CN101651211A - Anode material composition, and anode and battery comprising same - Google Patents
Anode material composition, and anode and battery comprising same Download PDFInfo
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- CN101651211A CN101651211A CN200810145711A CN200810145711A CN101651211A CN 101651211 A CN101651211 A CN 101651211A CN 200810145711 A CN200810145711 A CN 200810145711A CN 200810145711 A CN200810145711 A CN 200810145711A CN 101651211 A CN101651211 A CN 101651211A
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- Prior art keywords
- positive electrode
- positive
- lithium
- pole
- anode
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- 239000000203 mixture Substances 0.000 title claims abstract description 43
- 239000010405 anode material Substances 0.000 title abstract 6
- 229920001577 copolymer Polymers 0.000 claims abstract description 22
- -1 alkenyl halides Chemical class 0.000 claims abstract description 19
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 17
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000011230 binding agent Substances 0.000 claims abstract description 16
- 229910052744 lithium Inorganic materials 0.000 claims description 25
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 22
- 239000007774 positive electrode material Substances 0.000 claims description 21
- 238000010276 construction Methods 0.000 claims description 20
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 claims description 15
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 15
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 12
- 230000004888 barrier function Effects 0.000 claims description 11
- 239000003792 electrolyte Substances 0.000 claims description 11
- 229910052731 fluorine Inorganic materials 0.000 claims description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 9
- 239000011737 fluorine Substances 0.000 claims description 8
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 7
- 229910052740 iodine Inorganic materials 0.000 claims description 7
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 6
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 6
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 6
- 229910010707 LiFePO 4 Inorganic materials 0.000 claims description 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 6
- 239000005864 Sulphur Substances 0.000 claims description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 6
- 239000004411 aluminium Substances 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- 229910052796 boron Inorganic materials 0.000 claims description 6
- 229910052804 chromium Inorganic materials 0.000 claims description 6
- 239000011651 chromium Substances 0.000 claims description 6
- 229910017052 cobalt Inorganic materials 0.000 claims description 6
- 239000010941 cobalt Substances 0.000 claims description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 6
- 229910052733 gallium Inorganic materials 0.000 claims description 6
- 239000011630 iodine Substances 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 6
- 229910052749 magnesium Inorganic materials 0.000 claims description 6
- 239000011777 magnesium Substances 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 238000007789 sealing Methods 0.000 claims description 6
- 229910052719 titanium Inorganic materials 0.000 claims description 6
- 239000010936 titanium Substances 0.000 claims description 6
- 229910052727 yttrium Inorganic materials 0.000 claims description 6
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 6
- 229910052725 zinc Inorganic materials 0.000 claims description 6
- 239000011701 zinc Substances 0.000 claims description 6
- 125000005843 halogen group Chemical group 0.000 claims description 5
- 229910017018 Ni0.8Co0.15Al0.05 Inorganic materials 0.000 claims description 4
- 239000000853 adhesive Substances 0.000 claims description 3
- 230000001070 adhesive effect Effects 0.000 claims description 3
- 150000002641 lithium Chemical class 0.000 claims description 3
- 239000011572 manganese Substances 0.000 claims description 3
- 229910052723 transition metal Inorganic materials 0.000 claims description 3
- 150000003624 transition metals Chemical class 0.000 claims description 3
- MIZLGWKEZAPEFJ-UHFFFAOYSA-N 1,1,2-trifluoroethene Chemical group FC=C(F)F MIZLGWKEZAPEFJ-UHFFFAOYSA-N 0.000 claims description 2
- 229910015014 LiNiCoAlO Inorganic materials 0.000 claims description 2
- 229910013210 LiNiMnCoO Inorganic materials 0.000 claims description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical compound FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims 2
- 238000000034 method Methods 0.000 abstract description 17
- 239000006258 conductive agent Substances 0.000 abstract description 12
- 239000002002 slurry Substances 0.000 abstract description 11
- 239000013543 active substance Substances 0.000 abstract 1
- 239000011884 anode binding agent Substances 0.000 abstract 1
- 239000006256 anode slurry Substances 0.000 abstract 1
- 238000002360 preparation method Methods 0.000 description 26
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 13
- 239000003795 chemical substances by application Substances 0.000 description 13
- 238000004513 sizing Methods 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 11
- 239000000047 product Substances 0.000 description 10
