CN104205444A - Positive electrode paste for cell - Google Patents

Positive electrode paste for cell Download PDF

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Publication number
CN104205444A
CN104205444A CN201380018597.6A CN201380018597A CN104205444A CN 104205444 A CN104205444 A CN 104205444A CN 201380018597 A CN201380018597 A CN 201380018597A CN 104205444 A CN104205444 A CN 104205444A
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CN
China
Prior art keywords
copolymer
positive electrode
paste
component units
battery paste
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Pending
Application number
CN201380018597.6A
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Chinese (zh)
Inventor
桑原一夫
稻家修一
伊藤裕一
辻田幸平
佐俣光彦
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kao Corp
GS Yuasa International Ltd
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Kao Corp
GS Yuasa International Ltd
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Application filed by Kao Corp, GS Yuasa International Ltd filed Critical Kao Corp
Priority to CN201810399579.1A priority Critical patent/CN108767258A/en
Publication of CN104205444A publication Critical patent/CN104205444A/en
Pending legal-status Critical Current

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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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

Provided is a positive electrode paste for a cell, in which the time taken to dry the positive electrode mixture can be shortened without reducing the adhesion performance of the positive electrode mixture or the coating performance. This invention includes a positive electrode active material, an electroconductive agent, a solvent, and a copolymer, and the copolymer includes two types of constituent units having specific structures.

Description

Positive electrode for battery paste
Technical field
The present invention relates to positive electrode for battery paste.
Background technology
The positive pole that nonaqueous electrolyte battery is used is, by making, positive active material, conductive agent and binding agent are scattered in to the anodal paste forming in solvent, and it is coated on the collector bodies such as aluminium foil continuously, its method of removing desolventizing by volatilizing in drying oven is manufactured.If accelerate the line speed of this pole plate painting process, the time of being detained in drying oven due to pole plate shortens, so produce dry not enough.
For fear of this point, consider to improve the temperature in drying oven, method that air quantity is accelerated rate of drying, but the problem that the adaptation of dry generation anode composite material layer sharply reduces or the imflammable gas concentration in drying oven becomes too high this class with an organic solvent time.
Or, can consider to guarantee the method for the residence time in drying oven by setting up and extending drying oven, but produce the such problem of equipment investment that needs great number.
As the method beyond above-mentioned, think and, reduce the content of solvent by the mass ratio (following, to be called paste solid constituent) occupying by improving solid matter in anodal paste, can shorten drying time.But, now, because the viscosity of paste improves, exist coatings such as producing the style of calligraphy characterized by hollow strokes to reduce such problem.
In patent documentation 1, disclose by making monomer be chemically bound in the surface of conductive agent, heated polymerizable thereafter, uses it for anodal paste, thereby can improve the dispersiveness of anodal paste, can reduce the technology of the viscosity of anodal paste.But, in order to make polymer chemistry be bonded in the surface of conductive agent, for being generally the poor conductive agent of micropowder and operability, need the technique of multistage chemical reaction etc., think that loaded down with trivial details and manufacturing cost raises.
In patent documentation 2, the dispersed technology that can improve the conductive agent in anodal paste by adding surfactant is disclosed.But, before input conductive agent, need to add dispersant and stir, thus, carry out repeatedly mixing operation, worry that production efficiency declines.
In patent documentation 3, there is following record: in order to improve the mobility of the anodal paste that contains in a large number the conductive agent that specific area is large, use the technology of dispersant.But, do not demonstrate clearly the comparing data of the reduced viscosity effect of bringing thus.In addition, dispersant is only a kind as used herein, is still not clear for whole dispersants, whether all to obtain reduced viscosity effect.
Patent documentation
Patent documentation 1: the JP 2002-100360 of Japan communique
Patent documentation 2: the JP 2002-151057 of Japan communique
Patent documentation 3: the JP 2005-197073 of Japan communique
Summary of the invention
The object of the present invention is to provide the high positive electrode for battery paste of solid constituent that can shorten the drying time of anode composite material under the prerequisite of adaptation of the anode composite material after the coating that does not damage anodal paste, coating.
The inventor etc. have carried out various research, found that while using the copolymer with ad hoc structure as dispersant, according to the difference of its structure, the reduced viscosity effect of anodal paste and be coated with anodal paste and the adaptation of anode composite material layer have bigger difference.
For formation of the present invention and action effect, combination technology thought describes.Wherein, for the mechanism of action, comprise and infer content, its correctness does not limit the present invention.Should illustrate, in the situation that not departing from spirit of the present invention or principal character, can implement the present invention with other variety of way.Therefore, execution mode described later or experimental example are only simply illustrating from all angles, can not be construed as limiting interpretation.In addition, belong to the scope of patent request equal scope modification or change all within the scope of the invention.
The first invention is a kind of positive electrode for battery paste, be the positive electrode for battery paste that contains positive active material, conductive agent, solvent and copolymer, above-mentioned copolymer is the copolymer of the Component units (b) that contains Component units (a) that following general formula (1) represents and following general formula (2) expression.
(in formula, R 1, R 2, R 3, R 5, R 6, R 7and R 9identical or different, represent hydrogen atom, methyl or ethyl, R 4represent the alkyl of carbon number 8～30, R 8represent the alkylidene of the straight or branched of carbon number 2～4, X 1, X 2represent oxygen atom or NH, p represents 1～50 number)
According to the present invention, can provide drying time and the high positive electrode for battery paste of solid constituent that the adaptation of the anode composite material after coating in the case of not damaging anodal paste and coating, can shorten anode composite material.
Brief description of the drawings
Fig. 1 is the chart that represents the addition of copolymer and the relation of paste viscosity.
