CN1967915B - Battery anode and lithium ion battery used the same and their preparing method - Google Patents
Battery anode and lithium ion battery used the same and their preparing method Download PDFInfo
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- CN1967915B CN1967915B CN200510114869XA CN200510114869A CN1967915B CN 1967915 B CN1967915 B CN 1967915B CN 200510114869X A CN200510114869X A CN 200510114869XA CN 200510114869 A CN200510114869 A CN 200510114869A CN 1967915 B CN1967915 B CN 1967915B
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- lithium ion
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Links
- 229910001416 lithium ion Inorganic materials 0.000 title claims description 56
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims description 49
- 238000000034 method Methods 0.000 title claims description 15
- 239000006258 conductive agent Substances 0.000 claims abstract description 88
- 239000000853 adhesive Substances 0.000 claims abstract description 26
- 230000001070 adhesive effect Effects 0.000 claims abstract description 26
- 238000002360 preparation method Methods 0.000 claims description 36
- 239000007774 positive electrode material Substances 0.000 claims description 30
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 25
- 239000008151 electrolyte solution Substances 0.000 claims description 21
- 241000209094 Oryza Species 0.000 claims description 18
- 235000007164 Oryza sativa Nutrition 0.000 claims description 18
- 235000009566 rice Nutrition 0.000 claims description 18
- 239000002002 slurry Substances 0.000 claims description 16
- 239000002904 solvent Substances 0.000 claims description 14
- 239000006229 carbon black Substances 0.000 claims description 13
- 229910002804 graphite Inorganic materials 0.000 claims description 13
- 239000010439 graphite Substances 0.000 claims description 13
- 239000003792 electrolyte Substances 0.000 claims description 12
- 229910013716 LiNi Inorganic materials 0.000 claims description 11
- 230000004888 barrier function Effects 0.000 claims description 11
- 239000006230 acetylene black Substances 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- 239000011248 coating agent Substances 0.000 claims description 6
- 238000000576 coating method Methods 0.000 claims description 6
- 238000003490 calendering Methods 0.000 claims description 3
- 229910052744 lithium Inorganic materials 0.000 abstract description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 6
- 239000010405 anode material Substances 0.000 abstract description 3
- 229910013421 LiNixCoyMn1-x-yO2 Inorganic materials 0.000 abstract 1
- 229910013427 LiNixCoyMn1−x−yO2 Inorganic materials 0.000 abstract 1
- 239000011149 active material Substances 0.000 abstract 1
- 239000006183 anode active material Substances 0.000 abstract 1
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 27
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 17
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 17
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 14
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 14
- 239000004810 polytetrafluoroethylene Substances 0.000 description 14
- -1 polytetrafluoroethylene Polymers 0.000 description 13
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 12
- 238000007600 charging Methods 0.000 description 12
- 235000019241 carbon black Nutrition 0.000 description 11
- 239000011572 manganese Substances 0.000 description 11
- 239000007773 negative electrode material Substances 0.000 description 11
- 238000005520 cutting process Methods 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- 239000002033 PVDF binder Substances 0.000 description 9
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 8
- 239000012528 membrane Substances 0.000 description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 7
- 239000005030 aluminium foil Substances 0.000 description 7
- 229910013872 LiPF Inorganic materials 0.000 description 6
- 101150058243 Lipf gene Proteins 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 239000011889 copper foil Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 229910013870 LiPF 6 Inorganic materials 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 238000005096 rolling process Methods 0.000 description 5
- 238000007789 sealing Methods 0.000 description 5
- 238000004513 sizing Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 4
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 4
- 229910015645 LiMn Inorganic materials 0.000 description 4
- 229910013290 LiNiO 2 Inorganic materials 0.000 description 4
- SUAKHGWARZSWIH-UHFFFAOYSA-N N,N‐diethylformamide Chemical compound CCN(CC)C=O SUAKHGWARZSWIH-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 229910052731 fluorine Inorganic materials 0.000 description 4
- 239000011737 fluorine Substances 0.000 description 4
- 229920000098 polyolefin Polymers 0.000 description 4
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000004087 circulation Effects 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 2
- 235000013339 cereals Nutrition 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- VUPKGFBOKBGHFZ-UHFFFAOYSA-N dipropyl carbonate Chemical compound CCCOC(=O)OCCC VUPKGFBOKBGHFZ-UHFFFAOYSA-N 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 229910003002 lithium salt Inorganic materials 0.000 description 2
- 159000000002 lithium salts Chemical class 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 238000004804 winding Methods 0.000 description 2
- 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
- 238000004438 BET method Methods 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 229910013733 LiCo Inorganic materials 0.000 description 1
- 229910013985 LiNi0.2Co0.2Mn0.6O2 Inorganic materials 0.000 description 1
- 229910013823 LiNi0.33Co0.33Mn0.34O2 Inorganic materials 0.000 description 1
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000004698 Polyethylene Substances 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
- NOJZFGZMTUAHLD-UHFFFAOYSA-N [Li].[Cl] Chemical compound [Li].[Cl] NOJZFGZMTUAHLD-UHFFFAOYSA-N 0.000 description 1
- IDSMHEZTLOUMLM-UHFFFAOYSA-N [Li].[O].[Co] Chemical compound [Li].[O].[Co] IDSMHEZTLOUMLM-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- SIXOAUAWLZKQKX-UHFFFAOYSA-N carbonic acid;prop-1-ene Chemical compound CC=C.OC(O)=O SIXOAUAWLZKQKX-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000010280 constant potential charging Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010292 electrical insulation Methods 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
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 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
- URIIGZKXFBNRAU-UHFFFAOYSA-N lithium;oxonickel Chemical compound [Li].[Ni]=O URIIGZKXFBNRAU-UHFFFAOYSA-N 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229910001437 manganese ion Inorganic materials 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- JEMDLNFQNCQAKN-UHFFFAOYSA-N nickel;oxomanganese Chemical compound [Ni].[Mn]=O JEMDLNFQNCQAKN-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 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
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000008053 sultones Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to an anode of lithium battery, wherein said anode comprises conductive base, and anode material coated and/filled on conductive base; said anode material comprises anode active material, conductive agent and adhesive; the active material is LiNixCoyMn1-x-yO2, while 0.1<=x<=0.5 and 0.1<=y<=0.5; the conductive agent contains sheet conductive agent and ball conductive agent. The invention also provides relative lithium battery, with high charge capacity and discharge capacity.