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 7
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 239000006230 acetylene black Substances 0.000 description 6
- 239000007773 negative electrode material Substances 0.000 description 6
- 239000004698 Polyethylene Substances 0.000 description 5
- 239000005030 aluminium foil Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000012528 membrane Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 238000005096 rolling process Methods 0.000 description 5
- 108010010803 Gelatin Proteins 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000008273 gelatin Substances 0.000 description 4
- 229920000159 gelatin Polymers 0.000 description 4
- 235000019322 gelatine Nutrition 0.000 description 4
- 235000011852 gelatine desserts Nutrition 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 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
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 3
- 239000001768 carboxy methyl cellulose Substances 0.000 description 3
- 230000006835 compression Effects 0.000 description 3
- 238000007906 compression Methods 0.000 description 3
- 239000011889 copper foil Substances 0.000 description 3
- 229910003002 lithium salt Inorganic materials 0.000 description 3
- 159000000002 lithium salts Chemical class 0.000 description 3
- 229920000098 polyolefin Polymers 0.000 description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- COVXBJIKNGVTNV-UHFFFAOYSA-N 1-chloro-1,2,2-trifluoroethene;1,1-difluoroethene Chemical group FC(F)=C.FC(F)=C(F)Cl COVXBJIKNGVTNV-UHFFFAOYSA-N 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 2
- SUAKHGWARZSWIH-UHFFFAOYSA-N N,N‐diethylformamide Chemical compound CCN(CC)C=O SUAKHGWARZSWIH-UHFFFAOYSA-N 0.000 description 2
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 238000003490 calendering Methods 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 2
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 229960001760 dimethyl sulfoxide Drugs 0.000 description 2
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 2
- 125000001153 fluoro group Chemical group F* 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
- 230000014759 maintenance of location Effects 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 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
- 229910000676 Si alloy Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- NOJZFGZMTUAHLD-UHFFFAOYSA-N [Li].[Cl] Chemical compound [Li].[Cl] NOJZFGZMTUAHLD-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000001246 bromo group Chemical group Br* 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
- 229910052799 carbon Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000002950 deficient 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
- 238000010292 electrical insulation Methods 0.000 description 1
- 239000011883 electrode binding agent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 239000011152 fibreglass Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000006232 furnace black Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 235000015110 jellies Nutrition 0.000 description 1
- 239000008274 jelly Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- YQNQTEBHHUSESQ-UHFFFAOYSA-N lithium aluminate Chemical compound [Li+].[O-][Al]=O YQNQTEBHHUSESQ-UHFFFAOYSA-N 0.000 description 1
- RSNHXDVSISOZOB-UHFFFAOYSA-N lithium nickel Chemical compound [Li].[Ni] RSNHXDVSISOZOB-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
- 238000005259 measurement Methods 0.000 description 1
- 150000002895 organic esters Chemical class 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000002006 petroleum coke Substances 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
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 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 provides an anode material composition for a lithium-ion secondary battery. The composition comprises an anode active substance, a conductive agent and an anode binding agent, wherein the binding agent is copolymer, which comprises a structural unit formed by VDF and a structural unit formed by alkenyl halides. The invention further provides an anode of the lithium-ion secondary battery. The anode comprises a current collector and an anode material loaded on the current collector, wherein the anode material is the anode material composition provided by the invention. The invention further provides a lithium-ion secondary battery. When preparing anode slurry from the anode material composition provided by the invention, the gel phenomenon is difficult to happen and strip breakage cannot occur in the slurry process. The prepared pole piece has excellent flexibility and high yield; besides, the lithium-ion battery provided by the invention has high initial capacity and goodcycle performance.
Description
Technical field
The present invention relates to a kind of positive electrode composition and comprise the anodal of said composition and comprise the battery that this is anodal.
Background technology
Lithium rechargeable battery has obtained huge development with advantages such as its high-energy-density, high voltage, little, in light weight, the memoryless property of volume over past ten years, become one of main energy sources of communication class electronic product.