Embodiment
The present invention is based on following opinion: by will contain positive active material, conductive agent, solvent and comprise Component units (a) that above-mentioned general formula (1) represents and the paste of the copolymer of the Component units (b) that above-mentioned general formula (2) represents for the manufacture of positive electrode for battery, thereby the coating in the case of not damaging anodal paste can be provided and be coated with after the adaptation of anode composite material can shorten drying time and the high positive electrode for battery paste of solid constituent of anode composite material.
The detailed mechanism that effect of the present invention presents is still not clear, and applicant infers as follows.Think if improve the solid constituent of anodal paste, the positive active material in paste, conductive agent particle coacervation and form three-dimensional network, thereby tackify.Think the contained copolymer of positive electrode for battery paste of the present invention by the Component units (b) that there is the Component units (a) of hydrophobic grouping and be adsorbed on securely the particle surface of positive active material in paste, conductive agent and there is polyoxy alkylidene to bringing powerful steric repulsion power between particle, produce thus the cohesion inhibition of the particle in paste and make the reduced viscosity of paste.
On the other hand, in order to make positive pole, anodal paste with must guarantee good adaptation as the aluminium foil of positive electrode collector etc., but conventionally act on the interface of positive electrode collector and anode composite material due to dispersant, thereby reduction adaptation.But, in the present invention, because utilizing Component units (a), copolymer is adsorbed on securely the positive active material in paste, the particle surface of conductive agent, control the dissolubility of copolymer in solvent, therefore suppress to there is dispersed copolymer and ooze out to positive electrode collector interface, make that adaptation is good and anode composite material peel strength is also good.But these are just inferred, the present invention is not limited to these mechanism.
Below, embodiments of the present invention are specifically described.
[copolymer]
The Component units (b) that the Component units (a) that copolymer used in the present invention contains above-mentioned general formula (1) expression and above-mentioned general formula (2) represent.
In above-mentioned general formula (1), consider R from the viewpoint of the reduced viscosity effect of anodal paste and viewpoint from the easiness of Component units (a) to copolymer that import 1and R 2be preferably hydrogen atom, R 3be preferably hydrogen atom or methyl, more preferably methyl.Consider R from the reduced viscosity effect of anodal paste and the viewpoint maintaining of anode composite material peel strength 4be preferably alkyl or alkenyl, from the same viewpoint, R 4carbon number be more than 8, be preferably more than 10, more preferably more than 12, in addition from the same viewpoint, be preferably below 26, more preferably, below 22, be further preferably below 20.Comprehensive these viewpoints, R 4carbon number be preferably 8～26, more preferably 10～22, more preferably 12～20.As R 4, particularly can enumerate octyl group, 2-ethylhexyl, decyl, dodecyl, myristyl, cetyl, octadecyl, oil base, docosyl etc.Consider X from the viewpoint of the easiness to copolymer importing Component units (a) 1be preferably oxygen atom.
When synthetic copolymer used in the present invention, (following as the monomer that gives above-mentioned Component units (a), also referred to as monomer (a)) concrete example, can enumerate the ester compounds such as (methyl) 2-EHA, (methyl) 2-ethyl hexyl acrylate, (methyl) dodecylacrylate, (methyl) acrylic acid stearyl, (methyl) acrylic acid isooctadecane base ester, (methyl) acrylic acid docosyl ester; The amide compounds such as 2-ethylhexyl (methyl) acrylamide, octyl group (methyl) acrylamide, dodecyl (methyl) acrylamide, octadecyl (methyl) acrylamide, docosyl (methyl) acrylamide.Wherein, consider preferably (methyl) dodecylacrylate, (methyl) acrylic acid stearyl and (methyl) acrylic acid docosyl ester from the reduced viscosity effect of anodal paste and viewpoint from the easiness of Component units (a) to copolymer that import.In these monomers, can use one kind or two or more.
Consider from the reduced viscosity effect of anodal paste and the viewpoint maintaining of anode composite material peel strength, more than the ratio that Component units (a) occupies in copolymer used in the present invention is preferably 5 quality %, more preferably more than 10 quality %, more preferably more than 15 quality %.In addition, from the same viewpoint, be preferably below 90 quality %, more preferably, below 85 quality %, more preferably, below 80 quality %, be further preferably below 72 quality %.Comprehensive these viewpoints, the ratio that Component units (a) occupies in copolymer used in the present invention is preferably 5～90 quality %, more preferably 10～85 quality %, more preferably 15～80 quality %, are further preferably 15～72 quality %.
In above-mentioned general formula (2), consider R from the viewpoint that improves the dispersed of positive active material anodal paste and conductive agent and import the easiness of Component units (b) to copolymer 5and R 6be preferably hydrogen atom, R 7and R 9be preferably hydrogen atom or methyl, more preferably methyl.From the same viewpoint, R 8be preferably ethylidene or propylidene, more preferably ethylidene.From the reduced viscosity effect of anodal paste and to copolymer import Component units (b) easiness viewpoint consider, p is preferably more than 1, more preferably more than 2, more preferably more than 3.In addition from the same viewpoint, be preferably below 50, more preferably below 35, more preferably below 20.Comprehensive above viewpoint, p is preferably 1～50, and more preferably 2～35, more preferably 3～20.Consider X from the viewpoint of the easiness to copolymer importing Component units (b) 2be preferably oxygen atom.
As Component units (b), can enumerate from having imported structure of nonionic group etc. after the structure of non-ionic monomer, polymerization.
When synthetic copolymer used in the present invention, (following as the monomer that gives above-mentioned Component units (b), also referred to as monomer (b)), can enumerate methoxy poly (ethylene glycol) (methyl) acrylate, single (methyl) acrylate of methoxyl group poly-(ethylene glycol/propylene glycol), single (methyl) acrylate of ethyoxyl poly-(ethylene glycol/propylene glycol), polyethyleneglycol (methyl) acrylate, polypropylene glycol list (methyl) acrylate, 2-methoxy ethyl (methyl) acrylamide, 2-ethoxyethyl group (methyl) acrylamide, 3-methoxy-propyl (methyl) acrylamide etc.
