CN107732154A - Small lithium ion battery of loss of capacitance and preparation method thereof after a kind of circulation electric discharge - Google Patents

Small lithium ion battery of loss of capacitance and preparation method thereof after a kind of circulation electric discharge Download PDF

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Publication number
CN107732154A
CN107732154A CN201711105817.5A CN201711105817A CN107732154A CN 107732154 A CN107732154 A CN 107732154A CN 201711105817 A CN201711105817 A CN 201711105817A CN 107732154 A CN107732154 A CN 107732154A
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China
Prior art keywords
lithium ion
ion battery
capacitance
electric discharge
loss
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CN201711105817.5A
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Chinese (zh)
Inventor
周寿斌
汪的华
彭创
毛旭辉
刘畅
王雅琼
肖巍
钱帮芬
姜庆海
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JIANGSU HUAFU STORAGE NEW TECHNOLOGY Co Ltd
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JIANGSU HUAFU STORAGE NEW TECHNOLOGY Co Ltd
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Priority to CN201711105817.5A priority Critical patent/CN107732154A/en
Publication of CN107732154A publication Critical patent/CN107732154A/en
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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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/137—Electrodes based on electro-active polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1399—Processes of manufacture of electrodes based on electro-active polymers
    • 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)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The present invention relates to small lithium ion battery of loss of capacitance after a kind of circulation electric discharge and preparation method thereof, belong to technical field of lithium ion.The lithium ion battery negative material of the present invention is prepared after removing wherein solvent by cathode size, and cathode size is made up of following component by weight：0.5~1 part of 0.5~1 part of 0.1~0.5 part of particle, coalescents, the surfactant of 100~160 parts of waterborne acrylic ester-polyurethane resin emulsion, containing metal oxide.The negative material of lithium ion battery can be prepared using cathode size provided by the invention, the lithium ion battery being prepared using this negative material has the advantages of loss of capacitance is small after circulation electric discharge.

Description

Small lithium ion battery of loss of capacitance and preparation method thereof after a kind of circulation electric discharge
Technical field
Circulate small lithium ion battery of loss of capacitance and preparation method thereof after electric discharge the present invention relates to a kind of, belong to lithium from Sub- cell art.
Background technology
Lithium ion battery refers to that reversibly insertion and the compound of the lithium ion of deintercalation are used as both positive and negative polarity by the use of two respectively The secondary cell of composition.When being charged to battery, there is lithium ion abjection on the positive pole of battery, the lithium ion of generation is by electricity Liquid movement is solved to negative pole.When discharging battery (i.e. we use the process of battery), lithium in negative pole carbon-coating from Son abjection, is returned to positive pole.In the charge and discharge process of battery, lithium ion is in the motion shape from positive pole → negative pole → positive pole State --- rocking chair type battery.
Lithium ion battery advantage：Voltage is high, bigger than energy, has extended cycle life, has a safety feature, nuisanceless, memoryless effect Should, self discharge is small, some systems can fast charging and discharging, operating temperature range is wide.Shortcoming：Battery cost is higher, and some materials are not Energy heavy-current discharge is, it is necessary to protection circuit control (overcharging protection, Cross prevention).
The composition and preparation method of cathode size, significantly affect the cycle life of lithium ion battery, and particularly high magnification follows The ring life-span, or even as its restraining factors.The preparation of traditional cathode size is typically from single graphite as negative electrode active material. When preparing slurry, usually binding agent, conductive agent and negative pole graphite are sequentially added into solvent and stirred, or negative pole graphite is divided Add several times, cathode size is obtained after stirring.This negative pole selection and preparation method can not meet under lithium ion battery high magnification The demand of circulation.
CN104577042A discloses a kind of extended-life lithium ion battery cathode size and preparation method.The present invention is using following Technical scheme：Lithium ion battery cathode slurry, the slurry are the mixture of negative pole dry powder and solvent, and negative pole dry powder is lived by negative pole Property material, oxalic acid, binding agent and conductive agent composition, each component mass percent is：Negative electrode active material 88-94%, oxalic acid 0.1-0.3%, binding agent 3-6%, conductive agent 3-6%.CN104300118A discloses a kind of lithium ion battery cathode slurry Preparation method, comprise the following steps：1) take sodium carboxymethylcellulose to add in deionized water, carry out vacuumizing place after being dispersed with stirring Reason, obtains glue A and glue liquid B；2) active material, conductive agent is taken to be mixed and stirred for obtaining powder mixture；3) prepared by slurry：Take one Divide powder mixture to be added in glue A, after being dispersed with stirring, add remaining powder mixture and glue liquid B, after being dispersed with stirring, Adhesive and solvent are added, is dispersed with stirring, filters, produce.CN105206819A provides a kind of lithium ion battery cathode slurry And the preparation method of cathode size and the preparation method of cathode pole piece.Lithium ion battery cathode slurry includes by weight：It is negative Pole active material：85-92.5 parts；Conductive agent：3.5-6 part；Binding agent：4-9 parts；Solvent：172-295 parts；Negative electrode active material It is made up of lithium-titanium composite oxide and acid compound additive, by weight, lithium-titanium composite oxide 82.5-92.2 parts, acid Property compound additive 0.26-2.78 parts.
But above-mentioned negative material is prepared after lithium ion battery negative material, there is lithium ion battery circulation After electric discharge the problem of hydraulic performance decline.
The content of the invention
The purpose of the present invention is：Solve caused by the size performance that uses is bad on lithium ion battery negative material lithium from After sub- circulating battery electric discharge the problem of hydraulic performance decline.