At present, when the preparation lithium ion battery, the anode sizing agent instability often appears; When positive active material is Li
xNi
1-yCoA
zO
2, Li
1+aM
bMn
2-bO
4, Li
mMn
2-nB
nO
2And LiFePO
4In one or more, wherein, 0.9≤x≤1.1,0≤y≤1.0,0≤z≤0.2 ,-0.1≤a≤0.2,0≤b≤1.0, A is a kind of in boron, magnesium, aluminium, titanium, chromium, iron, cobalt, nickel, copper, zinc, gallium, yttrium, fluorine, iodine and the element sulphur, M is a kind of in lithium, boron, magnesium, aluminium, titanium, chromium, iron, cobalt, nickel, copper, zinc, gallium, yttrium, fluorine, iodine and the element sulphur, and B is one or more in the transition metal, 0.9≤m≤1.1,0≤n≤1.0, this phenomenon is more obvious.As when positive active material is the lithium nickel compound, be prone to gelatin phenomenon in the process of preparation slurry, slurry retrogradation gradually in the pulling phase broken belt frequently occurs so that can't slurry, and the pole piece of making is more crisp, fall material easily, thereby cause anodal rate of finished products low.
Summary of the invention
The objective of the invention is to overcome the unstable and low shortcoming of anodal rate of finished products of anode sizing agent in the prior art, a kind of positive electrode composition and the positive pole and the battery that contain this positive electrode composition that can improve the stability of anode sizing agent is provided.
The present inventor is surprised to find that, when the binding agent in the positive electrode is to contain the construction unit that formed by vinylidene fluoride and during the copolymer of the construction unit that formed by alkenyl halide, the anode sizing agent of preparation is stable, be not prone to gelatin phenomenon, in the pulling phase broken belt can not appear, and the pole piece of making has pliability preferably, the rate of finished products height.
The invention provides a kind of positive electrode composition that is used for lithium rechargeable battery, said composition comprises positive active material, conductive agent and anodal binding agent, wherein, described binding agent is a copolymer, and this copolymer contains construction unit that is formed by vinylidene fluoride and the construction unit that is formed by alkenyl halide.
The present invention also provides a kind of lithium ion secondary battery positive electrode, and this positive pole comprises collector and the positive electrode that loads on the collector, and wherein, described positive electrode is a positive electrode composition provided by the invention.
The present invention also provides a kind of lithium rechargeable battery, this lithium rechargeable battery comprises battery case, pole piece and electrolyte, described pole piece and electrolyte sealing are contained in the battery case, described pole piece comprises positive pole, negative pole and the barrier film between positive pole and negative pole, wherein, described positive pole just very provided by the invention.
When adopting positive electrode preparation of compositions anode sizing agent provided by the invention, be not prone to gelatin phenomenon, broken belt can not occur in the pulling phase, and the pole piece of making has pliability preferably, the rate of finished products height; In addition, the initial capacity of lithium ion battery provided by the invention is higher, and cycle performance is better.
Embodiment
The invention provides a kind of positive electrode composition that is used for lithium rechargeable battery, said composition comprises positive active material and anodal binding agent, wherein, described binding agent is a copolymer, and this copolymer contains construction unit that is formed by vinylidene fluoride and the construction unit that is formed by alkenyl halide.
The described copolymer that contains the construction unit that formed by vinylidene fluoride and formed by alkenyl halide can contain construction unit that is formed by vinylidene fluoride and the copolymer that is formed by alkenyl halide for any.A kind of preferred embodiment in, in described copolymer, total amount with described copolymer is a benchmark, the content of the construction unit that is formed by vinylidene fluoride is 30-90 weight %, 50-80 weight % more preferably, the content of the construction unit that is formed by perhalogeno alkene is 10-70 weight %, more preferably 15-60 weight %; In another preferred embodiment, the described weight average molecular weight that contains the copolymer of the construction unit that is formed by vinylidene fluoride can be 200000-700000, more preferably 200000-450000.The example of the described copolymer that contains the construction unit that formed by vinylidene fluoride and formed by alkenyl halide can be vinylidene fluoride-alkenyl halide copolymer, described alkenyl halide can be preferably the C that is replaced by halogen atom for the various alkene that replaced by halogen atom except that vinylidene fluoride
2-6Alkene, the C that is replaced by halogen atom more preferably
2-3Alkene.Described halogen atom can be in fluorine atom, chlorine atom, bromine atoms and the iodine atom one or more, is preferably fluorine atom and/or chlorine atom.The example of described alkenyl halide includes but not limited to one or more in hexafluoropropylene, chlorotrifluoroethylene, tetrafluoroethene, trifluoro-ethylene, the PVF.These copolymers can be by commercially available or can prepare according to the conventional preparation method of copolymer.
