CN103026535B - Anode of secondary cell and secondary cell - Google Patents

Anode of secondary cell and secondary cell Download PDF

Info

Publication number
CN103026535B
CN103026535B CN201180036571.5A CN201180036571A CN103026535B CN 103026535 B CN103026535 B CN 103026535B CN 201180036571 A CN201180036571 A CN 201180036571A CN 103026535 B CN103026535 B CN 103026535B
Authority
CN
China
Prior art keywords
active material
adhesive
monomer
polymerized unit
secondary cell
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201180036571.5A
Other languages
Chinese (zh)
Other versions
CN103026535A (en
Inventor
胁坂康寻
薮内庸介
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Zeon Corp
Original Assignee
Nippon Zeon Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nippon Zeon Co Ltd filed Critical Nippon Zeon Co Ltd
Publication of CN103026535A publication Critical patent/CN103026535A/en
Application granted granted Critical
Publication of CN103026535B publication Critical patent/CN103026535B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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

Landscapes

  • 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

The invention provides one can thick-film, can prevent the generation of chapping, and can improve the cycle characteristics (particularly high-temperature cycle) of the secondary cell obtained and the anode of secondary cell of fail safe.Anode of secondary cell of the present invention comprises collector body and positive electrode active material layer, described positive electrode active material layer is stacked on described collector body, and containing the positive active material containing manganese or iron, fibrous carbon and adhesive, it is characterized in that, described adhesive is by the polymerized unit containing (methyl) acrylate monomer, there is the polymerized unit of the vinyl monomer of sour composition, α, the polymer of the polymerized unit of alpha, beta-unsaturated nitriles monomer is formed, described there is the polymerized unit of the vinyl monomer of sour composition in whole polymerized units of polymer, account for 1.0 ~ 3.0 quality % containing proportional.