Technical scheme is：
The small lithium ion battery of loss of capacitance after a kind of circulation electric discharge, including negative material, the negative material is by bearing Pole slurry is prepared after removing wherein solvent, and the cathode size is made up of following component by weight：Aqueous acrylamide Sour 100~160 parts of ester-polyurethane resin emulsion, 0.5~1 part of 0.1~0.5 part of particle, the coalescents of containing metal oxide, surface 0.5~1 part of activating agent.
Being selected from for described containing metal oxide contains Al2O3、ZrO2、TiO2、SnO2, it is a kind of or several in ZnO, MgO The particle of kind.
Described metal oxide particle is aluminium oxide-zirconium oxide-titanium carbide composite particles.
Described waterborne acrylic ester-polyurethane resin emulsion refers to be total to by acrylic monomers, polyalcohol and isocyanate-monomer It is poly- to react obtained water-based emulsion.
Described coalescents are selected from lactate, butoxy ethanol, phthalic acid ester, 2- (2- Butoxyethoxies) Ethanol, methyl phenyl carbinol, ethylene glycol, diethylene glycol, diacetone alcohol, propane diols, ethylene glycol or propane diols monoesters and diester, Etc..
Described surfactant is selected from nonionic surfactant.
The preparation method of described lithium-ion negative pole slurry, comprises the following steps：By aqueous acrylic urethane resins breast After liquid, the particle of containing metal oxide, coalescents, surfactant are mixed to form mixture, then by the mixture and bear Pole active material is well mixed with solvent.
Beneficial effect
The small lithium ion battery of loss of capacitance, the negative material used are starched for negative pole after circulation electric discharge provided by the invention The advantages of material is prepared after removing wherein solvent, and loss of capacitance is small after being discharged with circulation.
Embodiment
The present invention is described in further detail below by embodiment.But those skilled in the art will manage Solution, the following example is merely to illustrate the present invention, and should not be taken as limiting the scope of the invention.Unreceipted specific skill in embodiment Art or condition person, carried out according to the technology described by document in the art or condition or according to product description.Examination used Agent or the unreceipted production firm person of instrument, being can be by the conventional products of acquisition purchased in market.
Word " comprising " used herein, "comprising", " having " or its any other variant are intended to cover non-exclusionism Including.Technique, method, article or the equipment for e.g., including listing key element are not necessarily limited by those key elements, but can include it He is not expressly set out or belonged to this technique, method, article or the intrinsic key element of equipment.
Scope is used as using what the value of range format expression should be interpreted as not only including clearly including in a flexible way The numerical value of limit value, but also including covering all single numbers or subinterval within the range, just as each numerical value and sub-district Between be expressly recited out.For example, " about 0.1% to about 5% " concentration range should be understood to not only include clearly including About 0.1% to about 5% concentration, 4%) and son in addition to the single concentration (e.g., 1%, 2%, 3% and in the range of alluding to Section (for example, 0.1% to 0.5%, 1% to 2.2%, 3.3% to 4.4%).Percentage in the present invention is without specified otherwise In the case of refer to percentage by weight.
Slurry provided by the present invention, it is made up of following component by weight：
100~160 parts of waterborne acrylic ester-polyurethane resin emulsion, 0.1~0.5 part of the particle of containing metal oxide, film forming 0.5~1 part of auxiliary agent, 0.5~1 part of surfactant.
Wherein, described waterborne acrylic ester-polyurethane resin emulsion refers to by acrylic monomers, polyalcohol and isocyanates Monomer copolymerization reacts obtained water-based emulsion.
Here acrylic monomer, there is no particular limitation, can illustrate such as：(methyl) methyl acrylate (refers to third Any one of e pioic acid methyl ester or methyl methacrylate, similarly hereinafter), (methyl) ethyl acrylate, (methyl) n-butyl acrylate, (the first containing alkyl such as (methyl) isobutyl acrylate, (methyl) acrylic acid-2-ethyl caproite, (methyl) cyclohexyl acrylate Base) acrylic monomer；(methyl) acrylic monomer containing hydroxyl such as (methyl) acrylic acid 2- hydroxy methacrylates；(methyl) third The ethene unsaturated carboxylic acid such as olefin(e) acid；(methyl) acrylate, (methyl) acrylate propyl ester Deng (methyl) acrylic monomer containing amino；(methyl) acrylamide, ethyl (methyl) acrylamide etc. contain acid amides (methyl) acrylic monomer；(methyl) acrylic monomer containing itrile group such as acrylonitrile；(methyl) glycidyl (methyl) acrylic monomer containing epoxy radicals such as ester etc..