In described positive electrode composition, the content of described positive active material and binding agent can be the customary amount in this area; A kind of preferred embodiment in, with respect to the positive active material of 100 weight portions, the content of described adhesive can be the 0.05-12 weight portion, is preferably the 0.1-8 weight portion.
Described positive active material can be preferably Li for any positive active material that can be purchased in the prior art
xNi
1-yCo
wA
zO
2, Li
1+aM
bMn
2-bO
4, Li
mMn
2-nB
nO
2And LiFePO
4In one or more, wherein, 0.9≤x≤1.1,0≤y≤1.0,0≤w≤1.0,0≤z≤1 ,-0.1≤a≤0.2 and 0≤b≤1.0, A is a kind of in boron, magnesium, aluminium, titanium, chromium, manganese, iron, cobalt, nickel, copper, zinc, gallium, yttrium, fluorine, iodine and the element sulphur, M is a kind of in lithium, boron, magnesium, aluminium, titanium, chromium, iron, cobalt, nickel, copper, zinc, gallium, yttrium, fluorine, iodine and the element sulphur, B is one or more in the transition metal, 0.9≤m≤1.1,0≤n≤1.0.A kind of preferred embodiment in, described positive active material is Li[Ni
0.8Co
0.15Al
0.05] O
2, LiFePO
4, LiNiCoAlO
2And LiNiMnCoO
2In one or more.Because when using these compounds to prepare slurry as positive active material, slurry is very unstable, gelatin phenomenon very easily occurs, pulling phase broken belt frequently occurs and the pole piece made is more crisp, fall material easily, and rate of finished products is low; And, adopt the capacity at the beginning of lithium ion battery of these compound lower, cycle performance is relatively poor, and therefore, when positive active material was these compounds, composition provided by the invention can greatly improve described defective.
A kind of preferred embodiment in, positive electrode composition of the present invention can also comprise conductive agent, described conductive agent can be the anodal conductive agent of this area routine, as in acetylene black, conductive carbon black and the electrically conductive graphite one or more.The content of described conductive agent can be the 2-12 weight portion, is preferably the 3-10 weight portion.
The present invention also provides a kind of lithium ion secondary battery positive electrode, and this positive pole comprises collector and the positive electrode that loads on the collector, and wherein, described positive electrode is a positive electrode composition provided by the invention.
Described plus plate current-collecting body is a plus plate current-collecting body known in those skilled in the art, for example can be selected from aluminium foil, Copper Foil or various Punching steel strip.
The positive pole of lithium rechargeable battery provided by the invention can make according to the preparation method of the lithium ion cell positive of routine, for example with positive electrode composition and solvent, makes anode sizing agent; Anode sizing agent is applied and/or is filled on the plus plate current-collecting body, and drying is rolled or is not rolled, and can obtain positive pole.Wherein, drying, the method for calendering and condition are method known in those skilled in the art.
Described solvent can be in N-methyl pyrrolidone (NMP), dimethyl formamide (DMF), diethylformamide (DEF), dimethyl sulfoxide (DMSO) (DMSO), oxolane (THF) and water and the alcohol one or more.The consumption of solvent can make described anode sizing agent have viscosity and flowability, can be coated on the described collector to get final product.In general, be benchmark with the weight of positive active material, the consumption of described solvent can be 40-100 weight %.
The present invention also provides a kind of lithium rechargeable battery, this lithium rechargeable battery comprises battery case, pole piece and electrolyte, described pole piece and electrolyte sealing are contained in the battery case, described pole piece comprises positive pole, negative pole and the barrier film between positive pole and negative pole, wherein, described positive pole just very provided by the invention.
