CN102437369B - Lithium ion battery - Google Patents
Lithium ion battery Download PDFInfo
- Publication number
- CN102437369B CN102437369B CN201110428152.8A CN201110428152A CN102437369B CN 102437369 B CN102437369 B CN 102437369B CN 201110428152 A CN201110428152 A CN 201110428152A CN 102437369 B CN102437369 B CN 102437369B
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- China
- Prior art keywords
- lithium ion
- ion battery
- water
- active material
- weight
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- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 81
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 239000006258 conductive agent Substances 0.000 claims abstract description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 84
- 239000011230 binding agent Substances 0.000 claims description 63
- 239000000203 mixture Substances 0.000 claims description 52
- 150000001875 compounds Chemical class 0.000 claims description 50
- 239000007774 positive electrode material Substances 0.000 claims description 46
- 239000003232 water-soluble binding agent Substances 0.000 claims description 43
- 239000008367 deionised water Substances 0.000 claims description 36
- 229910021641 deionized water Inorganic materials 0.000 claims description 36
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 35
- -1 siloxanes Chemical class 0.000 claims description 31
- 239000002562 thickening agent Substances 0.000 claims description 30
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 29
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 26
- 239000003792 electrolyte Substances 0.000 claims description 26
- 239000003607 modifier Substances 0.000 claims description 22
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 21
- 239000003292 glue Substances 0.000 claims description 21
- 239000010439 graphite Substances 0.000 claims description 18
- 229910002804 graphite Inorganic materials 0.000 claims description 18
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 12
- 239000002202 Polyethylene glycol Substances 0.000 claims description 12
- 229910052744 lithium Inorganic materials 0.000 claims description 12
- 239000012528 membrane Substances 0.000 claims description 12
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-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
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 10
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 claims description 10
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 claims description 10
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 claims description 10
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 10
- 150000003384 small molecules Chemical group 0.000 claims description 10
- 229920002125 Sokalan® Polymers 0.000 claims description 9
- 239000004584 polyacrylic acid Substances 0.000 claims description 9
- 229920002689 polyvinyl acetate Polymers 0.000 claims description 9
- 239000011118 polyvinyl acetate Substances 0.000 claims description 9
- 229920001223 polyethylene glycol Polymers 0.000 claims description 8
- 239000006230 acetylene black Substances 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical class C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 6
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 claims description 6
- 239000004354 Hydroxyethyl cellulose Substances 0.000 claims description 6
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 claims description 6
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 claims description 6
- 239000001863 hydroxypropyl cellulose Substances 0.000 claims description 6
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 claims description 6
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 claims description 6
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 claims description 5
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims description 5
- 125000001340 2-chloroethyl group Chemical class [H]C([H])(Cl)C([H])([H])* 0.000 claims description 5
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 claims description 5
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 5
- 239000004593 Epoxy Substances 0.000 claims description 5
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 5
- 150000004645 aluminates Chemical class 0.000 claims description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 5
- 229920001400 block copolymer Polymers 0.000 claims description 5
- 239000004917 carbon fiber Substances 0.000 claims description 5
- 229910021385 hard carbon Inorganic materials 0.000 claims description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 5
- 239000004800 polyvinyl chloride Substances 0.000 claims description 5
- 239000011347 resin Substances 0.000 claims description 5
- 229920005989 resin Polymers 0.000 claims description 5
- 238000007789 sealing Methods 0.000 claims description 5
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims 1
- 229920003123 carboxymethyl cellulose sodium Polymers 0.000 claims 1
- 229940063834 carboxymethylcellulose sodium Drugs 0.000 claims 1
- 125000004386 diacrylate group Chemical group 0.000 claims 1
- 229920002239 polyacrylonitrile Polymers 0.000 claims 1
- 229920000915 polyvinyl chloride Polymers 0.000 claims 1
- 239000000853 adhesive Substances 0.000 abstract description 16
- 230000001070 adhesive effect Effects 0.000 abstract description 16
- 239000002131 composite material Substances 0.000 abstract description 12
- 238000004519 manufacturing process Methods 0.000 abstract description 12
- 239000000463 material Substances 0.000 abstract description 6
- 238000002788 crimping Methods 0.000 abstract description 4
- 230000007547 defect Effects 0.000 abstract description 3
- 239000013543 active substance Substances 0.000 abstract 2
- 238000005336 cracking Methods 0.000 abstract 1
- 238000000034 method Methods 0.000 description 66
- 238000002360 preparation method Methods 0.000 description 37
- 239000000243 solution Substances 0.000 description 37
- 239000004698 Polyethylene Substances 0.000 description 33
- 229920001577 copolymer Polymers 0.000 description 24
- 229920000573 polyethylene Polymers 0.000 description 24
- 150000002825 nitriles Chemical class 0.000 description 23
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 20
- 239000004926 polymethyl methacrylate Substances 0.000 description 20
- 238000003756 stirring Methods 0.000 description 19
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 17
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 17
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 12
- 239000007767 bonding agent Substances 0.000 description 12
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 12
- 239000006245 Carbon black Super-P Substances 0.000 description 10
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 7
- 239000011149 active material Substances 0.000 description 7
- 230000004888 barrier function Effects 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 7
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- 229910013870 LiPF 6 Inorganic materials 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 239000004743 Polypropylene Substances 0.000 description 6
- 239000005030 aluminium foil Substances 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 239000011889 copper foil Substances 0.000 description 6
- 239000007770 graphite material Substances 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 5
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 102220043159 rs587780996 Human genes 0.000 description 5
- 229910015645 LiMn Inorganic materials 0.000 description 4
- 239000001768 carboxy methyl cellulose Substances 0.000 description 4
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 239000002033 PVDF binder Substances 0.000 description 3
- 230000004087 circulation Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 description 2
- 229960001760 dimethyl sulfoxide Drugs 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Chemical compound [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 description 2
- 229920000609 methyl cellulose Polymers 0.000 description 2
- 239000001923 methylcellulose Substances 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
- 229910015014 LiNiCoAlO Inorganic materials 0.000 description 1
- 229910013210 LiNiMnCoO Inorganic materials 0.000 description 1
- 229910013290 LiNiO 2 Inorganic materials 0.000 description 1
