CN102437369A - Lithium ion battery - Google Patents
Lithium ion battery Download PDFInfo
- Publication number
- CN102437369A CN102437369A CN2011104281528A CN201110428152A CN102437369A CN 102437369 A CN102437369 A CN 102437369A CN 2011104281528 A CN2011104281528 A CN 2011104281528A CN 201110428152 A CN201110428152 A CN 201110428152A CN 102437369 A CN102437369 A CN 102437369A
- Authority
- CN
- China
- Prior art keywords
- lithium ion
- water
- ion battery
- active material
- soluble binder
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 82
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 79
- 239000006258 conductive agent Substances 0.000 claims abstract description 39
- 239000000853 adhesive Substances 0.000 claims abstract description 27
- 230000001070 adhesive effect Effects 0.000 claims abstract description 27
- 239000003232 water-soluble binding agent Substances 0.000 claims description 70
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 65
- 150000001875 compounds Chemical class 0.000 claims description 58
- 239000000203 mixture Substances 0.000 claims description 52
- 239000007774 positive electrode material Substances 0.000 claims description 46
- -1 polyethylene Polymers 0.000 claims description 44
- 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
- 239000004698 Polyethylene Substances 0.000 claims description 34
- 239000011230 binding agent Substances 0.000 claims description 32
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 30
- 239000002562 thickening agent Substances 0.000 claims description 30
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 26
- 239000003792 electrolyte Substances 0.000 claims description 26
- 229920000573 polyethylene Polymers 0.000 claims description 25
- 150000002825 nitriles Chemical class 0.000 claims description 24
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 22
- 239000003607 modifier Substances 0.000 claims description 22
- 239000003292 glue Substances 0.000 claims description 21
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 21
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 21
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 18
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 18
- 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
- 239000012528 membrane Substances 0.000 claims description 12
- 239000002202 Polyethylene glycol Substances 0.000 claims description 11
- 229910052744 lithium Inorganic materials 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
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 10
- 229920002125 Sokalan® Polymers 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
- 239000004584 polyacrylic acid Substances 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
- 229920002689 polyvinyl acetate Polymers 0.000 claims description 9
- 239000011118 polyvinyl acetate Substances 0.000 claims description 9
- 239000006230 acetylene black Substances 0.000 claims description 7
- 229920001223 polyethylene glycol Polymers 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
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 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
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 5
- 229920001400 block copolymer Polymers 0.000 claims description 5
- 239000007767 bonding agent Substances 0.000 claims description 5
- 239000004917 carbon fiber Substances 0.000 claims description 5
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 5
- 239000008112 carboxymethyl-cellulose 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
- 229920000915 polyvinyl chloride Polymers 0.000 claims 1
- 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
- 239000013543 active substance Substances 0.000 abstract description 3
- 239000002131 composite material Substances 0.000 abstract 4
- 238000005336 cracking Methods 0.000 abstract 1
- 230000007547 defect Effects 0.000 abstract 1
- 238000000034 method Methods 0.000 description 63
- 238000002360 preparation method Methods 0.000 description 37
- 239000000243 solution Substances 0.000 description 37
- 229920001577 copolymer Polymers 0.000 description 24
- 238000003756 stirring Methods 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 14
- 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
- 229910010707 LiFePO 4 Inorganic materials 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
- 239000011149 active material 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
- 229910010710 LiFePO 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
- 239000003960 organic solvent Substances 0.000 description 5
- 102220043159 rs587780996 Human genes 0.000 description 5
- 229910015645 LiMn Inorganic materials 0.000 description 4
- 238000005516 engineering process Methods 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
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000013459 approach Methods 0.000 description 2
- 230000002950 deficient Effects 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
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-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
- QOSMNYMQXIVWKY-UHFFFAOYSA-N Propyl levulinate Chemical compound CCCOC(=O)CCC(C)=O QOSMNYMQXIVWKY-UHFFFAOYSA-N 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
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-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
- 230000000994 depressogenic effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 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
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 1
- 229940116007 ferrous phosphate Drugs 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000011521 glass Substances 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
- BMANCNNUKXPJTN-UHFFFAOYSA-N lithium;1,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfonic acid Chemical compound [Li].OS(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F BMANCNNUKXPJTN-UHFFFAOYSA-N 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
- 150000002894 organic compounds Chemical class 0.000 description 1
- 150000002895 organic esters Chemical class 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
- 238000011084 recovery Methods 0.000 description 1
- 238000011160 research Methods 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
- 238000012360 testing method Methods 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
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 the lithium ion battery field.
Background technology
Compare with other chemical power source; Lithium rechargeable battery has the performance of many excellences; High like energy density, have extended cycle life, open circuit voltage height, memory-less effect, safety non-pollution etc.; Develop rapidly through recent two decades is applied in fields such as mobile phone, notebook computer, digital camera widely.In recent years along with the development of electric automobile, press for 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 the high specific energy of employing; The 2nd, improve the content of active substance in the battery through improving technology.
