, obtain coiling body.As Dividing plate, employs thick 20 μm polypropylene microporous film.From a direction with the speed compression coiling body of 10mm/ second to thickness Reach 4.5mm.Coiling body is disassembled after compression, is observed positive electrode, and is evaluated according to following metewands.
A ... crack-free
The small rupture of B ...
C ... is from stripping electrode
(high potential cycle characteristics)
For nonaqueous electrolyte battery, under 25 DEG C of environment with 600mA charge to cell voltage reach 4.8V, with 600mA It is discharged to cell voltage and 3V is reached, and the operation is repeated 100 times.
Then, the ratio of the discharge capacity of the 100th time with respect to primary discharge capacity is calculated.
(acrylate copolymer of nitrile group-containing)
Acrylate copolymer (1)～(6) of nitrile group-containing are prepared for as described below.
[preparation example 1]
The manufacture of the acrylate copolymer (1) of nitrile group-containing
To in the autoclave with mixer add 164 parts of ion exchange water, 67.5 parts of 2-EHA (2EHA), 17 parts of methacrylic acid (MAA), 15 parts of acrylonitrile (AN), 0.5 part of 2- acrylamide-2-methyl propane sulfonic (AMPS), conduct are poly- 0.3 part of potassium peroxydisulfate and 1.6 parts of the lauryl sodium sulfate as surfactant of initiator is closed, after being sufficiently stirred for, 70 Heat 3 hours at DEG C, heat at 80 DEG C further and be polymerized for 2 hours, obtain the water of the acrylate copolymer (1) of nitrile group-containing Dispersion liquid.Wherein, the polymerisation conversion that is obtained by solid component concentration is 96%.In addition, adding in 100 parts of the aqueous dispersions 500 parts of 1-METHYLPYRROLIDONE, makes water and residual monomer evaporation under reduced pressure, then makes 81 parts of 1-METHYLPYRROLIDONE evaporations, Obtain the nmp solution of 8 mass % of the acrylate copolymer (1) of nitrile group-containing.Now nonaqueous electrolytic solution swellbility is 2 times, and THF is not Melt into component is less than 10%.In addition, the SP value of the acrylate copolymer of nitrile group-containing is 9.9 (cal/cm3)1/2.
[preparation example 2～6]
The manufacture of acrylate copolymer (2)～(6) of nitrile group-containing
The inventory of monomer, species are changed as shown in table 1, in addition, is implemented in the same manner as preparation example 1. It should be noted that in table 1, AN refer to acrylonitrile, 2EHA refer to 2-EHA, EA refer to ethyl acrylate, BA refers to that butyl acrylate, MAA are that methacrylic acid, AMPS refer to that 2- acrylamide-2-methyl propane sulfonic, GMA are nails Base glycidyl acrylate.Nonaqueous electrolytic solution swellbility, THF insoluble component amount and SP value are shown in table 1.
[table 1]
(embodiment 1)
[manufacture of positive pole paste compound and positive pole]
Using the Li excess lamellar compound (Li [Ni as positive active material0.17Li0.2Co0.07Mn0.56]O2) 100 parts, Acetylene black (AB35, Denki Kagaku Kogyo kabushiki's DENKA BLACK powdery product as positive conductive material：Number average bead diameter 35nm, specific surface area 68m2/ g) 2.0 parts, as positive pole binding agent fluoropolymer mixing Kynoar (ARKEMA The 1 of company system KYNAR HSV900 and KYNAR720：1 mixture) 1.6 parts, as nitrile group-containing acrylate copolymer above-mentioned The acrylate copolymer (1) of nitrile group-containing is with 0.4 part of the gauge equivalent to solid constituent and appropriate NMP planetary-type mixer Stirring, is prepared for positive pole paste compound.Wherein, KYNAR HSV900 with ASTM D3835/232 DEG C 100sec-1Determine Melt viscosity for 50kpoise, KYNAR720 melt viscosity be 9kpoise.
As collector, thick 15 μm aluminium foil is prepared.By above-mentioned positive pole paste compound with dried coating weight For 25mg/cm2Mode coat the two sides of aluminium foil, in 60 DEG C of dryings 20 minutes, in 120 DEG C of dryings 20 minutes, then, in 150 DEG C of heating for carrying out 2 hours, obtain positive original film.By these operations, using the acrylate copolymer of nitrile group-containing (1) positive active material and the collector surface not covered by positive active material have been coated.By the positive original film roll-in Machine rolls, and it is 3.9g/cm to have made by density3Positive electrode active material layer and aluminium foil constitute sheet-like anode.It is cut into Wide 4.8mm, long 50cm, connect aluminum lead.In addition, the positive pole to obtaining has carried out the evaluation of the flexural property of coiling body.As a result It is shown in table 2.
[manufacture of negative electrode slurry composition and negative pole]
Using the spherical Delanium (particle diameter as negative electrode active material：12 μm) 90 parts and SiOx (particle diameter：10 μm) 10 parts, Styrene butadiene ribber (particle diameter as binding agent：180nm, glass transition temperature：- 40 DEG C) 1 part, as tackifier 1 part of carboxymethylcellulose calcium and appropriate water are stirred with planetary-type mixer, are prepared for negative electrode slurry composition.