- OHLUUHNLEMFGTQ-UHFFFAOYSA-N N-methylacetamide Chemical compound CNC(C)=O OHLUUHNLEMFGTQ-UHFFFAOYSA-N 0.000 description 1
- ORJLWVJIEZZMSJ-UHFFFAOYSA-N N=[S+]F.[Li] Chemical compound N=[S+]F.[Li] ORJLWVJIEZZMSJ-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- NOJZFGZMTUAHLD-UHFFFAOYSA-N [Li].[Cl] Chemical compound [Li].[Cl] NOJZFGZMTUAHLD-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000000994 depressogenic effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- BDUPRNVPXOHWIL-UHFFFAOYSA-N dimethyl sulfite Chemical compound COS(=O)OC BDUPRNVPXOHWIL-UHFFFAOYSA-N 0.000 description 1
- VUPKGFBOKBGHFZ-UHFFFAOYSA-N dipropyl carbonate Chemical compound CCCOC(=O)OCCC VUPKGFBOKBGHFZ-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229940116007 ferrous phosphate Drugs 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910000155 iron(II) phosphate Inorganic materials 0.000 description 1
- SDEKDNPYZOERBP-UHFFFAOYSA-H iron(ii) phosphate Chemical compound [Fe+2].[Fe+2].[Fe+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O SDEKDNPYZOERBP-UHFFFAOYSA-H 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- YQNQTEBHHUSESQ-UHFFFAOYSA-N lithium aluminate Chemical compound [Li+].[O-][Al]=O YQNQTEBHHUSESQ-UHFFFAOYSA-N 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- WDGKXRCNMKPDSD-UHFFFAOYSA-N lithium;trifluoromethanesulfonic acid Chemical compound [Li].OS(=O)(=O)C(F)(F)F WDGKXRCNMKPDSD-UHFFFAOYSA-N 0.000 description 1
- KKQAVHGECIBFRQ-UHFFFAOYSA-N methyl propyl carbonate Chemical compound CCCOC(=O)OC KKQAVHGECIBFRQ-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 150000002895 organic esters Chemical class 0.000 description 1
- 125000005003 perfluorobutyl group Chemical group FC(F)(F)C(F)(F)C(F)(F)C(F)(F)* 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- 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
Landscapes
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to a lithium ion battery, belonging to the field of lithium ion batteries. In the manufacture of the battery, a composite water-soluble adhesive is used as an adhesive; the adhesive comprises the following components in percentage by weight: 10-40% of amorphous statepolyoxyethylene water-soluble adhesive and 60-90% of gel-type water-soluble adhesive; the amorphous statepolyoxyethylene water-soluble adhesive in the composite water-soluble adhesive has high flexibility, and the flexibility of a pole piece is improved, so that defects of material falling, cracking, crimping, chipping and the like occurring during the manufacture of poles can be reduced, and scale production can be performed favorably. The gel-type water-soluble adhesive has good cohesiveness and stability; the contacts between active substances and conductive agents and between active substances and current collectors are improved; and internal resistance of the battery is reduced. Therefore the composite water-soluble adhesive mentioned in the invention, positive poles containing the adhesive and lithium ion batteries using the composite water-soluble adhesive positive poles all have the advantages of high capacity and long service life.
Description
Technical field
The present invention relates to a kind of lithium ion battery, belong to lithium ion battery field.
Background technology
Compared with other chemical power source, lithium rechargeable battery has the performance of many excellences, as high in energy density, have extended cycle life, open circuit voltage is high, memory-less effect, safety non-pollution etc., through the develop rapidly of recent two decades, be applied in widely the fields such as mobile phone, notebook computer, digital camera.In recent years along with the development of electric automobile, in the urgent need to more high-energy-density and the more vehicle-mounted electrical source of power of high power density, lithium ion battery is the most potential chemical power source that is applied to electric automobile of generally acknowledging.The energy density and the power density that improve chemical cell have two kinds of methods, and the one, the active material of employing high specific energy; The 2nd, improve the content of the active material in battery by improving technique.
In the manufacturing process of lithium ion battery, must complete with suitable binding agent the preparation of electrode, binding agent in battery, be mainly active material is bonded to each other with electrode current collecting body together with.At present, lithium ion cell positive mostly adopts Kynoar (PVDF) as binding agent, if N-dimethyl pyrrolidone (NMP), dimethyl formamide (DMF), dimethyl sulfoxide (DMSO) (DMSO) etc. are as the solvent of PVDF, adopt organic system coating film-making with the organic compound of strong polarity.The organic solvent that adopts when this system coating film-making is expensive and have corrosivity, and use amount is large and be difficult to reclaim, and production cost is large; And coating film-making process need removes organic solvent heating volatilization, for preventing the corrosivity organic solvent contaminated environment of volatilizing arbitrarily, must install a large amount of environmental protection equipments additional, increase equally production cost and be unfavorable for production operation; More disadvantageously in organic system, PVDF consumption of binder is larger, too much binder component not only reduces the specific capacity of battery, and affect smoothness and the baking property of pole coating, a large amount of binding agents is coated on the surface of active particle in addition, will increase the contact impedance of particle, the polarization that increases battery charging and discharging, therefore seriously restrict the lifting of battery specific power, especially outstanding for the performance of nano level active material.Be 03144276.5 as State Intellectual Property Office discloses an application number in 2005.3.23, name is called the patent of invention of " manufacture method of corrosion-resistance electrode for battery ", it provides a kind of manufacture method of corrosion-resistance electrode for battery, main processes: by crosslinking agent, initator and organic solvent are mixed into the clear solution containing crosslinked Kynoar and uncrosslinked polyethylene glycol oxide, with electrode active material, conductive agent stirs into viscous paste, be coated on collector and heat, being depressed into thickness is the crosslinked electrode for the treatment of of 0.05～0.5mm, be placed on again in the constant temperature oven of 90～400 DEG C, after 5 minutes～6 hours, naturally cool to constant temperature, after taking-up, be corrosion-resistance electrode for battery.The bonding agent that Kynoar and polyethylene glycol oxide mix is wherein disclosed, there is following defect: first, in electrode, contain the initator of some, in charge and discharge process, initator can resolve into micromolecular material, certainly will cause the sharply deterioration of battery performance; Finally, this hybrid adhesive still need to dissolve in organic solvent, therefore, in slurrying and coating process, not only produces a large amount of organic exhaust gas waste liquids, and greatly increases battery production cost.
Therefore, positive pole of low cost, pollution-free, low content binding agent and preparation method thereof becomes study hotspot.At present, more feasible is water-soluble binder and water system coating film-making.Be characterized in: adopt water miscible binding agent, therefore can adopt the liquid medium of water as slurry.But in existing water system positive pole, water-soluble binder adopts butadiene-styrene rubber (SBR) more.The cohesive force of SBR a little less than, and along with battery charging and discharging circulation, constantly degraded and losing efficacy of the carbon-to-carbon double bond in SBR molecule, finally cause battery active material bonding not firm, fall material, cause capacity and cycle life to decline; In addition in water system coating process, because caking property is bad and stress distribution inequality, pole piece baking process in very easily there is falling the phenomenons such as material, be full of cracks, crimping, chip, have a strong impact on normally carrying out of production, and the battery capacity making and cycle performance on the low side.
