CN102891299B - High-rate lithium ion battery cathode material and preparation method and application thereof - Google Patents
High-rate lithium ion battery cathode material and preparation method and application thereof Download PDFInfo
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- CN102891299B CN102891299B CN201210335980.1A CN201210335980A CN102891299B CN 102891299 B CN102891299 B CN 102891299B CN 201210335980 A CN201210335980 A CN 201210335980A CN 102891299 B CN102891299 B CN 102891299B
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- Prior art keywords
- lithium
- solid solution
- cobalt
- manganese oxide
- nickel
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Links
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 33
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 239000010406 cathode material Substances 0.000 title abstract description 10
- 239000000463 material Substances 0.000 claims abstract description 83
- 239000003990 capacitor Substances 0.000 claims abstract description 29
- 229910000572 Lithium Nickel Cobalt Manganese Oxide (NCM) Inorganic materials 0.000 claims abstract description 27
- FBDMTTNVIIVBKI-UHFFFAOYSA-N [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] Chemical compound [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] FBDMTTNVIIVBKI-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 22
- 239000000126 substance Substances 0.000 claims abstract description 18
- 238000005245 sintering Methods 0.000 claims abstract description 4
- 239000006104 solid solution Substances 0.000 claims description 68
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 37
- 229910052744 lithium Inorganic materials 0.000 claims description 33
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 25
- 229910017052 cobalt Inorganic materials 0.000 claims description 25
- 239000010941 cobalt Substances 0.000 claims description 25
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 25
- 238000001035 drying Methods 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 239000013078 crystal Substances 0.000 claims description 19
- 239000011572 manganese Substances 0.000 claims description 19
- 229910052748 manganese Inorganic materials 0.000 claims description 19
- 239000000203 mixture Substances 0.000 claims description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 239000000843 powder Substances 0.000 claims description 18
- 239000007788 liquid Substances 0.000 claims description 17
- 229910052759 nickel Inorganic materials 0.000 claims description 17
- 239000007864 aqueous solution Substances 0.000 claims description 16
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 15
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 14
- 238000001556 precipitation Methods 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 13
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 12
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 11
- 230000008569 process Effects 0.000 claims description 11
- 230000002441 reversible effect Effects 0.000 claims description 11
- 239000002131 composite material Substances 0.000 claims description 10
- -1 lithium halide Chemical class 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 9
- 239000003153 chemical reaction reagent Substances 0.000 claims description 8
- 239000002086 nanomaterial Substances 0.000 claims description 8
- 238000004140 cleaning Methods 0.000 claims description 7
- 239000012153 distilled water Substances 0.000 claims description 7
- 239000008151 electrolyte solution Substances 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 7
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 6
- 239000010405 anode material Substances 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 6
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 6
- 235000017550 sodium carbonate Nutrition 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 5
- 239000007784 solid electrolyte Substances 0.000 claims description 5
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 4
- 238000000498 ball milling Methods 0.000 claims description 4
- 229940011182 cobalt acetate Drugs 0.000 claims description 4
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 4
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 4
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 4
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 4
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 4
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 4
- 229940071125 manganese acetate Drugs 0.000 claims description 4
- 229940099596 manganese sulfate Drugs 0.000 claims description 4
- 239000011702 manganese sulphate Substances 0.000 claims description 4
- 235000007079 manganese sulphate Nutrition 0.000 claims description 4
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 4
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 4
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 4
- 229910021645 metal ion Inorganic materials 0.000 claims description 4
- 229940078494 nickel acetate Drugs 0.000 claims description 4
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 4
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 4
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 4
- 238000001694 spray drying Methods 0.000 claims description 4
- 229910052723 transition metal Inorganic materials 0.000 claims description 4
- OAVRWNUUOUXDFH-UHFFFAOYSA-H 2-hydroxypropane-1,2,3-tricarboxylate;manganese(2+) Chemical compound [Mn+2].[Mn+2].[Mn+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O OAVRWNUUOUXDFH-UHFFFAOYSA-H 0.000 claims description 3
- VAIVGJYVKZVQAA-UHFFFAOYSA-N 2-hydroxypropane-1,2,3-tricarboxylic acid;nickel Chemical compound [Ni].OC(=O)CC(O)(C(O)=O)CC(O)=O VAIVGJYVKZVQAA-UHFFFAOYSA-N 0.000 claims description 3
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 3
- 239000001099 ammonium carbonate Substances 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- QXOLLBTXUCQAEQ-UHFFFAOYSA-N cobalt;2-hydroxypropane-1,2,3-tricarboxylic acid Chemical compound [Co].OC(=O)CC(O)(C(O)=O)CC(O)=O QXOLLBTXUCQAEQ-UHFFFAOYSA-N 0.000 claims description 3
- 230000026030 halogenation Effects 0.000 claims description 3
- 238000005658 halogenation reaction Methods 0.000 claims description 3
- 238000007603 infrared drying Methods 0.000 claims description 3
- 238000002386 leaching Methods 0.000 claims description 3
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 3
- 229940071264 lithium citrate Drugs 0.000 claims description 3
- WJSIUCDMWSDDCE-UHFFFAOYSA-K lithium citrate (anhydrous) Chemical compound [Li+].[Li+].[Li+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O WJSIUCDMWSDDCE-UHFFFAOYSA-K 0.000 claims description 3
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 claims description 3
- 238000003760 magnetic stirring Methods 0.000 claims description 3
- 239000011564 manganese citrate Substances 0.000 claims description 3
- 235000014872 manganese citrate Nutrition 0.000 claims description 3
- 229940097206 manganese citrate Drugs 0.000 claims description 3
- 239000003595 mist Substances 0.000 claims description 3
- 229940072033 potash Drugs 0.000 claims description 3
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 3
- 235000015320 potassium carbonate Nutrition 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 claims description 3
- 230000009466 transformation Effects 0.000 claims description 3
- 150000003624 transition metals Chemical class 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 238000000975 co-precipitation Methods 0.000 abstract description 6
- 238000007599 discharging Methods 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 4
- 239000002243 precursor Substances 0.000 abstract description 3