Description

Anode of secondary cell and secondary cell
Technical field
The present invention relates to anode of secondary cell, more particularly, relate to for the anode of secondary cell with high-rate characteristics and cycle characteristics in lithium rechargeable battery etc.In addition, the invention still further relates to the secondary cell with this electrode.
Background technology
Even if in the battery that oneself uses, lithium rechargeable battery also demonstrates the highest energy density, is particularly widely used in miniaturized electronics.In addition, except mini-plant uses, also expect to use expansion on motor vehicle.Wherein, urgent expect to improve further lithium rechargeable battery high power and the reliability of cycle characteristics etc.
As the positive active material of lithium rechargeable battery constituent material, consider from by the limited this point of expensive and reserves of cobalt system active material used as main flow, to the active material transfer containing cheap manganese, nickel.But expect to become in the manganese system active material of main flow from now on, when repeating discharge and recharge more than high temperature, particularly 40 DEG C, manganese ion is solution modeling in the electrolytic solution, and result causes battery capacity to decline, and this has become large problem.
In addition, separated out in negative terminal surface reduction by the manganese ion from positive pole solution modeling, form tree-shaped metal precipitate, it destroys dividing plate, the large problem that the fail safe becoming battery declines.
In addition, electrode used in lithium rechargeable battery, usually there is electrode active material layer lamination structure on the current collector, in electrode active material layer, except the active material of electrode, also use for the adhesive making electrode active material be bonded to one another and electrode active material and collector body bond.
Describe in patent documentation 1 containing the LiFePO with olivine-type structure as positive active material 4, carbon and as (methyl) acrylate of adhesive and α, the positive pole of the copolymer of alpha, beta-unsaturated nitriles compound.
In addition, describe in patent documentation 2 containing the LiFePO with olivine-type crystal structure as positive active material 4, carbon fiber, positive pole as the polyvinylidene chloride (PVDF) of adhesive.
Prior art document
Patent documentation
Patent documentation 1:WO2006/038652 publication (corresponding U.S. Patent bulletin: U.S. Patent Application Publication No. 2008/096109 specification)
Patent documentation 2: Japanese Unexamined Patent Publication 2005-222933 publication (corresponding U.S. Patent bulletin: U.S. Patent application No. 2007/275302 specification)
Summary of the invention
The problem that invention will solve
But, can be judged by the discussion of present inventor: as the LiFePO with olivine-type structure that positive active material uses in patent documentation 1 4, as during positive active material because particle diameter is little, when making positive electrode active material layer thick-film, sometimes exist occur be full of cracks and so on problem.In addition, can also judge: the positive pole of patent documentation 2, identical with using the situation of manganese class active material in described positive active material, when at high temperature repeatedly carrying out discharge and recharge, iron ion is solution modeling in the electrolytic solution, and result exists the problem of battery capacity decline and so on, and, because the iron ion of solution modeling is in the tree-shaped precipitation of negative terminal surface, then the problem of fail safe decline that there is battery and so on.
Therefore, the object of the invention is, provides one can thick-film, can prevent the generation of chapping, can improve the cycle characteristics (particularly high-temperature cycle) of the secondary cell obtained and the anode of secondary cell of fail safe.In addition, the object of the invention is also, provides a kind of secondary cell possessing this anode of secondary cell.
The method of dealing with problems
As described below by the main points of the present invention solved for the purpose of above-mentioned problem.
(1) anode of secondary cell, its collector body and positive electrode active material layer, described positive electrode active material layer is stacked on described collector body, and containing containing the positive active material of manganese or iron, fibrous carbon and adhesive, wherein,
Described adhesive is by the polymerized unit containing (methyl) acrylate monomer, the polymerized unit with the vinyl monomer of sour composition and α, and the polymer that the polymerized unit of alpha, beta-unsaturated nitriles monomer is formed is formed,
Described there is the polymerized unit of the vinyl monomer of sour composition in all polymerized units of polymer, account for 1.0 ~ 3.0 quality % containing proportional.
(2) anode of secondary cell Gen Ju (1), wherein, described positive active material contains iron, and has olivine-type structure.
(3) according to (1) or the anode of secondary cell described in (2), wherein, the fiber diameter of described fibrous carbon is 0.01 ~ 1.0 μm.
(4) according to the anode of secondary cell according to any one of (1) ~ (3), wherein, the mean aspect ratio of described fibrous carbon is 5 ~ 50000.
(5) vinyl monomer according to the anode of secondary cell according to any one of (1) ~ (4), wherein, with sour composition is the monomer with carboxylic acid group.
(6) according to the anode of secondary cell according to any one of (1) ~ (5), wherein, described adhesive is further containing the polymerized unit with bridging property.
(7) secondary cell, it possesses positive pole, negative pole, dividing plate and electrolyte, the anode of secondary cell according to any one of described just very (1) ~ (6).
Invention effect
According to the present invention, by containing fibrous carbon in positive electrode active material layer, then can improve the toughness of positive electrode active material layer, therefore can prevent the generation that positive electrode active material layer chaps, and can positive electrode active material layer be thickened.In addition, adhesive contained in positive electrode active material layer is the polymerized unit containing (methyl) acrylate monomer, the polymerized unit with the vinyl monomer of sour composition and α, the polymer of the polymerized unit formation of alpha, beta-unsaturated nitriles monomer, by the polymerized unit of the vinyl monomer by having sour composition containing the proportional ratio being set to regulation, then can trap by the metal ion of positive active material solution modeling (manganese ion or iron ion), therefore, cycle characteristics (particularly high-temperature cycle) and the fail safe of secondary cell can be improved.
Embodiment
The present invention is described in detail in detail below.Anode of secondary cell of the present invention has collector body and positive electrode active material layer, and described positive electrode active material layer on the current collector, and is formed containing containing the positive active material of manganese or iron, fibrous carbon and adhesive.
(positive active material)
As positive active material used in the present invention, as long as also reversibly insert/release the material of lithium ion containing manganese or iron, be not particularly limited, but, the transition metal oxide wherein preferably containing lithium.
As containing manganese containing the transition metal oxide of lithium, can enumerate: the composite metal oxide containing lithium with layer structure, the composite metal oxide containing lithium with spinel structure, there is the composite metal oxide etc. containing lithium of olivine-type structure.
As the composite metal oxide containing lithium with layer structure, can enumerate: LiMnO 2and by the Li of a part of Mn by other Transition metal substituted x[Mn ym 1-y] O 2(in formula, x=0.02 ~ 1.2,0<y<1, M are Cr, Fe, Co, Ni, Cu etc.) etc.
As the composite metal oxide containing lithium with spinel structure, can enumerate: LiMn 2o 4and by the Li of a part of Mn by other Transition metal substituted x[Mn ym 2-y] O 4(in formula, x=0.02 ~ 1.2,0<y<2, M are Cr, Fe, Co, Ni, Cu, V etc.) etc.
As the composite metal oxide containing lithium with olivine-type structure, can enumerate: Li xmnPO 4and by the Li of a part of Mn by other Transition metal substituted xmn ym 1-ypO 4the olivine-type lithium phosphate compound of (in formula, x=0.02 ~ 1.2,0<y<1, M are at least one be selected from Fe, Co, Ni, Cu, Mg, Zn, V, Ca, Sr, Ba, Ti, Al, Si, B and Mo).
In these, particularly because the stripping of Mn ion easily causes the deteriorated LiMnO with layer structure that circulates 2and substituent, there is the LiMn of spinel structure 2o 4and substituent, most preferably there is the LiMn of spinel structure 2o 4and substituent, the effect improving secondary cell cycle characteristics of the present invention because of it is large.In the present invention, also can use two or more above-mentioned positive active material, in addition, containing the positive active material of manganese and the mixture of positive active material not containing manganese also harmless.Further, the content of manganese is more, more easily causes circulation deterioration by the solution modeling of Mn ion, therefore, adopt the raising effect of the cycle characteristics of anode of secondary cell of the present invention large.In the present invention, the Fe content in positive active material is preferably 10 ~ 80 quality %, more preferably 15 ~ 65 quality %.By the Fe content in positive active material is set in above-mentioned scope, the effect of the sour composition trapping manganese ion by adhesive of the present invention can be presented significantly.
As the lithium-containing transition metal oxide of iron content, can enumerate: Li yfeXO 4(in formula, X represents at least one element in the element of the 4th race ~ the 7th race and the 14th race ~ the 17th race being selected from periodic table.Y is 0<y<2).
The lithium-containing transition metal oxide of above-mentioned iron content, usually has element X and be positioned on tetrahedral lattice point, and lithium and iron is positioned at the structure on octahedra lattice-site simultaneously.The structure of above-mentioned positive active material, when representing with lattice-site, with { X} [Li yfe] O 4to represent (in formula, represent in tetrahedral lattice point, [] in { } and represent octahedra lattice-site), but as the element X giving such structure, preference is as the 15th race's elements such as vanadium etc. the 5th race's element and phosphorus, arsenic, antimony, bismuths.
The lithium-containing transition metal oxide of above-mentioned iron content, preferably has the olivine-type structure of the tightly packed oxygen atom skeleton of six sides, or has spinelle or inverse spinel structure that cubic close piles up oxygen atom skeleton, is particularly preferably olivine-type structure.Olivine-type structure and the difference of spinel structure containing inverse spinel are that oxonium ion is that the tightly packed or cubic close of six sides is piled up, and change its rock-steady structure according to the kind of X element.Such as: LiFePO 4for stable olivine-type structure, and LiFeVO 4in become stable phase for inverse spinel structure.
There is the Li of olivine-type structure or spinel structure yfeXO 4, the ammonium salt of mixed lithiated compound, divalent iron compound and element (X) can be passed through, then, carry out firing manufacturing under non-active gas atmosphere gas or under reduction atmosphere gas.As lithium compound, Li can be enumerated 2cO 3, LiOH, LiNO 3deng.
As the concrete example of the iron compound of divalent, FeC can be enumerated 2o 42H 2o, Fe (CH 3cOO) 2, FeCI 2deng.As the concrete example of the ammonium salt of element (X), (NH can be enumerated 4) 2hPO 4, NH 4h 2pO 4, (NH 4) 3pO 4deng phosphate; NH 4hSO 4, (NH 4) 2sO 4in sulfate etc.
In addition, the iron compound with NASICON type structure other than the above can also be used as positive active material.As NASICON sections compound, concrete enumerates: by Li 2fe 2-nv n(XO 4) 3the compound that (in formula, 0≤n<2, preferably 0≤n≤1) represents.
In these, particularly consider from making with qualification rate this point of effect of the present invention that presents using the electrode of small particle diameter positive active material so well, the more preferably iron compound of olivine-type structure.
The amount of positive active material contained in the positive electrode active material layer of anode of secondary cell of the present invention is preferably 80 ~ 99.5 quality %, is more preferably 90 ~ 99 quality %.When the amount of positive active material is more than 99.5 quality %, adhesive in positive electrode active material layer and the ratio of conductivity-imparting agent diminish, therefore, the caking property that there is positive active material caking property each other and positive active material and following collector body declines and the power characteristic of battery situation about also declining.In addition, when the amount of positive active material is lower than 80 quality %, have the situation that battery capacity declines.
The particle diameter (average grain diameter) of positive active material contained in the positive electrode active material layer of anode of secondary cell of the present invention is preferably 0.01 ~ 10 μm, is more preferably 0.02 ~ 5 μm.When the particle diameter of positive active material is more than 10 μm, the dispersiveness in slurry declines, and is difficult to manufacture good slurry.The situation that in addition, when the particle diameter of positive active material is lower than 0.01 μm, the conductivity having active material declines, the internal electrical resistive of battery is large.
(fibrous carbon)
The present invention uses fibrous carbon.By using fibrous carbon, the toughness of positive electrode active material layer can be improved, therefore can prevent the generation that positive electrode active material layer chaps, and can positive electrode active material layer be thickened.Consequently, the fail safe of the secondary cell employing anode of secondary cell of the present invention can be improved.
As long as fibrous carbon threadiness used in the present invention just can play effect of the present invention, but when the fibre diameter of fibrous carbon is excessive, the space in electrode becomes large, can not improve electrode density, therefore not preferred.In addition, when fibre diameter is too small, be buried between active material particle, the grid in electrode can not be formed, in addition, the space between active material can not be generated, therefore not preferred.In view of above reason, may 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 μm, be more preferably 0.01 ~ 0.2 μm.By using the fiber diameter of fibrous carbon at the fibrous carbon of above-mentioned scope, the dispersion stabilization of following anode of secondary battery slurry can be improved, and the secondary cell of high power capacity can be made.
