CN113903884A - Positive electrode active material, preparation method thereof, positive electrode and lithium ion battery - Google Patents
Positive electrode active material, preparation method thereof, positive electrode and lithium ion battery Download PDFInfo
- Publication number
- CN113903884A CN113903884A CN202111163841.0A CN202111163841A CN113903884A CN 113903884 A CN113903884 A CN 113903884A CN 202111163841 A CN202111163841 A CN 202111163841A CN 113903884 A CN113903884 A CN 113903884A
- Authority
- CN
- China
- Prior art keywords
- cobalt
- nickel
- manganese
- active material
- lithium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 85
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title abstract description 17
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 claims abstract description 95
- 239000000463 material Substances 0.000 claims abstract description 61
- 239000000203 mixture Substances 0.000 claims abstract description 36
- 239000002243 precursor Substances 0.000 claims abstract description 34
- 239000011247 coating layer Substances 0.000 claims abstract description 27
- 238000000576 coating method Methods 0.000 claims abstract description 26
- 239000011248 coating agent Substances 0.000 claims abstract description 25
- 239000003513 alkali Substances 0.000 claims abstract description 24
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 23
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 23
- 239000011259 mixed solution Substances 0.000 claims abstract description 21
- 238000010438 heat treatment Methods 0.000 claims abstract description 19
- 238000002156 mixing Methods 0.000 claims abstract description 17
- 150000001868 cobalt Chemical class 0.000 claims abstract description 16
- 150000002696 manganese Chemical class 0.000 claims abstract description 16
- 150000002815 nickel Chemical class 0.000 claims abstract description 16
- 239000002019 doping agent Substances 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 12
- 238000005245 sintering Methods 0.000 claims abstract description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000001301 oxygen Substances 0.000 claims abstract description 11
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 11
- 238000004519 manufacturing process Methods 0.000 claims abstract description 6
- -1 alumina Chemical class 0.000 claims description 31
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- XGRSAFKZAGGXJV-UHFFFAOYSA-N 3-azaniumyl-3-cyclohexylpropanoate Chemical compound OC(=O)CC(N)C1CCCCC1 XGRSAFKZAGGXJV-UHFFFAOYSA-N 0.000 claims description 13
- 229960004711 sodium monofluorophosphate Drugs 0.000 claims description 13
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims description 12
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 229910013467 LiNixCoyMnzO2 Inorganic materials 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- 229910001386 lithium phosphate Inorganic materials 0.000 claims description 7
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 claims description 7
- IRPGOXJVTQTAAN-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanal Chemical compound FC(F)(F)C(F)(F)C=O IRPGOXJVTQTAAN-UHFFFAOYSA-N 0.000 claims description 6
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminum fluoride Inorganic materials F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 claims description 6
- 229910019142 PO4 Inorganic materials 0.000 claims description 6
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 claims description 6
- CPSYWNLKRDURMG-UHFFFAOYSA-L hydron;manganese(2+);phosphate Chemical compound [Mn+2].OP([O-])([O-])=O CPSYWNLKRDURMG-UHFFFAOYSA-L 0.000 claims description 6
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 claims description 6
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 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
- IGILRSKEFZLPKG-UHFFFAOYSA-M lithium;difluorophosphinate Chemical compound [Li+].[O-]P(F)(F)=O IGILRSKEFZLPKG-UHFFFAOYSA-M 0.000 claims description 6
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 claims description 6
- 229910001635 magnesium fluoride Inorganic materials 0.000 claims description 6
- ISPYRSDWRDQNSW-UHFFFAOYSA-L manganese(II) sulfate monohydrate Chemical compound O.[Mn+2].[O-]S([O-])(=O)=O ISPYRSDWRDQNSW-UHFFFAOYSA-L 0.000 claims description 6
- 235000021317 phosphate Nutrition 0.000 claims description 6
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 5
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 5
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 claims description 4
- 229910001429 cobalt ion Inorganic materials 0.000 claims description 4
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims description 4
- 229910001437 manganese ion Inorganic materials 0.000 claims description 4
- 229910001453 nickel ion Inorganic materials 0.000 claims description 4
- 229910003678 NixCoyMnz(OH)2 Inorganic materials 0.000 claims description 3
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 claims description 3
- 229910001863 barium hydroxide Inorganic materials 0.000 claims description 3
- GFHNAMRJFCEERV-UHFFFAOYSA-L cobalt chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Co+2] GFHNAMRJFCEERV-UHFFFAOYSA-L 0.000 claims description 3
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 claims description 3
- 229940044175 cobalt sulfate Drugs 0.000 claims description 3
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 3
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 3
- MEYVLGVRTYSQHI-UHFFFAOYSA-L cobalt(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Co+2].[O-]S([O-])(=O)=O MEYVLGVRTYSQHI-UHFFFAOYSA-L 0.000 claims description 3
- WLQXLCXXAPYDIU-UHFFFAOYSA-L cobalt(2+);disulfamate Chemical compound [Co+2].NS([O-])(=O)=O.NS([O-])(=O)=O WLQXLCXXAPYDIU-UHFFFAOYSA-L 0.000 claims description 3
- BZRRQSJJPUGBAA-UHFFFAOYSA-L cobalt(ii) bromide Chemical compound Br[Co]Br BZRRQSJJPUGBAA-UHFFFAOYSA-L 0.000 claims description 3
- RJYMRRJVDRJMJW-UHFFFAOYSA-L dibromomanganese Chemical compound Br[Mn]Br RJYMRRJVDRJMJW-UHFFFAOYSA-L 0.000 claims description 3
- PQVSTLUFSYVLTO-UHFFFAOYSA-N ethyl n-ethoxycarbonylcarbamate Chemical compound CCOC(=O)NC(=O)OCC PQVSTLUFSYVLTO-UHFFFAOYSA-N 0.000 claims description 3
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 3
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 3
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 3
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium hydroxide monohydrate Substances [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 claims description 3
- 229940040692 lithium hydroxide monohydrate Drugs 0.000 claims description 3
- 229940099596 manganese sulfate Drugs 0.000 claims description 3
- 239000011702 manganese sulphate Substances 0.000 claims description 3
- 235000007079 manganese sulphate Nutrition 0.000 claims description 3
- ALIMWUQMDCBYFM-UHFFFAOYSA-N manganese(2+);dinitrate;tetrahydrate Chemical compound O.O.O.O.[Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ALIMWUQMDCBYFM-UHFFFAOYSA-N 0.000 claims description 3
- KEXSCPNGYFGPFU-UHFFFAOYSA-L manganese(2+);disulfamate Chemical compound [Mn+2].NS([O-])(=O)=O.NS([O-])(=O)=O KEXSCPNGYFGPFU-UHFFFAOYSA-L 0.000 claims description 3