Description
Technical field
The invention relates to a kind of anode and use this anodal battery and their preparation method, specifically, the invention relates to a kind of anode and use this anodal lithium ion battery and their preparation method.
Background technology
Lithium ion battery is as a kind of chemical power source, refers to respectively the secondary cell that constitutes as both positive and negative polarity with two compounds that can reversibly embed with the removal lithium embedded ion.When battery charge, lithium ion takes off embedding from positive pole, in negative pole, embed, otherwise during discharge.Lithium ion battery mainly comprises electrode group and nonaqueous electrolytic solution, described electrode group and nonaqueous electrolytic solution are sealed in the battery container, described electrode group comprises battery electrode and barrier film, described battery electrode comprises positive pole and negative pole, described positive pole comprises conducting base and coating and/or is filled in positive electrode on the conducting base that described positive electrode comprises positive active material, conductive agent and adhesive.The anode preparation method comprises that the slurry that will contain positive electrode and solvent applies and/or is filled on the conducting base, and drying is rolled or do not rolled.
Positive electrode active materials in the anode material for lithium-ion batteries commonly used at present mainly contains lithium cobalt oxygen (LiCoO
2), lithium nickel oxygen (LiNiO
2) and nickel manganese oxygen (LiMn
2O
4).LiCoO
2Have good circulation (reversible discharging and recharging) and bigger discharge capacity (140mAh/g) greater than 500 times, but LiCoO
2The defective that can't remedy is arranged itself: the one, cobalt belongs to rare metal, and the reserves in the earth's crust are few, thereby cost an arm and a leg, and are drilled with poison simultaneously, and environment is had destruction; The 2nd, LiCoO
2Destroy at overcharge (charging voltage is higher than 4.2V) easy recurring structure, thermal stability is relatively poor, so charging voltage low (higher limit of charging voltage is 4.2V).LiNiO
2And LiMn
2O
4Price lower, environment is not polluted, but LiNiO
2The layer structure poor stability, and stoichiometric LiNiO
2Be difficult to synthesize, under the high temperature synthesis condition, can take place again the mixing occupy-place of lithium nickel at low temperatures.LiMn
2O
4Synthetic simple, but specific capacity little (120mAh/g), and since the manganese ion of high price under higher temperature, be easy to react LiMn with electrolyte
2O
4High temperature (50 ℃) cycle performance extreme difference.
Therefore, Many researchers has been placed on LiNiCoMnO with research emphasis recently
2On the ternary system, for example CN1614801A disclose a class novel the lithium ion battery multi-element composite positive pole material, the composition expression formula of this positive electrode is: LiCo
xNi
yMn
1-x-yO
2, 0.1≤x in the formula≤0.6,0.1≤y≤0.5, x+y≤1.This class composite positive pole has charging voltage height, specific capacity height and the good advantage of thermal stability.The raising of charging voltage can improve anodal specific capacity, but under higher charging voltage, because the specific area of existing anodal conductive agent is too big, decomposition reaction takes place on the conductive agent surface of positive pole in the organic solvent of electrolyte easily, cause electrolyte to reduce, make that the cycle performance of battery is relatively poor.Simultaneously,, but anodal electric conductivity is affected, makes battery capacity lower if adopt the less conductive agent of specific surface can reduce the reaction of electrolyte decomposition.
Summary of the invention
Goal of the invention of the present invention is to overcome existing use LiNiCoMnO
2The shortcoming that the lithium ion battery cycle performance is relatively poor, battery capacity is lower of composite material provides a kind of and can improve the lithium ion battery cycle performance simultaneously and improve the anode of battery capacity and use this anodal lithium ion battery.
Another object of the present invention provides the preparation method of anode and uses the preparation method of this anodal lithium ion battery.