As Component units (b), consider from the dispersed viewpoint that improves positive active material anodal paste and conductive agent, be preferably the monomer that following general formula (3) represents.
(in formula, R 5, R 6, R 7and R 9identical or different, represent hydrogen atom, methyl or ethyl, R 8represent the alkylidene of the straight or branched of carbon number 2～4, X 2represent oxygen atom or NH, p represents 1～50 number)
In above-mentioned general formula (3), consider R from the viewpoint that improves the dispersed of positive active material anodal paste and conductive agent and import the easiness of Component units (b) to copolymer 5and R 6be preferably hydrogen atom, R 7and R 9be preferably hydrogen atom or methyl, more preferably methyl.From the same viewpoint, R 8be preferably ethylidene or propylidene, more preferably ethylidene.From the reduced viscosity effect of anodal paste and to copolymer import Component units (b) easiness viewpoint consider, p is preferably more than 1, more preferably more than 2, more preferably more than 3.In addition from the same viewpoint, be preferably below 50, more preferably below 35, more preferably below 20.Comprehensive above viewpoint, p is preferably 1～50, and more preferably 2～35, more preferably 3～20.Consider X from the viewpoint of the easiness to copolymer importing Component units (b) 2be preferably oxygen atom.
In these monomers, can use one kind or two or more.
Consider from the reduced viscosity effect of anodal paste and the viewpoint maintaining of anode composite material peel strength, more than the ratio that Component units (b) occupies in copolymer used in the present invention is preferably 10 quality %, more preferably more than 15 quality %, more preferably more than 20 quality %, more than being further preferably 23 quality %.In addition, from the same viewpoint, be preferably below 85 quality %, more preferably below 80 quality %, more preferably below 75 quality %.Comprehensive these viewpoints, the ratio that Component units (b) occupies in copolymer used in the present invention is preferably 10～85 quality %, more preferably 15～80 quality %, more preferably 20～75 quality %, are further preferably 23～75 quality %.
Consider from the reduced viscosity effect of anodal paste and the viewpoint maintaining of anode composite material peel strength, the contained Component units (a) of copolymer of the present invention is preferably more than 0.1 with the mass ratio (Component units (a)/Component units (b)) of Component units (b), more preferably more than 0.2.In addition, from the same viewpoint, be preferably below 10.0, more preferably, below 5.4, more preferably, below 4.0, be further preferably below 3.2.Comprehensive above viewpoint, the contained Component units (a) of copolymer of the present invention is preferably 0.1～10.0 with the mass ratio (Component units (a)/Component units (b)) of Component units (b), more preferably 0.2～5.33, more preferably 0.2～4.0, be further preferably 0.2～3.2.
Copolymer used in the present invention can have above-mentioned Component units (a) and above-mentioned Component units (b) Component units (c) in addition.When synthetic copolymer used in the present invention, the monomer that gives Component units (c) is (following, also referred to as monomer (c)) as long as can just be not particularly limited with monomer (a), monomer (b) copolymerization, can use one kind or two or more.
As monomer (c), can enumerate the acid monomers such as (methyl) acrylic acid; (methyl) esters of acrylic acids such as (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) butyl acrylate, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl) benzyl acrylate, (methyl) cyclohexyl acrylate, (methyl) isobornyl acrylate, (methyl) acrylic acid 2-hydroxy methacrylate, (methyl) acrylic acid dimethylamino ethyl ester; (methyl) acrylic amides such as (methyl) acrylamide, dimethyl (methyl) acrylamide, isopropyl (methyl) acrylamide, the tert-butyl group (methyl) acrylamide; The vinyl esters such as the phenylethylene such as styrene, p-methylstyrene, vinyl acetate; The vinylpyridine classes such as 2-vinylpyridine; The vinyl pyrrolidone classes such as vinyl pyrrolidone etc.
Consider from the reduced viscosity effect of anodal paste and the viewpoint maintaining of anode composite material peel strength, more than Component units (a) in copolymer of the present invention and the content of Component units (b) amount to and are preferably 40 quality %, more preferably more than 60 quality %, more preferably more than 80 quality %, more preferably more than 90 quality %, more than being further preferably 95 quality %.
Consider from the reduced viscosity effect of anodal paste and the viewpoint maintaining of anode composite material peel strength, the ratio that Component units (c) occupies in copolymer used in the present invention is preferably 0～60 quality %, more preferably 0～40 quality %, more preferably 0～30 quality %, further be preferably 0～20 quality %, further be preferably 0～10 quality %, be further preferably 0～5 quality %.Be below 60 quality % by making the ratio of Component units (c), can guarantee Component units (a) and the content of Component units (b) in paste, make the reduced viscosity effect of anodal paste higher.
Consider from the viewpoint of the reduced viscosity effect of anodal paste, more than the content of the above-mentioned copolymer in positive electrode for battery paste of the present invention is preferably 0.02 quality %, more preferably more than 0.05 quality %, more preferably more than 0.1 quality %, more than being further preferably 0.2 quality %.In addition, consider from the viewpoint that maintains battery output, be preferably below 1 quality %, more preferably, below 0.8 quality %, more preferably, below 0.6 quality %, be further preferably below 0.5 quality %.Comprehensive above viewpoint, the content of the above-mentioned copolymer in positive electrode for battery paste of the present invention is preferably 0.02～1 quality %, more preferably 0.05～0.8 quality %, more preferably 0.1～0.6 quality %, is further preferably 0.2～0.5 quality %.