- CNFDGXZLMLFIJV-UHFFFAOYSA-L manganese(II) chloride tetrahydrate Chemical compound O.O.O.O.[Cl-].[Cl-].[Mn+2] CNFDGXZLMLFIJV-UHFFFAOYSA-L 0.000 claims description 3
- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 claims description 3
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 3
- 229940053662 nickel sulfate Drugs 0.000 claims description 3
- RRIWRJBSCGCBID-UHFFFAOYSA-L nickel sulfate hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-]S([O-])(=O)=O RRIWRJBSCGCBID-UHFFFAOYSA-L 0.000 claims description 3
- 229940116202 nickel sulfate hexahydrate Drugs 0.000 claims description 3
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 claims description 3
- KERTUBUCQCSNJU-UHFFFAOYSA-L nickel(2+);disulfamate Chemical compound [Ni+2].NS([O-])(=O)=O.NS([O-])(=O)=O KERTUBUCQCSNJU-UHFFFAOYSA-L 0.000 claims description 3
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 3
- 239000003002 pH adjusting agent Substances 0.000 claims description 3
- UQPSGBZICXWIAG-UHFFFAOYSA-L nickel(2+);dibromide;trihydrate Chemical compound O.O.O.Br[Ni]Br UQPSGBZICXWIAG-UHFFFAOYSA-L 0.000 claims description 2
- 239000006182 cathode active material Substances 0.000 abstract description 26
- 230000008569 process Effects 0.000 abstract description 5
- 239000006183 anode active material Substances 0.000 abstract description 4
- 238000005253 cladding Methods 0.000 abstract description 3
- 238000004134 energy conservation Methods 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 32
- 239000003792 electrolyte Substances 0.000 description 17
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 14
- 229910052744 lithium Inorganic materials 0.000 description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 12
- 239000000243 solution Substances 0.000 description 11
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 10
- 239000002033 PVDF binder Substances 0.000 description 10
- 238000002441 X-ray diffraction Methods 0.000 description 10
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 10
- 238000001878 scanning electron micrograph Methods 0.000 description 10
- 239000006230 acetylene black Substances 0.000 description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 8
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 238000000227 grinding Methods 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical group [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 5
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- 239000007784 solid electrolyte Substances 0.000 description 5
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 4
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 239000001569 carbon dioxide Substances 0.000 description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- 238000005265 energy consumption Methods 0.000 description 4
- 239000011888 foil Substances 0.000 description 4
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(II) nitrate Inorganic materials [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 239000006258 conductive agent Substances 0.000 description 3
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- 230000005012 migration Effects 0.000 description 3
- 238000013508 migration Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- 239000004709 Chlorinated polyethylene Substances 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- 229910015872 LiNi0.8Co0.1Mn0.1O2 Inorganic materials 0.000 description 2
- 229910013872 LiPF Inorganic materials 0.000 description 2
- 101150058243 Lipf gene Proteins 0.000 description 2
- 229910017223 Ni0.8Co0.1Mn0.1(OH)2 Inorganic materials 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 150000003949 imides Chemical class 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 2
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 2
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 2
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 2
- 229920000379 polypropylene carbonate Polymers 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910021585 Nickel(II) bromide Inorganic materials 0.000 description 1
- RJEIKIOYHOOKDL-UHFFFAOYSA-N [Li].[La] Chemical compound [Li].[La] RJEIKIOYHOOKDL-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical group FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 229910052743 krypton Inorganic materials 0.000 description 1
- DNNSSWSSYDEUBZ-UHFFFAOYSA-N krypton atom Chemical compound [Kr] DNNSSWSSYDEUBZ-UHFFFAOYSA-N 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- IPLJNQFXJUCRNH-UHFFFAOYSA-L nickel(2+);dibromide Chemical compound [Ni+2].[Br-].[Br-] IPLJNQFXJUCRNH-UHFFFAOYSA-L 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 229920000128 polypyrrole Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- H—ELECTRICITY
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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Abstract
A preparation method of a cladding co-doping modified positive electrode active material comprises the following steps: providing nickel salt, cobalt salt, manganese salt, lithium salt, strong alkali liquor and a coating co-doping agent; mixing the nickel salt, the cobalt salt, the manganese salt and the strong alkali liquor to obtain a mixed liquor; heating the mixed solution in an inert atmosphere to obtain a nickel-cobalt-manganese precursor; mixing the nickel-cobalt-manganese precursor, the lithium salt and the coating co-dopant to obtain a mixture; and sintering the mixture in an oxygen atmosphere to obtain the anode active material, wherein the anode active material comprises a nickel-cobalt-manganese ternary material and a coating layer coated outside the nickel-cobalt-manganese ternary material. The application also provides a positive active material prepared by the preparation method of the positive active material, a positive electrode applying the positive active material and a lithium ion battery applying the positive electrode. The preparation method of the cathode active material has the advantages of simple process, energy conservation, high efficiency and low production cost.
Description
Technical Field
The application relates to the technical field of lithium ion batteries, in particular to a preparation method of a positive active material, the positive active material prepared by the preparation method of the positive active material, a positive electrode using the positive active material and a lithium ion battery using the positive electrode.
Background
With the rapid development of electric vehicles, the requirements of people on power batteries are continuously improved. Currently, lithium ion batteries are currently the most promising power batteries due to their good performance and lower cost.
The nickel-cobalt-manganese (NCM) ternary positive active material applicable to the lithium ion battery has the advantages of high specific capacity, good cycle performance, stable structure, low cost and the like. However, the existing NCM ternary cathode active material has the defects of low conductivity, coating of 'residual alkali' substances on the surface, easy reaction with electrolyte, easy Li/Ni ion mixed discharge, easy generation of layered-spinel phase transformation and the like, thereby limiting the application of the NCM ternary cathode active material.
