CN103026535A - Positive electrode for secondary battery, and secondary battery - Google Patents

Positive electrode for secondary battery, and secondary battery Download PDF

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Publication number
CN103026535A
CN103026535A CN2011800365715A CN201180036571A CN103026535A CN 103026535 A CN103026535 A CN 103026535A CN 2011800365715 A CN2011800365715 A CN 2011800365715A CN 201180036571 A CN201180036571 A CN 201180036571A CN 103026535 A CN103026535 A CN 103026535A
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active material
adhesive
anode
monomer
secondary cell
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CN2011800365715A
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CN103026535B (en
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胁坂康寻
薮内庸介
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Zeon Corp
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Nippon Zeon Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/134—Electrodes based on metals, Si or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Secondary Cells (AREA)

Abstract

Disclosed is a positive electrode for a secondary battery, which can be formed into a thick film and is capable of preventing occurrence of cracks. The positive electrode for a secondary battery is capable of providing a secondary battery that has improved cycle characteristics (especially high-temperature cycle characteristics) and improved safety. Specifically disclosed is a positive electrode for a secondary battery, which is characterized by being composed of a collector and a positive electrode active material layer that is arranged on the collector and contains fibrous carbon, a binder and a positive electrode active material containing manganese or iron. The positive electrode for a secondary battery is also characterized in that the binder is composed of a polymer that contains a (meth)acrylate monomer polymerization unit, a vinyl monomer polymerization unit having an acid component and an [alpha],[beta]-unsaturated nitrile monomer polymerization unit, and the content of the vinyl monomer polymerization unit having an acid component is 1.0-3.0% by mass of the total polymerization units of the polymer.

Description

Anode of secondary cell and secondary cell
Technical field
The present invention relates to anode of secondary cell, more particularly, relate to the anode of secondary cell with high-rate characteristics and cycle characteristics for lithium rechargeable battery etc.In addition, the invention still further relates to the secondary cell with this electrode.
Background technology
Even in the battery that oneself uses, lithium rechargeable battery also demonstrates the highest energy density, particularly is widely used in miniaturized electronics.In addition, except mini-plant uses, also expect on motor vehicle, to use expansion.Wherein, the reliability of the high power of the further raising of urgent expectation lithium rechargeable battery and cycle characteristics etc.
As the positive active material of lithium rechargeable battery constituent material, be the limited this point consideration of expensive and reserves of active material from the cobalt that is used as the main flow use, shift to the active material that contains cheap manganese, nickel.But the manganese of main flow is in the active material to expect to become from now on, and at high temperature, when particularly repeating to discharge and recharge more than 40 ℃, manganese ion dissolves in electrolyte separates out, and the result causes battery capacity to descend, and this has become large problem.
In addition, separate out in the negative terminal surface reduction by the manganese ion of separating out from the positive pole dissolving, form tree-shaped metal precipitate, it destroys dividing plate, becomes the large problem of the fail safe decline of battery.
In addition, used electrode in the lithium rechargeable battery, usually have electrode active material layer and be stacked in structure on the collector body, in the electrode active material layer, except the active material of electrode, the adhesive that also use to be used for making the bonded to one another and electrode active material of electrode active material and collector body to bond.
Put down in writing the LiFePO with olivine-type structure that contains as positive active material in the patent documentation 1 4, carbon and as (methyl) acrylate and the α of adhesive, the positive pole of the copolymer of alpha, beta-unsaturated nitriles compound.
In addition, put down in writing the LiFePO with olivine-type crystal structure that contains as positive active material in the patent documentation 2 4, carbon fiber, as the positive pole of the polyvinylidene chloride (PVDF) of adhesive.
The prior art document
Patent documentation
Patent documentation 1:WO2006/038652 communique (corresponding U.S. Patent bulletin: No. 2008/096109 specification of U.S. Patent Application Publication)
Patent documentation 2: TOHKEMY 2005-222933 communique (corresponding U.S. Patent bulletin: No. 2007/275302 specification of U.S. Patent application)
Summary of the invention
The problem that invention will solve
But, can judge by present inventor's discussion: the LiFePO with olivine-type structure that uses as positive active material in the patent documentation 1 4, little because of particle diameter during as positive active material, when making the positive electrode active material layer thick-film, sometimes there is the problem that be full of cracks and so on occurs.In addition, can also judge: the positive pole of patent documentation 2, identical with the situation of using manganese class active material in the described positive active material, when at high temperature repeatedly discharging and recharging, iron ion dissolves in electrolyte separates out, and there is the problem of battery capacity decline and so in the result, and, because the dissolving iron ion of separating out is separated out in that negative terminal surface is tree-shaped, the problem that then exists the fail safe of battery to descend and so on.
Therefore, the object of the invention is, provide a kind of can thick-film, can prevent from the generation of chapping from can improving the cycle characteristics (particularly high-temperature cycle) of the secondary cell that obtains and the anode of secondary cell of fail safe.In addition, the object of the invention also is, a kind of secondary cell that possesses this anode of secondary cell is provided.
The method of dealing with problems
Take solve above-mentioned problem as the main points of the present invention of purpose as described below.
(1) a kind of anode of secondary cell, its collector body and positive electrode active material layer, described positive electrode active material layer is stacked on the described collector body, and contains positive active material, fibrous carbon and the adhesive of manganese or iron, wherein,
Described adhesive by the polymerized unit that contains (methyl) acrylate monomer, have polymerized unit and the α of the vinyl monomer of sour composition, the polymer that the polymerized unit of alpha, beta-unsaturated nitriles monomer forms forms,
The polymerized unit of described vinyl monomer with sour composition contain proportional 1.0 ~ 3.0 quality % that in all polymerized units of polymer, account for.
(2) according to (1) described anode of secondary cell, wherein, described positive active material contains iron, and has olivine-type structure.
(3) according to (1) or (2) described anode of secondary cell, wherein, the fiber diameter of described fibrous carbon is 0.01 ~ 1.0 μ m.
(4) according to each described anode of secondary cell in (1) ~ (3), wherein, the mean aspect ratio of described fibrous carbon is 5 ~ 50000.
(5) according to each described anode of secondary cell in (1) ~ (4), wherein, described vinyl monomer with sour composition is the monomer with carboxylic acid group.
(6) according to each described anode of secondary cell in (1) ~ (5), wherein, described adhesive further contains the polymerized unit with bridging property.
(7) a kind of secondary cell, it possesses positive pole, negative pole, dividing plate and electrolyte, each described anode of secondary cell in described just very (1) ~ (6).
The invention effect
According to the present invention, by in positive electrode active material layer, containing fibrous carbon, then can improve the toughness of positive electrode active material layer, therefore the generation of positive electrode active material layer be full of cracks can be prevented, and positive electrode active material layer can be thickened.In addition, adhesive contained in the positive electrode active material layer is the polymerized unit that contains (methyl) acrylate monomer, polymerized unit and the α with vinyl monomer of sour composition, the polymer that the polymerized unit of alpha, beta-unsaturated nitriles monomer forms, the polymerized unit of the vinyl monomer by will having sour composition contain the proportional ratio of setting regulation for, then can capture the metal ion (manganese ion or iron ion) of being separated out by the positive active material dissolving, therefore, can improve cycle characteristics (particularly high-temperature cycle) and the fail safe of secondary cell.
Embodiment
The below describes the present invention in detail.Anode of secondary cell of the present invention has collector body and positive electrode active material layer, and described positive electrode active material layer and contains positive active material, fibrous carbon and the adhesive of manganese or iron and consists of on collector body.
(positive active material)
As positive active material used among the present invention, so long as the material that contains manganese or iron and can reversibly insert/emit lithium ion gets final product, be not particularly limited, still, wherein preferably contain the transition metal oxide of lithium.
As the transition metal oxide that contains lithium that contains manganese, can enumerate: have layer structure the composite metal oxide that contains lithium, have spinel structure the composite metal oxide that contains lithium, have the composite metal oxide that contains lithium of olivine-type structure etc.
As the composite metal oxide that contains lithium with layer structure, can enumerate: LiMnO 2And with the part of the Mn Li with other Transition metal substituted x[Mn yM 1-y] O 2(in the formula, x=0.02 ~ 1.2,0＜y＜1, M is Cr, Fe, Co, Ni, Cu etc.) etc.
As the composite metal oxide that contains lithium with spinel structure, can enumerate: LiMn 2O 4And with the part of the Mn Li with other Transition metal substituted x[Mn yM 2-y] O 4(in the formula, x=0.02～1.2,0＜y＜2, M are Cr, Fe, Co, Ni, Cu, V etc.) etc.
As the composite metal oxide that contains lithium with olivine-type structure, can enumerate: Li xMnPO 4And with the part of the Mn Li with other Transition metal substituted xMn yM 1-yPO 4The olivine-type lithium phosphate compound of (in the formula, x=0.02～1.2,0＜y＜1, M are selected from least a among Fe, Co, Ni, Cu, Mg, Zn, V, Ca, Sr, Ba, Ti, Al, Si, B and the Mo).
In these, particularly because the stripping of Mn ion causes the LiMnO with layer structure that circulation is deteriorated easily 2And substituent, has the LiMn of spinel structure 2O 4And substituent, most preferably has a LiMn of spinel structure 2O 4And substituent, because of its effect that improves secondary cell cycle characteristics of the present invention large.Among the present invention, also can use above-mentioned positive active material more than 2 kinds, in addition, contain the positive active material of manganese and do not contain the mixture of positive active material of manganese also harmless.Have, the content of manganese is more again, separates out by the dissolving of Mn ion to cause that circulation is deteriorated easilier, therefore, adopts the raising effect of cycle characteristics of anode of secondary cell of the present invention large.Among the present invention, the manganese content in the positive active material is preferably 10 ~ 80 quality %, more preferably 15 ~ 65 quality %.By the manganese content in the positive active material is set in above-mentioned scope, can present significantly the effect that captures manganese ion by the sour composition of adhesive of the present invention.
As the lithium-containing transition metal oxide of iron content, can enumerate: Li yFeXO 4(in the formula, X represents to be selected from least a element in the element of the 4th family of periodic table ~ the 7th family and the 14th family ~ the 17th family.Y is 0＜y＜2).