Consider from the viewpoint of the reduced viscosity effect of anodal paste, the content of the above-mentioned copolymer in positive electrode for battery paste of the present invention is with respect to above-mentioned conductive agent 100 mass parts, more than being preferably 0.5 mass parts, more preferably more than 1.5 mass parts, more preferably more than 3 mass parts, more than being further preferably 6 mass parts.In addition, consider from the viewpoint that maintains battery output, with respect to above-mentioned conductive agent 100 mass parts, be preferably below 35 mass parts, more preferably, below 30 mass parts, more preferably, below 25 mass parts, be further preferably below 20 mass parts.Comprehensive above viewpoint, the content of the above-mentioned copolymer in positive electrode for battery paste of the present invention is preferably 0.5～35 mass parts, more preferably 1.5～30 mass parts, more preferably 3～25 mass parts, are further preferably 6～20 mass parts.
Consider from the viewpoint of the reduced viscosity effect of anodal paste, in positive electrode for battery paste of the present invention, more than being preferably 0.5 mass parts with respect to the content total of the contained Component units (a) of the above-mentioned copolymer of above-mentioned conductive agent 100 mass parts and Component units (b), more preferably more than 1 mass parts, more preferably more than 2 mass parts, more than being further preferably 5 mass parts.In addition, consider from the viewpoint that maintains battery output, be preferably below 30 mass parts, more preferably, below 25 mass parts, more preferably, below 20 mass parts, be further preferably below 15 mass parts.Comprehensive above viewpoint, in positive electrode for battery paste of the present invention, amount to and be preferably 0.5～30 mass parts with respect to the content of the contained Component units (a) of the above-mentioned copolymer of above-mentioned conductive agent 100 mass parts and Component units (b), more preferably 1～25 mass parts, more preferably 2～20 mass parts, are further preferably 5～15 mass parts.
The synthetic method of copolymer of the present invention is not particularly limited, and uses the polymerization method used of common (methyl) esters of acrylic acid.For example, there is radical polymerization, living radical polymerization, anionic polymerization, active anionic polymerization method.For example, use when radical polymerization, the known methods such as the monomer component polymerization that can make to contain monomer (a) and monomer (b) with solution polymerization process obtain.
The solvent using as polymerisation in solution, for example, can use the organic solvents such as hydrocarbon (hexane, heptane), fragrant family hydrocarbon (toluene, dimethylbenzene etc.), lower alcohol (ethanol, isopropyl alcohol etc.), ketone (acetone, methylethylketone), ether (oxolane, diethylene glycol dimethyl ether), 1-METHYLPYRROLIDONE.Quantity of solvent, in the mass ratio with respect to monomer total amount, is preferably 0.5～10 times of amount.
As polymerization initiator, can use known radical polymerization initiator, for example can enumerate azo is polymerization initiator, hydroperoxide kind, dialkyl class, peroxidating diacyl class, ketone peroxide class etc.Polymerization initiator amount, with respect to monomer component total amount, is preferably 0.01～5 % by mole, more preferably 0.01～3 % by mole, is particularly preferably 0.01～1 % by mole.Polymerization reaction preferably flows down at nitrogen, carries out with the temperature ranges of 60～180 DEG C, and the reaction time is preferably 0.5～20 hour.
In addition, can use the known chain-transferring agent for Molecular regulator amount.For example, can enumerate the sulfhydryl compound such as isopropyl alcohol, mercaptoethanol.
In copolymer of the present invention, the sequence of Component units (a), Component units (b) can be any in random, block or grafting.In addition, can contain these Component units Component units in addition.
Consider from the viewpoint that maintains of anode composite material peel strength, the weight average molecular weight of copolymer is preferably more than 9000, more preferably more than 1.5 ten thousand, more preferably more than 30,000, is further preferably more than 50,000.In addition, consider from the viewpoint of the reduced viscosity effect of anodal paste, be preferably below 1,000,000, more preferably, below 800,000, more preferably, below 600,000, be further preferably below 500,000.Comprehensive above viewpoint, the weight average molecular weight of copolymer is preferably 9000～1,000,000, and more preferably 1.5 ten thousand～800,000, more preferably 30,000～600,000, be further preferably 4.5 ten thousand～500,000.Should illustrate, weight average molecular weight is the value of utilizing GPC (gel permeation chromatography) to measure, and the details of condition determination as shown in the Examples.
In anodal paste of the present invention, can contain above-mentioned copolymer dispersant in addition.In anodal paste of the present invention, with respect to the total of the dispersant beyond above-mentioned copolymer and above-mentioned copolymer, more than the content of above-mentioned copolymer is preferably 40 quality %, more preferably more than 60 quality %, more preferably more than 80 quality %, more preferably 100 quality %.
[positive active material]
As positive active material, as long as inorganic compound is just not particularly limited, for example, can use compound, the lithium-transition metal composite oxide with olivine structural.As the compound with olivine structural, can illustrate general formula Li xm1 spO 4the compound that (wherein, M1 is 3d transition metal, 0≤x≤2,0.8≤s≤1.2) represents.Having the compound of olivine structural can coating amorphous carbon etc. use.As lithium-transition metal composite oxide, can enumerate have spinel structure lithium manganese oxide, there is the general formula Li of layer structure xmO 2-δthe lithium-transition metal composite oxide that (wherein, M is transition metal, 0.4≤x≤1.2,0≤δ≤0.5) represents etc.As above-mentioned transition metal M, can comprise Co, Ni or Mn.Above-mentioned lithium-transition metal composite oxide can further contain one or two or more kinds the element being selected from Al, Mn, Fe, Ni, Co, Cr, Ti, Zn, P, B.
[conductive agent]
As conductive agent, preferably use carbon series conductive agent.As carbon series conductive agent, can use the carbon blacks such as acetylene black, furnace black, Ketjen black, graphite etc.Also can use the carbon system electric conductive polymers in addition such as polyaniline etc.
[binding agent]
As binding agent, can be used alone or as a mixture Kynoar (PVDF), vinylidene fluoride-hexafluoropropylene copolymer, styrene butadiene rubbers, polyacrylonitrile etc.