Summary of the invention
The object of the invention is to solve the bad adhesion of preparing the water-soluble binder of lithium ion battery in prior art, easily degrade, cause battery capacity and the problem such as cycle performance is poor, a kind of low cost, high power capacity and long-life lithium ion battery are provided.
In order to realize foregoing invention object, technical scheme of the present invention is as follows:
(1)for the preparation of a compound water-soluble binder for lithium battery, comprise following component by weight percentage:
Amorphous poly ethylene oxide water soluble adhesive 10～40%
Gel-type water-soluble binder 60～90%.
Preferred:
Amorphous poly ethylene oxide class water-soluble binder 20～30%
Gel-type water-soluble binder 70～80%.
Said two devices mixed dissolution forms compound water-soluble binder;
Amorphous poly ethylene oxide class water-soluble binder of the present invention refers to the block copolymer that inserts small molecule structure unit and form on polyethylene glycol oxide (PEO) strand
Above-mentioned small molecule structure mainly comprises the several of a kind of or arbitrary proportion in sub-methoxyl group, epoxy chloroethanes, siloxanes, phosphoric acid resin and Aluminate.
Gel-type water-soluble binder of the present invention refers to that the binding agent that has better toughness and can form gel is the several of a kind of or arbitrary proportion in polyethylene nitrile (PAN), polyvinyl chloride (PVC), polyvinyl acetate (PVAC), polyacrylic acid glycol ester (PEGDA), polymethyl methacrylate (PMMA).
Above-mentioned preferably polyethylene nitrile (PAN) or polymethyl methacrylate (PMMA).
(2)a kind of employing
(1)in the lithium ion cell positive made of the composite water-soluble bonding agent that provides, comprise collector and load on the lithium ion battery anode glue size on collector, described lithium ion battery anode glue size comprises positive active material, conductive agent, thickener, compound water-soluble binder, deionized water.
Above-mentioned each component is taking the weight of positive active material as benchmark:
The content of conductive agent be positive active material weight 0.5～10%, preferably 3～8%;
The content of thickener be positive active material weight 0.5～5%, preferably 1～3%;
The content of compound water-soluble binder be positive active material weight 0.5～10%, preferably 2～6%;
The content of deionized water be positive active material weight 40～150%, preferably 50～80%.
The preparation method of lithium ion battery anode glue size of the present invention is technology known in those skilled in the art, mixes by positive active material, conductive agent, compound water-soluble binder, thickener and water.
Positive active material of the present invention is: LiCoO
2, LiFePO
4, LiNiO
2, LiNiCoAlO
2, LiMn
2o
4and LiNiMnCoO
2in a kind of or arbitrary proportion several, preferably LiFePO
4or LiMn
2o
4.
Conductive agent of the present invention is: a kind of or arbitrary proportion in carbon black, acetylene black, carbon fiber, flake graphite several, under preferable case, contain flake graphite.
Thickener of the present invention is: carboxymethyl cellulose is received (CMC), a kind of or arbitrary proportion in hydroxyethylcellulose (HEC), hydroxypropyl methylcellulose (HPMC), hydroxypropyl cellulose (HPC), methylcellulose (MC) and polyacrylic acid several.
Lithium ion battery anode glue size of the present invention also contains surface tension modifier, and this surface tension modifier is the mixture of alcohol or ether or both arbitrary proportions.
The content of above-mentioned surface tension modifier is: taking the weight of positive active material as benchmark, and 5～40% of the weight that its content is positive active material, preferably 10～20%.
Above-mentioned alcohol is the several of a kind of or arbitrary proportion in ethanol, ethylene glycol, butanols and propyl alcohol.
Above-mentioned ether is the several of a kind of or arbitrary proportion in ethylene glycol ethyl ether, butyl glycol ether and n-butyl ether.
Above-mentioned a kind of lithium ion cell positive, preparation method is technology known in those skilled in the art, is evenly coated on collector by lithium ion battery anode glue size, thickness is 50～200 microns; Baking is removed moisture and is made positive pole again, and baking temperature is 80～120 degree, time 3min～30min.
(3)a kind of lithium ion battery, this lithium ion battery comprises battery case, pole piece and electrolyte, described pole piece and electrolyte sealing are contained in battery case, and described pole piece comprises positive pole, negative pole and the membrane layer between positive pole and negative pole, it is characterized in that: described just very the present invention
(2)in the employing that provides
(1)in the positive pole made of composite water-soluble bonding agent.
Membrane layer of the present invention is polypropylene micro-porous film (PP), microporous polyethylene film (PE), glass mat or PP/PE/PP, and preferred, described barrier film is PP/PE/PP.
Negative pole of the present invention is by negative electrode active material, and as Delanium, native graphite, agraphitic carbon, hard carbon or lithium titanate are evenly coated on collector, thickness is 50～200 microns, and preferred, described negative electrode active material is Delanium or native graphite.
Electrolyte of the present invention contains lithium salts and nonaqueous solvents, and described lithium salts is the several of a kind of or arbitrary proportion in lithium hexafluoro phosphate, LiBF4, hexafluoroarsenate lithium, lithium perchlorate, trifluoromethyl sulfonic acid lithium, perfluoro butyl Sulfonic Lithium, lithium aluminate, chlorine lithium aluminate, fluoro sulfimide lithium, lithium chloride and lithium iodide; Described nonaqueous solvents can be gamma-butyrolacton, methyl ethyl carbonate, methyl propyl carbonate, dipropyl carbonate, acid anhydrides, N-METHYLFORMAMIDE, N-methylacetamide, acetonitrile, sulfolane, methyl-sulfoxide, dimethyl sulfite and other is fluorine-containing, a kind of or arbitrary proportion in the ring-type organic ester of sulfur-bearing or unsaturated bond several.
The concentration of lithium salts of the present invention in electrolyte is 0.5～2.0 mol/L, is preferably 0.8～1.2 mol/L.
Beneficial effect of the present invention is as follows:
Amorphous poly ethylene oxide molecules chain in the compound water-soluble binder of the present invention has height compliance, has improved the pliability of pole piece, therefore can reduce in electrode manufacture process and occur falling the defects such as material, be full of cracks, crimping and chip being conducive to large-scale production; Gel-type water-soluble binder has good caking property and stability, improves battery contact between active material and conductive agent, active material and collector in charge and discharge process, has reduced the internal resistance of battery.Therefore adopt compound water-soluble binder of the present invention, contain the anodal of this binding agent and adopt the lithium ion battery that contains compound water-soluble binder positive pole all to there is high power capacity and long-life advantage.
