CN117878295B - Composite positive electrode active material, and preparation method and application thereof - Google Patents
Composite positive electrode active material, and preparation method and application thereof Download PDFInfo
- Publication number
- CN117878295B CN117878295B CN202410275557.XA CN202410275557A CN117878295B CN 117878295 B CN117878295 B CN 117878295B CN 202410275557 A CN202410275557 A CN 202410275557A CN 117878295 B CN117878295 B CN 117878295B
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- China
- Prior art keywords
- positive electrode
- carbon
- source
- composite positive
- active material
- Prior art date
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- 239000007774 positive electrode material Substances 0.000 title claims abstract description 70
- 239000002131 composite material Substances 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000000463 material Substances 0.000 claims abstract description 71
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 39
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 39
- 239000004966 Carbon aerogel Substances 0.000 claims abstract description 34
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 12
- 150000003624 transition metals Chemical group 0.000 claims abstract description 12
- 150000001721 carbon Chemical class 0.000 claims abstract description 10
- 239000000126 substance Substances 0.000 claims abstract description 5
- 238000000498 ball milling Methods 0.000 claims description 40
- 238000010438 heat treatment Methods 0.000 claims description 32
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 26
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 25
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 23
- 229910002090 carbon oxide Inorganic materials 0.000 claims description 23
- 239000010936 titanium Substances 0.000 claims description 22
- 239000011575 calcium Substances 0.000 claims description 20
- 239000000460 chlorine Substances 0.000 claims description 20
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 18
- 239000002243 precursor Substances 0.000 claims description 18
- 239000012046 mixed solvent Substances 0.000 claims description 16
- 238000005245 sintering Methods 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 15
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 14
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 14
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical group O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 14
- 239000011812 mixed powder Substances 0.000 claims description 14
- 230000000630 rising effect Effects 0.000 claims description 14
- 238000000227 grinding Methods 0.000 claims description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 12
- 239000006183 anode active material Substances 0.000 claims description 12
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 12
- 238000007254 oxidation reaction Methods 0.000 claims description 12
- 239000011324 bead Substances 0.000 claims description 11
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 10
- 229920001661 Chitosan Polymers 0.000 claims description 10
- 239000010405 anode material Substances 0.000 claims description 10
- 239000003575 carbonaceous material Substances 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- 238000007710 freezing Methods 0.000 claims description 9
- 230000008014 freezing Effects 0.000 claims description 9
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- ZZZCUOFIHGPKAK-UHFFFAOYSA-N D-erythro-ascorbic acid Natural products OCC1OC(=O)C(O)=C1O ZZZCUOFIHGPKAK-UHFFFAOYSA-N 0.000 claims description 7
- 229930003268 Vitamin C Natural products 0.000 claims description 7
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 7
- 239000003638 chemical reducing agent Substances 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 239000007800 oxidant agent Substances 0.000 claims description 7
- 230000001590 oxidative effect Effects 0.000 claims description 7
- 239000004408 titanium dioxide Substances 0.000 claims description 7
- 235000019154 vitamin C Nutrition 0.000 claims description 7
- 239000011718 vitamin C Substances 0.000 claims description 7
- 238000005303 weighing Methods 0.000 claims description 7
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 6
- 125000003827 glycol group Chemical group 0.000 claims description 6
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 6
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 6
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 6
- 239000012266 salt solution Substances 0.000 claims description 6
- 229920006395 saturated elastomer Polymers 0.000 claims description 6
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 238000004108 freeze drying Methods 0.000 claims description 5
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 5
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 4
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052791 calcium Inorganic materials 0.000 claims description 4
- 239000001110 calcium chloride Substances 0.000 claims description 4
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 4
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 4
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 4
- 238000005119 centrifugation Methods 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 4
- 229910052744 lithium Inorganic materials 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims description 4
- 239000011574 phosphorus Substances 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 235000013162 Cocos nucifera Nutrition 0.000 claims description 3
- 244000060011 Cocos nucifera Species 0.000 claims description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 3
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 3
- 229910001940 europium oxide Inorganic materials 0.000 claims description 3
- AEBZCFFCDTZXHP-UHFFFAOYSA-N europium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Eu+3].[Eu+3] AEBZCFFCDTZXHP-UHFFFAOYSA-N 0.000 claims description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 3
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims description 3
- 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 3
- YWECOPREQNXXBZ-UHFFFAOYSA-N praseodymium(3+);trinitrate Chemical compound [Pr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YWECOPREQNXXBZ-UHFFFAOYSA-N 0.000 claims description 3
- YZDZYSPAJSPJQJ-UHFFFAOYSA-N samarium(3+);trinitrate Chemical compound [Sm+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YZDZYSPAJSPJQJ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052693 Europium Inorganic materials 0.000 claims description 2
- 229910017569 La2(CO3)3 Inorganic materials 0.000 claims description 2
- 239000001506 calcium phosphate Substances 0.000 claims description 2
- 229910000389 calcium phosphate Inorganic materials 0.000 claims description 2
- 235000011010 calcium phosphates Nutrition 0.000 claims description 2