The invention provides a kind of lithium ion cell positive, this positive pole comprises conducting base and coating and/or is filled in positive electrode on the conducting base, and described positive electrode comprises positive active material, conductive agent and adhesive, and described positive active material is LiNi
xCo
yMn
1-x-yO
2, 0.1≤x≤0.5,0.1≤y≤0.5, wherein, described conductive agent contains sheet conductive agent and spherical conductive agent.
The invention provides a kind of preparation method of lithium ion cell positive, this method comprises that the slurry that will contain positive electrode and solvent applies and/or is filled on the conducting base, dry, roll or do not roll, described positive electrode comprises positive active material, conductive agent and adhesive, and described positive active material is LiNi
xCo
yMn
1-x-yO
2, 0.1≤x≤0.5,0.1≤y≤0.5, wherein, described conductive agent contains sheet conductive agent and spherical conductive agent.
The invention provides a kind of lithium ion battery, this lithium ion battery comprises electrode group and nonaqueous electrolytic solution, described electrode group and nonaqueous electrolytic solution are sealed in the battery container, described electrode group comprises positive pole, negative pole and barrier film, described positive pole comprises conducting base and coating and/or is filled in positive electrode on the conducting base, described positive electrode comprises positive active material, conductive agent and adhesive, and described positive active material is LiNi
xCo
yMn
1-x-yO
2, 0.1≤x≤0.5,0.1≤y≤0.5, wherein, described conductive agent contains sheet conductive agent and spherical conductive agent.
The invention provides a kind of preparation method of lithium ion battery, this method comprises positive pole and the negative pole for preparing this battery, and positive pole, negative pole and barrier film are prepared into an electrode group, the electrode group and the electrolyte that obtain are sealed in the battery case, the preparation method of described positive pole comprises that the slurry that will contain positive electrode and solvent applies and/or is filled on the conducting base, dry, roll or do not roll, described positive electrode comprises positive active material, conductive agent and adhesive, and described positive active material is LiNi
xCo
yMn
1-x-yO
2, 0.1≤x≤0.5,0.1≤y≤0.5, wherein, described conductive agent contains sheet conductive agent and spherical conductive agent.
The conductive agent of lithium ion cell positive provided by the invention contains sheet conductive agent and spherical conductive agent, because the average grain diameter of sheet material with carbon element such as native graphite is relatively large, its specific area is less, generally at 50 meters
2Below/the gram; And the average grain diameter of spherical material with carbon element such as acetylene black is less relatively, and its specific area is bigger, at 200 meters
2About/gram, these two kinds of conductive agents are filled in the anodal dissimilar space mutually, played the effect of conduction well, improve the battery capacity of lithium ion battery, effectively avoid simultaneously the excessive shortcoming of conductive agent specific surface in the positive electrode again, suppress the decomposition of electrolyte, thereby improve the cycle performance of lithium ion battery.
Embodiment
The lithium ion cell positive that the invention provides comprises conducting base and coating and/or is filled in positive electrode on the conducting base, and described positive electrode comprises positive active material, conductive agent and adhesive, and described positive active material is LiNi
xCo
yMn
1-x-yO
2, 0.1≤x≤0.5,0.1≤y≤0.5, wherein, described conductive agent contains sheet conductive agent and spherical conductive agent.
The specific area of described sheet conductive agent is a 10-50 rice
2/ gram is preferably 20-45 rice
2/ gram.The kind of sheet conductive agent comprises graphite, is preferably native graphite.Described native graphite specific area is a 10-50 rice
2/ gram is preferably 20-45 rice
2/ gram.Wherein, in the present invention, specific area adopts cryogenic nitrogen absorption BET method to measure.Weight with described positive active material is benchmark, and the content of described sheet conductive agent is 0.2-5 weight %, is preferably 0.5-3 weight %.
The specific area of described spherical conductive agent is a 80-850 rice
2/ gram is preferably 100-800 rice
2/ gram.The kind of spherical conductive agent comprises acetylene black and carbon black.The specific area of described acetylene black is a 80-350 rice
2/ gram is preferably 100-300 rice
2/ gram.The specific area of described carbon black is a 400-850 rice
2/ gram is preferably 450-800 rice
2/ gram.Weight with described positive active material is benchmark, and the content of described spherical conductive agent is 0.2-5.5 weight %, is preferably 0.5-5 weight %.
According to lithium ion cell positive provided by the invention, described positive active material is LiNi
xCo
yMn
1-x-yO
2, 0.1≤x≤0.5,0.1≤y≤0.5 wherein.This positive active material has been conventionally known to one of skill in the art, can be commercially available, also can be by existing method preparation, for example disclosed method among the CN1614801A.
The kind of described adhesive 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), the butadiene-styrene rubber (SBR).In general, according to the difference of adhesive therefor kind, be benchmark with the weight of positive active material, the content of adhesive is 0.01-8 weight %, is preferably 0.02-5 weight %.
The kind of described anodal conducting base has been conventionally known to one of skill in the art, for example can be selected from aluminium foil, Punching steel strip.In the specific embodiment of the present invention, use aluminium foil as anodal conducting base.
