CN104025350A - Positive-electrode mixture, positive electrode, and non-aqueous electrolyte secondary battery using same - Google Patents
Positive-electrode mixture, positive electrode, and non-aqueous electrolyte secondary battery using same Download PDFInfo
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- CN104025350A CN104025350A CN201280064831.4A CN201280064831A CN104025350A CN 104025350 A CN104025350 A CN 104025350A CN 201280064831 A CN201280064831 A CN 201280064831A CN 104025350 A CN104025350 A CN 104025350A
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- positive
- anode mixture
- acid
- active material
- electrode
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
-
- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
- H01M4/622—Binders being polymers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
- H01M10/34—Gastight accumulators
- H01M10/345—Gastight metal hydride accumulators
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
Provided is an aqueous positive-electrode mixture that has excellent dispersibility of positive-electrode active materials, storage stability, and coatability when coated onto a charge collector, and that, after being coated onto a charge collector, can produce a positive electrode having excellent adhesion between the charge collector and the positive-electrode active materials. Also provided are a positive electrode and a non-aqueous electrolyte secondary battery using same. This positive-electrode mixture contains a positive-electrode active material, a water-dispersible polymeric binder resin, a conductive assistant, and a surfactant.
Description
Technical field
The rechargeable nonaqueous electrolytic battery that the present invention relates to anode mixture, positive pole and use it, specifically, screening characteristics when relating to dispersiveness, the storage stability of positive active material and being coated on collector body is excellent, and is coated on and can accesses after collector body and anode mixture, the positive pole of the anodal water system of the adaptation excellence of collector body and positive active material and the rechargeable nonaqueous electrolytic battery that uses it.
Background technology
The miniaturization of electronic unit in recent years, multifunction development, portable electronic device goes on the market in a large number.They are expected for miniaturization, lightweight, as in the battery of its power supply, are requiring similarly miniaturization, lightweight.In addition, take environmental problem, resource problem is background, starts exploitation, manufactures, sells hybrid vehicle, electric automobile etc.For so so-called motor vehicle, small-sized and light weight, can charge and effective utilization of electric discharge, supply unit that energy density is high is indispensable.As these supply units, utilize the secondary cells such as lithium ion battery, Ni-MH battery, double electric layer capacitor etc.Especially for take the rechargeable nonaqueous electrolytic battery that lithium rechargeable battery is representative, from the height of energy density, can tolerate the height of the durability of charging repeatedly, electric discharge, it is concerned as supply unit, and deeply develops.
The electrode of secondary cell consists of active material, conductive auxiliary agent and the resin glue that bonds them collector body.Therefore secondary cell is negative or positive electrode volumetric expansion repeatedly, contraction when discharging and recharging, thereby exist, causes that coming off of active material, conductive auxiliary agent shorten the situation of the cycle life discharging and recharging.Therefore, require secondary cell can tolerate the swelling of electrode, the flexibility of contraction with resin glue, in the past, positive pole and negative pole were all used the fluororesin such as polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE) in a large number.
Yet common fluororesin is insufficient for the adaptation of collector body, therefore can not tackle the further requirement of rising of cycle life discharging and recharging.Especially, when polyvinylidene fluoride is used as to resin glue, a little less than the cohesive force of collector body or filler (positive active material and conductive auxiliary agent), therefore during battery manufacture and battery produce peeling off of collector body and electrode composition in using, there is the problem of the internal resistance increase of battery.
For such problem, for example, in patent documentation 1, as the fluororesin of resin glue, the copolymer of the monoesters isopolarity monomer of vinylidene fluoride and unsaturated dibasic acid has been proposed.Thus, can improve the caking property of fluororesin and collector body.In addition, in patent documentation 2 and patent documentation 3, as the resin glue of negative electrode active material, the aqueous dispersion emulsion of Styrene-Butadiene (SBR) particle has been proposed, by the sodium salt of SBR particle and carboxymethyl cellulose (CMC) or the composition that ammonium salt forms.As patent documentation 2 and 3 by use SBR particle in resin glue, thereby can prevent coming off of negative electrode active material when secondary cell uses.
And then, patent documentation 4 has proposed following technology: in being dissolved in the acrylic resin of resin glue of solvent, adding crosslinking agent, heating during by electrode fabrication, crimping process react acrylic resin and crosslinking agent, obtain three-dimensional crosslinking structure body, thus the coming off of the active material while preventing the discharging and recharging of secondary cell, conductive agent.And then, patent documentation 5 has proposed following technology: the positive active material surface that is 0.01～0.5 μ m by the coated average grain diameter of surfactant, thereby the surface area that makes to be supplied in the positive active material of reaction increases, and prevents the cohesion of positive active material, makes secondary cell high output.
Prior art document
Patent documentation
Patent documentation 1: No. 3121943 communique of Japan Patent
Patent documentation 2: No. 3101775 communique of Japan Patent
Patent documentation 3: No. 3260972 communique of Japan Patent
Patent documentation 4: No. 3066682 communique of Japan Patent
Patent documentation 5: TOHKEMY 2008-21415 communique
Summary of the invention
the problem that invention will solve
Yet, for the fluorine resin proposing in patent documentation 1, consider as when being used as the resin glue that non-aqueous secondary battery electrode uses while using under critical conditions, be difficult to be called and still there is enough solvent resistances, chemical reagent resistance.In addition, in the use of patent documentation 2 and 3 resin glues of recording, although even if SBR particle has advantages of also difficult drop-off of repeated charge, negative electrode active material, there is the problem that can not obtain battery capacious.In addition, SBR particle is easily adsorbed in the material with carbon element as negative electrode active material, has the tendency of carbon coated material surface.Therefore, exist the electrolyte that comprises lithium ion to be difficult for permeating, can not obtaining the situation of enough electrical characteristics.And then, while using the resin glue of the dissolution with solvents type proposing in patent documentation 4, after resin solution is applied to electrode matrix, while removing organic solvent, because causing electrode active material surface, resin is seamlessly coated.Therefore there is the problem that can not obtain enough electrical characteristics.And then, for the secondary cell proposing in patent documentation 5, there is the bonding of easy obstruction positive active material, the problem of the durability deficiency of positive active material mixture layer.In addition, in patent documentation 1 and 4, as resin glue, use fluororesin, but only swelling, dissolving in the specific solvents such as 1-METHYLPYRROLIDONE of fluororesin, the foreign odors while therefore there is electrode fabrication etc. are to human body, the infectious problem of environment.
Therefore, the object of the invention is to, screening characteristics when dispersiveness, the storage stability of positive active material being provided and being coated on collector body is excellent, and is coated on and can obtains after collector body and anode mixture, the positive pole of the anodal water system of the adaptation excellence of collector body and positive active material and the rechargeable nonaqueous electrolytic battery that uses it.
for the scheme of dealing with problems
The inventor furthers investigate in order to address the above problem, found that and in anode mixture, add surfactant and specific macromolecular material is used as to water dispersible high polymer binder resin, thereby positive active material is easily disperseed equably in solvent, in addition, screening characteristics when resulting anode mixture is coated collector body is excellent, the anodal anode mixture layer that is dried and obtains and the adaptation of collector plate are excellent, thereby have completed the present invention.