In lithium rechargeable battery of the present invention, membrane layer is arranged between positive pole and the negative pole, has electrical insulation capability and liquid retainability energy.Described membrane layer can be selected from and well known to a person skilled in the art various membrane layers used in the lithium rechargeable battery, for example polyolefin micro porous polyolefin membrane (PP), polyethylene felt (PE), glass mat or ultra-fine fibre glass paper or PP/PE/PP.As preferred embodiment a kind of, described barrier film is PP/PE/PP.
Consisting of of described negative pole is conventionally known to one of skill in the art.In general, negative pole comprises collector and loads on negative material on the collector that described negative material comprises negative electrode active material and binding agent; Under the preferable case, described negative pole also comprises conductive agent.
Described negative electrode active material can be the negative electrode active material that embeds and disengage lithium of this area routine, such as in native graphite, Delanium, petroleum coke, organic cracking carbon, carbonaceous mesophase spherules, carbon fiber, ashbury metal, the silicon alloy one or more, be preferably electrographite.
The kind of described negative pole binding agent and content are conventionally known to one of skill in the art, for example one or more in fluorine resin and polyolefin compound such as polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), butadiene-styrene rubber (SBR) and the sodium carboxymethylcellulose (CMC); In general, according to the difference of used binding agent kind, with respect to the negative electrode active material of 100 weight portions, the content of negative pole binding agent is the 0.005-8 weight portion, is preferably the 0.008-5 weight portion.
Described conductive agent can be the conductive agent of this area routine, such as in carbon black, acetylene black, furnace black, carbon fiber, conductive carbon black and the electrically conductive graphite one or more.With respect to the negative electrode active material of 100 weight portions, the content of described conductive agent can be the 0-15 weight portion, is preferably the 1-10 weight portion.
The collector of described negative pole can be for negative current collector commonly used in the lithium ion battery, as stamped metal, metal forming, net metal and foamed metal, and preferred Copper Foil.
The preparation method of described negative pole can adopt conventional preparation method.For example, negative electrode active material, conductive agent and negative pole binding agent and solvent are made cathode size, apply and/or be filled on the described collector body, drying is rolled or is not rolled, and can obtain described negative pole.Wherein, drying, the method for calendering and condition are conventionally known to one of skill in the art.
Described electrolyte contains lithium salts and nonaqueous solvents, and described lithium salts can be 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 one or more; Described nonaqueous solvents can be gamma-butyrolacton, methyl ethyl carbonate, carbonic acid first propyl ester, dipropyl carbonate, acid anhydrides, N-methyl pyrrolidone, N-methylformamide, N-methylacetamide, acetonitrile, N, and dinethylformamide, sulfolane, methyl-sulfoxide, dimethyl sulfite and other are fluorine-containing, sulfur-bearing or contain in the ring-type organic ester of unsaturated bond one or more.The concentration of described lithium salts in electrolyte can be the 0.3-4 mol, is preferably the 0.5-2 mol.
The preparation method of lithium rechargeable battery provided by the invention can be method as well known to those skilled in the art, in general, this method comprises positive pole, negative pole and the barrier film between positive pole and the negative pole formation pole piece of reeling successively, pole piece is inserted in the battery case, add electrolyte, sealing then, wherein, described positive pole comprises collector and the positive electrode that loads on the collector, described positive electrode contains positive active material, conductive agent and anodal binding agent, wherein, described anodal binding agent and/or described negative pole binding agent are adhesive composition provided by the invention.Wherein, the method for coiling and sealing is that those skilled in the art are known.The consumption of electrolyte is a conventional amount used.
Below be that example illustrates lithium rechargeable battery of the present invention with 053450 size battery.
Embodiment 1
Present embodiment is used to illustrate lithium rechargeable battery provided by the invention and preparation method thereof.
Positive electrode composition: with Li[Ni
0.8Co
0.15Al
0.05] O
2(Japanese JFE), acetylene black (DENKA_50% compression) and vinylidene fluoride-chlorotrifluoroethylene (7500PVDF of Wu Yu chemical company, vinylidene fluoride construction unit content is 75 weight %, and weight average molecular weight is 250000-300000) mixed by weight 100: 3: 1.2.
Anodal: as the positive electrode composition of above-mentioned preparation is made into slurry and is two-sided dressing on 12 microns the aluminium foil at thickness with NMP, smear evenly.90 ℃ of oven dry down, roll, rolling cut becomes positive plate, and the pole piece size is 50.0cm (length) * 4.4cm (wide) * 0.012cm (thick), contains 8 gram positive active materials.