The polyol compound of the present invention is diol compound and three alcoholic compounds etc., as the polyalcohol of the invention used Composition, mainly using PEPA, polycarbonate polyol or PPG etc., polyurethane is used as wherein can use The ordinary matter of the raw material of resin, is not provided particularly.More particularly, as PEPA, adjacent benzene can be used Dioctyl phthalate, M-phthalic acid, terephthalic acid (TPA), naphthalene dicarboxylic acids, butanedioic acid, tartaric acid, malonic acid, ethanedioic acid, glutaric acid, oneself two Acid, pimelic acid, azelaic acid, Isosorbide-5-Nitrae-cyclohexyl dicarboxylic acid, α-hydromuconic acid, β-hydromuconic acid, α, β-diethyl Base butanedioic acid, maleic acid, fumaric acid, other binary acid etc. it is one kind or two or more with ethylene glycol, 1,2-PD, 1,3- the third two Alcohol, 1,2- butanediols, 1,3-BDO, BDO, 1,5-PD, 1,6- hexylene glycols, 1,8- ethohexadiols, 1,9- nonyls two Alcohol, 3- methyl isophthalic acids, 5- pentanediols, 3,3- dihydroxymethyls heptane, diethylene glycol, DPG, neopentyl glycol, hexamethylene-Isosorbide-5-Nitrae- The addition products such as glycol, hexamethylene-Isosorbide-5-Nitrae-dimethanol, the oxirane of bisphenol-A, expoxy propane, double (beta-hydroxyethyl) benzene, benzene diformazan The PEPA that the polycondensation reaction of the polyalcohols such as alcohol, other glycol or glycerine, trimethylolpropane, pentaerythrite obtains. Further, it is also possible to it is (interior to enumerate the cyclic esters such as 6-caprolactone, alkyl substitution 6-caprolactone, δ-valerolactone, alkyl substitution δ-valerolactone Ester) etc. monomer the obtained PEPA of lactone of ring-opening polymerisation, can also use a part for low molecular polylol It is polynary to become the low molecule such as hexamethylene diamine, IPD, MEA amine, the polyesteramide of low molecule amino alcohol Alcohol etc..As PPG, can use with glycols as mentioned, polyalcohols or they with ethylenediamine, propane diamine, The amines such as toluenediamine, m-phenylene diamine (MPD), diphenylmethanediamiand, benzene dimethylamine have more than 2 like that, preferably 2-3 activity The compound of hydrogen group is as the alkylene such as initiator, the one kind or two or more oxirane of addition polymerization, expoxy propane, epoxy butane The ring-type ethers such as the alkyl or aryl glycidol such as oxygen class, methyl glycidyl ether, phenyl glycidyl ether ethers, tetrahydrofuran The PPG that monomer etc. obtains.As polycarbonate polyol, can use by low-molecular-weight diol class as described above, low Polycarbonate polyol obtained from the reaction of molecule triol and ethylene carbonate, diethyl carbonate, diphenyl carbonate etc..Separately Outside, the polyalcohol generated by the ester exchange of polycarbonate polyol and PEPA can also be suitably used.Other are also Can use the polyol as made from PPG and omega-dicarboxylic acids and by polyester, makrolon and epoxides, The polyester ether polylol that the reaction of cyclic ether obtains, it can also use with more than 2 hydroxyls, polybutadiene, the poly- fourth of hydrogenation The polyolefin polyhydric alcohol of diene, polyisoprene, hydrogenated polyisoprene etc..
As isocyanate-monomer, can include hexamethylene diisocyanate, trimethyl hexamethylene diisocyanate, The aliphatic diisocyanate compound such as dimer acid diisocyanate, lysine diisocyanate；These diisocyanate chemical combination Biuret form addition product, the isocyanurate ring addition product of thing；IPDI, 4,4 '-di-2-ethylhexylphosphine oxide (cyclohexyl Isocyanates), hexahydrotoluene -2,4- (or -2,6-) diisocyanate, 1,3- (or 1,4-) two (isocyanatomethyl) Hexamethylene, 1,4- cyclohexane diisocyanates, 1,3- pentamethylene diisocyanate, 1,2- cyclohexane diisocyanates etc. are alicyclic Diisocyanate cpd；Biuret form addition product, the isocyanurate ring addition product of these diisocyanate；Dimethylbenzene two is different Cyanate, m xylene diisocyanate, tetramethylxylene diisocyanate, toluene di-isocyanate(TDI), 4,4 '-diphenyl-methane Diisocyanate, 1,5- naphthalene diisocyanates, 1,4- naphthalene diisocyanates, 4,4 '-toluidine diisocyanate, 4,4 '-hexichol Base ether isocyanates, (or to) phenylene diisocyanate, 4,4 '-biphenylene diisocyanate, 3,3 '-dimethyl -4,4 '-Asia The aromatic series two such as biphenylene diisocyanate, double (4- isocyanatophenyis) sulfones, isopropylidene double (4- phenyl isocyanates) Isocyanate compound；Biuret form addition product, the isocyanurate ring addition product of these diisocyanate cpds；Triphenyl Methane -4,4 ', 4 "-triisocyanate, the isocyanato- benzene of 1,3,5- tri-, the isocyanato- toluene of 2,4,6- tri-, 4,4 '-diformazan Base diphenyl methane -2,2 ', 5,5 '-tetraisocyanate etc. have the polyisocyanic acid of more than three NCOs in 1 molecule Ester compounds；Biuret form addition product, the isocyanurate ring addition product of these polyisocyanate compounds；With relative to second two The polyalcohols such as alcohol, propane diols, 1,4- butanediols, dihydromethyl propionic acid, PAG, trimethylolpropane, hexane triol Hydroxyl for NCO turn into excessive ratio so that polyisocyanate compound and these polyalcohols reacted and Into urethane addition product；Biuret form addition product, the isocyanurate ring of these urethane addition products add Into thing etc..
In addition, in the course of the polymerization process, can also add as the other monomers that can be copolymerized with acrylic monomer, can be with Illustration has the aromatic hydrocarbon vinyl monomer such as styrene, methyl styrene, chlorostyrene, vinyl toluene；Maleic acid, itaconic acid, The α such as crotonic acid, fumaric acid, citraconic acid, β-ethene unsaturated carboxylic acid；The second containing sulfonic acid such as styrene sulfonic acid, vinyl sulfonic acid Alkene monomer；The acid anhydrides of maleic anhydride, itaconic anhydride etc.；The fluorochemical monomers such as vinyl chloride, vinylidene chloride, chlorobutadiene；Ethoxy The alkyl vinyl ethers containing hydroxyl such as vinyl ethers, hydroxypropyl vinyl ethers；Ethylene glycol monoallyl ether, propane diols monoene third The alkylene glycol mono allyl ethers such as base ether diethylene glycol mono allyl ether；The alpha-olefins such as ethene, propylene, isobutene；Vinyl acetate The vinyl acetates such as ester, propionate, vinyl butyrate, vinyl pivalate；Ethylene methacrylic ether, ethyl vinyl ether, butyl The vinethenes such as vinethene, cyclohexyl vinyl ether；Allyl ethers such as ethyl allyl ether, butyl allyl ether etc..