- 239000007790 solid phase Substances 0.000 abstract 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 26
- 238000005516 engineering process Methods 0.000 description 16
- 230000004888 barrier function Effects 0.000 description 14
- 239000000243 solution Substances 0.000 description 11
- 239000003792 electrolyte Substances 0.000 description 10
- 239000011230 binding agent Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 238000002441 X-ray diffraction Methods 0.000 description 7
- 239000006258 conductive agent Substances 0.000 description 7
- 239000012071 phase Substances 0.000 description 7
- 239000004698 Polyethylene Substances 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 238000004146 energy storage Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000006230 acetylene black Substances 0.000 description 4
- 238000012983 electrochemical energy storage Methods 0.000 description 4
- 239000011152 fibreglass Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 229910052493 LiFePO4 Inorganic materials 0.000 description 3
- 239000002033 PVDF binder Substances 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 238000012856 packing Methods 0.000 description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 150000005846 sugar alcohols Polymers 0.000 description 3
- QGHDLJAZIIFENW-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical group C1=C(CC=C)C(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C(CC=C)=C1 QGHDLJAZIIFENW-UHFFFAOYSA-N 0.000 description 2
- OTYYBJNSLLBAGE-UHFFFAOYSA-N CN1C(CCC1)=O.[N] Chemical compound CN1C(CCC1)=O.[N] OTYYBJNSLLBAGE-UHFFFAOYSA-N 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- 229910001228 Li[Ni1/3Co1/3Mn1/3]O2 (NCM 111) Inorganic materials 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 239000005030 aluminium foil Substances 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 2
- 239000008139 complexing agent Substances 0.000 description 2
- 230000001143 conditioned effect Effects 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005518 electrochemistry Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 229910001092 metal group alloy Inorganic materials 0.000 description 2
- 239000002923 metal particle Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 150000004702 methyl esters Chemical class 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910010271 silicon carbide Inorganic materials 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
- 229910032387 LiCoO2 Inorganic materials 0.000 description 1
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 1
- 229910015645 LiMn Inorganic materials 0.000 description 1
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000011449 brick Substances 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 230000009194 climbing Effects 0.000 description 1
- 229910001429 cobalt ion Inorganic materials 0.000 description 1
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000002050 diffraction method Methods 0.000 description 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000013455 disruptive technology Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- OVAQODDUFGFVPR-UHFFFAOYSA-N lithium cobalt(2+) dioxido(dioxo)manganese Chemical compound [Li+].[Mn](=O)(=O)([O-])[O-].[Co+2] OVAQODDUFGFVPR-UHFFFAOYSA-N 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
-
- 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
- Y02E60/13—Energy storage using capacitors
-
- 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
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/60—Other road transportation technologies with climate change mitigation effect
- Y02T10/70—Energy storage systems for electromobility, e.g. batteries
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a lithium nickel cobalt manganese oxide sosoloid material and a preparation method thereof, and the lithium nickel cobalt manganese oxide sosoloid material serving as a cathode material of a high-rate and high-capacity secondary battery and a super capacitor. The chemical formula of the material is Li1+sigmaNixCoyMn1-x-yO2, wherein sigma is more than 0.0 and less than or equal to 12, x is more than 0.0 and less than or equal to 0.6, y is more than or equal to 0 and less than 0.5, and 1-x-y is more than 0.0 and less than or equal to 0.5. The invention also discloses a preparation method for the material. The method comprises the following steps of: preparing a precursor by a coprecipitation method; and obtaining the material by two-step solid phase sintering. The invention also discloses the material serving as the cathode material and application of the current lithium ion battery in compatibility with a mixed super capacitor. Compared with the prior art, the lithium nickel cobalt manganese oxide sosoloid material has the advantage that industrialization is easy to implement; discharging is executed by 1.6A/g(10C) current; a complete charging and discharging cycle is executed for more than 60 times within 2.5 to 4.3V; and the final discharging is 120mAh/g higher than the capacity. The material obtained by the invention can be used in the lithium ion battery and can be used for power supplies of an electric tool, an electric automobile and an intelligent power grid.
Description
Technical field
The invention belongs to electrode material field and electrochemical energy storage field, be specifically related to a kind of lithium nickel cobalt manganese oxide sosoloid material and preparation method thereof, and the purposes of positive electrode as high magnification high-capacity secondary battery and ultracapacitor.
Background technology
The energy is the engine of national economy, and new energy development decides the autonomy of the future economy.The energy comprises fossil energy and clean energy resource, and along with fossil energy is because it is non-renewable and problem of environmental pollution, the utilization of clean energy resource is current forefront, most crucial global problems.Because clean energy resource does not usually have continuity aborning, as solar energy, wind energy, be comparatively limited by region and weather, therefore energy storage technology is critical support technology indispensable in clean energy resource and industry thereof.The fields such as information, the energy, traffic, military affairs are widely used in the electrochemical energy storage technology that lithium ion battery and ultracapacitor are representative, be known as and likely change the disruptive technology of the world's (energy) general layout, their application in electric automobile, intelligent grid get most of the attention.
Lithium ion battery, except having high-energy-density, also possesses the advantages such as memory-less effect, self discharge be little, becomes the first-selection of electric bicycle, Prospect of EVS Powered with Batteries.But current lithium ion battery high rate performance is poor (only 3C) generally, makes discharge and recharge overlong time.Low range causes battery big current power amplifier ability, and electric automobile is difficult to obtain the great current powers such as acceleration, climbing and drives function; Big current ability to bear difference also can aggravate thermal runaway security risk during power supply release big current, and directly causes falling sharply of battery actual life.Current ultracapacitor has the advantages such as fast charging and discharging (high magnification), high power density, high security, long circulation life, but its operating voltage is generally no more than 3V, and energy density is generally very low, is difficult to the electronic continuation of the journey requirement supporting long duration distance.