The preparation method of described positive pole can adopt conventional preparation method.For example, with described positive electrode and solvent, apply and/or be filled on the described conducting base, drying is rolled or is not rolled, and can obtain described positive pole.Under the preferable case, earlier spherical conductive agent and sheet conductive agent are mixed, then conductive agent, positive active material, adhesive and the solvent that mixes evenly formed slurry, this slurry is applied and/or is filled on the conducting base, drying is rolled or is not rolled.Wherein, described solvent can be selected from one or more in N-methyl pyrrolidone (NMP), dimethyl formamide (DMF), diethylformamide (DEF), dimethyl sulfoxide (DMSO) (DMSO), the oxolane (THF); The consumption of solvent can make described pastel have viscosity and flowability, can be coated on the described conducting base to get final product.In general the weight with positive active material is benchmark, and the content 30-90 weight % of described solvent is preferably 35-85 weight %.Wherein, drying, the method for calendering and condition are conventionally known to one of skill in the art.
Lithium ion battery provided by the present invention comprises electrode group and nonaqueous electrolytic solution, and described electrode group and nonaqueous electrolytic solution are sealed in the battery container, and described electrode group comprises positive pole, negative pole and barrier film.Except using, can use conventional negative pole, barrier film, nonaqueous electrolytic solution by the positive pole provided by the invention.
Because the positive active material of lithium ion battery provided by the invention is LiNi
xCo
yMn
1-x-yO
2, the charging voltage of wherein 0.1≤x≤0.5,0.1≤y≤0.5, so lithium ion battery provided by the invention is more than or equal to 4.4 volts.
Described barrier film is arranged between positive pole and the negative pole, has electrical insulation capability and liquid retainability energy.Described barrier film can be selected from various barrier films used in the lithium ion battery, as polyolefin micro porous polyolefin membrane, polyethylene felt, glass mat or ultra-fine fibre glass paper.The position of described barrier film, character and kind are conventionally known to one of skill in the art.
Consisting of of described negative pole is conventionally known to one of skill in the art.In general, negative pole comprises conducting base and coating and/or is filled in negative material on the conducting base that described negative material comprises negative electrode active material and negative pole adhesive.
Described negative electrode active material is not particularly limited, can use embedding of this area routine to disengage the negative electrode active material of lithium, such as in native graphite, Delanium, petroleum coke, organic cracking carbon, carbonaceous mesophase spherules, carbon fiber, ashbury metal, the silicon alloy one or more, preferred natural graphite.
The kind of described negative pole adhesive 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), the butadiene-styrene rubber (SBR); In general, according to the difference of adhesive therefor kind, be benchmark with the weight of negative electrode active material, the content of negative pole adhesive is 0.01-8 weight %, is preferably 0.02-5 weight %.
Described negative material can also comprise conductive agent, and described conductive agent is not particularly limited, and can be the cathode conductive agent of this area routine, such as in carbon black, nickel powder, the copper powder one or more.Weight with negative electrode active material is benchmark, and the content of described conductive agent is 0-15 weight %, is preferably 2-10 weight %.
The negative pole conducting base can be for negative pole conducting base conventional in the lithium ion battery, as stamped metal, and metal forming, net metal, foamed metal uses Copper Foil as the negative pole conducting base in specific embodiments of the present invention.
The preparation method of described negative pole can adopt conventional preparation method.For example, with negative material and solvent, apply and/or be filled on the described conducting base, drying is rolled or is not rolled, and can obtain described negative pole.Wherein, described solvent can be selected from one or more in N-methyl pyrrolidone (NMP), dimethyl formamide (DMF), diethylformamide (DEF), dimethyl sulfoxide (DMSO) (DMSO), oxolane (THF) and water and the alcohols.The consumption of solvent can make described pastel have viscosity and flowability, can be coated on the described conducting base to get final product.In general, be benchmark with the weight of negative electrode active material, the content 30-90 weight % of described solvent is preferably 35-85 weight %.Wherein, drying, the method for calendering and condition are conventionally known to one of skill in the art.For example, the temperature of described drying is generally 100-150 ℃.
Described nonaqueous electrolytic solution is the mixed solution of electrolyte lithium salt and nonaqueous solvents, and it is not particularly limited, and can use the nonaqueous electrolytic solution of this area routine.Be selected from lithium hexafluoro phosphate (LiPF such as electrolyte lithium salt
6), in lithium perchlorate, LiBF4, hexafluoroarsenate lithium, lithium halide, chlorine lithium aluminate and the fluorocarbon based sulfonic acid lithium one or more.Organic solvent is selected chain acid esters and ring-type acid esters mixed solution for use, wherein the chain acid esters can be dimethyl carbonate (DMC), diethyl carbonate (DEC), methyl ethyl carbonate (EMC), carbonic acid first propyl ester (MPC), dipropyl carbonate (DPC) and other are fluorine-containing, sulfur-bearing or contain at least a in the chain organosilane ester of unsaturated bond, the ring-type acid esters can be ethylene carbonate (EC), propene carbonate (PC), vinylene carbonate (VC), gamma-butyrolacton (γ-BL), sultone and other are fluorine-containing, sulfur-bearing or contain at least a in the ring-type organosilane ester of unsaturated bond.The injection rate of electrolyte is generally 1.5-4.9g/Ah, the concentration of electrolyte be generally 0.5-2.9 rub/liter.