At present, a high-temperature sintering method can be adopted to reduce the mixed-arrangement degree of cations in the NCM ternary positive active material so as to improve the stability of a crystal structure. And a low-temperature coating method can be adopted to reduce the interface reaction between the NCM ternary positive active material and the electrolyte so as to improve the cycle performance of the lithium ion battery. However, the existing preparation method of the NCM ternary cathode active material has the defects of complex process, high energy consumption and high cost.
Disclosure of Invention
In view of the above, it is necessary to provide a method for preparing a cathode active material to solve the disadvantages of the existing NCM ternary cathode active material, such as complicated process, high energy consumption and high cost.
In addition, it is necessary to provide a positive electrode active material.
In addition, it is necessary to provide a positive electrode.
In addition, a lithium ion battery is also needed to be provided.
A method for preparing a positive electrode active material, comprising the steps of:
providing nickel salt, cobalt salt, manganese salt, lithium salt, strong alkali liquor and a coating co-doping agent;
mixing the nickel salt, the cobalt salt, the manganese salt and the strong alkali liquor to obtain a mixed liquor;
heating the mixed solution in an inert atmosphere to obtain a nickel-cobalt-manganese precursor, wherein the structural formula of the nickel-cobalt-manganese precursor is NixCoyMnz(OH)2Wherein x + y + z is 1, x is more than 0.33 and less than 1, y is more than 0 and less than 0.33, and z is more than 0 and less than 0.33;
mixing the nickel-cobalt-manganese precursor, the lithium salt and the coating co-dopant to obtain a mixture;
sintering the mixture in an oxygen atmosphere to obtain a positive active material, wherein the positive active material comprises a nickel-cobalt-manganese ternary material and a coating layer coated outside the nickel-cobalt-manganese ternary material, and the structural formula of the nickel-cobalt-manganese ternary material is LiNixCoyMnzO2Wherein x + y + z is 1, x is more than 0.33 and less than 1, y is more than 0 and less than 0.33, and z is more than 0 and less than 0.33.
Further, the thickness of the coating layer is 1-20 nm; and/or
The particle size of the nickel-cobalt-manganese ternary material is 5-15 mu m.
Further, the nickel salt is at least one of nickel sulfate, nickel sulfate hexahydrate, nickel nitrate hexahydrate, nickel chloride hexahydrate, nickel bromide and nickel sulfamate; and/or
The cobalt salt is at least one of cobalt sulfate, cobalt sulfate heptahydrate, cobalt nitrate hexahydrate, cobalt chloride hexahydrate, cobalt bromide and cobalt sulfamate; and/or
The manganese salt is at least one of manganese sulfate, manganese sulfate monohydrate, manganese nitrate tetrahydrate, manganese chloride tetrahydrate, manganese bromide and manganese sulfamate; and/or
The lithium salt is at least one of lithium nitrate, lithium carbonate, lithium hydroxide monohydrate, lithium acetate and lithium bromide; and/or
The coating codopant is at least one of phosphates such as alumina, zirconia, ferroferric oxide, lithium fluoride, magnesium fluoride, aluminum fluoride, lithium phosphate, manganese phosphate, lithium iron phosphate, aluminum phosphate and the like, and sodium monofluorophosphate, sodium hexafluorophosphate, lithium hexafluorophosphate and lithium difluorophosphate; and/or
The solute of the strong alkali liquor is at least one of sodium hydroxide, potassium hydroxide and barium hydroxide.
Further, the concentration sum of nickel ions, cobalt ions and manganese ions in the mixed solution is 1.5-3.5 mol/L; and/or
The concentration of the strong alkali liquor is 3.75-4.25 mol/L;
the molar ratio of the lithium salt to the nickel-cobalt-manganese precursor is 1.0-1.1: 1;
in the mixture, the mass percent content of the coating co-dopant is 0.05-2 wt.%.
Further, the preparation method of the positive active material further comprises the following steps:
providing a pH adjusting agent;
and mixing the nickel salt, the cobalt salt, the manganese salt, the strong alkali liquor and the pH regulator to obtain the mixed liquor, wherein the pH value of the mixed liquor is 11-11.4.
Further, the sintering treatment temperature is 500-1000 ℃, and the time is 4-20 h.
Further, the temperature of the heating treatment is 20-80 ℃, and the time is 10-48 h.
The positive active material comprises a nickel-cobalt-manganese ternary material and a coating layer coated outside the nickel-cobalt-manganese ternary material, wherein the structural formula of the nickel-cobalt-manganese ternary material is LiNixCoyMnzO2Wherein x + y + z is 1,0.33<x<1,0<y<0.33,0<z<0.33。
the coating layer is made of at least one of aluminum oxide, zirconium oxide, ferroferric oxide, lithium fluoride, magnesium fluoride, aluminum fluoride, phosphates such as lithium phosphate, manganese phosphate, lithium iron phosphate and aluminum phosphate, sodium monofluorophosphate, sodium hexafluorophosphate, lithium hexafluorophosphate and lithium difluorophosphate; and/or
The thickness of the coating layer is 1-20 nm.
Furthermore, the particle size of the nickel-cobalt-manganese ternary material is 5-15 mu m.
A positive electrode contains the positive electrode active material.
A lithium ion battery includes the positive electrode.
According to the preparation method of the positive active material, under the inert atmosphere, the mixed liquid containing nickel salt, cobalt salt, manganese salt and strong alkali liquor is heated to obtain a nickel-cobalt-manganese precursor, and then under the oxygen atmosphere, the mixture containing the nickel-cobalt-manganese precursor, lithium salt and coating co-doping agent is sintered to obtain the positive active material. The positive active material comprises a nickel-cobalt-manganese ternary material and a coating layer coated outside the nickel-cobalt-manganese ternary material, and the structural formula of the nickel-cobalt-manganese ternary material is LiNixCoyMnzO2Wherein x + y + z is 1, x is more than 0.33 and less than 1, y is more than 0 and less than 0.33, and z is more than 0 and less than 0.33. According to the preparation method of the cathode active material, the mixture containing the nickel-cobalt-manganese precursor, the lithium salt and the coating codopant is sintered to obtain the coating codoped cathode active material, the steps of pre-sintering, secondary sintering, grinding and the like are reduced, the process flow is simplified, the energy consumption is reduced, and the production cost of the cathode active material is reduced. Furthermore, the coating layer coated outside the nickel-cobalt-manganese ternary material can isolate the nickel-cobalt-manganese ternary material from water and carbon dioxide in the air, so that residual alkali is prevented from being generated on the surface of the nickel-cobalt-manganese ternary material, electrolyte can be prevented from corroding the nickel-cobalt-manganese ternary material, and the positive active material has better circulation stability. The nickel-cobalt-manganese ternary material can reduce the content of the nickel-cobalt-manganese ternary materialThe Li/Ni mixed-discharging degree in the nickel-cobalt-manganese ternary material inhibits transition metal migration and reduces oxygen loss, so that the structure of the nickel-cobalt-manganese ternary material is stabilized, the phase transition temperature of the nickel-cobalt-manganese ternary material is increased, and the electrochemical performance of the anode active material is improved.