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 claims description 2
- 235000013399 edible fruits Nutrition 0.000 claims description 2
- GAGGCOKRLXYWIV-UHFFFAOYSA-N europium(3+);trinitrate Chemical compound [Eu+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GAGGCOKRLXYWIV-UHFFFAOYSA-N 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- NZPIUJUFIFZSPW-UHFFFAOYSA-H lanthanum carbonate Chemical compound [La+3].[La+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O NZPIUJUFIFZSPW-UHFFFAOYSA-H 0.000 claims description 2
- 229960001633 lanthanum carbonate Drugs 0.000 claims description 2
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 claims description 2
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 2
- MMKQUGHLEMYQSG-UHFFFAOYSA-N oxygen(2-);praseodymium(3+) Chemical compound [O-2].[O-2].[O-2].[Pr+3].[Pr+3] MMKQUGHLEMYQSG-UHFFFAOYSA-N 0.000 claims description 2
- 229910003447 praseodymium oxide Inorganic materials 0.000 claims description 2
- 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 2
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000000243 solution Substances 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 10
- 239000010410 layer Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical class [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 5
- 238000011161 development Methods 0.000 description 5
- 239000000706 filtrate Substances 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- 238000009831 deintercalation Methods 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 4
- 238000009830 intercalation Methods 0.000 description 3
- 230000002687 intercalation Effects 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical class Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000011165 3D composite Substances 0.000 description 1
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical class [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- -1 lithium hexafluorophosphate Chemical compound 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000002345 surface coating layer Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical class [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 1
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
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/455—Phosphates containing halogen
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
-
- 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
- H01M4/36—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
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
-
- 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
- H01M4/52—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
-
- 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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/582—Halogenides
-
- 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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Composite Materials (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to the technical field of lithium ion battery materials, and particularly discloses a composite positive electrode active material, a preparation method and application thereof. The composite positive electrode material comprises a high-entropy doped positive electrode active material and a modified carbon aerogel layer coated on the surface of the positive electrode active material; the chemical formula of the high-entropy doped positive electrode active material is LiaCabAlcNi0.2Ti0.05Me0.1Fe0.5PxClyO2‑(3x+y)/2;, and the material of the modified carbon aerogel layer is transition metal doped carbon aerogel. The lithium ion battery prepared by the composite positive electrode material has good low temperature resistance, can keep good electrochemical performance at a lower temperature, and effectively solves the problem that the lithium ion battery in the prior art can not keep good electrochemical performance in a low-temperature environment.
Description
Technical Field
The invention relates to the technical field of lithium ion battery materials, and particularly discloses a composite positive electrode active material, a preparation method and application thereof.
Background
Lithium Ion Batteries (LIBs) are considered to be green-friendly secondary batteries because of their advantages of stable working potential, high energy density, high discharge specific energy, long service life, light weight, portability, low self-discharge rate, no memory effect during charge and discharge, and the like. Currently, lithium ion batteries have become an important research object for the sustainable development of new energy industries.
With the rapid development of new energy automobiles, the requirements for power lithium ion batteries of core components of the new energy automobiles are also improved. The lithium ion battery is very sensitive to temperature, and particularly under the low-temperature working condition, the performance of the lithium ion battery can be rapidly reduced, and the lowest air temperature in winter in northern China can reach minus 30 ℃ to minus 40 ℃, so that the new energy automobile faces a great challenge in winter in northern China. Therefore, improving the low-temperature performance of the lithium ion battery has great progress significance for the development of the lithium ion battery.
In recent years, research on low-temperature lithium ion batteries has been advanced to a certain extent, and by means of development of electrolyte, regulation and control of electrolyte composition, modification of anode and cathode materials, development or change of the structure of a traditional low-temperature lithium ion battery and the like, the performance of the lithium ion battery at low temperature is improved to a certain extent, but the traditional lithium ion battery still cannot keep good electrochemical performance at-30 ℃ to-40 ℃. Based on the above, it is of great practical significance to develop a lithium ion battery which still has excellent electrochemical properties in a low-temperature environment.
Disclosure of Invention
Aiming at the problem that the lithium ion battery in the prior art can not keep good electrochemical performance in a low-temperature environment of minus 30 ℃ to minus 40 ℃, the invention provides a composite positive electrode material and a preparation method and application thereof. The invention designs a composite positive electrode material, which comprises a high-entropy doped positive electrode active material inner core part and a modified carbon aerogel layer coated on the surface of the positive electrode active material inner core part, wherein a lithium ion battery prepared by using the composite positive electrode material has good low-temperature resistance and can keep good electrochemical performance at a lower temperature.
In order to achieve the above purpose, the present invention provides the following technical solutions.
