CN1485940A - Lithium ion cell, electrode of lithium ion cell and its preparation method - Google Patents
Lithium ion cell, electrode of lithium ion cell and its preparation method Download PDFInfo
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- CN1485940A CN1485940A CNA031538746A CN03153874A CN1485940A CN 1485940 A CN1485940 A CN 1485940A CN A031538746 A CNA031538746 A CN A031538746A CN 03153874 A CN03153874 A CN 03153874A CN 1485940 A CN1485940 A CN 1485940A
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- lithium ion
- water
- ion battery
- lithium
- based adhesive
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- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title description 6
- 230000001070 adhesive effect Effects 0.000 claims abstract description 67
- 239000000853 adhesive Substances 0.000 claims abstract description 66
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 53
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000000034 method Methods 0.000 claims abstract description 17
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000011889 copper foil Substances 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims abstract description 6
- 239000000843 powder Substances 0.000 claims abstract description 6
- 239000006258 conductive agent Substances 0.000 claims description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 11
- 229910003002 lithium salt Inorganic materials 0.000 claims description 11
- 159000000002 lithium salts Chemical class 0.000 claims description 11
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 10
- 239000003792 electrolyte Substances 0.000 claims description 10
- 239000000839 emulsion Substances 0.000 claims description 10
- 229910052744 lithium Inorganic materials 0.000 claims description 10
- 239000007773 negative electrode material Substances 0.000 claims description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 8
- 239000006229 carbon black Substances 0.000 claims description 8
- 229910002804 graphite Inorganic materials 0.000 claims description 8
- 239000010439 graphite Substances 0.000 claims description 8
- 239000002562 thickening agent Substances 0.000 claims description 8
- 239000000654 additive Substances 0.000 claims description 6
- 230000000996 additive effect Effects 0.000 claims description 6
- 239000005030 aluminium foil Substances 0.000 claims description 6
- 230000004888 barrier function Effects 0.000 claims description 6
- -1 polypropylene Polymers 0.000 claims description 6
- 239000002002 slurry Substances 0.000 claims description 6
- 229910019142 PO4 Inorganic materials 0.000 claims description 5
- 239000004743 Polypropylene Substances 0.000 claims description 5
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 5
- 239000002174 Styrene-butadiene Substances 0.000 claims description 5
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims description 5
- 239000002131 composite material Substances 0.000 claims description 5
- 239000012046 mixed solvent Substances 0.000 claims description 5
- 239000010452 phosphate Substances 0.000 claims description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 5
- 229920001155 polypropylene Polymers 0.000 claims description 5
- 159000000000 sodium salts Chemical class 0.000 claims description 5
- 239000011115 styrene butadiene Substances 0.000 claims description 5
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 5
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 4
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 4
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 claims description 4
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 claims description 4
- 239000012982 microporous membrane Substances 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 229910000077 silane Inorganic materials 0.000 claims description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 4
- 229920002554 vinyl polymer Polymers 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 239000002931 mesocarbon microbead Substances 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 claims description 3
- 229910000314 transition metal oxide Inorganic materials 0.000 claims description 3
- QGHDLJAZIIFENW-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical group C1=C(CC=C)C(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C(CC=C)=C1 QGHDLJAZIIFENW-UHFFFAOYSA-N 0.000 claims description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 2
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 2
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 2
- 239000007774 positive electrode material Substances 0.000 claims description 2
- 239000000243 solution Substances 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract 1
- 229910052782 aluminium Inorganic materials 0.000 abstract 1
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- 239000011888 foil Substances 0.000 abstract 1
- 239000000758 substrate Substances 0.000 abstract 1
- 238000000576 coating method Methods 0.000 description 14
- 239000002033 PVDF binder Substances 0.000 description 10
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 10
- 239000011248 coating agent Substances 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- 238000005303 weighing Methods 0.000 description 9
- 235000019241 carbon black Nutrition 0.000 description 7
- 238000001125 extrusion Methods 0.000 description 7
- 238000003756 stirring Methods 0.000 description 6
- 239000011149 active material Substances 0.000 description 5
- 230000014759 maintenance of location Effects 0.000 description 5
- 238000010586 diagram Methods 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 3
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 3
- 229910013870 LiPF 6 Inorganic materials 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 2
- 230000004087 circulation Effects 0.000 description 2
- 239000011263 electroactive material Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920000058 polyacrylate Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- ODLMAHJVESYWTB-UHFFFAOYSA-N propylbenzene Chemical compound CCCC1=CC=CC=C1 ODLMAHJVESYWTB-UHFFFAOYSA-N 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000010008 shearing Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- ZVKRVGZVXQYLPZ-UHFFFAOYSA-N [Li].[V].P(O)(O)(O)=O Chemical compound [Li].[V].P(O)(O)(O)=O ZVKRVGZVXQYLPZ-UHFFFAOYSA-N 0.000 description 1
- LCJHLOJKAAQLQW-UHFFFAOYSA-N acetic acid;ethane Chemical compound CC.CC(O)=O LCJHLOJKAAQLQW-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229920003180 amino resin Polymers 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 206010025482 malaise Diseases 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000007581 slurry coating method Methods 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 229920001909 styrene-acrylic polymer Polymers 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
- H01M4/0404—Methods of deposition of the material by coating on electrode collectors
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention refers to the electrodes of lithium ion battery and making method, as well as the lithium ion battery. Mix positive and/or negative active substrate powder 85-98%, electric agent 0.5-10%, and water-based adhesive 1.5-10% according to weight percentage, add in water to adjust into 4000-12000mPa s plasm; smear the plasm on two surfaces of positive current collector aluminum foil and/or negative current collector copper foil; roll and slice to obtain the electrodes. It can be widely applied to the making field of lithium ion battery.