[anodal paste]
Anodal paste is by by above-mentioned copolymer, positive active material, conductive agent, binding agent, make for mixing, the stirring such as solvent that regulate solid constituent etc.Also can add other dispersant, functional material etc.As above-mentioned solvent, can use non-water solvent or the water etc. such as METHYLPYRROLIDONE (NMP), dimethyl formamide (DMF), dimethyl sulfoxide (DMSO) (DMSO).In addition, in anodal paste of the present invention, preferably use non-water solvent, wherein, more preferably use NMP.
Mixing, stirring can be used planetary mixer, ball mill, jet pulverizer etc.In addition, also can be used together them.
While dropping into material, can drop into by limit Stirring blade edge.Thus, can suppress the mechanical load of agitating device, suppress the volume of the material in stirred vessel, carry out the premixed of each material.In addition, also can not drop into whole amounts and divide several times and drop into.Thus, can suppress the mechanical load of agitating device.
Copolymer of the present invention can be used as solid matter and uses, and also can be dissolved in advance non-water solvent or water equal solvent uses.According to patent documentation 2, for fear of being the cohesion that the fibrillatable between binding agent causes by fluorine, dispersant must add before dropping into binding agent, but for copolymer of the present invention, due to anodal paste in solvent and the compatibility of Binder Composition high, so can drop in any stage of mixing operation, the front and back that also can drop at copolymer are carried out repeatedly mixing.For example, by the early stage input copolymer in mixing operation, can reduce the viscosity of paste, reduce the mechanical load of kneading device and required energy, and can improve the solid constituent of paste, so preferably.If dropped into copolymer before the later stage of mixing operation or the paste that is near completion, till in the mixing operation of mixed copolymer, very highland keeps paste viscosity, by paste being applied to strong shear stress, the dispersity raising of paste, so preferably.Like this, copolymer of the present invention, in order to obtain target paste, can drop in any stage of mixing operation.In addition, if only mixed with the powder such as positive active material, conductive agent composition simultaneously, may be agglomerating, therefore each material can drop in the stage that becomes paste-like.For example, before putting into pulverous material, together drop into binding agent or solvent, or can after part or all of binding agent or solvent and dusty material mixed, drop into.Or, also can be pre-mixed in the solution of binding agent.
[positive pole]
Positive pole is made by above-mentioned anodal paste is applied on the collector bodies such as aluminium foil and is dried.In order to improve anodal density, also can utilize press to carry out densification.
The coating of anodal paste can be used die head, comma scraper reverse roll, direct-coupled roll (direct roll), gravity-roller etc.Dry heating, ventilation, infrared radiation etc. can being carried out alone or in combination after coating.
Anodal compacting can utilize roll squeezer etc. to carry out.
Embodiment
Below, embodiments of the invention and comparative example are shown, but the invention is not restricted to this.
The copolymer using in following examples and comparative example and the details of homopolymers are as shown in table 1～6.At this, writing a Chinese character in simplified form of the raw material using in table 1～6 and following examples is as follows.
LMA: lauryl methacrylate (aerochemistry company of Mitsubishi system, numbering: GE-410) (R 4: C 12h 25)
SMA: methacrylic acid stearyl (chemical industrial company of Xin Zhong village system, numbering: NK-ESTER S) (R 4: C 18h 37)
BHMA: methacrylic acid docosyl ester (chemical industrial company of Xin Zhong village system, numbering: NK-ESTER BH) (R 4: C 22h 45)
PEG (2) MA: methoxy polyethylene glycol methacrylate-styrene polymer (chemical industrial company of Xin Zhong village system, numbering: NK-ESTER M-20G, the average addition molal quantity p:2 of oxirane)
PEG (9) MA: methoxy polyethylene glycol methacrylate-styrene polymer (chemical industrial company of Xin Zhong village system, numbering: NK-ESTER M-90G, the average addition molal quantity p:9 of oxirane)
PEG (23) MA: methoxy polyethylene glycol methacrylate-styrene polymer (chemical industrial company of Xin Zhong village system, numbering: NK-ESTER TM-230G, the average addition molal quantity p:23 of oxirane)
MAA: methacrylic acid (with Guang Chun medicine industrial group system)
MPD:3-sulfydryl-1,2-PD (with Guang Chun medicine industrial group system)
N-DM: lauryl mercaptan (Tokyo changes into industrial group's system)
NMP:N-N-methyl-2-2-pyrrolidone N-(with Guang Chun medicine industrial group system)
Hexane: n-hexane (with Guang Chun medicine industrial group system)
V-65B:2, two (2,4-methyl pentane nitrile) (with Guang Chun medicine industrial group system) of 2 '-azo
Table 1
[table 1]
Table 2
[table 2]
Table 3
[table 3]
Table 4
[table 4]
Table 5
[table 5]
Table 6
[table 6]
[synthesis example 1 of copolymer]
As " initial input monomer liquid ", the mixed solution that preparation is made up of the SMA of 3g, the PEG of 14g (23) MA, the MAA of 3g and the NMP of 17g.As " dropping monomer liquid ", the mixed solution that preparation is made up of the SMA of 27g, the PEG of 126g (23) MA, the MAA of 27g and the NMP mixed liquor of 153g.As " initator liquid ", the mixed solution that preparation is made up of the V-65B of 0.6g and the NMP of 3g.As " drip and use initator liquid ", the mixed solution that preparation is made up of the V-65B of 5.4g and the NMP of 27g.