Drawings
Fig. 1 is an XRD pattern of a positive active material according to example one of the present application;
fig. 2 is an SEM image of the positive active material according to the first embodiment of the present disclosure.
Fig. 3 is an XRD pattern of the cathode active material of example two of the present application.
Fig. 4 is an SEM image of the positive electrode active material according to example two of the present application.
Fig. 5 is an XRD pattern of the positive active material of comparative example one of the present application;
fig. 6 is an SEM image of a positive electrode active material of comparative example one of the present application;
fig. 7 is an XRD pattern of the cathode active material of comparative example no.
Fig. 8 is an SEM image of the positive electrode active material of comparative example No. 8.
The following detailed description will further illustrate the present application in conjunction with the above-described figures.
Detailed Description
In order that the above objects, features and advantages of the present application can be more clearly understood, a detailed description of the present application will be given below with reference to the accompanying drawings and detailed description. In addition, the embodiments and features of the embodiments of the present application may be combined with each other without conflict. In the following description, numerous specific details are set forth to provide a thorough understanding of the present application, and the described embodiments are merely a subset of the embodiments of the present application, rather than all embodiments. All other embodiments obtained by a person of ordinary skill in the art without any inventive work based on the embodiments in the present application are within the scope of protection of the present application.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used herein in the description of the present application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. As used herein, the term "and/or" includes all and any combination of one or more of the associated listed items.
The embodiment of the application provides a preparation method of a positive electrode active material, which comprises the following steps:
step S1: providing nickel salt, cobalt salt, manganese salt, lithium salt, strong alkali liquor and a coating co-doping agent;
step S2: mixing the nickel salt, the cobalt salt, the manganese salt and the strong alkali liquor to obtain a mixed liquor;
step S3: heating the mixed solution in an inert atmosphere to obtain a nickel-cobalt-manganese precursor, wherein the structural formula of the nickel-cobalt-manganese precursor is NixCoyMnz(OH)2Wherein x + y + z is 1, x is more than 0.33 and less than 1, y is more than 0 and less than 0.33, and z is more than 0 and less than 0.33;
step S4: mixing the nickel-cobalt-manganese precursor, the lithium salt and the coating co-dopant to obtain a mixture;
step S5: sintering the mixture in an oxygen atmosphere to obtain a positive active material, wherein the positive active material comprises a nickel-cobalt-manganese ternary material and a coating layer coated outside the nickel-cobalt-manganese ternary material, and the structural formula of the nickel-cobalt-manganese ternary material is LiNixCoyMnzO2Wherein x + y + z is 1, x is more than 0.33 and less than 1, y is more than 0 and less than 0.33, and z is more than 0 and less than 0.33.
In at least one embodiment, the thickness of the coating layer is 1 to 20nm, such as 1nm, 5nm, 10nm, 15nm, and 20 nm.
In at least one embodiment, the particle size of the nickel-cobalt-manganese ternary material is 5 to 15 μm, such as 5 μm, 10 μm, and 15 μm.
In at least one embodiment, the nickel salt is at least one of nickel sulfate, nickel sulfate hexahydrate, nickel nitrate hexahydrate, nickel chloride hexahydrate, nickel bromide, and nickel sulfamate.
In at least one embodiment, the cobalt salt is at least one of cobalt sulfate, cobalt sulfate heptahydrate, cobalt nitrate hexahydrate, cobalt chloride hexahydrate, cobalt bromide, and cobalt sulfamate.
In at least one embodiment, the manganese salt is at least one of manganese sulfate, manganese sulfate monohydrate, manganese nitrate tetrahydrate, manganese chloride tetrahydrate, manganese bromide, and manganese sulfamate.
In at least one embodiment, the lithium salt is at least one of lithium nitrate, lithium carbonate, lithium hydroxide monohydrate, lithium acetate, and lithium bromide.
In at least one embodiment, the coating co-dopant is at least one of phosphates such as alumina, zirconia, ferroferric oxide, lithium fluoride, magnesium fluoride, aluminum fluoride, lithium phosphate, manganese phosphate, lithium iron phosphate, aluminum phosphate, and the like, and sodium monofluorophosphate, sodium hexafluorophosphate, lithium hexafluorophosphate, and lithium difluorophosphate.
In at least one embodiment, the solute of the strong alkali solution is at least one of sodium hydroxide, potassium hydroxide and barium hydroxide.
In at least one embodiment, the total concentration of the nickel ions, the cobalt ions, and the manganese ions in the mixed solution is 1.5-3.5 mol/L, for example, the total concentration of the nickel ions, the cobalt ions, and the manganese ions is 1.5mol/L, 2mol/L, 2.5mol/L, 3mol/L, and 3.5 mol/L.
In at least one embodiment, the concentration of the strong alkali solution is 3.75-4.25 mol/L.
In at least one embodiment, the molar ratio of the lithium salt to the nickel-cobalt-manganese precursor is 1.0-1.1: 1, for example 1: 1. 1.05: 1. 1.1: 1.
in at least one embodiment, the mass percentage of the cladding co-dopant in the mixture is 0.05-2 wt.%, for example, the mass percentage of the cladding co-dopant is 0.05 wt.%, 0.1 wt.%, 0.5 wt.%, 1 wt.%, 1.5 wt.%, 2 wt.%.
In at least one embodiment, the temperature of the heating treatment is 20-80 ℃ and the time is 10-48 h.
In at least one embodiment, the sintering temperature is 500-1000 ℃ and the time is 4-20 h. Specifically, the temperature is raised to 500 ℃ at a temperature raising rate of 5 ℃/min, and then raised to 1000 ℃ at a temperature raising rate of 2 ℃/min.