Must use suitable binding agent to accomplish the preparation of electrode in the manufacturing process of lithium ion battery, binding agent mainly is that active material and electrode current collecting body is together bonded to each other in battery.At present; Lithium ion cell positive mostly adopts Kynoar (PVDF) as binding agent; With the solvent as PVDF such as the organic compound of strong polarity such as N-dimethyl pyrrolidone (NMP), dimethyl formamide (DMF), dimethyl sulfoxide (DMSO) (DMSO), promptly adopt organic system coating film-making.The organic solvent that adopts during this system coating film-making is expensive and have corrosivity, and use amount is big and be difficult to recovery, and production cost is big; And coating film-making process need removes the organic solvent heated volatile, for preventing the corrosivity organic solvent contaminated environment of volatilizing arbitrarily, must install a large amount of environmental protection equipments additional, increases production cost equally and is unfavorable for production operation; More disadvantageous is in organic system, PVDF binding agent large usage quantity, and too much binder component not only reduces the specific capacity of battery; And influence the smoothness and the baking property of pole piece coating; A large amount of in addition binding agents is coated on the surface of active particle, with the contact impedance that increases particle, increases the polarization of battery charging and discharging; The lifting of therefore serious restriction battery specific power, especially outstanding for the performance of nano level active material.Disclosing an application number like State Intellectual Property Office in 2005.3.23 is 03144276.5; Name is called the patent of invention of " battery is with the manufacturing approach of corrosion-resistant electrode "; It provides the manufacturing approach of a kind of battery with corrosion-resistant electrode; Main processes: crosslinking agent, initator and organic solvent are mixed into the clear solution that contains cross-linked vinylidene and uncrosslinked polyethylene glycol oxide, stir into viscous paste, be coated on the collector and heat with electrode active material, conductive agent; Being depressed into thickness is the crosslinked electrode of treating of 0.05～0.5mm; Be placed on again in 90～400 ℃ the constant temperature oven, naturally cool to constant temperature after 5 minutes～6 hours, be battery after the taking-up and use corrosion-resistant electrode.The bonding agent that Kynoar and polyethylene glycol oxide mix is wherein disclosed; There is following defective: at first; The initator that contains some in the electrode, initator can resolve into micromolecular material in charge and discharge process, certainly will cause the rapid deterioration of battery performance; At last, this hybrid adhesive still need dissolve in organic solvent, therefore in slurrying and coating process, not only produces a large amount of organic exhaust gas waste liquids, and increases the battery production cost greatly.
Therefore, positive pole of low-cost, pollution-free, low content binding agent and preparation method thereof becomes the research focus.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 the 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 the SBR molecule, finally cause the battery active material bonding not firm, fall material, cause capacity and cycle life to descend; In addition in the water system coating process; Because caking property is bad uneven with stress distribution; Pole piece phenomenons such as material, be full of cracks, crimping, chip very easily occur falling in the process of baking, have a strong impact on normally carrying out of production, and the battery capacity that makes and cycle performance are on the low side.
Summary of the invention
The objective of the invention is to solve in the prior art water-soluble binder of preparation lithium ion battery bad adhesion, be prone to degraded, cause problems such as battery capacity and cycle performance difference, a kind of low cost, high power capacity and long-life lithium ion battery are provided.
In order to realize the foregoing invention purpose, technical scheme of the present invention is following:
(1)A kind of compound water-soluble binder that is used to prepare lithium battery comprises following component by weight percentage:
Amorphous poly ethylene oxide water soluble adhesive 10～40%
Gel-type water-soluble binder 60～90%.
Preferably:
Amorphous poly ethylene oxide class water-soluble binder 20～30%
Gel-type water-soluble binder 70～80%.
The said two devices mixed dissolution forms compound water-soluble binder;
Amorphous poly ethylene oxide class water-soluble binder of the present invention is meant the block copolymer that on polyethylene glycol oxide (PEO) strand, inserts the small molecule structure unit and form
Above-mentioned small molecule structure mainly comprises several kinds of a kind of or arbitrary proportion in inferior methoxyl group, epoxy chloroethanes, siloxanes, phosphoric acid resin and the aluminic acid ester.
Gel-type water-soluble binder of the present invention is meant that the binding agent that has better toughness and can form gel is several kinds of a kind of or arbitrary proportion in polyethylene nitrile (PAN), polyvinyl chloride (PVC), polyvinyl acetate (PVAC), polyacrylic acid glycol ester (PEGDA), the 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 processed of the compound water soluble adhesive that provides; Comprise collector and load on the lithium ion battery anode glue size on the 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 a benchmark with the weight of positive active material:
The content of conductive agent be positive active material weight 0.5～10%, preferred 3～8%;
The content of thickener be positive active material weight 0.5～5%, preferred 1～3%;
The content of compound water-soluble binder be positive active material weight 0.5～10%, preferred 2～6%;
The content of deionized water be positive active material weight 40～150%, preferred 50～80%.
The preparation method of lithium ion battery anode glue size of the present invention is a technology known in those skilled in the art, and soon positive active material, conductive agent, compound water-soluble binder, thickener and water mix and gets final product.