The first aspect of the present invention provides a composite positive electrode material, characterized in that: the composite positive electrode material comprises a high-entropy doped positive electrode active material and a modified carbon aerogel layer coated on the surface of the positive electrode active material;
The chemical formula of the high-entropy doped positive electrode active material is ：LiaCabAlcNi0.2Ti0.05Me0.1Fe0.5PxClyO2-(3x+y)/2,, wherein Me is any one of La, ce, pr, sm or Eu, a+b+c=1, and all of a, b and c are not 0, x is more than 0 and less than or equal to 0.5, and y is more than 0 and less than 0.5;
The material of the modified carbon aerogel layer is transition metal doped carbon aerogel, wherein the transition metal is any one or two of Co, mn, V or Zn.
Compared with the prior art, the composite positive electrode material provided by the invention can be mainly divided into two parts, namely a high-entropy doped positive electrode active material and a modified carbon aerogel layer coated on the surface of the positive electrode active material. According to the invention, high entropy doping is performed on the basis of lithium iron phosphate, and the rare earth element and the high entropy element are doped to influence the bonding energy between bonds in a crystal structure, so that the diffusion channel of lithium ions in the structure is enlarged, the intercalation and deintercalation of lithium ions are easier, and the rate capability and the cycle performance of the anode material are improved. However, the lithium ion battery can not maintain good electrochemical performance at low temperature by doping the guest ions only, and the surface of the doped positive electrode active material is coated with a modified carbon aerogel layer.
The carbon aerogel is a novel three-dimensional porous carbon material, has the characteristics of large specific surface area, high porosity, strong adsorption capacity and the like, and has higher conductivity in a wide temperature range. According to the invention, the transition metal doped carbon aerogel is used as the surface coating layer, so that the contact area of the positive electrode and the electrolyte is increased, more transmission channels in the process of lithium ion intercalation and deintercalation are provided, and the utilization rate of the positive electrode material is improved. Meanwhile, the three-dimensional composite conductive network formed by the porous carbon aerogel layer is beneficial to rapid deintercalation of lithium ions, and the diffusion efficiency of lithium ions in the electrode is improved in an auxiliary manner, so that the cycle performance of the lithium ion battery at low temperature is greatly improved.
Preferably, the high entropy doped positive electrode active material has a chemical formula of ：Li0.6Ca0.2Al0.2Ni0.2Ti0.05La0. 1Fe0.5P0.4Cl0.4O1.2、Li0.6Ca0.2Al0.2Ni0.2Ti0.05Ce0.1Fe0.5P0.5Cl0.35O1.075、Li0.6Ca0.2Al0.2Ni0.2Ti0.05Eu0.1Fe0.5P0.3Cl0.3O1.4、Li0.6Ca0.2Al0.2Ni0.2Ti0.05Pr0.1Fe0.5P0.4Cl0.4O1.2 or Li0.6Ca0.2Al0.2Ni0.2Ti0.05Sm0.1Fe0.5P0.3Cl0.4O1.35.
Preferably, the preparation method of the high-entropy doped positive electrode active material comprises the following steps:
s1, weighing a lithium source, a calcium source, an aluminum source, a nickel source, a titanium source, a Me source, an iron source, a phosphorus source and a chlorine source according to a designed proportion, uniformly mixing, and ball milling to obtain mixed powder;
S2, heating the mixed powder to 200-350 ℃ for one time, preserving heat for 0.5-1h, heating to 750-900 ℃ for the second time, sintering and grinding to obtain the high-entropy doped anode active material.
The invention adopts a simple solid-phase sintering method, and achieves the purpose of obtaining a brand new anode active material by doping lithium iron phosphate with high entropy through a means of precalcination and high-temperature sintering combination. The doping of the guest element changes the structure of the lithium iron phosphate, so that the material has a more flexible surface structure, and is convenient for the intercalation and deintercalation of lithium ions, thereby improving the capacity retention rate of the lithium ion battery in the charge and discharge process.
Further preferably, in S1, the lithium source is any one of lithium carbonate, lithium nitrate, and lithium sulfate.
Further preferably, in S1, the calcium source is any one or two of calcium carbonate, calcium nitrate, and calcium sulfate.
Further preferably, in S1, the aluminum source is any one of aluminum chloride and aluminum oxide.
Further preferably, in S1, the nickel source is any one or two of nickel nitrate, nickel sulfate or nickel oxide.
Further preferably, in S1, the titanium source is titanium dioxide.
Further preferably, in S1, the Me source is any one of lanthanum nitrate, lanthanum carbonate, lanthanum oxide, cerium chloride, praseodymium oxide, praseodymium nitrate, samarium nitrate, europium nitrate, and europium oxide.
Further preferably, in S1, the iron source is any one or two of ferric oxide, ferric chloride or ferric nitrate.
Further preferably, in S1, the phosphorus source is any one of calcium phosphate and phosphoric acid.
Further preferably, in S1, the chlorine source is any one of calcium chloride and aluminum chloride.
Further preferably, in S1, the rotation speed of the ball milling is 300-500rpm, the diameter of ball milling beads is 0.1-2mm, the ball-material ratio is 5:1-10:1, and the ball milling time is 4-6h.
Further preferably, in S2, the sintering time is 6 to 15 hours.
Further preferably, in S2, the primary temperature rising and the secondary temperature rising are both in a temperature programming mode, wherein the temperature rising rate of the primary temperature rising is 3-8 ℃/min, and the temperature rising rate of the secondary temperature rising is 5-10 ℃/min.