In addition, the inventor finds by add the surfactant with specific physical property in anode mixture, thereby positive active material is easily disperseed equably in solvent, in addition, screening characteristics when resulting anode mixture is coated collector body is excellent, is dried and the adaptation excellence of the anodal anode mixture layer that obtains and collector plate.
That is, anode mixture of the present invention is characterised in that, contains positive active material, water dispersible high polymer binder resin, conductive auxiliary agent and surfactant.
In anode mixture of the present invention, the HLB value of aforementioned surfactants is preferably 13.0～20.0.In addition,, in anode mixture of the present invention, as solvent, preferably comprise water.
In addition, positive pole of the present invention is characterised in that, is coated with the anode mixture of the invention described above on collector body.
And then rechargeable nonaqueous electrolytic battery of the present invention is characterised in that, uses the positive pole of the invention described above.
the effect of invention
According to the present invention, screening characteristics when dispersiveness, the storage stability of positive active material can be provided and be coated on collector body is excellent, and is coated on and can obtains after collector body and anode mixture, the positive pole of the anodal water system of the adaptation excellence of collector body and positive active material and the rechargeable nonaqueous electrolytic battery that uses it.
Embodiment
Below, for embodiments of the present invention, be elaborated.
< anode mixture >
Anode mixture of the present invention contains positive active material, water dispersible high polymer binder resin, conductive auxiliary agent and surfactant.By adding surfactant in anode mixture, can make positive active material and water dispersible high polymer binder resin be scattered in equably in the solvent of water system with the short time.In addition, positive active material and water dispersible high polymer binder resin are difficult for causing cohesion, precipitation, and therefore the screening characteristics for collector body also rises.And then, use the positive pole of anode mixture of the present invention and the adaptation of collector body and positive active material and flexible excellence.And then, for the rechargeable nonaqueous electrolytic battery that uses gained positive pole, can suppress, owing to repeatedly charging and the reduction of the discharge capacity of the charging and discharging under hot environment that causes of discharge, generate heat in circulating, can access long-life secondary cell.Below, for each composition of anode mixture of the present invention, with and manufacture method be described in detail.
< positive active material >
In anode mixture of the present invention, as positive active material, for example, can use transition metal oxide, transient metal sulfide and lithium-contained composite metal oxide etc.As transition metal, for example, can list Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Mo etc., as transition metal oxide, for example, can use aptly MnO, MnO
2, V
2o
5, V
6o
13, TiO
2, Cu
2v
2o
3, amorphous V
2o-P
2o
5, MoO
3, V
2o
5, V
6o
13deng.Especially, from viewpoint MnO, the V of cyclical stability and capacity
2o
5, V
6o
13, TiO
2suitable.As transient metal sulfide, can use aptly TiS
2, TiS
3, amorphous MoS
2, FeS etc.In addition, the structure for lithium-contained composite metal oxide, is not particularly limited, and can use aptly layer structure, spinel structure or olivine-type structure etc.
As the lithium-contained composite metal oxide with layer structure, can list containing lithium and cobalt oxides (LiCoO
2), containing lithium nickel oxide (LiNiO
2), the composite oxides of Co-Ni-Mn of the take lithium-contained composite metal oxide that is primary structure, the composite oxides of Ni-Mn-Al of the take lithium-contained composite metal oxide that is primary structure, the composite oxides of Ni-Co-Al of the take lithium-contained composite metal oxide that is primary structure.
As the lithium-contained composite metal oxide with spinel structure, can list LiMn2O4 (LiMn
2o
4), with other the Li[Mn of a part of Transition metal substituted Mn
3/2m
1/2] O
4(at this, M is Cr, Fe, Co, Ni, Cu etc.) etc.
As the lithium-contained composite metal oxide with olivine-type structure, can list by Li
xmPO
4the olivine-type lithium phosphate compound that (in formula, M is at least a kind, 0≤X≤2 that are selected from Mn, Fe, Co, Ni, Cu, Mg, Zn, V, Ca, Sr, Ba, Ti, Al, Si, B and Mo) represents.Among lithium-contained composite metal oxide, LiFePO
4, LiCoPO
4conductivity low, therefore mostly make its micronize use, they have a large amount of pores, so surface area is large, poor with the compatibility of resin as binding agent.Yet anode mixture of the present invention contains surfactant, even if be therefore LiFePO
4, LiCoPO
4also can use aptly.
In anode mixture of the present invention, as positive active material, can use aptly average grain diameter is more than 0.01 μ m and the material of less than 50 μ m, is more appropriately 0.1 μ m～30 μ m.If particle diameter, in above-mentioned scope, can reduce the compounding amount of water dispersible high polymer binder resin, the reduction of the capacity of battery can be suppressed, and the cohesion of positive active material can be prevented, make the favorable dispersibility of anode mixture, obtain uniform electrode.At this, particle diameter refers to the maximum distance L among the distance between any 2 on the outline line of particle, the value of average grain diameter refers to the Observations Means that uses scanning electron microscopy (SEM), transmission electron microscope (TEM) etc., the value of calculating in the mode of the mean value of the particle diameter of the particle observed in several～tens visual field.
It should be noted that, as positive active material, while using the ferrous oxide of poorly conductive, when reduction sintering, have carbon source material, thereby can be used as with the positive active material that material with carbon element covers, use.These carbon source materials can be for partly carrying out the material of element replacement.In addition, positive electrode active material for nonaqueous electrolyte secondary battery can be the mixture of organic compound with electroconductive polymers such as polyacetylene, poly for above-mentioned inorganic compound.
< water dispersible high polymer binder resin >
In anode mixture of the present invention, water dispersible high polymer binder resin refers to the high polymer binder resin that can disperse in water solvent described later.As water dispersible high polymer binder resin, can list the fluorine based polymers such as the non-fluorine based polymer such as vinyl based polymer, acrylic acid series polymeric compounds, nitrile based polymer, polyurethane series polymer, diene polymer, PVDF, PTFE.Especially, viewpoint from the zygosity with collector body, anode mixture, be preferably non-fluorine based polymer, more preferably acrylic resin or the weight average molecular weight that at least formed by polyalcohol and polyisocyanates are 8,000～1,500,000, weight average molecular weight is 10,000～1 aptly, 000,000 polyurethane resin.
While using acrylic resin as water dispersible macromolecule resin binding agent, the material that can use the copolymer by acrylate, methacrylate and other functional monomer to form.In addition, while using polyurethane resin as water dispersible macromolecule resin binding agent, weight average molecular weight less than 8,000 o'clock, there is the situation of the durability reduction of binding agent, on the other hand, weight average molecular weight surpasses 1,500,000 o'clock, although the durability of binding agent rises, there is binding agent self cohesion, dispersed, the significantly reduced situation of screening characteristics.In addition, as particle diameter, be preferably 0.05～5 μ m, 0.1～1 μ m more preferably.When particle diameter surpasses 5 μ m, worry that caking property reduces, on the other hand, during particle diameter less than 0.05 μ m, worry to cover the surface of positive active material, internal resistance is increased.Synthetic middle polyalcohol and the polyisocyanates using as above-mentioned polyurethane resin is not particularly limited, and can use known material.In addition, as aforesaid propylene acid resin, be not particularly limited, can use known material.And then, for the acrylate, methacrylate and other the monomer that use in aforesaid propylene acid resin synthetic, be not particularly limited, can use known material.It should be noted that, in anode mixture of the present invention, polyurethane resin, acrylic resin can be used with the form of water-based emulsion, aqueous dispersion.