Positive active material of the present invention is: LiCoO
2, LiFePO
4, LiNiO
2, LiNiCoAlO
2, LiMn
2O
4And LiNiMnCoO
2In several kinds of a kind of or arbitrary proportion, preferred LiFePO
4Or LiMn
2O
4
Conductive agent of the present invention is: several kinds of a kind of or arbitrary proportion in carbon black, acetylene black, carbon fiber, the flake graphite, contain flake graphite under the preferable case.
Thickener of the present invention is: carboxymethyl cellulose is received (CMC), several kinds of a kind of or arbitrary proportion in hydroxyethylcellulose (HEC), hydroxypropyl methylcellulose (HPMC), hydroxypropyl cellulose (HPC), methylcellulose (MC) and the polyacrylic acid.
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: the weight with positive active material is benchmark, its content be positive active material weight 5～40%, preferred 10～20%.
Above-mentioned alcohol is several kinds of a kind of or arbitrary proportion in ethanol, ethylene glycol, butanols and the propyl alcohol.
Above-mentioned ether is several kinds of a kind of or arbitrary proportion in ethylene glycol ethyl ether, butyl glycol ether and the n-butyl ether.
Above-mentioned a kind of lithium ion cell positive, the preparation method is a technology known in those skilled in the art, is about to lithium ion battery anode glue size and evenly is coated on the collector, thickness is 50～200 microns; Baking is removed moisture and is processed 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; Said pole piece and electrolyte sealing are contained in the battery case, and said pole piece comprises positive pole, negative pole and the membrane layer between positive pole and negative pole, it is characterized in that: said just very the present invention
(2)In the employing that provides
(1)In the positive pole processed of compound water soluble adhesive.
Membrane layer of the present invention is polypropylene micro-porous film (PP), microporous polyethylene film (PE), glass mat or PP/PE/PP, and preferred, said barrier film is PP/PE/PP.
Negative pole of the present invention is with negative electrode active material, evenly is coated on the collector like Delanium, native graphite, agraphitic carbon, hard carbon or lithium titanate, and thickness is 50～200 microns, and preferred, said 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 several kinds of a kind of or arbitrary proportion in lithium hexafluoro phosphate, LiBF4, hexafluoroarsenate lithium, lithium perchlorate, trifluoromethyl sulfonic acid lithium, perfluoro butyl sulfonic acid lithium, lithium aluminate, chlorine lithium aluminate, fluoro sulfimide lithium, lithium chloride and the lithium iodide; Said nonaqueous solvents can be fluorine-containing for gamma-butyrolacton, methyl ethyl carbonate, carbonic acid first propyl ester, dipropyl carbonate, acid anhydrides, N-NMF, N-methylacetamide, acetonitrile, sulfolane, methyl-sulfoxide, dimethyl sulfite and other, several kinds of a kind of or arbitrary proportion in the ring-type organic ester of sulfur-bearing or unsaturated bond.
The concentration of lithium salts of the present invention in electrolyte is 0.5～2.0 mol, is preferably 0.8～1.2 mol.
Beneficial effect of the present invention is following:
Amorphous poly ethylene oxide molecules chain in the compound water-soluble binder of the present invention has the height compliance, has improved the pliability of pole piece, therefore can reduce to occur falling defectives such as material, be full of cracks, crimping and chip in the electrode manufacture process, helps large-scale production; The gel-type water-soluble binder has good caking property and stability, improves battery contact between active material and conductive agent, active material and the 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 have 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 the capacity and the cycle performance of the anodal battery of forming obtained by this method further improved.
Embodiment
Embodiment 1
Compound water-soluble binder solution: with 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 the deionized water after evenly mixing, form compound water-soluble binder solution.Its quality proportioning is the methylene ethylene oxide copolymer: polyethylene nitrile: deionized water=4:6:30.
Positive electrode composition: at first thickener CMC is made into the aqueous solution of 4% weight, mixes 1.5h, add nanometer LiFePO then with conductive agent Super-P and flake graphite KS-6
4Carry out (D50=120nm) and mix fully, stir 3h, add the compound water-soluble binder solution of 40% weight again, fully stir 1h, the ethanol water that adds 20% weight at last stirs 30min, obtains the water system positive pole, and 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: with positive electrode composition single face dressing on 16 microns aluminium foil of above-mentioned preparation; Vacuum bakeout 3.5h under 90 ℃ of conditions (vacuum degree for-90kPa), roll, cut into slices; The anodal energy density of gained is 1.0mAh/cm
2
Negative pole: prepare cathode size single face dressing on 12 microns Copper Foil with graphite material, vacuum bakeout 3.5h under 90 ℃ of conditions (vacuum degree for-90kPa), roll, cut into slices; The energy density of gained negative pole is 1.4mAh/cm
2
Lithium ion battery: with prepared positive pole of said method and negative pole, 20 microns PE perforated membrane is a barrier film, 1M LiPF
6Dimethyl carbonate (DMC)/methyl ethyl carbonate (EMC)/vinyl carbonate (EC) (volume ratio 1/1/1) solution in humidity-controlled glove box, prepare button cell as electrolyte.