Further preferably, in S2, the grinding time is 20 to 40min.
The second aspect of the invention provides a preparation method of the composite positive electrode material, which comprises the following steps:
Dispersing a carbon material in deionized water, adding an oxidant for oxidation reaction, centrifuging, filtering, and drying the obtained solid filter material to obtain a carbon oxide material;
dispersing the carbon oxide material in an organic mixed solvent, sequentially adding chitosan, a reducing agent and a saturated soluble transition metal salt solution, heating to 60-80 ℃, preserving heat for 2-3h, and cooling to obtain a carbon aerogel precursor;
step three, mixing the carbon aerogel precursor with the high-entropy doped anode active material, performing ball milling for 3-6 hours at one time, and performing freeze drying to obtain a mixed material;
And step four, sintering the mixed material for 4-8 hours at 700-800 ℃ in an inert atmosphere, and grinding to obtain the composite anode material.
Preferably, in the first step, the carbon material is any one of coconut shell carbon, palm carbon and fruit shell carbon.
Preferably, in the first step, the mass volume ratio of the carbon material to the deionized water is 1g to 2mL to 3mL.
Preferably, in the first step, the oxidant is any one or two of nitric acid, hydrogen peroxide or ammonium persulfate.
Preferably, in the first step, the mass ratio of the carbon material to the oxidant is 0.5-1.2:3-6.
Preferably, in the first step, the rotation speed of the centrifugation is 300-500rpm, and the centrifugation time is 5-10min.
Preferably, in the first step, the temperature of the oxidation reaction is 80-110 ℃, and the time of the oxidation reaction is 12-20h.
Preferably, in the first step, the drying temperature is 80-90 ℃, and the drying time is 6-12h.
Preferably, in the second step, the organic mixed solvent is ethylene glycol and water in a volume ratio of 1:3-4.
Preferably, in the second step, the mass-volume ratio of the carbon oxide material to the organic mixed solvent is 1g:2mL-3mL.
Preferably, in the second step, the mass ratio of the carbon oxide material to the chitosan is 1:0.3-0.8.
Preferably, in the second step, the reducing agent is vitamin C.
Preferably, in the second step, the mass ratio of the reducing agent to the carbon oxide material is 0.5-0.8:1.5-2.
Preferably, in the second step, the mass ratio of the saturated soluble transition metal salt solution to the carbon oxide material is 3-5:1.
Further preferably, in the second step, the saturated soluble transition metal salt solution is a saturated manganese chloride solution, a saturated cobalt nitrate solution, a saturated ammonium metavanadate solution or a saturated zinc chloride solution.
Preferably, in the third step, the mass ratio of the carbon aerogel precursor to the high-entropy doped positive electrode active material is 3-5:0.5-1.
Preferably, in the third step, the rotating speed of the primary ball milling is 300-500rpm, the diameter of ball milling beads is 0.1-2mm, and the ball-material ratio is 5:1-10:1.
Preferably, in the third step, the freezing temperature of the freeze drying is-20-0 ℃, and the freezing time is 8-16h.
Preferably, in the fourth step, the sintering is heated in a temperature programming mode, and the temperature rising rate is 5-12 ℃/min.
Preferably, in the fourth step, the grinding time is 1-2h.
The third aspect of the invention provides an application of the composite positive electrode material or the composite positive electrode material prepared by the preparation method of the composite positive electrode material in a low-temperature lithium ion battery.
In summary, the invention provides a composite positive electrode material, a preparation method thereof and application thereof in low-temperature lithium ion batteries. The invention designs a composite positive electrode material, which comprises a high-entropy doped positive electrode active material inner core part and a modified carbon aerogel layer coated on the surface of the positive electrode active material inner core part, wherein a lithium ion battery prepared by using the composite positive electrode material has good low-temperature resistance and can keep good electrochemical performance at a lower temperature. The test shows that the capacity retention rate of the lithium ion battery prepared by the composite positive electrode material provided by the invention can still reach more than 83% after the lithium ion battery is cycled for 200 circles at low temperature.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The embodiment provides a preparation method of a composite positive electrode active material, which specifically comprises the following steps.
Weighing 0.3mmol of lithium carbonate, 0.2mmol of calcium carbonate, 0.2mmol of aluminum chloride, 0.2mmol of nickel sulfate, 0.05mmol of titanium dioxide, 0.1mmol of lanthanum nitrate, 0.5mmol of ferric nitrate and 0.4mmol of phosphoric acid according to a designed proportion, uniformly mixing, and ball-milling for 5 hours by adopting ball-milling balls with the diameter of 0.5mm at the ball-material ratio of 8:1 and the rotating speed of 400rpm to obtain mixed powder;
Step two, the mixed powder is heated to 300 ℃ at a heating rate of 5 ℃/min for 0.5h, and then heated to 860 ℃ at a heating rate of 8 ℃/min for two times, sintered for 10h and ground for 30min, so as to obtain the high-entropy doped anode active material Li0.6Ca0.2Al0.2Ni0.2Ti0.05La0.1Fe0.5P0.4Cl0.4O1.2.