Lithium ion battery anode glue size of the present invention also contains surface tension modifier, can reduce the surface tension of water system anode sizing agent, edge-curl phenomenon be can alleviate better, and capacity and the cycle performance of the battery of anodal composition obtained by this method further improved.
Embodiment
embodiment 1
Compound Water dissolubility binder solution: by the methylene ethylene oxide copolymer (-(CH of 40% weight
2(OCH
2cH
2)
m)
n-) and the polyethylene nitrile (PAN) of 60% weight be dissolved in deionized water after evenly mixing, form Compound Water dissolubility binder solution.Its quality proportioning is methylene ethylene oxide copolymer: polyethylene nitrile: deionized water=4:6:30.
Positive electrode composition: first thickener CMC is made into the aqueous solution of 4% weight, is uniformly mixed 1.5h with conductive agent Super-P and flake graphite KS-6, then add nanometer LiFePO
4carry out (D50=120nm) and mix fully, stir 3h, then add the Compound Water dissolubility binder solution of 40% weight, fully stir 1h, finally add the ethanol water of 20% weight to stir 30min, obtain water system positive pole, it consists of LiFePO
4: conductive agent (Super-P/KS-6/=3/1): CMC: binding agent (methylene ethylene oxide copolymer/polyethylene nitrile=4/6): ethanol: deionized water=100:4:1:2:20:110
Anodal: by the one side dressing on the aluminium foil of 16 microns of the positive electrode composition of above-mentioned preparation; Under 90 DEG C of conditions, vacuum bakeout 3.5h(vacuum degree is-90kPa), roll, cut into slices; The energy density of gained positive pole is 1.0mAh/cm
2.
Negative pole: prepare cathode size one side dressing on the Copper Foil of 12 microns with graphite material, vacuum bakeout 3.5h(vacuum degree is-90kPa under 90 DEG C of conditions), roll, cut into slices; The energy density of gained negative pole is 1.4mAh/cm
2.
Lithium ion battery: with the prepared positive pole of said method and negative pole, the PE perforated membrane of 20 microns is barrier film, 1M LiPF
6dimethyl carbonate (DMC)/methyl ethyl carbonate (EMC)/vinyl carbonate (EC) (volume ratio 1/1/1) solution as electrolyte, in humidity-controlled glove box, prepare button cell.
contrast preparation A:
Compound Water dissolubility binder solution: binding agent is single methylene ethylene oxide copolymer.
Positive electrode composition: prepare according to the method described above positive electrode composition.
Anodal: preparation is anodal according to the method described above.
Negative pole: prepare according to the method described above negative pole
Lithium ion battery: prepare according to the method described above lithium ion battery.
contrast preparation B:
Compound Water dissolubility binder solution: binding agent is single polyethylene nitrile (PAN).
Positive electrode composition: prepare according to the method described above positive electrode composition.
Anodal: preparation is anodal according to the method described above.
Negative pole: prepare according to the method described above negative pole
Lithium ion battery: prepare according to the method described above lithium ion battery.
embodiment 2
Compound Water dissolubility binder solution: by the methylene ethylene oxide copolymer (-(CH of 10% weight
2(OCH
2cH
2)
m)
n-) and the polyethylene nitrile (PAN) of 90% weight be dissolved in deionized water after evenly mixing, form Compound Water dissolubility binder solution.Its quality proportioning is methylene ethylene oxide copolymer: polyethylene nitrile: deionized water=1:9:30.
Positive electrode composition: first thickener CMC is made into the aqueous solution of 4% weight, is uniformly mixed 1.5h with conductive agent Super-P and flake graphite KS-6, then add nanometer LiFePO
4carry out (D50=120nm) and mix fully, stir 3h, then add the Compound Water dissolubility binder solution of 40% weight, fully stir 1h, finally add the ethanol water of 20% weight to stir 30min, obtain water system positive pole, it consists of LiFePO
4: conductive agent (Super-P/KS-6/=3/1): CMC: binding agent (methylene ethylene oxide copolymer/polyethylene nitrile=1/9): ethanol: deionized water=100:4:1:2:20:110
Anodal: by the one side dressing on the aluminium foil of 16 microns of the positive electrode composition of above-mentioned preparation; Under 90 DEG C of conditions, vacuum bakeout 3.5h(vacuum degree is-90kPa), roll, cut into slices; The energy density of gained positive pole is 1.0mAh/cm
2.
Negative pole: prepare cathode size one side dressing on the Copper Foil of 12 microns with graphite material, vacuum bakeout 3.5h(vacuum degree is-90kPa under 90 DEG C of conditions), roll, cut into slices; The energy density of gained negative pole is 1.4mAh/cm
2.
Lithium ion battery: with the prepared positive pole of said method and negative pole, the PE perforated membrane of 20 microns is barrier film, 1M LiPF
6dimethyl carbonate (DMC)/methyl ethyl carbonate (EMC)/vinyl carbonate (EC) (volume ratio 1/1/1) solution as electrolyte, in humidity-controlled glove box, prepare button cell.
contrast preparation A:
Compound Water dissolubility binder solution: binding agent is single methylene ethylene oxide copolymer.
Positive electrode composition: prepare according to the method described above positive electrode composition.
Anodal: preparation is anodal according to the method described above.
Negative pole: prepare according to the method described above negative pole
Lithium ion battery: prepare according to the method described above lithium ion battery.
contrast preparation B:
Compound Water dissolubility binder solution: binding agent is single polyethylene nitrile (PAN).
Positive electrode composition: prepare according to the method described above positive electrode composition.
Anodal: preparation is anodal according to the method described above.
Negative pole: prepare according to the method described above negative pole
Lithium ion battery: prepare according to the method described above lithium ion battery.
embodiment 3
Compound Water dissolubility binder solution: by the dimethyl siloxane-ethylene oxide copolymer of 10% weight (-((CH
3)
2(SiOOCH
2cH
2)
m)
n-) and the polyethylene nitrile (PAN) of 90% weight be dissolved in deionized water after evenly mixing, form Compound Water dissolubility binder solution.Its quality proportioning is dimethyl siloxane-ethylene oxide copolymer: polyethylene nitrile: deionized water=1:9:30.