Degree of crystallinity (so-called degree of graphitization) the preferred high person of fibrous carbon.The degree of graphitization of usual 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 by material with carbon element graphitization, as long as usually at high temperature carry out processing, as treatment temperature now, different from the difference of fibrous carbon used, but preferably more than 2000 DEG C, preferably more than 2500 DEG C further.In addition, in this case, before heat treatment, it is effective for adding the graphitization co-catalyst boron that effectively can promote degree of graphitization and Si etc.The addition of co-catalyst is not particularly limited, but when addition is very few, does not have effect, time too much, as impurities left, 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, but, by the centre plane interval d of X-ray diffraction method 002be preferably below 0.344nm, be more preferably below 0.339nm, the axial thickness Lc of C of crystal is below 40nm.
The fibre length of fibrous carbon is longer, and more can increase the conductivity in electrode, the intensity of electrode, electrolyte guarantor fluidity, therefore preferably, but time long, the fiber dispersion in electrode is impaired, therefore not preferred.The scope of average fiber length, different because of the kind of fibrous carbon used and fibre diameter, but be preferably 0.5 ~ 100 μm, be more preferably 1 ~ 50 μm.The preferable range of average fiber length, when representing by mean aspect ratio (ratio relative to the average fiber length of fiber diameter), is preferably the scope of 5 ~ 50000, the more preferably scope of 10 ~ 15000.By using the average fiber length of fibrous carbon and mean aspect ratio at the fibrous carbon of above-mentioned scope, the dispersion stabilization of following anode of secondary battery slurry can be improved, and the effect that effectively can suppress the be full of cracks of positive electrode active material layer and improve further as the conductive path in positive electrode active material layer.
When containing the structure of branched (branched) in fibrous carbon, fluidity protected by the conductivity of electrode entirety, the intensity of electrode, electrolyte increases further, therefore preferably.But when branched fiber is too much, and fibre length is same, and the dispersiveness in electrode is impaired, therefore, preferably contains with the ratio of appropriateness.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 such as: the method for the precursor that heat treated is made up of macromolecule and the pitch of spinned fiber shape and by direct for the organic steams such as benzene jet on the substrate of about 1000 DEG C, using the method (chemical vapour deposition) etc. of the carbon crystals of growing up as catalyst such as iron granules.
The content of fibrous carbon, relative to positive active material, adhesive and the total amount of tackifier that coordinates as required, is preferably 0.05 ~ 20 quality %, is more preferably 0.1 ~ 15 quality %, is particularly preferably 0.5 ~ 10 quality %.When content is more than 20 quality %, the active material ratio in electrode diminishes, and therefore battery capacity diminishes.When content is lower than 0.05 quality %, be difficult to the generation of the be full of cracks suppressing electrode.In order to content is adjusted to above-mentioned scope, by carrying out to add in proportion in method for making.
In order to control fibrous carbon dispersity in the electrodes, the fibrous carbon of surface treatment also can be used.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 process modulation.In addition, the coating and mechanochemistry process etc. of phenolic resins etc. can also be enumerated.When excessively carrying out surface treatment, the conductivity of fibrous carbon and intensity are significantly impaired, are therefore necessary for the process of appropriateness.Oxidation processes, can by such as: by fibrous carbon in atmosphere, heat 1 hours to carry out at 500 DEG C.The hydrophily of fibrous carbon is improved by this process.
(adhesive)
Polymerized unit containing (methyl) acrylate monomer in the adhesive of anode of secondary cell of the present invention, the polymerized unit with the vinyl monomer of sour composition and α, the polymerized unit of alpha, beta-unsaturated nitriles monomer.Specifically, it is characterized in that, containing above-mentioned each polymerized unit in the polymer as above-mentioned adhesive.
As the polymerized unit of (methyl) acrylate monomer in the present invention, can enumerate: the alkyl acrylates such as methyl acrylate, ethyl acrylate, n-propyl, isopropyl acrylate, n-butyl acrylate, tert-butyl acrylate, amyl acrylate, Hexyl 2-propenoate, heptylacrylate, 2-ethyl hexyl acrylate, 2-EHA, acrylic acid ester in the ninth of the ten Heavenly Stems, decyl acrylate, lauryl acrylate, n-myristyl base ester, stearyl acrylate acyl ester, methyl methacrylate, EMA, n propyl methacrylate, isopropyl methacrylate, n-BMA, Tert-butyl Methacrylate, pentylmethacrylate, hexyl methacrylate, metering system heptyl heptylate, 2-Propenoic acid, 2-methyl-, octyl ester, 2-Ethylhexyl Methacrylate, nonyl methacrylate, decyl-octyl methacrylate, lauryl methacrylate, methacrylic acid n-tetradecane base ester, the alkyl methacrylates such as methacrylic acid stearoyl ester.In these, from not solution modeling in the electrolytic solution, and show the conductivity of the lithium ion caused by the swelling of the appropriateness to electrolyte, be difficult in addition cause in the crosslinked aggegation that causes due to polymer in the dispersion of active material and consider, preferably be bonded to the heptylacrylate of the alkyl acrylate of the carbon number 7 ~ 13 of the alkyl on 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 the 2-ethyl hexyl acrylate of the carbon number 8 ~ 10 of the alkyl on non-carbonyl oxygen atom is bonded to, 2-EHA, acrylic acid ester in the ninth of the ten Heavenly Stems.
As the preferred exemplary with the polymerized unit of the vinyl monomer of sour composition in the present invention, can enumerate: there is the monomer of-COOH base (carboxylic acid group), there is the monomer of-OH base (hydroxyl), there is-SO 3the monomer of H base (sulfonic group), there is-PO 3h 2the monomer of base, there is the monomer of-PO (OH) (OR) base (R represents alkyl) and there is 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 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 methyl allyl esters such as methyl maleate, 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-hydroxybutyl, itaconic acid two-2-hydroxy propyl ester; General formula CH 2=CR 1-COO (C nh 2no) m(m represents that integer, the n of 2 ~ 9 represent integer, the R of 2 ~ 4 to-H 1represent hydrogen atom or methyl) represented by PAG and (methyl) acrylic acid ester class; List (methyl) esters of acrylic acid of the dihydroxy ester of the dicarboxylic acids such as 2-hydroxyethyl-2 '-(methyl) acryloxy phthalic acid ester, 2-hydroxyethyl-2 '-(methyl) acryloxy succinate; The vinyl ethers such as 2-hydroxyethyl vinyl ether, 2-hydroxypropyl vinyl ethers; List (methyl) allyl ether series of the aklylene glycol of (methyl) pi-allyl-2-hydrxyethyl ether, (methyl) pi-allyl-2-hydroxypropyl ether, (methyl) pi-allyl-3-hydroxypropyl 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 monoallyl ethers such as diethylene glycol list (methyl) allyl ether, DPG list (methyl) allyl ether; The halogen of (gathering) aklylene glycol and list (methyl) allyl ethers of hydroxyl substituent such as glycerol list (methyl) allyl ether, (methyl) pi-allyl-2-chloro-3-hydroxyl propyl ether, (methyl) pi-allyl-2-hydroxyl-3-chloro propyl ether; List (methyl) allyl ether of the polyhydric phenols of eugenol, isoeugenol etc. and halogen substituents 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, 2-acrylamide-2-methyl propane sulfonic, 3-allyloxy-2-hydroxy-propanesulfonic acid etc.
As having-PO 3h 2the monomer of base and/or-PO (OH) (OR) base (R represents alkyl), can enumerate: phosphoric acid-2-(methyl) acryloyloxyethyl ester, phosphoric acid methyl-2-(methyl) acryloyloxyethyl ester, ethyl-(methyl) acryloyloxyethyl ester etc.
As the monomer with rudimentary polyoxy alkylidene, can enumerate: poly-(epoxides) of poly-(oxirane) etc. etc.
In these, consider from the reason of the excellent adhesion of so-called and following collector body and the manganese ion or iron ion that effectively trap solution modeling from positive active material well, preferably there is the monomer of carboxylic acid group, wherein, the dicarboxylic acids of the monocarboxylic acid preferably with the carboxylic acid group of the carbon number less than 5 of acrylic acid, methacrylic acid etc. and the carboxylic acid group with 2 carbon numbers such as maleic acid, itaconic acid less than 5.And then, high from the viewpoint of the storage stability of the adhesive of so-called making, preferred acrylic acid and methacrylic acid.
As the α in the present invention, the polymerized unit of alpha, beta-unsaturated nitriles monomer, from the viewpoint of so-called raising mechanical strength and cohesive force, preferred acrylonitrile and methacrylonitrile.
In the present invention, the polymerized unit of (methyl) acrylate monomer in adhesive (following, to be sometimes expressed as " composition A ") containing proportional, be preferably 50 ~ 95 quality %, be more preferably 60 ~ 90 quality %.In addition, α, the polymerized unit of alpha, beta-unsaturated nitriles monomer (following, to be sometimes expressed as " composition B ") containing proportional, be preferably 3 ~ 40 quality %, be more preferably 5 ~ 30 quality %.In addition, have the polymerized unit (following, be sometimes expressed as " composition C ") of the vinyl monomer of sour composition containing proportional be 1.0 ~ 3.0 quality %, be preferably 1.5 ~ 2.5 quality %.Composition A containing proportional more than 95 quality % time, the mechanical strength of adhesive declines.In addition, composition A containing proportional lower than 50 quality % time, the flexibility of adhesive declines, and electrode is hardening, is therefore difficult to the generation preventing from chapping.Composition B containing proportional more than 40 quality % time, the flexibility of adhesive declines, and electrode is hardening, is therefore difficult to the generation preventing from chapping.In addition, composition B containing proportional lower than 3 quality % time, the mechanical strength of adhesive declines, and the adaptation of electrode declines.When the content of composition C is more than 3.0 quality %, the manufacture stability of adhesive and storage stability decline.In addition, composition C containing proportional lower than 1.0 quality % time, the caking property as adhesive is not enough, and the life characteristic of battery declines.
The adhesive used in the present invention, preferably also containing above-mentioned composition A, composition B, the polymerized unit with bridging property beyond composition C.As importing the method with the polymerized unit of bridging property in above-mentioned adhesive, can enumerate: the method for the method of the crosslinkable groups of lead-in light bridging property and the crosslinkable groups of importing heat cross-linking in adhesive.In these, the method of the crosslinkable groups of heat cross-linking is imported in adhesive, adhesive can be made to be cross-linked by carrying out heat treated to pole plate after coating on pole plate, and the dissolving that can suppress to electrolyte, tough and the pole plate of softness can be obtained, and the life characteristic of battery can be improved, therefore preferably.When importing the crosslinkable groups of heat cross-linking in adhesive, there is following method: use has the method with mono-functional's monomer of 1 alkene double bond of the crosslinkable groups of heat cross-linking and uses the method with at least 2 multi-functional monomers of alkene double bond.As the crosslinkable groups with heat cross-linking contained in mono-functional's monomer of 1 alkene double bond, be preferably selected from by epoxy radicals, N-methylol amide base, oxetanyl Ji at least one in the group that forms of oxazolinyl, epoxy radicals easily regulates this point to consider from crosslinked and crosslink density, is preferred.
As the monomer with epoxy radicals.Can enumerate: the monomer containing carbon-to-carbon double bond and epoxy radicals and the monomer containing halogen atom and epoxy radicals.
As the monomer containing 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.; The diene of butadiene monoepoxide, chlorobutadiene monoepoxide, 4,5-epoxy-2-amylenes, 3,4-epoxy-1-VCHs, 1,2-epoxy-5,9-ring 12 carbon diene etc. or the monoepoxide of polyenoid; The alkenyl epoxides of 3,4-epoxy-1-butylene, 1,2-epoxy-5-hexene, 1,2-Huan Yang ー 9-decene etc.; The ethylene oxidic ester class of the unsaturated carboxylic acid of glycidyl acrylate, glycidyl methacrylate, butenoic acid ethylene oxidic ester, glycidol-4-heptenoate, sorbic acid ethylene oxidic ester, linoleic acid ethylene oxidic ester, glycidol-4-methyl-3-heptenoate, the ethylene oxidic ester of 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, Epiiodohydrin, epifluorohydrin, β methyl epoxy chloropropane etc.; To chlorostyrene oxide; Dibromo phenyl glycidol ether.
As the monomer containing N-methylol amide base, can enumerate: (methyl) acrylic amide with methylol of N-methylol (methyl) acrylamide etc.
As the monomer containing oxetanyl, can enumerate: 3-((methyl) acryloyloxymethyl) oxetanes, 3-((methyl) acryloyloxymethyl)-2-trifluoromethyl oxetanes, 3-((methyl) acryloyloxymethyl)-2-phenyl oxetanes, 2-((methyl) acryloyloxymethyl) oxetanes, 2-((methyl) acryloyloxymethyl)-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 at least 2 alkene double bonds, preferred allyl acrylate or allyl methacrylate, trimethylolpropane-triacrylate, trimethylolpropane-methacrylate, DPG diallyl ether, polyethylene glycol diallyl ether, triethyleneglycol divinylether, hydroquinones diallyl ether, other pi-allyl of tetraallyl hydroxyl ethane or multi-functional alcohol or vinyl ethers, tetraethylene glycol diacrylate, triallylamine, trimethylolpropane-diallyl ether, methylene diacrylamine and/or divinylbenzene.Particularly allyl acrylate, allyl methacrylate, trimethylolpropane-triacrylate and/or trimethylolpropane-methacrylate etc. can be enumerated.
In these, easily improve this point from crosslink density to consider, preferably there is the multi-functional monomer of at least 2 alkene double bonds, have again, high and combined polymerization is high from the viewpoint of crosslink density, preferred allyl acrylate or allyl methacrylate etc. have allylic acrylate or methacrylate.
The crosslinkable groups of the heat cross-linking in adhesive containing proportional, the monomer as the crosslinkable groups containing heat cross-linking during polymerization is preferably 0.01 ~ 0.5 quality % relative to monomer total amount 100 quality %, is more preferably the scope of 0.3 ~ 0.05 quality %.The crosslinkable groups of the heat cross-linking in adhesive containing proportional, can when manufacturing adhesive, by monomeric charge than being controlled.The crosslinking group of the heat cross-linking in adhesive containing proportional, time in above-mentioned scope, bloating tendency relative to electrolyte of appropriateness can be shown, excellent speed characteristic and cycle characteristics can also be shown.
Adhesive used in the present invention, also can containing other the polymerized unit beyond above-mentioned composition.Other polymerized unit so-called is the polymerized unit of the vinyl monomer from other, such as, as can with the monomer of these combined polymerizations, can enumerate: ethylene glycol dimethacrylate, dimethacrylate etc. have the carboxylic acid esters of more than 2 carbon-to-carbon double bonds; The monomer containing halogen atom such as vinyl chloride, vinylidene chloride; 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. are containing the vinyl compound of heterocycle.