On the manufacture of above-mentioned carbamate prepolymer, existing known method can be based on and carried out.
Above-mentioned acrylic monomers, isocyanates, monomeric polyol are gathered in the presence of catalyst and initiator Close, react after terminating, then mixed with defoamer, nertralizer, deionized water, emulsion can be prepared, preferably use and turn Phase emulsion process.First, a small amount of water is added into the oil (organic solvent containing resin) for adding emulsifying agent, is mixed, thus W/o type emulsion can be obtained.Then, while being slowly added into water, while making its phase inversion, O/W type emulsions may finally be obtained.With Shaft mixer and homogenizer, homomixer, colloid mill with rotating vane etc. can be enumerated in the device of mixing.Separately Outside, emulsifying temperature is preferably in 10-80 DEG C of scope, more preferably in 20-30 DEG C of scope.The average grain diameter of emulsion is not special Limit, usually 0.01-10 μm or so, preferably 0.1-1 μm or so.
, can be without restriction using existing known polymerization initiator, such as hexamethylene can be included as polymerization initiator Double (the t-butyl peroxies of ketone peroxide, 3,3,5 trimethyl hexanone peroxide, methyl cyclohexanone peroxide, 1,1- Base) -3,3,5- trimethyl-cyclohexanes, 1,1-bis(t-butylperoxy)cyclohexane, normal-butyl -4,4- bis(t-butylperoxy)s Valerate, cumene hydroperoxide, 2,5- dimethylhexane -2,5- dihydro-peroxidases, 1,3- pairs (tert-butyl hydroperoxide - Isopropyl) benzene, 2,5- dimethyl -2,5- two (t-butylperoxy) hexane, dicumyl peroxide, butyl-cumyl peroxide Compound, decanol peroxide, lauroyl peroxide, benzoyl peroxide, DCBP 2,4 dichlorobenzoyl peroxide, two uncles Amyl peroxide, double (tert-butylcyclohexyl) peroxy dicarbonates, tert butyl peroxy benzoate, 2,5- dimethyl- The peroxide type polymerization initiators such as 2,5- bis- (benzoylperoxy) hexane, peroxide -2-ethyl hexanoic acid tert-butyl；2, Double -2- the methylbutyronitriles of 2 '-azo double (isobutyronitrile), 2,2 '-azo, 1,1 '-azo double (hexamethylene -1- formonitrile HCNs), azocumene, Double -2,4- the methyl pentane nitriles of 2,2 '-azo double (2- methylbutyronitriles), 2,2 '-azo, 4,4 '-azo double (4- cyanopentanoic acids), 2- (tert-butyl group azo) -2- dicyanopropanes, 2,2 '-azo double (2,4,4- trimethylpentanes), double (the 2- methyl-props of 2,2 '-azo Alkane), 2,2 '-azo double [2- methyl-N- (2- ethoxys)-propionamide], dimethyl 2,2 '-azo double (2 Methylpropionic acid esters), 1,1 '-azo double (1- hexamethylene -1- formonitrile HCNs), 2,2 '-azo double [2- (2- imidazoline -2- bases) propane], dimethyl -2,2 ' - The azo type polymerization initiator such as azobisisobutylonitrile acid esters.
As nertralizer, if the nertralizer that carboxyl is neutralized then can be not particularly limited, for example, hydrogen can be enumerated Sodium oxide molybdena, potassium hydroxide, trimethylamine, dimethylaminoethanol, 2- methyl-2-amino -1- propyl alcohol, triethylamine, ammonia etc..
In addition, used defoamer is not particularly limited when carrying out emulsion polymerization, such as dialkyl sulfosuccinate amber can be enumerated Meticortene Solu-Delta-cortef, neopelex, NaLS, polyethylene glycol oxide alkyl phenyl ether sodium sulfate and alkyl diphenyl base The anionic emulsifiers such as ether sodium disulfonate, the nonionic such as polyoxyethylene higher alcohol ether and polyethylene glycol oxide alkyl phenyl ether Property emulsifying agent and with free-radical polymerised double bond anionic property or cationic reactive emulsifier.
Reactive emulsifier refers to together there is nonionic group, anionic property group and cationic in the molecule The emulsifying agent of wantonly more than a kind of group and polymerism unsaturated group in group, as polymerism unsaturated group, specific row Enumerate (methyl) pi-allyl, (methyl) acryloyl group, acrylic, cyclobutenyl etc..
Can being selected from for containing metal oxide contains Al used by above-mentioned2O3、ZrO2、TiO2、SnO2, in ZnO, MgO One or several kinds of particles；It can also be that these are metal oxide supported on specific support in addition, preferably aoxidize Aluminium-zirconium oxide-titanium carbide composite particles.Its preparation method can be：
1st step, by Ti3AlC2Powder ball milling, then dried after carrying out, the ceramic powder refined；
2nd step, the ceramic powder of refinement is taken in 5~15g submergence 80mL~150mL hydrofluoric acid solutions and reacted, will be corroded Product is cleaned to neutrality with deionized water, then uses washes of absolute alcohol；Gained solid sample is dried, the pottery after being corroded Porcelain powder；
3rd step, take 2~5g to be put into 2~4L absolute ethyl alcohols the ceramic powder after corroding obtained by the 2nd step, stir, then add Enter 15~25g nitric acid aluminium powder and 5~10gZrOCl2Powder, then 120~180ml of watery hydrochloric acid is slowly added dropwise, it is anti-to continue stirring Should, with deionized water eccentric cleaning is used after absolute ethyl alcohol eccentric cleaning again, solid sample is dried, produce aluminium oxide-zirconium oxide- Titanium carbide composite particles.