Comparative preparation A:
Compound water-soluble binder solution: binding agent is single methylene ethylene oxide copolymer.
Positive electrode composition: prepare positive electrode composition according to the method described above.
Anodal: preparation is anodal according to the method described above.
Negative pole: prepare negative pole according to the method described above
Lithium ion battery: prepare lithium ion battery according to the method described above.
Comparative preparation B:
Compound water-soluble binder solution: binding agent is single polyethylene nitrile (PAN).
Positive electrode composition: prepare positive electrode composition according to the method described above.
Anodal: preparation is anodal according to the method described above.
Negative pole: prepare negative pole according to the method described above
Lithium ion battery: prepare lithium ion battery according to the method described above.
Embodiment 2
Compound water-soluble binder solution: with 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 the deionized water after evenly mixing, form compound water-soluble binder solution.Its quality proportioning is the methylene ethylene oxide copolymer: polyethylene nitrile: deionized water=1:9:30.
Positive electrode composition: at first thickener CMC is made into the aqueous solution of 4% weight, mixes 1.5h, add nanometer LiFePO then with conductive agent Super-P and flake graphite KS-6
4Carry out (D50=120nm) and mix fully, stir 3h, add the compound water-soluble binder solution of 40% weight again, fully stir 1h, the ethanol water that adds 20% weight at last stirs 30min, obtains the water system positive pole, and 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: with positive electrode composition single face dressing on 16 microns aluminium foil of above-mentioned preparation; Vacuum bakeout 3.5h under 90 ℃ of conditions (vacuum degree for-90kPa), roll, cut into slices; The anodal energy density of gained is 1.0mAh/cm
2
Negative pole: prepare cathode size single face dressing on 12 microns Copper Foil with graphite material, vacuum bakeout 3.5h under 90 ℃ of conditions (vacuum degree for-90kPa), roll, cut into slices; The energy density of gained negative pole is 1.4mAh/cm
2
Lithium ion battery: with prepared positive pole of said method and negative pole, 20 microns PE perforated membrane is a barrier film, 1M LiPF
6Dimethyl carbonate (DMC)/methyl ethyl carbonate (EMC)/vinyl carbonate (EC) (volume ratio 1/1/1) solution in humidity-controlled glove box, prepare button cell as electrolyte.
Comparative preparation A:
Compound water-soluble binder solution: binding agent is single methylene ethylene oxide copolymer.
Positive electrode composition: prepare positive electrode composition according to the method described above.
Anodal: preparation is anodal according to the method described above.
Negative pole: prepare negative pole according to the method described above
Lithium ion battery: prepare lithium ion battery according to the method described above.
Comparative preparation B:
Compound water-soluble binder solution: binding agent is single polyethylene nitrile (PAN).
Positive electrode composition: prepare positive electrode composition according to the method described above.
Anodal: preparation is anodal according to the method described above.
Negative pole: prepare negative pole according to the method described above
Lithium ion battery: prepare lithium ion battery according to the method described above.
Embodiment 3
Compound water-soluble binder solution: with dimethyl siloxane-ethylene oxide copolymer (-((CH of 10% weight
3)
2(SiOOCH
2CH
2)
m)
n-) and the polyethylene nitrile (PAN) of 90% weight be dissolved in the deionized water after evenly mixing, form compound water-soluble binder solution.Its quality proportioning is dimethyl siloxane-ethylene oxide copolymer: polyethylene nitrile: deionized water=1:9:30.
Positive electrode composition: at first thickener CMC is made into the aqueous solution of 4% weight, mixes 1.5h, add nanometer LiFePO then with conductive agent Super-P and flake graphite KS-6
4Carry out (D50=120nm) and mix fully, stir 3h, add the compound water-soluble binder solution of 40% weight again, fully stir 1h, the ethanol water that adds 20% weight at last stirs 30min, obtains the water system positive pole, and 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: with positive electrode composition single face dressing on 16 microns aluminium foil of above-mentioned preparation; Vacuum bakeout 3.5h under 90 ℃ of conditions (vacuum degree for-90kPa), roll, cut into slices; The anodal energy density of gained is 1.0mAh/cm
2
Negative pole: prepare cathode size single face dressing on 12 microns Copper Foil with graphite material, vacuum bakeout 3.5h under 90 ℃ of conditions (vacuum degree for-90kPa), roll, cut into slices; The energy density of gained negative pole is 1.4mAh/cm
2
Lithium ion battery: with prepared positive pole of said method and negative pole, 20 microns PE perforated membrane is a barrier film, 1M LiPF
6Dimethyl carbonate (DMC)/methyl ethyl carbonate (EMC)/vinyl carbonate (EC) (volume ratio 1/1/1) solution in humidity-controlled glove box, prepare button cell as electrolyte.
Comparative preparation A:
Compound water-soluble binder solution: binding agent is single dimethyl siloxane-ethylene oxide copolymer.
Positive electrode composition: prepare positive electrode composition according to the method described above.