In at least one embodiment, the nickel-cobalt-manganese precursor precipitate obtained after the heating treatment of the mixed solution may be filtered, washed, and dried to obtain the nickel-cobalt-manganese precursor. The temperature of the drying treatment can be 60-150 ℃, and the time can be 2-24 h.
In at least one embodiment, the inert atmosphere may be nitrogen, helium, neon, argon, krypton, or xenon.
In at least one embodiment, the oxygen atmosphere may be oxygen or air.
It can be understood that the mixed solution can be stirred at the speed of 300-1000 r/min.
According to the preparation method of the positive active material, under the inert atmosphere, the mixed liquid containing nickel salt, cobalt salt, manganese salt and strong alkali liquor is heated to obtain a nickel-cobalt-manganese precursor, and then under the oxygen atmosphere, the mixture containing the nickel-cobalt-manganese precursor, lithium salt and coating co-doping agent is sintered to obtain the positive active material. The positive active material comprises a nickel-cobalt-manganese ternary material and a coating layer coated outside the nickel-cobalt-manganese ternary material, and the structural formula of the nickel-cobalt-manganese ternary material is LiNixCoyMnzO2Wherein x + y + z is 1, x is more than 0.33 and less than 1, y is more than 0 and less than 0.33, and z is more than 0 and less than 0.33. According to the preparation method of the cathode active material, the mixture containing the nickel-cobalt-manganese precursor, the lithium salt and the coating codopant is sintered to obtain the coating codoped cathode active material, the steps of pre-sintering, secondary sintering, grinding and the like are reduced, the process flow is simplified, the energy consumption is reduced, and the production cost of the cathode active material is reduced. Furthermore, the coating layer coated outside the nickel-cobalt-manganese ternary material can not only isolate the nickel-cobalt-manganese ternary material from water and carbon dioxide in the air, avoid the generation of residual alkali on the surface of the nickel-cobalt-manganese ternary material, but also prevent electrolyte from corroding the nickel and cobaltThe manganese ternary material enables the positive active material to have better cycling stability. The nickel-cobalt-manganese ternary material can reduce the degree of Li/Ni mixed discharge in the nickel-cobalt-manganese ternary material, inhibit transition metal migration and reduce oxygen loss, so that the structure of the nickel-cobalt-manganese ternary material is stabilized, the phase transition temperature of the nickel-cobalt-manganese ternary material is increased, and the electrochemical performance of the positive active material is improved.
The preparation method of the positive active material further comprises the following steps:
providing a pH adjusting agent; and
and mixing the nickel salt, the cobalt salt, the manganese salt, the strong alkali liquor and the pH regulator to obtain the mixed liquor, wherein the pH value of the mixed liquor is 11-11.4.
In at least one embodiment, the pH regulator can be ammonia water with a concentration of 1-4 mol/L.
In this application technical scheme, can will the pH regulator adds to mixed liquid in, in order to adjust the pH value of mixed liquid, so that it is right the mixed liquid carries out heat treatment's in-process and obtains nickel cobalt manganese precursor deposit.
The preparation method of the positive active material further comprises the following steps:
grinding the mixture to obtain uniform powder; and
and screening the mixture after the grinding treatment to obtain the mixture with the particle size of less than 0.334 mm.
In the preparation method of the cathode active material, the mixture can be ground and screened to obtain a mixture with a particle size of less than 0.334 mm. Since the size of the mixture is small and uniform, the size of the positive active material is also small and uniform.
The embodiment of the application also provides a positive electrode active material.
The positive active material comprises a nickel-cobalt-manganese ternary material and a coating layer coated outside the nickel-cobalt-manganese ternary material, and the structural formula of the nickel-cobalt-manganese ternary material is LiNixCoyMnzO2Which isWherein x + y + z is 1, x is more than 0.33 and less than 1, y is more than 0 and less than 0.33, and z is more than 0 and less than 0.33.
In at least one embodiment, the material of the coating layer is at least one of alumina, zirconia, ferroferric oxide, lithium fluoride, magnesium fluoride, aluminum fluoride, phosphates such as lithium phosphate, manganese phosphate, lithium iron phosphate, and aluminum phosphate, sodium monofluorophosphate, sodium hexafluorophosphate, lithium hexafluorophosphate, and lithium difluorophosphate.
In at least one embodiment, the thickness of the coating layer is 1 to 20nm, such as 1nm, 5nm, 10nm, 15nm, and 20 nm.
In at least one embodiment, the particle size of the nickel-cobalt-manganese ternary material is 5 to 15 μm, such as 5 μm, 10 μm, and 15 μm.
The application discloses positive active material, the coating outside nickel cobalt manganese ternary material not only can with water and carbon dioxide in nickel cobalt manganese ternary material and the air keep apart, avoid in "residual alkali" is generated on the surface of nickel cobalt manganese ternary material, still can block electrolyte to corrode nickel cobalt manganese ternary material makes positive active material has the circulation stability of preferred. The nickel-cobalt-manganese ternary material can reduce the degree of Li/Ni mixed discharge in the nickel-cobalt-manganese ternary material, inhibit transition metal migration and reduce oxygen loss, thereby stabilizing the structure of the nickel-cobalt-manganese ternary material, increasing the phase transition temperature of the nickel-cobalt-manganese ternary material and improving the electrochemical performance of the anode active material.
The embodiment of the application also provides a positive electrode.
The positive electrode contains the positive electrode active material, a conductive agent, and a binder.
In at least one embodiment, the conductive agent is at least one of graphene, graphite, carbon black, acetylene black, carbon fiber, polypyrrole, and carbon nanotube.
In at least one embodiment, the binder is at least one of polyethylene oxide, polyvinyl chloride, polyvinylidene fluoride, polymethyl ethylene carbonate, polyvinylpyrrolidone, polypropylene carbonate, chlorinated polyethylene, and polyethylene carbonate.
In at least one embodiment, the positive electrode active material is 60-90% by mass, the conductive agent is 5-30% by mass, and the binder is 5-10% by mass.
Since the positive electrode adopts various positive electrode active materials provided in the embodiments of the present application, at least all the beneficial effects brought by the positive electrode active materials of the embodiments are obtained, and are not described in detail herein.
The embodiment of the application also provides a lithium ion battery.
The lithium ion battery comprises the anode, the lithium cathode and electrolyte, wherein the anode and the lithium cathode are both arranged in the electrolyte.