Preparation method as water-based emulsion; can adopt known gimmick; for example; by use the surfactants such as soap surfactant method, the water-soluble polymers such as polyvinyl alcohol are manufactured as the emulsion polymerisation of the colloid method of protecting colloid etc., can use disposable polymerization, pre-emulsion dripping method, monomer dropping method etc.In addition, by the control of monomer concentration, reaction temperature, mixing speed etc., thereby can change the average grain diameter of the various polymer in water-based emulsion.By emulsion polymerisation, can make the particle size distribution sharpening of polymer, by using such water-based emulsion, thereby can make the various composition homogeneous in electrode.
As aqueous dispersion, can use aptly polytetrafluoroethylene is aqueous dispersion.It should be noted that, in the preparation method of aqueous dispersion, can adopt known gimmick, polytetrafluoroethylene is that aqueous dispersion can be distributed to polytetrafluoroethylene in water and obtain.
Polyalcohol as using in the polyurethane resin described in anode mixture of the present invention synthetic, can be used polyester polyols alcohols aptly.As polyester polyols alcohols, such as listing PEPA, polyester-polycarbonate polyalcohol, polycarbonate polyol etc.Among these polyalcohols, for PEPA, when polyurethane resin is used for to resin glue, can give good durability, intensity, therefore preferably.
As PEPA, can list can be by low molecular polylol and the amount fewer than the stoichiometric amount of low molecular polylol polybasic carboxylic acid or the material that direct esterification is reacted and/or ester exchange reaction obtains of the ester formative derivative such as its ester, acid anhydride, halide.
As low molecular polylol, for example, can list ethylene glycol, 1, 2-propylene glycol, 1, ammediol, 2-methyl isophthalic acid, ammediol, 2-butyl-2-ethyl-1, ammediol, 1, 4-butanediol, neopentyl glycol, 3-methyl-2, 4-pentanediol, 2, 4-pentanediol, 1, 5-pentanediol, 3-methyl isophthalic acid, 5-pentanediol, 2-methyl-2, 4-pentanediol, 2, 4-diethyl-1, 5-pentanediol, 1, 6-hexylene glycol, 1, 7-heptandiol, 3, 5-heptandiol, 1, 8-ethohexadiol, 2-methyl isophthalic acid, 8-ethohexadiol, 1, 9-nonanediol, 1, 10-decanediol, diethylene glycol, the aliphatic diol classes such as triethylene glycol, the ester ring type such as cyclohexanedimethanol, cyclohexanediol glycols, trimethylolethane, trimethylolpropane, hexitol (hexitol) class, pentitol (pentitol) class, the alcohols more than ternary such as glycerine, pentaerythrite, tetra methylol propane.They can use separately a kind, also can be mixed with two or more.
As polybasic carboxylic acid or its ester formative derivative, for example, can list oxalic acid, malonic acid, butanedioic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, decanedioic acid, dodecyl diacid, 2-dimethyl succinic acid, 2-methyl adipic acid, 3-methyl adipic acid, 3-methylglutaric acid, 2-methyl suberic acid, 3,8-dimethyl decanedioic acid, 3, the aliphatic dicarboxylic acid classes such as 7-dimethyl decanedioic acid, hydrogenated dimer acids, dimeric dibasic acid; The aromatic dicarboxylic acid classes such as phthalic acid, terephthalic acid (TPA), M-phthalic acid, naphthalene dicarboxylic acids; The ester ring type omega-dicarboxylic acids such as cyclohexane dicarboxylic acid; The polybasic carboxylic acids such as the unsaturated tricarboxylic acids such as the tripolymer of trimellitic acid, trimesic acid, Castor Oil Fatty Acid, the acid anhydrides of these polybasic carboxylic acids, the halide such as the chloride of these polybasic carboxylic acids, bromide, the lactone such as the lower member esters such as the methyl esters of above-mentioned polybasic carboxylic acid, ethyl ester, propyl ester, isopropyl ester, butyl ester, isobutyl ester, pentyl ester, γ-hexalactone, δ-caprolactone, 6-caprolactone, dimethyl-6-caprolactone, δ-valerolactone, gamma-valerolactone, gamma-butyrolacton.They can use separately a kind, also can be mixed with two or more.
In addition, as the polyisocyanates using in the polyurethane resin described in anode mixture of the present invention synthetic, be not particularly limited, can use known polyisocyanates.As polyisocyanates, the mixture of vulcabond and triisocyanate is because therefore favorable dispersibility and the cheapness of resulting polyurethane resin are suitable.
As vulcabond, for example, can list 2, 4-and/or 2, 6-toluene di-isocyanate(TDI), diphenyl methane-4, 4 '-vulcabond, to phenylene vulcabond, XDI, 1, 5-naphthalene diisocyanate, 3, 3 '-dimethyl diphenyl-4, 4 '-vulcabond, dianisidine vulcabond, the aromatic diisocyanate classes such as tetramethylxylene diisocyanate, IPDI, dicyclohexyl methyl hydride-4, 4 '-vulcabond, anti-form-1, 4-cyclohexyl diisocyanate, the ester ring type diisocyanates such as norborene vulcabond, 1, 6-hexamethylene diisocyanate, 2, 2, 4 (2, 4, 4)-trimethyl hexamethylene diisocyanate, the aliphatic diisocyanate classes such as LDI.Particularly the hydrolytic resistance of ester ring type vulcabond is excellent, therefore preferably.They can use separately a kind, also can be mixed with two or more.
As triisocyanate, can list triphenylmethane triisocyanate, 1-methylbenzene-2, the isocyanuric acid ester trimerization compound of 4,6-triisocyanate, above-mentioned vulcabond, biuret trimerization compound, trimethylolpropane add joint compound etc.Particularly isocyanuric acid ester trimerization compound is given stable dispersity for polyurethane resin, therefore preferably.They can use separately a kind, also can be mixed with two or more.
In anode mixture of the present invention, as polyurethane resin, can use the polyurethane resin being polymerized with chain extender.That is,, as polyurethane resin, while needing the material of HMW, can use the known chain extender using in polyurethane resin synthetic.As chain extender, preferred polyamine compound, polynary primary alconol compound etc., more preferably polyamine compound.
As polyamine compound, the alcohol hydroxyl group that can list the above-mentioned illustrative low molecular polylols such as ethylene diamine, trimethylene diamine is substituted by amino low molecule polyamines class; The polyether polyamine classes such as diethylenetriamines, trien, tetren, polyoxy trimethylene diamine, polyoxy propylidene triamine; The Meng alkane diamines, IPD, norborene diamines, two (4-amino-3-methyl bicyclic hexyl) methane, diamino-dicyclohexyl methane, two (amino methyl) cyclohexane, N-amino methyl piperazine, 3, two (the 3-aminopropyls) 2 of 9-, 4,8, the ester ring type polyamines classes such as 10-tetra-oxaspiros (5,5) hendecane; M-xylene diamine, α-(/ p-aminophenyl) ethylamine, m-phenylene diamine (MPD), diaminodiphenyl-methane, diamino diphenyl sulfone, diaminourea diethyl-dimethyl diphenyl methane, diaminourea diethyl diphenyl methane, dimethyl disulfide be for toluenediamine, diethyl toluene diamine, α, α '-bis-(4-aminophenyl)-to aromatic polyamine classes such as diisopropyl benzene, phenyl disulfide amine; Hydrazides, ethylene diamine, trimethylene diamine, benzene dimethylamine, adipic dihydrazide, IPD, piperazine with and derivative, phenylenediamine, toluenediamine, benzene dimethylamine, isophthalic dihydrazide etc.In anode mixture of the present invention, they can use separately a kind, also can be mixed with two or more.