The lithium-containing transition metal oxide of above-mentioned iron content usually has element X and is positioned on the tetrahedron lattice-site, and lithium and iron are positioned at the structure on the octahedra lattice-site simultaneously.The structure of above-mentioned positive active material is when representing with lattice-site, with { X}[Li yFe] O 4Expression (in the formula, in { } in expression tetrahedron lattice-site, [] the octahedra lattice-site of expression), still, as the element X that gives such structure, preference is such as vanadium grade in an imperial examination 5 family's elements and phosphorus, arsenic, antimony, bismuth grade in an imperial examination 15 family's elements.
The lithium-containing transition metal oxide of above-mentioned iron content is preferably the olivine-type structure with the tightly packed oxygen atom skeleton of six sides, or has cube spinelle of tightly packed oxygen atom skeleton or an inverse spinel structure, is particularly preferably olivine-type structure.It is tightly packed or cube tightly packed that olivine-type structure and the difference that contains the spinel structure of inverse spinel are that oxonium ion is six sides, changes its rock-steady structure according to the kind of X element.For example: LiFePO 4Be stable olivine-type structure, and LiFeVO 4In become stable phase for inverse spinel structure.
Li with olivine-type structure or spinel structure yFeXO 4, can pass through the ammonium salt of mixed lithiated compound, divalent iron compound and element (X), then, firing to make under the non-active gas atmosphere gas or under the reduction atmosphere gas.As lithium compound, can enumerate Li 2CO 3, LiOH, LiNO 3Deng.
As the concrete example of the iron compound of divalent, can enumerate FeC 2O 42H 2O, Fe (CH 3COO) 2, FeCI 2Deng.As the concrete example of the ammonium salt of element (X), can enumerate (NH 4) 2HPO 4, NH 4H 2PO 4, (NH 4) 3PO 4Deng phosphate; NH 4HSO 4, (NH 4) 2SO 4In sulfate etc.
In addition, can also use the above-mentioned iron compound with NASICON type structure in addition as positive active material.As NASICON sections compound, concrete enumerates: by Li 2Fe 2-nV n(XO 4) 3The compound of (in the formula, 0≤n＜2, be preferably 0≤n≤1) expression.
In these, particularly consider from making well such this point of effect of the present invention that presents of electrode that uses the small particle diameter positive active material with qualification rate, more preferably the iron compound of olivine-type structure.
The amount of contained positive active material is preferably 80 ~ 99.5 quality % in the positive electrode active material layer of anode of secondary cell of the present invention, more preferably 90 ~ 99 quality %.When the amount of positive active material surpasses 99.5 quality %, the ratio of the adhesive in the positive electrode active material layer and conductivity imparting agent diminishes, therefore, there are positive active material caking property each other and the situation that the caking property of positive active material and following collector body descends and the power characteristic of battery also descends.In addition, when the amount of positive active material is lower than 80 quality %, have the situation that battery capacity descends.
The particle diameter of contained positive active material (average grain diameter) is preferably 0.01 ~ 10 μ m in the positive electrode active material layer of anode of secondary cell of the present invention, more preferably 0.02 ~ 5 μ m.When the particle diameter of positive active material surpassed 10 μ m, the dispersiveness in the slurry descended, and is difficult to make good slurry.In addition, when the particle diameter of positive active material was lower than 0.01 μ m, the conductivity that has active material descended, the large situation of internal electrical resistive of battery.
(fibrous carbon)
The present invention uses fibrous carbon.By using fibrous carbon, can improve the toughness of positive electrode active material layer, therefore the generation of positive electrode active material layer be full of cracks can be prevented, and positive electrode active material layer can be thickened.Consequently, can improve the fail safe of the secondary cell that has used anode of secondary cell of the present invention.
Used fibrous carbon among the present invention is so long as fibrously just can bring into play effect of the present invention, but when the fibre diameter of fibrous carbon was excessive, it is large that the space in the electrode becomes, and can not improve electrode density, therefore not preferred.In addition, when fibre diameter is too small, bury between active material particle, can not form the grid in the electrode, in addition, can not generate the space between active material, therefore not preferred.In view of above reason, can be used for the fiber diameter of the fibrous carbon of anode of secondary cell of the present invention, be preferably 0.01 ~ 1.0 μ m, more preferably 0.01 ~ 0.2 μ m.Fiber diameter by using fibrous carbon is at the fibrous carbon of above-mentioned scope, can improve following anode of secondary battery with the dispersion stabilization of slurry, and can make the secondary cell of high power capacity.
The preferred high person of the degree of crystallinity of fibrous carbon (so-called degree of graphitization).Usually the degree of graphitization of material with carbon element is higher, and layer structure reaches all the more, becomes harder, in addition, can also improve conductivity, therefore, is suitable for the use of anode of secondary cell.During with the material with carbon element graphitization, usually so long as at high temperature process and get final product, as the treatment temperature of this moment, according to the difference of used fibrous carbon and difference is still preferred more than 2000 ℃, further preferred more than 2500 ℃.In addition, in this case, before heat treatment, interpolation can promote effectively that the graphitization co-catalyst boron of degree of graphitization and Si etc. are effective.The addition of co-catalyst is not particularly limited, but addition does not have effect when very few, and is residual as impurity in the time of too much, therefore not preferred.Preferred addition is 0.1 ~ 100000ppm, more preferably 10 ~ 50000ppm.
The degree of crystallinity of these fibrous carbons is not particularly limited, still, and by the centre plane interval d of X-ray diffraction method 002Be preferably below the 0.344nm, more preferably below the 0.339nm, the axial thickness Lc of the C of crystal is below the 40nm.
The fibre length of fibrous carbon is longer, and conductivity, the intensity of electrode, the electrolyte that more can increase in the electrode are protected fluidity, and is therefore preferred, but when long, the fiber dispersion in the electrode is impaired, and is therefore not preferred.The scope of average fiber length, different because of kind and the fibre diameter of used fibrous carbon, but be preferably 0.5 ~ 100 μ m, more preferably 1 ~ 50 μ m.The preferable range of average fiber length during with mean aspect ratio (with respect to the ratio of the average fiber length of fiber diameter) expression, is preferably 5 ~ 50000 scope, more preferably 10 ~ 15000 scope.Average fiber length by using fibrous carbon and mean aspect ratio are at the fibrous carbon of above-mentioned scope, the following anode of secondary battery dispersion stabilization of slurry can be improved, and be full of cracks and the further effect that improves as the conductive path in the positive electrode active material layer of positive electrode active material layer can be effectively suppressed.
When containing the structure of branched (branched) in the fibrous carbon, all conductivity, the intensity of electrode, the electrolyte guarantor fluidities of electrode further increase, and are therefore preferred.But when branched fiber is too much, and fibre length is same, dispersed impaired in the electrode, and therefore, preferably the ratio with appropriateness contains.The ratio of these branched fibers can be controlled by manufacture method and subsequent pulverization process degree.
The manufacture method of fibrous carbon is not particularly limited, can enumerate the precursor that is consisted of by macromolecule and the pitch of spinned fiber shape such as: heat treated method, and with the direct jet of the organic steams such as benzene on the substrate about 1000 ℃, with iron granules etc. as the grow up method (chemical vapour deposition) etc. of carbon crystal of catalyst.
The content of fibrous carbon reaches the as required total amount of the tackifier of cooperation with respect to positive active material, adhesive, is preferably 0.05 ~ 20 quality %, and more preferably 0.1 ~ 15 quality % is particularly preferably 0.5 ~ 10 quality %.When content surpassed 20 quality %, the active material ratio in the electrode diminished, so battery capacity diminishes.When content is lower than 0.05 quality %, be difficult to suppress the generation of the be full of cracks of electrode.For content being adjusted to above-mentioned scope, in the method for making by carrying out to add in proportion.
In order to control the dispersity of fibrous carbon in electrode, also can use surface treatment fibrous carbon.The surface-treated method is not particularly limited, but can enumerate, and imports oxygen-containing functional group by oxidation processes, and modulation becomes hydrophilic method, and becomes hydrophobic method by fluorination treatment and silicon processing modulation.In addition, also can enumerate the coating of phenolic resins etc. and mechanochemistry processing etc.When excessively carrying out surface treatment, the conductivity of fibrous carbon and intensity are significantly impaired, therefore are necessary for the processing of appropriateness.Oxidation processes, can be by for example: with fibrous carbon in air, 500 ℃ of lower heating carried out in about 1 hour.Process the hydrophily that improves fibrous carbon by this.
(adhesive)
Contain in the adhesive of anode of secondary cell of the present invention (methyl) acrylate monomer polymerized unit, have polymerized unit and the α of the vinyl monomer of sour composition, the polymerized unit of alpha, beta-unsaturated nitriles monomer.Particularly, it is characterized in that, in the polymer as above-mentioned adhesive, contain above-mentioned each polymerized unit.
As the polymerized unit of (methyl) acrylate monomer among the present invention, can enumerate: the alkyl acrylates such as methyl acrylate, ethyl acrylate, acrylic acid n-propyl, isopropyl acrylate, n-butyl acrylate, tert-butyl acrylate, acrylic acid pentyl ester, Hexyl 2-propenoate, acrylic acid heptyl ester, 2-ethyl hexyl acrylate, 2-EHA, acrylic acid ester in the ninth of the ten Heavenly Stems, decyl acrylate, lauryl acrylate, acrylic acid n-tetradecane base ester, stearyl acrylate acyl ester; Methyl methacrylate, EMA, n propyl methacrylate, isopropyl methacrylate, n-BMA, Tert-butyl Methacrylate, the methacrylic acid pentyl ester, hexyl methacrylate, the metering system heptyl heptylate, 2-Propenoic acid, 2-methyl-, octyl ester, 2-Ethylhexyl Methacrylate, nonyl methacrylate, decyl-octyl methacrylate, lauryl methacrylate, methacrylic acid n-tetradecane base ester, the alkyl methacrylates such as methacrylic acid stearoyl ester.In these, from insoluble parsing electrolyte, and show the conductivity of the lithium ion that causes by the swelling to the appropriateness of electrolyte, be difficult in addition cause in the dispersion of active material owing to consider aspect the crosslinked aggegation that polymer causes, be preferably the acrylic acid heptyl ester of the alkyl acrylate of the carbon number 7 ~ 13 that is bonded to the alkyl on the non-carbonyl oxygen atom, 2-ethyl hexyl acrylate, 2-EHA, acrylic acid ester in the ninth of the ten Heavenly Stems, decyl acrylate, lauryl acrylate more preferably is bonded to the 2-ethyl hexyl acrylate of the carbon number 8 ~ 10 of the alkyl on the non-carbonyl oxygen atom, 2-EHA, acrylic acid ester in the ninth of the ten Heavenly Stems.