Adhesive used in the present invention, uses under the state of the solution of the dispersion liquid be scattered in dispersant or dissolving.Wherein consider from the bloating tendency reason of so-called suppression electrolyte, preferably disperse with particle shape in dispersant.
Adhesive disperses with particle shape in dispersant, be preferably 50 ~ 500nm, more preferably 70 ~ 400nm with the average grain diameter (dispersion particle diameter) of the adhesive of particle shape dispersion, most preferably be 100 ~ 250nm.The average grain diameter of adhesive is when this scope, and the intensity of the electrode obtained and flexibility become good.In addition, as dispersant, can with an organic solvent and water, but, wherein consider from the reason of so-called quickening rate of drying, preferably use water as dispersant.
Adhesive disperses with 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 manufacturing following anode of secondary battery slurry is good.
The glass transition temperature (Tg) of adhesive used in the present invention is preferably-50 ~ 25 DEG C, is more preferably-45 ~ 15 DEG C, is particularly preferably-40 ~ 5 DEG C.By the Tg of adhesive is set in above-mentioned scope, can obtain that there is excellent intensity and flexibility, and the electrode for secondary battery of high power characteristic.It should be noted that, the glass transition temperature of adhesive is regulated by combining various monomer.
The manufacture method of binder polymer used in the present invention is not particularly limited, any one method such as solution polymerization process, suspension polymerization, mass polymerization, emulsion polymerization can be adopted.As polymerization, any one method such as ionic polymerization, radical polymerization, active free radical polymerization can be used.As polymerization initiator used in polymerization, can enumerate such as: 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, azo-compound or ammonium persulfate, the potassium peroxydisulfates etc. such as α '-azodiisobutyronitrile.
For adhesive used in the present invention, dispersant used in these polymerizations, for the dispersant used in usual synthesis, as a specific example, can be able to 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, ethylene nonyl phenyl ether sodium sulfate salt; Paraffin sulfonate; Alkyl ether phosphates ester sodium salt; The non-ionic emulsifiers such as ethylene nonyl phenyl ether, polyoxyethylene sorbitol acid anhydride dodecyl ester, polyox-yethylene-polyoxypropylene block copolymer; Gelatin, maleic anhydride-styrene copolymers, PVP, Sodium Polyacrylate, the degree of polymerization more than 700 and the water soluble polymers etc. such as the polyvinyl alcohol of saponification degree more than 75%, these both can be used alone and also may be two kinds or more.The benzene sulfonate such as neopelex, dodecylphenyl ether sulfonic acid sodium is preferably in these; The alkyl sulfate such as lauryl sodium sulfate, sodium tetradecyl sulfate, considers from this point of so-called oxidative resistance excellence, is more preferably the benzene sulfonate such as neopelex, dodecylphenyl ether sulfonic acid sodium.The addition of dispersant can at random set, about being generally 0.01 ~ 10 mass parts relative to monomer total amount 100 mass parts.
PH when adhesive used in the present invention is scattered in dispersant is preferably 5 ~ 13, is more preferably 5 ~ 12, most preferably is 10 ~ 12.By the pH of adhesive is set in above-mentioned scope, the storage stability of adhesive can be improved, also can improve mechanical stability.
Regulate the pH adjusting agent of adhesive pH to illustrate to have: 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 the metal hydroxides of the IIIA genus in long period rule table; The alkali carbonate such as sodium carbonate, potash, the carbonate etc. such as alkaline earth metals carbonate such as magnesium carbonate, as organic amine, can enumerate: the alkyl amines such as ethamine, diethylamine, propylamine; The alcaminess such as single carbinolamine, monoethanolamine, single Propanolamine; The Ammonias etc. such as ammoniacal liquor.In these, from the viewpoint of caking property and operability, preferred alkali metal hydroxide, particularly preferably NaOH, potassium hydroxide, lithium hydroxide.
The content of the adhesive in positive electrode active material layer is preferably 0.1 ~ 10 mass parts relative to positive active material 100 mass parts, is more preferably 0.5 ~ 5 mass parts.By the content of the adhesive in anode of secondary battery is set in above-mentioned scope, positive active material each other and the caking property of positive active material and collector body excellent, in addition, flexibility can be kept not hinder again lithium ion move and do not increase resistance.
In positive electrode active material layer used in the present invention, except mentioned component, conductive imparting material, reinforcing material, dispersant, levelling agent, antioxidant, tackifier can also be contained, there is other composition such as electrolysis additive, other binding agent suppressing the functions such as electrolyte decomposition, can also be contained in following anode of secondary battery slurry.These however bring impact to be just not particularly limited to cell reaction.
Give material as conductivity, the conductive carbon such as acetylene black, Ketjen black, carbon black, graphite can be used.The fine wire and paper tinsel etc. of the carbon dusts such as graphite, various metal can be enumerated.By using conductivity to give material, electrode active material electrical contact each other can be improved, particularly when for lithium rechargeable battery, can also discharge characteristics on load be improved
As reinforcing material, various inorganic and organically spherical, sheet or bar-shaped filler can be used.By using reinforcing material, the tough and electrode of softness can be obtained, and the long-term cycle characteristics that display is excellent.Conductivity gives the consumption of material and reinforcing agent, is generally 0.01 ~ 20 mass parts relative to positive active material 100 mass parts, is preferably 1 ~ 10 mass parts.By giving material and reinforcing agent containing the conductivity in above-mentioned scope, high capacity and high part throttle characteristics can be shown.
As dispersant, there can be exemplified: anionic property compound, cationic compound, nonionic compound, macromolecular compound.Dispersant can be given material according to positive active material used and conductivity and select.Containing of dispersant in positive electrode active material layer is proportional, is preferably 0.01 ~ 10 quality %.By the amount of dispersant is set in above-mentioned scope, the excellent in stability of following positive pole slurry can be obtained and level and smooth electrode, and high battery capacity can be shown.
As levelling agent, can enumerate: the surfactants such as alkyl-based surfactant, silicon class surfactant, fluorine class surfactant, metal species surfactant.By mixing above-mentioned surfactant, not only can prevent the shrinkage cavity of the generation when being coated with on the current collector by following anode of secondary battery slurry but also the slickness of electrode can be improved.Levelling agent in positive electrode active material layer containing proportional be preferably 0.01 ~ 10 quality %.Productivity ratio, slickness and battery behavior during electrode fabrication can be made excellent by levelling agent being set in above-mentioned scope.
As antioxidant, can enumerate: phenolic compound, hydroquinones compound, organic phosphorus compound, sulphur compound, phenylenediamine compound, polymer-type phenolic compound etc.Polymer-type phenolic compound is the polymer in molecule with phenol structure, and preferably use weight average molecular weight is the polymer-type phenolic compound of 200 ~ 1000, preferably 600 ~ 700.Containing of antioxidant in positive electrode active material layer is proportional, is preferably 0.01 ~ 10 quality %, is more preferably 0.05 ~ 5 quality %.By antioxidant is set in above-mentioned scope, the stability of following positive pole slurry, battery capacity and cycle characteristics can be made excellent.
As tackifier, can enumerate: the cellulosic polymers such as carboxymethyl cellulose, methylcellulose, hydroxypropyl cellulose and their ammonium salt and alkali metal salt; (modification) poly-(methyl) acrylic acid and their ammonium salt and alkali metal salt; The polyvinyl alcohol of the copolymer of the copolymer of (modification) polyvinyl alcohol, acrylic acid or acrylates and vinyl alcohol, maleic anhydride or maleic acid or 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.In the present invention, " (modification) gathers " implication is: " unmodified poly-" or " modification gathers ", " (methyl) acrylic acid " implication is: " acrylic acid " or " methacrylic acid ".Containing of tackifier in positive electrode active material layer is proportional, is preferably 0.01 ~ 10 quality %.By tackifier are set in above-mentioned scope, following anode of secondary battery slurry is made to become good to the coating of collector body.In addition, the excellent dispersion of the active material in following positive pole slurry etc. can be made, thus obtain level and smooth electrode, and the part throttle characteristics of display excellence and cycle characteristics.
Electrolysis additive can use in following anode of secondary battery slurry and the vinylene carbonate etc. used in electrolyte.Electrolysis additive in positive electrode active material layer containing proportional be preferably 0.01 ~ 10 quality %.By electrolysis additive is set in above-mentioned scope, cycle characteristics and hot properties excellence can be made.In addition, also can enumerate: the nano-corpuscules such as gas silicon dioxide and gaseous oxidation aluminium; The surfactants such as alkyl-based surfactant, silicon class surfactant, fluorine class surfactant, metal species surfactant.By mixing above-mentioned nano-corpuscule, can the thixotropy of control electrode formation slurry, and then the levelability of the electrode obtained can be improved thus.Containing of nano-corpuscule in positive electrode active material layer is proportional, is preferably 0.01 ~ 10 quality %.By nano-corpuscule is set in above-mentioned scope, Stability of Slurry, productivity ratio can be made excellent, and show high battery behavior.By mixing above-mentioned surfactant, the dispersiveness of the active material in secondary cell Zheng Very slurry etc. can be improved, and then the slickness of the electrode obtained can be improved thus.Containing of surfactant in positive electrode active material layer is proportional, is preferably 0.01 ~ 10 quality %.By surfactant is set in above-mentioned scope, the stability of following anode of secondary battery slurry, electrode smoother can be made excellent, and show high productivity ratio.
(collector body)
Collector body used in the present invention has conductivity, and as long as there is the material of electrochemistry durability, and to be not particularly limited, but, from the viewpoint of having thermal endurance, preference is 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 of thickness about 0.001 ~ 0.5mm.In order to improve the adhesive strength of positive electrode active material layer, collector body uses after preferably carrying out roughened process in advance.As roughened method, can enumerate: mechanical milling method, electrolytic polishing method, chemical grinding method etc.In mechanical milling method, use and be fixed with the abrasive cloth paper of abrasive particle, grinding stone, emery wheel, be equipped with the steel brush etc. of steel wire etc.In addition, in order to improve adhesive strength and the conductivity of positive electrode active material layer, intermediate layer can be formed on collector body surface.
As the method for manufacture anode of secondary cell of the present invention, as long as positive electrode active material layer can be bonded to the method for stratiform at least one side of above-mentioned collector body, preferably two sides.Such as: be coated with on the current collector by following positive pole slurry and carry out drying, then, more than 120 DEG C, heat treated forms electrode in more than 1 hour.Positive pole slurry coating method is on the current collector not particularly limited.Can enumerate such as: scrape the method such as the skill in using a kitchen knife in cookery, dipping (ジ Star プ) method, reverse roll rubbing method, directly rolling method, gravure coat method, extrusion coated method, spread coating.As drying means, can enumerate such as: by the drying of warm braw, hot blast, low wet wind, vacuumize, seasoning by irradiation such as (far) infrared ray and electron ray etc.
Secondly, moulding press and roll squeezer etc. is preferably used to reduce the voidage of electrode by pressurized treatments.The preferred scope of voidage is 5 ~ 15%, is more preferably 7 ~ 13%.When voidage is too high, charge efficiency and discharging efficiency bad.When voidage is too low, be difficult to obtain high volume capacity, so-called electrode can be produced and easily peel off, bad problem easily occurs.Further, when using the polymer of curability, be preferably cured.
The thickness of anode of secondary cell of the present invention is generally 5 ~ 150 μm, is preferably 10 ~ 100 μm.By thickness of electrode is set in above-mentioned scope, part throttle characteristics and energy density can be made to show high characteristic simultaneously.
(anode of secondary battery slurry)
Anode of secondary battery slurry used in the present invention, comprise: containing manganese or iron positive active material and, fibrous carbon and, by containing the polymerized unit of (methyl) acrylate monomer, the polymerized unit with the vinyl monomer of sour composition and α, the adhesive that the polymer of the polymerized unit of alpha, beta-unsaturated nitriles monomer is formed and, solvent.As positive active material, fibrous carbon and the polymerized unit containing (methyl) acrylate monomer, the polymerized unit with the vinyl monomer of sour composition and α, the adhesive of the polymerized unit of alpha, beta-unsaturated nitriles monomer, can use above-mentioned substance.
(solvent)
As solvent, as long as adhesive used in the present invention can be dissolved equably or disperses just to be not particularly limited.As solvent used in positive pole slurry, any one of water and organic solvent can be used.As organic solvent, can enumerate: the annular aliphatic such as pentamethylene, cyclohexane hydro carbons; 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 be used alone and also two or more mixing can be used as mixed solvent.In these, especially for excellent dispersion, boiling point is low, volatility the is high solvent of the excellent dispersion of adhesive of the present invention, electrode active material and conductivity-imparting agent, can remove under low temperature in the short time, therefore preferably.Preferred acetone, toluene, cyclohexanone, pentamethylene, oxolane, cyclohexane, dimethylbenzene, water or 1-METHYLPYRROLIDONE or these mixed solvent.In addition, effect of the present invention, when using water-dispersion type particle shape macromolecule as adhesive, can be seen significantly, as solvent, and particularly preferably water.
As long as the solid component concentration of anode of secondary battery slurry used in the present invention be can be coated with, the degree of flooding and the degree that can form the viscosity with mobility be just not particularly limited, but be generally about 10 ~ 80 quality %.