Positive electrode composition: first thickener CMC is made into the aqueous solution of 4% weight, is uniformly mixed 1.5h with conductive agent Super-P and flake graphite KS-6, then add nanometer LiFePO
4carry out (D50=120nm) and mix fully, stir 3h, then add the Compound Water dissolubility binder solution of 40% weight, fully stir 1h, finally add the ethanol water of 20% weight to stir 30min, obtain water system positive pole, it consists of LiFePO
4: conductive agent (Super-P/KS-6/=3/1): CMC: binding agent (dimethyl siloxane-ethylene oxide copolymer/polyethylene nitrile=1/9): ethanol: deionized water=100:4:1:2:20:110
Anodal: by the one side dressing on the aluminium foil of 16 microns of the positive electrode composition of above-mentioned preparation; Under 90 DEG C of conditions, vacuum bakeout 3.5h(vacuum degree is-90kPa), roll, cut into slices; The energy density of gained positive pole is 1.0mAh/cm
2.
Negative pole: prepare cathode size one side dressing on the Copper Foil of 12 microns with graphite material, vacuum bakeout 3.5h(vacuum degree is-90kPa under 90 DEG C of conditions), roll, cut into slices; The energy density of gained negative pole is 1.4mAh/cm
2.
Lithium ion battery: with the prepared positive pole of said method and negative pole, the PE perforated membrane of 20 microns is barrier film, 1M LiPF
6dimethyl carbonate (DMC)/methyl ethyl carbonate (EMC)/vinyl carbonate (EC) (volume ratio 1/1/1) solution as electrolyte, in humidity-controlled glove box, prepare button cell.
contrast preparation A:
Compound Water dissolubility binder solution: binding agent is single dimethyl siloxane-ethylene oxide copolymer.
Positive electrode composition: prepare according to the method described above positive electrode composition.
Anodal: preparation is anodal according to the method described above.
Negative pole: prepare according to the method described above negative pole
Lithium ion battery: prepare according to the method described above lithium ion battery.
contrast preparation B:
Compound Water dissolubility binder solution: binding agent is single polyethylene nitrile (PAN).
Positive electrode composition: prepare according to the method described above positive electrode composition.
Anodal: preparation is anodal according to the method described above.
Negative pole: prepare according to the method described above negative pole
Lithium ion battery: prepare according to the method described above lithium ion battery.
embodiment 4
Compound Water dissolubility binder solution: by the dimethyl siloxane-ethylene oxide copolymer of 10% weight (-((CH
3)
2(SiOOCH
2cH
2)
m)
n-) and the polymethyl methacrylate (PMMA) of 90% weight be dissolved in deionized water after evenly mixing, form Compound Water dissolubility binder solution.Its quality proportioning is dimethyl siloxane-ethylene oxide copolymer: polyethylene nitrile: deionized water=1:9:30.
Positive electrode composition: first thickener CMC is made into the aqueous solution of 4% weight, is uniformly mixed 1.5h with conductive agent Super-P and flake graphite KS-6, then add nanometer LiFePO
4carry out (D50=120nm) and mix fully, stir 3h, then add the Compound Water dissolubility binder solution of 40% weight, fully stir 1h, finally add the ethanol water of 20% weight to stir 30min, obtain water system positive pole, it consists of LiFePO
4: conductive agent (Super-P/KS-6/=3/1): CMC: binding agent (dimethyl siloxane-ethylene oxide copolymer/polymethyl methacrylate=1/9): ethanol: deionized water=100:4:1:2:20:110
Anodal: by the one side dressing on the aluminium foil of 16 microns of the positive electrode composition of above-mentioned preparation; Under 90 DEG C of conditions, vacuum bakeout 3.5h(vacuum degree is-90kPa), roll, cut into slices; The energy density of gained positive pole is 1.0mAh/cm
2.
Negative pole: prepare cathode size one side dressing on the Copper Foil of 12 microns with graphite material, vacuum bakeout 3.5h(vacuum degree is-90kPa under 90 DEG C of conditions), roll, cut into slices; The energy density of gained negative pole is 1.4mAh/cm
2.
Lithium ion battery: with the prepared positive pole of said method and negative pole, the PE perforated membrane of 20 microns is barrier film, 1M LiPF
6dimethyl carbonate (DMC)/methyl ethyl carbonate (EMC)/vinyl carbonate (EC) (volume ratio 1/1/1) solution as electrolyte, in humidity-controlled glove box, prepare button cell.
contrast preparation A:
Compound Water dissolubility binder solution: binding agent is single dimethyl siloxane-ethylene oxide copolymer.
Positive electrode composition: prepare according to the method described above positive electrode composition.
Anodal: preparation is anodal according to the method described above.
Negative pole: prepare according to the method described above negative pole
Lithium ion battery: prepare according to the method described above lithium ion battery.
contrast preparation B:
Compound Water dissolubility binder solution: binding agent is single polymethyl methacrylate (PMMA).
Positive electrode composition: prepare according to the method described above positive electrode composition.
Anodal: preparation is anodal according to the method described above.
Negative pole: prepare according to the method described above negative pole
Lithium ion battery: prepare according to the method described above lithium ion battery.
embodiment 5
Compound Water dissolubility binder solution: by the methylene ethylene oxide copolymer (-(CH of 10% weight
2(OCH
2cH
2)
m)
n-) and the polyethylene nitrile (PAN) of 90% weight be dissolved in deionized water after evenly mixing, form Compound Water dissolubility binder solution.Its quality proportioning is methylene ethylene oxide copolymer: polyethylene nitrile: deionized water=1:9:30.
Positive electrode composition: first thickener CMC is made into the aqueous solution of 4% weight, is uniformly mixed 1.5h with conductive agent Super-P and flake graphite KS-6, then add LiMn
2o
4mix fully, stir 3h, then add the Compound Water dissolubility binder solution of 40% weight, fully stir 1h, finally add the ethanol water of 20% weight to stir 30min, obtain water system positive pole, it consists of LiMn
2o
4: conductive agent (Super-P/KS-6/=3/1): CMC: binding agent (methylene ethylene oxide copolymer/polyethylene nitrile=1/9): ethanol: deionized water=100:4:1:2:20:110
Anodal: by the one side dressing on the aluminium foil of 16 microns of the positive electrode composition of above-mentioned preparation; Under 90 DEG C of conditions, vacuum bakeout 3.5h(vacuum degree is-90kPa), roll, cut into slices; The energy density of gained positive pole is 1.0mAh/cm
2.
Negative pole: prepare cathode size one side dressing on the Copper Foil of 12 microns with graphite material, vacuum bakeout 3.5h(vacuum degree is-90kPa under 90 DEG C of conditions), roll, cut into slices; The energy density of gained negative pole is 1.4mAh/cm
2.