Dispersing 5g of coconut shell carbon in 15mL of deionized water, adding 20g of hydrogen peroxide, carrying out oxidation reaction at 100 ℃ for 16h, centrifuging a reaction system at 400rpm for 6min after the reaction is finished, filtering, and drying the obtained solid filtrate at 85 ℃ for 10h to obtain 7.64g of carbon oxide material; dispersing the carbon oxide material in 20mL of organic mixed solvent, sequentially adding 3.6g of chitosan, 3g of vitamin C and 32g of saturated manganese chloride solution, heating to 70 ℃, preserving heat for 2.5h, and cooling to obtain a carbon aerogel precursor;
Mixing the carbon aerogel precursor with 10g of the high-entropy doped positive electrode active material, performing primary ball milling for 4 hours by adopting ball milling beads with the diameter of 0.8mm at the ball-material ratio of 5:1 and the rotating speed of 350rpm, freezing the slurry after ball milling at the temperature of-18 ℃ for 10 hours, and naturally drying to obtain a mixed material;
and fifthly, under an inert atmosphere, heating the mixed material to 720 ℃ at a heating rate of 10 ℃/min, sintering for 6 hours, and grinding the sintered material for 1 hour to obtain the composite anode material.
Wherein the organic mixed solvent is glycol and water with the volume ratio of 1:3.
Example 2
The embodiment provides a preparation method of a composite positive electrode active material, which specifically comprises the following steps.
Weighing 0.3mmol of lithium carbonate, 0.2mmol of calcium carbonate, 0.2mmol of aluminum chloride, 0.2mmol of nickel sulfate, 0.05mmol of titanium dioxide, 0.1mmol of cerium oxide, 0.5mmol of ferric nitrate and 0.4mmol of phosphoric acid according to a designed proportion, uniformly mixing, and ball-milling for 6 hours by adopting ball-milling beads with the diameter of 0.6mm at the ball-material ratio of 5:1 and the rotating speed of 300rpm to obtain mixed powder;
Step two, the mixed powder is heated to 240 ℃ at a heating rate of 6 ℃/min for 1h, and then heated to 800 ℃ at a heating rate of 10 ℃/min for 12h, sintered, and ground for 20min, so as to obtain the high-entropy doped anode active material Li0.6Ca0.2Al0.2Ni0.2Ti0.05Ce0.1Fe0.5P0.5Cl0.35O1.075.
Dispersing 5g of palm carbon in 12.5mL of deionized water, adding 15g of nitric acid, carrying out oxidation reaction at 90 ℃ for 16h, centrifuging a reaction system at a rotating speed of 450rpm for 5min after the reaction is finished, filtering, and drying the obtained solid filtrate at 90 ℃ for 10h to obtain 7.82g of carbon oxide material; dispersing the carbon oxide material in 20mL of organic mixed solvent, sequentially adding 4.5g of chitosan, 2g of vitamin C and 35g of saturated cobalt nitrate solution, heating to 80 ℃, preserving heat for 3h, and cooling to obtain a carbon aerogel precursor;
Mixing the carbon aerogel precursor with 10g of the high-entropy doped positive electrode active material, performing primary ball milling for 5 hours by adopting ball milling beads with the diameter of 0.3mm at the ball-material ratio of 10:1 and the rotating speed of 400rpm, freezing the slurry after ball milling at the temperature of-15 ℃ for 10 hours, and naturally drying to obtain a mixed material;
And fifthly, under an inert atmosphere, heating the mixed material to 750 ℃ at a heating rate of 10 ℃/min, sintering for 5 hours, and grinding the sintered material for 1.5 hours to obtain the composite anode material.
Wherein the organic mixed solvent is glycol and water with the volume ratio of 1:4.
Example 3
The embodiment provides a preparation method of a composite positive electrode active material, which specifically comprises the following steps.
Weighing 0.6mmol of lithium nitrate, 0.2mmol of calcium chloride, 0.2mmol of aluminum chloride, 0.2mmol of nickel sulfate, 0.05mmol of titanium dioxide, 0.05mmol of europium oxide, 0.5mmol of ferric chloride and 0.3mmol of phosphoric acid according to a designed proportion, uniformly mixing, and ball-milling for 5 hours by adopting ball-milling beads with the diameter of 1.0mm at the ball-material ratio of 5:1 and the rotating speed of 400rpm to obtain mixed powder;
step two, the mixed powder is heated to 350 ℃ at a heating rate of 5 ℃/min for 0.5h, and then heated to 900 ℃ at a heating rate of 10 ℃/min for two times, sintered for 6h and ground for 35min, so as to obtain the high-entropy doped anode active material Li0.6Ca0.2Al0.2Ni0.2Ti0.05Eu0.1Fe0.5P0.3Cl0.3O1.4.