Description
Technical field:
The present invention relates to a kind of lithium ion battery, particularly a kind of electrode of the lithium ion battery with water-based adhesive preparation and its preparation method, and adopt the lithium ion battery of this electrode.
Background technology:
Since nineteen ninety came out, lithium ion battery had become the rechargeable battery of new generation of function admirable, is widely used in mobile phone, notebook computer, motor vehicle, electric tool etc., and demonstrates great application prospect in fields such as space flight, national defence gradually.Wherein the research of lithium ion battery material and technology is the research focus in this field always.Lithium ion battery mainly is made up of anode pole piece, cathode pole piece, barrier film and electrolyte, wherein the making of both positive and negative polarity pole piece generally is that both positive and negative polarity active material, adhesive and conductive agent are mixed on the aluminium foil (positive pole) and Copper Foil (negative pole) that is coated in behind the uniform slurry as collector, makes through roll extrusion and shearing then.Wherein the main effect of adhesive has: (1) with electroactive substance powder furnishing pulpous state, so as with the slurry coating of homogenizing on the collector two sides, and satisfy the qualification rate requirement of pole piece in the coating process.(2) bonding with collector again after pulverous active material is bonded together, satisfy the adhesive strength requirement in intensification, shearing and charge and discharge process, and help the comprehensive safety of battery.Compare with traditional secondary cell, lithium ion battery is owing to use the electrode material and the organic electrolyte of reversible embedding of energy and removal lithium embedded ion, requirement to adhesive is also more special, adhesive needs to tolerate the erosion of the big carbonates organic solvent of electrolyte Semi-polarity on the one hand, also answer anticathode tool irreducibility simultaneously, align and have non-oxidizablely, promptly satisfy its stability under electrochemical environment.On the other hand, adhesive should have cushioning effect to the volumetric expansion and the contraction of both positive and negative polarity active material in the charge and discharge process.Because above-mentioned specific (special) requirements makes optional adhesive scope be subjected to very big restriction, also be the focus that lithium ion battery circle is paid close attention to so seek suitable bonding always.
Current in lithium ion battery main type adhesive Kynoar (PVDF) with an organic solvent, solvent is N, dinethylformamide (DMF), N-methylpyrrole cyclic ketones (NMP) etc., the about geometric ratio of the usage ratio of solvent is in the amount of used active material, not only production cost height, recovery cost are big, serious environment pollution, production scene toxicity are big, and also need explosion-proof processing in the coating dry run.On the other hand, owing to contain fluorine among the PVDF, easy and lithium intercalated graphite etc. reacts, and causes the lithium ion battery decreased performance, and the insulation characterisitic of ion and electronics also influenced the performance of battery performance because of PVDF itself.