It can be understood that the lithium ion battery also comprises necessary elements such as a negative electrode shell, a diaphragm, a gasket, a spring plate, a positive electrode shell and the like.
In at least one embodiment, the electrolyte contains lithium salt with a concentration of 1-2 mol/L and a solvent. The solvent contains the following components in a volume ratio of 1: 1: 1 fluoroethylene carbonate, methylethyl carbonate, and diethyl carbonate, or said solvent comprises a solvent having a volume ratio of 1: 1: 1 ethylene carbonate, diethyl carbonate, dimethyl carbonate. The lithium salt is selected from at least one of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium perchlorate, lithium difluorooxalato borate, lithium bis (oxalato) borate, lithium bis (trifluoromethylsulfonyl) imide and lithium bis (fluorosulfonato) imide.
In at least one embodiment, the lithium ion battery comprises the positive electrode, the lithium negative electrode and a solid electrolyte, wherein the positive electrode and the lithium negative electrode are respectively positioned on two sides of the solid electrolyte.
In at least one embodiment, the solid electrolyte contains a polymer and a lithium salt and a filler dispersed in the polymer. The lithium salt is selected from at least one of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium perchlorate, lithium difluorooxalato borate, lithium bis (oxalato) borate, lithium bis (trifluoromethylsulfonyl) imide and lithium bis (fluorosulfonato) imide.
The polymer is at least one of polyethylene oxide, polyvinyl chloride, polyvinylidene fluoride, polymethyl ethylene carbonate, polyvinylpyrrolidone, polypropylene carbonate, chlorinated polyethylene and polyethylene carbonate.
The filler is at least one of lanthanum zirconate and lanthanum lithium zirconate so as to further improve the transmission efficiency of lithium ions and the ionic conductivity of the solid electrolyte lithium ion battery. The mass ratio of lithium salt, polymer and filler in the solid electrolyte is 7-9: 1-3: 1 to 2, for example, 8: 1: 1.
since the lithium ion battery can adopt various anodes of all the embodiments, at least all the beneficial effects brought by the technical solutions of the embodiments are achieved, and no further description is given here.
The present application will be specifically described below with reference to specific examples.
Example one
Providing Ni (NO)3)2·6H2O、Co(NO3)2·6H2O、Mn(NO3)2·6H2O and water, wherein Ni: co: the molar ratio of Mn is 8: 1: 1;
mixing Ni (NO)3)2·6H2O、Co(NO3)2·6H2O、Mn(NO3)2·6H2Adding O into water to obtain a mixed solution, wherein the ion concentration sum of the mixed solution is 2 mol/L;
providing a sodium hydroxide solution with the concentration of 4mol/L and an ammonia water solution with the concentration of 4 mol/L;
simultaneously pouring the mixed solution, the sodium hydroxide solution and the ammonia water solution into a reactor at the speed of 30ml/min, 10ml/min and 8ml/min respectively to obtain a mixed solution with the pH value of 11.2;
heating the mixed solution to 50 ℃, introducing nitrogen into the reactor, continuously stirring the mixed solution at the rotating speed of 300r/min, and filtering to obtain a nickel-cobalt-manganese precursor precipitate;
washing the nickel-cobalt-manganese precursor precipitate, and drying in an oven at 80 ℃ for 24h to obtain a nickel-cobalt-manganese precursor with a structureIs of the formula Ni0.8Co0.1Mn0.1(OH)2;
To provide LiOH. H2O and sodium monofluorophosphate, wherein the LiOH. H2The molar ratio of O to the nickel-cobalt-manganese precursor is 1.05: 1;
mixing the LiOH. H2O, sodium monofluorophosphate and a nickel-cobalt-manganese precursor to obtain a mixture, wherein the mass percent of the sodium monofluorophosphate in the mixture is 0.33 wt.%;
grinding the mixture;
placing the ground mixture in a tube furnace, heating to 500 ℃ at a heating rate of 5 ℃/min under a pure oxygen atmosphere, preserving heat for 5h, heating to 780 ℃ at a heating rate of 2 ℃/min, preserving heat for 11h, and cooling to a low temperature along with the furnace to obtain the positive active material (see figures 1 and 2) of the comparative example I, wherein the structural formula of the positive active material of the example I is LiNi0.8Co0.1Mn0.1O2;
Providing acetylene black, polyvinylidene fluoride, N-methyl pyrrolidone and an aluminum foil, wherein the mass ratio of the positive electrode active material, the acetylene black and the polyvinylidene fluoride in the first embodiment is 8: 1: 1, the mass sum of the positive electrode active material, the acetylene black and the polyvinylidene fluoride of the first embodiment is 500 mg;
mixing the positive electrode active material of the first embodiment, acetylene black, polyvinylidene fluoride and N-methyl pyrrolidone to obtain a slurry;
coating the slurry on an aluminum foil, and drying to obtain the anode of the first embodiment;
providing a negative electrode shell, a lithium negative electrode, 40 mu L of electrolyte, a diaphragm, a gasket, a spring plate and a positive electrode shell, wherein the electrolyte contains LiPF with the concentration of 1mol/L6And a solvent comprising, by volume, 1: 1: 1 ethylene carbonate, diethyl carbonate, dimethyl carbonate;
and in a glove box filled with argon, assembling the negative electrode shell, the lithium negative electrode, the electrolyte, the diaphragm, the electrolyte, the positive electrode of the first embodiment, the gasket, the elastic sheet and the positive electrode shell into the button cell of the first embodiment as required.
Referring to fig. 1, the XRD diffraction peak of the positive electrode active material of the first example is sharp, which indicates that the positive electrode active material of the first example has higher crystallinity and no impurity phase.
Referring to fig. 2, the positive active material of the first embodiment has a coating layer.
Example two
The difference from the first embodiment comprises: in the mixture, the mass percent content of the sodium monofluorophosphate is 1 wt.%.
Other steps are the same as the first embodiment and are not repeated.
Referring to fig. 3, the XRD diffraction peak of the cathode active material of the second example is sharp, which indicates that the cathode active material of the second example has higher crystallinity and no impurity phase.
Referring to fig. 4, the cathode active material of the second embodiment has a coating layer.
EXAMPLE III
The difference from the first embodiment comprises: replacing sodium monofluorophosphate in the mixture with sodium hexafluorophosphate.
Other steps are the same as the first embodiment and are not repeated.