Anodal: preparation is anodal according to the method described above.
Negative pole: prepare negative pole according to the method described above
Lithium ion battery: prepare lithium ion battery according to the method described above.
Comparative preparation B:
Compound water-soluble binder solution: binding agent is single polyethylene nitrile (PAN).
Positive electrode composition: prepare positive electrode composition according to the method described above.
Anodal: preparation is anodal according to the method described above.
Negative pole: prepare negative pole according to the method described above
Lithium ion battery: prepare lithium ion battery according to the method described above.
Embodiment 4
Compound water-soluble binder solution: with dimethyl siloxane-ethylene oxide copolymer (-((CH of 10% weight
3)
2(SiOOCH
2CH
2)
m)
n-) and the polymethyl methacrylate (PMMA) of 90% weight be dissolved in the deionized water after evenly mixing, form compound water-soluble binder solution.Its quality proportioning is dimethyl siloxane-ethylene oxide copolymer: polyethylene nitrile: deionized water=1:9:30.
Positive electrode composition: at first thickener CMC is made into the aqueous solution of 4% weight, mixes 1.5h, add nanometer LiFePO then with conductive agent Super-P and flake graphite KS-6
4Carry out (D50=120nm) and mix fully, stir 3h, add the compound water-soluble binder solution of 40% weight again, fully stir 1h, the ethanol water that adds 20% weight at last stirs 30min, obtains the water system positive pole, and 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: with positive electrode composition single face dressing on 16 microns aluminium foil of above-mentioned preparation; Vacuum bakeout 3.5h under 90 ℃ of conditions (vacuum degree for-90kPa), roll, cut into slices; The anodal energy density of gained is 1.0mAh/cm
2
Negative pole: prepare cathode size single face dressing on 12 microns Copper Foil with graphite material, vacuum bakeout 3.5h under 90 ℃ of conditions (vacuum degree for-90kPa), roll, cut into slices; The energy density of gained negative pole is 1.4mAh/cm
2
Lithium ion battery: with prepared positive pole of said method and negative pole, 20 microns PE perforated membrane is a barrier film, 1M LiPF
6Dimethyl carbonate (DMC)/methyl ethyl carbonate (EMC)/vinyl carbonate (EC) (volume ratio 1/1/1) solution in humidity-controlled glove box, prepare button cell as electrolyte.
Comparative preparation A:
Compound water-soluble binder solution: binding agent is single dimethyl siloxane-ethylene oxide copolymer.
Positive electrode composition: prepare positive electrode composition according to the method described above.
Anodal: preparation is anodal according to the method described above.
Negative pole: prepare negative pole according to the method described above
Lithium ion battery: prepare lithium ion battery according to the method described above.
Comparative preparation B:
Compound water-soluble binder solution: binding agent is single polymethyl methacrylate (PMMA).
Positive electrode composition: prepare positive electrode composition according to the method described above.
Anodal: preparation is anodal according to the method described above.
Negative pole: prepare negative pole according to the method described above
Lithium ion battery: prepare lithium ion battery according to the method described above.
Embodiment 5
Compound water-soluble binder solution: with 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 the deionized water after evenly mixing, form compound water-soluble binder solution.Its quality proportioning is the methylene ethylene oxide copolymer: polyethylene nitrile: deionized water=1:9:30.
Positive electrode composition: at first thickener CMC is made into the aqueous solution of 4% weight, mixes 1.5h, add LiMn then with conductive agent Super-P and flake graphite KS-6
2O
4Mix fully, stir 3h, add the compound water-soluble binder solution of 40% weight again, fully stir 1h, the ethanol water that adds 20% weight at last stirs 30min, obtains the water system positive pole, and 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: with positive electrode composition single face dressing on 16 microns aluminium foil of above-mentioned preparation; Vacuum bakeout 3.5h under 90 ℃ of conditions (vacuum degree for-90kPa), roll, cut into slices; The anodal energy density of gained is 1.0mAh/cm
2
Negative pole: prepare cathode size single face dressing on 12 microns Copper Foil with graphite material, vacuum bakeout 3.5h under 90 ℃ of conditions (vacuum degree for-90kPa), roll, cut into slices; The energy density of gained negative pole is 1.4mAh/cm
2
Lithium ion battery: with prepared positive pole of said method and negative pole, 20 microns PE perforated membrane is a barrier film, 1M LiPF
6Dimethyl carbonate (DMC)/methyl ethyl carbonate (EMC)/vinyl carbonate (EC) (volume ratio 1/1/1) solution in humidity-controlled glove box, prepare button cell as electrolyte.
Comparative preparation A:
Compound water-soluble binder solution: binding agent is single methylene ethylene oxide copolymer.
Positive electrode composition: prepare positive electrode composition according to the method described above.
Anodal: preparation is anodal according to the method described above.
Negative pole: prepare negative pole according to the method described above
Lithium ion battery: prepare lithium ion battery according to the method described above.
Comparative preparation B:
Compound water-soluble binder solution: binding agent is single polyethylene nitrile (PAN).