To middle all above-mentioned " the initial input monomer liquid " of amount that drop into of the detachable flask (reactive tank) that return duct, agitating device, thermometer and nitrogen ingress pipe are installed, to carrying out nitrogen displacement in reactive tank, temperature in groove (dropping into the temperature of raw material) is heated to 65 DEG C.After in groove, temperature arrives 65 DEG C, in the tank diameter of limit, all above-mentioned " initator liquid " of amount is added in limit in groove.Next, with 3 hours, above-mentioned " dropping monomer liquid " and above-mentioned " drip and use initator liquid " is added drop-wise in groove simultaneously.After dropping finishes, and then, stir 1 hour at 65 DEG C.Next, limit continues to stir, and limit was warming up to 75 DEG C with approximately 30 minutes by temperature in groove, after intensification, to stirring in groove 2 hours again.Then, with water-bath, temperature in groove is cooled to below 40 DEG C.In order to regulate concentration, in groove, add NMP and mix, obtain the nmp solution of copolymer A.The nonvolatile component of copolymer A solution is 40 quality %, and the weight average molecular weight of copolymer A is 55000.
[synthesis example 2 of copolymer]
The composition of " initial input monomer liquid ", " dropping monomer liquid ", " initator liquid " and " dripping initator liquid " is changed according to the record of table 1 respectively, in addition, utilize the method same with the synthesis example 1 of above-mentioned copolymer, synthetic copolymer B～AE.The synthetic middle initially whole monomers of input and all polymerization in the lump of initator of adopting of copolymer H, J, K and AE should be described.
[synthesis example of homopolymers]
To the middle mixed solution being formed by the SMA of 200g and the hexane of 180g (initial input monomer liquid) that drops into full dose of the detachable flask (reactive tank) that return duct, agitating device, thermometer and nitrogen ingress pipe are installed, to carrying out nitrogen displacement in reactive tank, temperature in groove (dropping into the temperature of raw material) is heated to 65 DEG C.After in groove, temperature arrives 65 DEG C, in the tank diameter of limit, the mixed solution (initator liquid) being made up of the V-65B of 2.2g and the hexane of 20g is added on limit.And then, stir after 5 hours in to groove at 65 DEG C, temperature in groove is cooled to below 40 DEG C with water-bath.By the hexane solution of the homopolymers Q with respect to obtained, volume ratio is that the ethanol (with the pure pharmaceutical worker of light industry system) of 10 times of amounts joins in beaker, and stir in beaker on limit, and limit is added drop-wise to the solution of the homopolymers Q obtaining in beaker.The solid that isolated by filtration is separated out, with vacuum drying apparatus under 10kPa, the condition of 80 DEG C dry 12 hours, obtains homopolymers Q.The weight average molecular weight of homopolymers Q is 69000.To the NMP that adds 90g in the homopolymers Q of the 10g obtaining, stir 30 minutes at 80 DEG C, but do not dissolve, so cannot use homopolymers Q to make anodal paste.
[mensuration of nonvolatile component]
The nonvolatile component of copolymer solution is measured as follows.In culture dish, put into drying anhydrous sodium sulfate 10g and glass bar, measure its overall quality, be designated as W 3(g).And then, in this culture dish, add the nmp solution 2g of the copolymer obtaining in the synthesis example 1 and 2 of above-mentioned copolymer as sample, measure its overall quality, be designated as W 1(g).In culture dish with above-mentioned glass bar combination drying anhydrous sodium sulfate and sample, in culture dish, put under the state of the drying anhydrous sodium sulfate, sample and the glass bar that mix with glass bar, with the pressure Reduction Dryers of 140 DEG C (nitrogen flows down, pressure 40kPa) by culture dish volume drying 12 hours.The quality of measuring dried culture dish entirety, is designated as W 2(g).Using the value being obtained by following formula as nonvolatile component.
Nonvolatile component (quality %)=100-(W 1-W 2)/(W 1-W 3) × 100
[mensuration of the weight average molecular weight of copolymer and homopolymers]
The weight average molecular weight of copolymer utilizes GPC method to measure.Detailed conditions is as follows.
Determinator: HLC-8320GPC (TOSOH company system)
Post: α-M+ α-M (TOSOH company system)
Column temperature: 40 DEG C
Detector: differential refraction rate
The H of eluent: 60mmol/L 3pO 4dMF (DMF) solution with the LiBr of 50mmol/L
Flow velocity: 1mL/min
The standard specimen that calibration curve uses: the monodisperse polystyrene 5.26 × 10 that TOSOH company manufactures 2, 1.02 × 10 5, 8.42 × 10 6; The monodisperse polystyrene 4.0 × 10 that Xi Wei industrial group manufactures 3, 3.0 × 10 4, 9.0 × 10 5(numeral is respectively molecular weight)
Sample solution: the DMF solution of the solid constituent of the copolymer that contains 0.5wt%
The injection rate of sample solution: 100 μ L
Wherein, about copolymer O, P, AB, AC, AD, AE and homopolymers Q, owing to being not dissolved in DMF, so adopt following condition.
Determinator: HLC-8220GPC (TOSOH company system)
Post: GMHXL+GMHXL (TOSOH company system)
Column temperature: 40 DEG C
Detector: differential refraction rate
The LCH of eluent: 50mmol 3oxolane (THF) solution of COOH
Flow velocity: 1mL/min
The standard specimen that calibration curve uses: the monodisperse polystyrene 5.26 × 10 that TOSOH company manufactures 2, 1.02 × 10 5, 8.42 × 10 6; The monodisperse polystyrene 4.0 × 10 that Xi Wei industrial group manufactures 3, 3.0 × 10 4, 9.0 × 10 5(numeral is respectively molecular weight)
Sample solution: the THF solution of the copolymer that contains 0.2wt% or the solid constituent of homopolymers
The injection rate of sample solution: 100 μ L
[anodal paste and anodal making and evaluation]
Writing a Chinese character in simplified form of the material using in the anodal paste of following examples and comparative example is as follows.