In the 1st described step, 4~6h of Ball-milling Time, rotational speed of ball-mill 700r/min, ball material mass ratio 5:1；Drying temperature is 60~70 DEG C.
In the 2nd described step, 30~40wt% of concentration of hydrofluoric acid solution, 3~6h of reaction time.
In the 3rd described step, the mass concentration of watery hydrochloric acid is 3~6wt%；5~10h of reaction time；Drying temperature is 120 ~140 DEG C.
Many usual coalescents can increase flowing, reduce foam, and some coalescents are：Lactate, 2- butoxy Ethanol, phthalic acid ester, 2- (2- Butoxyethoxies) ethanol, methyl phenyl carbinol, ethylene glycol, diethylene glycol, diacetone Alcohol, propane diols, ethylene glycol or propane diols monoesters and diester, etc..
Surfactant used in the present invention, preferably nonionic surfactant, for example, line style polyoxyalkylene alkane Base ethers, such as polyethylene glycol oxide hexyl ether, polyoxyethylene octyl ether, polyethylene glycol oxide decyl ethers, polyoxyethylene lauryl base Ether and polyethylene glycol oxide cetyl ether；Branched polyoxyalkylenes primary alkyl ethers, such as polyethylene glycol oxide 2- ethylhexyl ethers, gather Ethylene oxide isocetyl ether and polyethylene glycol oxide iso stearyl ether；The branched secondary alkyl ether of polyoxyalkylene, such as polyoxyethylene Alkene 1- hexyl hexyl ethers, polyethylene glycol oxide 1- octyl group hexyl ethers, polyethylene glycol oxide 1- hexyl Octyl Ethers, polyethylene glycol oxide 1- amyl groups Heptyl ether and polyethylene glycol oxide 1- heptyl amyl ethers；Polyoxyalkylene alkenyl ethers class, such as polyethylene glycol oxide oleyl ether；Polyoxygenated Allylic alkylation phenyl ethers, such as polyoxyethylene octylphenyl ether, polyoxyethylene nonylplenyl ether, and polyethylene glycol oxide dodecane Base phenyl ether；Polyoxyalkylene alkyl aryl phenyl ethers, such as polyethylene glycol oxide tri-styryl phenyl ether, polyethylene glycol oxide hexichol Vinyl phenyl ether, polyethylene glycol oxide styrylphenyl ether, polyethylene glycol oxide tribenzyl phenyl, polyethylene glycol oxide dibenzyl benzene Base ether, and polyethylene glycol oxide benzyl phenyl ether；Polyoxyalkylene fatty acid ester class, such as polyethylene glycol oxide monolaurate, polyoxy Change ethene monoleate, polyoxyethylene monostearate ester, polyethylene glycol oxide list myristinate, polyethylene glycol oxide tin dilaurate Ester, polyethylene glycol oxide dioleate, the myristinate of polyethylene glycol oxide two, and polyethylene glycol oxide distearate；It is dehydrated mountain Pears sugar alcohol esters, such as span 40 and dehydrated sorbitol mono-fatty acid ester；Polyoxyalkylene sorbitan Polyol fatty acid esters, such as TWEEN 60 and polyoxyethylene sorbitan list oleic acid Ester；Glycerine fatty acid esters, such as glyceryl monostearate, glyceryl monolaurate and glycerol monopalmitate；Polyoxyalkylene mountain Pears sugar alcohol fatty acid esters；Sucrose-fatty esters；Polyoxyalkylene castor oil ethers, such as polyoxyethylene castor oil ether；Polyoxy Change alkene rilanit special ethers, such as polyoxyethylene hydrogenated castor oil ether；Polyoxyalkylene alkyl amino ethers, such as polyethylene glycol oxide Lauryl amino ether and polyethylene glycol oxide stearyl ether；Ethylene oxide-propylene oxide block or random copolymer；End alkane Oxyethylene group-oxypropylene group the block or random copolymer of base etherificate；With ethylene oxide-oxidation of end sucrose-etherificate Polypropylene block or random copolymer.
The preparation method of described lithium-ion negative pole slurry, comprises the following steps：By aqueous acrylic urethane resins breast After liquid, the particle of containing metal oxide, coalescents, surfactant are mixed to form mixture, then by the mixture and bear Pole active material is well mixed with solvent.
Wherein, the negative electrode active material is not particularly limited the present invention, can use this area is conventional to be embedded in The negative electrode active material of lithium, such as carbon material are disengaged, the carbon material is selected from non-graphitic carbon, graphite or by polyacetylene high score Charcoal or pyrolytic carbon that sub- material is obtained by high-temperature oxydation, coke, organic polymer sinter, one kind in activated carbon or several Kind.The organic polymer sinter can be by sintering phenolic resin, epoxy resin etc. and products therefrom after carbonizing.