As the preferred exemplary of the polymerized unit of the vinyl monomer with sour composition among the present invention, can enumerate: have-monomer of COOH base (carboxylic acid group), have-monomer of OH base (hydroxyl), have-SO 3The monomer of H base (sulfonic group), have-PO 3H 2The monomer of base, have-PO (OH) (OR) base (R represents alkyl) monomer and have the monomer of rudimentary polyoxy alkylidene.
As the monomer with carboxylic acid group, can enumerate: monocarboxylic acid and derivative thereof and dicarboxylic acids and acid anhydrides thereof and these derivative etc.As monocarboxylic acid, can enumerate: acrylic acid, methacrylic acid, butenoic acid etc.As the monocarboxylic acid derivative, can enumerate: 2-ethylacrylic acid, methacrylate, α-acetoxy group acrylic acid, β-trans aryloxy group acrylic acid, α-chloro-β-E-methoxy acrylic acid, β-diaminourea acrylic acid etc.As dicarboxylic acids, can enumerate: maleic acid, fumaric acid, itaconic acid etc.As the acid anhydrides of dicarboxylic acids, can enumerate: maleic anhydride, acrylic anhydride, methyl maleic anhydride, dimethyl maleic anhydride etc.As dicarboxylic acid derivatives, can enumerate: the maleates such as the maleic acid methyl allyl esters such as maleic acid methyl esters, dimethyl maleate, phenyl maleic acid, chloromaleic acid, dichloro-maleic acid, fluoro maleic acid, maleic acid diphenyl ester, maleic acid ester in the ninth of the ten Heavenly Stems, maleic acid ester in the last of the ten Heavenly stems, maleic acid dodecyl ester, maleic acid stearyl, maleic acid fluoroalkyl.
As the monomer with hydroxyl, can enumerate: the ethene unsaturated alcohols such as (methyl) allyl alcohol, 3-butene-1-ol, 5-hexen-1-ol; The alkane alkoxide of the ethene unsaturated carboxylic acids such as 2-Hydroxy ethyl acrylate, 2-hydroxypropyl acrylate, methacrylic acid-2-hydroxy methacrylate, methacrylic acid-2-hydroxy propyl ester, maleic acid two-2-hydroxy methacrylate, maleic acid two-4-hydroxyl butyl ester, itaconic acid two-2-hydroxy propyl ester; General formula CH 2=CR 1-COO (C nH 2nO) m(m represents that 2 ~ 9 integer, n represent 2 ~ 4 integer, R to-H 1Expression hydrogen atom or methyl) represented PAG and (methyl) acrylic acid ester class; List (methyl) esters of acrylic acid of the dihydroxy ester of 2-hydroxyethyl-2 '-(methyl) acryloxy phthalic acid ester, 2-hydroxyethyl-2 '-dicarboxylic acids such as (methyl) acryloxy succinate; The vinyl ethers such as 2-hydroxyethyl vinyl ethers, 2-hydroxypropyl vinyl ethers; List (methyl) allyl ether series of the aklylene glycol of (methyl) pi-allyl-2-hydroxyl ether, (methyl) pi-allyl-2-hydroxyl propyl ether, (methyl) pi-allyl-3-hydroxyl propyl ether, (methyl) pi-allyl-2-hydroxyl butyl ether, (methyl) pi-allyl-3-hydroxyl butyl ether, (methyl) pi-allyl-4-hydroxyl butyl ether, (methyl) pi-allyl-6-hydroxyl hexyl ether etc.; Polyether polyols (methyl) the mono allyl ether classes such as diethylene glycol list (methyl) allyl ether, DPG list (methyl) allyl ether; Glycerol list (methyl) allyl ether, (methyl) pi-allyl-2-chloro-3-hydroxyl propyl ether, (methyl) pi-allyl-2-hydroxyl-halogen of (gathering) aklylene glycols such as 3-chloro propyl ether and list (methyl) allyl ether of hydroxyl substituent; (methyl) allyl ether such as the list of the polyhydric phenols of eugenol, isoeugenol etc. and halogen substituent thereof; (methyl) allyl sulfide ethers of the aklylene glycol of (methyl) pi-allyl-2-hydroxyethyl thioether, (methyl) pi-allyl-2-hydroxypropyl thioether etc.; Deng.
As having sulfonic monomer, can enumerate: vinyl sulfonic acid, methyl ethylene sulfonic acid, (methyl) allyl sulphonic acid, styrene sulfonic acid, (methyl) acrylic acid-2-sulfonic acid ethyl ester, 2-acrylamide-2-methyl propane sulfonic, 3-allyloxy-2-hydroxy-propanesulfonic acid etc.
As having-PO 3H 2The base and/or-PO (OH) (OR) base (R represents alkyl) monomer, can enumerate: phosphoric acid-2-(methyl) acryloxy ethyl ester, phosphoric acid methyl-2-(methyl) acryloxy ethyl ester, phosphoric acid ethyl-(methyl) acryloxy ethyl ester etc.
As the monomer with rudimentary polyoxy alkylidene, can enumerate: poly-(epoxides) of poly-(oxirane) etc. etc.
In these, excellent and effectively capture well dissolving is separated out from positive active material manganese ion or the reason consideration of iron ion from the adaptation of so-called and following collector body, the monomer that preferably has the carboxylic acid group, wherein, preferably have acrylic acid, methacrylic acid etc. the carboxylic acid group of carbon number below 5 monocarboxylic acid and have the carboxylic acid groups of carbon number below 5 such as 2 maleic acids, itaconic acid dicarboxylic acids.And then, consider preferred acrylic acid and methacrylic acid from the viewpoint that the storage stability of the adhesive of so-called making is high.
As the α among the present invention, the polymerized unit of alpha, beta-unsaturated nitriles monomer is considered from the viewpoint of so-called raising mechanical strength and cohesive force, preferred acrylonitrile and methacrylonitrile.
Among the present invention, containing of the polymerized unit of (methyl) acrylate monomer in the adhesive (below, sometimes be expressed as " composition A ") is proportional, is preferably 50 ~ 95 quality %, more preferably 60 ~ 90 quality %.In addition, α, containing of the polymerized unit of alpha, beta-unsaturated nitriles monomer (below, sometimes be expressed as " composition B ") is proportional, is preferably 3 ~ 40 quality %, more preferably 5 ~ 30 quality %.In addition, have the vinyl monomer of sour composition polymerized unit (below, sometimes be expressed as " composition C ") contain proportional to be 1.0 ~ 3.0 quality %, to be preferably 1.5 ~ 2.5 quality %.Containing of composition A is proportional when surpassing 95 quality %, and the mechanical strength of adhesive descends.In addition, containing of composition A is proportional when being lower than 50 quality %, and the flexibility of adhesive descends, and therefore the electrode hardening is difficult to prevent the generation of chapping.Containing of composition B is proportional when surpassing 40 quality %, and the flexibility of adhesive descends, and therefore the electrode hardening is difficult to prevent the generation of chapping.In addition, containing of composition B is proportional when being lower than 3 quality %, and the mechanical strength of adhesive descends, and the adaptation of electrode descends.When the content of composition C surpassed 3.0 quality %, the manufacturing stability of adhesive and storage stability descended.In addition, containing of composition C is proportional when being lower than 1.0 quality %, and be not enough as the caking property of adhesive, and the life characteristic of battery descends.
The adhesive that uses among the present invention preferably also contains above-mentioned composition A, the polymerized unit with bridging property beyond the composition B, composition C.As the method that in above-mentioned adhesive, imports the polymerized unit with bridging property, can enumerate: the method for the crosslinkable groups of the method for the crosslinkable groups of lead-in light bridging property and importing heat cross-linking in adhesive.In these, in adhesive, import the method for the crosslinkable groups of heat cross-linking, can make adhesive crosslinked by after the pole plate coating, pole plate being carried out heat treated, and can suppress dissolving to electrolyte, can obtain tough and soft pole plate, and can improve the life characteristic of battery, therefore preferred.When in adhesive, importing the crosslinkable groups of heat cross-linking, has following method: use method and the use of the simple function monomer with the two keys of 1 alkene of the crosslinkable groups with heat cross-linking to have the method for the two multi-functional monomers of key of at least 2 alkene.Crosslinkable groups as heat cross-linking contained in the simple function monomer with the two keys of 1 alkene, be preferably selected from by epoxy radicals, N-methylol amide base, oxetanyl Ji at least a in the group that oxazolinyl consists of, epoxy radicals is regulated this point consideration easily from crosslinked and crosslink density, is preferred.
As the monomer with epoxy radicals.Can enumerate: contain the monomer of carbon-to-carbon double bond and epoxy radicals and contain halogen atom and the monomer of epoxy radicals.
As the monomer that contains carbon-to-carbon double bond and epoxy radicals, can enumerate such as the unsaturated glycidyl ether of vinyl glycidyl ether, allyl glycidyl ether, cyclobutenyl glycidol ether, o-allyl base glycidol ether etc.; Butadiene monoepoxide, chlorobutadiene monoepoxide, 4,5-epoxy-2-amylene, 3,4-epoxy-1-VCH, 1,2-epoxy-5,9-encircle the diene of 12 carbon diene etc. or the monoepoxide of polyenoid; 3,4-epoxy-1-butylene, 1,2-epoxy-5-hexene, 1, the alkenyl epoxides of 2-Huan Yang ー 9-decene etc.; The ethylene oxidic ester class of the unsaturated carboxylic acid of the ethylene oxidic ester of glycidyl acrylate, glycidyl methacrylate, butenoic acid ethylene oxidic ester, glycidol-4-heptenoic acid ethyl ester, sorbic acid ethylene oxidic ester, linoleic acid ethylene oxidic ester, glycidol-4-methyl-3-heptenoic acid ethyl ester, 3-cyclohexene carboxylate, the ethylene oxidic ester of 4-methyl-3-cyclohexene carboxylate etc.