In addition, in anode of secondary battery slurry, except containing manganese or iron positive active material and, fibrous carbon and, the polymerized unit by containing (methyl) acrylate monomer, the polymerized unit with the vinyl monomer of sour composition and α, the adhesive that the polymer that the polymerized unit of alpha, beta-unsaturated nitriles monomer is formed is formed and, beyond solvent, also containing what use in above-mentioned anode of secondary cell, there is other compositions such as the electrolysis additive suppressing the function such as dispersant and electrolyte decomposition.These however bring impact to be just not particularly limited to cell reaction.
(method for making of anode of secondary battery slurry)
In the present invention, the method for making of anode of secondary battery slurry is not particularly limited, by mixing above-mentioned positive active material, fibrous carbon, adhesive and solvent and other composition of adding as required can obtain.The mentioned component of the application of the invention, no matter how are mixed method and order by merging, can obtain the positive pole slurry of positive active material and fibrous carbon high degree of dispersion.As long as the device that mentioned component mixes equably can just be not particularly limited by mixing arrangement, ball mill, ball mill, roller mill, sand mill, pigment dispersion machine, pulverizing mill, ultrasonic dispersing machine, homogenizer, planetary mixer, filling mixer (FILMICS) etc. can be used, but particularly preferably use ball mill, roller mill, pigment dispersion machine, pulverizing mill, the planetary mixer that wherein can disperse in higher concentrations.
The viscosity of positive pole slurry, from the viewpoint of uniform applicability, slurry ageing stability, is preferably 10 ~ 100000mPas, is more preferably 100 ~ 50000mPas.Above-mentioned viscosity be use Brookfield viscometer 25 DEG C, measure under revolution 60rpm time value.
(secondary cell)
Secondary cell of the present invention possesses positive pole, negative pole, dividing plate and electrolyte, above-mentioned just having collector body and positive electrode active material layer, described positive electrode active material layer on the current collector, and containing containing manganese or iron positive active material and, fibrous carbon and, above-mentioned adhesive forms.
As above-mentioned secondary cell, can enumerate: lithium rechargeable battery, nickel-hydrogen secondary cell etc., but from the viewpoint of as purposes expect the performance raisings such as the raising of the raising power characteristic of long-term cycle characteristics most time, preferred lithium ion secondary battery.Below, situation about using for lithium rechargeable battery is described.
(electrolyte solution for lithium ion secondary battery)
As the electrolyte of lithium rechargeable battery, use the organic electrolyte be dissolved in by supporting electrolyte in organic solvent.As supporting electrolyte, lithium salts can be used.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, the high degree of dissociation of display of solvent is preferably easily dissolved in: LiPF 6, LiCIO 4, CF 3sO 3li.More than two kinds can combinationally use by these.Use the higher supporting electrolyte of degree of dissociation more can improve lithium ion conduction degree, therefore, lithium ion conduction degree can be regulated by the kind of supporting electrolyte.
As the organic solvent of the electrolyte for lithium rechargeable battery, as long as the solvent that can dissolve supporting electrolyte is just not particularly limited, but preferably use the carbonates such as dimethyl carbonate (DMC), ethylene carbonate (EC), diethyl carbonate (DEC), propylene carbonate (PC), butylene carbonate (BC), methyl ethyl carbonate (MEC); The ester such as gamma-butyrolacton, methyl formate class; The ethers such as 1,2-dimethoxy-ethane, oxolane; The sulfur-containing compound such as sulfolane, dimethyl sulfoxide (DMSO) class.In addition, the mixed liquor of these solvents can also be used.Wherein, the carbonates that the potential areas that preferred permittivity is high, stable is wide.The viscosity of solvent used is lower, and lithium ion conduction degree is higher, therefore, by the kind of solvent, can regulate lithium ion conduction degree.
In addition, for above-mentioned electrolyte, also can use the electrolyte containing additive.As additive, the compound of the carbonates such as the vinylene carbonate (VC) used in above-mentioned anode of secondary battery slurry can be enumerated.
The concentration of the supporting electrolyte in the electrolyte of lithium rechargeable battery, is generally 1 ~ 30 quality %, is preferably 5 ~ 20 quality %.In addition, according to the kind of supporting electrolyte, usually use under the concentration of 0.5 ~ 2.5 mole/L.No matter the concentration of supporting electrolyte is too low or too high, all can there is the tendency that ionic conductivity declines.
In addition, as electrolyte, the gel-polymer electrolyte matter and LiI, Li that impregnated of electrolyte in the polymer dielectric such as poly(ethylene oxide), polyacrylonitrile and above-mentioned polymer dielectric can be used in 3the inorganic solid electrolytes such as N.
(separator for lithium ion secondary battery)
As dividing plate, microporous barrier or the nonwoven fabrics of the polyolefin such as polyethylene, polypropylene can be used; The known materials such as the porous resin film (コ-ト, coat) containing inorganic ceramic powder.
As separator for lithium ion secondary battery, the microporous barrier or nonwoven fabrics that form containing the vistanex such as polyethylene, polypropylene and aromatic polyamide resin can be used; The known materials such as the porous resin film containing inorganic ceramic powder.Can enumerate such as: the microporous barrier be made up of TPO (polyethylene, polypropylene, polybutene, polyvinyl chloride) and the resin such as these mixture or copolymer; The fabric that the microporous barrier be made up of resins such as PETG, polycyclic alkene, polyether sulfone, polyamide, polyimides, polyimide amide, Nomex, polycyclic alkene, nylon, polytetrafluoroethylene or polyolefin fibrids are made into or its nonwoven fabrics; The aggregation etc. of insulating properties material particle.In these, in order to make the thinning capacity improving active material ratio in battery and unit volume of the thickness of dividing plate entirety, the micro-porous film be preferably made up of polyolefin resin.
The thickness of dividing plate is generally 0.5 ~ 40 μm, is preferably 1 ~ 30 μm, is more preferably 1 ~ 10 μm.When becoming this scope by making the thickness of dividing plate, in the resistance decreasing that battery inner route clapboard causes, operability when making battery is in addition excellent.
(lithium ion secondary battery negative pole)
Lithium ion secondary battery cathode, is formed by collector body and lamination contains negative electrode active material and adhesive on the current collector negative electrode active material layer.As adhesive and collector body, material same in the explanation with anode of secondary cell can be enumerated.
(lithium ion secondary battery cathode active material)
As the electrode active material (negative electrode active material) of lithium ion secondary battery negative pole, can enumerate such as: the carbonaceous materials such as armorphous carbon, graphite, native graphite, meso carbon microballoon, pitch-based carbon fiber; The electroconductive polymers etc. such as coalescence benzene.In addition, as negative electrode active material, metal and their alloys such as silicon, tin, zinc, manganese, iron, nickel can be used; The oxide of above-mentioned metal or alloy and sulfate.In addition, the lithium alloy such as lithium metal, Li-Al, Li-Bi-Cd, Li-Sn-Cd, lithium transition-metal nitride, silicon etc. can also be used.Negative electrode active material also can use the material being given material by mechanically modifying method in surface attachment conductivity.The particle diameter of negative electrode active material carries out suitable selection under other constitutive requirements taking into account battery, but, from the viewpoint of battery behaviors such as raising initial efficiency, part throttle characteristics, cycle characteristicss, 50% volume-cumulative particle diameter is generally 1 ~ 50 μm, is preferably 15 ~ 30 μm.
Containing of negative electrode active material in negative electrode active material layer is proportional, is preferably 90 ~ 99.9 quality %, is more preferably 95 ~ 99 quality %.By the content of the negative electrode active material in negative electrode active material layer is set in above-mentioned scope, both can show high capacity, high flexibility, caking property can be shown again.
For lithium ion secondary battery cathode, in addition to the aforementioned ingredients, containing the dispersant used in above-mentioned anode of secondary cell and other compositions such as the electrolysis additive that suppresses the functions such as electrolyte decomposition can also be had.These however bring the material of impact to be just not particularly limited to cell reaction.
(lithium ion secondary battery negative pole adhesive)
As lithium ion secondary battery negative pole adhesive, be not particularly limited, known adhesive can be used.Can use such as: the soft polymers such as resin and acrylic compounds soft polymer, dienes soft polymer, olefines soft polymer, vinyl-based soft polymer such as polyethylene, polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), tetrafluoraoethylene-hexafluoropropylene copolymer (FEP), polyacrylic acid derivative, HPAM Degraded Bacteria.These both can be used alone also can two or more also use.
As collector body, can use and state the collector body used in anode of secondary cell, as long as there is conductivity and have on electrochemistry durability material can and be not particularly limited, but as negative pole used time of lithium rechargeable battery, particularly preferably copper.
The thickness of lithium ion secondary battery negative pole, is generally 5 ~ 300 μm, is preferably 10 ~ 250 μm.By thickness of electrode is set in above-mentioned scope, part throttle characteristics and energy density can be made to show high characteristic simultaneously.
Lithium ion secondary battery negative pole, can carry out same operation to manufacture with above-mentioned lithium ion secondary battery positive electrode.
As the concrete manufacture method of lithium rechargeable battery, following method can being enumerated: overlap getting involved dividing plate between positive pole and negative pole, being reeled according to cell shapes, folding, then, put into battery case, in battery case, inject electrolyte and carry out envelope ロ.Can as required, put into metal lath and fuse, PTC element etc. prevent the element of overload current, lead plate etc. from preventing cell internal pressure from rising and crossing discharge and recharge.The shape of battery can be any one in Coin shape, button type, flap-type, column type, square, platypelloid type etc.
Embodiment
Below, enumerate embodiment and the present invention is described, but the present invention is not limited to these embodiments.In addition, the part in the present embodiment and % are quality criteria in case of no particular description.In embodiment and comparative example, various physical property is evaluated in the following manner.
< battery behavior: high-temperature cycle >
10 pieces are filled up the Coin-shaped battery of electrolyte, under 60 DEG C of atmosphere gas, adopt 0.2C to determine current method, charge to 4.3V, be discharged to 3.0V, repeatedly carry out discharge and recharge, measure capacitance.Using 10 pieces of mean values as measured value, the charge/discharge capacity conservation rate that the ratio (%) of capacitance when capacitance when obtaining 50 loop terminations and 5 loop terminations represents, it can be used as the metewand of cycle characteristics, evaluate with following benchmark.This value is higher, and high-temperature cycle is more excellent.
More than A:80%
More than B:70% and lower than 80%
More than C:50% and lower than 70%
More than D:30% and lower than 50%
E: lower than 30%
< adhesive properties: storage stability >
By the aqueous dispersions of polymer obtained, preserving 50 days in sombre dark place (is a) by the weight set of the aqueous dispersions before preserving.By the aqueous dispersions of the polymer after 50 days, filter with the sieve in 200 mesh sieve holes, the weight set of residue (is b) by the dry weight obtaining on sieve residual solids, obtain the ratio (%) of the dry weight (b) of solids residual on the weight (a) of the aqueous dispersions before preservation and sieve, it can be used as the metewand of the storage stability of adhesive, evaluate with following benchmark.This value is less, and the storage stability of adhesive is more excellent.
A: lower than 0.001%
More than B:0.001% and lower than 0.01%
More than C:0.01% and lower than 0.1%
More than D:0.1%
< electrode characteristic: be full of cracks measures >
Electrode is cut into the rectangle of fabric width 3cm × length 9cm, make test piece.The facing down of current collection side of test piece is placed on kitchen table, along the stainless steel bar of fabric width direction landscape configuration diameter 1mm on the face on the central authorities (position from end 4.5cm) of length direction, current collection side.Using this stainless steel bar as center, test piece is converted into 180 ° by the mode becoming outside with active material layer.Test 10 pieces of test pieces, that observes the dogleg section of the active material layer of each test piece has flawless or stripping, is judged by following benchmark.Crackle or peel off fewer, electrode be full of cracks generation fewer, fail safe is more excellent.
Crackle or stripping is all can't see in A:10 piece
See having crackle or stripping for 1 ~ 3 piece in B:10 piece
See having crackle or stripping for 4 ~ 9 pieces in C:10 piece
Crackle or stripping is all seen in D:10 piece
(embodiment 1)
(A) manufacture of adhesive
2-EHA 10.75 parts is added in polymerization tank A, acrylonitrile 1.25 parts, lauryl sodium sulfate 0.12 part, ion exchange water 79 parts, then, add the ammonium persulfate 0.2 part as polymerization initiator, ion exchange water 10 parts, to heat to 60 DEG C and after stirring 90 minutes, 2-EHA 67 parts is added in another polymerization tank B, acrylonitrile 19 parts, methacrylic acid 2.0 parts, lauryl sodium sulfate 0.7 part, ion exchange water 46 parts also stirs, after the emulsion made being placed about 180 minutes and successively add in polymerization tank A from polymerization tank B, stir about 120 minutes, cooling is carried out and cessation reaction when monomer consumption reaches 95%, thereafter 4%NaOH aqueous solution adjust ph is used, obtain the aqueous dispersions of adhesive A.The glass transition temperature of the adhesive A obtained is-32 DEG C, and dispersion particle diameter is 0.15 μm, and the pH value of the aqueous dispersions of adhesive A is 10.5.The result using the aqueous dispersions obtained to evaluate adhesive storage stability is shown in table 1.
The polymerized unit of (methyl) acrylate monomer in adhesive A containing proportional be 78%, have the polymerized unit of the vinyl monomer of sour composition containing proportional be 2.0%, α, the polymerized unit of alpha, beta-unsaturated nitriles monomer containing proportional be 20%, have the polymerized unit of bridging property containing proportional be 0%.
(B) manufacture of positive pole slurry and positive pole