Negative pole: is 100: 100: 1.0 with Delanium, water, CMC and SBR according to weight ratio: 2.5 evenly mix.Be two-sided dressing on 8 microns the Copper Foil at thickness, smear evenly.90 ℃ of oven dry down, roll, rolling cut becomes negative plate, and the pole piece size is 51.4cm (length) * 4.5cm (wide) * 0.0137cm (thick), and negative material graphite weighs 4.26 grams.
Barrier film: adopt the PP/PE/PP film.
With the lithium-ion electric core of an above-mentioned positive and negative plate and a square of membrane coil coiled and be received in the rectangular cell shell, inject 1 mol LiPF subsequently
6/ (EC+DEC+DMC) (EC, DEC and DMC weight ratio are 1: 1: 1) electrolyte, the lithium ion battery C1 of 053450 type is made in sealing.
Comparative Examples 1
This Comparative Examples is used to illustrate lithium rechargeable battery that prior art provides and preparation method thereof.
Method according to embodiment 1 is carried out, and different is that when the preparation positive electrode composition, 7500PVDF replaces with polyvinylidene fluoride.Make lithium ion battery CC1.
Embodiment 2
Present embodiment is used to illustrate lithium rechargeable battery provided by the invention and preparation method thereof.
Positive electrode composition: with Li[Ni
0.8Co
0.15Al
0.05] O
2(identical), acetylene black (DENKA 50% compression) and vinylidene fluoride-tetrafluoraoethylene-hexafluoropropylene copolymer (ElfAltochem with the source of embodiment 1, vinylidene fluoride construction unit content is 65 weight %, and weight average molecular weight is 600000-650000) mixed by weight 100: 3: 3.5.
Anodal: as the positive electrode composition of above-mentioned preparation is mixed with slurry and is two-sided dressing on 12 microns the aluminium foil at thickness with NMP, smear evenly.90 ℃ of oven dry down, roll, rolling cut becomes positive plate, and the pole piece size is 50.0cm (length) * 4.4cm (wide) * 0.012cm (thick), contains 8 gram positive active materials.
Negative pole: the method for preparing negative pole according to embodiment 1 is carried out.
Barrier film: identical with embodiment 1.
Method assembled battery C2 according to embodiment 1.
Embodiment 3
Present embodiment is used to illustrate lithium rechargeable battery provided by the invention and preparation method thereof.
Positive electrode composition: with LiFePO
4(this special blue CP02 of Tianjin), acetylene black (DENKA and vinylidene difluoride-hexafluoropropylene copolymer (ArkemaInc., weight average molecular weight is 400000-450000, vinylidene fluoride construction unit content is 65 weight %) mixed by weight 100: 3: 7.
Anodal: as the positive electrode composition of above-mentioned preparation is mixed with slurry and is two-sided dressing on 12 microns the aluminium foil at thickness with NMP, smear evenly.90 ℃ of oven dry down, roll, rolling cut becomes positive plate, and the pole piece size is 50.0cm (length) * 4.4cm (wide) * 0.012cm (thick), contains 8 gram positive active materials.Negative pole: the method for preparing negative pole according to embodiment 1 is carried out.
Barrier film: adopt the barrier film identical with embodiment 1.
Method assembled battery C3 according to embodiment 1.
Embodiment 4
Present embodiment is used to illustrate lithium rechargeable battery provided by the invention and preparation method thereof.
Positive electrode composition: with Li (CoNiMn) O2 (Japanese three morals), acetylene black (DENKA_50% compression) and vinylidene fluoride-chlorotrifluoroethylene (Wu Yu chemical company, vinylidene fluoride construction unit content is 80 weight %, and weight average molecular weight is 350000-400000) mixed by weight 100: 3: 0.4.
Anodal: as the positive electrode composition of above-mentioned preparation is mixed with slurry and is two-sided dressing on 12 microns the aluminium foil at thickness with NMP, smear evenly.90 ℃ of oven dry down, roll, rolling cut becomes positive plate, and the pole piece size is 50.0cm (length) * 4.4cm (wide) * 0.012cm (thick), contains 8 gram positive active materials.