Positive electrode is that lithium ion battery and hybrid super capacitor (are also called lithium-ion capacitor, or electric chemical super capacitor) in most important part, be the key factor of restriction lithium ion battery and the capacity of capacitor, multiplying power, security performance, cycle-index, useful life and product price etc.Inversely, i.e. discharge and recharge faster (high rate capability), the energy of storage or release is fewer for conventional batteries stored energy capacitance (energy density) and charge-discharge velocity (power density).Therefore, electrochemical energy storage field in the urgent need to developing a kind of high magnification, high power capacity, excellent electrochemical performance, positive electrode with low cost.The emphasis and focus that modification is electrochemical energy storage technical research and exploitation in global range is optimized to existing anode material for lithium-ion batteries.
Positive electrode conventional at present mainly contains cobalt acid lithium (LiCoO
2), cobalt nickel lithium manganate ternary material (LiNi
1/3co
1/3mn
1/3o
2), LiMn2O4 (LiMn
2o
4), LiFePO4 (LiFePO
4) etc.Cobalt acid lithium technology is the lithium ion battery technology that the first generation is the most ripe, the leading position in baby battery market, but because of its applied in limitation particularly by the impact that cobalt is expensive, in recent years replace by ternary material technology compatible with it.The most ripe with LiMn2O4 technology at present in Prospect of EVS Powered with Batteries, but its reversible capacity is lower, and actual only have about 110mAh/g, and easily recurring structure phase transformation in the circulating cycle, cause capacity to fall sharply; And LiFePO4 technology is because of by its low-work voltage and low range performance impact, fail to obtain the accreditation of international electric automobile market, and its battery performance is without the leeway of technology raising always.Existing nickle cobalt lithium manganate technology is because of the lattice micro-nano structure instability of prepared ternary material, fail safe is poor, be restricted in the application in electrokinetic cell field, and laboratory scale to prepare the process of high-quality ternary material very complicated, as the various different element mixing of 3M company required for its patent (200480035045.7) specific embodiments and the order of grinding thereof, significantly improve industrialization cost.The multiplying power level of current international market lithium ion battery technology generally only reaches electric discharge in 3C(20 minute), the needs of power type and long-life type battery can not be met, seriously hinder the development of the energy storage technologies such as lithium ion battery and the utilization of clean energy resource.
Summary of the invention
The object of the invention is to provide a kind of high magnification (10C), high power capacity, excellent electrochemical performance, lithium nickel cobalt manganese oxide solid solution cathode material with low cost and preparation method thereof, and its purposes in secondary cell and ultracapacitor.The present invention is by wet-chemical reaction and solid phase reaction Comprehensive Control element proportioning, grain morphology, thus the obtained positive electrode with stable micro-nano structure; The reversible capacity of this positive electrode between 2.5-4.3V is higher than 160mAh/g, and first charge-discharge efficiency is higher than 98%, and the reversible capacity of 10C is higher than 120mAh/g.The electrochemical applications of positive electrode of the present invention and the technical requirement compatibility of existing lithium ion battery and ultracapacitor, solve the technical bottlenecks such as the multiplying power of the high current charge-discharge that lithium ion battery faces when applying as energy storage device as electrokinetic cell application, lithium-ion capacitor, capacity, circulation and fail safe.
First aspect present invention provides a kind of lithium nickel cobalt manganese oxide solid solution anode material for lithium-ion batteries, and its chemical general formula is: Li
1+δ Ni
xco
ymn
1-x-yo
2wherein 0.0< δ≤0.12,0.0<x≤0.6,0≤y<0.5,0.0<1-x-y≤0.5.
Described solid solution cathode material has stable micro-nano structure in electrochemical applications: at room temperature in lithium ion battery, and the reversible capacity between 2.5-4.3V is higher than 160mAh/g, and first charge-discharge efficiency is higher than 98%; With 1.6A/g (10C) current discharge, experience complete charge-discharge cycles more than 60 times, this solid solution not recurring structure phase transformation and circulation final state specific discharge capacity higher than 120mAh/g.
The stable micro-nano structure that described solid solution cathode material has, its solid solution crystal grain comprises following four aspects:
A. solid solution crystal grain Xrd is characterized by single-phase layered crystal structure, has space group R-3m(international crystallography table space group No. 166) feature;
B. solid solution grain morphology be reunited by nanoscale crystal grain there is micro-meter scale offspring porous bulky grain that is spherical, subsphaeroidal, polyhedron shape;
C. a crystal grain meso-position radius of solid solution crystal grain nanoscale is of a size of 100-800 nanometer;
D. the offspring particle meso-position radius of solid solution crystal grain micro-meter scale is of a size of 1-50 micron.
In another preference, in described solid solution cathode material chemical general formula, be more preferably 0.02≤δ≤0.09,0.2≤x≤0.6,0.1≤y≤0.4,0.1≤1-x-y≤0.4.
Second aspect present invention provides the preparation method of the solid solution cathode material described in a kind of first aspect present invention, comprises step:
A. nickel source material, cobalt source material, manganese source material are mixed with by nickel, cobalt, manganese mol ratio x:y:1-x-y deionized water or distilled water in chemical general formula the transparent mixed aqueous solution without precipitation of soluble salt that concentration of metal ions is 0.1-1.8mol/L;
B. mixed aqueous solution obtained by steps A is placed in water-bath or oil bath thermostat is incubated, thermostat temperature is 25-95
0c, in mixed aqueous solution, evenly add the precipitation reagent aqueous solution again, stir simultaneously, mixer used is electric mixer, magnetic stirring apparatus, agitator air, mixer rotating speed is 150-3000 rev/min, and precipitation process terminates the suspension-turbid liquid obtaining the aqueous solution, coprecipitate;
C. step B gained suspension-turbid liquid is filtered, be precipitated powder, with deionized water or distilled water cleaning powder more than three times; Suspension-turbid liquid filter method is one or more in centrifugal filtration, negative pressure leaching, press filtration;
D. be placed in drying box by step C gained powder, drying box adopts infrared drying oven, vacuum drying chamber, air dry oven, microwave drying oven, at 80-160
0in C temperature, dry 6-24 hour, obtains presoma;
E. step D gained presoma is mixed to obtain drying composite with lithium source material by the mol ratio 1:1+ δ of transition metal Ni+Co+Mn and Li in chemical general formula, or mix in deionized water and absolute ethyl alcohol, drying obtains drying composite again, and drying composite grinder grinding or ball mill ball milling are obtained mixture of powders in 0.1-24 hour;
F. by step e gained mixture of powders first at 300-550
0constant temperature calcining 2-24 hour at C temperature, more continuous in 1-12
0c/ divides ramp to 650-1100
0c, then calcining at constant temperature 4-24 hour, cool to room temperature, sieves and finally obtains oxide solid solution positive electrode of the present invention.