Manufacture method for the polyurethane resin described in anode mixture of the present invention is not particularly limited, and can use known manufacture method.For example, the prepolymer method being preferably as follows: polyalcohol, vulcabond and triisocyanate are reacted in the lump, and previously prepared polyurethane prepolymer, can make chain extension in its water under chain extender exists.
Consumption for chain extender is not particularly limited, can select to measure arbitrarily to use, for example, during as the synthetic selection prepolymer method of polyurethane resin, with respect to the quantity 1 of the NCO in prepolymer, the quantity of the reactive hydrogen of chain extender is 0.1～1.5, the favorable dispersibility of resulting aqueous dispersion type polyurethane composition, nondiscolouring, therefore preferably, more preferably 0.5～1.0.
Acrylate and methacrylate as using in the acrylic resin described in anode mixture of the present invention synthetic, can list methyl acrylate, methyl methacrylate, ethyl acrylate, EMA, acrylic acid n-propyl, n propyl methacrylate, n-butyl acrylate, n-BMA, tert-butyl acrylate, Tert-butyl Methacrylate, the just own ester of acrylic acid, the just own ester of methacrylic acid, acrylic acid-2-ethyl caproite, methacrylic acid-2-Octyl Nitrite, cyclohexyl acrylate, cyclohexyl methacrylate, the hard ester acyl of acrylic acid ester, the hard ester acyl of methacrylic acid ester, acrylic acid stearyl, methacrylic acid stearyl, phenyl acrylate, phenyl methacrylate, benzyl acrylate, benzyl methacrylate, acrylic acid chloromethyl ester, methacrylic acid chloromethyl ester, acrylic acid-2-chloroethene ester, methacrylic acid-2-chloroethene ester, 2-Hydroxy ethyl acrylate, methacrylic acid-2-hydroxy methacrylate, acrylic acid-3-hydroxy propyl ester, methacrylic acid-3-hydroxy propyl ester, acrylic acid-2, the own ester of 3,4,5,6-penta hydroxy group, methacrylic acid-2, the own ester of 3,4,5,6-penta hydroxy group, acrylic acid-2,3,4,5-tetrahydroxy pentyl ester, methacrylic acid-2,3,4,5-tetrahydroxy pentyl ester, acrylic-amino ethyl ester, acrylic acid propyl group amino ethyl ester, dimethylaminoethyl methacrylate, methacrylic acid ethylamino propyl ester, methacrylic acid phenyl amino ethyl ester and methacrylic acid cyclohexyl amino ethyl ester etc.They can use separately or use two or more.
In acrylic resin described in anode mixture of the present invention, except aforesaid propylene acid esters and above-mentioned methacrylate, can also add functional monomer.For example, as simple function monomer, can list the aromatic vinyl base system monomers such as styrene, AMS, 1-vinyl naphthalene, 3-methyl styrene, 4-propylstyrene, 4-cyclohexyl benzene ethene, 4-dodecyl styrene, 2-ethyl-4-benzyl styrene, 4-(phenyl butyl) styrene, halogenated styrenes; The vinyl cyanide such as acrylonitrile, methacrylonitrile base system monomer; Butadiene, isoprene, 2,3-dimethyl butadiene, 2-methyl-3-ethyl butadiene, 1,3-pentadiene, 3-methyl isophthalic acid, 3-pentadiene, 2-ethyl-1,3-pentadiene, 1,3-hexadiene, 2-methyl isophthalic acid, 3-hexadiene, 3,4-dimethyl-1,3-hexadiene, 1,3-heptadiene, 3-methyl isophthalic acid, 3-heptadiene, 1,3-octadiene, cyclopentadiene, chlorobutadiene, laurene equiconjugate diene monomer.In addition, as multi-functional monomer, for example, can list allyl methacrylate, allyl acrylate, cyanuric acid alkatriene propyl diester, isocyanuric acid triallyl ester, diallyl phthalate, maleic acid diallyl ester, adipic acid divinyl ester, divinylbenzene ethylene glycol dimethacrylate, divinylbenzene glycol diacrylate, diethylene glycol dimethylacrylate, diethylene glycol diacrylate, TEGDMA, triethylene glycol diacrylate, trimethylol-propane trimethacrylate, trimethylolpropane triacrylate, tetramethylol methane tetramethyl acrylate, tetramethylol methane tetraacrylate, DPG dimethylacrylate and propylene glycol diacrylate etc., two or more kinds may be used for they.
Manufacture method for acrylic resin described in the present invention is not particularly limited, and can use known manufacture method.
It should be noted that, in anode mixture of the present invention, in water dispersible macromolecular resin glue, also can add other polymer beads as required.As polymer beads, for example, can list the non-fluorine based polymers such as vinyl based polymer, acrylic acid series polymeric compounds, nitrile based polymer, polyurethane series polymer, diene polymer; The fluorine such as PVDF, PTFE based polymer; Particularly from the preferred non-fluorine based polymer of viewpoint of zygosity.It should be noted that, in anode mixture of the present invention, these polymer beads can be used separately a kind, also can be mixed with two or more.
In anode mixture of the present invention, water dispersible high polymer binder resin (polymer beads) with respect to 100 mass parts positive active materials, with solid component meter, be preferably 0.1～10 mass parts containing proportional, 0.5～5 mass parts more preferably.By make polymer beads containing proportional in above-mentioned scope, thereby can improve, anode mixture of the present invention is coated with/is dried on collector body and the adaptation for collector plate of the anode mixture layer obtaining and flexibility.
It should be noted that, in anode mixture of the present invention, the average grain diameter of water dispersible macromolecular resin glue is preferably 0.05～5 μ m, 0.1～1 μ m more preferably.When particle diameter is excessive, worry that caking property reduces, when particle diameter is too small, worry to cover positive active material surface, internal resistance is increased.
< conductive auxiliary agent >
In anode mixture of the present invention, as conductive auxiliary agent, can use the conductive carbon such as acetylene black, Ketjen black, carbon black, graphite, vapour deposition carbon fiber and carbon nano-tube, graphite are rare, fullerene.By using conductive auxiliary agent, thereby can improve electrically contacting between positive active material, while using, can improve discharge rate characteristic in rechargeable nonaqueous electrolytic battery.The compounding amount of conductive auxiliary agent is with respect to 100 mass parts positive active materials, is preferably 0.1～20 mass parts, 0.1～10 mass parts more preferably.
< surfactant >
In anode mixture of the present invention, as surfactant, as long as high to electrolytical dispersiveness, low and do not hinder the ionic conduction in electrolyte with the reactivity of lithium ion etc., be not particularly limited.For example, as surfactant, can list cationic surfactant, anionic surfactant, amphoteric surfactant, nonionic surfactant, particularly preferably use nonionic surfactant.The reactivity of nonionic surfactant and ion (lithium ion etc.) is around low, does not therefore hinder in electrolyte and the ionic conduction on active material surface.In anode mixture of the present invention, surfactant can be used separately a kind, also can be mixed with two or more.