Positive electrode composition: prepare positive electrode composition according to the method described above.
Anodal: preparation is anodal according to the method described above.
Negative pole: prepare negative pole according to the method described above
Lithium ion battery: prepare lithium ion battery according to the method described above.
Embodiment 6
Compound water-soluble binder solution: with dimethyl siloxane-ethylene oxide copolymer (-((CH of 50% weight
3)
2(SiOOCH
2CH
2)
m)
n-) and the polymethyl methacrylate (PMMA) of 50% weight be dissolved in the deionized water after evenly mixing, form compound water-soluble binder solution.Its quality proportioning is dimethyl siloxane-ethylene oxide copolymer: polyethylene nitrile: deionized water=5:5:30.
Positive electrode composition: at first thickener CMC is made into the aqueous solution of 4% weight, mixes 1.5h, add nanometer LiFePO then with conductive agent acetylene black and flake graphite KS-6
4Carry out (D50=120nm) and mix fully, stir 3h, add the compound water-soluble binder solution of 40% weight again, fully stir 1h, the glycol water that adds 15% weight at last stirs 30min, obtains the water system positive pole, and 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: with positive electrode composition single face dressing on 16 microns aluminium foil of above-mentioned preparation; Vacuum bakeout 3.5h under 90 ℃ of conditions (vacuum degree for-90kPa), roll, cut into slices; The anodal energy density of gained is 1.0mAh/cm
2
Negative pole: prepare cathode size single face dressing on 12 microns Copper Foil with graphite material, vacuum bakeout 3.5h under 90 ℃ of conditions (vacuum degree for-90kPa), roll, cut into slices; The energy density of gained negative pole is 1.4mAh/cm
2
Lithium ion battery: with prepared positive pole of said method and negative pole, 20 microns PE perforated membrane is a barrier film, 1M LiPF
6Dimethyl carbonate (DMC)/methyl ethyl carbonate (EMC)/vinyl carbonate (EC) (volume ratio 1/1/1) solution in humidity-controlled glove box, prepare button cell as electrolyte.
Comparative preparation A:
Compound water-soluble binder solution: binding agent is single dimethyl siloxane-ethylene oxide copolymer.
Positive electrode composition: prepare positive electrode composition according to the method described above.
Anodal: preparation is anodal according to the method described above.
Negative pole: prepare negative pole according to the method described above
Lithium ion battery: prepare lithium ion battery according to the method described above.
Comparative preparation B:
Compound water-soluble binder solution: binding agent is single polymethyl methacrylate (PMMA).
Positive electrode composition: prepare positive electrode composition according to the method described above.
Anodal: preparation is anodal according to the method described above.
Negative pole: prepare negative pole according to the method described above
Lithium ion battery: prepare lithium ion battery according to the method described above.
Embodiment 7
Electrochemical property test
Under the room temperature, the lithium ion battery that embodiment 1-6 and comparative preparation 1-6 are made is with 0.2mAh/cm
2Charging.Ferrous phosphate lithium battery upper voltage limit 3.8V is with 0.5 mAh/cm
2Discharge, lower voltage limit 2.5V; Other battery upper voltage limit 4.2V is with 0.5 mAh/cm
2Discharge, lower voltage limit 3.0V.A charge and discharge process is a circulation, and record is discharge capacity for the first time, and calculates specific capacity.After 100,500 circulations, measure the capacity of battery, and the calculated capacity surplus ratio.As shown in table 1.
Table 1
Can find out from embodiment 1-6 and comparative preparation 1-6, adopt the anode pole piece of compound water-soluble binder not have bad phenomenon such as the material of falling, be full of cracks, crimping, show that pole piece is in apparent good order and condition; The anodal prepared lithium battery cycle characteristics of this compound water-soluble binder obviously is superior to single cycle performance of planting the anodal prepared lithium battery of water-soluble binder.
Embodiment 8
A kind of lithium ion battery; Comprise battery case, pole piece and electrolyte; Said pole piece and electrolyte sealing are contained in the battery case; Said pole piece comprises positive pole, negative pole and the membrane layer between positive pole and negative pole, and described positive pole comprises collector and load on the lithium ion battery anode glue size on the collector that 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, comprises 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 is meant the block copolymer that on polyethylene glycol oxide (PEO) strand, inserts the small molecule structure unit and form;
Described gel-type water-soluble binder is several kinds of a kind of or arbitrary proportion in polyethylene nitrile (PAN), polyvinyl chloride (PVC), polyvinyl acetate (PVAC), polyacrylic acid glycol ester (PEGDA), the polymethyl methacrylate (PMMA).
Embodiment 9
A kind of lithium ion battery; Comprise battery case, pole piece and electrolyte; Said pole piece and electrolyte sealing are contained in the battery case; Said pole piece comprises positive pole, negative pole and the membrane layer between positive pole and negative pole, and described positive pole comprises collector and load on the lithium ion battery anode glue size on the collector that 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, comprises 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 is meant the block copolymer that on polyethylene glycol oxide (PEO) strand, inserts the small molecule structure unit and form;
Described gel-type water-soluble binder is several kinds of a kind of or arbitrary proportion in polyethylene nitrile (PAN), polyvinyl chloride (PVC), polyvinyl acetate (PVAC), polyacrylic acid glycol ester (PEGDA), the polymethyl methacrylate (PMMA).