Described steps A. described in nickel source material be one or more in nickelous sulfate, nickel nitrate, nickel acetate, citric acid nickel, nickel halogenide; Described cobalt source material is one or more in cobaltous sulfate, cobalt nitrate, cobalt acetate, citric acid cobalt, halogenation cobalt; Described manganese source material is one or more in manganese sulfate, manganese nitrate, manganese acetate, manganese citrate, manganese halide.
In described step B., the precipitation reagent aqueous solution dissolves obtained by one or more in solubility precipitation reagent ammoniacal liquor, NaOH, potassium hydroxide, carbonic acid ammonia, sodium carbonate, potash, ammonium hydrogencarbonate, sodium acid carbonate, saleratus deionized water or distilled water.
In another preference, in described step D., precursor power method is: gained powder after step C cleaning is mixed with suspension-turbid liquid, at 100-300
0mist projection granulating under C condition, the preferred 150-220 of inlet temperature in spray-drying process
0c, obtains presoma.
Described step e. described in lithium source material be one or more in lithium carbonate, lithium sulfate, lithium nitrate, lithium acetate, lithium citrate, lithium hydroxide, lithium halide.
In another preference, in described step F, two sections of warm area sintering carry out continuously under air atmosphere in high temperature Muffle furnace, rotary furnace, tunnel cave or roller kilns.
Third aspect present invention provides a kind of anode, and described positive electrode contains the lithium nickel cobalt manganese oxide solid solution described in first aspect present invention.
In another preference, the positive electrode active materials of described anode is used alone the lithium nickel cobalt manganese oxide solid solution described in first aspect present invention.
In another preference, the positive electrode active materials of described anode uses the lithium nickel cobalt manganese oxide solid solution described in first aspect present invention with other as the anode material for lithium-ion batteries such as spinel lithium manganate, LiFePO4, cobalt acid lithium combine.
In another preference, described anode is also containing conductive agent and binding agent.
In another preference, described conductive agent is acetylene black, conductive black, carbon nano-tube, carbon fiber, Graphene.
In another preference, described binding agent is Kynoar (PVDF);
Fourth aspect present invention provides a kind of secondary cell, described secondary cell comprises positive electrode, negative material, barrier film, electrolyte and shell, wherein, described positive electrode comprises the lithium nickel cobalt manganese oxide solid solution described in first aspect present invention, and described secondary cell includes the anode described in third aspect present invention.
In another preference, described electrolyte is non-aqueous electrolytic solution or solid electrolyte.
In another preference, described negative material comprises native graphite, electrographite, carbonaceous mesophase spherules, carborundum, metal lithium sheet, lithium titanate or metal alloy.
In another preference, described barrier film is PP & PE barrier film or fibreglass diaphragm.
In another preference, described shell is stainless steel box hat, aluminum hull or polyalcohol flexible packing.
Fifth aspect present invention provides a kind of lithium-ion capacitor or hybrid super capacitor, described capacitor comprises positive electrode, negative material, barrier film, electrolyte and shell, wherein, described positive electrode comprises the lithium nickel cobalt manganese oxide solid solution described in first aspect present invention, and described capacitor includes the anode described in third aspect present invention.
In another preference, described electrolyte is non-aqueous electrolytic solution or solid electrolyte.
In another preference, described negative material comprises activated carbon, activated carbon and fake capacitance hopcalite, activated carbon and the mixture of lithium metal particle or the mixture of activated carbon and high polymer coated metal lithium particle.
In another preference, described barrier film is PP & PE barrier film or fibreglass diaphragm.
In another preference, described shell is stainless steel box hat, aluminum hull or polyalcohol flexible packing.
In another preference, described hybrid super capacitor adopts as United States Patent (USP) (6222723), or United States Patent (USP) (7766981B2), or Subaru sandwich sandwich, or configuration shown in Jsr Micro laminated construction.
Sixth aspect present invention provides the purposes of the solid-solution material described in a kind of first aspect present invention, for the preparation of the manufacture of the ultracapacitor described in the anode described in third aspect present invention, the secondary cell described in fourth aspect present invention and fifth aspect present invention.
Major advantage of the present invention and good effect are:
1. solid-solution material of the present invention has excellent chemical property: have the high potential platform (2.5-4.3V) with the technical requirement compatibility of existing lithium ion battery and ultracapacitor, high reversible capacity (higher than 160mAh/g), (first charge-discharge efficiency is higher than 98% for good circulation stability, circulate and have no obvious decay 60 times), high magnification excellent cycle performance (10C circulates the reversible capacity of more than 60 times higher than 120mAh/g).
2. solid-solution material of the present invention is easy to large-scale industrialized production: owing to adopting controllable co-precipitation flow process, the solid solution cathode material that transiting metal nickel cobalt manganese is uniformly distributed, micro-nano structure is stable of atom level level can be obtained, by the good control to process of lapping, subsphaeroidal, the polyhedral porous bulky grain of high density can be obtained, effectively improve the processing density of battery material, thus improve volume, the mass energy density of battery and capacitor.Optimize the consumption that element proportioning effectively can reduce expensive cobalt ions, namely decrease the consumption of expensive cobalt element, farthest reduce the cost of raw material.The various raw material adopted in production and equipment are being easy to buy on the market, are easy to the large-scale production realizing battery manufacture.Meanwhile, the present invention does not adopt the organic complexing agent, chelating agent, dispersant etc. that generally use in multi-element composite material preparation method to control the technological means of crystal grain, without compacting process after grinding, without the need to shattering process after sintering, directly final material.Therefore, preparation process environmental protection of the present invention, synthetic method simply, very easily realize serialization large-scale production.