Using the LiFePO of the olivine-type crystal structure as electrode active material 4(fiber diameter: 150nm, average fiber are long: 8 μm, mean aspect ratio: 53, be sometimes recited as below " carbon fiber 1 " for (particle diameter: 0.2 μm) 100 parts, carbon fiber.) 1 part, acetylene black (HS-100: electrochemically industry) 5 parts, above-mentioned adhesive A aqueous dispersions 2.5 parts (solid component concentration 40%), be the carboxymethyl cellulose aqueous solution 40 parts (solid component concentration 2%) of 0.8 and appropriate water as the degree of etherification falling of tackifier, stir in planetary mixer, make positive pole slurry.By above-mentioned positive pole slurry, be coated with spot printing machine on the aluminium foil of thickness 20 μm, make dried thickness become about 70 μm, at 60 DEG C after dry 20 minutes, at 150 DEG C, heat treated 2 hours, obtains electrode blank.Roll this electrode blank with roll squeezer roller, making density is 2.1g/cm 3and the THICKNESS CONTROL be made up of aluminium foil and electrode active material layer is at the anode plate of 65 μm.The pole plate made is used to carry out the mensuration occurred that chaps.Show the result in table 1.
(C) making of battery
Above-mentioned anode plate is die-cut into the discoid of diameter 16mm, in the active material aspect side of this positive pole, the dividing plate that the discoid polypropylene perforated membrane of diameter 18mm, thickness 25 μm is formed, the lithium metal used as negative pole, expanding metal place it in the Coin shape exterior package container (diameter 20mm, highly 1.8mm, stainless steel thickness 0.25mm) of the stainless steel being configured with polypropylene packaging material after carrying out lamination successively.Electrolyte is injected in this embodiment in the mode not remaining air, by polypropylene packaging material, in exterior package container, the stainless cover of thickness 0.2mm on cover is also fixing, sealed cell tank, makes diameter 20mm, lithium ion Coin-shaped battery that thickness is about 2mm.It should be noted that, as electrolyte, in the mixed solvent using ethylene carbonate (EC) and diethyl carbonate (DEC) to mix with the ratio of EC:DEC=1:2 (volumetric ratios at 20 DEG C), with the concentration dissolving LiPF of 1 mol/L 6solution.Use this cell evaluation high-temperature cycle.The results are shown in table 1.
(embodiment 2)
(A) manufacture of adhesive
2-EHA 10.75 parts is added in polymerization tank A, acrylonitrile 1.25 parts, lauryl sodium sulfate 0.12 part, ion exchange water 79 parts, add the ammonium persulfate 0.2 part as polymerization initiator again, ion exchange water 10 parts, to heat to 60 DEG C and after stirring 90 minutes, 2-EHA 67 parts is added in another polymerization tank B, acrylonitrile 19 parts, methacrylic acid 2.0 parts, metering system allyl ester 0.2 part, lauryl sodium sulfate 0.7 part, ion exchange water 46 parts also stirs, after the emulsion made being placed about 180 minutes and successively add in polymerization tank A from polymerization tank B, stir about 120 minutes, cooling is carried out and cessation reaction when monomer consumption reaches 95%, thereafter, by 4%NaOH aqueous solution adjust ph, obtain the aqueous dispersions of adhesive B.The glass transition temperature of the adhesive B obtained is-32 DEG C, dispersion particle diameter is 0.15 μm, the pH value of the aqueous dispersions of adhesive B is 10.1.The result using the aqueous dispersions obtained to evaluate adhesive storage stability is shown in table 1.The polymerized unit of (methyl) acrylate monomer in adhesive B containing proportional be 78%, have the polymerized unit of the vinyl monomer of sour composition containing proportional be 2.0%, α, the polymerized unit of alpha, beta-unsaturated nitriles monomer containing proportional be 20%, have the polymerized unit of bridging property containing proportional be 0.2%.
Except using the aqueous dispersions of above-mentioned adhesive B as except positive pole adhesive, operating similarly to Example 1, making anode plate, lithium ion Coin-shaped battery.Then, measure the be full of cracks of this pole plate and use lithium ion Coin-shaped battery to evaluate high-temperature cycle.The results are shown in table 1.
(embodiment 3)
Except using 1 part of fiber diameter: 50nm, average fiber length as carbon fiber: 1 μm, mean aspect ratio: the carbon fiber of 20 is (following, sometimes be recited as " carbon fiber 2 ") substitute beyond carbon fiber 1, operate similarly to Example 1, make anode plate, lithium ion Coin-shaped battery.Then, measure the be full of cracks of this pole plate and use lithium ion Coin-shaped battery to evaluate high-temperature cycle.The results are shown in table 1.
(embodiment 4)
Except using 1 part for fiber diameter as carbon fiber: 500nm, average fiber length: 100 μm, mean aspect ratio: the carbon fiber of 200 is (following, sometimes be recited as " carbon fiber 3 ") substitute beyond carbon fiber 1, operate similarly to Example 1, make anode plate, lithium ion Coin-shaped battery.Then, measure the be full of cracks of this pole plate and use lithium ion Coin-shaped battery to evaluate high-temperature cycle.The results are shown in table 1.
(embodiment 5)
Be set as, except 5 parts, operating similarly to Example 1 except by the use number of carbon fiber 1, make anode plate, lithium ion Coin-shaped battery.Then, measure the be full of cracks of this pole plate and use lithium ion Coin-shaped battery to evaluate high-temperature cycle.The results are shown in table 1.
(embodiment 6)
The use number 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, measure the be full of cracks of this pole plate and use lithium ion Coin-shaped battery to evaluate high-temperature cycle.The results are shown in table 1.
(embodiment 7)
Spinel manganese (LiMn is used as positive active material 2o 4; Mn content 60%, average grain diameter 8 μm) 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, measure the be full of cracks of this pole plate and use lithium ion Coin-shaped battery to evaluate high-temperature cycle.The results are shown in table 1.It should be noted that, the density of positive electrode active material layer is now set as 2.5g/cm 3.
(embodiment 8)
Use the aqueous dispersions of adhesive B to substitute except the aqueous dispersions of adhesive A except as positive pole adhesive, operate similarly to Example 7, make anode plate, lithium ion Coin-shaped battery.Then, measure the be full of cracks of this pole plate and use lithium ion Coin-shaped battery to evaluate high-temperature cycle.The results are shown in table 1.
(embodiment 9)
(A) manufacture of adhesive
2-EHA 10.75 parts is added in polymerization tank A, acrylonitrile 1.25 parts, lauryl sodium sulfate 0.12 part, ion exchange water 79 parts, add the ammonium persulfate 0.2 part as polymerization initiator again, ion exchange water 10 parts, to heat to 60 DEG C and after stirring 90 minutes, 2-EHA 67 parts will be added in another polymerization tank B, acrylonitrile 19 parts, methacrylic acid 2.0 parts, allyl glycidyl ether 0.2 part, lauryl sodium sulfate 0.7 part, ion exchange water 46 parts the emulsion carried out stirring and make, place after about 180 minutes, successively add to after polymerization tank A from polymerization tank B, stir about 120 minutes, cooling is carried out and cessation reaction when monomer consumption reaches 95%, thereafter 4%NaOH aqueous solution adjust ph is used, obtain the aqueous dispersions of adhesive E.The glass transition temperature of the adhesive E obtained is-32 DEG C, and dispersion particle diameter is 0.15 μm, and the pH value of the aqueous dispersions of adhesive E is 10.1.The result using the aqueous dispersions obtained to evaluate adhesive storage stability is shown in table 1.The polymerized unit of (methyl) acrylate monomer in adhesive E containing proportional be 78%, have the polymerized unit of the vinyl monomer of sour composition containing proportional be 2.0%, α, the polymerized unit of alpha, beta-unsaturated nitriles monomer containing proportional be 20%, have the polymerized unit of bridging property containing proportional be 0.2%.
Except using the aqueous dispersions of above-mentioned adhesive E as except positive pole adhesive, operating similarly to Example 1, making anode plate, lithium ion Coin-shaped battery.Then, measure the be full of cracks of this pole plate and use lithium ion Coin-shaped battery to evaluate high-temperature cycle.The results are shown in table 1.
(embodiment 10)
(A) manufacture of adhesive
2-EHA 10.75 parts is added in polymerization tank A, acrylonitrile 1.25 parts, lauryl sodium sulfate 0.12 part, ion exchange water 79 parts, add the ammonium persulfate 0.2 part as polymerization initiator again, ion exchange water 10 parts, to heat to 60 DEG C and after carrying out stirring 90 minutes, 2-EHA 67 parts is added in another polymerization tank B, acrylonitrile 19 parts, methacrylic acid 2.0 parts, ethylene glycol dimethacrylate 0.2 part, lauryl sodium sulfate 0.7 part, ion exchange water 46 parts the emulsion carried out stirring and make, place after about 180 minutes, after successively adding in polymerization tank A from polymerization tank B, stir about 120 minutes, cooling is carried out and cessation reaction when monomer consumption reaches 95%, thereafter 4%NaOH aqueous solution adjust ph is used, obtain the aqueous dispersions of adhesive F.The glass transition temperature of the adhesive F obtained is-32 DEG C, and dispersion particle diameter is 0.15 μm, and the pH value of the aqueous dispersions of adhesive F is 10.1.The result using the aqueous dispersions obtained to evaluate adhesive storage stability is shown in table 1.The polymerized unit of (methyl) acrylate monomer in adhesive F containing proportional be 78%, have the polymerized unit of the vinyl monomer of sour composition containing proportional be 2.0%, α, the polymerized unit of alpha, beta-unsaturated nitriles monomer containing proportional be 20%, other polymerized unit containing proportional be 0.2%.
Except using the aqueous dispersions of above-mentioned adhesive F as except positive pole adhesive, operating similarly to Example 1, making anode plate, lithium ion Coin-shaped battery.Then, measure the be full of cracks of this pole plate and use lithium ion Coin-shaped battery to evaluate high-temperature cycle.The results are shown in table 1.
(comparative example 1)
Except not using except carbon fiber, operating similarly to Example 2, making anode plate, lithium ion Coin-shaped battery.Then, measure the be full of cracks of this pole plate and use lithium ion Coin-shaped battery to evaluate high-temperature cycle.The results are shown in table 1.
(comparative example 2)
Except not using except carbon fiber, operating similarly to Example 8, making anode plate, lithium ion Coin-shaped battery.Then, measure the be full of cracks of this pole plate and use lithium ion Coin-shaped battery to evaluate high-temperature cycle.The results are shown in table 1.
(comparative example 3)
(A) manufacture of adhesive
2-EHA 10.75 parts is added in polymerization tank A, acrylonitrile 1.25 parts, lauryl sodium sulfate 0.12 part, ion exchange water 79 parts, add the ammonium persulfate 0.2 part as polymerization initiator again, ion exchange water 10 parts, heating to 60 DEG C and carrying out stirring after 90 minutes, 2-EHA 68 parts is added in another polymerization tank B, acrylonitrile 19 parts, methacrylic acid 0.8 part, allyl methacrylate 0.2 part, lauryl sodium sulfate 0.7 part, ion exchange water 46 parts also carries out stirring and the emulsion that will make, place after about 180 minutes, after successively adding in polymerization tank A from polymerization tank B, stir about 120 minutes, cooling is carried out and cessation reaction when monomer consumption reaches 95%, thereafter 4%NaOH aqueous solution adjust ph is used, obtain the aqueous dispersions of adhesive C.The glass transition temperature of the adhesive C obtained is-32 DEG C, and dispersion particle diameter is 0.15 μm, and the pH value of the aqueous dispersions of adhesive C is 10.1.The result using the aqueous dispersions obtained to evaluate adhesive storage stability is shown in table 1.The polymerized unit of (methyl) acrylate monomer in adhesive C F containing proportional be 79%, have the polymerized unit of the vinyl monomer of sour composition containing proportional be 0.8%, α, the polymerized unit of alpha, beta-unsaturated nitriles monomer containing proportional be 20%, have the polymerized unit of bridging property containing proportional be 0.2%.
Except using the aqueous dispersions of above-mentioned adhesive C as except positive pole adhesive, operating similarly to Example 1, making anode plate, lithium ion Coin-shaped battery.Then, measure the be full of cracks of this pole plate and use lithium ion Coin-shaped battery to evaluate high-temperature cycle.The results are shown in table 1.
(comparative example 4)
(A) manufacture of adhesive
2-EHA 10.75 parts is added in polymerization tank A, acrylonitrile 1.25 parts, lauryl sodium sulfate 0.12 part, ion exchange water 79 parts, add the ammonium persulfate 0.2 part as polymerization initiator again, ion exchange water 10 parts, heating to 60 DEG C and carrying out stirring after 90 minutes, 2-EHA 65.3 parts is added in another polymerization tank B, acrylonitrile 19 parts, methacrylic acid 3.5 parts, allyl methacrylate 0.2 part, lauryl sodium sulfate 0.7 part, ion exchange water 46 parts also carries out stirring and the emulsion that will make, place after about 180 minutes, stir about 120 minutes after successively adding in polymerization tank A from polymerization tank B, cooling is carried out and cessation reaction when monomer consumption reaches 95%, thereafter 4%NaOH aqueous solution adjust ph is used, obtain the aqueous dispersions of adhesive D.The glass transition temperature of the adhesive D obtained is-32 DEG C, and dispersion particle diameter is 0.15 μm, and the pH value of the aqueous dispersions of adhesive D is 10.1.The result using the aqueous dispersions obtained to evaluate adhesive storage stability is shown in table 1.The polymerized unit of (methyl) acrylate monomer in adhesive D containing proportional be 76.3%, have the polymerized unit of the vinyl monomer of sour composition containing proportional be 3.5%, α, the polymerized unit of alpha, beta-unsaturated nitriles monomer containing proportional be 20%, have the polymerized unit of bridging property containing proportional be 0.2%.
Except using the aqueous dispersions of above-mentioned adhesive D as except positive pole adhesive, operating similarly to Example 1, making anode plate, lithium ion Coin-shaped battery.Then, measure the be full of cracks of this pole plate and use lithium ion Coin-shaped battery to evaluate high-temperature cycle.The results are shown in table 1.[table 1]
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: containing manganese or iron positive active material and, fibrous carbon and, the polymerized unit by containing (methyl) acrylate monomer, the polymerized unit with the vinyl monomer of sour composition and α, the adhesive of the polymer formation of the polymerized unit formation of alpha, beta-unsaturated nitriles monomer, it can prevent the generation of the be full of cracks in positive electrode active material layer, namely fail safe can be improved, 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 not containing fibrous carbon, the anode of secondary cell of 2, and there is in the adhesive used the comparative example 3 containing the proportional adhesive lower than 1.0 quality % of the polymerized unit of the vinyl monomer of sour composition, and use is more than the anode of secondary cell of the comparative example 4 of the adhesive of 3.0 quality %, be difficult to the generation of the be full of cracks prevented in positive electrode active material layer, the high-temperature cycle of battery declines.