Dispersing 5g of shell carbon in 10mL of deionized water, adding 15g of hydrogen peroxide, carrying out oxidation reaction at 90 ℃ for 16h, centrifuging a reaction system at 400rpm for 5min after the reaction is finished, filtering, and drying the obtained solid filtrate at 90 ℃ for 10h to obtain 7.94g of carbon oxide material; dispersing the carbon oxide material in 20mL of organic mixed solvent, sequentially adding 4.5g of chitosan, 2g of vitamin C and 35g of saturated cobalt nitrate solution, heating to 60 ℃, preserving heat for 3h, and cooling to obtain a carbon aerogel precursor;
mixing the carbon aerogel precursor with 10g of the high-entropy doped positive electrode active material, performing primary ball milling for 3 hours by adopting ball milling beads with the diameter of 0.5mm at the ball-material ratio of 7:1 and the rotating speed of 350rpm, freezing the slurry after ball milling at the temperature of-18 ℃ for 10 hours, and naturally drying to obtain a mixed material;
And fifthly, under an inert atmosphere, heating the mixed material to 800 ℃ at a heating rate of 10 ℃/min, sintering for 4 hours, and grinding the sintered material for 2 hours to obtain the composite anode material.
Wherein the organic mixed solvent is glycol and water with the volume ratio of 1:3.5.
Example 4
The embodiment provides a preparation method of a composite positive electrode active material, which specifically comprises the following steps.
Weighing 0.6mmol of lithium nitrate, 0.2mmol of calcium carbonate, 0.2mmol of aluminum chloride, 0.2mmol of nickel sulfate, 0.05mmol of titanium dioxide, 0.1mmol of praseodymium nitrate, 0.5mmol of ferric nitrate and 0.4mmol of phosphoric acid according to a designed proportion, uniformly mixing, and ball-milling for 4 hours by adopting ball-milling balls with the diameter of 0.5mm at the ball-material ratio of 5:1 and the rotating speed of 380rpm to obtain mixed powder;
Step two, the mixed powder is heated to 300 ℃ at a heating rate of 5 ℃/min for 0.5h, and then heated to 860 ℃ at a heating rate of 8 ℃/min for two times, sintered for 12h and ground for 40min, so as to obtain the high-entropy doped anode active material Li0.6Ca0.2Al0.2Ni0.2Ti0.05Pr0.1Fe0.5P0.4Cl0.4O1.2.
Dispersing 5g of palm carbon in 12.5mL of deionized water, adding 15g of nitric acid, carrying out oxidation reaction at 100 ℃ for 14h, centrifuging a reaction system at a rotating speed of 450rpm for 5min after the reaction is finished, filtering, and drying the obtained solid filtrate at 90 ℃ for 10h to obtain 7.73g of carbon oxide material; dispersing the carbon oxide material in 20mL of organic mixed solvent, sequentially adding 4.5g of chitosan, 2g of vitamin C and 35g of saturated cobalt nitrate solution, heating to 80 ℃, preserving heat for 3h, and cooling to obtain a carbon aerogel precursor;
Mixing the carbon aerogel precursor with 10g of the high-entropy doped positive electrode active material, performing primary ball milling for 3 hours by adopting ball milling beads with the diameter of 1.2mm at the ball-material ratio of 5:1 and the rotating speed of 500rpm, freezing the slurry after ball milling at the temperature of-18 ℃ for 10 hours, and naturally drying to obtain a mixed material;
and fifthly, under an inert atmosphere, heating the mixed material to 740 ℃ at a heating rate of 10 ℃/min, sintering for 5 hours, and grinding the sintered material for 1 hour to obtain the composite anode material.
Wherein the organic mixed solvent is glycol and water with the volume ratio of 1:3.
Example 5
The embodiment provides a preparation method of a composite positive electrode active material, which specifically comprises the following steps.
Weighing 0.3mmol of lithium carbonate, 0.2mmol of calcium chloride, 0.02mmol of aluminum chloride, 0.2mmol of nickel nitrate, 0.05mmol of titanium dioxide, 0.1mmol of samarium nitrate, 0.5mmol of ferric nitrate and 0.3mmol of phosphoric acid according to a designed proportion, uniformly mixing, and ball-milling for 4 hours by adopting ball-milling balls with the diameter of 0.8mm at the ball-material ratio of 6:1 and the rotating speed of 500rpm to obtain mixed powder;
step two, the mixed powder is heated to 300 ℃ at a heating rate of 5 ℃/min for 0.5h, and then heated to 780 ℃ at a heating rate of 8 ℃/min for 15h, sintered and ground for 30min, so as to obtain the high-entropy doped anode active material Li0.6Ca0.2Al0.2Ni0.2Ti0.05Sm0.1Fe0.5P0.3Cl0.4O1.35.