According to the preparation method of lithium ion battery provided by the invention, except described positive pole prepared according to method provided by the invention, other step was conventionally known to one of skill in the art.In general, described positive pole for preparing and negative pole winding are separated formation electrode group, electrode group and the electrolyte that obtains is sealed in the battery case, can obtain lithium ion battery provided by the invention by membrane layer.The method for winding of the membrane layer between positive pole and negative pole is conventionally known to one of skill in the art, does not repeat them here.
To the present invention be described in more detail by embodiment below.
Embodiment 1
This embodiment illustrates positive pole provided by the invention and contains this anodal lithium ion battery and their preparation method.
(1) Zheng Ji preparation
(specific area is 150 meters with the spherical conductive agent acetylene black of 4.5 weight portions
2/ gram) and the sheet conductive agent native graphite of 0.5 weight portion (specific area is 40 meters
2/ gram) mixes.
With 100 weight portion positive active material LiNi
0.33Co
0.33Mn
0.34O
2, 4 weight portion adhesive PVDF, the above-mentioned conductive agent that mixes of 5 weight portions join in the 40 weight portion N-methyl pyrrolidones (NMP), in de-airing mixer, stir then and form uniform anode sizing agent.
This slurry is coated on wide 400 millimeters, the thick 20 microns aluminium foil equably, and 120 ℃ of oven dry, roll-ins are cut on cutting machine and obtain being of a size of 385 millimeters * 42 millimeters * 135 microns positive pole afterwards then, wherein contain 4.8 gram cathode mixtures.
(2) preparation of negative pole
100 weight portion negative electrode active material native graphites, 4 weight portion adhesive polytetrafluoroethylene (PTFE)s, 4 weight portion conductive agent carbon blacks are joined in the 40 weight portion methyl-sulfoxides (DMSO), in de-airing mixer, stir then and form cathode size stable, homogeneous.
This slurry is coated on wide 400 millimeters, the thick 10 microns Copper Foil equably, after 120 ℃ of oven dry, rolling, on cutting machine, cuts and obtain being of a size of 43 millimeters * 355 millimeters * 135 microns negative pole, wherein contain 2.7 gram negative pole compounds.
(3) assembling of battery
With LiPF
6Be configured to LiPF with ethylene carbonate (EC) and diethyl carbonate (DEC)
6Concentration is the solution (wherein, the volume ratio of EC and DEC is 1: 1) of 1.0 mol, obtains nonaqueous electrolytic solution.The negative pole that positive pole, membrane layer, (2) that (1) is obtained obtain is successively with the stacked electrode group that is wound into scroll of up-coiler, the electrode group that obtains is put into the battery case of an end opening, and inject above-mentioned nonaqueous electrolytic solution with the amount of 3.8g/Ah, make lithium ion battery A1 after the sealing.
Embodiment 2
This embodiment illustrates positive pole provided by the invention and contains this anodal lithium ion battery and their preparation method.
(1) Zheng Ji preparation
(specific area is 600 meters with the spherical conductive agent carbon black of 4 weight portions
2/ gram) and the sheet conductive agent native graphite of 1 weight portion (specific area is 25 meters
2/ gram) mixes.
With 100 weight portion positive active material LiNi
0.1Co
0.1Mn
0.8O
2, 1 weight portion adhesive PVDF, the above-mentioned conductive agent that mixes of 5 weight portions join in the 70 weight portion N-methyl pyrrolidones (NMP), in de-airing mixer, stir then and form uniform anode sizing agent.
This slurry is coated on wide 400 millimeters, the thick 20 microns aluminium foil equably, and 120 ℃ of oven dry, roll-ins are cut on cutting machine and obtain being of a size of 385 millimeters * 42 millimeters * 135 microns positive pole afterwards then, wherein contain 4.8 gram cathode mixtures.
(2) preparation of negative pole
100 weight portion negative electrode active material native graphites, 2 weight portion adhesive polytetrafluoroethylene (PTFE)s, 6 weight portion conductive agent carbon blacks are joined in the 70 weight portion methyl-sulfoxides (DMSO), in de-airing mixer, stir then and form cathode size stable, homogeneous.
This slurry is coated on wide 400 millimeters, the thick 10 microns Copper Foil equably, after 120 ℃ of oven dry, rolling, on cutting machine, cuts and obtain being of a size of 43 millimeters * 355 millimeters * 135 microns negative pole, wherein contain 2.7 gram negative pole compounds.
(3) assembling of battery
With LiPF
6Be configured to LiPF with ethylene carbonate (EC) and diethyl carbonate (DEC)
6Concentration is the solution (wherein, the volume ratio of EC and DEC is 1: 1) of 1.0 mol, obtains nonaqueous electrolytic solution.The negative pole that positive pole, membrane layer, (2) that (1) is obtained obtain is successively with the stacked electrode group that is wound into scroll of up-coiler, the electrode group that obtains is put into the battery case of an end opening, and inject above-mentioned nonaqueous electrolytic solution with the amount of 3.8g/Ah, make lithium ion battery A2 after the sealing.