Embodiment 1
The preparation of Aqueous acrylic urethane's emulsion：
1st step：Polyalcohol (polyoxyethylene glycol) 15g, polyisocynate monomer (different Buddhist are added in reaction vessel Your ketone diisocyanate) 40g, hydrophilic chain extender (dihydromethyl propionic acid) 5g and catalyst (dibutyl tin laurate) 1g, Reacted 3~5 hours at 65~75 DEG C, obtain performed polymer；
2nd step：Temperature in reaction vessel is down to 60 DEG C, acrylic monomer (acrylonitrile) 20g is then added, by temperature 40 DEG C are down to, adds nertralizer (triethylamine) 3g, is reacted 20 minutes, is added deionized water 240g stirrings at room temperature, gathered Urethane emulsion；
3rd step：Initiator (double -2- methylbutyronitriles of 2,2 '-azo) 3g, emulsifying agent (lecithin) are added in reaction vessel 2g and acrylic monomer (Methacrylamide) 15g, reacts 4 hours at 80 DEG C, obtains Aqueous acrylic urethane's emulsion.
The preparation of aluminium oxide-zirconium oxide-titanium carbide composite particles：
1st step, by Ti3AlC2Powder ball milling, then dried after carrying out, the ceramic powder refined, Ball-milling Time 6h, ball Grind rotating speed 700r/min, ball material mass ratio 5:1；Drying temperature is 70 DEG C；
2nd step, the ceramic powder of refinement is taken in 15g submergences 150mL 40wt% hydrofluoric acid solutions and reacted, the reaction time 6h, corrosion product is cleaned to neutrality with deionized water, then uses washes of absolute alcohol；Gained solid sample is dried, obtained Ceramic powder after corrosion；
3rd step, take 5g to be put into 4L absolute ethyl alcohols the ceramic powder after corroding obtained by the 2nd step, stir, add 25g Nitric acid aluminium powder and 10gZrOCl2Powder, then 6wt% watery hydrochloric acid 180ml are slowly added dropwise, continue stirring reaction 10h, use is anhydrous Deionized water eccentric cleaning is used after ethanol eccentric cleaning again, by 140 DEG C of drying of solid sample, produces aluminium oxide-zirconium oxide-carbonization Titanium composite particles.
The preparation of cathode size：
By weight, aqueous 160 parts of acrylic ester-polyurethane resin emulsion, containing metal oxide 0.5 part of particle, into 1 part of film auxiliary agent (ethylene glycol), 1 part of nonionic surfactant (Arlacel-65).By the poly- ammonia of water soluble acrylic acid After ester resin emulsion, the particle of containing metal oxide, coalescents, surfactant are mixed to form mixture, then will be described mixed 2400 parts of compound and negative electrode active material graphite are well mixed for 1500 parts with water.
Embodiment 2
Difference with embodiment 1 is：In 3rd step of the preparation of Aqueous acrylic urethane's emulsion, monomer second is additionally added Base vinethene.
The preparation of Aqueous acrylic urethane's emulsion：
1st step：Polyalcohol (polyoxyethylene glycol) 15g, polyisocynate monomer (different Buddhist are added in reaction vessel Your ketone diisocyanate) 40g, hydrophilic chain extender (dihydromethyl propionic acid) 5g and catalyst (dibutyl tin laurate) 1g, Reacted 3~5 hours at 65~75 DEG C, obtain performed polymer；
2nd step：Temperature in reaction vessel is down to 60 DEG C, acrylic monomer (acrylonitrile) 20g is then added, by temperature 40 DEG C are down to, adds nertralizer (triethylamine) 3g, is reacted 20 minutes, is added deionized water 240g stirrings at room temperature, gathered Urethane emulsion；
3rd step：Initiator (double -2- methylbutyronitriles of 2,2 '-azo) 3g, emulsifying agent (lecithin) are added in reaction vessel 2g, monomer ethyl vinyl ether 7g and acrylic monomer (Methacrylamide) 15g, react 4 hours at 80 DEG C, obtain water-based Acroleic acid polyurethane emulsion.
The preparation of aluminium oxide-zirconium oxide-titanium carbide composite particles：
1st step, by Ti3AlC2Powder ball milling, then dried after carrying out, the ceramic powder refined, Ball-milling Time 6h, ball Grind rotating speed 700r/min, ball material mass ratio 5:1；Drying temperature is 70 DEG C；
2nd step, the ceramic powder of refinement is taken in 15g submergences 150mL 40wt% hydrofluoric acid solutions and reacted, the reaction time 6h, corrosion product is cleaned to neutrality with deionized water, then uses washes of absolute alcohol；Gained solid sample is dried, obtained Ceramic powder after corrosion；
3rd step, take 5g to be put into 4L absolute ethyl alcohols the ceramic powder after corroding obtained by the 2nd step, stir, add 25g Nitric acid aluminium powder and 10gZrOCl2Powder, then 6wt% watery hydrochloric acid 180ml are slowly added dropwise, continue stirring reaction 10h, use is anhydrous Deionized water eccentric cleaning is used after ethanol eccentric cleaning again, by 140 DEG C of drying of solid sample, produces aluminium oxide-zirconium oxide-carbonization Titanium composite particles.
The preparation of cathode size：
By weight, aqueous 160 parts of acrylic ester-polyurethane resin emulsion, containing metal oxide 0.5 part of particle, into 1 part of film auxiliary agent (ethylene glycol), 1 part of nonionic surfactant (Arlacel-65).By the poly- ammonia of water soluble acrylic acid After ester resin emulsion, the particle of containing metal oxide, coalescents, surfactant are mixed to form mixture, then will be described mixed 2400 parts of compound and negative electrode active material graphite are well mixed for 1500 parts with water.
Reference examples 1
Difference with embodiment 1 is：Titanium carbide is not carried in the preparation of aluminium oxide-zirconium oxide-titanium carbide composite particles Body carries out hydrofluoric acid corrosion.