It can be understood that the XRD patterns and SEM images of the cathode active material of example three are substantially the same as those of the cathode active material of example one.
Example four
Differences from the third embodiment include: in the mixture, the mass percent content of the sodium hexafluorophosphate is 1 wt.%.
Other steps are the same as those in the embodiment and are not repeated.
It can be understood that the XRD patterns and SEM images of the cathode active material of example four are substantially the same as those of the cathode active material of example two.
EXAMPLE five
The difference from the first embodiment comprises: replacing sodium monofluorophosphate in the mixture with lithium hexafluorophosphate.
Other steps are the same as the first embodiment and are not repeated.
It can be understood that the XRD patterns and SEM images of the cathode active material of example five are substantially the same as those of the cathode active material of example one.
EXAMPLE six
Differences from the fifth embodiment include: in the mixture, the mass percent content of the lithium hexafluorophosphate is 1 wt.%.
Other steps are the same as those in the fifth embodiment and are not repeated.
It can be understood that the XRD patterns and SEM images of the cathode active material of example six are substantially the same as those of the cathode active material of example two.
Comparative example 1
Providing Ni (NO)3)2·6H2O、Co(NO3)2·6H2O、Mn(NO3)2·6H2O and water, wherein Ni: co: the molar ratio of Mn is 8: 1: 1;
mixing Ni (NO)3)2·6H2O、Co(NO3)2·6H2O、Mn(NO3)2·6H2Adding O into water to obtain a mixed solution, wherein the ion concentration sum of the mixed solution is 2 mol/L;
providing a sodium hydroxide solution with the concentration of 4mol/L and an ammonia water solution with the concentration of 4 mol/L;
simultaneously pouring the mixed solution, the sodium hydroxide solution and the ammonia water solution into a reactor at the speed of 30ml/min, 10ml/min and 8ml/min respectively to obtain a mixed solution with the pH value of 11.2;
heating the mixed solution to 50 ℃, introducing nitrogen into the reactor, continuously stirring the mixed solution at the rotating speed of 300r/min, and filtering to obtain a nickel-cobalt-manganese precursor precipitate;
washing the nickel-cobalt-manganese precursor precipitate, and drying in an oven at 80 ℃ for 24h to obtain the nickel-cobalt-manganese precursor, wherein the structural formula of the nickel-cobalt-manganese precursor is Ni0.8Co0.1Mn0.1(OH)2;
Provide forLiOH·H2O, wherein the LiOH. H2The molar ratio of O to the nickel-cobalt-manganese precursor is 1.05: 1;
mixing the LiOH. H2O and a nickel-cobalt-manganese precursor to obtain a mixture;
grinding the mixture;
placing the mixture after grinding treatment in a tubular furnace, heating to 500 ℃ at a heating rate of 5 ℃/min under a pure oxygen atmosphere, preserving heat for 5h, heating to 780 ℃ at a heating rate of 2 ℃/min, preserving heat for 11h, and cooling to a low temperature along with the furnace to obtain the positive active material (see figures 5 and 6) of the first comparative example, wherein the structural formula of the positive active material of the first comparative example is LiNi0.8Co0.1Mn0.1O2;
Providing acetylene black, polyvinylidene fluoride, N-methyl pyrrolidone and an aluminum foil, wherein the mass ratio of the positive electrode active material of the first comparative example, the acetylene black and the polyvinylidene fluoride is 8: 1: 1, the sum of the mass of the positive electrode active material, acetylene black and polyvinylidene fluoride of the comparative example one is 500 mg;
mixing the positive electrode active material of the comparative example one, acetylene black, polyvinylidene fluoride and N-methyl pyrrolidone to obtain slurry;
coating the slurry on an aluminum foil, and drying to obtain the anode of the comparative example I;
providing a negative electrode shell, a lithium negative electrode, 40 mu L of electrolyte, a diaphragm, a gasket, a spring plate and a positive electrode shell, wherein the electrolyte contains LiPF with the concentration of 1mol/L6And a solvent comprising, by volume, 1: 1: 1 ethylene carbonate, diethyl carbonate, dimethyl carbonate;
and in the glove box filled with argon, assembling the negative electrode shell, the lithium negative electrode, the electrolyte, the diaphragm, the electrolyte, the positive electrode of the comparative example I, the gasket, the elastic sheet and the positive electrode shell into the button cell of the comparative example I according to requirements.
Referring to fig. 5, the positive electrode active material of comparative example i has a sharp XRD diffraction peak, indicating that the positive electrode active material of comparative example i has a higher crystallinity without a hetero phase.
Referring to fig. 6, the positive active material of the comparative example has no coating layer.
Comparative example No. two
The difference from the first embodiment comprises: in the mixture, the mass percent content of the sodium monofluorophosphate is 3 wt.%.
Other steps are the same as the first embodiment and are not repeated.
Referring to fig. 7, the XRD diffraction peak of the positive active material of comparative example ii is sharp, indicating that the positive active material of comparative example i has higher crystallinity and no hetero-phase.
Referring to fig. 8, the positive active material of the comparative example has a coating layer.
Comparative example No. three
Differences from the third embodiment include: in the mixture, the mass percent content of the sodium hexafluorophosphate is 3 wt.%.
Other steps are the same as those in the embodiment and are not repeated.
It can be understood that the XRD patterns and SEM images of the positive electrode active material of comparative example three are substantially the same as those of the positive electrode active material of comparative example two.
Comparative example No. four
Differences from the fifth embodiment include: in the mixture, the lithium hexafluorophosphate was contained in an amount of 3 wt.%.
Other steps are the same as those in the fifth embodiment and are not repeated.
It can be understood that the XRD patterns and SEM images of the positive electrode active material of comparative example four are substantially the same as those of the positive electrode active material of comparative example two.
Table 1 comparison of electrochemical performances of the button cells of examples one to six and of the buttons of comparative examples one to four
Under the working voltage of 2.8-4.7V and the multiplying power of 0.1C, the first charge specific capacity, the first discharge specific capacity, the first-cycle coulombic efficiency, the capacity retention rate after 200 cycles under the multiplying power of 1C and the coulombic efficiency after 200 cycles under the multiplying power of 1C of the button batteries of the first to sixth embodiments and the button batteries of the first to fourth comparative examples are measured.