Embodiment 3
This embodiment illustrates positive pole provided by the invention and contains this anodal lithium ion battery and their preparation method.
(1) Zheng Ji preparation
(specific area is 500 meters with the spherical conductive agent carbon black of 2 weight portions
2/ gram), (specific area is 200 meters to the spherical conductive agent acetylene black of 1 weight portion
2/ gram) and the sheet conductive agent native graphite of 1.5 weight portions (specific area is 30 meters
2/ gram) mixes.
With 100 weight portion positive active material LiNi
0.45Co
0.45Mn
0.1O
2, 3 weight portion adhesive PVDF, the above-mentioned conductive agent that mixes of 4.5 weight portions join in the 70 weight portion N-methyl pyrrolidones (NMP), in de-airing mixer, stir then and form uniform anode sizing agent.
This slurry is coated on wide 400 millimeters, the thick 20 microns aluminium foil equably, and 120 ℃ of oven dry, roll-ins are cut on cutting machine and obtain being of a size of 385 millimeters * 42 millimeters * 135 microns positive pole afterwards then, wherein contain 4.8 gram cathode mixtures.
(2) preparation of negative pole
100 weight portion negative electrode active material native graphites, 2 weight portion adhesive polytetrafluoroethylene (PTFE)s, 6 weight portion conductive agent carbon blacks are joined in the 70 weight portion methyl-sulfoxides (DMSO), in de-airing mixer, stir then and form cathode size stable, homogeneous.
This slurry is coated on wide 400 millimeters, the thick 10 microns Copper Foil equably, after 120 ℃ of oven dry, rolling, on cutting machine, cuts and obtain being of a size of 43 millimeters * 355 millimeters * 135 microns negative pole, wherein contain 2.7 gram negative pole compounds.
(3) assembling of battery
With LiPF
6Be configured to LiPF with ethylene carbonate (EC) and diethyl carbonate (DEC)
6Concentration is the solution (wherein, the volume ratio of EC and DEC is 1: 1) of 1.0 mol, obtains nonaqueous electrolytic solution.The negative pole that positive pole, membrane layer, (2) that (1) is obtained obtain is successively with the stacked electrode group that is wound into scroll of up-coiler, the electrode group that obtains is put into the battery case of an end opening, and inject above-mentioned nonaqueous electrolytic solution with the amount of 3.8g/Ah, make lithium ion battery A3 after the sealing.
Embodiment 4
This embodiment illustrates positive pole provided by the invention and contains this anodal lithium ion battery and their preparation method.
(1) Zheng Ji preparation
(specific area is 700 meters with the spherical conductive agent carbon black of 2 weight portions
2/ gram) and the sheet conductive agent native graphite of 2 weight portions (specific area is 30 meters
2/ gram) mixes.
With 100 weight portion positive active material LiNi
0.2Co
0.2Mn
0.6O
2, 3 weight portion adhesive PVDF, the above-mentioned conductive agent that mixes of 4.5 weight portions join in the 70 weight portion N-methyl pyrrolidones (NMP), in de-airing mixer, stir then and form uniform anode sizing agent.
This slurry is coated on wide 400 millimeters, the thick 20 microns aluminium foil equably, and 120 ℃ of oven dry, roll-ins are cut on cutting machine and obtain being of a size of 385 millimeters * 42 millimeters * 135 microns positive pole afterwards then, wherein contain 4.8 gram cathode mixtures.
(2) preparation of negative pole
100 weight portion negative electrode active material native graphites, 2 weight portion adhesive polytetrafluoroethylene (PTFE)s, 6 weight portion conductive agent carbon blacks are joined in the 70 weight portion methyl-sulfoxides (DMSO), in de-airing mixer, stir then and form cathode size stable, homogeneous.
This slurry is coated on wide 400 millimeters, the thick 10 microns Copper Foil equably, after 120 ℃ of oven dry, rolling, on cutting machine, cuts and obtain being of a size of 43 millimeters * 355 millimeters * 135 microns negative pole, wherein contain 2.7 gram negative pole compounds.
(3) assembling of battery
With LiPF
6Be configured to LiPF with ethylene carbonate (EC) and diethyl carbonate (DEC)
6Concentration is the solution (wherein, the volume ratio of EC and DEC is 1: 1) of 1.0 mol, obtains nonaqueous electrolytic solution.The negative pole that positive pole, membrane layer, (2) that (1) is obtained obtain is successively with the stacked electrode group that is wound into scroll of up-coiler, the electrode group that obtains is put into the battery case of an end opening, and inject above-mentioned nonaqueous electrolytic solution with the amount of 3.8g/Ah, make lithium ion battery A4 after the sealing.
Embodiment 5
This embodiment illustrates positive pole provided by the invention and contains this anodal lithium ion battery and their preparation method.
(1) Zheng Ji preparation
(specific area is 240 meters with the spherical conductive agent acetylene black of 1 weight portion
2/ gram) and the sheet conductive agent native graphite of 2.5 weight portions (specific area is 30 meters
2/ gram) mixes.