LiMO 2: lithium-transition metal composite oxide, composition: LiNi 1/3mn 1/3co 1/3o 2(D50:6.5 μ m, BET specific area: 0.7m 2/ g)
LiMn 2o 4: lithium manganese oxide, composition: LiMn 2o 4(D50:18 μ m, BET specific area: 0.2m 2/ g)
LiFePO 4: LiFePO4, composition: LiFePO 4(D50:10 μ m, BET specific area: 10.5m 2/ g)
Powder: acetylene black (Denki Kagaku Kogyo kabushiki's system, name of product: DenkaBlack powder)
FX35: acetylene black (Denki Kagaku Kogyo kabushiki's system, name of product: DenkaBlack FX-35)
HS100: acetylene black (Denki Kagaku Kogyo kabushiki's system, name of product: DenkaBlack HS-100)
[making of anodal paste]
Use copolymer, positive active material and the conductive agent shown in table 2～5 and as the Kynoar (PVDF) of binding agent with make anodal paste as the NMP of non-water solvent.At this, in table 7～9 and 11, as above-mentioned PVDF, use the 12%NMP solution of KUREHA company system #1100 early, in table 10, as above-mentioned PVDF, use the 8%NMP solution of the Kynar HSV900 processed of Arkema company.Should illustrate, the mass ratio of positive active material, binding agent and conductive agent is 90:5:5 (solid constituent conversion).Anodal paste is that the amount by regulating above-mentioned non-water solvent regulates solid constituent (quality %), and through having adopted the mixing operation of Multi-Blender Mill to make.At this, the solid constituent of anodal paste (quality %) is the quality % of the solid constituent of the material that forms of copolymer, positive active material, conductive agent and the binding agent contained by anodal paste.
[mensuration of the viscosity of anodal paste]
The viscosity of anodal paste is used rheometer measurement.The determinator of flow graph uses the Reo Stress 6000 of HAAKE company system, and the rotor of measuring use uses the Parallel Plate that diameter is 35mm.Making to measure temperature is 25 DEG C, is implemented as follows step: will be from shear rate 0.0001s -1to 1000s -1wang road and from shear rate 1000s -1to 0.0001s -1fan road is each continuously measures 200 seconds.As the typical value of viscosity, Jiang Wang road is at shear rate 10s -1time value as paste viscosity.
By except not adding copolymer of the present invention as the viscosity of the anodal paste of the comparative example of same composition is made as " paste viscosity R " to each embodiment, calculate the viscosity rate of descent bringing by adding copolymer with following formula, relatively its effect.
Viscosity rate of descent (%)={ ([paste viscosity R]-[paste viscosity])/(paste viscosity R) } × 100
Viscosity and viscosity rate of descent be the results are shown in to table 7～10.
Table 7
Table 8
Table 9
Table 10
[the coating test of anodal paste]
This test is as follows: taking the quality of dried anode composite material as 17mg/cm 2mode suitably adjust the gap of scraper, be coated with anodal paste at the one side of the aluminium foil of thickness 20 μ m.
Its result, the coating that exposes (style of calligraphy characterized by hollow strokes) poor for the stretching, extension of anodal paste, see aluminium foil on the coated face except end, is evaluated as " having " coating bad.Coating test be the results are shown in to table 7～10.
[mensuration of the dry required time of anodal paste]
For several embodiment in the positive pole after above-mentioned coating and the positive pole of comparative example, measure quality before dry and quality at regular intervals after the hot plate mounting of 60 DEG C.Moment that can't see mass change is considered as to dry end, as dry required time.The measurement result of dry required time is shown in to table 11.
Table 11
[table 11]
[mensuration of anodal peel strength]
Use the above-mentioned complete positive pole of shearing, in the surface of anode composite material layer laminating repair sheets bands (Mending tape) (Scotch company system, numbering: MP-18S), become the mode of 180 ° with the speed tractive of about 2.3cm/s with anodal angle with the face of this adhesive tape, use pull and push dynamometer (IMADA company system, DIGITAL FORCE GAUGE DPS-2) to measure stress now.Remove and peel off beginning and peel off the unsettled part of value of end, calculate the mean value of measured value, as peel strength.The measurement result of peel strength is shown in to table 7～10.
[result of the test and investigation]
[paste solid constituent, rate of drying and dry required time]
From embodiment 4 and comparative example 1,2, no matter have or not copolymer, the dry required time after the coating of the anodal paste that solid constituent is high is all short.
Hence one can see that, by reducing the containing ratio of the NMP in paste, that is, improves the solid constituent of anodal paste, can shorten dry required time.
[paste solid constituent and paste viscosity]
Comparative example 1,2 is compared known, if improve paste solid constituent, while coating, produce the style of calligraphy characterized by hollow strokes.If this anodal style of calligraphy characterized by hollow strokes is high and cause by paste illiquidity, viscosity,, can illustrate.
The anodal paste paste solid constituent same with comparative example 2 of embodiment 4 is high, but by adding copolymer A, can by paste reduced viscosity to comparative example 1 equal extent, in addition, hence one can see that, the style of calligraphy characterized by hollow strokes can eliminate anodal coating time.
[confirmation of paste reduced viscosity effect]
From embodiment 4 and 7～10 and comparative example 2～6 corresponding to difference, even if in the situation that using various positive active materials, conductive agent, also can confirm the paste reduced viscosity effect of being brought by copolymer A.The absolute value of paste viscosity changes because of kind or the paste solid constituent of positive electrode, therefore in order to confirm the additive effect of copolymer A, and appropriate the is absolute value of viscosity relatively not, and viscosity rate of descent relatively.Result by viscosity rate of descent can be confirmed, all sees by copolymer A and adds the paste reduced viscosity effect of bringing arbitrarily in paste.
[addition of copolymer]
Fig. 1 be for embodiment 1～6 and comparative example 2 anodal paste viscosity is marked and drawed and figure.As shown in Figure 1, the addition of copolymer is more, and paste viscosity is lower.But the addition of copolymer is many again, be also difficult to obtain the reduced viscosity effect corresponding with addition, therefore the addition of copolymer is preferably 1～16% in the mass ratio of conductive agent.