Claims (6)

1. an anode of secondary cell, it comprises collector body and positive electrode active material layer, and described positive electrode active material layer is stacked on described collector body, and contains the positive active material, fibrous carbon and the adhesive that contain manganese or iron, wherein,
Described adhesive is by the polymerized unit containing (methyl) acrylate monomer, the polymerized unit with the vinyl monomer of sour composition and α, and the polymer of the polymerized unit of alpha, beta-unsaturated nitriles monomer is formed,
Described there is the polymerized unit of the vinyl monomer of sour composition in whole polymerized units of polymer, account for 1.0 ~ 3.0 quality % containing proportional,
The polymerized unit of described (methyl) acrylate monomer in whole polymerized units of polymer, account for 50 ~ 95 quality % containing proportional,
Described α, the polymerized unit of alpha, beta-unsaturated nitriles monomer in whole polymerized units of polymer, account for 3 ~ 40 quality % containing proportional,
Described adhesive further containing the polymerized unit with heat cross-linking,
The described polymerized unit with heat cross-linking comprises: be derived from the polymerized unit with mono-functional's monomer of 1 alkene double bond of the crosslinkable groups with heat cross-linking and/or be derived from the polymerized unit of the multi-functional monomer with at least 2 alkene double bonds
The crosslinkable groups of described heat cross-linking is selected from by epoxy radicals, N-methylol amide base, oxetanyl Ji at least one in the group that forms of oxazolinyl.
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 μm.
4. anode of secondary cell according to claim 1 and 2, wherein, the mean aspect ratio of described fibrous carbon is 5 ~ 50000.
5. anode of secondary cell according to claim 1 and 2, wherein, described in there is sour composition vinyl monomer be the monomer with carboxylic acid group.
6. a secondary cell, it possesses positive pole, negative pole, dividing plate and electrolyte, described anode of secondary cell just very described in claim 1 or 2.
CN201180036571.5A 2010-05-25 2011-05-25 Anode of secondary cell and secondary cell Active CN103026535B (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP2010-119693 2010-05-25
JP2010119693 2010-05-25
PCT/JP2011/061963 WO2011148970A1 (en) 2010-05-25 2011-05-25 Positive electrode for secondary battery, and secondary battery