Referring to table 1, the button cells of examples one to six had better capacity, cycle performance, and rate performance compared to the button cells of comparative examples one to four. If the coating layer is not formed or the content of the coating layer is too high, the electrochemical performance of the corresponding button cell is not good. This indicates that, when the coating is present in an appropriate amount, the electrochemical performance of the corresponding button cell is better.
Specifically, the first charge specific capacity, the first discharge specific capacity, and the first-turn coulombic efficiency of the button cell batteries of the first to sixth embodiments are all improved to a certain extent, and the capacity retention rate is also greatly improved after 200 turns at a rate of 1C. The coating layer can isolate the nickel-cobalt-manganese ternary material from water and carbon dioxide in the air, so that residual alkali is prevented from being generated on the surface of the nickel-cobalt-manganese ternary material, the corrosion of electrolyte to the nickel-cobalt-manganese ternary material can be resisted, and the Li is not reduced+The cycle stability of the positive electrodes of examples one to six was maintained on the basis of the diffusion rate. When the content of the coating codopant is too high, a large amount of lithium phosphate is newly added in the phase structure of the positive active materials of the first to fourth comparative examples, and covers the surface of the nickel-cobalt-manganese ternary material, so that Li is prevented+The first charge specific capacity, the first discharge specific capacity, the first coulomb efficiency and the capacity retention rate of the positive electrodes of the comparative examples I to IV are further reduced.
Although the present application has been described in detail with reference to the preferred embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted without departing from the spirit and scope of the present application.
Claims (11)
1. A method for preparing a positive electrode active material, comprising the steps of:
providing nickel salt, cobalt salt, manganese salt, lithium salt, strong alkali liquor and a coating co-doping agent;
mixing the nickel salt, the cobalt salt, the manganese salt and the strong alkali liquor to obtain a mixed liquor;
heating the mixed solution in an inert atmosphere to obtain a nickel-cobalt-manganese precursor, wherein the structural formula of the nickel-cobalt-manganese precursor is NixCoyMnz(OH)2Wherein x + y + z is 1, x is more than 0.33 and less than 1, y is more than 0 and less than 0.33, and z is more than 0 and less than 0.33;
mixing the nickel-cobalt-manganese precursor, the lithium salt and the coating co-dopant to obtain a mixture; and
sintering the mixture in an oxygen atmosphere to obtain a positive active material, wherein the positive active material comprises a nickel-cobalt-manganese ternary material and a coating layer coated outside the nickel-cobalt-manganese ternary material, and the structural formula of the nickel-cobalt-manganese ternary material is LiNixCoyMnzO2Wherein x + y + z is 1, x is more than 0.33 and less than 1, y is more than 0 and less than 0.33, and z is more than 0 and less than 0.33.
2. The method for preparing a positive electrode active material according to claim 1, wherein the coating layer has a thickness of 1 to 20 nm; and/or
The particle size of the nickel-cobalt-manganese ternary material is 5-15 mu m.
3. The method for producing a positive electrode active material according to claim 1, wherein the nickel salt is at least one of nickel sulfate, nickel sulfate hexahydrate, nickel nitrate hexahydrate, nickel chloride hexahydrate, nickel bromide, and nickel sulfamate; and/or
The cobalt salt is at least one of cobalt sulfate, cobalt sulfate heptahydrate, cobalt nitrate hexahydrate, cobalt chloride hexahydrate, cobalt bromide and cobalt sulfamate; and/or
The manganese salt is at least one of manganese sulfate, manganese sulfate monohydrate, manganese nitrate tetrahydrate, manganese chloride tetrahydrate, manganese bromide and manganese sulfamate; and/or
The lithium salt is at least one of lithium nitrate, lithium carbonate, lithium hydroxide monohydrate, lithium acetate and lithium bromide; and/or
The coating codopant is at least one of phosphates such as alumina, zirconia, ferroferric oxide, lithium fluoride, magnesium fluoride, aluminum fluoride, lithium phosphate, manganese phosphate, lithium iron phosphate, aluminum phosphate and the like, and sodium monofluorophosphate, sodium hexafluorophosphate, lithium hexafluorophosphate and lithium difluorophosphate; and/or
The solute of the strong alkali liquor is at least one of sodium hydroxide, potassium hydroxide and barium hydroxide.
4. The method for producing a positive electrode active material according to claim 1, wherein the total concentration of nickel ions, cobalt ions, and manganese ions in the mixed solution is 1.5 to 3.5 mol/L; and/or
The concentration of the strong alkali liquor is 3.75-4.25 mol/L; and/or
The molar ratio of the lithium salt to the nickel-cobalt-manganese precursor is 1.0-1.1: 1; and/or
In the mixture, the mass percent content of the coating co-dopant is 0.05-2 wt.%.
5. The method for producing a positive electrode active material according to claim 1, further comprising the steps of:
providing a pH adjusting agent;
and mixing the nickel salt, the cobalt salt, the manganese salt, the strong alkali liquor and the pH regulator to obtain the mixed liquor, wherein the pH value of the mixed liquor is 11-11.4.
6. The method for preparing the positive electrode active material according to claim 1, wherein the sintering treatment is performed at a temperature of 500 to 1000 ℃ for 4 to 20 hours; and/or
The temperature of the heating treatment is 20-80 ℃, and the time is 10-48 h.
7. The positive active material is characterized by comprising a nickel-cobalt-manganese ternary material and a coating layer coated outside the nickel-cobalt-manganese ternary material, wherein the structural formula of the nickel-cobalt-manganese ternary material is LiNixCoyMnzO2Wherein x + y + z is 1, x is more than 0.33 and less than 1, y is more than 0 and less than 0.33, and z is more than 0 and less than 0.33.
8. The positive electrode active material according to claim 7, wherein the coating layer is made of at least one of alumina, zirconia, triiron tetroxide, lithium fluoride, magnesium fluoride, aluminum fluoride, phosphates such as lithium phosphate, manganese phosphate, lithium iron phosphate, and aluminum phosphate, sodium monofluorophosphate, sodium hexafluorophosphate, lithium hexafluorophosphate, and lithium difluorophosphate; and/or
The thickness of the coating layer is 1-20 nm.
9. The positive electrode active material according to claim 7, wherein the particle size of the ternary nickel-cobalt-manganese material is 5 to 15 μm.
10. A positive electrode comprising the positive electrode active material according to any one of claims 7 to 9.
11. A lithium ion battery, characterized in that it comprises a positive electrode according to claim 10.
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