Dispersing 5g of palm carbon in 12.5mL of deionized water, adding 15g of ammonium persulfate, carrying out oxidation reaction at 110 ℃ for 12h, centrifuging a reaction system at a rotating speed of 450rpm for 5min after the reaction is finished, filtering, and drying the obtained solid filtrate at 90 ℃ for 10h to obtain 7.69g of carbon oxide material; dispersing the carbon oxide material in 20mL of organic mixed solvent, sequentially adding 4.5g of chitosan, 2g of vitamin C and 35g of saturated cobalt nitrate solution, heating to 80 ℃, preserving heat for 3h, and cooling to obtain a carbon aerogel precursor;
Mixing the carbon aerogel precursor with 10g of the high-entropy doped positive electrode active material, performing primary ball milling for 4.5 hours by adopting ball milling beads with the diameter of 1.0mm at the ball-material ratio of 5:1 and the rotating speed of 450rpm, freezing the slurry after ball milling at the temperature of-15 ℃ for 10 hours, and naturally drying to obtain a mixed material;
and fifthly, under an inert atmosphere, heating the mixed material to 756 ℃ at a heating rate of 12 ℃/min, sintering for 5 hours, and grinding the sintered material for 2 hours to obtain the composite anode material.
Wherein the organic mixed solvent is glycol and water with the volume ratio of 1:3.
Comparative example 1
This comparative example provides a composite positive electrode material differing from example 1 in that the positive electrode active material is lithium iron phosphate, and the other materials remain the same as example 1 and are not described here again.
Comparative example 2
This comparative example provides a composite positive electrode material differing from example 1 in that the composite positive electrode material is Li0.6Ca0.2Al0.2Ni0.2Ti0.05La0.1Fe0.5P0.4Cl0.4O1.2, without a coating layer, and otherwise remains the same as example 1 and is not described here.
In order to show the technical effects of the invention, the composite positive electrode materials obtained in the examples 1-5 and the comparative examples 1-2 are applied to lithium ion batteries, and the electrochemical properties of the obtained lithium ion batteries at low temperature are tested, and are shown in test examples.
Test examples
The test example provides a lithium ion battery (60 mm multiplied by 80mm soft package battery, voltage is 4.0V), the positive plate material is the composite positive plate material provided by each example and each comparative example, the negative plate material is graphite, cellgard2500 is used as a battery diaphragm, the volume ratio of Ethylene Carbonate (EC): dimethyl carbonate (DMC) =3:7 is prepared into a solution, and 1.2mmol/L lithium hexafluorophosphate is dissolved in the solution to be used as lithium ion battery electrolyte.
The investigation parameters of low-temperature charge and discharge are as follows: the battery is carried out in a blue battery test system, the test voltage is 2.7V-4.2V, and the multiplying power performance test condition is as follows: charging at 0.2C, 0.5C, 1C and 2C respectively, standing at-35deg.C for 4 hr, discharging, and cycling for 200 weeks. The discharge capacity and the capacity retention rate in cyclic operation of the obtained lithium ion battery at low temperature were measured, and the results are shown in table 1.
Table 1 lithium ion battery performance test results
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, or alternatives falling within the spirit and principles of the invention.
Claims (9)
1. A composite positive electrode material is characterized in that: the composite positive electrode material comprises a high-entropy doped positive electrode active material and a modified carbon aerogel layer coated on the surface of the positive electrode active material;
The chemical formula of the high-entropy doped positive electrode active material is ：LiaCabAlcNi0.2Ti0.05Me0.1Fe0.5PxClyO2-(3x+y)/2,, wherein Me is any one of La, ce, pr, sm or Eu, a+b+c=1, and all of a, b and c are not 0, x is more than 0 and less than or equal to 0.5, and y is more than 0 and less than 0.5;
the material of the modified carbon aerogel layer is transition metal doped carbon aerogel, wherein the transition metal is any one or two of Co, mn, V or Zn;
the preparation method of the high-entropy doped positive electrode active material comprises the following steps:
s1, weighing a lithium source, a calcium source, an aluminum source, a nickel source, a titanium source, a Me source, an iron source, a phosphorus source and a chlorine source according to a designed proportion, uniformly mixing, and ball milling to obtain mixed powder;
S2, heating the mixed powder to 200-350 ℃ for one time, preserving heat for 0.5-1h, heating to 750-900 ℃ for the second time, sintering and grinding to obtain the high-entropy doped anode active material;
The preparation method of the composite positive electrode material comprises the following steps: dispersing a carbon material in deionized water, adding an oxidant for oxidation reaction, centrifuging, filtering, and drying the obtained solid filter material to obtain a carbon oxide material;
dispersing the carbon oxide material in an organic mixed solvent, sequentially adding chitosan, a reducing agent and a saturated soluble transition metal salt solution, heating to 60-80 ℃, preserving heat for 2-3h, and cooling to obtain a carbon aerogel precursor;
step three, mixing the carbon aerogel precursor with the high-entropy doped anode active material, performing ball milling for 3-6 hours at one time, and performing freeze drying to obtain a mixed material;
And step four, sintering the mixed material for 4-8 hours at 700-800 ℃ in an inert atmosphere, and grinding to obtain the composite anode material.