Negative pole: the method for preparing negative pole according to embodiment 1 is carried out.
Barrier film: adopt the barrier film identical with embodiment 1.
Method assembled battery C4 according to embodiment 1.
Battery performance test
1, the viscosity measurements of anode sizing agent
According to embodiment 1 and Comparative Examples 1 preparation anode sizing agent, slurry is at room temperature placed, and respectively when 0 minute, 15 minutes, 30 minutes, 45 minutes, 60 minutes and 120 minutes with the results are shown in the table 1 that viscosimeter (the outstanding bright scientific instrument in Shanghai, model RVDV-11+PRO) detects.
Table 1
As can be seen from Table 1: the anode sizing agent viscosity that adopts Comparative Examples 1 to prepare is very high and along with the time lengthening of placing, its viscosity increase is very fast, and in the time of 30 minutes, the anode sizing agent of Comparative Examples 1 preparation has become the jelly shape, can not apply; And adopt the anode sizing agent viscosity of embodiment 1 preparation very low and very stable, even after placing 120 minutes, its viscosity changes very little.
2, anodal rate of finished products detects
Prepare 30 of positive plates according to embodiment 1-4 and Comparative Examples 1, and write down the number that obtains normal positive plate respectively.What record the results are shown in the table 2.
3, the test of capacity
Under the room temperature, the battery that embodiment 1-4 and Comparative Examples 1 are made is respectively with 1C current charges to 4.2 volt, and after voltage rose to 4.2 volts, with 4.2 volts of constant-potential charges, cut-off current was 0.05C, shelved 5 minutes; Then battery is lied prostrate with 1C current discharge to 3.1 respectively, obtain the capacity of battery normal temperature 1C current discharge to 3.1 volt.What record the results are shown in the table 2.
4, the mensuration of cycle performance
Under the room temperature, the battery that embodiment 1-4 and Comparative Examples 1 are made lies prostrate with 1C current charges to 4.2 respectively, after voltage rises to 4.2 volts, with 4.2 volts of constant-potential charges, cut-off current is 0.05C, shelved 5 minutes, and then battery was lied prostrate with 1C current discharge to 3.1 respectively, obtain the capacity of battery normal temperature 1C current discharge to 3.1 volt; Discharge and recharge step 500 time more than the repetition, measure the capacity of 500 circulation backs of battery normal temperature 1C current discharge to 2.5V, and calculate the 500th capacity after the circulation according to following formula and keep the capacity of back 1C current discharge, and calculate the capability retention after the circulation the 500th time according to following formula to 2.5V.
500 circulation volume conservation rate=500th time circulation back discharge capacity/initial discharge capacity * 100%, test result is listed in table 2.
5, the mensuration of security performance
The battery that embodiment 1-4 and Comparative Examples 1 are made respectively with the constant current charge of 950mA to 12V, observe the phenomenon of battery surface.
Table 2
| The battery numbering | Anodal rate of finished products (%) | 1C discharge capacity (MAH) | Capability retention (%) | Security performance |
| C1 | 95 | ??1250 | 92 | Not on fire, no leakage |
| CC1 | 30 | ??1080 | 60 | Leakage, on fire takes place |
| C2 | 95 | ??1245 | 93 | Not on fire, no leakage |
| C3 | 96 | ??1245 | 90 | Not on fire, no leakage |
| C4 | 93 | ??1250 | 91.5 | Not on fire, no leakage |
As can be seen from Table 2: adopt method of the present invention when lithium ion anodal of preparation, anodal rate of finished products height is 95%, and when adopting the Comparative Examples preparation anodal, anodal rate of finished products is very low, is 30%; In addition, the capacity of the battery of employing the inventive method preparation and cycle performance are apparently higher than the lithium ion battery of Comparative Examples 1 preparation.
Claims (10)
1, a kind of positive electrode composition that is used for lithium rechargeable battery, said composition comprises positive active material and anodal binding agent, it is characterized in that described binding agent is a copolymer, this copolymer contains construction unit that is formed by vinylidene fluoride and the construction unit that is formed by alkenyl halide.
2, positive electrode composition according to claim 1, wherein, in described copolymer, be benchmark with the total amount of described copolymer, the content of the construction unit that is formed by vinylidene fluoride is 30-90 weight %, and the content of the construction unit that is formed by alkenyl halide is 10-70 weight %.