Publications (2)

Publication Number Publication Date
CN103026535A CN103026535A (en) 2013-04-03
CN103026535B true CN103026535B (en) 2016-03-09

Family

ID=45003959

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201180036571.5A Active CN103026535B (en) 2010-05-25 2011-05-25 Anode of secondary cell and secondary cell

Country Status (3)

Country Link
JP (1) JP5783172B2 (en)
CN (1) CN103026535B (en)
WO (1) WO2011148970A1 (en)

Families Citing this family (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5625007B2 (en) * 2012-03-08 2014-11-12 株式会社日立製作所 Positive electrode for lithium ion secondary battery, lithium ion secondary battery and battery module
JP6077347B2 (en) * 2012-04-10 2017-02-08 株式会社半導体エネルギー研究所 Method for producing positive electrode for non-aqueous secondary battery
JP5447720B1 (en) * 2012-05-31 2014-03-19 ダイソー株式会社 Battery electrode binder, and electrode and battery using the same
KR101858798B1 (en) * 2013-01-29 2018-05-16 가부시키가이샤 오사카소다 Binder for battery electrode, and electrode and battery using same
WO2014129188A1 (en) * 2013-02-19 2014-08-28 日本ゼオン株式会社 Slurry composition for positive electrodes of lithium ion secondary batteries, method for producing positive electrode for lithium ion secondary batteries, positive electrode for lithium ion secondary batteries, and lithium ion secondary battery
US20160118663A1 (en) * 2013-05-29 2016-04-28 Zeon Corporation Slurry composition for positive electrode of lithium ion secondary battery, method of producing positive electrode for lithium ion secondary battery, positive electrode for lithium ion secondary battery, and lithium ion secondary battery
JP2015056282A (en) * 2013-09-12 2015-03-23 八千代工業株式会社 Polymer solid electrolyte battery
KR101931418B1 (en) * 2013-10-29 2018-12-20 가부시키가이샤 오사카소다 Battery electrode binder and battery and electrode using same
US9385374B2 (en) * 2014-04-01 2016-07-05 Ppg Industries Ohio, Inc. Electrode binder composition for lithium ion electrical storage devices
EP3154113B1 (en) * 2014-06-04 2022-05-04 Zeon Corporation Binder composition for lithium ion secondary battery electrode-use, slurry composition for lithium ion secondary cell electrode-use, electroe for lithium secondary cell electrode-use, and lithium ion secondary cell
US10483525B2 (en) * 2015-03-24 2019-11-19 Sanyo Electric Co., Ltd. Non-aqueous electrolyte secondary battery
JP7108372B2 (en) * 2015-06-18 2022-07-28 帝人株式会社 Electrode mixture layer for non-aqueous electrolyte secondary battery, electrode for non-aqueous electrolyte secondary battery, and non-aqueous electrolyte secondary battery
JP6569324B2 (en) * 2015-06-24 2019-09-04 日本ゼオン株式会社 Conductive material dispersion for electrochemical device, slurry for electrochemical device positive electrode, method for producing slurry for positive electrode of electrochemical device, positive electrode for electrochemical device and electrochemical device
JP6572639B2 (en) * 2015-06-24 2019-09-11 日本ゼオン株式会社 Conductive material dispersion for electrochemical device, slurry for electrochemical device positive electrode, method for producing slurry for positive electrode of electrochemical device, positive electrode for electrochemical device and electrochemical device
US20180301744A1 (en) * 2015-06-24 2018-10-18 Zeon Corporation Composition for electrochemical device electrode, electrode for electrochemical device, electrochemical device, and method of producing composition for electrochemical device electrode
JP6670231B2 (en) 2016-12-22 2020-03-18 I&Tニューマテリアルズ株式会社 Electrode of power storage device, slurry for electrode of power storage device, and method of manufacturing the same
WO2018168657A1 (en) * 2017-03-13 2018-09-20 日本ゼオン株式会社 Slurry composition for nonaqueous secondary battery functional layers, functional layer for nonaqueous secondary batteries, and nonaqueous secondary battery
KR20210048493A (en) * 2018-08-31 2021-05-03 니폰 제온 가부시키가이샤 Binder composition for all-solid secondary battery, slurry composition for all-solid secondary battery electrode mixture layer, slurry composition for solid electrolyte layer for all-solid secondary battery, electrode for all-solid secondary battery, solid electrolyte layer for all-solid secondary battery, and all-solid secondary battery
JP7030766B2 (en) * 2019-12-05 2022-03-07 I&Tニューマテリアルズ株式会社 Electrodes of power storage devices and their manufacturing methods

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1402365A (en) * 2001-08-02 2003-03-12 松下电器产业株式会社 Anode for nonaqueous secondary cell and mfg. method thereof
CN101510623A (en) * 2008-02-13 2009-08-19 索尼株式会社 Cathode and nonaqueous electrolyte battery

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006335971A (en) * 2005-06-06 2006-12-14 Hitachi Chem Co Ltd Acrylic resin, binder composition using the same and secondary battery using the same
JP2007019108A (en) * 2005-07-05 2007-01-25 Fuji Heavy Ind Ltd Lithium ion capacitor
JP2007067088A (en) * 2005-08-30 2007-03-15 Fuji Heavy Ind Ltd Lithium ion capacitor
JP2009117159A (en) * 2007-11-06 2009-05-28 Sony Corp Positive electrode and lithium ion secondary battery

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1402365A (en) * 2001-08-02 2003-03-12 松下电器产业株式会社 Anode for nonaqueous secondary cell and mfg. method thereof
CN101510623A (en) * 2008-02-13 2009-08-19 索尼株式会社 Cathode and nonaqueous electrolyte battery

Also Published As

Publication number Publication date
CN103026535A (en) 2013-04-03
JP5783172B2 (en) 2015-09-24
JPWO2011148970A1 (en) 2013-07-25
WO2011148970A1 (en) 2011-12-01

Similar Documents

Publication Publication Date Title
CN103026535B (en) Anode of secondary cell and secondary cell
CN102473918B (en) Positive electrode for secondary batteries, and secondary battery
CN104396060B (en) Lithium rechargeable battery
US10559828B2 (en) Slurry for lithium ion secondary battery positive electrodes
CN102859777B (en) Lithium rechargeable battery
CN102549820B (en) Electrode for secondary battery, binder for secondary battery electrode and secondary cell
CN103283061B (en) Secondary battery porous membrane, slurry for secondary battery porous membrane, and secondary battery
JP4884774B2 (en) Method for producing electrode for electrochemical cell
CN103250273B (en) Secondary cell perforated membrane slurry, secondary cell perforated membrane, electrode for secondary battery, secondary battery separator and secondary cell
CN104685673B (en) The manufacture method of the manufacture method of anode of secondary cell, secondary cell and secondary cell laminated body
CN103069612B (en) Porous membrane for secondary battery, production method therefor, and use thereof
CN103119755B (en) Secondary battery porous membrane, slurry for secondary battery porous membrane, and secondary battery
CN104221194B (en) Lithium rechargeable battery
CN107710472A (en) Use in electrode for secondary battery adhesive composition, use in electrode for secondary battery conductive material paste composite, slurry for secondary battery electrode composition, electrode for secondary battery and secondary cell
CN103081181A (en) Slurry composition for porous film in battery, method for manufacturing porous film for secondary battery, porous film for secondary battery, electrode for secondary battery, separator for secondary battery, and secondary battery
JP6838551B2 (en) Binder composition for lithium ion secondary battery electrode, slurry composition for lithium ion secondary battery electrode, electrode for lithium ion secondary battery and lithium ion secondary battery
CN104011920A (en) Positive electrode for secondary batteries, method for producing same, slurry composition, and secondary battery
CN103797613A (en) Slurry for secondary batteries
CN105074977A (en) Binder composition for secondary battery electrodes, method for producing same, slurry composition for secondary battery electrodes, electrode for secondary batteries, and secondary battery
CN104823308A (en) Lithium ion secondary battery
US9843042B2 (en) Cathode active material composition and lithium secondary battery including the same
CN104247110A (en) Negative electrode for secondary cell, and secondary cell
CN110462898A (en) Binder composition for non-aqueous secondary battery electrode, non-aqueous secondary battery slurry composition for electrode, non-aqueous secondary battery electrode and non-aqueous secondary battery and non-aqueous secondary battery electrode manufacturing method
WO2013176092A1 (en) Electrode mixture
KR20190121303A (en) Binder composition for non-aqueous secondary batteries, slurry composition for non-aqueous secondary battery functional layers, functional layer for non-aqueous secondary batteries, and non-aqueous secondary batteries

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant