CN1290211C - Method for preparing slurry composition for electrode of secondary cell - Google Patents
Method for preparing slurry composition for electrode of secondary cell Download PDFInfo
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- CN1290211C CN1290211C CNB038157314A CN03815731A CN1290211C CN 1290211 C CN1290211 C CN 1290211C CN B038157314 A CNB038157314 A CN B038157314A CN 03815731 A CN03815731 A CN 03815731A CN 1290211 C CN1290211 C CN 1290211C
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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
- H01M4/04—Processes of manufacture in general
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical Kinetics & Catalysis (AREA)
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- General Chemical & Material Sciences (AREA)
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- Materials Engineering (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
A method for preparing a slurry composition for an electrode of a secondary cell, which comprises kneading an electrode active material and a dispersion in a solvent (SA) of a polymer (A) containing 50 wt % or more of a portion insoluble in the solvent (SA), and then kneading the above-kneaded fluid and a solution of a polymer (B) in a solvent (SB). A slurry composition prepared by the method is reduced in the change of the viscosity thereof due to the elapse of time and exhibits good sticking property, and provides an electrode of a secondary cell having a mixed layer of a flat surface and a uniform thickness through applying the composition on a collector followed by drying.
Description
Technical field
The present invention relates to a kind of slurry for secondary battery electrode preparation of compositions method.In more detail, relate to viscosity through the time with low uncertainty, coat the slurry for secondary battery electrode preparation of compositions method that collector body can obtain the level and smooth electrode of film coated surface.
Background technology
Removable window machines such as notebook computer, mobile phone, PDA are extensively popularized, and its power supply mostly is lithium rechargeable battery.Recently, removable window machine has been proposed to extend working time and shortens the requirement of height such as charging interval, also strong request realizes especially increasing the high performance of battery capacity and improve charging rate (speed characteristics) thereupon.
Lithium rechargeable battery disposes the dividing plate between positive pole and negative pole, and has the structure in electrolyte is included container in.(both are generically and collectively referred to as " electrode for secondary battery " for positive pole and negative pole, can abbreviate " electrode " as) be electrode active material (following can abbreviate " active material " as) and the conductivity imparting agent that uses in case of necessity etc., form by use in electrode for secondary battery binder polymer (being designated hereinafter simply as " adhesive ") and collector bodies adhesions such as aluminium or copper.Usually, bonding agent dissolving or be dispersed in the liquid medium, and obtain slurry for secondary battery electrode composition (being designated hereinafter simply as " paste compound ") after mixing with active material, conductivity imparting agent etc., again it is coated collector body, remove this liquid medium by methods such as dryings, adhesion becomes mixed layer and forms electrode.
But, because the dispersion of each composition is abundant inadequately in the paste compound, the viscosity time to time change of paste compound, the dispersity that exists paste compound is problem uniformly inadequately.If use uneven paste compound to make electrode, can cause by the unsmooth lower cell performance that causes of electrode surface, because of causing active material, the adhesive reduction of active material problem such as peels off from collector body.
As the method for the paste compound that obtains high degree of dispersion, open in the flat 8-195201 communique the spy, disclose in the mixed liquor of the adhesive that is scattered in tackifier solution, add active material and conductivity imparting agent and carry out method mixing, that disperse.But because the dispersion of conductivity imparting agent is abundant inadequately, the flatness that exists electrode surface is problem such as deficiency still among this preparation method.
In addition, as the paste compound preparation method, open the spy and to disclose step in the flat 9-204917 communique, the mixing paste compound that obtains is placed the tackify step of a period of time and the mixing once more step of the paste compound behind the tackify with mixing various compositions.But the technology of this method is loaded down with trivial details, also exists the preparation paste compound and takes long, the low inferior problem of production efficiency.
Open to disclose in the flat 2000-348713 communique tackifier to be divided into join respectively more than the secondary the spy and carry out mixingly in active material and the conductivity imparting agent, and then add adhesive and carry out batch mixing, with the preparation method of water as the paste compound of medium.But, this method also exist since the different adhesives of the kind of adhesive disperse abundant inadequately, the viscosity that causes through the time change excessive, the problem that adherence is low.
Summary of the invention
Based on above relevant situation, the object of the present invention is to provide a kind of viscosity through the time with low uncertainty, good adhesion, and can access the slurry for secondary battery electrode preparation of compositions method of the electrode of mixed layer with surface smoothing.
The present inventor is deeply inquiring on the basis of the paste compound method of producing active material and conductivity imparting agent high degree of dispersion, discovery is according to mixing the dispersion liquid and the active material that are dispersed with the polymer adhesive that is insoluble in solvent earlier, in this mixing liquid, be blended in the order of the solution of dissolving soluble polymer adhesive in this solvent subsequently, can obtain the paste compound of high degree of dispersion, when using this paste compound manufacturing electrode, can make the electrode of level and smooth mixed layer with no aggegation piece.Further deeply inquire into based on above cognition, finish the present invention.
The invention provides a kind of slurry for secondary battery electrode preparation of compositions method, this method comprises containing 50 weight % or the above solvent (S of 50 weight %
A) solvent (S of polymer (A) of insoluble component
A) dispersion liquid and electrode active material be mixing, then the solvent (S of the mixing liquid of gained and polymer (B)
B) solution carries out mixing.
In addition, the present invention also provides the manufacture method of electrode for secondary battery, and this method comprises being coated collector body and carried out drying by the paste compound of method for preparing.
Embodiment
Slurry for secondary battery electrode preparation of compositions method of the present invention comprises: containing solvent (S
A) solvent (S of the above polymer (A) of insoluble component 50 weight % or 50 weight %
A) dispersion liquid and electrode active material be mixing, then the solvent (S of the mixing liquid of gained and polymer (B)
B) solution carries out mixing.
At first, the used material of the present invention is described.
As employed solvent (S among the present invention
A) and solvent (S
B), preferred water and under atmospheric pressure boiling point be 80～350 ℃ non-water solvent.This non-water solvent can be exemplified as, for example, and amide-types such as N-methyl pyrrolidone, dimethyl formamide, dimethylacetylamide; Hydro carbons such as toluene, dimethylbenzene, n-dodecane, tetrahydronaphthalene; Alcohols such as 2-ethyl-1-hexanol, 1 nonyl alcohol, laruyl alcohol; Ketones such as methyl ethyl ketone, cyclohexanone, phorone, acetophenone, isophorone; Ester classes such as benzyl acetate, isoamyl butyrate, methyl lactate, ethyl lactate, butyl lactate; Amines such as ortho-aminotoluene, meta-aminotoluene, para-totuidine; Lactone such as gamma-butyrolacton, δ-butyrolactone; Sulfoxide such as dimethyl sulfoxide (DMSO), sulfolane sulfone class etc.Wherein preferred water and amide-type, preferred especially N-methyl pyrrolidone.
These solvents (S
A) and (S
B) can one or more are used in combination separately.In addition, be preferred for the solvent (S of polymer (A) dispersion liquid
A) be used for the solvent (S of polymer (B) solution
B) be same composition, even but they are different, as long as for for the mixed solvent composition of solution of the dispersion liquid of polymer (A) and polymer (B), the insoluble composition of polymer (A) is more than the 50 weight % or more than the 50 weight %, and polymer (B) just can use for solvable.
In the present invention, two kinds of polymer use as adhesive.For polymer A as a kind of composition in the polymer adhesive, be not particularly limited its kind, contain 50 weight % or the above solvent (S of 50 weight % but use
A) polymer of insoluble composition.Solvent (the S of polymer (A)
A) preferred 60 weight % of insoluble component or more than the 60 weight %, more preferably 70 weight % or more than the 70 weight %, and preferred 90 weight % or below the 90 weight %, preferred 87 weight % or below the 87 weight %.Infer as solvent (S
A) when insoluble component content was in this scope, polymer (A) was keeping granular or fibrous in paste compound, consequently can not cover the surface of active material and hinder the carrying out of cell reaction with membranaceous.As solvent (S
A) when insoluble component was very few, except that polymer (A) will become membranaceousization, the bonding persistence of active material was low, and the problem that battery capacity reduces can take place when repeated charge.In contrast, as using solvent (S
A) during the too much polymer (A) of insoluble component, then can produce the problems such as adhesiveness reduction of adhesive.
Solvent (S herein
A) amount of insoluble component to be, after 72 hours to filter 0.2 gram polymer in dipping under 60 ℃ of temperature in 20 milliliters of solvents through 80 order mesh screens, the polymer weight that obtains after the composition drying on the sieve and the percentage of dipping prepolymer weight are represented.
Contain a large amount of solvent (S as mentioned above
A) polymer (A) of insoluble component, the cross-linked copolymer of preferred simple function ethylene unsaturated monomer and/or conjugated diene and multifunctional ethylene unsaturated monomer.
As multifunctional ethylene unsaturated monomer, divinyl compounds such as preferred divinylbenzene; Dimethylacrylate such as diethylene glycol dimethacrylate, ethylene glycol dimethacrylate class; Trimethyl acrylic ester classes such as trimethylol-propane trimethacrylate; Diacrylate such as diethylene glycol diacrylate, 1,3 butyleneglycol diacrylate class; Triacrylate classes such as trimethylolpropane triacrylate etc.In addition, can use 1, non-conjugated diene classes such as 4-hexadiene, ethylidene norbornene, dicyclopentadiene.These multifunctional ethylene unsaturated monomers can be used alone or in combination of two or more.
For the used monomer total amount of preparation polymer, the ratio of multifunctional ethylene unsaturated monomer is generally 0.3～5 weight %, is preferably 0.5～3 weight %.
As the simple function ethylene unsaturated monomer that is used to prepare polymer (A), alpha-olefines such as ethene, propylene, 1-butylene, isobutene, 3-methyl-1-butene can have been enumerated; (methyl) acrylonitrile unsaturated nitrile compounds such as (meanings of acrylonitrile or methacrylonitrile);
(methyl) methyl acrylate (expression methyl acrylate or methyl methacrylate, below identical.), (methyl) esters of acrylic acid such as (methyl) ethyl acrylate, (methyl) butyl acrylate, (methyl) Hexyl 2-propenoate, (methyl) 2-EHA; Butenoate classes such as M Cr, butenoic acid 2-Octyl Nitrite, butenoic acid hydroxy propyl ester; (methyl) acrylic acid methoxyl group ethyl ester, (methyl) acrylic acid ethoxy ethyl ester etc. contain (methyl) esters of acrylic acid of alkoxyl; (methyl) dimethylaminoethyl acrylate, (methyl) acrylic acid lignocaine ethyl ester etc. contain amino esters of acrylic acid; (methyl) acrylic acid 2-hydroxy propyl ester, (methyl) acrylic acid hydroxy propyl ester etc. contain (methyl) acrylate of hydroxyl; (methyl) acrylate that on alkyl, has phosphate, sulfonic group, boronate etc.; Acrylic acid, methacrylic acid, butenoic acid, methacrylate, maleic acid, fumaric acid etc. contain the vinyl compound and the dicarboxylic anhydride compound of carboxyl; Aromatic ethenyl compound such as styrene, AMS etc.
Can enumerate 1,3-butadiene, 2-methyl isophthalic acid as conjugated diene, 3-butadiene (isoprene), 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene etc.These simple function ethylene unsaturated monomers and conjugated diene can be separately or two or more be used in combination.
When using conjugated diene, even under the situation of not using multifunctional ethylene unsaturated monomer, the polymerizing conditions such as amount by suitable adjustment polymerization temperature, polymerisation conversion and molecular weight adjustment agent can obtain cross-linked copolymer.
Glass transition temperature (the T of polymer (A)
g) be preferably-80～0 ℃, more preferably-60～-5 ℃.T
gWhen too high, the flexibility of electrode descends, and active material peeling off from collector body taken place in the process of repeated charge easily.In addition, T
gCross when hanging down, the situation that battery capacity descends can occur.
In order to make the T of polymer (A)
gBe in the above-mentioned scope, the repetitive in constituting as polymer molecule preferably has for example 2-EHA (homopolymers T
gBe-85 ℃), n-butyl acrylate (homopolymers T
g-54 ℃), methacrylic acid ester in the positive last of the ten Heavenly stems (homopolymers T
g-65 ℃), the T of its homopolymers such as 1,3-butadiene, isoprene
gBecome the monomeric repeating unit below 0 ℃ or 0 ℃.
2-EHA/methacrylic acid/acrylonitrile/diethylene glycol dimethacrylate copolymer, butyl acrylate/acrylic acid/acrylic rubbers such as trimethylol-propane trimethacrylate copolymer, acrylonitrile/butadiene copolymer rubber etc. can have been enumerated as preferred polymer (A).
Polymer (A) also can be the mixture of the polymer (A) of different monomers composition.In addition, at the solvent (S of polymer (A)
A) in the dispersion liquid, in the scope that does not influence effect of the present invention, also can contain a spot of solvent (S
A) polymer of insoluble component less than 50 weight %.
The average grain diameter of polymer (A) is preferably 0.005～1000 μ m, and more preferably 0.01～100 μ m is preferably 0.05～10 μ m especially.Average grain diameter is excessive, and then required amount of binder becomes too much, and the electrode internal resistance increases.On the contrary, average grain diameter is too small, then can hide the surface of active material, has hindered cell reaction.
The mensuration of average grain diameter is the diameter of measuring 100 polymer particles of picked at random by the photo of transmission electron microscope herein, gets the average grain diameter of its arithmetic mean as each particle of calculating.
Preparation method for polymer (A) does not do special qualification, for example can adopt known polymerizations such as emulsion polymerization method, suspension polymerization, dispersion copolymerization method or solution polymerization process to carry out polymerization and obtain.When adopting emulsion polymerization method, be scattered in solvent (S because of controlling easily
A) time particle diameter, so preferred this method that adopts.
As another composition polymer (B) of polymer adhesive, be the solvent (S that can be dissolved in as the paste compound medium
B) polymer.For polymer (B), solvent (S is not arranged as long as conform to
B) insoluble component, then unqualified, after making paste compound coat collector body, be easier to form mixed layer, preferred use can increase the polymer adhesive of the viscosity of paste compound.
During preparation polymer (B), can use simple function ethylene unsaturated monomer and/or conjugated diene, the material of using when its concrete example can be set forth in the above-mentioned polymer of preparation (A) as an example.These monomers can independent or multiple being used in combination.
As the example of above-mentioned polymer (B), can give an example acrylic acid nitrile/butadiene copolymer and hydride thereof, ethylene/methyl acrylate copolymer, styrene/butadiene copolymers, butadiene rubber, ethylene/vinyl alcohol copolymer, acrylonitrile/ethylene copolymer, acrylonitrile/methylmethacrylate copolymer etc.
Polymer (B) also can be a fluoropolymer.Fluoropolymer is the polymer that contains 50 moles of % or the 50 moles of above fluorochemical monofunctional ethene of % monomeric units, preferably contains 70 moles of % or 70 moles more than the %, more preferably contains 80 moles of % or 80 moles more than the %.Fluoropolymer can have been enumerated vinylidene, tetrafluoroethene, hexafluoropropylene, chlorine trifluoride ethene, PVF, perfluoroalkyl vinyl ether etc., preferred vinylidene.During fluorochemical monomer beyond using vinylidene, and use vinylidene, preferably making fluorochemical monomer total amount outside the vinylidene is 30 moles of % of whole fluorochemical monomers or 30 moles below the %, and more preferably 20 moles of % or 20 moles are below the %.
Non-fluorochemical monomer unit is 50 moles of % or 50 moles below the % in the above-mentioned fluoropolymer, and preferred 30 moles of % or 30 moles are below the %, and more preferably 20 moles of % or 20 moles are below the %.When the content of non-fluorine-containing monomer unit was too much, polymer descended the problem that causes active material easily to come off from electrode to the solvent resistance of electrolyte.
As can with the monomer of fluorochemical monofunctional ethene monomer copolymerization, can enumerate 1-alkene such as ethene, propylene, 1-butylene; (methyl) esters of acrylic acids such as (methyl) methyl acrylate, (methyl) butyl acrylate, (methyl) 2-EHA; Styrene, AMS, to aromatic ethenyl compounds such as t-butyl styrene; Unsaturated nitrile compounds such as (methyl) acrylonitrile; The not fluorine-containing simple function ethylene unsaturated monomer of (methyl) acrylamide compounds such as (methyl) acrylamide, N-methylol (methyl) acrylamide, N-butoxy (methyl) acrylic amine etc.
The mixture of the polymer (B) that the polymer among the present invention (B) also can be formed for difference.In addition, at the solvent (S of polymer (B)
B) in the solution, in the scope that does not influence effect of the present invention, can contain a small amount of solvent (S
B) insoluble polymer.
Preparation method for above-mentioned polymer (B) does not do special qualification.For example can adopt known polymerizations such as emulsion polymerization method, suspension polymerization, dispersion copolymerization method, solution polymerization process to carry out polymerization obtains.
With respect to active material 100 weight portions, preferred 0.1～5 weight portion of total amount of the polymer adhesive that polymer (A) and polymer (B) are formed, more preferably 0.2～3 weight portion, preferred especially 0.5～2 weight portion.The adhesive total amount is very few, and then active material easily comes off from electrode, otherwise too much the time, active material is hidden by adhesive, might hinder cell reaction.
The weight ratio of polymer (A) and polymer (B) is preferably 5/1～1/5, and more preferably 3/1～1/3, be preferably 2/1～1/2 especially.When the ratio of polymer (A) was excessive, adherence improved but the mobile reduction of paste compound, and the mixed layer that is coated on gained on the electrode will become unsmooth.Otherwise too small as the ratio of polymer (A), then adhesive may hide the active material surface and hinder cell reaction.
Electrode active material used in the present invention is according to the kind of secondary cell and difference.
Under the situation of lithium rechargeable battery, negative electrode active material, positive active material can use the identical material used with common lithium ion cell electrode.
Negative electrode active material as lithium rechargeable battery, can enumerate amorphous carbon, graphite, native graphite, the little packing ring of meso carbon (メ ソ カ-ボ Application マ イ Network ロ PVC one ズ, MCMB), carbonaceous material, polyacetylene electroconductive polymers such as (Port リ ァ セ Application) such as pitch-based carbon fiber.
As positive active material, can enumerate LiCoO
2, LiNiO
2, LiMnO
2, LiMn
2O
4Deng the composite metal oxide that contains lithium; TiS
2, TiS
3, amorphous state MoS
3Deng transient metal sulfide; Cu
2V
2O
3, amorphous state V
2O-P
2O
5, MoO
3, V
2O
5, V
6O
13Deng transition metal oxide etc.And, electroconductive polymer organic compounds such as also available polyacetylene, poly.
For nickel-hydrogen secondary cell, its negative electrode active material and positive active material all can be used the used material of common nickel-hydrogen secondary cell.Negative electrode active material can use and contain the hydrogen alloy.Positive active material can be used nickel oxyhydroxide, nickel hydroxide etc.
Solvent (the S of polymer (B)
B) preferably contain the conductivity imparting agent in the solution.In lithium rechargeable battery, use carbon as the conductivity imparting agent.The conductivity imparting agent that nickel-hydrogen secondary cell is used for the available cobalt oxide of positive pole, can use nickel powder, cobalt oxide, titanium oxide, carbon etc. for negative pole.
In the above-mentioned two class batteries,, acetylene carbon black, furnace black, graphite, carbon fiber, active carbon, Off ラ one レ Application class etc. can have been enumerated as the carbon of conductivity imparting agent.Wherein preferred acetylene carbon black, furnace black.
For per 100 weight portion active materials, the use amount of conductivity imparting agent is generally 1～20 weight portion, preferred 2～10 weight portions.
The preparation process of paste compound below is described.Among the present invention, will contain the above or above solvent (S of 50 weight % of 50 weight %
A) solvent (S of polymer (A) of insoluble component
A) dispersion liquid and the mixing preparation mixed liquor of electrode active material, and the solvent (S of prepared polymer (B) separately
B) solution, mixing two kinds of liquid then, this is very important in proper order.On the contrary, as take the order of first mixed polymer (A) and polymer (B), or the order of first mixed active material and polymer (B), will cause viscosity through the time alter a great deal or problem such as adherence reduction.
For the mixed liquor of prepared polymer (A) with active material, solvent (S
A) amount different and different with the kind of active material, can adsorbable " liquid absorption " with respect to active material, be preferably 80～120 weight %, more preferably 85～110 weight % most preferably are 90～100 weight %.When the quantity of solvent of this mixed liquor was less than 80 weight % of active material liquid absorption, the active material powdering was cut off weak effect when mixing, and active material and polymer (A) mixing inhomogeneous causes made paste compound flowability very poor.Otherwise the quantity of solvent of this mixed liquor is during more than 120 weight % of the liquid absorption of active material, and the viscosity of mixed liquor reduces, and it is invalid to cut off, and also can form the paste compound of mobile difference.
The active material adsorbance can be measured according to the following method of ASTM D 281 usefulness.That is, put into 20 active materials got of gram in vessel, splash into 0.5 milliliter of solvent with spatula in stirring at every turn, the quantity of solvent when recording active material powder and being consolidated into pie is converted into and is equivalent to 100 and restrains the pairing quantity of solvent of active materials.After carrying out measuring for three times, its mean value is as liquid absorption.
In the methods of the invention, for polymer (A) is scattered in solvent (S
A) in and make polymer (B) be dissolved in solvent (S
B) in mixer and mixing time be not particularly limited.As the mixer that is used for these occasions, for example can use the mixing channel, planetary-type mixer and the ribbon blender that have mixer.
In addition, as the method that polymer (A) is disperseed, as solvent (S
A) when being non-water solvent, consider from good aspects such as production efficiency, preferably take after polymer (A) particle being scattered in the aqueous dispersion of making polymer in the water method that the water in this aqueous polymer dispersion is cemented out with non-water solvent by usual method.Its method of replacing is add non-water solvent in the aqueous dispersion of polymer (A) after, the method that the moisture content in the decentralized medium is removed by for example way of distillation or decentralized medium phase inversion method.
When using the conductivity imparting agent, preferably in advance the conductivity imparting agent is dispersed in polymer (B) solution, use with the form of mixed liquor again.
Preparation is at the solvent (S of polymer (B)
B) when solution contains the mixed liquor of conductivity imparting agent, preferably regulate solvent (S
B) amount to make the solid component concentration of mixed liquor be 30～40 weight %, preferred especially 33～38 weight % also carry out mixing.The concentration of solid constituent is meant the ratio of the total amount of polymer (B) and conductivity imparting agent with respect to the mixed liquor total amount herein.When solid component concentration is in above-mentioned scope, be easy to make the conductivity imparting agent to mix.
Among the preparation method of the present invention, mixing with the solution of polymer (B) again the dispersion liquid of as above formulated polymer (A) and the mixing mixed liquor that forms of active material, make paste compound.When mixing,, can add solvent (S according to the kind of adhesive or electrode active material and conductivity imparting agent for the viscosity that obtains to be suitable for being coated with
A) or (S
B).
The suitableeest viscosity of paste compound, different with the shape of coating machine kind that on collector body, is coated with and coating streamline, when 23 ℃ of temperature with Brookfield L type viscosimeter, No. 4 impellers, with the viscosity of 30rpm rotational speed after 1 minute, be generally 1500～8000mPaS, be preferably 2000～6000mPaS.The viscosity of paste compound is crossed when low, in slurry sedimentation can take place through back after a while, or generation liquid extension (liquid グ レ) phenomenon during coating, otherwise when viscosity was too high, the flatness that coating thickness inequality or mixed layer surface can take place was low.
The dispersion liquid of polymer (A) and the mixing mixed liquor that forms of active material again with the solution of polymer (B) when mixing, and at solvent (S with polymer (A)
A) dispersion liquid and active material be mixing during with the modulation mixed liquor, and at the solvent (S to polymer (B)
B) in the solution during dispersed electro-conductive imparting agent, do not do special qualification for mixer and mixing time.The high shear type of advantageous applications mixer makes the particle of active material or conductivity imparting agent and binder polymer together mixing equably.
As high shear type mixer, can enumerate ball mill, sand mill, pigment dispersing machine, pulverizing mill, ultrasonic dispersing machine, homogenizer, planetary-type mixer etc., wherein preferred planetary-type mixer.
Mixing condition to high shear type mixer is not done special provision, and mixing temperature is generally 15～50 ℃, and incorporation time is generally 60～180 minutes.Degree of scatter can be measured by hondrometer, the preferred mixed agglutinator that does not exist at least greater than 100 μ m that is dispersed to.
By the paste compound of the inventive method gained, its viscosity through the time with low uncertainty, adherence is good, can obtain the electrode for secondary battery mixed layer of surface smoothing, thickness homogeneous.
Can make electrode for secondary battery by dry method after the slurry for secondary battery electrode composition of the inventive method gained being coated collector body.That is, electrode for secondary battery adheres to the mixed layer that evenly contains adhesive, active material and the conductivity imparting agent that adds as required, tackifier etc. and forms on collector body.
Can be used in positive pole, the negative pole any one by the electrode for secondary battery of said method gained, preferably be applicable to positive pole, especially preferably be suitable for the positive pole of lithium rechargeable battery.
Collector body then has no particular limits it as long as be made up of conductive material.Use metallic articles such as iron, copper, aluminium, nickel, stainless steel in lithium rechargeable battery, use aluminium at positive pole especially, negative pole uses under the situation of copper, and is the most obvious by the effect of the prepared paste compound of the inventive method.In nickel-hydrogen secondary cell, perforated metal (パ Application チ Application グ メ Le), expanding metal (エ キ ス パ Application De メ Le), wire netting, foaming metal, net metal fiber sintering body, plating resin plate etc. can have been enumerated.
Shape to collector body has no particular limits, and normally thickness is the tablet about 0.001～0.5mm.
Have no particular limits for the method that paste compound is applied on the collector body.For example can enumerate scraper plate method (De Network one Block レ one De method), infusion process (デ イ Star プ method), oppositely rolling process (リ バ one ス ロ one Le method), rolling process (グ イ レ Network ト method), woodburytype (グ ラ PVC ァ method), extrusion (エ Network ス ト Le one ジ ョ Application method), spread coating (ハ ケ Tu り method in the same way) etc.The amount of paste compound to coating does not have specific restriction yet, is generally in that liquid medium is removed by drying that the back forms, and the dried mixed layer thickness of being made up of active material, adhesive etc. is generally 0.005～5mm, the amount of preferred 0.01～2mm.
Do not do special restriction for the drying means that is coated on the paste compound on the collector body yet, for example can enumerate and adopt warm wind, hot blast, low wet wind to carry out drying, vacuumize, (far) infrared ray and electron beam irradiation drying means.
In addition, dried electrode is exerted pressure by methods such as roll-ins, can improve the density of electrode active material thus.
Parts such as the electrode for secondary battery that application makes according to the method described above, electrode solution, dividing plate can be made secondary cell by well-established law.For example, anodal and negative pole are piled up by dividing plate,, in battery case, seal behind the injection electrolyte according to the cell shapes battery case of packing into after with its convolution.Be shaped as coin shape, button-type, thin slice shape, cylindrical shape, dihedral, the pancake etc. of battery all can.
Electrolyte can use the used electrolyte of common secondary cell, and aqueous or gel all can.So long as the electrolyte of selecting according to the kind of negative electrode active material, positive active material that can bring into play battery functi on gets final product.
As electrolyte, in lithium rechargeable battery, can use existing known any lithium salts, as enumerating LiClO
4, LiBF
4, LiPF
6, LiCF
3CO
2Deng.
There is no particular limitation for the solvent that makes this electrolyte dissolution.Concrete example can have been enumerated carbonates such as ethylene carbonate, ethyl-methyl carbonic ester, propylene carbonate; Lactone such as gamma-butyrolacton; 1, ethers such as 2-dimethoxy-ethane, ether, oxolane, 2-methyltetrahydrofuran; Sulfoxide classes such as dimethyl sulfoxide (DMSO) etc.They can use separately or with multiple above mixed solvent form.
In addition, in nickel-hydrogen secondary cell, can use existing known concentration is 5 mol or the above potassium hydroxide aqueous solution of 5 mol.
Embodiment
The present invention will be described below to enumerate embodiment, but the present invention is not limited by this.
In addition, " part " of the following stated and " % " do not have specified otherwise, are weight basis.
Operation in embodiment and the comparative example and test are carried out in accordance with the following methods.
[characteristic of slurry constituent and paste compound]
(1) glass transition temperature (T
g)
Under 10 ℃/minute of programming rates, measure the T of polymer by differential scanning type calorimeter (DSC)
g
(2) amount of N-methyl pyrrolidone (NMP) insoluble composition
The amount of the NMP insoluble composition of polymer is represented the weight of gained after the composition drying on the sieve so that the 20g polymer, is filtered with 80 mesh sieves after 72 hours at dipping under 60 ℃ in 20m1NMP with respect to the percentage of the preceding weight of dipping.
(3) average grain diameter
The polymer average grain diameter is, 100 polymer particles of picked at random and measure its diameter in the transmission-type microphotograph calculate the average grain diameter of its mean value as each particle, and its unit is (μ m).
(4) composition of polymer
The content that each that constitutes polymer heavily covered the unit by
1H-reaches
13C-NMR measures and tries to achieve, and its unit is (mole %).
(5) liquid absorption of active material
Put into the 20g active material of being got in vessel, splash into 0.5mlNMP while stirring with spatula at every turn, the NMP that the mensuration active material adds when being consolidated into pie measures, and is converted into to be equivalent to the pairing quantity of solvent of 100g active material again.The mean value of measuring for three times is as liquid absorption.
(6) viscosity of paste compound, slurry viscosity sustainment rate
Paste compound viscosity is, with paste compound after preparation in 23 ℃ of storages, after 1 hour and after 24 hours, when temperature is 23 ℃ with Brookfield L type viscosimeter and No. 4 impellers, measure its viscosity with the rotation of 30rpm rotating speed respectively after 1 minute, unit is (mPaS).In addition, the viscosity sustainment rate of the percentage of viscosity number after 24 hours and the viscosity number after 1 hour as slurry.
[characteristic of electrode for secondary battery]
(7) making of lithium ion secondary battery positive electrode
The lithium ion secondary battery positive electrode for preparing in embodiment and the comparative example is coated on the aluminium foil (thickness 20 μ m) with the scraper plate method equably with paste compound, and the usefulness drying machine is following dry 15 minutes 120 ℃ of temperature.After in vacuum drier, carrying out 2 hours drying under reduced pressure again, be compressed to electrode density with the twin shaft roll squeezer and reach 3.2g/cm with 0.6kPa, 120 ℃
3, make lithium ion secondary battery positive electrode.
(8) arithmetic average roughness (Ra)
Based on JIS B0601, with the arithmetic average roughness (Ra) of the square scope of atomic force microscope observation electrode mixed layer surface 20 μ m.
(9) peel strength
On the lithium ion secondary battery positive electrode that makes from method described in above-mentioned (7), cut out the rectangle of long 100mm, wide 25mm and coating direction test film for long limit.Behind sticking glass masking tape on all surfaces of test film mixed layer, the tearing speed that the glass cement paper tape end of test film one end and collector body paillon foil end are divided with 50mm/ according to vertical direction is torn and is peeled off, and measures the stress (N/cm) of this moment.Stress is big more can judge that then the peel strength of mixed layer is big more.
[characteristic of secondary cell]
(10) manufacturing of lithium rechargeable battery
Use lithium metal as negative pole.Anodal and lithium anode cuts into the circle of diameter 15mm the aluminium that makes according to (7) described method, stack gradually dividing plate and the negative pole lithium metal that the circular polypropylene system perforated membrane of diameter 18mm, thickness 25 μ m is formed in electrode aspect one side of positive pole, the bottom surface that is configured to outer packaging container contacts with anodal aluminium foil, on negative pole, put into the expanding metal, they are put into the outer packaging container of coin type (diameter 20mm, height 1.8mm, stainless steel thickness are 0.25mm) of the stainless steel that is provided with polypropylene-made liner (パ Star キ Application).Inject electrolyte in this container, and note not residual air, cover the stainless steel top cover of thickness 0.2mm and fixing outside on the packaging container by polypropylene-made liner, the closing battery cylinder is made the coin type battery of diameter 20mm, the about 2mm of thickness.Electrolyte is for to be dissolved with 1 mol LiPF in ethylene carbonate/ethyl-methyl carbonic ester=33/67 (volume ratios under 20 ℃)
6Solution.
(11) battery capacity
Being determined as of battery capacity is 0.1C at 25 ℃ of following charge-discharge velocities, with constant flow method (current density: the 0.5mA/g-active material) charge to 1.2V, be discharged to 3V, and repeated charge each 5 times, measure battery capacity at every turn, the mean value of battery capacity of mensuration repeatedly as evaluation result.Unit is [mAh/g: active material (explanation of following relevant battery capacity is identical therewith)].
(12) discharge and recharge speed characteristics
Except condition determination being changed to constant current amount 1C, identical with the mensuration of battery capacity, discharge and recharge with constant flow method, measure the discharge capacity of circulation time [unit=mAh/g] for the third time.Calculate the percentage of discharge capacity when the discharge capacity of circulation time when 1C is with respect to 0.1C for the third time.This value is big more, shows that might carry out high speed more discharges and recharges.
In embodiment and comparative example as the composition of each used polymer of adhesive (unit: mole %) be shown in table 1.Polymer A-1,2 and polymer B-1～3 all make by the emulsification coincidence method.Kynoar then uses commercially available product.
Table 1
| Polymer | A-1 | A-2 | B-1 | B-2 | B-3 | |
| Form (mole %) | Ethene | - | - | - | 35 | - |
| Butadiene | - | - | 70*1 | - | - | |
| Acrylonitrile | 20 | 16 | 30 | - | 80 | |
| Methyl acrylate | - | - | - | 65 | - | |
| Butyl acrylate | - | 80 | - | - | - | |
| 2-EHA | 77 | - | - | - | 20 | |
| Methacrylic acid | 2 | 3 | - | - | - | |
| Diethylene glycol dimethacrylate | 1 | 1 | - | - | - | |
| Characteristic | T g(℃) | -50 | -38 | -10 | -6 | 22 |
| The amount of NMP insoluble composition (%) | 85 | 87 | ＜0.1 | ＜0.1 | ＜0.1 | |
| Average grain diameter (μ m) | 0.15 | 0.12 | - | - | - | |
Annotate
*1: polymer B-1 will be used behind the repetitive partial hydrogenation from the butadiene of acrylonitrile/butadiene copolymer.
Embodiment 1
0.4 part of polymer A-1 be scattered in 15.6 parts of NMP dispersion liquid, with 100 parts of cobalts acid lithium (LiCoO
2, active material (i), liquid absorption 15.6g), with mixing 60 minutes of the planetary mixture machine that has two pairs of spiral type agitators, be modulated into mixed liquor a.The solid constituent concentration of mixed liquor a is 86.6%.In addition, to in 6.3 parts of NMP, being dissolved with in the solution of 0.2 part of polymer B-1 and 0.2 part polymer B-3, add 3 parts of conductivity imparting agent acetylene carbon blacks (electrochemical industry society system, デ Application カ Block ラ Star Network granular), solid constituent concentration is 35.1%, with mixing with above-mentioned same planetary-type mixer, add 1.8 parts of NMP, make solid component concentration and be 29.6% mixed liquor b.In mixed liquor a, add mixed liquor b with above-mentioned planetary-type mixer, mixing again 30 minutes, make the paste compound that lithium ion secondary battery positive electrode is used.The solid shape concentration of component of paste compound is 81.4%.Slurry viscosity was 2200mPaS at the 1st hour, was 2270mPaS at the 24th hour, and the viscosity rate of change of slurry is 103%.
In table 2, put down in writing and used the electrode for secondary battery that the paste compound after 24 hours makes and the attribute testing result of secondary cell.
Embodiment 2～6
Press composition shown in the table 2 and quantity, prepare paste compound with method with embodiment 1.During preparation mixed liquor b, in the NMP amount that in table, writes down, when dissolve polymer (B), add 6.3 parts earlier, and add surplus again after the conductivity imparting agent mixes.But in embodiment 3, when dissolve polymer (B), the amount of record in the table is all added.Test paste compound, used the made electrode for secondary battery of paste compound and the characteristic of secondary cell.Result of the test is shown in table 2.
Table 2
| Embodiment | |||||||
| 1 | 2 | 3 | 4 | 5 | 6 | ||
| Active material | Kind *1 addition (part) | i 100 | i 100 | i 100 | ii 100 | iii 100 | i 100 |
| Polymer (A) | Kind addition (part) | A-1 0.4 | A-1 0.4 | A-1 0.4 | A-1 0.4 | A-1 0.4 | A-2 0.4 |
| Mixed liquor a mixing condition | Solid constituent concentration (%) acetylene carbon black (part) quantity of solvent (part) quantity of solvent (to active material liquid absorption %) | 86.6 - 15.6 100 | 88.6 - 12.9 83 | 84.5 - 18.4 118 | 88.5 - 13 99 | 85.0 - 17.7 99 | 86.6 - 15.6 100 |
| Polymer (B) | Kind a kind, 1 addition (part) | B-1 0.2 | B-1 0.2 | B-1 0.2 | B-1 0.2 | B-1 0.2 | B-2 0.2 |
| Kind 2 kinds, 1 additions (part) | B-3 0.2 | B-3 0.2 | B-3 0.2 | B-3 0.2 | B-3 0.2 | PVDF *2 0.2 | |
| Mixed liquor b mixing condition | Quantity of solvent (part) acetylene carbon black (part) solid constituent concentration (%) | 8.1 3 29.6 | 10.8 3 23.9 | 5.3 3 39.1 | 8.3 3 29.1 | 7.4 3 31.5 | 8.1 3 29.6 |
| Paste compound | Quantity of solvent (the corresponding umber of per 100 parts of active materials) solid constituent concentration (%) | 23.7 81.4 | 23.7 81.4 | 23.7 81.4 | 21.3 83.0 | 25.1 80.5 | 23.7 81.4 |
| Paste compound | The 1st hour (mPaS) slurry viscosity the 24th hour (mPaS) slurry viscosity sustainment rate (%) of slurry viscosity | 2200 2270 103 | 1940 1980 102 | 2320 2200 95 | 3560 3480 98 | 3600 3500 97 | 3940 3860 98 |
| Electrode for secondary battery | Arithmetic average roughness Ra (μ m) peel strength (N/cm) | 0.8 0.24 | 0.7 0.26 | 0.9 0.27 | 0.9 0.23 | 0.8 0.22 | 0.8 0.25 |
| Secondary cell | Battery capacity (mAh/g) discharges and recharges speed characteristics (%) | 147 94 | 145 93 | 146 94 | 144 95 | 148 93 | 145 93 |
Annotate
*1 i:LiCoO
2, liquid absorption 15.6g,
Ii:LiCoO
2, liquid absorption 13.1g,
Iii:LiCoO
2, liquid absorption 17.9g
*2PVDF: Kynoar (#1100, Wu Yu chemistry society system, NMP insoluble component less than 0.1%)
As shown in table 2, for three kinds of different active materials of liquid absorption, used the adhesive of indissoluble and soluble two kinds of polymer in solvent, paste compound by the inventive method preparation, make after 1 hour and all shown after 24 hours low and stable (through the time with low uncertainty) viscosity, these made electrode mixed layers in paste compounds coating back, its surface smoothing, peel strength is very big, and adherence is good.In addition, use the lithium rechargeable battery of these electrodes to have high power capacity and the high speed characteristics (embodiment 1-6) that discharge and recharge.
Comparative example 1
In 23.7 parts of NMP, add 0.2 part of polymer B-1 and 0.2 part polymer B-3 and make it dissolving, 0.4 part polymer A-1 is scattered in wherein, add 3 parts of acetylene carbon blacks and 100 parts of active materials (i) again, with mixing 90 minutes of the planetary mixture machine with two pairs of spiral type paddles, obtain the lithium ion secondary battery positive electrode paste compound.The solid constituent concentration of paste compound is 81.4%.The viscosity of slurry was 13400mPaS on the 1st hour, and the 24th hour is 2010mPaS, and the slurry viscosity rate of change is 15%.
In table 3, write down and used the electrode for secondary battery that the paste compound after 24 hours makes and the attribute testing result of secondary cell.
Comparative example 2
In 16.9 parts of NMP, add 0.2 part of polymer B-1 and 0.2 part polymer B-3 and make it dissolving, adding 0.4 part of polymer A-1 subsequently disperses, with this dispersion liquid and 3 parts of acetylene carbon blacks and 100 parts of active materials (i) with mixing 60 minutes of the planetary mixture machine with two pairs of spiral type paddles, add 6.8 parts of NMP, mixing again 30 minutes, obtain the lithium ion secondary battery positive electrode paste compound.The solid constituent concentration of paste compound is 81.4%.Slurry viscosity was 12800mPaS at the 1st hour, was 2120mPaS at the 24th hour, and the viscosity rate of change of slurry is 17%.
In table 3, write down and used the electrode for secondary battery that the paste compound after 24 hours makes and the attribute testing result of secondary cell.
Comparative example 3
In 16.1 parts of NMP, add 0.1 part of polymer B-1 and 0.1 part polymer B-3 and make it dissolving, with this solution and 3 parts of acetylene carbon blacks and 100 parts of active materials (i) with mixing 30 minutes of the planetary-type mixer with two pairs of spiral type paddles, in wherein being added in 3 parts of NMP, be dissolved with the solution of 0.1 part of polymer B-1 and 0.1 part polymer B-3, mixing again 30 minutes.In wherein being added in 4.6 parts of NMP, be dispersed with the dispersion liquid of 0.4 part of polymer A-1, mixed once more 30 minutes, make the lithium ion secondary battery positive electrode paste compound.The solid constituent concentration of paste compound is 81.4%.Slurry viscosity was 18400mPaS at the 1st hour, was 2050mPaS at the 24th hour, and the slurry viscosity rate of change is 11%.
In table 3, write down and used the electrode for secondary battery that the paste compound after 24 hours makes and the attribute testing result of secondary cell.
Comparative example 4
In 15.8 parts of NMP, dissolve in 0.2 part of polymer B-1 and 0.2 part polymer B-3, this solution and 100 parts of active materials (i) with mixing 60 minutes of the planetary mixture machine with two pairs of spiral type paddles, are made mixed liquor c.The solid constituent concentration of mixed liquor c is 86.4%.In addition,, add 3 parts of acetylene carbon blacks, and disperse, make solid constituent concentration and be 30.0% mixed liquor d with planetary mixture machine in 7.9 parts of NMP, being dispersed with in the dispersion liquid of 0.4 part of polymer A-1.In mixed liquor c, add mixed liquor d with above-mentioned planetary-type mixer, mixing 30 minutes, make the lithium ion secondary battery positive electrode paste compound.The solid constituent concentration of paste compound is 81.4%.Slurry viscosity was 8950mPaS at the 1st hour, was 1980mPaS at the 24th hour, and the slurry viscosity rate of change is 22%.
In table 3, write down and used the electrode for secondary battery that the paste compound after 24 hours makes and the attribute testing result of secondary cell.
Table 3
| Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | ||
| The 1st mixed liquor constituent (part) | B-1 B-3 A-1 acetylene carbon black active material (annotating) solvent with reference to table 2 | 0.2 0.2 0.4 3 100 23.7 | 0.2 0.2 0.4 3 100 16.9+6.8 (replenish and add) | 0.1 0.1 - 3 100 16.1 | 0.2 0.2 - - 100 15.8 |
| The mixing condition of the 1st mixed liquor | Quantity of solvent (to the liquid absorption % of active material) when solid constituent concentration (%) active material disperses | 81.4 147 | Add back (81.4) 108 86.0 replenish | 86.5 103 | 86.4 101 |
| The 2nd mixed liquor constituent (part) | B-1 B-3 A-1 acetylene carbon black solvent | - - - - - | - - - - - | 0.1 0.1 - - 3 | - - 0.4 3 7.9 |
| The mixing condition of the 2nd mixed liquor | Solid constituent concentration (%) | - | - | 6.3 | 30 |
| The 3rd mixed liquor constituent (part) | The A-1 solvent | - - | - - | 0.4 4.6 | - - |
| The mixing condition of the 3rd mixed liquor | Solid constituent concentration (%) | - | - | 8 | - |
| Paste compound | Quantity of solvent (the corresponding umbers of per 100 parts of active materials) solid constituent concentration (%) | 23.7 81.4 | 23.7 81.4 | 23.7 81.4 | 23.7 81.4 |
| The viscosity sustainment rate (%) of the 24th hour (mPaS) slurry of viscosity of the 1st hour (mPaS) slurry of the viscosity of slurry | 13400 2010 15 | 12800 2120 17 | 18400 2050 11 | 8850 1980 22 | |
| Electrode for secondary battery | Arithmetic average roughness Ra (μ m) peel strength (N/cm) | 16 0.07 | 0.4 0.1 | 1.5 0.06 | 1.8 0.05 |
| Secondary cell | Battery capacity (mAh/g) discharges and recharges speed characteristics (%) | 140 76 | 141 78 | 139 76 | 138 68 |
As shown in table 3, even use and foregoing invention example (embodiment 1～6) same composition, but all present not good result with the paste compound that the sequential steps different with the present invention makes with identical amount.Promptly, all the components beyond the solvent carries out mixing method in the full dose solvent according to being made an addition to successively, or take to make an addition to successively in the solvent of about 7 one-tenth quantity earlier, the method that adds the residual volume solvent after mixing again, the paste compound that obtains thus, the initial value of its viscosity is all higher, then sharply reduce very unstable subsequently, the surface of electrode mixed layer is very coarse, peel strength is obviously too small, with the made secondary cell of such electrode, its battery capacity, discharge and recharge speed characteristics all relatively poor (comparative example 1,2).
In addition, according to the paste compound that the method that adds the dispersion liquid of polymer A in the mixed liquor that is pre-mixed by polymer (B), conductivity imparting agent and active material obtains, the viscosity initial value will exceed 8～9 times, but reduces in time and rapidly.With electrode and the secondary cell that this paste compound makes, present the shortcoming (comparative example 3) same with comparative example 1,2.
In addition, if to being dissolved with polymer (B) and being dispersed with in the mixed liquor of active material, add the dispersion liquid of other polymer of preparing (A) and conductivity imparting agent and carry out mixing, take the preparation steps opposite with the present invention, its paste compound viscosity initial value of making is four times of the embodiment of the invention, but then greatly reduce subsequently, electrode that obtains and secondary cell have the shortcoming (comparative example 4) same with comparative example 1～3.
Industrial applicability
By the paste compound that the inventive method makes, the rheological parameters' change with time of its viscosity is few, and adherence is good, this composition is coated collector body and drying after, just can form have surface smoothing, the electrode for secondary battery of thickness homogeneous mixed layer.
Above-mentioned electrode for secondary battery all can use for anodal, negative pole, preferably is used in positive pole, particularly preferably is used in the positive pole of lithium rechargeable battery.
Claims (19)
1. slurry for secondary battery electrode preparation of compositions method, this method comprise comprising the above solvent S of 50 weight % or 50 weight %
AThe solvent S of the polymer A of insoluble component
ADispersion liquid and electrode active material carry out mixing, then with the mixing liquid of gained and the solvent S of polymer B
BSolution carries out mixing, forms the slurry for secondary battery electrode composition thus.
2. the preparation method of the described paste compound of claim 1, the solvent S of wherein said polymer A
AInsoluble component is 50 weight %～90 weight %.
3. the preparation method of the described paste compound of claim 1, the solvent S of wherein said polymer A
AInsoluble component is 50 weight %～87 weight %.
4. the preparation method of each described paste compound in the claim 1～3, wherein said polymer A are selected from least a monomer in simple function ethylene unsaturated monomer and the conjugated diene and the cross-linked copolymer of multifunctional ethylene unsaturated monomer.
5. the preparation method of each described paste compound in the claim 1～3, the glass transition temperature T of wherein said polymer A
gScope at-80 ℃～0 ℃.
6. the preparation method of each described paste compound in the claim 1～3, the average grain diameter of wherein said polymer A is in the scope of 0.005 μ m～1000 μ m.
7. the preparation method of each described paste compound in the claim 1～3, wherein said polymer B is at least a polymer of monomers that is selected from simple function ethylene unsaturated monomer and the conjugated diene.
8. the preparation method of each described paste compound in the claim 1～3, wherein said polymer B comprises the fluoropolymer that contains 50 moles of % or the 50 moles of above fluorochemical monofunctional ethene of % monomeric units.
9. the preparation method of each described paste compound in the claim 1～3, wherein with respect to 100 weight portion active materials, the total amount of described polymer A and polymer B is the scope of 0.1～5 weight portion.
10. the preparation method of each described paste compound in the claim 1～3, the weight ratio A/B of wherein said polymer A and polymer B is in 5/1～1/5 scope.
11. the preparation method of each described paste compound in the claim 1～3, wherein said solvent S
AAnd solvent S
BBe selected from boiling point under water and the atmospheric pressure and be 80 ℃～350 ℃ non-water solvent.
12. the preparation method of each described paste compound in the claim 1～3, wherein said solvent S
AAnd solvent S
BHas identical composition.
13. the preparation method of each described paste compound in the claim 1～3, the solvent S of wherein said polymer B
BSolution also contains the conductivity imparting agent.
14. the preparation method of paste compound described in the claim 13, the wherein said solvent S that contains the polymer B of conductivity imparting agent
BSolution, weight % is mixing makes with solid constituent concentration 30～40.
15. the preparation method of paste compound described in the claim 13, wherein with respect to per 100 weight portion active materials, the amount of described conductivity imparting agent is 1～20 weight portion.
16. the preparation method of each described paste compound in the claim 1～3, the solvent S of wherein said polymer A
AWhen dispersion liquid and electrode active material are mixing, solvent S
AAmount be 80～120 weight % of electrode active material liquid absorption.
17. the slurry for secondary battery electrode composition, it is according to the preparation method of each described paste compound in the claim 1～3 preparation.
18. the manufacture method of electrode for secondary battery, it comprises coats on the collector body paste compound described in the claim 17 and drying.
19. the manufacture method of electrode for secondary battery described in the claim 18, wherein, forming the thickness that comes from this paste compound on collector body is the mixed layer of 0.005mm～5mm.
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|---|---|---|---|
| JP193952/2002 | 2002-07-02 | ||
| JP2002193952 | 2002-07-02 |
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|---|---|
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| CN1290211C true CN1290211C (en) | 2006-12-13 |
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|---|---|---|---|
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|---|---|
| JP (1) | JP4470735B2 (en) |
| KR (1) | KR101083129B1 (en) |
| CN (1) | CN1290211C (en) |
| WO (1) | WO2004006361A1 (en) |
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|---|---|---|---|---|
| CN102612774A (en) * | 2009-11-18 | 2012-07-25 | 丰田自动车株式会社 | Lithium secondary battery and process for producing same |
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| JP4765253B2 (en) * | 2003-02-20 | 2011-09-07 | 三菱化学株式会社 | Negative electrode active material for lithium secondary battery, lithium secondary battery negative electrode and lithium secondary battery |
| CN102203990B (en) * | 2009-12-25 | 2014-11-12 | 日本A&L株式会社 | Binder for secondary battery electrode |
| JP6933478B2 (en) | 2017-03-21 | 2021-09-08 | 株式会社クレハ | Gel electrolyte |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1154113A (en) * | 1997-08-07 | 1999-02-26 | Toray Ind Inc | Manufacture of mix for electrode of nonaqueous secondary battery |
| JP4138923B2 (en) * | 1997-12-01 | 2008-08-27 | Ｔｄｋ株式会社 | Electrode manufacturing method |
| JPH11213989A (en) * | 1998-01-20 | 1999-08-06 | Toyota Central Res & Dev Lab Inc | Manufacture of positive electrode material for lithium secondary battery |
| TW519777B (en) * | 1999-10-18 | 2003-02-01 | Zeon Corp | The binder composition for the secondary battery electrode of lithium ion and its utilization |
| JP2002141060A (en) * | 2000-11-02 | 2002-05-17 | Matsushita Electric Ind Co Ltd | Manufacturing method of negative electrode mixture and non-aqueous system secondary battery using the same |
| JP4178953B2 (en) | 2000-11-13 | 2008-11-12 | 日本ゼオン株式会社 | Secondary battery positive electrode slurry composition, secondary battery positive electrode and secondary battery |
-
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| CN102612774A (en) * | 2009-11-18 | 2012-07-25 | 丰田自动车株式会社 | Lithium secondary battery and process for producing same |
| CN102612774B (en) * | 2009-11-18 | 2015-07-01 | 丰田自动车株式会社 | Lithium secondary battery and process for producing same |
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| Publication number | Publication date |
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| WO2004006361A1 (en) | 2004-01-15 |
| CN1666360A (en) | 2005-09-07 |
| JPWO2004006361A1 (en) | 2005-12-15 |
| KR101083129B1 (en) | 2011-11-11 |
| JP4470735B2 (en) | 2010-06-02 |
| KR20050016713A (en) | 2005-02-21 |
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