3. adopt solid-solution material of the present invention to prepare positive pole and can obtain the 10C lithium ion battery technology with high security high power capacity, produce and can reach 1600W/kg in power density, energy density can reach the lithium ion battery of 245W/kg; The hybrid super capacitor that operating voltage interval reaches 4.3V can be produced.The present invention, by a kind of breakthrough of positive electrode, drives two class electrochemistry to dominate the breakthrough of energy storage technology-lithium ion battery and hybrid super capacitor technology.Estimate not only in traditional lithium ion battery market, and be with a wide range of applications at electrokinetic cell and energy storage capacitor field.
Should be understood that within the scope of the present invention, above-mentioned each technical characteristic of the present invention and can combining mutually between specifically described each technical characteristic in below (eg embodiment), thus form new or preferred technical scheme.As space is limited, tiredly no longer one by one to state at this.
Accompanying drawing explanation
Figure 1A shows the x-ray diffraction pattern (Xrd) of solid-solution material prepared by embodiment 1.
Figure 1B shows the primary particle scanning electron microscope (SEM) photograph (SEM) of solid-solution material prepared by embodiment 1.
Fig. 1 C shows the offspring scanning electron microscope (SEM) photograph (SEM) of solid-solution material prepared by embodiment 1.
Fig. 1 D shows offspring agglomerated particle magnified sweep Electronic Speculum figure (SEM) of solid-solution material prepared by embodiment 1.
Fig. 2 A shows the first charge-discharge curve of secondary cell prepared by embodiment 7.
Fig. 2 B shows more than 60 times charge and discharge cycles of secondary cell prepared by embodiment 7.
Fig. 3 shows the 10C charge and discharge cycles of secondary cell prepared by embodiment 7.
Fig. 4 shows the charge and discharge cycles of hybrid super capacitor at 1.5-4.3V of embodiment 10 preparation.
Embodiment
Present inventor, through repeatedly testing, extensively and in depth studies, by optimizing element proportioning, adopt the excessive saturated lithium-transition metal mixing of lithium, thus the stability of control oxide solid solution micro-nano structure, improve the high rate performance of battery material, complete the present invention.
lithium nickel cobalt manganese oxide solid solution (Li 1+ δ
ni x co y mn 1-x-y o 2 )
At present, the positive electrode on market mainly contains cobalt acid lithium (LiCoO2), cobalt nickel lithium manganate ternary material (LiNi
1/3co
1/3mn
1/3o
2).Wherein, cobalt acid lithium cost is high, and fail safe, high rate performance difference can not be used for electrokinetic cell; Ternary material generally has (333), and variants such as (523), can only be used for the baby battery market of below 3C multiplying power, generally can not be used alone, and usually uses organic complexing agent etc. to improve its processing characteristics in preparation process, brings environmental pollution.
Term used herein " lithium nickel cobalt manganese oxide solid solution " refers to the crystal grain comprising lithium nickel cobalt manganese oxide, belongs to single-phase layered crystal structure.Described chemical formula is Li
1+δ Ni
xco
ymn
1-x-yo
2.Preferably, 0.0< δ≤0.12,0.0<x≤0.6,0≤y<0.5,0.0<1-x-y≤0.5; Be more preferably 0.02≤δ≤0.09,0.2≤x≤0.6,0.1≤y≤0.4,0.1≤1-x-y≤0.4.Lithium nickel cobalt manganese oxide solid solution is that a class and existing cobalt acid lithium battery and ternary material battery operating voltage platform (2.5-4.3V) are compatible, has the positive electrode of high reversible capacity (higher than 160mAh/g).
the preparation of lithium nickel cobalt manganese oxide solid solution cell positive material
In preparation method of the present invention, required lithium source material, nickel source material, cobalt source material, manganese source material, precipitation reagent and equipment all can be bought in market and obtain.The experimental technique of unreceipted actual conditions, the usually conveniently conditioned disjunction condition of advising according to manufacturer.
Described lithium source material is one or more in lithium carbonate, lithium sulfate, lithium nitrate, lithium acetate, lithium citrate, lithium hydroxide, lithium halide;
Described nickel source material is one or more in nickelous sulfate, nickel nitrate, nickel acetate, citric acid nickel, nickel halogenide;
Described cobalt source material is one or more in cobaltous sulfate, cobalt nitrate, cobalt acetate, citric acid cobalt, halogenation cobalt;
Described manganese source material is one or more in manganese sulfate, manganese nitrate, manganese acetate, manganese citrate, manganese halide;
Described precipitation reagent is one or more in ammoniacal liquor, NaOH, potassium hydroxide, carbonic acid ammonia, sodium carbonate, potash, ammonium hydrogencarbonate, sodium acid carbonate, saleratus.
The invention provides a kind of method preparing positive electrode of the present invention, comprise step:
A. nickel source material, cobalt source material, manganese source material are mixed with by nickel, cobalt, manganese mol ratio x:y:1-x-y deionized water or distilled water in chemical general formula the transparent mixed aqueous solution without precipitation of soluble salt that concentration of metal ions is 0.1-1.8mol/L;
B. mixed aqueous solution obtained by steps A is placed in water-bath or oil bath thermostat is incubated, thermostat temperature is 25-95
0c, in mixed aqueous solution, evenly add the precipitation reagent aqueous solution again, stir simultaneously, mixer used is electric mixer, magnetic stirring apparatus, agitator air, mixer rotating speed is 150-3000 rev/min, and precipitation process terminates the suspension-turbid liquid obtaining the aqueous solution, coprecipitate;
C. step B gained suspension-turbid liquid is filtered, be precipitated powder, with deionized water or distilled water cleaning powder more than three times; Suspension-turbid liquid filter method is one or more in centrifugal filtration, negative pressure leaching, press filtration;
D. be placed in drying box by step C gained powder, drying box adopts infrared drying oven, vacuum drying chamber, air dry oven, microwave drying oven, at 80-160
0in C temperature, dry 6-24 hour, obtains presoma;
E. step D gained presoma is mixed to obtain drying composite with lithium source material by the mol ratio 1:1+ δ of transition metal Ni+Co+Mn and Li in chemical general formula, or mix in deionized water and absolute ethyl alcohol, drying obtains drying composite again, and drying composite grinder grinding or ball mill ball milling are obtained mixture of powders in 0.1-24 hour;
F. by step e gained mixture of powders first at 300-550
0constant temperature calcining 2-24 hour at C temperature, more continuous in 1-12
0c/ divides ramp to 650-1100
0c, then calcining at constant temperature 4-24 hour, cool to room temperature, sieves and finally obtains oxide solid solution positive electrode of the present invention.