With 100 weight portion positive active material LiNi
0.15Co
0.35Mn
0.5O
2, 3 weight portion adhesive PVDF, the above-mentioned conductive agent that mixes of 4.5 weight portions join in the 70 weight portion N-methyl pyrrolidones (NMP), in de-airing mixer, stir then and form uniform anode sizing agent.
This slurry is coated on wide 400 millimeters, the thick 20 microns aluminium foil equably, and 120 ℃ of oven dry, roll-ins are cut on cutting machine and obtain being of a size of 385 millimeters * 42 millimeters * 135 microns positive pole afterwards then, wherein contain 4.8 gram cathode mixtures.
(2) preparation of negative pole
100 weight portion negative electrode active material native graphites, 2 weight portion adhesive polytetrafluoroethylene (PTFE)s, 6 weight portion conductive agent carbon blacks are joined in the 70 weight portion methyl-sulfoxides (DMSO), in de-airing mixer, stir then and form cathode size stable, homogeneous.
This slurry is coated on wide 400 millimeters, the thick 10 microns Copper Foil equably, after 120 ℃ of oven dry, rolling, on cutting machine, cuts and obtain being of a size of 43 millimeters * 355 millimeters * 135 microns negative pole, wherein contain 2.7 gram negative pole compounds.
(3) assembling of battery
With LiPF
6Be configured to LiPF with ethylene carbonate (EC) and diethyl carbonate (DEC)
6Concentration is the solution (wherein, the volume ratio of EC and DEC is 1: 1) of 1.0 mol, obtains nonaqueous electrolytic solution.The negative pole that positive pole, membrane layer, (2) that (1) is obtained obtain is successively with the stacked electrode group that is wound into scroll of up-coiler, the electrode group that obtains is put into the battery case of an end opening, and inject above-mentioned nonaqueous electrolytic solution with the amount of 3.8g/Ah, make lithium ion battery A5 after the sealing.
Comparative Examples 1
This Comparative Examples explanation reference positive pole and lithium ion battery and their preparation method thereof.
It is anodal and comprise this anodal lithium ion battery AC1 to prepare reference according to the content of the method identical with embodiment 1 and each material, and different is that anodal conductive agent is that (specific area is 150 meters to 5 weight portion acetylene blacks
2/ gram) (specific area is 150 meters to 4.5 weight portion acetylene blacks among the replacement embodiment 1
2/ gram) and 0.5 weight portion native graphite (specific area is 40 meters
2/ gram).
Comparative example 2
This Comparative Examples explanation reference positive pole and lithium ion battery and their preparation method thereof.
It is anodal and comprise this anodal lithium ion battery AC2 to prepare reference according to the content of the method identical with embodiment 1 and each material, and different is that anodal conductive agent is that (specific area is 40 meters to 5 weight portion native graphites
2/ gram) (specific area is 150 meters to 4.5 weight portion acetylene blacks among the replacement embodiment 1
2/ gram) and 0.5 weight portion native graphite (specific area is 40 meters
2/ gram).
Comparative example 3
This Comparative Examples explanation reference positive pole and lithium ion battery and their preparation method thereof.
It is anodal and comprise this anodal lithium ion battery AC3 to prepare reference according to the content of the method identical with embodiment 1 and each material, and the specific area of acetylene black in the anodal conductive agent that different is is 75 meters
2/ gram.
Performance test
Battery capacity method of testing below adopting and cycle performance method of testing are measured charge/discharge capacity and the cycle performance of the lithium ion battery AC1-AC3 that lithium ion battery A1-A5 that embodiment 1-5 obtains and Comparative Examples 1-3 obtain respectively, and the result is as shown in table 1.
The battery capacity method of testing: charge with constant voltage charging method, the restriction electric current is 0.1C (65mA), and final voltage is 4.4 volts; Discharge in the constant-current discharge mode, discharging current is 1C (650mA), and the cut-ff voltage of discharge is 3.0 volts, and is recorded in the discharge voltage of the mid point of discharge curve.
Loop test: under 23 ℃ of conditions, with battery respectively with the 1C current charges to 4.2V, with constant-potential charge, cut-off current is 0.05C after voltage rises to 4.4V, shelves 10 minutes; Battery, was shelved 5 minutes to 3.0V with the 1C current discharge.Repeat above step 500 time, obtain the capacity of 100 circulation backs of battery 1C current discharge to 3.0V, by capacity sustainment rate before and after the following formula computation cycles:
Capacity sustainment rate=(the 100th cyclic discharge capacity/cyclic discharge capacity) first * 100%
The cycle performance of the high expression of capacity sustainment rate battery is good, and the cycle performance of the low expression of capacity sustainment rate battery is poor.