As cationic surfactant, for example, can list quaternary ammonium salt, alkylamine salt of list/double long-chain alkyl type etc.In addition; as anionic surfactant; for example, can list alkylbenzenesulfonate, alkyl sulfate, alkyl ether sulfate, alkenyl ether sulfate, alkenyl sulfate, alpha-alkene sulfonate, alpha-sulfo-fatty acid or its ester salt, alkylsulfonate, Salt of saturated fatty acid, unsaturated fatty acid salt, alkyl ether carboxy acid salt, alkenyl ether carboxylic acid salt, amino acid type surfactant, N-acyl amino acid type surfactant, alkyl phosphate or its salt, alkenyl phosphate or its salt, alkyl sulfo succinate etc.As amphoteric surfactant, can list carboxyl type amphoteric surfactant, sulfobetaines type amphoteric surfactant etc.
As nonionic surfactant, for example, can use aptly the polyoxyethylene alkyl ethers such as polyoxyethylene laurel ether, PCE, the hard ester ether of polyoxyethylene, polyoxyethylene oleyl ether, polyoxyethylene senior alkyl ether; The polyoxyethylene alkylaryl ethers such as polyoxyethylene nonylplenyl ether; The polyoxyethylene sorbitan fatty acid esters such as polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monolaurate, polyethenoxy sorbitan monopalmitate, polyethenoxy sorbitan monostearate, polyethenoxy sorbitan tristearate, polyoxyethylene sorbitan monooleate, polyethenoxy sorbitan trioleate; Sucrose fatty ester; The polyoxyethylene sorbitol fatty acid esters such as four oleic acid polyoxyethylene sorbitol esters; The polyoxyethylene fatty acid esters such as polyethylene glycol monolaurate, polyethylene glycol mono stearate, polyglycol distearate, polyethylene glycol monooleate; Polyoxyethylene alkyl amine; Polyoxyethylene hardened castor oil; The block copolymer of oxirane and expoxy propane; The fatty acid esters of sorbitan such as Arlacel-20, anhydro sorbitol list myristinate, Arlacel-40, Arlacel-60, Arlacel-65, Arlacel-80, sorbitan trioleate, half times of oleate of anhydro sorbitol, anhydro sorbitol distearate; The fatty acid glycerides such as glycerol monostearate, glycerol monoleate, two glycerol monoleates, self-emulsifying type glycerol monostearate; Alkyl chain triacontanol acid amides etc.
In anode mixture of the present invention, while using non-ionic surface active agent as surfactant, non-ionic surface active agent is preferably macromolecular material, and the weight average molecular weight of non-ionic surface active agent is preferably more than 500.By the weight average molecular weight of nonionic surfactant is made as more than 500, thereby the dispersion effect of surfactants based positive active material is brought into play well.Think this be due to, by high molecular surfactant, make the compatibility of solvent and surfactant uprise, easily near particle, keep solvent, therefore can suppress intergranular cohesion.On the other hand, for the upper limit of weight average molecular weight, be not particularly limited, be preferably below 100,000.The scope of the weight average molecular weight preferably of the non-ionic surface active agent in anode mixture of the present invention is 1,000～50,000.By making weight average molecular weight in this scope, thereby the movement better and ion of the dispersiveness of positive active material is successfully carried out.
Among nonionic surfactant, preferred ion conductibility is high, operable polyethylene glycol is surfactant in the electrolyte of lithium ion battery, more preferably cithrol is surfactant, more preferably the stearate class of polyethylene glycol.The Efficient Adhesive Promotion precipitation agglomeration preventing effect high, active material of the stearate class of polyethylene glycol is also excellent.In addition, by use polyethylene glycol in active material coated, be surfactant, can promote the movement of the lithium ion in surfactant.It should be noted that, in the present invention, polyethylene glycol is that surfactant refers to the material that comprises glycol chain in compound active agent.
For the surfactant using in anode mixture of the present invention, the HLB that is preferably based on lattice Lifei method is 13～20, more preferably 15～20.Particularly, in solvent not with an organic solvent time, HLB more preferably 16～20.While using the surfactant of HLB in this scope, the hydrophilic radical of surfactant and hydrophobic grouping balance are arranged well, promote positive active material and the resin glue with polarity to disperse uniformly in aqueous solvent.It should be noted that, lattice Lifei method is to take the formula weight of hydrophilic radical of surfactant and molecular weight as according to defining by following formula.
Summation/the molecular weight of the formula weight of HLB value=20 * hydrophilic portion
In anode mixture of the present invention, the compounding amount of surfactant is preferably 0.1～10 mass parts, 0.5～5 mass parts more preferably with respect to 100 mass parts positive active materials.By making the compounding amount of surfactant in above-mentioned scope, thereby can obtain the anode mixture of dispersiveness and the screening characteristics excellence of the positive active material in anode mixture.
< solvent >
As the solvent using in anode mixture of the present invention, if water dispersible high polymer binder resin and positive active material are disperseed equably and have compatibility with the surfactant that hinders precipitation cohesion, being not particularly limited, can be also organic solvent for water.In addition, in anode mixture of the present invention, as solvent, especially water can be made aptly, in the scope that does not hinder above-mentioned effect, also organic solvent can be contained.As described organic solvent, for example, can list the annular aliphatic hydro carbons such as pentamethylene, cyclohexane; Toluene, dimethylbenzene, ethylo benzene etc. are aromatic hydrocarbon based; The ketone of acetone, methylethylketone, diisopropyl ketone, cyclohexanone, hexahydrotoluene, ethyl cyclohexane etc.; The chlorine such as methene chloride, chloroform, carbon tetrachloride are aliphatic hydrocarbon; The ester classes such as ethyl acetate, butyl acetate, gamma-butyrolacton, 6-caprolactone; The alkane such as acetonitrile, propionitrile nitrile; 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.
Other additive of < >
For anode mixture of the present invention, it is important only containing positive active material, water dispersible high polymer binder resin, conductive auxiliary agent and surfactant, in addition be not particularly limited, except mentioned component with in the scope cell reaction not being exerted an influence, also can contain additive.For example, in anode mixture of the present invention, except mentioned component, can contain the compositions such as reinforcing material, thickener, froth breaking/levelling agent, electrolyte decomposition inhibitor.
As reinforcing material, can use various inorganic and organic spherical, tabular, bar-shaped or fibrous fillers.By using reinforcing material, and then tough and soft electrode can be obtained, excellent long-term cycle characteristics can be given.They can use separately a kind, also can be mixed with two or more.The compounding amount of reinforcing material, with respect to 100 mass parts positive active materials, is generally 0.01～20 mass parts, is preferably 1～10 mass parts.By the compounding amount of reinforcing material is made as to above-mentioned scope, thereby can give high power capacity and top load characteristic.
As thickener, if the material of the material settling out of other use when the solvent using when electrode is manufactured, electrolyte, battery are used is not particularly limited.For example, can use carboxymethyl cellulose, methylcellulose, CMC, ethyl cellulose, polyvinyl alcohol, oxidized starch, phosphorylated starch, casein etc.They can use separately a kind, also can be mixed with two or more.The compounding amount of thickener is generally 0.01～20 mass parts, is preferably 1～10 mass parts with respect to 100 mass parts positive active materials.By the compounding amount of thickener is made as to above-mentioned scope, thereby can prevent well the precipitation cohesion than heavy positive active material.