2. The composite positive electrode material according to claim 1, wherein: the high entropy doped positive electrode active material has a chemical formula of ：Li0.6Ca0.2Al0.2Ni0.2Ti0.05La0.1Fe0.5P0.4Cl0.4O1.2、Li0.6Ca0.2Al0.2Ni0.2Ti0.05Ce0.1Fe0. 5P0.5Cl0.35O1.075、Li0.6Ca0.2Al0.2Ni0.2Ti0.05Eu0.1Fe0.5P0.3Cl0.3O1.4、Li0.6Ca0.2Al0.2Ni0.2Ti0.05Pr0.1Fe0.5P0.4Cl0.4O1.2 or Li0.6Ca0.2Al0.2Ni0.2Ti0.05Sm0.1Fe0.5P0.3Cl0.4O1.35.
3. The composite positive electrode material according to claim 1, wherein: in S1, the lithium source is any one of lithium carbonate, lithium nitrate or lithium sulfate; and/or
In S1, the calcium source is any one or two of calcium carbonate, calcium nitrate or calcium sulfate; and/or
In S1, the aluminum source is any one of aluminum chloride or aluminum oxide; and/or
In S1, the nickel source is any one or two of nickel nitrate, nickel sulfate or nickel oxide; and/or
In S1, the titanium source is titanium dioxide.
4. The composite positive electrode material according to claim 1, wherein: in the S1, the Me source is any one of lanthanum nitrate, lanthanum carbonate, lanthanum oxide, cerium chloride, praseodymium oxide, praseodymium nitrate, samarium nitrate, europium nitrate or europium oxide; and/or
In S1, the iron source is any one or two of ferric oxide, ferric chloride or ferric nitrate; and/or
In S1, the phosphorus source is any one of calcium phosphate or phosphoric acid; and/or
In S1, the chlorine source is any one of calcium chloride and aluminum chloride.
5. The composite positive electrode material according to claim 1, wherein: in the step S1, the rotating speed of the ball milling is 300-500rpm, the diameter of ball milling beads is 0.1-2mm, the ball-material ratio is 5:1-10:1, and the ball milling time is 4-6h; and/or
S2, sintering for 6-15 hours; and/or
In S2, the primary temperature rising and the secondary temperature rising adopt a temperature programming mode, wherein the temperature rising rate of the primary temperature rising is 3-8 ℃/min, and the temperature rising rate of the secondary temperature rising is 5-10 ℃/min.
6. A method for preparing the composite positive electrode material according to any one of claims 1 to 5, characterized in that: the method comprises the following steps:
Dispersing a carbon material in deionized water, adding an oxidant for oxidation reaction, centrifuging, filtering, and drying the obtained solid filter material to obtain a carbon oxide material;
dispersing the carbon oxide material in an organic mixed solvent, sequentially adding chitosan, a reducing agent and a saturated soluble transition metal salt solution, heating to 60-80 ℃, preserving heat for 2-3h, and cooling to obtain a carbon aerogel precursor;
step three, mixing the carbon aerogel precursor with the high-entropy doped anode active material, performing ball milling for 3-6 hours at one time, and performing freeze drying to obtain a mixed material;
And step four, sintering the mixed material for 4-8 hours at 700-800 ℃ in an inert atmosphere, and grinding to obtain the composite anode material.
7. The method for preparing a composite positive electrode material according to claim 6, wherein: in the first step, the carbon material is any one of coconut shell carbon, palm carbon and fruit shell carbon; and/or
In the first step, the oxidant is any one or two of nitric acid, hydrogen peroxide or ammonium persulfate; and/or
In the first step, the mass ratio of the carbon material to the oxidant is 0.5-1.2:3-6; and/or
In the first step, the rotating speed of the centrifugation is 300-500rpm, and the time of the centrifugation is 5-10min; and/or
In the first step, the temperature of the oxidation reaction is 80-110 ℃, and the time of the oxidation reaction is 12-20h.
8. The method for preparing a composite positive electrode material according to claim 6, wherein: in the second step, the organic mixed solvent is glycol and water with the volume ratio of 1:3-4; and/or
In the second step, the mass ratio of the carbon oxide material to the chitosan is 1:0.3-0.8; and/or
In the second step, the reducing agent is vitamin C; and/or
In the second step, the mass ratio of the reducing agent to the carbon oxide material is 0.5-0.8:1.5-2; and/or
In the second step, the mass ratio of the saturated soluble transition metal salt solution to the carbon oxide material is 3-5:1; and/or
In the third step, the mass ratio of the carbon aerogel precursor to the high-entropy doped anode active material is 3-5:0.5-1; and/or
In the third step, the rotating speed of the primary ball milling is 300-500rpm, the diameter of ball milling beads is 0.1-2mm, and the ball-material ratio is 5:1-10:1; and/or
In the third step, the freezing temperature of freeze drying is-20-0 ℃, and the freezing time is 8-16h; and/or
In the fourth step, the sintering is heated in a temperature programming mode, and the temperature rising rate is 5-12 ℃/min; and/or
In the fourth step, the grinding time is 1-2h.
9. Use of the composite positive electrode material according to any one of claims 1 to 5 or the composite positive electrode material prepared by the preparation method of the composite positive electrode material according to any one of claims 6 to 8 in a low-temperature lithium ion battery.
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