CN115036451A - Positive active material and lithium ion battery comprising same - Google Patents
Positive active material and lithium ion battery comprising same Download PDFInfo
- Publication number
- CN115036451A CN115036451A CN202110247399.3A CN202110247399A CN115036451A CN 115036451 A CN115036451 A CN 115036451A CN 202110247399 A CN202110247399 A CN 202110247399A CN 115036451 A CN115036451 A CN 115036451A
- Authority
- CN
- China
- Prior art keywords
- active material
- positive electrode
- lithium ion
- core
- electrode active
- 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.)
- Pending
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- 239000007774 positive electrode material Substances 0.000 title claims abstract description 80
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 48
- 238000000034 method Methods 0.000 claims abstract description 32
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 24
- 239000010941 cobalt Substances 0.000 claims abstract description 24
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000002243 precursor Substances 0.000 claims abstract description 21
- 239000011258 core-shell material Substances 0.000 claims abstract description 14
- 239000002245 particle Substances 0.000 claims description 88
- 239000011162 core material Substances 0.000 claims description 58
- 239000011257 shell material Substances 0.000 claims description 29
- 229910052727 yttrium Inorganic materials 0.000 claims description 11
- 229910052782 aluminium Inorganic materials 0.000 claims description 10
- 239000011230 binding agent Substances 0.000 claims description 10
- 239000006258 conductive agent Substances 0.000 claims description 10
- 238000009826 distribution Methods 0.000 claims description 10
- 229910052749 magnesium Inorganic materials 0.000 claims description 9
- 239000002994 raw material Substances 0.000 claims description 9
- 230000002902 bimodal effect Effects 0.000 claims description 7
- 229910052746 lanthanum Inorganic materials 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 229910044991 metal oxide Inorganic materials 0.000 claims description 6
- 150000004706 metal oxides Chemical class 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 229910052719 titanium Inorganic materials 0.000 claims description 6
- 229910052726 zirconium Inorganic materials 0.000 claims description 6
- 229910052748 manganese Inorganic materials 0.000 claims description 5
- 229910001512 metal fluoride Inorganic materials 0.000 claims description 5
- 229910001463 metal phosphate Chemical class 0.000 claims description 5
- 150000001642 boronic acid derivatives Chemical class 0.000 claims description 3
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- 239000011824 nuclear material Substances 0.000 claims description 2
- 229910052706 scandium Inorganic materials 0.000 claims description 2
- 229910052712 strontium Inorganic materials 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 125000002467 phosphate group Chemical class [H]OP(=O)(O[H])O[*] 0.000 claims 1
- 229910052744 lithium Inorganic materials 0.000 abstract description 55
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 54
- 230000008569 process Effects 0.000 abstract description 20
- 230000002829 reductive effect Effects 0.000 abstract description 17
- 238000007599 discharging Methods 0.000 abstract description 15
- 239000000463 material Substances 0.000 abstract description 12
- 230000001351 cycling effect Effects 0.000 abstract description 4
- 150000002500 ions Chemical class 0.000 abstract description 3
- 229910052596 spinel Inorganic materials 0.000 abstract description 3
- 239000011029 spinel Substances 0.000 abstract description 3
- 230000007704 transition Effects 0.000 abstract description 2
- 239000011777 magnesium Substances 0.000 description 18
- 150000001875 compounds Chemical class 0.000 description 17
- 238000001354 calcination Methods 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 14
- 238000002156 mixing Methods 0.000 description 14
- 238000002360 preparation method Methods 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 11
- 239000003792 electrolyte Substances 0.000 description 11
- 210000004027 cell Anatomy 0.000 description 10
- 230000008859 change Effects 0.000 description 10
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 9
- -1 borate compound Chemical class 0.000 description 9
- 230000010287 polarization Effects 0.000 description 9
- 238000005303 weighing Methods 0.000 description 9
- 239000013543 active substance Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 239000010936 titanium Substances 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 239000010410 layer Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000012716 precipitator Substances 0.000 description 6
- 229910001429 cobalt ion Inorganic materials 0.000 description 5
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- 238000005245 sintering Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 4
- 150000001868 cobalt Chemical class 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 239000007773 negative electrode material Substances 0.000 description 4
- 239000012266 salt solution Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical group [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 3
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- 239000002033 PVDF binder Substances 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000008139 complexing agent Substances 0.000 description 3
- 150000005676 cyclic carbonates Chemical class 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 3
- 229910052808 lithium carbonate Inorganic materials 0.000 description 3
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 3
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 3
- 239000000395 magnesium oxide Substances 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 3
- 229910052761 rare earth metal Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- 102000008297 Nuclear Matrix-Associated Proteins Human genes 0.000 description 2
- 108010035916 Nuclear Matrix-Associated Proteins Proteins 0.000 description 2