Compare with solvent type adhesive, characteristics such as water-based adhesives has solvent-free release, meets environmental requirement, and cost is low, does not fire, and is safe in utilization become the important development direction of adhesive industry.Water-based adhesives commonly used at present has phenolic resin type, amino resins type, polyacrylate, rubber-type emulsion glue, ethane-acetic acid ethyenyl ester type etc.Water-based adhesives can be incorporated into and also become the focus that chemical power source circle is in recent years paid close attention in the pole piece coating process of lithium ion battery, but such adhesive generally all contains hydrophilic radical, how eliminating the influence to battery performance of this type of hydrophilic radical and solvent for use water, is its key that is successfully applied to the commercialization lithium ion battery.(Chinese patent, publication number: be CH CN1328102A) such as Zheng Weizhong with general formula
2=CR
1R
2Hydrophilic monomer and the lipophile monomer polyacrylate water-based adhesive that can be applicable to electrodes of lithium-ion batteries coating for the starting polymerization monomer has prepared, can be applicable to the coating of negative pole graphite powder, and to the cycle performance of the battery effect that has some improvement, but because electrode polarization etc. are former thereby be unwell to the coating of positive pole (as cobalt acid lithium).(Electrochimica Acta (2003) 883--889) such as Jernej Drofenik also mainly is that the graphite-like negative pole is suitable for cellulose as aqueous binder.Because good as the graphitic conductive of negative pole, to the requirement of water-based adhesive mostly be pay close attention to adhesion characteristic, coating processing characteristics and adhesive with the negative interaction of hydrophilic radical.And as anodal active material, as cobalt acid lithium, LiMn2O4, LiFePO 4 etc., the poorly conductive of material itself, electron conduction be the conductive agent by adding mainly, wait as graphite, conductive black and to finish, also should consider influence when therefore selecting water-based adhesive the pole piece electric conductivity.
Summary of the invention:
The object of the present invention is to provide a kind of employing to be suitable for the electrode of lithium ion battery of the water-based adhesive of both positive and negative polarity coating and the lithium ion battery that adopts kind electrode.
The present invention also aims to provide a kind of preparation method of lithium ion cell electrode.
The electrode of lithium ion battery of the present invention comprises positive pole and/or negative electrode active material, conductive agent, and adhesive, wherein adhesive is a water-based adhesive; Positive pole and/or negative electrode active material, conductive agent, the percentage by weight of water-based adhesive is followed successively by: 85-98%, 0.5-10%, 1.5-10%.
Water-based adhesive of the present invention adopts following method to make: thickener is mixed with the aqueous solution of 0.5-5.5%, adds the tackifier of 1.0-6.5% and the additive of 0-4.0% and mix.
Described thickener is selected from CMC, EMC, HPMC lithium salts or sodium salt; Tackifier are selected from styrene-butadiene emulsion, benzene emulsion, and additive is selected from soluble silane coupling agents such as vinyl three (beta-methoxy-ethyoxyl) silane, gamma-aminopropyl-triethoxy-silane, N-dimethylamino trimethoxy silane.
Described positive active material is selected from the transition metal oxide or the phosphate of embedding lithium, comprising: phosphate positive electrodes such as the transition metal oxide of embedding lithiums such as cobalt acid lithium, lithium nickelate, LiMn2O4 and LiFePO 4, phosphoric acid vanadium lithium;
Negative pole is selected from modified graphite or MCMB; Described conductive agent is selected from graphite or carbon black, perhaps their mixture, and its mixed weight is than being (1-2): (2-3).
The preparation method of lithium ion cell electrode of the present invention, its step comprises
1, with positive pole and/or negative electrode active material powder, conductive agent, water-based adhesive, 85-98% by weight percentage, 0.5-10% after the ratio batching of 1.5-10%, adds the slurry of water furnishing 4000-12000mPas viscosity;
2, above-mentioned slurry is coated on the two sides of plus plate current-collecting body aluminium foil and/or negative current collector Copper Foil;
3, roll section, obtain electrode plates.
Lithium ion battery of the present invention comprises the both positive and negative polarity pole piece, electrolyte, and barrier film, described both positive and negative polarity pole piece comprises positive pole and/or negative electrode active material, conductive agent, water-based adhesive; Positive pole and/or negative electrode active material, conductive agent, the percentage by weight of water-based adhesive is followed successively by: 85-98%, 0.5-10%, 1.5-10%.
Described electrolyte is that concentration is one mole every liter the organic mixed solvent solution of lithium salts, wherein lithium salts is selected from lithium perchlorate or lithium hexafluoro phosphate, organic solvent is selected from ethylene carbonate, diethyl carbonate, dimethyl carbonate, two kinds of combinations in them, volume ratio is (2: 8)-(8: 2), or their combinations of three kinds, volume ratio is 1: 1: 1; Described barrier film is the high molecular polymer microporous membrane, comprises polypropylene microporous film or polypropylene and poly MULTILAYER COMPOSITE microporous membrane.