As the monomer with halogen atom and epoxy radicals, can enumerate such as the epoxyhalopropane of epoxychloropropane, epoxy bromopropane, epoxy iodopropane, epoxy fluoro-propane, β methyl epoxy chloropropane etc.; To the chlorostyrene oxide; The dibromo phenyl glycidol ether.
As the monomer that contains N-methylol amide base, can enumerate: (methyl) acrylic amide with methylol of N-methylol (methyl) acrylamide etc.
As the monomer that contains oxetanyl, can enumerate: 3-((methyl) acryloyl-oxy ylmethyl) oxetanes, 3-((methyl) acryloyl-oxy ylmethyl)-2-trifluoromethyl oxetanes, 3-((methyl) acryloyl-oxy ylmethyl)-2-phenyl oxetanes, 2-((methyl) acryloyl-oxy ylmethyl) oxetanes, 2-((methyl) acryloyl-oxy ylmethyl)-4-trifluoromethyl oxetanes etc.
As the monomer of Han You oxazolinyl, 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, 2-isopropenyl-5-ethyl-2-oxazoline etc.
As the multi-functional monomer with the two keys of at least 2 alkene, preferred allyl acrylate or allyl methacrylate, trimethylolpropane-triacrylate, trimethylolpropane-methacrylate, the DPG diallyl ether, the polyethylene glycol diallyl ether, the triethylene glycol divinyl ether, the hydroquinones diallyl ether, the pi-allyl of other of tetraallyl hydroxyl ethane or multi-functional alcohol or vinyl ethers, tetraethylene glycol diacrylate, triallylamine, trimethylolpropane-diallyl ether, methylene diacrylamine and/or divinylbenzene.Can enumerate particularly allyl acrylate, allyl methacrylate, trimethylolpropane-triacrylate and/or trimethylolpropane-methacrylate etc.
In these, improving easily this point from crosslink density considers, the multi-functional monomer that preferably has the two keys of at least 2 alkene, have again, consider that from crosslink density height and the high viewpoint of combined polymerization preferred allyl acrylate or allyl methacrylate etc. have allylic acrylate or methacrylate.
Containing of the crosslinkable groups of the heat cross-linking in the adhesive is proportional, and the monomer of the crosslinkable groups that contains heat cross-linking during as polymerization is preferably 0.01 ~ 0.5 quality %, the scope of 0.3 ~ 0.05 quality % more preferably with respect to monomer total amount 100 quality %.Containing of the crosslinkable groups of the heat cross-linking in the adhesive is proportional, can be when making adhesive, by monomeric charge than being controlled.Containing of the crosslinking group of the heat cross-linking in the adhesive is proportional, in the time of in above-mentioned scope, can show the swelling with respect to electrolyte of appropriateness, can also show excellent speed characteristic and cycle characteristics.
Used adhesive among the present invention also can contain other the polymerized unit beyond the above-mentioned composition.So-called other polymerized unit is the polymerized unit from other vinyl monomer, for example, as can with the monomer of these combined polymerizations, can enumerate: ethylene glycol dimethacrylate, diethylene glycol dimethylacrylate etc. has the carboxylic acid esters of 2 above carbon-to-carbon double bonds; Vinyl chloride, vinylidene chloride etc. contain the monomer of halogen atom; The vinyl esters such as vinyl acetate, propionate, vinyl butyrate; The vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether; The vinyl ketones such as methyl vinyl ketone, ethyl vinyl ketone, butyl vinyl ketone, hexyl vinyl ketone, isopropenyl vinyl ketone; NVP, vinylpyridine, vinyl imidazole etc. contain the vinyl compound of heterocycle.
Used adhesive among the present invention uses under the state of the dispersion liquid in being scattered in dispersant or the solution of dissolving.Wherein consider from the reason of the swelling of so-called inhibition electrolyte, preferably in dispersant, disperse with the particle shape.
In the situation that adhesive disperses with the particle shape in dispersant, the average grain diameter (dispersion particle diameter) of the adhesive that disperses with the particle shape is preferably 50 ~ 500nm, and more preferably 70 ~ 400nm most preferably is 100 ~ 250nm.The average grain diameter of adhesive is when this scope, and it is good that the intensity of the electrode that obtains and flexibility become.In addition, as dispersant, can with an organic solvent reach water, still, wherein consider from the reason of so-called quickening rate of drying, preferably make water as dispersant.
In the situation that adhesive disperses with the particle shape in dispersant, the solid component concentration of dispersion liquid is generally 15 ~ 70 quality %, is preferably 20 ~ 65 quality %, more preferably 30 ~ 60 quality %.Solid component concentration is when this scope, and the operability when making following anode of secondary battery with slurry is good.
The glass transition temperature of used adhesive (Tg) is preferably-50 ~ 25 ℃ among the present invention, more preferably-45 ~ 15 ℃, be particularly preferably-40 ~ 5 ℃.Be set in above-mentioned scope by the Tg with adhesive, can obtain having excellent intensity and flexibility, and the electrode for secondary battery of high power characteristic.Need to prove that the glass transition temperature of adhesive can be regulated by making up various monomers.
Manufacture method to binder polymer used among the present invention is not particularly limited, and can adopt any methods such as solution polymerization process, suspension polymerization, mass polymerization, emulsion polymerization.As polymerization, can use any methods such as ionic polymerization, radical polymerization, active free radical polymerization.As polymerization initiator used in the polymerization, for example can enumerate: lauroyl peroxide, di-isopropyl peroxydicarbonate, peroxy dicarbonate two-2-Octyl Nitrite, the peroxidating trimethylace tonitric tert-butyl ester, 3,3, organic peroxide, the α such as 5-trimethyl acetyl peroxide, α '-azo-compound or ammonium persulfate, potassium peroxydisulfates etc. such as azodiisobutyronitrile.
For adhesive used among the present invention, used dispersant in these polymerizations, can for employed dispersant in usually synthesizing, as a specific example, can enumerate: the benzene sulfonates such as neopelex, dodecylphenyl ether sulfonic acid sodium; The alkyl sulfate such as lauryl sodium sulfate, sodium tetradecyl sulfate; The sulfosuccinates such as dioctyl sodium sulphosuccinate, dihexyl sodium sulfosuccinate; The soaps such as sodium laurate; The ethoxy sulfates such as sodium laureth sulfate salt, polyoxyethylene nonylplenyl ether sodium sulfate salt; Paraffin sulfonate; The alkyl ether phosphate sodium salt; The non-ionic emulsifiers such as polyoxyethylene nonylplenyl ether, polyoxyethylene sorbitol acid anhydride dodecyl ester, polyox-yethylene-polyoxypropylene block copolymer; Gelatin, maleic anhydride-styrene copolymers, PVP, Sodium Polyacrylate, the degree of polymerization are more than 700 and the water soluble polymer such as the polyvinyl alcohol of saponification degree more than 75% etc., and these both can use separately also and can more than 2 kinds and use.Be preferably the benzene sulfonates such as neopelex, dodecylphenyl ether sulfonic acid sodium in these; The alkyl sulfate such as lauryl sodium sulfate, sodium tetradecyl sulfate is considered from this point of so-called oxidative resistance excellence, more preferably the benzene sulfonate such as neopelex, dodecylphenyl ether sulfonic acid sodium.The addition of dispersant can at random be set, and is generally about 0.01 ~ 10 mass parts with respect to monomer total amount 100 mass parts.
PH when used adhesive is scattered in the dispersant among the present invention is preferably 5 ~ 13, and more preferably 5 ~ 12, most preferably be 10 ~ 12.Be set in above-mentioned scope by the pH with adhesive, can improve the storage stability of adhesive, also can improve mechanical stability.
The pH adjusting agent illustration of regulating adhesive pH has: the alkali metal hydroxides such as lithium hydroxide, NaOH, potassium hydroxide, the alkaline-earth metal hydroxide such as calcium hydroxide, magnesium hydroxide, barium hydroxide, aluminium hydroxide etc. belong to the hydroxide such as metal hydroxides that the IIIA in the long period rule table belongs to; The alkali carbonate such as sodium carbonate, potash, the carbonate such as the alkaline earth metals carbonates such as magnesium carbonate etc. as organic amine, can be enumerated: the alkyl amines such as ethamine, diethylamine, propylamine; The alcaminess such as single carbinolamine, monoethanolamine, single Propanolamine; The Ammonias such as ammoniacal liquor etc.In these, consider preferred alkali metal hydroxide, particularly preferably NaOH, potassium hydroxide, lithium hydroxide from the viewpoint of caking property and operability.
The content of the adhesive in the positive electrode active material layer is preferably 0.1 ~ 10 mass parts with respect to positive active material 100 mass parts, more preferably 0.5 ~ 5 mass parts.Be set in above-mentioned scope by the content with the adhesive in the anode of secondary battery, the caking property that positive active material reaches positive active material and collector body each other is excellent, in addition, can keep flexibility not hinder again that lithium ion moves and do not increase resistance.
Among the present invention in the used positive electrode active material layer, except mentioned component, other compositions such as conductivity is given material, reinforcing material, dispersant, levelling agent, antioxidant, tackifier, had the electrolysis additive that suppresses the functions such as electrolyte decomposition, other binding agent can also be contained, following anode of secondary battery can also be contained in in the slurry.These however bring impact just to be not particularly limited to cell reaction.
Give material as conductivity, can use the conductive carbon such as acetylene black, Ketjen black, carbon black, graphite.Can enumerate the fine wire of the carbon dusts such as graphite, various metals and paper tinsel etc.By using conductivity to give material, can improve electrode active material electrically contacting each other, particularly when being used for lithium rechargeable battery, can also improve discharge characteristics on load
As reinforcing material, can use various inorganic and organically spherical, sheet or bar-shaped fillers.By using reinforcing material, can obtain tough and soft electrode, and show excellent long-term cycle characteristics.Conductivity is given the consumption of material and reinforcing agent, is generally 0.01 ~ 20 mass parts with respect to positive active material 100 mass parts, is preferably 1 ~ 10 mass parts.Give material and reinforcing agent by the conductivity that contains in the above-mentioned scope, can show high capacity and high part throttle characteristics.