Wherein, in described step D., precursor power method can also be: gained powder after step C cleaning is mixed with suspension-turbid liquid, at 100-300
0mist projection granulating under C condition, the preferred 150-220 of inlet temperature in spray-drying process
0c, obtains presoma.
anode
Anode of the present invention contains solid solution cathode material of the present invention.
Anode of the present invention can also contain conductive agent and binding agent, and wherein said conductive agent is acetylene black, conductive black, carbon nano-tube, carbon fiber, Graphene; Described binding agent is PVDF.
Preferred preparation method comprises step:
By positive electrode respectively with conductive agent, binding agent Homogeneous phase mixing in the solution (as nitrogen methyl pyrrolidone (NMP)), regulate the mass ratio of suitable positive electrode, conductive agent and binding agent (as 80-90:5-10:5-10, preferably 90:5:5,80:10:10 or 85:10:5), then compressing tablet is applied on aluminium foil, dry, compressing tablet, obtained anode pole piece.
secondary cell
Secondary cell provided by the invention, comprises positive electrode and negative material, and wherein, described positive electrode comprises lithium nickel cobalt manganese oxide solid solution cell positive material of the present invention, and described power brick contains anode of the present invention.
Secondary cell provided by the invention also comprises barrier film, electrolyte, shell.
Described negative material is native graphite, electrographite, carbonaceous mesophase spherules, carborundum, metal lithium sheet, lithium titanate or metal alloy, described barrier film is PP & PE barrier film or fibreglass diaphragm, and described electrolyte is that secondary cell commonly uses nonaqueous electrolytic solution or solid-state electrolytic solution.
hybrid super capacitor
Hybrid super capacitor provided by the invention comprises positive electrode, negative material, barrier film, electrolyte and shell, wherein, described positive electrode comprises the lithium nickel cobalt manganese oxide solid solution described in first aspect present invention, and described capacitor includes anode of the present invention.
Described electrolyte is that secondary cell commonly uses non-aqueous electrolytic solution or solid electrolyte, or hybrid super capacitor commonly uses non-aqueous electrolytic solution or solid electrolyte.
Described negative material comprises activated carbon, activated carbon and hopcalite, activated carbon and the mixture of lithium metal particle or the mixture of activated carbon and high polymer coated metal lithium particle.
Described barrier film is PP & PE barrier film or fibreglass diaphragm.
Described shell is stainless steel box hat, aluminum hull or polyalcohol flexible packing.
Described hybrid super capacitor adopts as United States Patent (USP) (6222723), or United States Patent (USP) (7766981B2), or Subaru sandwich sandwich, or configuration shown in Jsr Micro laminated construction.
Unless otherwise defined, all specialties used in literary composition and scientific words and one skilled in the art the meaning be familiar with identical.In addition, any method similar or impartial to described content and material all can be applicable in the inventive method.The use that better implementation method described in literary composition and material only present a demonstration.The above-mentioned feature that the present invention mentions, or the feature that embodiment is mentioned can combination in any.All features that this case specification discloses can in any combination and use, each feature disclosed in specification, can anyly to provide identical, alternative characteristics that is impartial or similar object replaces.Therefore apart from special instruction, the feature disclosed is only general example that is impartial or similar features.
Below in conjunction with specific embodiment, set forth the present invention further.Should be understood that these embodiments are only not used in for illustration of the present invention to limit the scope of the invention.The experimental technique of unreceipted actual conditions in the following example, the usually conveniently conditioned disjunction condition of advising according to manufacturer.
Embodiment 1: take nickelous sulfate, cobaltous sulfate, manganese sulfate by nickel, cobalt, manganese molar ratio 0.35:0.33:0.32, adds deionized water and fully dissolves and be mixed with the clear solution that ion concentration is 1mol/L, be placed in water-bath constant temperature 70
0c, then the sodium hydroxide solution slowly evenly adding same concentration, stir simultaneously, rotating speed is 600 revs/min, until add sodium hydroxide solution, reaction gained suspension-turbid liquid color no longer changes, stop adding NaOH, continue at the uniform velocity to stir after more than 30 minutes, terminate coprecipitation reaction.Reaction suspension-turbid liquid is obtained co-precipitation solid by centrifugal filtration, after repeatedly refiltering 4 times by washed with de-ionized water, puts into air dry oven, at 120 DEG C, drying 16 hours, obtains presoma.After taking-up, presoma and lithium hydroxide are pressed 1:1.1 mixed in molar ratio, be put in planetary ball mill ball milling 8 hours, grind even drying composite.Mixture is placed in high temperature Muffle furnace, heats up with the 10 DEG C/min rate of heat addition, be warmed up to 450 DEG C of roastings 12 hours, continue to be warming up to 900 DEG C of roastings 16 hours with the 12 DEG C/min rate of heat addition.Naturally take out mixture after cooling, products therefrom is obtained Li
1.07 ± 0.01ni
0.34 ± 0.02co
0.33 ± 0.02mn
0.32 ± 0.020
2solid-solution material.In solid-solution material, the stoichiometric proportion of lithium, nickel, cobalt, manganese metal ion can confirm described chemical formula by ICP elementary analysis.