The preparation of Aqueous acrylic urethane's emulsion：
1st step：Polyalcohol (polyoxyethylene glycol) 15g, polyisocynate monomer (different Buddhist are added in reaction vessel Your ketone diisocyanate) 40g, hydrophilic chain extender (dihydromethyl propionic acid) 5g and catalyst (dibutyl tin laurate) 1g, Reacted 3~5 hours at 65~75 DEG C, obtain performed polymer；
2nd step：Temperature in reaction vessel is down to 60 DEG C, acrylic monomer (acrylonitrile) 20g is then added, by temperature 40 DEG C are down to, adds nertralizer (triethylamine) 3g, is reacted 20 minutes, is added deionized water 240g stirrings at room temperature, gathered Urethane emulsion；
3rd step：Initiator (double -2- methylbutyronitriles of 2,2 '-azo) 3g, emulsifying agent (lecithin) are added in reaction vessel 2g and acrylic monomer (Methacrylamide) 15g, reacts 4 hours at 80 DEG C, obtains Aqueous acrylic urethane's emulsion.
The preparation of aluminium oxide-zirconium oxide-titanium carbide composite particles：
1st step, by Ti3AlC2Powder ball milling, then dried after carrying out, the ceramic powder refined, Ball-milling Time 6h, ball Grind rotating speed 700r/min, ball material mass ratio 5:1；Drying temperature is 70 DEG C；
2nd step, take 15g to be cleaned with deionized water to neutrality the ceramic powder of refinement, then use washes of absolute alcohol；Will Gained solid sample is dried, ceramic powder after being handled；
3rd step, ceramic powder takes 5g to be put into 4L absolute ethyl alcohols after being handled obtained by the 2nd step, stirs, adds 25g's Nitric acid aluminium powder and 10gZrOCl2Powder, then 6wt% watery hydrochloric acid 180ml are slowly added dropwise, continue stirring reaction 10h, with anhydrous second Deionized water eccentric cleaning is used after alcohol eccentric cleaning again, by 140 DEG C of drying of solid sample, produces aluminium oxide-zirconium oxide-titanium carbide Composite particles.
The preparation of cathode size：
By weight, aqueous 160 parts of acrylic ester-polyurethane resin emulsion, containing metal oxide 0.5 part of particle, into 1 part of film auxiliary agent (ethylene glycol), 1 part of nonionic surfactant (Arlacel-65).By the poly- ammonia of water soluble acrylic acid After ester resin emulsion, the particle of containing metal oxide, coalescents, surfactant are mixed to form mixture, then will be described mixed 2400 parts of compound and negative electrode active material graphite are well mixed for 1500 parts with water.
Performance test
1st, peel strength test：Obtained cathode size is coated with copper foil current collector, then toasted at 90 DEG C dry It is dry, thick 105um pole piece is obtained, after being cut into 4*10cm small pieces, peel strength test is carried out on peel strength machine.
2nd, swelling capacity is tested：Obtained cathode size is coated with copper foil current collector, then toasts drying at 90 DEG C, Thick 105um pole piece is obtained, is cut into 4*4cm small pieces, after 100 DEG C of vacuum drying, weigh M0, is then immersed in dress It is ethylene carbonate (EC): diethyl carbonate (DEC)=1: 1, lithium hexafluoro phosphate (LiPF to have volume ratio6) concentration is 1mol/L In the air-tight bottle of nonaqueous electrolytic solution, sealing is put into vacuum drying chamber, 60 DEG C of placement 48h, takes out air-tight bottle, by pole piece weighing M1, Mass change obtains swelling and crossed before and after calculating pole piece immersion, i.e.=(M1-M0)/M0*100% is crossed in swelling.
3rd, discharge performance is tested：
3.1 prepare the negative pole of lithium ion battery
Whole cathode sizes that step 1 is obtained are coated on the copper foil of 8 μ m-thicks, 90 DEG C of dryings 10 minutes, then with pressure Piece machine tabletting, finally cuts into slices, and is grown × the anode plate for lithium ionic cell of width x thickness=55cm × 3.5cm × 110 μm.
3.2 prepare lithium ion cell positive
Weigh LiFePO4 (LiFePO4) 1.5kg, and conductive black (CB), polyvinylidene fluoride (PVDF), N- methyl Pyrrolidones (NMP) compares LiFePO according to weight4: prepare anode sizing agent at CB: PVDF: NMP=100: 5: 3.5: 110, and stirring is equal It is coated in after even on the aluminium foil of 12 μ m-thicks, then 100 DEG C of dryings 10 minutes, then with tabletting machine, finally cut into slices, grown × The based lithium-ion battery positive plate of width x thickness=55cm × 3.5cm × 110 μm.
3.3 prepare lithium ion battery
By negative electrode of lithium ion battery made from foregoing 3.1 and 3.2 steps, positive pole and thick 25 μm polypropylene screen barrier film according to Positive plate, barrier film, the order of negative plate stack successively, then wind, and the pole piece of lithium ion battery is made.The pole piece is put into height 50mm, thick 5mm, wide 34mm steel square lithium ion battery shell in, 3.8g electrolyte is then injected into, outside finally sealed battery Shell, LP053450AR0U type square lithium ion batteries are made.The composition of electrolyte is：1mol/L lithium hexafluoro phosphate (LiPF6) (solvent is according to volume ratio ethylene carbonate (EC): the mixed solvent that dimethyl carbonate (DMC)=1: 1 mixes).
By battery at normal temperatures with 0.5C charge and discharge cycles 500 times (CC-CV, 4.25V/3.1V, cut-off current 36mA), survey Determine electric capacitance change amount.