As dispersant, there can be exemplified: anionic property compound, cationic compound, nonionic compound, macromolecular compound.Dispersant can be given material according to used positive active material and conductivity and select.Containing of dispersant in the positive electrode active material layer is proportional, is preferably 0.01 ~ 10 quality %.Be set in above-mentioned scope by the amount with dispersant, can obtain following the positive pole excellent in stability of slurry and level and smooth electrode, and can show high battery capacity.
As levelling agent, can enumerate: the surfactants such as alkyls surfactant, silicon class surfactant, fluorine class surfactant, metal species surfactant.By mixing above-mentioned surfactant, not only can prevent the shrinkage cavity that when being coated on collector body on slurry following anode of secondary battery, occurs but also can improve the slickness of electrode.Levelling agent in the positive electrode active material layer contain proportional 0.01 ~ 10 quality % that is preferably.Productivity ratio in the time of can making electrode fabrication by levelling agent being set in above-mentioned scope, slickness and battery behavior are excellent.
As antioxidant, can enumerate: phenolic compound, hydroquinones compound, organic phosphorus compound, sulphur compound, phenylenediamine compound, polymer-type phenolic compound etc.The polymer-type phenolic compound is the polymer that has the phenol structure in the molecule, and preferably using weight average molecular weight is 200 ~ 1000, preferred 600 ~ 700 polymer-type phenolic compound.Containing of antioxidant in the positive electrode active material layer is proportional, is preferably 0.01 ~ 10 quality %, 0.05 ~ 5 quality % more preferably.By antioxidant being set in above-mentioned scope, can make following anodal stability with slurry, battery capacity and cycle characteristics excellent.
As tackifier, can enumerate: cellulosic polymer and their ammonium salt and the alkali metal salts such as carboxymethyl cellulose, methylcellulose, hydroxypropyl cellulose; (modification) poly-(methyl) acrylic acid and their ammonium salt and alkali metal salt; The polyvinyl alcohol of copolymer, maleic anhydride or the maleic acid of (modification) polyvinyl alcohol, acrylic acid or acrylates and vinyl alcohol or the copolymer of fumaric acid and vinyl alcohol etc.; Polyethylene glycol, poly(ethylene oxide), PVP, modified polyacrylic acid, oxidized starch, starch phosphate, casein, various modified starch, acrylonitrile-butadiene copolymer hydride etc.Among the present invention, " (modification) is poly-" implication is: " unmodified poly-" or " modification is poly-", " (methyl) acrylic acid " implication is: " acrylic acid " or " methacrylic acid ".Containing of tackifier in the positive electrode active material layer is proportional, is preferably 0.01 ~ 10 quality %.By tackifier being set in above-mentioned scope, make following anode of secondary battery become good with slurry to the coating of collector body.In addition, can make following anodal excellent dispersion with the active material in the slurry etc., thereby obtain level and smooth electrode, and show excellent part throttle characteristics and cycle characteristics.
Electrolysis additive can use following anode of secondary battery with employed vinylene carbonate in the slurry and in the electrolyte etc.Electrolysis additive in the positive electrode active material layer contain proportional 0.01 ~ 10 quality % that is preferably.By electrolysis additive being set in above-mentioned scope, can make cycle characteristics and hot properties excellent.In addition, also can enumerate: the nano-corpuscules such as gas silicon dioxide and gas aluminium oxide; The surfactants such as alkyls surfactant, silicon class surfactant, fluorine class surfactant, metal species surfactant.By mixing above-mentioned nano-corpuscule, can form the thixotropy of using slurry by control electrode, and then can improve thus the levelability of the electrode that obtains.Containing of nano-corpuscule in the positive electrode active material layer is proportional, is preferably 0.01 ~ 10 quality %.By nano-corpuscule being set in above-mentioned scope, can making Stability of Slurry, productivity ratio excellence, and show high battery behavior.By mixing above-mentioned surfactant, can improve secondary cell Zheng Very with the dispersiveness of the active material in the slurry etc., and then can improve thus the slickness of the electrode that obtains.Containing of surfactant in the positive electrode active material layer is proportional, is preferably 0.01 ~ 10 quality %.By surfactant being set in above-mentioned scope, can making following anode of secondary battery excellent with stability, the electrode slickness of slurry, and show high productivity ratio.
(collector body)
Collector body used among the present invention has conductivity, and get final product so long as have the material of electrochemistry durability, and be not particularly limited, still, consider that from having stable on heating viewpoint preference is such as metal materials such as iron, copper, aluminium, nickel, stainless steel, titanium, tantalum, gold, platinum.Wherein, as the positive electrode material of lithium rechargeable battery, particularly preferably aluminium.The shape of collector body is not particularly limited, but is preferably the sheet about thickness 0.001 ~ 0.5mm.In order to improve the adhesive strength of positive electrode active material layer, collector body preferably carries out using after the roughened processing in advance.As roughened method, can enumerate: mechanical milling method, electrolytic polishing method, chemical grinding method etc.In the mechanical milling method, use abrasive cloth paper, grinding stone, the emery wheel be fixed with abrasive particle, be equipped with the steel brush of steel wire etc. etc.In addition, for adhesive strength and the conductivity that improves positive electrode active material layer, can form the intermediate layer on the collector body surface.
As the method for manufacturing anode of secondary cell of the present invention, get final product so long as can at least one side of above-mentioned collector body, preferred two sides, positive electrode active material layer be bonded to the method for stratiform.For example: be coated on collector body on slurry following positive pole and carry out drying, then, form electrode in heat treated more than 120 ℃ more than 1 hour.Positive pole is not particularly limited with the method that slurry is coated on the collector body.Can enumerate such as: scrape the skill in using a kitchen knife in cookery, dipping (ジ Star プ) method, reverse roll rubbing method, direct methods such as rolling method, intaglio printing rubbing method, extrusion coated method, spread coating.As drying means, can enumerate the seasoning of shining such as: the drying by warm braw, hot blast, low wet wind, vacuumize, by (far) infrared ray and electron ray etc.
Secondly, preferably use moulding press and roll squeezer etc. to reduce the voidage of electrode by pressurized treatments.The preferred scope of voidage is 5 ~ 15%, more preferably 7 ~ 13%.When voidage was too high, charge efficiency and discharging efficiency were bad.Voidage is crossed when hanging down, and is difficult to obtain high volume capacity, can produce so-called electrode and peel off easily, occurs easily bad problem.Have again, when using the polymer of curing property, preferably be cured.
The thickness of anode of secondary cell of the present invention is generally 5 ~ 150 μ m, is preferably 10 ~ 100 μ m.By thickness of electrode being set in above-mentioned scope, can make part throttle characteristics and energy density show simultaneously high characteristic.
(anode of secondary battery slurry)
Used anode of secondary battery slurry among the present invention, comprise: contain manganese or iron positive active material and, fibrous carbon and, by the polymerized unit that contains (methyl) acrylate monomer, have polymerized unit and the α of the vinyl monomer of sour composition, the adhesive that the polymer of the polymerized unit of alpha, beta-unsaturated nitriles monomer consists of and, solvent.As positive active material, fibrous carbon and contain (methyl) acrylate monomer polymerized unit, have polymerized unit and the α of the vinyl monomer of sour composition, the adhesive of the polymerized unit of alpha, beta-unsaturated nitriles monomer can use above-mentioned substance.
(solvent)
As solvent, just be not particularly limited as long as adhesive used among the present invention can be dissolved equably or disperses.As positive pole used solvent in the slurry, can make any of water and organic solvent.As organic solvent, can enumerate: the annular aliphatic hydro carbons such as pentamethylene, cyclohexane; Toluene, dimethylbenzene, ethylbenzene etc. are aromatic hydrocarbon based; The ketones such as acetone, methylethylketone, diisobutyl acetone, cyclohexanone, hexahydrotoluene, ethyl cyclohexane; The chlorine class aliphatic hydrocarbons such as carrene, chloroform, carbon tetrachloride; The ester classes such as ethyl acetate, butyl acetate, gamma-butyrolacton, 6-caprolactone; The acyl cyanide such as acetonitrile, propionitrile (ア シ ロ ニ ト リ Le) class; The ethers such as oxolane, ethylene glycol diethyl ether: the alcohols such as methyl alcohol, ethanol, isopropyl alcohol, ethylene glycol, glycol monoethyl ether; The amide-type such as 1-METHYLPYRROLIDONE, DMF.These solvents can use separately also and can use as mixed solvent mixing more than 2 kinds.In these, especially for the solvent that excellent dispersion, boiling point are low, volatility is high of excellent dispersion, electrode active material and the conductivity imparting agent of adhesive of the present invention, can under short time and low temperature, remove, therefore preferred.Preferred acetone, toluene, cyclohexanone, pentamethylene, oxolane, cyclohexane, dimethylbenzene, water or 1-METHYLPYRROLIDONE or these mixed solvent.In addition, effect of the present invention can see when using water-dispersion type particle shape macromolecule as adhesive significantly, as solvent, and water particularly preferably.
Among the present invention used anode of secondary battery with the solid component concentration of slurry as long as for the degree that can be coated with, flood and the degree that can form the viscosity with flowability just are not particularly limited, still be generally about 10 ~ 80 quality %.
In addition, anode of secondary battery is with in the slurry, except the positive active material that contains manganese or iron and, fibrous carbon and, by the polymerized unit that contains (methyl) acrylate monomer, have polymerized unit and the α of the vinyl monomer of sour composition, the adhesive that the polymer that the polymerized unit of alpha, beta-unsaturated nitriles monomer forms consists of and, beyond the solvent, also contain other compositions such as electrolysis additive with functions such as suppressing dispersant and electrolyte decomposition that use in the above-mentioned anode of secondary cell.These however bring impact just to be not particularly limited to cell reaction.
(the anode of secondary battery method for making of slurry)
Among the present invention, anode of secondary battery is not particularly limited with the method for making of slurry, can obtain by other composition that mixes above-mentioned positive active material, fibrous carbon, adhesive and solvent and add as required.The mentioned component of the application of the invention is no matter mixed method and order by merging how, can obtain the positive pole slurry of positive active material and fibrous carbon high degree of dispersion.Mixing arrangement so long as the device that mentioned component can be mixed equably just be not particularly limited, can use ball mill, ball mill, roller mill, sand mill, Pigments machine, pulverizing mill, ultrasonic dispersing machine, homogenizer, planetary mixing roll, fill mixer (FILMICS) etc., but particularly preferably use ball mill, roller mill, Pigments machine, pulverizing mill, the planetary mixing roll that wherein can under high concentration, disperse.