With above-mentioned each material according to its functional requirement routinely technology be assembled into the battery of various models, be lithium ion battery of the present invention.
In water-based adhesive prescription of the present invention, use the less relatively rubber-type latax of polar group content as tackifier, crosslinked action by the silane coupling agent that adds is simultaneously strengthening between the powder and between powder and the collector in the bonding effect, also eliminate the influence of active group, avoided the battery capacity loss and the loop attenuation that cause because of adhesive.On the other hand, the lithium salts of cellulosic polymer or sodium salt have higher ionic conductivity, adopt it to be dispersed in the whole slurry with molecular level as thickener, form in the both positive and negative polarity pole piece after coating between the electroactive material particle each other, between electroactive material particle and the conductive agent and and electrolyte between equally distributed thin layer, and strengthened the ionic conductivity of solid liquid interface, can improve the high-rate discharge ability and the cryogenic property of battery.Therefore, the lithium ion battery that the present invention is prepared, binder dosage is few, cost is low, pollution-free in the manufacturing process, prepared pole piece bond properties is good, and the lithium ion battery of assembling has good cycle, discharge voltage plateau height and the good characteristics of low temperature performance.
Make the battery that adhesive does with PVDF and compare, advantage of the present invention is:
(1) Pei Zhi water-based adhesive adhesive property is good, cost is low and environmental friendliness, can be suitable for the coating of lithium ion battery plus-negative plate system simultaneously;
(2) prepared lithium ion battery has excellent cycle performance and good cryogenic property, and the higher voltage platform is arranged in discharge curve, its platform can be in follow-up cyclic process kept stable.
Battery use of the present invention is extensive, comprising: be used for mobile phone, notebook computer, video camera, electric bicycle, electric automobile, electronic toy etc., because of it can be made into the different shape that varies in size, be applicable to and variously use with electrical domain.
Description of drawings:
Fig. 1 presses the cycle performance of battery comparison diagram that embodiment 1 makes: 1, adopt water-based adhesive; 2, with PVDF be adhesive (control group).
Fig. 2 press battery that embodiment 1 makes under-20C temperature by the capacity of different multiplying discharge and normal temperature (25 ℃) battery 0.2C capacity comparison diagram down: curve 1, employing water-based adhesive; Curve 2, be adhesive (control group) with PVDF.
Fig. 3 presses 3.6 volts of voltage platform comparison diagrams of battery that embodiment 3 makes: curve 1, employing water-based adhesive; Curve 2, be adhesive (control group) with PVDF.
Embodiment:
In order to be illustrated more clearly in the present invention, enumerate following examples, but it there is not any restriction to the present invention.
Take by weighing the lithium salts of 40 gram CMC, be dissolved in 1000 ml deionized water, add 80 gram styrene-butadiene emulsions (50% solid content) again, and add 5g vinyl three (beta-methoxy-ethyoxyl) silane coupler, continue to be stirred to into homogeneous system, be water-based adhesive.Prepare electrode then as follows.
Take by weighing 180 gram water-based adhesives, add 10 gram carbon blacks, adding 500 gram composite graphites after stirring, add deionized water and adjust viscosity to 8500mPas, are applied to the Copper Foil two sides by the conventional coating process of battery, and roll extrusion, branch cut into negative plate;
Take by weighing 200 gram water-based adhesives, add 5 gram carbon blacks and 5 gram graphite, add 500 gram LiCoO
2, after stirring, add deionized water and adjust viscosity to 7000mPas, coat the aluminium foil two sides, roll extrusion, branch cut into anode pole piece.
As a comparison, with being dissolved in PVDF among the NMP as adhesive, prepared both positive and negative polarity pole piece routinely, wherein binder dosage accounts for 4.5% of coating amount.