Lithium ion battery: with the prepared positive pole of said method and negative pole, the PE perforated membrane of 20 microns is barrier film, 1M LiPF
6dimethyl carbonate (DMC)/methyl ethyl carbonate (EMC)/vinyl carbonate (EC) (volume ratio 1/1/1) solution as electrolyte, in humidity-controlled glove box, prepare button cell.
contrast preparation A:
Compound Water dissolubility binder solution: binding agent is single methylene ethylene oxide copolymer.
Positive electrode composition: prepare according to the method described above positive electrode composition.
Anodal: preparation is anodal according to the method described above.
Negative pole: prepare according to the method described above negative pole
Lithium ion battery: prepare according to the method described above lithium ion battery.
contrast preparation B:
Compound Water dissolubility binder solution: binding agent is single polyethylene nitrile (PAN).
Positive electrode composition: prepare according to the method described above positive electrode composition.
Anodal: preparation is anodal according to the method described above.
Negative pole: prepare according to the method described above negative pole
Lithium ion battery: prepare according to the method described above lithium ion battery.
embodiment 6
Compound Water dissolubility binder solution: by the dimethyl siloxane-ethylene oxide copolymer of 50% weight (-((CH
3)
2(SiOOCH
2cH
2)
m)
n-) and the polymethyl methacrylate (PMMA) of 50% weight be dissolved in deionized water after evenly mixing, form Compound Water dissolubility binder solution.Its quality proportioning is dimethyl siloxane-ethylene oxide copolymer: polyethylene nitrile: deionized water=5:5:30.
Positive electrode composition: first thickener CMC is made into the aqueous solution of 4% weight, is uniformly mixed 1.5h with conductive agent acetylene black and flake graphite KS-6, then add nanometer LiFePO
4carry out (D50=120nm) and mix fully, stir 3h, then add the Compound Water dissolubility binder solution of 40% weight, fully stir 1h, finally add the glycol water of 15% weight to stir 30min, obtain water system positive pole, it consists of LiFePO
4: conductive agent (acetylene black/KS-6/=3/1): CMC: binding agent (dimethyl siloxane-ethylene oxide copolymer/polymethyl methacrylate=1/9): ethanol: deionized water=100:4:1:2:20:115
Anodal: by the one side dressing on the aluminium foil of 16 microns of the positive electrode composition of above-mentioned preparation; Under 90 DEG C of conditions, vacuum bakeout 3.5h(vacuum degree is-90kPa), roll, cut into slices; The energy density of gained positive pole is 1.0mAh/cm
2.
Negative pole: prepare cathode size one side dressing on the Copper Foil of 12 microns with graphite material, vacuum bakeout 3.5h(vacuum degree is-90kPa under 90 DEG C of conditions), roll, cut into slices; The energy density of gained negative pole is 1.4mAh/cm
2.
Lithium ion battery: with the prepared positive pole of said method and negative pole, the PE perforated membrane of 20 microns is barrier film, 1M LiPF
6dimethyl carbonate (DMC)/methyl ethyl carbonate (EMC)/vinyl carbonate (EC) (volume ratio 1/1/1) solution as electrolyte, in humidity-controlled glove box, prepare button cell.
contrast preparation A:
Compound Water dissolubility binder solution: binding agent is single dimethyl siloxane-ethylene oxide copolymer.
Positive electrode composition: prepare according to the method described above positive electrode composition.
Anodal: preparation is anodal according to the method described above.
Negative pole: prepare according to the method described above negative pole
Lithium ion battery: prepare according to the method described above lithium ion battery.
contrast preparation B:
Compound Water dissolubility binder solution: binding agent is single polymethyl methacrylate (PMMA).
Positive electrode composition: prepare according to the method described above positive electrode composition.
Anodal: preparation is anodal according to the method described above.
Negative pole: prepare according to the method described above negative pole
Lithium ion battery: prepare according to the method described above lithium ion battery.
embodiment 7
Electrochemical property test
Under room temperature, the lithium ion battery that embodiment 1-6 and contrast preparation 1-6 are made is with 0.2mAh/cm
2charging.Ferrous phosphate lithium battery upper voltage limit 3.8V, with 0.5 mAh/cm
2electric discharge, lower voltage limit 2.5V; Other battery upper voltage limit 4.2V, with 0.5 mAh/cm
2electric discharge, lower voltage limit 3.0V.One time charge and discharge process is a circulation, records discharge capacity for the first time, and calculates specific capacity.After 100,500 circulations, measure the capacity of battery, and calculated capacity surplus ratio.As shown in table 1.
Table 1
Can find out from embodiment 1-6 and contrast preparation 1-6, adopt the anode pole piece of compound water-soluble binder without falling the bad phenomenon such as material, be full of cracks, crimping, show that pole piece is in apparent good order and condition; The prepared lithium battery cycle characteristics of positive pole of this compound water-soluble binder is obviously better than the cycle performance of the prepared lithium battery of single positive pole of planting water-soluble binder.
embodiment 8
A kind of lithium ion battery, comprise battery case, pole piece and electrolyte, described pole piece and electrolyte sealing are contained in battery case, described pole piece comprises positive pole, negative pole and the membrane layer between positive pole and negative pole, described positive pole comprises collector and loads on the lithium ion battery anode glue size on collector, described lithium ion battery anode glue size comprises positive active material, conductive agent, thickener, binding agent, deionized water, it is characterized in that: described bonding agent is compound water-soluble binder, comprise following component by weight percentage:
Amorphous poly ethylene oxide water soluble adhesive 10%
With gel-type water-soluble binder 90%;
Described amorphous poly ethylene oxide class water-soluble binder refers to the block copolymer that inserts small molecule structure unit and form on polyethylene glycol oxide (PEO) strand;
Described gel-type water-soluble binder is the several of a kind of or arbitrary proportion in polyethylene nitrile (PAN), polyvinyl chloride (PVC), polyvinyl acetate (PVAC), polyacrylic acid glycol ester (PEGDA), polymethyl methacrylate (PMMA).