Embodiment 10
A kind of lithium ion battery; Comprise battery case, pole piece and electrolyte; Said pole piece and electrolyte sealing are contained in the battery case; Said pole piece comprises positive pole, negative pole and the membrane layer between positive pole and negative pole, and described positive pole comprises collector and load on the lithium ion battery anode glue size on the collector that 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, comprises 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 is meant the block copolymer that on polyethylene glycol oxide (PEO) strand, inserts the small molecule structure unit and form;
Described gel-type water-soluble binder is several kinds of a kind of or arbitrary proportion in polyethylene nitrile (PAN), polyvinyl chloride (PVC), polyvinyl acetate (PVAC), polyacrylic acid glycol ester (PEGDA), the polymethyl methacrylate (PMMA).
Embodiment 11
On the basis of embodiment 8-10:
Described small molecule structure unit is several kinds of a kind of or arbitrary proportion in inferior methoxyl group, epoxy chloroethanes, siloxanes, phosphoric acid resin and the aluminic acid ester.
Proportioning between positive active material, conductive agent, thickener, compound water soluble adhesive, the deionized water is: conductive agent, thickener, compound water soluble adhesive, deionized water are benchmark with the weight of positive active material: the content of conductive agent be positive active material weight 0.5%; 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 several kinds of a kind of or arbitrary proportion in carbon black, acetylene black, carbon fiber, the flake graphite.
Described thickener is that carboxymethyl cellulose is received, several kinds of a kind of or arbitrary proportion in hydroxyethylcellulose, hydroxypropyl methylcellulose, hydroxypropyl cellulose, methylcellulose and the polyacrylic acid.
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 evenly to be coated in Delanium, native graphite, agraphitic carbon, hard carbon or lithium titanate on the 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.
Embodiment 12
On the basis of embodiment 8-10:
Described small molecule structure unit is several kinds of a kind of or arbitrary proportion in inferior methoxyl group, epoxy chloroethanes, siloxanes, phosphoric acid resin and the aluminic acid ester.
Proportioning between positive active material, conductive agent, thickener, compound water soluble adhesive, the deionized water is: conductive agent, thickener, compound water soluble adhesive, deionized water are benchmark with the weight of positive active material: the content of conductive agent be positive active material weight 10%; 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 several kinds of a kind of or arbitrary proportion in carbon black, acetylene black, carbon fiber, the flake graphite.
Described thickener is that carboxymethyl cellulose is received, several kinds of a kind of or arbitrary proportion in hydroxyethylcellulose, hydroxypropyl methylcellulose, hydroxypropyl cellulose, methylcellulose and the polyacrylic acid.
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 evenly to be coated in Delanium, native graphite, agraphitic carbon, hard carbon or lithium titanate on the 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.
Embodiment 13
On the basis of embodiment 8-10:
Described small molecule structure unit is several kinds of a kind of or arbitrary proportion in inferior methoxyl group, epoxy chloroethanes, siloxanes, phosphoric acid resin and the aluminic acid ester.
Proportioning between positive active material, conductive agent, thickener, compound water soluble adhesive, the deionized water is: conductive agent, thickener, compound water soluble adhesive, deionized water are benchmark with the weight of positive active material: the content of conductive agent be positive active material weight 5.25%; 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 several kinds of a kind of or arbitrary proportion in carbon black, acetylene black, carbon fiber, the flake graphite.
Described thickener is that carboxymethyl cellulose is received, several kinds of a kind of or arbitrary proportion in hydroxyethylcellulose, hydroxypropyl methylcellulose, hydroxypropyl cellulose, methylcellulose and the polyacrylic acid.
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 evenly to be coated in Delanium, native graphite, agraphitic carbon, hard carbon or lithium titanate on the 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.
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 is for being benchmark with the weight of positive active material, its content be positive active material weight 5%.
Described alcohol is several kinds of a kind of or arbitrary proportion in ethanol, ethylene glycol, butanols and the propyl alcohol; Described ether is several kinds of a kind of or arbitrary proportion in ethylene glycol ethyl ether, butyl glycol ether and the 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 is for being benchmark with the weight of positive active material, its content be positive active material weight 40%.
Described alcohol is several kinds of a kind of or arbitrary proportion in ethanol, ethylene glycol, butanols and the propyl alcohol; Described ether is several kinds of a kind of or arbitrary proportion in ethylene glycol ethyl ether, butyl glycol ether and the 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 is for being benchmark with the weight of positive active material, its content be positive active material weight 22.5%.
Described alcohol is several kinds of a kind of or arbitrary proportion in ethanol, ethylene glycol, butanols and the propyl alcohol; Described ether is several kinds of a kind of or arbitrary proportion in ethylene glycol ethyl ether, butyl glycol ether and the n-butyl ether.