To be dissolved in the 1.0molL in ethyl carbonate+diethyl carbonate (volume ratio 1: 1) mixed solvent
-1LiPF
6Be electrolyte, polypropylene microporous film is a barrier film, be assembled into 063048 rectangular cell, Fig. 1 is the cycle performance comparison of pressing identical subsequent technique institute preparing lithium ion battery respectively with made pole piece of water-based adhesive of the present invention and the made pole piece of conventional P VDF adhesive means, electric current by the 1C multiplying power discharges and recharges, the system of discharging and recharging is: constant current charge to 4.2 volt back is reduced to 20mA at the 4.2V constant voltage charge to electric current, constant-current discharge to 2.75 volt, and system is carried out cyclic test according to this.The battery capacity of doing is 760mAh, circulates 100 times, and capability retention 97.5%, and test capability retention in contrast is 92.0%.Fig. 2 curve be respectively with the made pole piece of water-based adhesive of the present invention and the made pole piece of conventional P VDF adhesive means by identical subsequent technique institute preparing lithium ion battery-20 ℃ the time under different multiplying the capacity during discharge keep figure.The made battery of the present invention under-20 ℃ when 0.2C discharges, battery capacity has kept 91.1%, the 0.5C discharge time has kept 79.1%, 1C has kept 51.3% during discharge; Capability retention when Zu battery discharges under different multiplying in the time of-20 ℃ in contrast is followed successively by 77% (0.2C), and 31% (0.5C) is corresponding discharge-rate in 3% (1C), bracket.
Take by weighing the lithium salts of 5 gram EMC, be dissolved in 1000 ml deionized water, add 130 gram styrene-butadiene emulsions (50% solid content) again, and add 40g gamma-aminopropyl-triethoxy-silane coupling agent, continue to be stirred to into homogeneous system, be water-based adhesive.Prepare electrode then as follows.
Take by weighing 70 gram water-based adhesives, add 3 gram carbon blacks, adding 500 gram composite graphites after stirring, add deionized water and adjust viscosity to 5000mPas, are applied to the Copper Foil two sides by the conventional coating process of battery, and roll extrusion, branch cut into negative plate;
Take by weighing 80 gram water-based adhesives, add 20 gram carbon blacks and 30 gram graphite, add 500 gram LiCoO
2, after stirring, add deionized water and adjust viscosity to 11000mPas, coat the aluminium foil two sides, roll extrusion, branch cut into anode pole piece.
Then by the method assembled battery of embodiment 1 and carry out corresponding test, wherein to be dissolved in the 1.0molL in ethyl carbonate+diethyl carbonate (volume ratio 2: 8) mixed solvent
-1LiPF
6Be electrolyte.The capacity of made battery is 775mAh, circulates 100 times, and it is 48% of normal temperature 0.2C capacity by 1C multiplying power discharging capacity that capacity keeps 94.5% ,-20 ℃.
Embodiment 3
Take by weighing the lithium salts of 110 gram HPMC, be dissolved in 2000 ml deionized water, add 40 gram propyl benzene emulsions (50% solid content) again, 20 gram N-dimethylamino trimethoxy silanes continue to be stirred to into homogeneous system, are water-based adhesive.Prepare electrode then as follows.
Take by weighing 800 gram water-based adhesives, add 3 gram carbon blacks, adding 500 gram MCMB after stirring, add deionized water and adjust viscosity to 10000mPas, are applied to the Copper Foil two sides by the conventional coating process of battery, and roll extrusion, branch cut into negative plate;
Take by weighing 450 gram water-based adhesives, add 20 gram carbon blacks and 10 gram graphite, add 500 gram LiCoO
2, after stirring, add deionized water and adjust viscosity to 9000mPas, coat the aluminium foil two sides, roll extrusion, branch cut into anode pole piece.
Then by the method assembled battery of embodiment 1 and carry out corresponding test, wherein to be dissolved in the 1.0molL in ethyl carbonate+diethyl carbonate (volume ratio 8: 2) mixed solvent
-1LiPF
6Be electrolyte.The capacity of made battery is 750mAh, circulates 100 times, and it is 45% of normal temperature 0.2C capacity by 1C multiplying power discharging capacity that capacity keeps 94% ,-20 ℃.
Embodiment 4
Tackifier are styrene-acrylic latex in the water-based adhesive, each amounts of components and all the other correlation step are all by the method for embodiment 1, the battery capacity that is assembled into is 750mAh, circulate 100 times, capacity keeps 97%, Fig. 3 is 3.6 volts of voltage platform comparison diagrams of made battery of this example and control group battery, and wherein curve 1 is the situation of change of the pairing discharge capacity of the cell of average working voltage 3.6V and total discharge capacity ratio in the battery cyclic process, and curve 2 is the situation of control group.
Embodiment 5
Thickener is used the sodium salt of CMC instead, and all the other steps are prepared into water-based adhesive and are assembled into respective battery all by example 1, and battery capacity is 775mAh, circulates 100 times, and it is 46% of normal temperature 0.2C capacity by 1C multiplying power discharging capacity that capacity keeps 96.8% ,-20 ℃.