embodiment 9
A kind of lithium ion battery, comprise battery case, pole piece and electrolyte, described pole piece and electrolyte sealing are contained in battery case, described pole piece comprises positive pole, negative pole and the membrane layer between positive pole and negative pole, described positive pole comprises collector and loads on the lithium ion battery anode glue size on collector, described lithium ion battery anode glue size comprises positive active material, conductive agent, thickener, binding agent, deionized water, it is characterized in that: described bonding agent is compound water-soluble binder, comprise following component by weight percentage:
Amorphous poly ethylene oxide water soluble adhesive 40%
With gel-type water-soluble binder 60%;
Described amorphous poly ethylene oxide class water-soluble binder refers to the block copolymer that inserts small molecule structure unit and form on polyethylene glycol oxide (PEO) strand;
Described gel-type water-soluble binder is the several of a kind of or arbitrary proportion in polyethylene nitrile (PAN), polyvinyl chloride (PVC), polyvinyl acetate (PVAC), polyacrylic acid glycol ester (PEGDA), polymethyl methacrylate (PMMA).
embodiment 10
A kind of lithium ion battery, comprise battery case, pole piece and electrolyte, described pole piece and electrolyte sealing are contained in battery case, described pole piece comprises positive pole, negative pole and the membrane layer between positive pole and negative pole, described positive pole comprises collector and loads on the lithium ion battery anode glue size on collector, described lithium ion battery anode glue size comprises positive active material, conductive agent, thickener, binding agent, deionized water, it is characterized in that: described bonding agent is compound water-soluble binder, comprise following component by weight percentage:
Amorphous poly ethylene oxide water soluble adhesive 25%
With gel-type water-soluble binder 75%;
Described amorphous poly ethylene oxide class water-soluble binder refers to the block copolymer that inserts small molecule structure unit and form on polyethylene glycol oxide (PEO) strand;
Described gel-type water-soluble binder is the several of a kind of or arbitrary proportion in polyethylene nitrile (PAN), polyvinyl chloride (PVC), polyvinyl acetate (PVAC), polyacrylic acid glycol ester (PEGDA), polymethyl methacrylate (PMMA).
embodiment 11
On the basis of embodiment 8-10:
Described small molecule structure unit is the several of a kind of or arbitrary proportion in sub-methoxyl group, epoxy chloroethanes, siloxanes, phosphoric acid resin and Aluminate.
Proportioning between positive active material, conductive agent, thickener, composite water-soluble bonding agent, deionized water is: conductive agent, thickener, composite water-soluble bonding agent, deionized water are taking the weight of positive active material as benchmark: the content of conductive agent is 0.5% of the weight of positive active material; The content of thickener be positive active material weight 0.5%; The content of compound water-soluble binder be positive active material weight 0.5%; The content of deionized water be positive active material weight 40%.
Described conductive agent is the several of a kind of or arbitrary proportion in carbon black, acetylene black, carbon fiber, flake graphite.
Described thickener is that carboxymethyl cellulose is received, a kind of or arbitrary proportion in hydroxyethylcellulose, hydroxypropyl methylcellulose, hydroxypropyl cellulose, methylcellulose and polyacrylic acid several.
Described lithium ion battery anode glue size also contains surface tension modifier, and this surface tension modifier is the mixture of alcohol or ether or both arbitrary proportions.
Described negative pole is for to be evenly coated in Delanium, native graphite, agraphitic carbon, hard carbon or lithium titanate on collector, and thickness is 50 microns.
Described electrolyte contains lithium salts and nonaqueous solvents, and wherein the concentration of lithium salts in electrolyte is 0.5 mol/L.
embodiment 12
On the basis of embodiment 8-10:
Described small molecule structure unit is the several of a kind of or arbitrary proportion in sub-methoxyl group, epoxy chloroethanes, siloxanes, phosphoric acid resin and Aluminate.
Proportioning between positive active material, conductive agent, thickener, composite water-soluble bonding agent, deionized water is: conductive agent, thickener, composite water-soluble bonding agent, deionized water are taking the weight of positive active material as benchmark: the content of conductive agent is 10% of the weight of positive active material; The content of thickener be positive active material weight 5%; The content of compound water-soluble binder be positive active material weight 10%; The content of deionized water be positive active material weight 150%.
Described conductive agent is the several of a kind of or arbitrary proportion in carbon black, acetylene black, carbon fiber, flake graphite.
Described thickener is that carboxymethyl cellulose is received, a kind of or arbitrary proportion in hydroxyethylcellulose, hydroxypropyl methylcellulose, hydroxypropyl cellulose, methylcellulose and polyacrylic acid several.
Described lithium ion battery anode glue size also contains surface tension modifier, and this surface tension modifier is the mixture of alcohol or ether or both arbitrary proportions.
Described negative pole is for to be evenly coated in Delanium, native graphite, agraphitic carbon, hard carbon or lithium titanate on collector, and thickness is 200 microns.
Described electrolyte contains lithium salts and nonaqueous solvents, and wherein the concentration of lithium salts in electrolyte is 2.0 mol/L.
embodiment 13
On the basis of embodiment 8-10:
Described small molecule structure unit is the several of a kind of or arbitrary proportion in sub-methoxyl group, epoxy chloroethanes, siloxanes, phosphoric acid resin and Aluminate.
Proportioning between positive active material, conductive agent, thickener, composite water-soluble bonding agent, deionized water is: conductive agent, thickener, composite water-soluble bonding agent, deionized water are taking the weight of positive active material as benchmark: the content of conductive agent is 5.25% of the weight of positive active material; The content of thickener be positive active material weight 2.75%; The content of compound water-soluble binder be positive active material weight 5.25%; The content of deionized water be positive active material weight 95%.
Described conductive agent is the several of a kind of or arbitrary proportion in carbon black, acetylene black, carbon fiber, flake graphite.
Described thickener is that carboxymethyl cellulose is received, a kind of or arbitrary proportion in hydroxyethylcellulose, hydroxypropyl methylcellulose, hydroxypropyl cellulose, methylcellulose and polyacrylic acid several.
Described lithium ion battery anode glue size also contains surface tension modifier, and this surface tension modifier is the mixture of alcohol or ether or both arbitrary proportions.
Described negative pole is for to be evenly coated in Delanium, native graphite, agraphitic carbon, hard carbon or lithium titanate on collector, and thickness is 125 microns.
Described electrolyte contains lithium salts and nonaqueous solvents, and wherein the concentration of lithium salts in electrolyte is 1.25 mol/L.
embodiment 14
On the basis of embodiment 8-13:
Described lithium ion battery anode glue size also contains surface tension modifier, and this surface tension modifier is the mixture of alcohol or ether or both arbitrary proportions.
The content of described surface tension modifier be weight taking positive active material as benchmark, 5% of the weight that its content is positive active material.
Described alcohol is the several of a kind of or arbitrary proportion in ethanol, ethylene glycol, butanols and propyl alcohol; Described ether is the several of a kind of or arbitrary proportion in ethylene glycol ethyl ether, butyl glycol ether and n-butyl ether.
embodiment 15
On the basis of embodiment 8-13:
Described lithium ion battery anode glue size also contains surface tension modifier, and this surface tension modifier is the mixture of alcohol or ether or both arbitrary proportions.