Anodal viscosity with slurry is considered from the viewpoint of even coating, slurry ageing stability, is preferably 10 ~ 100000mPas, more preferably 100 ~ 50000mPas.The value of above-mentioned viscosity when using Brookfield viscometer under 25 ℃, revolution 60rpm, to measure.
(secondary cell)
Secondary cell of the present invention possesses positive pole, negative pole, dividing plate and electrolyte, above-mentioned just having collector body and a positive electrode active material layer, described positive electrode active material layer on collector body, and contain manganese or iron positive active material and, fibrous carbon and, above-mentioned adhesive consists of.
As above-mentioned secondary cell, can enumerate: lithium rechargeable battery, nickel-hydrogen secondary cell etc., but when considering as the performance raising aspects such as raising of the raising power characteristic of expecting long-term cycle characteristics most of purposes, the preferred lithium ion secondary battery.Below, situation about using for lithium rechargeable battery describes.
(electrolyte solution for lithium ion secondary battery)
The electrolyte of using as lithium rechargeable battery uses supporting electrolyte is dissolved in organic electrolyte in the organic solvent.As supporting electrolyte, can use lithium salts.As lithium salts, be not particularly limited, but can enumerate: LiPF 6, LiAsF 6, LiBF 4, LiSbF 6, LiAICI 4, LiCIO 4, CF 3SO 3Li, C 4F 9SO 3Li, CF 3COOLi, (CF 3CO) 2NLi, (CF 3SO 2) 2NLi, (C 2F 5SO 2) NLi etc.Wherein, preferably be dissolved in easily the high degree of dissociation of demonstration of solvent: LiPF 6, LiCIO 4, CF 3SO 3Li.These can will be used in combination more than two kinds.Use the higher supporting electrolyte of degree of dissociation more can improve the lithium ion conduction degree, therefore, can regulate the lithium ion conduction degree by the kind of supporting electrolyte.
Organic solvent as the electrolyte of using for lithium rechargeable battery, just be not particularly limited as long as can dissolve the solvent of supporting electrolyte, but the preferred carbonates such as dimethyl carbonate (DMC), ethylene carbonate (EC), diethyl carbonate (DEC), propylene carbonate (PC), butylene carbonate (BC), methyl ethyl carbonate (MEC) that use; The ester such as gamma-butyrolacton, methyl formate class; The ethers such as 1,2-dimethoxy-ethane, oxolane; The sulfur-containing compound such as sulfolane, dimethyl sulfoxide (DMSO) class.In addition, also can use the mixed liquor of these solvents.Wherein, the wide carbonates in current potential zone that preferred permittivity is high, stable.The viscosity of used solvent is lower, and the lithium ion conduction degree is higher, therefore, can by the kind of solvent, regulate the lithium ion conduction degree.
In addition, for above-mentioned electrolyte, also can use the electrolyte that contains additive.As additive, can enumerate above-mentioned anode of secondary battery with the compound of the carbonates such as employed vinylene carbonate (VC) in the slurry.
The concentration of the supporting electrolyte in the electrolyte that lithium rechargeable battery is used is generally 1 ~ 30 quality %, is preferably 5 ~ 20 quality %.In addition, according to the kind of supporting electrolyte, usually under the concentration of 0.5 ~ 2.5 mole/L, use.No matter the concentration of supporting electrolyte cross low or too high, the tendency that all can exist ionic conductivity to descend.
In addition, as electrolyte, can use the gelatinous polymer electrolyte and LiI, the Li that in the polymer dielectrics such as poly(ethylene oxide), polyacrylonitrile and above-mentioned polymer dielectric, have flooded electrolyte 3The inorganic solid electrolytes such as N.
(separator for lithium ion secondary battery)
As dividing plate, can use microporous barrier or the nonwoven fabrics of the polyolefin systems such as polyethylene, polypropylene; The porous resin that the contains inorganic ceramic powder known materials such as (コ-ト, coat) of filming.
As separator for lithium ion secondary battery, microporous barrier or the nonwoven fabrics that can use vistanexes such as containing polyethylene, polypropylene and aromatic polyamide resin to consist of; The known materials such as porous resin film that contain inorganic ceramic powder.Can enumerate such as the microporous barrier that consisted of by resins such as TPO (polyethylene, polypropylene, polybutene, polyvinyl chloride) and these mixture or copolymers; Fabric or its nonwoven fabrics that the microporous barrier that is made of resins such as PETG, poly-cycloolefin, polyether sulfone, polyamide, polyimides, polyimide amide, Nomex, poly-cycloolefin, nylon, polytetrafluoroethylene or TPO fiber are made into; The aggregation of insulating properties material particle etc.In these, improve active material ratio in the battery and the capacity of unit volume, the micro-porous film that is preferably consisted of by polyolefin resin in order to make all thickness attenuation of dividing plate.
The thickness of dividing plate is generally 0.5 ~ 40 μ m, is preferably 1 ~ 30 μ m, more preferably 1 ~ 10 μ m.When becoming this scope by the thickness that makes dividing plate, in the resistance decreasing that the battery inner route clapboard causes, the operability when making battery in addition is excellent.
(lithium ion secondary battery negative pole)
Lithium ion secondary battery cathode forms by collector body with at the negative electrode active material layer that the collector body superimposed layer contains negative electrode active material and adhesive.As adhesive and collector body, can enumerate material same in the explanation with anode of secondary cell.
(lithium ion secondary battery cathode active material)
As the electrode active material (negative electrode active material) that lithium ion secondary battery negative pole is used, can enumerate such as carbonaceous materials such as armorphous carbon, graphite, native graphite, meso carbon microballoon, pitch-based carbon fibers; The electroconductive polymers such as poly-acene etc.In addition, as negative electrode active material, can use metal and their alloys such as silicon, tin, zinc, manganese, iron, nickel; The oxide of above-mentioned metal or alloy and sulfate.In addition, also can use the lithium alloys such as lithium metal, Li-Al, Li-Bi-Cd, Li-Sn-Cd, lithium transition-metal nitride, silicon etc.Negative electrode active material also can use the material of giving material by the mechanically modifying method in surface attachment conductivity.The particle diameter of negative electrode active material is being taken into account the selection that suits under other constitutive requirements of battery, but, consider that from the viewpoint that improves the battery behaviors such as initial stage efficient, part throttle characteristics, cycle characteristics 50% volume accumulation particle diameter is generally 1 ~ 50 μ m, is preferably 15 ~ 30 μ m.
Containing of negative electrode active material in the negative electrode active material layer is proportional, is preferably 90 ~ 99.9 quality %, more preferably 95 ~ 99 quality %.Be set in above-mentioned scope by the content with the negative electrode active material in the negative electrode active material layer, both can show high capacity, can show high flexibility, caking property again.
For lithium ion secondary battery cathode, except mentioned component, can also contain the dispersant that uses in the above-mentioned anode of secondary cell and have other compositions such as electrolysis additive that suppress the functions such as electrolyte decomposition.These however bring the material of impact just to be not particularly limited to cell reaction.
(lithium ion secondary battery negative pole adhesive)
As the lithium ion secondary battery negative pole adhesive, be not particularly limited, can use known adhesive.Can use such as the soft polymer such as the resin such as polyethylene, polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), tetrafluoraoethylene-hexafluoropropylene copolymer (FEP), polyacrylic acid derivative, polyacrylonitrile derivative and acrylic compounds soft polymer, dienes soft polymer, olefines soft polymer, vinyl-based soft polymer.These both can use separately also and can more than 2 kinds and use.
As collector body, can use the collector body that in stating anode of secondary cell, uses, so long as have conductivity and can and be not particularly limited at the material that electrochemistry has a durability, but as negative pole time spent of lithium rechargeable battery, particularly preferably copper.
The thickness of lithium ion secondary battery negative pole is generally 5 ~ 300 μ m, is preferably 10 ~ 250 μ m.By thickness of electrode being set in above-mentioned scope, can make part throttle characteristics and energy density show simultaneously high characteristic.
Lithium ion secondary battery negative pole can carry out same operation with above-mentioned lithium ion secondary battery positive electrode and make.
Concrete manufacture method as lithium rechargeable battery, can enumerate following method: will be between positive pole and negative pole get involved dividing plate and overlap, according to cell shapes with its coiling, folding etc., then, put into battery case, in battery case, inject electrolyte and seal ロ.Can be as required, put into element that metal lath and fuse, PTC element etc. prevent overload current, lead plate etc. and prevent that cell internal pressure from rising and crossing and discharge and recharge.The shape of battery can be in Coin shape, button type, sheet type, column type, square, platypelloid type etc. any.
Embodiment
Below, enumerate embodiment the present invention is described, but the present invention is not limited to these embodiment.In addition, part and % in the present embodiment are not having to be quality criteria in the situation about specifying.In embodiment and the comparative example, various physical property are estimated by following mode.
＜battery behavior: high-temperature cycle 〉
With 10 Coin-shaped batteries that fill up electrolyte, under 60 ℃ of atmosphere gas, adopt 0.2C to decide current method, charge to 4.3V, be discharged to 3.0V, repeatedly discharge and recharge, measure capacitance.As measured value, the charge/discharge capacity conservation rate of the ratio (%) of the capacitance the when capacitance when obtaining 50 loop terminations and 5 loop terminations expression with its metewand as cycle characteristics, is estimated with following benchmark with 10 mean values.This value is higher, and high-temperature cycle is more excellent.
More than the A:80%
B:70% is above and be lower than 80%
C:50% is above and be lower than 70%
D:30% is above and be lower than 50%
E: be lower than 30%
＜adhesive properties: storage stability 〉
With the aqueous dispersions of the polymer that obtains, preserve in sombre dark place that (weight of the aqueous dispersions before will preserving was set as a) in 50 days.Will be through the aqueous dispersions of the polymer after 50 days, sieve with 200 mesh sieve holes filters, obtain the dry weight (weight of residue is set as b) of solids residual on the sieve, obtain the ratio (%) of the dry weight (b) of solids residual on the weight (a) of the aqueous dispersions before preserving and the sieve, with its metewand as the storage stability of adhesive, estimate with following benchmark.This value is less, and the storage stability of adhesive is more excellent.