Embodiment 1 Embodiment 2 Reference examples 1
Peel strength/N/m 3.2 3.6 2.9
/ % is crossed in swelling 28.4 25.3 36.4
Electric capacitance change 500 circulates/% 93.5 94.7 91.0
As can be seen from the above table, the negative material that cathode size provided by the invention is prepared can apply to lithium ion Making, and with preferable adhesion strength, relatively low swelling capacity, circulation electric discharge after capacitance it is higher；In embodiment 2, lead to Cross the addition ethyl vinyl ether in Aqueous acrylic urethane's slurry to be polymerize, the peel strength of material can be effectively improved And reduce swelling capacity；Embodiment 3, due to not carrying out hydrofluoric acid corrosion to titanium carbide material, makes oxidation for reference examples 1 Zirconium, aluminum oxide are bad in the tack of primary surface, make peel strength low, and there is also zirconium oxide and titanium oxide to divide in the slurry The problem of property is bad is dissipated, and then causes capacitance after circulating electric discharge the problem of declining to be present.

Claims (6)

  1. A kind of 1. small lithium ion battery of loss of capacitance after circulation electric discharge, it is characterised in that including negative material, the negative pole Material is prepared after removing wherein solvent by cathode size, and the cathode size is made up of following component by weight： 100~160 parts of waterborne acrylic ester-polyurethane resin emulsion, 0.1~0.5 part of the particle of containing metal oxide, coalescents 0.5~ 1 part, 0.5~1 part of surfactant.
  2. 2. the small lithium ion battery of loss of capacitance after circulation electric discharge according to claim 1, it is characterised in that described Being selected from for containing metal oxide contains Al2O3、ZrO2、TiO2、SnO2, one or several kinds of particles in ZnO, MgO.
  3. 3. the small lithium ion battery of loss of capacitance after circulation electric discharge according to claim 1, it is characterised in that described Metal oxide particle is aluminium oxide-zirconium oxide-titanium carbide composite particles.
  4. 4. the small lithium ion battery of loss of capacitance after circulation electric discharge according to claim 1, it is characterised in that described Waterborne acrylic ester-polyurethane resin emulsion refers to the water obtained by acrylic monomers, polyalcohol and isocyanate-monomer copolyreaction Property emulsion.
  5. 5. the small lithium ion battery of loss of capacitance after circulation electric discharge according to claim 1, it is characterised in that described Coalescents are selected from lactate, butoxy ethanol, phthalic acid ester, 2- (2- Butoxyethoxies) ethanol, aminomethyl phenyl Methanol, ethylene glycol, diethylene glycol, diacetone alcohol, propane diols, ethylene glycol or propane diols monoesters and diester, etc.；Described table Face activating agent is selected from nonionic surfactant.
  6. 6. the preparation method of the small lithium ion battery of loss of capacitance after any described circulation electric discharge of Claims 1 to 5, it is special Sign is that the preparation method of the cathode size comprises the following steps：By waterborne acrylic ester-polyurethane resin emulsion, containing metal oxygen After particle, coalescents, the surfactant of compound are mixed to form mixture, then by the mixture and negative electrode active material with Solvent is well mixed.
CN201711105817.5A 2017-11-10 2017-11-10 Small lithium ion battery of loss of capacitance and preparation method thereof after a kind of circulation electric discharge Pending CN107732154A (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102487138A (en) * 2010-12-02 2012-06-06 上海比亚迪有限公司 Cathode slurry and preparation method thereof, cathode of lithium ion battery and lithium ion battery
CN105226322A (en) * 2015-10-27 2016-01-06 宁德新能源科技有限公司 Cathode size and comprise negative plate, the lithium ion battery of this cathode size
CN105470476A (en) * 2015-11-02 2016-04-06 万向A一二三系统有限公司 Lithium ion battery negative electrode for reducing irreversible capacity loss and preparation method of lithium ion battery negative electrode
CN105602497A (en) * 2016-01-26 2016-05-25 浙江中科立德新材料有限公司 Polyurethane-modified acrylic acid waterborne binder and preparing method and application thereof
CN106147588A (en) * 2016-07-22 2016-11-23 成都拜迪新材料有限公司 One group is applied to the aqueous finish paint of 25 type passenger vehicles, varnish and preparation method thereof
CN106654171A (en) * 2015-10-29 2017-05-10 深圳市比克动力电池有限公司 A composite dispersant, lithium ion battery anode slurry, an anode and a lithium ion battery

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102487138A (en) * 2010-12-02 2012-06-06 上海比亚迪有限公司 Cathode slurry and preparation method thereof, cathode of lithium ion battery and lithium ion battery
CN105226322A (en) * 2015-10-27 2016-01-06 宁德新能源科技有限公司 Cathode size and comprise negative plate, the lithium ion battery of this cathode size
CN106654171A (en) * 2015-10-29 2017-05-10 深圳市比克动力电池有限公司 A composite dispersant, lithium ion battery anode slurry, an anode and a lithium ion battery
CN105470476A (en) * 2015-11-02 2016-04-06 万向A一二三系统有限公司 Lithium ion battery negative electrode for reducing irreversible capacity loss and preparation method of lithium ion battery negative electrode
CN105602497A (en) * 2016-01-26 2016-05-25 浙江中科立德新材料有限公司 Polyurethane-modified acrylic acid waterborne binder and preparing method and application thereof
CN106147588A (en) * 2016-07-22 2016-11-23 成都拜迪新材料有限公司 One group is applied to the aqueous finish paint of 25 type passenger vehicles, varnish and preparation method thereof

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