The content of described surface tension modifier be weight taking positive active material as benchmark, 40% of the weight that its content is positive active material.
Described alcohol is the several of a kind of or arbitrary proportion in ethanol, ethylene glycol, butanols and propyl alcohol; Described ether is the several of a kind of or arbitrary proportion in ethylene glycol ethyl ether, butyl glycol ether and n-butyl ether.
embodiment 16
On the basis of embodiment 8-13:
Described lithium ion battery anode glue size also contains surface tension modifier, and this surface tension modifier is the mixture of alcohol or ether or both arbitrary proportions.
The content of described surface tension modifier be weight taking positive active material as benchmark, 22.5% of the weight that its content is positive active material.
Described alcohol is the several of a kind of or arbitrary proportion in ethanol, ethylene glycol, butanols and propyl alcohol; Described ether is the several of a kind of or arbitrary proportion in ethylene glycol ethyl ether, butyl glycol ether and n-butyl ether.
Claims (9)
1. a lithium ion battery, comprise battery case, pole piece and electrolyte, described pole piece and electrolyte sealing are contained in battery case, described pole piece comprises positive pole, negative pole and the membrane layer between positive pole and negative pole, described positive pole comprises collector and loads on the lithium ion battery anode glue size on collector, described lithium ion battery anode glue size comprises positive active material, conductive agent, thickener, binding agent, deionized water, it is characterized in that: described binding agent is compound water-soluble binder, comprise following component by weight percentage:
Amorphous poly ethylene oxide water-soluble binder 10～40%
Gel-type water-soluble binder 60～90%;
Described amorphous poly ethylene oxide class water-soluble binder refers to the block copolymer that inserts small molecule structure unit and form on polyethylene glycol oxide strand;
Described gel-type water-soluble binder is the several of a kind of or arbitrary proportion in polyacrylonitrile, polyvinyl chloride, polyvinyl acetate, polyethyleneglycol diacrylate;
Described small molecule structure unit is the several of a kind of or arbitrary proportion in sub-methoxyl group, epoxy chloroethanes, siloxanes, phosphoric acid resin and Aluminate.
2. a kind of lithium ion battery according to claim 1, is characterized in that: the proportioning between positive active material, conductive agent, thickener, compound water-soluble binder, deionized water is: conductive agent, thickener, compound water-soluble binder, deionized water are taking the weight of positive active material as benchmark: the content of conductive agent is 0.5～10% of the weight of positive active material; The content of thickener be positive active material weight 0.5～5%; The content of compound water-soluble binder be positive active material weight 0.5～10%; The content of deionized water be positive active material weight 40～150%.
3. a kind of lithium ion battery according to claim 1 and 2, is characterized in that: described conductive agent is the several of a kind of or arbitrary proportion in acetylene black, carbon fiber, flake graphite.
4. a kind of lithium ion battery according to claim 1 and 2, is characterized in that: described thickener is the several of a kind of or arbitrary proportion in carboxymethyl cellulose sodium, hydroxyethylcellulose, hydroxypropyl methylcellulose, hydroxypropyl cellulose, methylcellulose and polyacrylic acid.
5. a kind of lithium ion battery according to claim 1 and 2, is characterized in that: described lithium ion battery anode glue size also contains surface tension modifier, and this surface tension modifier is the mixture of alcohol or ether or both arbitrary proportions.
6. a kind of lithium ion battery according to claim 5, is characterized in that: the content of described surface tension modifier be weight taking positive active material as benchmark, 5～40% of the weight that its content is positive active material.
7. a kind of lithium ion battery according to claim 5, is characterized in that: described alcohol is the several of a kind of or arbitrary proportion in ethanol, ethylene glycol, butanols and propyl alcohol; Described ether is the several of a kind of or arbitrary proportion in ethylene glycol ethyl ether, butyl glycol ether and n-butyl ether.
8. a kind of lithium ion battery according to claim 1 and 2, is characterized in that: described negative pole is for to be evenly coated in Delanium, native graphite, hard carbon or lithium titanate on collector, and thickness is 50-200 micron.
9. a kind of lithium ion battery according to claim 1 and 2, is characterized in that: described electrolyte contains lithium salts and nonaqueous solvents, wherein the concentration of lithium salts in electrolyte is 0.5～2.0 mol/L.
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| CN103035901B (en) * | 2012-12-20 | 2015-02-04 | 中国东方电气集团有限公司 | Nanometer oxide coated lithium titanate negative electrode material of lithium battery, and preparation method for negative electrode material |
| CN104466187B (en) * | 2014-12-10 | 2017-09-22 | 东莞新能源科技有限公司 | A kind of anode electrode film and the lithium ion battery for applying the electrode film |
| CN106450486A (en) * | 2016-12-15 | 2017-02-22 | 衡阳市鑫晟新能源有限公司 | Preparation technique of aluminum-case lithium-ion battery for mobile phone |
| CN108963185A (en) * | 2017-05-17 | 2018-12-07 | 北京中友锂泰能源科技有限公司 | A kind of high security fast charging type lithium ion battery anode active material, cathode and lithium ion battery |
| CN109360936B (en) * | 2018-11-01 | 2020-08-11 | 天能电池集团股份有限公司 | Lithium ion battery positive plate and preparation method thereof |
| CN109888170B (en) * | 2019-01-23 | 2022-10-25 | 西安交通大学 | Three-dimensional network adhesive for secondary battery, preparation method of three-dimensional network adhesive, negative electrode slurry and negative electrode material |
| CN112599726B (en) * | 2020-12-25 | 2023-05-16 | 上海奥威科技开发有限公司 | Gel polymer lithium ion capacitor battery and preparation method thereof |
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| CN101504994A (en) * | 2009-03-04 | 2009-08-12 | 张贵萍 | Lithium manganese phosphate or lithium manganese silicate power cell, positive and negative pole manufacturing method thereof |
| CN102104140A (en) * | 2010-12-29 | 2011-06-22 | 常州华科新能源科技有限公司 | Power battery electrode and manufacturing method thereof |
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| CN101504994A (en) * | 2009-03-04 | 2009-08-12 | 张贵萍 | Lithium manganese phosphate or lithium manganese silicate power cell, positive and negative pole manufacturing method thereof |
| CN102104140A (en) * | 2010-12-29 | 2011-06-22 | 常州华科新能源科技有限公司 | Power battery electrode and manufacturing method thereof |
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