A: be lower than 0.001%
B:0.001% is above and be lower than 0.01%
C:0.01% is above and be lower than 0.1%
More than the D:0.1%
＜electrode characteristic: be full of cracks is measured 〉
Electrode is cut into the rectangle of fabric width 3cm * length 9cm, make test piece.Facing down of the current collection side of test piece places on the kitchen table, on the face on the central authorities (from the position of end 4.5cm) of length direction, current collection side along the stainless steel bar of fabric width direction landscape configuration diameter 1mm.As the center, the mode that becomes the outside with active material layer is converted into 180 ° with test piece with this stainless steel bar.10 pieces of test pieces are tested, observed flawless is arranged or the peeling off of dogleg section of the active material layer of each test piece, judge by following benchmark.Crackle or peel off fewlyer, the generation of electrode be full of cracks is fewer, and fail safe is more excellent.
All can't see crackle in A:10 piece or peel off
See crackle is arranged or peeling off for 1 ~ 3 piece in B:10 piece
See crackle is arranged or peeling off for 4 ~ 9 pieces in C:10 piece
All see crackle in D:10 piece or peel off
(embodiment 1)
(A) manufacturing of adhesive
In polymerization tank A, add 10.75 parts of 2-EHAs, 1.25 parts of acrylonitrile, 0.12 part of lauryl sodium sulfate, 79 parts of ion exchange waters, then, adding is as 0.2 part of the ammonium persulfate of polymerization initiator, 10 parts of ion exchange waters, heat to 60 ℃ and stir 90 minutes after, in another polymerization tank B, add 67 parts of 2-EHAs, 19 parts of acrylonitrile, 2.0 parts of methacrylic acids, 0.7 part of lauryl sodium sulfate, 46 parts of ion exchange waters also stir, after the emulsion of making being placed about 180 minutes and from polymerization tank B, adding to one by one among the polymerization tank A, stir about 120 minutes, when reaching 95%, monomer consumption cools off and cessation reaction, with the 4%NaOH aqueous solution regulate pH value, obtain the aqueous dispersions of adhesive A thereafter.The glass transition temperature of the adhesive A that obtains is-32 ℃, and disperseing particle diameter is 0.15 μ m, and the pH value of the aqueous dispersions of adhesive A is 10.5.The aqueous dispersions that use obtains is estimated the table 1 that the results are shown in of adhesive storage stability.
The polymerized unit of (methyl) acrylate monomer in the adhesive A to contain proportional be 78%, have sour composition vinyl monomer polymerized unit to contain proportional be 2.0%, α, the polymerized unit of alpha, beta-unsaturated nitriles monomer to contain proportional be 20%, have bridging property polymerized unit to contain proportional be 0%.
(B) anodal with slurry and anodal manufacturing
Will be as the LiFePO of the olivine-type crystal structure of electrode active material 4(particle diameter: (fiber diameter: 150nm, average fiber are long: 8 μ m, mean aspect ratio: 53, following sometimes be recited as " carbon fiber 1 " for 0.2 μ m) 100 parts, carbon fiber.) 1 part, acetylene black (HS-100: electrochemical industry) 5 parts, the aqueous dispersions of above-mentioned adhesive A 2.5 parts (solid component concentration 40%), be 0.8 40 parts (solid component concentrations 2%) of carboxymethyl cellulose aqueous solution and an amount of water as the degree of etherification falling of tackifier, in planetary mixing roll, stir, make the positive pole slurry.With above-mentioned positive pole slurry, be coated with the aluminium foil of spot printing machine at thickness 20 μ m, dried thickness is become about 70 μ m, at 60 ℃ after lower dry 20 minutes, 150 ℃ of lower heat treated 2 hours, obtain electrode blank.With the roll squeezer roller this electrode blank is rolled, making density is 2.1g/cm 3And the THICKNESS CONTROL that is made of aluminium foil and electrode active material layer is at the anode plate of 65 μ m.The mensuration that the pole plate that use is made chaps and occurs.Show the result in table 1.
(C) making of battery
Above-mentioned anode plate is die-cut into the discoid of diameter 16mm, in this anodal active material aspect side, carry out after the lamination successively the dividing plate that the discoid polypropylene of diameter 18mm, thickness 25 μ m perforated membrane processed is consisted of, lithium metal, the expanding metal of using as negative pole, places it in the outer packaging container of Coin shape (diameter 20mm, highly 1.8mm, stainless steel thickness 0.25mm) of the stainless steel that has disposed polypropylene packaging material processed.In this container, there is not the mode of air to inject electrolyte with residual, by polypropylene packaging material processed, outside on the packaging container, the stainless cover of thickness 0.2mm and fixing on the cover, the sealed cell tank is made the lithium ion Coin-shaped battery of diameter 20mm, the about 2mm of thickness.Need to prove, as electrolyte, use in the mixed solvent that ethylene carbonate (EC) and diethyl carbonate (DEC) mix with the ratio of EC:DEC=1:2 (volumetric ratios under 20 ℃), dissolve LiPF with the concentration of 1 mol/L 6The solution that forms.Use this cell evaluation high-temperature cycle.To the results are shown in table 1.
(embodiment 2)
(A) manufacturing of adhesive
In polymerization tank A, add 10.75 parts of 2-EHAs, 1.25 parts of acrylonitrile, 0.12 part of lauryl sodium sulfate, 79 parts of ion exchange waters, add again as 0.2 part of the ammonium persulfate of polymerization initiator, 10 parts of ion exchange waters, heat to 60 ℃ and stir 90 minutes after, in another polymerization tank B, add 67 parts of 2-EHAs, 19 parts of acrylonitrile, 2.0 parts of methacrylic acids, 0.2 part of metering system allyl ester, 0.7 part of lauryl sodium sulfate, 46 parts of ion exchange waters also stir, after the emulsion of making being placed about 180 minutes and from polymerization tank B, adding to one by one among the polymerization tank A, stir about 120 minutes, when reaching 95%, monomer consumption cools off and cessation reaction, thereafter, regulate the pH value with the 4%NaOH aqueous solution, obtain the aqueous dispersions of adhesive B.The glass transition temperature of the adhesive B that obtains for-32 ℃, to disperse particle diameter be that the pH value of the aqueous dispersions of 0.15 μ m, adhesive B is 10.1.The aqueous dispersions that use obtains is estimated the table 1 that the results are shown in of adhesive storage stability.The polymerized unit of (methyl) acrylate monomer among the adhesive B to contain proportional be 78%, have sour composition vinyl monomer polymerized unit contain proportionally be 2.0%, α, the polymerized unit of alpha, beta-unsaturated nitriles monomer to contain proportional be 20%, have bridging property polymerized unit to contain proportional be 0.2%.
Except the aqueous dispersions that uses above-mentioned adhesive B as positive pole with the adhesive, operate similarly to Example 1, make anode plate, lithium ion Coin-shaped battery.Then, be full of cracks and the use lithium ion Coin-shaped battery of measuring this pole plate are estimated high-temperature cycle.To the results are shown in table 1.
(embodiment 3)
Except using 1 part of fiber diameter: 50nm, average fiber length as carbon fiber: 1 μ m, mean aspect ratio: 20 carbon fiber (below, sometimes be recited as " carbon fiber 2 ") substitute beyond the carbon fiber 1, operate similarly to Example 1, make anode plate, lithium ion Coin-shaped battery.Then, be full of cracks and the use lithium ion Coin-shaped battery of measuring this pole plate are estimated high-temperature cycle.To the results are shown in table 1.
(embodiment 4)
Except using 1 part to be fiber diameter: 500nm, average fiber length as carbon fiber: 100 μ m, mean aspect ratio: 200 carbon fiber (below, sometimes be recited as " carbon fiber 3 ") substitute beyond the carbon fiber 1, operate similarly to Example 1, make anode plate, lithium ion Coin-shaped battery.Then, be full of cracks and the use lithium ion Coin-shaped battery of measuring this pole plate are estimated high-temperature cycle.To the results are shown in table 1.
(embodiment 5)
Except the use umber with carbon fiber 1 is set as 5 parts, operate similarly to Example 1, make anode plate, lithium ion Coin-shaped battery.Then, be full of cracks and the use lithium ion Coin-shaped battery of measuring this pole plate are estimated high-temperature cycle.To the results are shown in table 1.
(embodiment 6)
The use umber of carbon fiber 1 is set as 8 parts, in addition carries out similarly operating with embodiment 1, make anode plate, lithium ion Coin-shaped battery.Then, be full of cracks and the use lithium ion Coin-shaped battery of measuring this pole plate are estimated high-temperature cycle.To the results are shown in table 1.
(embodiment 7)
Use spinel manganese (LiMn as positive active material 2O 4Mn content 60%, average grain diameter 8 μ m) LiFePO of 100 parts of alternative olivine-type crystal structures 4, in addition, operate similarly to Example 1, make anode plate, lithium ion Coin-shaped battery.Then, be full of cracks and the use lithium ion Coin-shaped battery of measuring this pole plate are estimated high-temperature cycle.To the results are shown in table 1.Need to prove that the density of the positive electrode active material layer of this moment is set as 2.5g/cm 3
(embodiment 8)
Except using the aqueous dispersions of adhesive B to substitute the aqueous dispersions of adhesive A as anodal with adhesive, operate similarly to Example 7, make anode plate, lithium ion Coin-shaped battery.Then, be full of cracks and the use lithium ion Coin-shaped battery of measuring this pole plate are estimated high-temperature cycle.To the results are shown in table 1.