[mass ratio of Component units (a) and Component units (b)]
From embodiment 35～37 and reference example 3, when the mass ratio (a) of Component units (a) and Component units (b)/(b) be large value, there is the copolymer that is difficult to obtain paste minimizing effect.This is presumably because following reason: because the ratio of Component units in copolymer (b) is very few, the cohesion inhibition of the particle in the paste due to the interparticle strong steric repulsion power of therefore being brought by Component units (b) diminishes.The mass ratio (a) of Component units (a) and Component units (b) thus/(b) had better not be excessive.
Should illustrate, even if be difficult to obtain the copolymer of paste minimizing effect, by increasing the content of the copolymer in paste, also can play paste and reduce effect.
[kind of binding agent]
Embodiment shown in table 4 and comparative example be by the binding agent in paste change to HMW type more PVDF and result.By making binding agent realize HMW, can improve anode composite material peel strength, so preferably.Particularly, in the case of with bulky positive active material, by micronized positive active material, the positive active material etc. that is coated with carbon make anodal preferably.
As shown in Table 4, even if change the kind of binding agent, also can see by copolymer and add the paste reduced viscosity effect of bringing.
In addition, the comparison by embodiment 3 and embodiment 50 and embodiment 24 are more known with embodiment's 51, and as the binding agent in paste, low-molecular-weight type can obtain more excellent paste reduced viscosity effect.Thus, in the scope not having problems in anode composite material peel strength, the binding agent in paste is preferably low-molecular-weight type.
In addition, from comparative example 7,8, there is the copolymer that can not get paste reduced viscosity effect.
From these, in order to ensure the peel strength of paste reduced viscosity effect and anode composite material, the structure of copolymer is extremely important.Its details is considered as follows.
With regard to comparative example 7,8, think owing to being not containing the copolymer of Component units (a), so insufficient to the suction-operated of positive active material or conductive agent.In addition, meanwhile, think that the copolymer of absorption is not adsorbed in PVDF etc., the adaptation of anode composite material and aluminium foil reduces.
In addition, though be not shown on this, even if the inventor etc. have confirmed to add in a large number the copolymer using in comparative example 7,8, do not find paste reduced viscosity effect yet.
As mentioned above, according to the present invention, can provide drying time and the high positive electrode for battery paste of solid constituent that the adaptation of the anode composite material after coating in the case of not damaging anodal paste, coating, can shorten anode composite material.
Although describe the present invention in detail with reference to specific mode, it is evident that to those skilled in the art without departing from the spirit and scope of the present invention and can make various changes and modifications.
Should illustrate, the Japanese patent application (Japanese Patent Application 2012-085003) of the application based on application on April 3rd, 2012, mode is by reference quoted its entirety.Whole references of quoting at this in addition, are taken in overall mode.

Claims (17)

1. a positive electrode for battery paste, contain positive active material, conductive agent, solvent and copolymer, described copolymer is the copolymer of the Component units (b) that contains Component units (a) that following general formula (1) represents and following general formula (2) expression
In formula, R 1, R 2, R 3, R 5, R 6, R 7and R 9identical or different, represent hydrogen atom, methyl or ethyl, R 4represent the alkyl of carbon number 8～30, R 8represent the alkylidene of the straight or branched of carbon number 2～4, X 1, X 2represent oxygen atom or NH, p represents 1～50 number.
2. positive electrode for battery paste according to claim 1, wherein, the weight average molecular weight of described copolymer is 9000～1,000,000.
3. positive electrode for battery paste according to claim 1 and 2, wherein, in described copolymer, the mass ratio of Component units (a) and Component units (b),, Component units (a)/Component units (b) is 0.1～10.0.
4. according to the positive electrode for battery paste described in any one in claim 1～3, wherein, more than the Component units (a) in described copolymer and the content of Component units (b) add up to 40 quality %.
5. according to the positive electrode for battery paste described in any one in claim 1～4, wherein, the content of described copolymer is 0.5～30 mass parts with respect to described conductive agent 100 mass parts.
6. according to the positive electrode for battery paste described in any one in claim 1～5, wherein, the content of the Component units (a) in described copolymer is 5 quality %～90 quality %.
7. according to the positive electrode for battery paste described in any one in claim 1～6, wherein, the content of the Component units (b) in described copolymer is 10 quality %～85 quality %.
8. according to the positive electrode for battery paste described in any one in claim 1～7, wherein, the R of described general formula (1) 4carbon number be 8～26.
9. according to the positive electrode for battery paste described in any one in claim 1～8, wherein, the p of described general formula (2) is 1～35.
10. according to the positive electrode for battery paste described in any one in claim 1～9, wherein, the X of described general formula (1) 1for oxygen atom.
11. according to the positive electrode for battery paste described in any one in claim 1～10, wherein, and the R of described general formula (1) 3for hydrogen atom or methyl.
12. according to the positive electrode for battery paste described in any one in claim 1～11, wherein, and the R of described general formula (1) 1and R 2for hydrogen atom.
13. according to the positive electrode for battery paste described in any one in claim 1～12, wherein, and the X of described general formula (2) 2for oxygen atom.
14. according to the positive electrode for battery paste described in any one in claim 1～13, wherein, and the R of described general formula (2) 7for hydrogen atom or methyl.
15. according to the positive electrode for battery paste described in any one in claim 1～14, wherein, and the R of described general formula (2) 5and R 6for hydrogen atom.
16. according to the positive electrode for battery paste described in any one in claim 1～15, wherein, and the R of described general formula (2) 8for ethylidene or propylidene.
17. according to the positive electrode for battery paste described in any one in claim 1～16, and wherein, the viscosity rate of descent of described positive electrode for battery paste is greater than 0.
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