As froth breaking/levelling agent, can use alkyl is that surfactant, silicone-based surfactant, fluorine are that surfactant, metal are the surfactants such as surfactant.By mixed surfactant, thereby the contraction producing in the time of can preventing from applying in addition, can make the flatness of electrode rise.The compounding amount of froth breaking/levelling agent is preferably 0.01～5 mass parts with respect to 100 mass parts positive active materials.By the compounding amount of froth breaking/levelling agent is made as to above-mentioned scope, thereby the coating in the time of can preventing electrode coating is bad, makes productivity ratio increase.
As electrolyte decomposition inhibitor, can use carbonic acid ethenylidene ester using in electrolyte etc.The compounding amount of the electrolyte decomposition inhibitor in electrode is preferably 0.01～5 mass parts with respect to 100 mass parts positive active materials.By making the compounding amount of electrolyte decomposition inhibitor in above-mentioned scope, thereby can further improve cycle characteristics and hot properties.In addition, can list the nanoparticles such as aerosil, gaseous oxidation aluminium.By mixing nanoparticle, thereby can form the thixotropy with mixture by control electrode.The compounding amount of the nanoparticle of anode mixture of the present invention is preferably 0.01～5 mass parts with respect to 100 mass parts positive active materials.By the compounding amount of nanoparticle is made as to above-mentioned scope, thereby mixture stability, productivity ratio can be further improved, higher battery behavior can be given.
The manufacture method > of < anode mixture
Anode mixture of the present invention can mix above-mentioned positive active material, water dispersible high polymer binder resin, conductive auxiliary agent and surfactant and solvent, in addition as required other additive and obtain.While manufacturing anode mixture of the present invention, for mixed method, be not particularly limited, for example, can adopt the method for using stirring-type, oscillatory type and rotary etc. mixing arrangement.In addition, can adopt the method for using homogenizer, ball mill, sand mill, roller mill and planetary mixing roll etc. to disperse kneading device.
The anodal > of <
Then, for positive electrode for nonaqueous electrolyte secondary battery of the present invention, describe.
Positive pole of the present invention is the anode mixture of the invention described above to be applied to collector body form.Positive pole of the present invention can be manufactured via following operation: the anode mixture of the invention described above is applied to the painting process on collector body, makes the dry drying process that forms anode mixture layer of resulting collector body.In positive pole of the present invention, can form anode mixture layer at the one side of collector body, preferably on two sides, form.Below, formation and the manufacture method for positive pole of the present invention is described in detail.
< collector body >
If the material that the collector body using in positive pole of the present invention has conductivity and has an electrochemistry durability is not particularly limited, preferably there is stable on heating metal material.Such as enumerating, tap a blast furnace, copper, aluminium, nickel, stainless steel, titanium, tantalum, gold, platinum etc.Especially, the few viewpoint of oxidative degradation during from charging, preferably aluminum or aluminum alloy.The shape of collector body is not particularly limited, aptly the sheet of used thickness 5～100 μ m left and right.
In positive pole of the present invention, for collector body, in order to improve the bond strength with anode mixture layer, preferably carry out in advance roughened processing and use.As roughened method, can list mechanical milling method, electrolytic polishing method, chemical grinding method etc.In mechanical milling method, can use to stick together has the abrasive cloth of abrasive particles paper, grinding stone, polishing roll, possesses wire brush of steel wire etc. etc.In addition,, in order to improve bond strength, the conductivity of electrode layer, can form intermediate layer on collector body surface.
< coating process >
For the method that the anode mixture of the invention described above is applied on collector body, be also not particularly limited, can use known method.As coating process, for example, can enumerate depanning rubbing method, scraper for coating (doctor coating) method, dip coated method, roller rubbing method, spraying process, intaglio plate rubbing method, silk screen print method or quiet electric Tu dress method etc.
< drying means >
As the dry method of collector body that makes to obtain by above-mentioned coating process, be not particularly limited, for example, can list and utilize the dry of warm braw, hot blast, low wet wind, vacuumize, utilizes the seasoning of the irradiation of (far) infrared ray, electron beam etc.Be generally 5～30 minutes drying time, baking temperature is generally 40～180 ℃.
< rolls >
In manufacture method of the present invention, preferably after via painting process, drying process, via the calendering procedure that uses mould compacting, roll-in system etc. to be made the voidage of anode mixture layer reduce by pressurized treatments.The suitable scope of voidage is 5%～15%, is preferably 7%～13%.When voidage surpasses 15%, charge efficiency, discharging efficiency worsen, therefore not preferred.On the other hand, during voidage less than 5%, worry that generation is difficult to obtain high volume capacity or bad problem is peeled off, easily produced to anode mixture layer easily from collector body.It should be noted that, as resin glue, while using curable resin, preferably to there is the operation that makes this curable resin curing.
The thickness of positive pole of the present invention is generally 5～400 μ m, is preferably 30～300 μ m.By making anodal thickness in above-mentioned scope, thereby can obtain flexibility, the adaptation of good pole plate.
< rechargeable nonaqueous electrolytic battery >
Then, for rechargeable nonaqueous electrolytic battery of the present invention, describe.
Rechargeable nonaqueous electrolytic battery of the present invention is used the positive pole of the invention described above, has positive pole, negative pole, barrier film and electrolyte.Below, for the formation of rechargeable nonaqueous electrolytic battery of the present invention with and manufacture method be described in detail.
< anode for nonaqueous electrolyte secondary battery >
Anode for nonaqueous electrolyte secondary battery described in the present invention can be manufactured as follows: mix negative electrode active material, conductive auxiliary agent, water dispersible high polymer binder resin, solvent and other additive as required etc. and adjust cathode agent slurry, coating on collector body, dry, as required via calendering, manufacture thus.
As negative electrode active material, if can absorb, emit the active material of lithium ion, can use the known material of always using so far, can use carbon is that active material and non-carbon are any in active material.As carbon, be active material, for example, can list graphite, soft carbon, hard carbon etc.As non-carbon, be active material, for example, can use lithium metal, lithium alloy, oxide, sulfide, contain the known materials such as lithium-metal composite oxides.
As conductive auxiliary agent and solvent, can use the above-mentioned conductive auxiliary agent and the above-mentioned solvent that in the making of positive pole of the present invention, use.In addition,, as resin glue, can use the normally used material in rechargeable nonaqueous electrolytic battery such as SBR particle, PVDF resin.
As the collector body using in the anode for nonaqueous electrolyte secondary battery described in the present invention, same with positive electrode for nonaqueous electrolyte secondary battery of the present invention, if the material that has conductivity and have an electrochemistry durability is not particularly limited, can use the same material of collector body using in the positive electrode for nonaqueous electrolyte secondary battery with the invention described above.
< electrolyte >
For the electrolyte using in the present invention, be not particularly limited, for example, can use the material that is dissolved with lithium salts in the solvent of non-water system as supporting electrolyte.As lithium salts, for example, can list LiPF
6, LiAsF
6, LiBF
4, LiSbF
6, LiAlCl
4, LiClO
4, CF
3sO
3li, C
4f
9sO
3li, CF
3cOOLi, (CF
3cO)
2nLi, (CF
3sO
2)
2nLi, (C
2f
5sO
2) NLi etc.Particularly can use in solvent aptly the LiPF that easily dissolves, shows high degree of dissociation
6, LiClO
4, CF
3sO
3li.They can use separately a kind, also can be mixed with two or more.The addition of supporting electrolyte with respect to electrolyte be generally 1 quality % above, be preferably 5 quality % more than, be generally in addition 30 quality % following, be preferably below 20 quality %.The amount of supporting electrolyte is very few or too much all cause that ionic conductivity reduces, the charge characteristic of battery, flash-over characteristic reduce.