As collector, thick 15 μm Copper Foil is prepared.By above-mentioned negative electrode slurry composition with dried coating weight For 10mg/cm2Mode coat the two sides of Copper Foil, in 60 DEG C of dryings 20 minutes, in 120 DEG C of dryings 20 minutes, then in 150 DEG C heat 2 hours, obtain negative original film.The negative original film is rolled with roll squeezer, it is 1.8g/cm to have made by density3 Negative electrode active material layer and Copper Foil constitute sheet-like cathode.Wide 5.0mm, long 52cm is cut into, connects nickel down-lead.
[manufacture of lithium rechargeable battery]
The sheet-like anode for obtaining and sheet-like cathode are wound across dividing plate using the core of diameter 20mm, are wound Body.Thick 20 μm polypropylene microporous film is used as dividing plate.From a direction with the speed compression coiling body of 10mm/ second to Thickness reaches 4.5mm.Above-mentioned generally oblong major diameter is 7.7 with respect to the ratio of minor axis.
In addition, being 3 to the weight ratio of ethylene carbonate and methyl ethyl carbonate:Mix the fluoro of 5 mass % in 7 mixture Ethylene carbonate, and lithium hexafluoro phosphate is dissolved with the concentration of 1mol/L, add the vinylene carbonate of 2vol%, prepared non-aqueous Electrolyte.
Above-mentioned coiling body is accommodated in given aluminium laminated material housing together with the nonaqueous electrolytic solution of 3.2g.So Afterwards, negative wire and positive wire are connected on given position, then, the opening portion of housing are sealed using heat, complete Lithium rechargeable battery as convoluted bag-type battery.The battery is wide 35mm, high 48mm, the pouch-shaped of thickness 5mm, the mark of battery Capacity is called 700mAh.The high potential cycle characteristics of gained secondary cell is shown in table 2.
(embodiment 2)
Replace the acrylate copolymer (1) of nitrile group-containing using above-mentioned polymer (2), in addition, similarly to Example 1 Ground is implemented.As a result table 2 is shown in.
(embodiment 3)
Replace the acrylate copolymer (1) of nitrile group-containing using above-mentioned polymer (3), in addition, similarly to Example 1 Ground is implemented.As a result table 2 is shown in.
(embodiment 4)
Replace the acrylate copolymer (1) of nitrile group-containing using above-mentioned polymer (4), in addition, similarly to Example 1 Ground is implemented.As a result table 2 is shown in.
(embodiment 5)
Replace the acrylate copolymer (1) of nitrile group-containing using above-mentioned polymer (5), in addition, similarly to Example 1 Ground is implemented.As a result table 2 is shown in.
(comparative example 1)
Not using the acrylate copolymer (1) of nitrile group-containing, in addition, implement similarly to Example 1.As a result table is shown in 2.
(comparative example 2)
Replace the acrylate copolymer (1) of nitrile group-containing using polypropylene (and the pure medicine Polypropylene of light), except this it Outward, implement similarly to Example 1.As a result table 2 is shown in.It should be noted that polyacrylic SP value is 8.35 (cal/cm3 )1/2, cannot clad anode active material using polypropylene.In addition, polyacrylic nonaqueous electrolytic solution swellbility is 1.1 times, THF is not Melt into component is 0 mass %.
(comparative example 3)
Replace the acrylate copolymer (1) of nitrile group-containing using above-mentioned polymer (6), in addition, similarly to Example 1 Ground is implemented.As a result table 2 is shown in.
[table 2]
Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 Embodiment 5 Comparative example 1 Comparative example 2 Comparative example 3
The bendability of coiling body A B A A A B C C
High potential cycle characteristics 85% 70% 70% 75% 70% 60% 45% 60%
From table 1 and 2, meeting the embodiment of important document of the present invention, to obtain balance for all assessment items good As a result.On the other hand, not using the acrylate copolymer of nitrile group-containing comparative example 1,2 and employ SP value particular range it The comparative example 3 of the acrylate copolymer of outer nitrile group-containing is all poor for the result of whole assessment items.

Claims (9)

1. a kind of lithium rechargeable battery, which possesses positive pole, negative pole and nonaqueous electrolytic solution,
Wherein,
The positive pole contains positive active material, positive pole binding agent and conductive material,
The positive active material is 9～11 (cal/cm by SP value3)1/2Nitrile group-containing acrylate copolymer cladding,
The acrylate copolymer of the nitrile group-containing contains ethylenic unsaturated acid monomeric unit,
The positive pole binding agent contains fluoropolymer.
2. lithium rechargeable battery according to claim 1, wherein, the positive active material be containing Li, Mn, Co and The lithium excess lamellar compound of Ni.
3. lithium rechargeable battery according to claim 1 and 2, wherein, the negative pole contains alloy type active material.
4. lithium rechargeable battery according to claim 1 and 2, wherein, the acrylate copolymer of the nitrile group-containing is non- Swellbility in water electrolysis liquid is less than 3 times, and its THF insoluble component amount is below 30 mass %.
5. lithium rechargeable battery according to claim 1 and 2, wherein, the particle diameter of the conductive material is 5～40nm.
6. lithium rechargeable battery according to claim 1 and 2, wherein, with respect to 100 mass of the positive active material Part, the content of conductive material is 1～3 mass parts, the content of positive pole binding agent is 0.4～2 mass parts.
7. lithium rechargeable battery according to claim 1 and 2, wherein, the fluoropolymer is Kynoar.
8. lithium rechargeable battery according to claim 1, wherein, olefinic in the acrylate copolymer of the nitrile group-containing The content ratio of unsaturated acid monomer unit is 10～30 mass %.
9. lithium rechargeable battery according to claim 1 and 2, which is convoluted bag-type battery.
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