As shown in Figure 1A, the single-phase layered crystal structure feature of space group R-3m is obvious for the x-ray diffraction pattern (XRD) of gained solid-solution material; A crystal grain of solid-solution material, as shown in the SEM of Figure 1B, is evenly distributed on 100-200 nanometer; The secondary agglomeration particle of solid-solution material, as shown in the SEM of Fig. 1 C, is evenly distributed on 2-10 micron; The SEM of secondary agglomeration particle enlarged drawing as Fig. 1 D of solid-solution material shows subsphaeroidal feature, and porous character is obvious.
Embodiment 2: take nickel nitrate, cobalt nitrate, manganese nitrate by nickel, cobalt, manganese molar ratio 0.45:0.23:0.32, adds deionized water and fully dissolves and be mixed with the clear solution that ion concentration is 1mol/L, be placed in water-bath constant temperature 60
0c, then the sodium carbonate liquor slowly evenly adding same concentration, stir simultaneously, rotating speed is 1200 revs/min, until add sodium carbonate liquor, reaction suspension-turbid liquid color does not change, stop adding sodium carbonate, continue at the uniform velocity to stir after more than 60 minutes, terminate coprecipitation reaction.Presoma and lithium hydroxide press 1:1.09 mixed in molar ratio.All the other are identical with embodiment 1, and its x-ray diffraction pattern (XRD) and SEM figure are similar to Figure 1A-1D.
Embodiment 3: take nickel acetate, cobalt acetate, manganese acetate by nickel, cobalt, manganese molar ratio 1.0:1.0:1.0, adds deionized water and fully dissolves and be mixed with the clear solution that ion concentration is 1mol/L, be placed in water-bath constant temperature 60
0c, then the sodium bicarbonate solution slowly evenly adding same concentration, stir simultaneously, rotating speed is 1200 revs/min, until add sodium bicarbonate solution, reaction suspension-turbid liquid color does not change, stop adding sodium acid carbonate, continue at the uniform velocity to stir after more than 60 minutes, terminate coprecipitation reaction.Filter, cleaning coprecipitated product four times, is configured to suspension-turbid liquid, obtains presoma by spray drying granulation.1:1.09 mixed in molar ratio pressed by presoma and lithium carbonate.All the other are identical with embodiment 1, and its x-ray diffraction pattern (XRD) and SEM figure are similar to Figure 1A-1D.
Embodiment 4: by the solid-solution material prepared by embodiment 1 respectively with conductive agent acetylene black, binding agent Kynoar (PVDF) Homogeneous phase mixing in nitrogen methyl pyrrolidone (NMP) solution, the mass ratio of solid-solution material, acetylene black and binding agent is respectively 85:10:5, then compressing tablet is applied on aluminium foil, dry, compressing tablet, obtained battery positive pole piece.
Embodiment 5: the preparation of battery positive pole piece, with the preparation method of embodiment 4 battery positive pole piece, is solid-solution material prepared by embodiment 2 unlike solid-solution material.
Embodiment 6: the preparation of battery positive pole piece, with the preparation method of embodiment 4 battery positive pole piece, is solid-solution material prepared by embodiment 3 unlike solid-solution material.
Embodiment 7: by embodiment 4 gained battery positive pole piece, be negative pole with metal lithium sheet, the ethylene carbonate of 1mol/L lithium hexafluoro phosphate and carbonic acid two
The solution of methyl esters is as electrolyte, and the polyethylene of 20 micron thickness is barrier film, is assembled into CR2032 type button secondary cell.Fig. 2 A charges with 0.2C for this button cell, the first charge-discharge curve of 1C electric discharge, and the embodiment 4 positive pole first charge-discharge efficiency made by visible embodiment 1 gained solid-solution material is higher than 98%, and the reversible capacity of specific discharge capacity is higher than 160mAh/g; Fig. 2 B is the 0.2C charging between 2.5-4.3V of this button cell, and 1C discharge cycles more than 60 times, reversible capacity has no obvious decay.Visible, embodiment 1 gained solid-solution material has good electrochemistry cycle performance as anode material for lithium-ion batteries, with can produce the lithium ion battery that energy density reaches 245W/kg.
Fig. 3 charges with 1C for this button cell, 10C discharge cycles more than 60 times, and reversible capacity has no obvious decay, and charge and discharge cycles final state specific discharge capacity is higher than 120mAh/g.Visible, embodiment 1 gained solid-solution material has excellent 10C high power charging-discharging cycle performance, with can produce the lithium ion battery that power density reaches 1600W/kg, realize the 10C lithium ion battery technology of high security high power capacity.
Embodiment 8: the preparation of secondary cell is identical with embodiment 7, replaces embodiment 4 gained battery positive pole piece unlike with embodiment 5 gained battery positive pole piece.The chemical property of this button cell is similar to Fig. 2 A-2B and Fig. 3.
Embodiment 9: the preparation of secondary cell is identical with embodiment 7, replaces embodiment 4 gained battery positive pole piece unlike with embodiment 6 gained battery positive pole piece.The chemical property of this button cell is similar to Fig. 2 A-2B and Fig. 3.
Embodiment 10: by embodiment 4 gained battery positive pole piece, be negative pole with activated carbon, the ethylene carbonate of 1mol/L lithium hexafluoro phosphate and carbonic acid two
The solution of methyl esters is as electrolyte, and the polyethylene of 20 micron thickness is barrier film, is assembled into CR2032 type button hybrid super capacitor.Fig. 4 is the electrochemical properties of this button capacitor, can work in 1.5-4.3V interval.
Embodiment 11: the preparation of hybrid super capacitor is identical with embodiment 10, replaces embodiment 4 gained battery positive pole piece unlike with embodiment 5 gained battery positive pole piece.The chemical property of this hybrid super capacitor is similar to Fig. 4.
Embodiment 12: the preparation of hybrid super capacitor is identical with embodiment 10, replaces embodiment 4 gained battery positive pole piece unlike with embodiment 6 gained battery positive pole piece.The chemical property of this hybrid super capacitor is similar to Fig. 4.