As the solvent using in electrolyte, if the material that supporting electrolyte dissolves is not particularly limited, can uses the alkyl carbonate classes such as dimethyl carbonate (DMC), ethylene carbonate (EC), diethyl carbonate (DEC), propylene carbonate (PC), butylene carbonate (BC) and methyl ethyl carbonate (MEC); The ester such as gamma-butyrolacton, methyl formate class, 1, the ethers such as 2-dimethoxy-ethane and oxolane; The sulfur-containing compound such as sulfolane and dimethyl sulfoxide (DMSO) class.Especially owing to easily obtaining high ion-conductivity, serviceability temperature scope is wide, therefore preferably dimethyl carbonate, ethylene carbonate, propylene carbonate, diethyl carbonate, methyl ethyl carbonate.They can use separately a kind, also can be mixed with two or more.
It should be noted that, in electrolyte, also can add other additive.As additive, can list compound, cyclohexyl benzene or the diphenyl ether etc. of the carbonic ester systems such as carbonic acid ethenylidene ester (VC).
While using the electrolyte beyond above-mentioned in rechargeable nonaqueous electrolytic battery of the present invention, for example, can use the gelatinous polymer electrolyte that is impregnated with electrolyte in the polymer dielectrics such as poly(ethylene oxide), polyacrylonitrile, lithium sulfide, LiI, Li
3the inorganic solid electrolytes such as N.
< barrier film >
Barrier film is the porous substrate with pore portion, can use (a) to there is the porousness barrier film of pore portion, (b) in one or two sides, be formed with the porousness barrier film of polymeric coating layer, or (c) be formed with the resin-coated porousness barrier film of the Porous that comprises inorganic ceramic powder, for example, can list polypropylene-based, polyethylene-based, polyolefin, aramid fiber is porousness barrier film, Kynoar, poly(ethylene oxide), polyacrylonitrile, the solid macromolecule electrolytes such as Kynoar hexafluoropropylene copolymer are used, the polymeric membrane that gel polyelectrolyte is used, be coated with the barrier film of gelation polymeric coating layer or be coated with and comprise inorganic filler, the barrier film of the porous rete of inorganic filler use dispersant etc.
The manufacture method > of < rechargeable nonaqueous electrolytic battery
Manufacture method for rechargeable nonaqueous electrolytic battery of the present invention is not particularly limited.For example, make negative pole and anodal across barrier film, overlap, it being carried out to curling, bending etc. according to cell shapes and pack in battery case, in battery case, injecting electrolyte and seal.In rechargeable nonaqueous electrolytic battery of the present invention, put into the overcurrent such as expanding metal (expandmetal) as required, connecting pin, PTC element and prevent element, lead plate etc., can prevent inside battery pressure rise, cross and discharge and recharge.The shape of battery can be the arbitrary shapes such as laminated units type, coin shape, button-type, sheet type, cylinder type, square, platypelloid type.
Embodiment
Below, use embodiment to illustrate in greater detail the present invention.
< embodiment 1>
The ternary system active material as positive active material of compounding solid constituent ratio 95 quality % is the CELLSEED NMC-111 (LiNi that Japanese chemical industrial company manufactures
1/3co
1/3mn
1/3o
2), the VGCF-H (vapour deposition carbon fiber) that the Zhao He electrician company as conductive auxiliary agent of solid constituent ratio 2 quality % manufactures, ADEKA BONTIGHTER HUX-822 (the polyaminoester emulsion resin: solid constituent 40 quality %) that the ADEKA company as water dispersible high polymer binder resin of solid constituent ratio 1.5 quality % manufactures, the EMANON3299RV (polyglycol distearate) that KAO. Corp. SA as surfactant of solid constituent ratio 1.5 quality % manufactures, and as the water of solvent so that mixture solid constituent is 60 quality %, with 1700rpm, carrying out 10 minutes propeller types stirs, make anode mixture.
By standing 24 hours of the anode mixture of making, then, at the one side of the aluminium foil of thickness 20 μ m, use the coating device of 50 μ m to be coated with.Then, in heated air circulation type box drying oven, at 150 ℃, be dried 20 minutes, remove the water as solvent.After being cooled to room temperature, in the plate of the stainless steel of 1mm, clamp, use dull and stereotyped press, at 1.5ton/cm
2pressure under carry out at normal temperatures the calendering of 1 minute, manufacture the anode electrode plate of the active material mixture layer with one side 80 μ m.About from the making to the operation till the making of anode electrode plate of anode mixture, for dispersed, precipitation cohesion stability, dried outward appearance, dried adaptation, the outward appearance of electrode layer, the resistance value of the adaptation of electrode layer and electrode layer, evaluate.Evaluation method in detail as described below.In table 1, describe in the lump resulting result.
< embodiment 2～9, comparative example 1,2>
The formula that water dispersible high polymer binder resin, surfactant, thickener, conductive auxiliary agent, positive active material are changed to as shown in table 1～4 forms, carry out similarly to Example 1 in addition stirring/mixing, make anode mixture, evaluate stability dispersed, precipitation cohesion.The anode mixture of use, is coated with similarly to Example 1/is dried/roll, and makes positive plate.In table 1～4, describe in the lump evaluation result.
The dispersed > of <
While the anode mixture of making being coated on the positive electrode collector of aluminium foil, by by disperseing the piece of bad and Undec thick active material particle, the piece of gelatinous resin and in the situation that applicator surface leaves the vestige of striated, be designated as " bad ", the situation that leaves some vestiges be designated as " can ", the situation that does not leave the vestige of striated is designated as to " good ", carry out visual valuation.
< precipitation cohesion stability >
The anode mixture of standing making, produces bottom surface at anode mixture the situation of precipitation condensation product or is designated as " bad ", will have vicissitudinous situation to be designated as " good " in the situation of the separated water outlet of liquid level, evaluates.
The dried outward appearance > of <
After anode mixture is coated with/is dried to positive electrode collector, the situation that produces the paint film defects such as bubble, contraction in film coated surface is designated as to " bad ", will does not have abnormal situation to be designated as " good ", the visual valuation of filming.
The dried adaptation > of <
After anode mixture is coated with/is dried to positive electrode collector, film coated surface be take to JIS K-5600 and with cutting interval 2mm, carry out the cross-cut of 25 of grid patterns as benchmark, the situation that the powder falling of intersection point is violent be designated as " bad ", the few situation of powder falling be designated as " can ", the situation that there is no powder falling is completely designated as to " good ", evaluate.
The outward appearance > of < electrode layer
The situation that electrode plate surface making is produced to projection, crackle etc. is designated as " bad ", will does not have abnormal, level and smooth situation to be designated as " good ", carries out the visual valuation of electrode surface.
The adaptation > of < electrode layer
The battery lead plate of use, take JIS K-5600 as benchmark, by testing with the cross-cut method of 25 of cutting interval 2mm, grid patterns, evaluates the adaptation between collector body and active material.Evaluation was carried out with 6 stages of 0～5, and the fewer expression adaptation of numeral is better.