Embodiment 6
Method by example 1 prepares the composite graphite electrode as negative pole, the anodal spinel lithium manganate that adopts, method assembled battery according to embodiment 1, battery capacity is 708mAh (696mAh), circulate 100 times, capability retention is 97% (89%), and the corresponding capacity of the 3.7V platform that discharges first accounts for 88% (87%) of total capacity, after 100 circulations, the corresponding capacity of 3.7V platform accounts for 84% (71%) of total capacity.Numerical value in the bracket is to be the data of the control group battery of adhesive with PVDF.
Embodiment 7
The anodal LiFePO 4 that adopts, all by the method for embodiment 1, the battery capacity of being assembled is 652mAh (438mAh) for all the other, capability retention is 96.3% (91.4%) after 100 circulations.Numerical value in the bracket is to be the data of the control group battery of adhesive with PVDF.
Claims (8)
1, a kind of electrode of lithium ion battery comprises positive pole and/or negative electrode active material, conductive agent, and adhesive is characterized in that described adhesive is a water-based adhesive; Positive pole and/or negative electrode active material, conductive agent, the percentage by weight of water-based adhesive is followed successively by: 85-98%, 0.5-10%, 1.5-10%.
2, the electrode of lithium ion battery as claimed in claim 1 is characterized in that described water-based adhesive adopts subordinate's method to make: thickener is mixed with the aqueous solution of 0.5-5.5%, adds the tackifier of 1.0-6.5% and the additive of 0-4.0% and mix.
3, the electrode of lithium ion battery as claimed in claim 2 is characterized in that described thickener is selected from CMC, EMC, HPMC lithium salts or sodium salt; Tackifier are selected from styrene-butadiene emulsion, benzene emulsion, and additive is selected from soluble silane coupling agents such as vinyl three (beta-methoxy-ethyoxyl) silane, gamma-aminopropyl-triethoxy-silane, N-dimethylamino trimethoxy silane.
4, the electrode of lithium ion battery as claimed in claim 1 is characterized in that described positive active material is selected from the transition metal oxide or the phosphate of embedding lithium; Negative pole is selected from modified graphite or MCMB; Described conductive agent is selected from graphite or carbon black, perhaps their mixture.
5, each method of a kind of system of lithium ion cell electrode, its step comprises
1) with positive pole and/or negative electrode active material powder, conductive agent, water-based adhesive, 85-98% by weight percentage, 0.5-10% after the ratio batching of 1.5-10%, adds the slurry of water furnishing 4000-12000mPa.s viscosity;
2) above-mentioned slurry is coated on the two sides of plus plate current-collecting body aluminium foil and/or negative current collector Copper Foil;
3) roll section, obtain electrode plates.
6, a kind of lithium ion battery comprises the both positive and negative polarity pole piece, electrolyte, and barrier film is characterized in that described both positive and negative polarity pole piece comprises positive pole and/or negative electrode active material, conductive agent, water-based adhesive; Positive pole and/or negative electrode active material, conductive agent, the percentage by weight of water-based adhesive is followed successively by: 85-98%, 0.5-10%, 1.5-10%.
7, lithium ion battery as claimed in claim 6 is characterized in that described water-based adhesive adopts following method to make: thickener is mixed with the aqueous solution of 0.5-5.5%, adds the tackifier of 1.0-6.5% and the additive of 0-4.0% and mix; Described thickener is selected from CMC, EMC, HPMC lithium salts or sodium salt; Tackifier are selected from styrene-butadiene emulsion, benzene emulsion, and additive is selected from soluble silane coupling agents such as vinyl three (beta-methoxy-ethyoxyl) silane, gamma-aminopropyl-triethoxy-silane, N-dimethylamino trimethoxy silane.
8, lithium ion battery as claimed in claim 6, it is characterized in that described electrolyte is that concentration is one mole every liter the organic mixed solvent solution of lithium salts, wherein lithium salts is selected from lithium perchlorate or lithium hexafluoro phosphate, organic solvent is selected from one of ethylene carbonate, diethyl carbonate, dimethyl carbonate, or two kinds of combinations in them, volume ratio is (2: 8)-(8: 2), or their combinations of three kinds, and volume ratio is 1: 1: 1; Described barrier film is the high molecular polymer microporous membrane, comprises polypropylene microporous film or polypropylene and poly MULTILAYER COMPOSITE microporous membrane.
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