The all documents mentioned in the present invention are quoted as a reference all in this application, just as each section of document is quoted separately as a reference.In addition should be understood that those skilled in the art can make various changes or modifications the present invention, and these equivalent form of values belong to the application's appended claims limited range equally after having read above-mentioned instruction content of the present invention.
Claims (9)
1., at a kind of high-rate lithium ion battery anode material lithium nickel cobalt manganese oxide solid solution, its chemical general formula is: Li
1+δ Ni
xco
ymn
1-x-yo
2wherein 0.02< δ≤0.12,0.0<x≤0.6,0≤y<0.5,0.0<1-x-y≤0.5, is characterized in that this solid solution has stable micro-nano structure in electrochemical applications; At room temperature in lithium ion battery, between 2.5-4.3V with 0.2C electric discharge reversible capacity higher than 160mAh/g, first charge-discharge efficiency is higher than 98%, and with 1.6A/g (10C) current discharge, experience complete charge-discharge cycles more than 60 times, this solid solution not recurring structure phase transformation and circulation final state specific discharge capacity higher than 120mAh/g.
2. the stable micro-nano structure of lithium nickel cobalt manganese oxide solid solution according to claim 1, is characterized in that, solid solution crystal grain comprises following four aspects:
A. solid solution crystal grain Xrd is characterized by single-phase layered crystal structure, has space group R-3m;
B. solid solution grain morphology be reunited by nanoscale crystal grain there is micro-meter scale offspring porous bulky grain that is spherical, subsphaeroidal, polyhedron shape; ~
C. a crystal grain meso-position radius of solid solution crystal grain nanoscale is of a size of 100 nanometer ~ 800 nanometers;
D. the offspring particle meso-position radius of solid solution crystal grain micro-meter scale is of a size of 1 micron ~ 50 microns.
3. lithium nickel cobalt manganese oxide solid solution according to claim 1, is characterized in that: 0.02< δ≤0.09,0.2≤x≤0.6,0.1≤y≤0.4,0.1≤1-x-y≤0.4.
4. the purposes of a high magnification positive electrode, it is characterized in that, described positive electrode be lithium nickel cobalt manganese oxide solid solution according to claim 1 as positive electrode, can with non-aqueous electrolytic solution or solid electrolyte, and negative material is together, the application in composition lithium rechargeable battery.
5. a purposes for high magnification positive electrode, is characterized in that, described positive electrode is that lithium nickel cobalt manganese oxide solid solution according to claim 1 is preparing the application as positive electrode in lithium-ion capacitor.
6. for the preparation of a preparation method for lithium nickel cobalt manganese oxide solid solution according to claim 1, it is characterized in that, comprise following six steps:
A. nickel source material, cobalt source material, manganese source material are mixed with by nickel, cobalt, manganese mol ratio x:y:1-x-y deionized water or distilled water in chemical general formula the transparent mixed aqueous solution without precipitation of soluble salt that concentration of metal ions is 0.1-1.8mol/L;
B. steps A is obtained mixed aqueous solution and be placed in water-bath or oil bath thermostat is incubated, thermostat temperature is 25-95
0c, in mixed aqueous solution, evenly add the precipitation reagent aqueous solution again, stir simultaneously, mixer used is the one in electric mixer, magnetic stirring apparatus, agitator air, mixer rotating speed is 150-3000 rev/min, and precipitation process terminates the suspension-turbid liquid obtaining the aqueous solution, coprecipitate;
C. filtered by step B gained suspension-turbid liquid, be precipitated powder, with deionized water or distilled water cleaning powder more than three times, suspension-turbid liquid filter method is one or more in centrifugal filtration, negative pressure leaching, press filtration;
D. be placed in drying box by step C gained powder, drying box adopts the one in infrared drying oven, vacuum drying chamber, air dry oven, microwave drying oven, at 80-160
0in C temperature, dry 6-24 hour, obtains presoma;
E. step D gained presoma is mixed to obtain drying composite with lithium source material by the mol ratio 1:1+ δ of transition metal Ni+Co+Mn and Li in chemical general formula, or mix in deionized water and absolute ethyl alcohol, drying obtains drying composite again, and mixture grinder grinding or ball mill ball milling are obtained mixture of powders in 0.1-24 hour;
F. by step e gained mixture of powders first at 300-550
0constant temperature calcining 2-24 hour at C temperature, more continuous in 1-12
0c/ divides ramp to 650-1100
0c, then calcining at constant temperature 4-24 hour, cool to room temperature, sieves and finally obtains oxide solid solution positive electrode according to claim 1.
7. a preparation method for lithium nickel cobalt manganese oxide solid solution according to claim 6, is characterized in that: described lithium source material is one or more in lithium carbonate, lithium sulfate, lithium nitrate, lithium acetate, lithium citrate, lithium hydroxide, lithium halide; Described nickel source material is one or more in nickelous sulfate, nickel nitrate, nickel acetate, citric acid nickel, nickel halogenide; Described cobalt source material is one or more in cobaltous sulfate, cobalt nitrate, cobalt acetate, citric acid cobalt, halogenation cobalt; Described manganese source material is one or more in manganese sulfate, manganese nitrate, manganese acetate, manganese citrate, manganese halide; Described precipitation reagent is one or more in ammoniacal liquor, NaOH, potassium hydroxide, carbonic acid ammonia, sodium carbonate, potash, ammonium hydrogencarbonate, sodium acid carbonate, saleratus.
8. a preparation method for lithium nickel cobalt manganese oxide solid solution according to claim 6, is characterized in that, gained powder after step C cleaning is mixed with suspension-turbid liquid, at 100-300
0mist projection granulating under C condition, inlet temperature 150-220 in spray-drying process
0c, obtains presoma.
9. a preparation method for lithium nickel cobalt manganese oxide solid solution according to claim 6, is characterized in that: described step F two sections of warm area sintering also carry out continuously in air atmosphere in high temperature Muffle furnace, rotary furnace, tunnel cave or roller kilns.
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| CN111204813B (en) * | 2020-01-16 | 2021-09-03 | 昆明理工大学 | Preparation method of vanadium-doped lithium-rich manganese-based positive electrode material |
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