Table 1
| The embodiment numbering | The battery numbering | Charging capacity (mAh) | Discharge capacity (mAh) | Capability retention (%) after 100 circulations |
| Embodiment 1 | A1 | 766 | 693 | 94.1 |
| Embodiment 2 | A2 | 762 | 686 | 93.8 |
| Embodiment 3 | A3 | 759 | 685 | 93.4 |
| Embodiment 4 | A4 | 754 | 674 | 92.4 |
| Embodiment 5 | A5 | 752 | 661 | 91.3 |
| Comparative example 1 | AC1 | 770 | 694 | 87.3 |
| Comparative example 2 | AC2 | 742 | 635 | 94.5 |
| Comparative example 3 | AC3 | 750 | 642 | 92.1 |
From the result of table 1 as can be seen, though charging capacity and the discharge capacity of the lithium ion battery AC1 that comparative example 1 obtains are higher, the cycle performance of this battery is poor; Though the cycle performance of the lithium ion battery AC2 that comparative example 2 obtains is better, the charging capacity and the discharge capacity of this battery are low; Cycle performance, charging capacity and the discharge capacity of the lithium ion battery AC3 that comparative example 3 obtains are all not ideal.Compare with the lithium ion battery that Comparative Examples 1-3 obtains, lithium ion battery provided by the invention has higher charging capacity and discharge capacity, keeps excellent cycle performance simultaneously.
Claims (8)
1. lithium ion cell positive, this positive pole comprise conducting base and coating and/or be filled in positive electrode on the conducting base, and described positive electrode comprises positive active material, conductive agent and adhesive, and described positive active material is LiNi
xCo
yMn
1-x-yO
2, 0.1≤x＜0.5,0.1≤y＜0.5 is characterized in that, and described conductive agent is made up of sheet conductive agent and spherical conductive agent, and the specific area of described sheet conductive agent is a 10-50 rice
2/ gram, the specific area of described spherical conductive agent is a 80-850 rice
2/ gram; Weight with described positive active material is benchmark, and the content of described sheet conductive agent is 0.2-5 weight %, and the content of described spherical conductive agent is 0.2-5.5 weight %.
2. positive pole according to claim 1, wherein, the specific area of described sheet conductive agent is a 20-45 rice
2/ gram, the specific area of described spherical conductive agent is a 100-800 rice
2/ gram; Weight with described positive active material is benchmark, and the content of described sheet conductive agent is 0.5-3 weight %, and the content of described spherical conductive agent is 0.5-5 weight %.
3. positive pole according to claim 1, wherein, described sheet conductive agent is a native graphite; Described spherical conductive agent is acetylene black and/or carbon black.
4. positive pole according to claim 3, wherein, the specific area of described acetylene black is a 100-300 rice
2/ gram, the specific area of described carbon black is a 450-800 rice
2/ gram.
5. the preparation method of the described lithium ion cell positive of claim 1, this method comprise that the slurry that will contain positive electrode and solvent applies and/or is filled on the conducting base, drying, calendering or do not roll.
6. preparation method according to claim 5, wherein, the specific area of described sheet conductive agent is a 20-45 rice
2/ gram, the specific area of described spherical conductive agent is a 100-800 rice
2/ gram; Weight with described positive active material is benchmark, and the content of described sheet conductive agent is 0.5-3 weight %, and the content of described spherical conductive agent is 0.5-5 weight %.
7. lithium ion battery, this battery comprises electrode group and nonaqueous electrolytic solution, and described electrode group and nonaqueous electrolytic solution are sealed in the battery container, and described electrode group comprises positive pole, negative pole and barrier film, it is characterized in that any described positive pole among the described just very claim 1-4.
8. the preparation method of the described lithium ion battery of claim 7, this method comprises positive pole and the negative pole for preparing this battery, and positive pole, negative pole and barrier film are prepared into the electrode group, and electrode group and the electrolyte that obtains is sealed in the battery case.
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| JP2011034675A (en) * | 2009-07-29 | 2011-02-17 | Sony Corp | Cathode for secondary battery and secondary battery |
| CN103633291B (en) * | 2012-08-23 | 2016-06-15 | 万向电动汽车有限公司 | A kind of anode slice of lithium ion battery and preparation method |
| US9819050B2 (en) | 2013-05-17 | 2017-11-14 | Nissan Motor Co., Ltd. | Non-aqueous electrolyte secondary battery |
| CN112366320A (en) * | 2020-11-17 | 2021-02-12 | 惠州亿纬锂能股份有限公司 | High-voltage positive electrode conductive agent and application thereof |
| JP2025518058A (en) * | 2022-10-21 | 2025-06-12 | 香港時代新能源科技有限公司 | Secondary battery, its manufacturing method and power consumption device |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1219287A (en) * | 1997-03-11 | 1999-06-09 | 松下电器产业株式会社 | Secondary battery |
| CN1430796A (en) * | 2000-05-24 | 2003-07-16 | 三菱电线工业株式会社 | Lithium secondary cell and positive electrode active material, positive plate, and method for manufacturing them |
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2005
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1219287A (en) * | 1997-03-11 | 1999-06-09 | 松下电器产业株式会社 | Secondary battery |
| CN1430796A (en) * | 2000-05-24 | 2003-07-16 | 三菱电线工业株式会社 | Lithium secondary cell and positive electrode active material, positive plate, and method for manufacturing them |
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| JP特开2001-68093A 2001.03.16 |
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