(embodiment 9)
(A) manufacturing of adhesive
In polymerization tank A, add 10.75 parts of 2-EHAs, 1.25 parts of acrylonitrile, 0.12 part of lauryl sodium sulfate, 79 parts of ion exchange waters, add again as 0.2 part of the ammonium persulfate of polymerization initiator, 10 parts of ion exchange waters, heat to 60 ℃ and stir 90 minutes after, to in another polymerization tank B, add 67 parts of 2-EHAs, 19 parts of acrylonitrile, 2.0 parts of methacrylic acids, 0.2 part of allyl glycidyl ether, 0.7 part of lauryl sodium sulfate, 46 parts of ion exchange waters also stir and the emulsion made, after placing about 180 minutes, after polymerization tank B adds to the polymerization tank A one by one, stir about 120 minutes, when reaching 95%, monomer consumption cools off and cessation reaction, with the 4%NaOH aqueous solution regulate pH value, obtain the aqueous dispersions of adhesive E thereafter.The glass transition temperature of the adhesive E that obtains is-32 ℃, and disperseing particle diameter is 0.15 μ m, and the pH value of the aqueous dispersions of adhesive E is 10.1.The aqueous dispersions that use obtains is estimated the table 1 that the results are shown in of adhesive storage stability.The polymerized unit of (methyl) acrylate monomer among the adhesive E to contain proportional be 78%, have sour composition vinyl monomer polymerized unit contain proportionally be 2.0%, α, the polymerized unit of alpha, beta-unsaturated nitriles monomer to contain proportional be 20%, have bridging property polymerized unit to contain proportional be 0.2%.
Except the aqueous dispersions that uses above-mentioned adhesive E as positive pole with the adhesive, operate similarly to Example 1, make anode plate, lithium ion Coin-shaped battery.Then, be full of cracks and the use lithium ion Coin-shaped battery of measuring this pole plate are estimated high-temperature cycle.To the results are shown in table 1.
(embodiment 10)
(A) manufacturing of adhesive
In polymerization tank A, add 10.75 parts of 2-EHAs, 1.25 parts of acrylonitrile, 0.12 part of lauryl sodium sulfate, 79 parts of ion exchange waters, add again as 0.2 part of the ammonium persulfate of polymerization initiator, 10 parts of ion exchange waters, heat to 60 ℃ and stir 90 minutes after, in another polymerization tank B, add 67 parts of 2-EHAs, 19 parts of acrylonitrile, 2.0 parts of methacrylic acids, 0.2 part of ethylene glycol dimethacrylate, 0.7 part of lauryl sodium sulfate, 46 parts of ion exchange waters also stir and the emulsion made, after placing about 180 minutes, after from polymerization tank B, adding to one by one among the polymerization tank A, stir about 120 minutes, when reaching 95%, monomer consumption cools off and cessation reaction, with the 4%NaOH aqueous solution regulate pH value, obtain the aqueous dispersions of adhesive F thereafter.The glass transition temperature of the adhesive F that obtains is-32 ℃, and disperseing particle diameter is 0.15 μ m, and the pH value of the aqueous dispersions of adhesive F is 10.1.The aqueous dispersions that use obtains is estimated the table 1 that the results are shown in of adhesive storage stability.The polymerized unit of (methyl) acrylate monomer among the adhesive F to contain proportional be 78%, have sour composition vinyl monomer polymerized unit to contain proportional be 2.0%, α, the polymerized unit of alpha, beta-unsaturated nitriles monomer to contain proportional be 20%, other polymerized unit to contain proportional be 0.2%.
Except the aqueous dispersions that uses above-mentioned adhesive F as positive pole with the adhesive, operate similarly to Example 1, make anode plate, lithium ion Coin-shaped battery.Then, be full of cracks and the use lithium ion Coin-shaped battery of measuring this pole plate are estimated high-temperature cycle.To the results are shown in table 1.
(comparative example 1)
Except not using carbon fiber, operate similarly to Example 2, make anode plate, lithium ion Coin-shaped battery.Then, be full of cracks and the use lithium ion Coin-shaped battery of measuring this pole plate are estimated high-temperature cycle.To the results are shown in table 1.
(comparative example 2)
Except not using carbon fiber, operate similarly to Example 8, make anode plate, lithium ion Coin-shaped battery.Then, be full of cracks and the use lithium ion Coin-shaped battery of measuring this pole plate are estimated high-temperature cycle.To the results are shown in table 1.
(comparative example 3)
(A) manufacturing of adhesive
In polymerization tank A, add 10.75 parts of 2-EHAs, 1.25 parts of acrylonitrile, 0.12 part of lauryl sodium sulfate, 79 parts of ion exchange waters, add again as 0.2 part of the ammonium persulfate of polymerization initiator, 10 parts of ion exchange waters, heat to 60 ℃ and stir 90 minutes after, in another polymerization tank B, add 68 parts of 2-EHAs, 19 parts of acrylonitrile, 0.8 part of methacrylic acid, 0.2 part of allyl methacrylate, 0.7 part of lauryl sodium sulfate, 46 parts of ion exchange waters also stir and with the emulsion of making, after placing about 180 minutes, after from polymerization tank B, adding to one by one among the polymerization tank A, stir about 120 minutes, when reaching 95%, monomer consumption cools off and cessation reaction, with the 4%NaOH aqueous solution regulate pH value, obtain the aqueous dispersions of adhesive C thereafter.The glass transition temperature of the adhesive C that obtains is-32 ℃, and disperseing particle diameter is 0.15 μ m, and the pH value of the aqueous dispersions of adhesive C is 10.1.The aqueous dispersions that use obtains is estimated the table 1 that the results are shown in of adhesive storage stability.The polymerized unit of (methyl) acrylate monomer among the adhesive C F to contain proportional be 79%, have sour composition vinyl monomer polymerized unit to contain proportional be 0.8%, α, the polymerized unit of alpha, beta-unsaturated nitriles monomer to contain proportional be 20%, have bridging property polymerized unit to contain proportional be 0.2%.
Except the aqueous dispersions that uses above-mentioned adhesive C as positive pole with the adhesive, operate similarly to Example 1, make anode plate, lithium ion Coin-shaped battery.Then, be full of cracks and the use lithium ion Coin-shaped battery of measuring this pole plate are estimated high-temperature cycle.To the results are shown in table 1.
(comparative example 4)
(A) manufacturing of adhesive
In polymerization tank A, add 10.75 parts of 2-EHAs, 1.25 parts of acrylonitrile, 0.12 part of lauryl sodium sulfate, 79 parts of ion exchange waters, add again as 0.2 part of the ammonium persulfate of polymerization initiator, 10 parts of ion exchange waters, heat to 60 ℃ and stir 90 minutes after, in another polymerization tank B, add 65.3 parts of 2-EHAs, 19 parts of acrylonitrile, 3.5 parts of methacrylic acids, 0.2 part of allyl methacrylate, 0.7 part of lauryl sodium sulfate, 46 parts of ion exchange waters also stir and with the emulsion of making, after placing about 180 minutes, stir about is 120 minutes after adding to one by one among the polymerization tank A from polymerization tank B, when reaching 95%, monomer consumption cools off and cessation reaction, with the 4%NaOH aqueous solution regulate pH value, obtain the aqueous dispersions of adhesive D thereafter.The glass transition temperature of the adhesive D that obtains is-32 ℃, and disperseing particle diameter is 0.15 μ m, and the pH value of the aqueous dispersions of adhesive D is 10.1.The aqueous dispersions that use obtains is estimated the table 1 that the results are shown in of adhesive storage stability.The polymerized unit of (methyl) acrylate monomer among the adhesive D to contain proportional be 76.3%, have sour composition vinyl monomer polymerized unit to contain proportional be 3.5%, α, the polymerized unit of alpha, beta-unsaturated nitriles monomer to contain proportional be 20%, have bridging property polymerized unit to contain proportional be 0.2%.
Except the aqueous dispersions that uses above-mentioned adhesive D as positive pole with the adhesive, operate similarly to Example 1, make anode plate, lithium ion Coin-shaped battery.Then, be full of cracks and the use lithium ion Coin-shaped battery of measuring this pole plate are estimated high-temperature cycle.To the results are shown in table 1.[table 1]
Figure BDA00002776807300281
As shown in Table 1, the anode of secondary cell of embodiment 1 ~ 10 has positive electrode active material layer, this positive electrode active material layer comprises: contain manganese or iron positive active material and, fibrous carbon and, by the polymerized unit that contains (methyl) acrylate monomer, have polymerized unit and the α of the vinyl monomer of sour composition, the adhesive that the polymer that the polymerized unit of alpha, beta-unsaturated nitriles monomer forms consists of, it can prevent the generation of the be full of cracks in the positive electrode active material layer, namely can improve fail safe, and the high-temperature cycle of battery is good.In addition, the storage stability of this adhesive is good.
On the other hand, use the comparative example 1 that does not contain fibrous carbon, 2 anode of secondary cell, and have in the adhesive that uses sour composition vinyl monomer polymerized unit contain the proportional comparative example 3 that is lower than the adhesive of 1.0 quality %, and the anode of secondary cell that uses the comparative example 4 of the adhesive that surpasses 3.0 quality %, be difficult to prevent the generation of the be full of cracks in the positive electrode active material layer, the high-temperature cycle of battery descends.

Claims (7)

1. anode of secondary cell, it comprises collector body and positive electrode active material layer, and described positive electrode active material layer is stacked on the described collector body, and contains positive active material, fibrous carbon and the adhesive of manganese or iron, wherein,
Described adhesive by the polymerized unit that contains (methyl) acrylate monomer, have polymerized unit and the α of the vinyl monomer of sour composition, the polymer of the polymerized unit of alpha, beta-unsaturated nitriles monomer forms,
The polymerized unit of described vinyl monomer with sour composition contain proportional 1.0 ~ 3.0 quality % that in whole polymerized units of polymer, account for.
2. anode of secondary cell according to claim 1, wherein, described positive active material contains iron, and has olivine-type structure.
3. anode of secondary cell according to claim 1 and 2, wherein, the fiber diameter of described fibrous carbon is 0.01 ~ 1.0 μ m.
4. each described anode of secondary cell according to claim 1 ~ 3, wherein, the mean aspect ratio of described fibrous carbon is 5 ~ 50000.
5. each described anode of secondary cell according to claim 1 ~ 4, wherein, described vinyl monomer with sour composition is the monomer with carboxylic acid group.
6. each described anode of secondary cell according to claim 1 ~ 5, wherein, described adhesive further contains the polymerized unit with bridging property.
7. secondary cell, it possesses positive pole, negative pole, dividing plate and electrolyte, each described anode of secondary cell in the described just very claim 1 ~ 6.
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