The resistance value > of < electrode layer
At the electrode plate surface of making, use tester (the Mohm HiTESTER3540 that Zhi company manufactures) to measure surperficial resistance value.
Table 1
Table 2
Table 3
Table 4
1) ADEKA BONTIGHTER HUX-822 (polyurethane resin molecular weight: 800,000～900,000) company of Asahi Denka Co., Ltd. manufactures
2) HSV-900 (polyvinylidene fluoride resin) Arkema Co. manufactures
3) the Japanese synthetic chemistry of Movinyl LDM7523 (acrylic acid/organic siliconresin) Co., Ltd. manufactures
4) (polyglycol distearate is non-ionic surface active agent HLB:19.2 molecular weight to EMANON3299RV: approximately 11200) KAO. Corp. SA manufactures
5) (polyethylene glycol mono stearate is non-ionic surface active agent HLB:19.4 molecular weight to EMANON3199V: approximately 6800) KAO. Corp. SA manufactures
6) (polyethylene glycol monolaurate is non-ionic surface active agent HLB:13.7 molecular weight to EMANON1112: approximately 730) KAO. Corp. SA manufactures
7) company of Adekamin4MAC-30 (cationic surfactant) Asahi Denka Co., Ltd. manufactures
8) Daicel CMC#2200Daicel FineChem Co. manufactures
9) VGCF-H (vapour deposition carbon fiber) Zhao He electrician company manufactures
10) the Japanese graphite of SP-270 (powdered graphite) Industrial Co., Ltd manufactures
11) CELLSEED NMC111 (LiNi
1/3co
1/3mn
1/3o
2) manufacture of Japan Chemical Industry company
12) LFP (LiFePO4: LiFePO
4)
13) NMP (1-METHYLPYRROLIDONE)
From table 1～4, the dispersiveness of the positive active material of anode mixture of the present invention, storage stability and excellent for the screening characteristics of collector body, used it and the adaptation excellence of the anodal anode mixture layer manufactured and collector body.Comparative example seems to disperse well under the state of slurry, but the piece of residual big particle shape etc., and bad dispersibility, filming forms difficulty.
Claims (5)
1. an anode mixture, is characterized in that, comprises positive active material, water dispersible high polymer binder resin, conductive auxiliary agent and surfactant.
2. anode mixture according to claim 1, wherein, the HLB value of described surfactant is 13.0～20.0.
3. anode mixture according to claim 1 and 2, wherein, comprises water as solvent.
4. a positive pole, is characterized in that, is coated with the anode mixture described in any one in claim 1～3 on collector body.
5. a rechargeable nonaqueous electrolytic battery, is characterized in that, right to use requires the positive pole described in 4.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
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| JP2011-284203 | 2011-12-26 | ||
| JP2011284201 | 2011-12-26 | ||
| JP2011284203 | 2011-12-26 | ||
| JP2011-284201 | 2011-12-26 | ||
| PCT/JP2012/081151 WO2013099520A1 (en) | 2011-12-26 | 2012-11-30 | Positive-electrode mixture, positive electrode, and non-aqueous electrolyte secondary battery using same |
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|---|---|
| CN104025350A true CN104025350A (en) | 2014-09-03 |
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ID=48697018
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Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP6055782B2 (en) |
| KR (1) | KR20140116143A (en) |
| CN (1) | CN104025350A (en) |
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| CN113690440A (en) * | 2021-07-30 | 2021-11-23 | 深圳市研一新材料有限责任公司 | Electrode slurry composition, pole piece and secondary battery thereof |
| WO2021254157A1 (en) * | 2020-06-17 | 2021-12-23 | Guangdong Haozhi Technology Co., Limited | Slurry composition for flexible electrode in secondary battery |
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| US11355744B2 (en) * | 2010-10-28 | 2022-06-07 | Electrovaya Inc. | Lithium ion battery electrode with uniformly dispersed electrode binder and conductive additive |
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| US10468674B2 (en) | 2018-01-09 | 2019-11-05 | South Dakota Board Of Regents | Layered high capacity electrodes |
| JP6856812B1 (en) * | 2020-10-21 | 2021-04-14 | 第一工業製薬株式会社 | Binder composition for electrodes, coating liquid composition for electrodes, electrodes for power storage devices and power storage devices |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP4406832B2 (en) * | 2004-03-24 | 2010-02-03 | 株式会社デンソー | Lithium secondary battery electrode and lithium secondary battery |
| JP4779327B2 (en) * | 2004-09-14 | 2011-09-28 | 株式会社デンソー | ELECTRODE FOR LITHIUM SECONDARY BATTERY AND LITHIUM SECONDARY BATTERY USING THE ELECTRODE |
| JP4876515B2 (en) * | 2005-09-30 | 2012-02-15 | 株式会社デンソー | ELECTRODE FOR LITHIUM SECONDARY BATTERY, ITS MANUFACTURING METHOD, AND LITHIUM SECONDARY BATTERY |
| JP2008021415A (en) * | 2006-07-10 | 2008-01-31 | Nissan Motor Co Ltd | Electrode for non-aqueous electrolyte secondary battery |
| JP2012195129A (en) * | 2011-03-16 | 2012-10-11 | Panasonic Corp | Coin-shaped battery and method for manufacturing the same |
-
2012
- 2012-11-30 WO PCT/JP2012/081151 patent/WO2013099520A1/en active Application Filing
- 2012-11-30 JP JP2013551551A patent/JP6055782B2/en active Active
- 2012-11-30 KR KR1020147020659A patent/KR20140116143A/en not_active Application Discontinuation
- 2012-11-30 CN CN201280064831.4A patent/CN104025350A/en active Pending
- 2012-12-20 TW TW101148776A patent/TW201342698A/en unknown
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104282956A (en) * | 2014-09-28 | 2015-01-14 | 广西师范大学 | Method for mixing slurry in electrode preparation process of lithium ion battery or super-capacitor |
| US20230155132A1 (en) * | 2019-12-25 | 2023-05-18 | Ningde Amperex Technology Limited | Electrochemical device and electronic device including same |
| WO2021254157A1 (en) * | 2020-06-17 | 2021-12-23 | Guangdong Haozhi Technology Co., Limited | Slurry composition for flexible electrode in secondary battery |
| CN114762152A (en) * | 2020-06-17 | 2022-07-15 | 广东省皓智科技有限公司 | Slurry composition for flexible electrode in secondary battery |
| CN114762152B (en) * | 2020-06-17 | 2023-09-01 | 广东省皓智科技有限公司 | Slurry composition for flexible electrode in secondary battery |
| CN112838210A (en) * | 2021-01-26 | 2021-05-25 | 江西安驰新能源科技有限公司 | Water-soluble lithium battery positive electrode slurry mixing process |
| CN113690440A (en) * | 2021-07-30 | 2021-11-23 | 深圳市研一新材料有限责任公司 | Electrode slurry composition, pole piece and secondary battery thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP6055782B2 (en) | 2016-12-27 |
| JPWO2013099520A1 (en) | 2015-04-30 |
| TW201342698A (en) | 2013-10-16 |
| WO2013099520A1 (en) | 2013-07-04 |
| KR20140116143A (en) | 2014-10-01 |
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