3, positive electrode composition according to claim 1 and 2, wherein, the weight average molecular weight of described copolymer is 200000-700000.
4, positive electrode composition according to claim 1 and 2, wherein, the C of described alkenyl halide for being replaced by halogen atom
2-6Alkene.
5, positive electrode composition according to claim 4, wherein, described alkenyl halide is one or more in hexafluoropropylene, chlorotrifluoroethylene, tetrafluoroethene and the trifluoro-ethylene.
6, positive electrode composition according to claim 1, wherein, with respect to the positive active material of 100 weight portions, the content of described adhesive is the 0.1-8 weight portion.
7, according to claim 1 or 6 described positive electrode compositions, wherein, described positive active material is Li
xNi
1-yCo
wA
zO
2, Li
1+aM
bMn
2-bO
4, Li
mMn
2-nB
nO
2And LiFePO
4In one or more, wherein, 0.9≤x≤1.1,0≤y≤1.0,0≤w≤1.0,0≤z≤1 ,-0.1≤a≤0.2 and 0≤b≤1.0, A is a kind of in boron, magnesium, aluminium, titanium, chromium, manganese, iron, cobalt, nickel, copper, zinc, gallium, yttrium, fluorine, iodine and the element sulphur, M is a kind of in lithium, boron, magnesium, aluminium, titanium, chromium, iron, cobalt, nickel, copper, zinc, gallium, yttrium, fluorine, iodine and the element sulphur, B is one or more in the transition metal, 0.9≤m≤1.1,0≤n≤1.0.
8, positive electrode composition according to claim 7, wherein, described positive active material is Li[Ni
0.8Co
0.15Al
0.05] O
2, LiFePO
4, LiNiCoAlO
2And LiNiMnCoO
2In one or more.
9, a kind of lithium ion secondary battery positive electrode, this positive pole comprise collector and the positive electrode that loads on the collector, it is characterized in that described positive electrode is any described positive electrode composition among the claim 1-8.
10, a kind of lithium rechargeable battery, this lithium rechargeable battery comprises battery case, pole piece and electrolyte, described pole piece and electrolyte sealing are contained in the battery case, described pole piece comprises positive pole, negative pole and the barrier film between positive pole and negative pole, it is characterized in that the described positive pole of described just very claim 9.
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| CN102449818A (en) * | 2010-03-31 | 2012-05-09 | 松下电器产业株式会社 | Positive electrode for lithium ion battery, method for producing same, and lithium ion battery using same |
| CN102449818B (en) * | 2010-03-31 | 2014-06-04 | 松下电器产业株式会社 | Positive electrode for lithium ion battery, method for producing same, and lithium ion battery using the positive electrode |
| CN101872863A (en) * | 2010-07-13 | 2010-10-27 | 深圳邦凯新能源股份有限公司 | Disposable cylindrical polymer lithium-ion battery and manufacturing method thereof |
| CN102074732A (en) * | 2010-12-25 | 2011-05-25 | 东莞市良源电池科技有限公司 | Lithium ion battery provided with high molecular weight adhesive |
| CN103579589A (en) * | 2012-07-25 | 2014-02-12 | 海洋王照明科技股份有限公司 | Graphene-silicon-graphene composite material, preparation method of graphene-silicon-graphene composite material, lithium ion battery and preparation method of lithium ion battery |
| CN104064736A (en) * | 2013-03-21 | 2014-09-24 | 海洋王照明科技股份有限公司 | Carbon nanotube/silicon/graphene composite material, preparation method thereof and lithium ion battery |
| CN107834058A (en) * | 2016-09-16 | 2018-03-23 | 株式会社东芝 | Nonaqueous electrolyte battery, battery bag and vehicle |
| CN112952092A (en) * | 2019-12-10 | 2021-06-11 | 惠州比亚迪电池有限公司 | Positive electrode binder and preparation method thereof, positive electrode slurry, positive electrode and lithium ion battery |
| CN112952092B (en) * | 2019-12-10 | 2022-11-11 | 惠州比亚迪电池有限公司 | Positive electrode binder and preparation method thereof, positive electrode slurry, positive electrode and lithium ion battery |
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