Claims (10)
1. lithium ion battery; Comprise battery case, pole piece and electrolyte; Said pole piece and electrolyte sealing are contained in the battery case; Said pole piece comprises positive pole, negative pole and the membrane layer between positive pole and negative pole, and described positive pole comprises collector and load on the lithium ion battery anode glue size on the collector that 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, comprises following component by weight percentage:
Amorphous poly ethylene oxide water soluble adhesive 10～40%
With gel-type water-soluble binder 60～90%;
Described amorphous poly ethylene oxide class water-soluble binder is meant the block copolymer that on the polyethylene glycol oxide strand, inserts the small molecule structure unit and form;
Described gel-type water-soluble binder is several kinds of a kind of or arbitrary proportion in polyethylene nitrile, polyvinyl chloride, polyvinyl acetate, polyacrylic acid glycol ester, the polymethyl methacrylate.
2. a kind of lithium ion battery according to claim 1 is characterized in that: described small molecule structure unit is several kinds of a kind of or arbitrary proportion in inferior methoxyl group, epoxy chloroethanes, siloxanes, phosphoric acid resin and the aluminic acid ester.
3. 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 adhesive, the deionized water is: conductive agent, thickener, compound water soluble adhesive, deionized water are benchmark with the weight of positive active material: the content of conductive agent be positive active material weight 0.5～10%; 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%.
4. according to claim 1 or 3 described a kind of lithium ion batteries, it is characterized in that: described conductive agent is several kinds of a kind of or arbitrary proportion in carbon black, acetylene black, carbon fiber, the flake graphite.
5. according to claim 1 or 3 described a kind of lithium ion batteries, it is characterized in that: described thickener is that carboxymethyl cellulose is received, several kinds of a kind of or arbitrary proportion in hydroxyethylcellulose, hydroxypropyl methylcellulose, hydroxypropyl cellulose, methylcellulose and the polyacrylic acid.
6. according to claim 1 or 3 described a kind of lithium ion batteries, it 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.
7. a kind of lithium ion battery according to claim 6 is characterized in that: the content of described surface tension modifier is for being benchmark with the weight of positive active material, its content be positive active material weight 5～40%.
8. a kind of lithium ion battery according to claim 6 is characterized in that: described alcohol is several kinds of a kind of or arbitrary proportion in ethanol, ethylene glycol, butanols and the propyl alcohol; Described ether is several kinds of a kind of or arbitrary proportion in ethylene glycol ethyl ether, butyl glycol ether and the n-butyl ether.
9. according to claim 1 or 3 described a kind of lithium ion batteries, it is characterized in that: described negative pole is for evenly to be coated in Delanium, native graphite, agraphitic carbon, hard carbon or lithium titanate on the collector, and thickness is the 50-200 micron.
10. according to claim 1 or 3 described a kind of lithium ion batteries, it is characterized in that: described electrolyte contains lithium salts and nonaqueous solvents, and wherein the concentration of lithium salts in electrolyte is 0.5～2.0 mol.
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| CN103035901A (en) * | 2012-12-20 | 2013-04-10 | 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 |
| CN104466187A (en) * | 2014-12-10 | 2015-03-25 | 东莞新能源科技有限公司 | Positive electrode membrane and lithium ion battery using same |
| 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 |
| CN109360936A (en) * | 2018-11-01 | 2019-02-19 | 天能电池集团有限公司 | A kind of based lithium-ion battery positive plate and preparation method thereof |
| CN109888170A (en) * | 2019-01-23 | 2019-06-14 | 西安交通大学 | Three-dimensional network adhesive and preparation method and negative electrode slurry and negative electrode material for secondary cell |
| CN112599726A (en) * | 2020-12-25 | 2021-04-02 | 上海奥威科技开发有限公司 | Gel polymer lithium ion capacitor battery and electrode 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 |
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| CN103035901A (en) * | 2012-12-20 | 2013-04-10 | 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 |
| CN104466187A (en) * | 2014-12-10 | 2015-03-25 | 东莞新能源科技有限公司 | Positive electrode membrane and lithium ion battery using same |
| 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 |
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| CN109360936A (en) * | 2018-11-01 | 2019-02-19 | 天能电池集团有限公司 | A kind of based lithium-ion battery positive plate and preparation method thereof |
| CN109888170A (en) * | 2019-01-23 | 2019-06-14 | 西安交通大学 | Three-dimensional network adhesive and preparation method and negative electrode slurry and negative electrode material for secondary cell |
| 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 |
| CN112599726A (en) * | 2020-12-25 | 2021-04-02 | 上海奥威科技开发有限公司 | Gel polymer lithium ion capacitor battery and electrode and preparation method thereof |
| 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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Effective date of registration: 20180424 Address after: 610000, No. 18, West core road, hi tech West District, Sichuan, Chengdu Patentee after: Dongfang Electric Co., Ltd. Address before: Jinniu District Chengdu City, Sichuan province 610036 Shu Road No. 333 Patentee before: Dongfang Electric Corporation |