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910021383 artificial graphite Inorganic materials 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 150000007942 carboxylates Chemical class 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 239000011267 electrode slurry Substances 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000002427 irreversible effect Effects 0.000 description 2
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 2
- 229910003002 lithium salt Inorganic materials 0.000 description 2
- 159000000002 lithium salts Chemical class 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 239000011356 non-aqueous organic solvent Substances 0.000 description 2
- 210000000299 nuclear matrix Anatomy 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 2
- 230000005476 size effect Effects 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 1
- UHOPWFKONJYLCF-UHFFFAOYSA-N 2-(2-sulfanylethyl)isoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N(CCS)C(=O)C2=C1 UHOPWFKONJYLCF-UHFFFAOYSA-N 0.000 description 1
- VTHRQKSLPFJQHN-UHFFFAOYSA-N 3-[2-(2-cyanoethoxy)ethoxy]propanenitrile Chemical compound N#CCCOCCOCCC#N VTHRQKSLPFJQHN-UHFFFAOYSA-N 0.000 description 1
- 229910016569 AlF 3 Inorganic materials 0.000 description 1
- 229910017119 AlPO Inorganic materials 0.000 description 1
- 229910020599 Co 3 O 4 Inorganic materials 0.000 description 1
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 206010063385 Intellectualisation Diseases 0.000 description 1
- 229910018119 Li 3 PO 4 Inorganic materials 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- BTGRAWJCKBQKAO-UHFFFAOYSA-N adiponitrile Chemical compound N#CCCCCC#N BTGRAWJCKBQKAO-UHFFFAOYSA-N 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000006183 anode active material Substances 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- ZJRWDIJRKKXMNW-UHFFFAOYSA-N carbonic acid;cobalt Chemical compound [Co].OC(O)=O ZJRWDIJRKKXMNW-UHFFFAOYSA-N 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 229940044175 cobalt sulfate Drugs 0.000 description 1
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- MULYSYXKGICWJF-UHFFFAOYSA-L cobalt(2+);oxalate Chemical compound [Co+2].[O-]C(=O)C([O-])=O MULYSYXKGICWJF-UHFFFAOYSA-L 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000036757 core body temperature Effects 0.000 description 1
- 239000007771 core particle Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229920003244 diene elastomer Polymers 0.000 description 1
- YNQRWVCLAIUHHI-UHFFFAOYSA-L dilithium;oxalate Chemical compound [Li+].[Li+].[O-]C(=O)C([O-])=O YNQRWVCLAIUHHI-UHFFFAOYSA-L 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910021385 hard carbon Inorganic materials 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 150000002641 lithium Chemical class 0.000 description 1
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 1
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 1
- 229940071264 lithium citrate Drugs 0.000 description 1
- WJSIUCDMWSDDCE-UHFFFAOYSA-K lithium citrate (anhydrous) Chemical compound [Li+].[Li+].[Li+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O WJSIUCDMWSDDCE-UHFFFAOYSA-K 0.000 description 1
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- 229910001947 lithium oxide Inorganic materials 0.000 description 1
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002931 mesocarbon microbead Substances 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 239000011255 nonaqueous electrolyte Substances 0.000 description 1
- 150000003891 oxalate salts Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 229940090181 propyl acetate Drugs 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- IAHFWCOBPZCAEA-UHFFFAOYSA-N succinonitrile Chemical compound N#CCCC#N IAHFWCOBPZCAEA-UHFFFAOYSA-N 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 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
- H01M4/364—Composites as mixtures
-
- 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
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- 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
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- H01M4/00—Electrodes
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- H01M4/00—Electrodes
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Abstract
The invention provides a positive active material and a lithium ion battery comprising the same, wherein the positive active material has a core-shell structure, and is a precursor Me containing Al and Z-doped cobalt 3 O 4 The material is Al and Z to replace Co ion, so as to ensure the stability of layered structure in the charging and discharging process and avoid frequent transition of lithium cobaltate in the charging and discharging process between layered hexagonal system and spinel monoclinic system. Meanwhile, the positive active material is introduced into the lithium ion secondary batteryThe charging capacity and the cycling stability of the battery are improved, the temperature rise of the battery cell during charging at 2C-10C is reduced, and the use safety performance of the battery cell is improved.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a positive active material suitable for a quick charge system and a lithium ion battery containing the positive active material.
Background
The lithium ion battery has high energy density, high working voltage, environmental friendliness and strong manufacturability, and is widely applied to the fields of mobile phones, notebook computers, electric automobiles and energy storage at present. With the acceleration of the pace of life and the popularization of the intellectualization of communication devices such as mobile phones, the requirements for lithium ion batteries are constantly changing, and the requirements for new generation lithium ion batteries are met by long standby time and quick charging. In order to shorten the charging time, many manufacturers propose a 5-10C quick charging concept, but the conventional positive electrode material cannot meet the requirement of quick charging at present, and meanwhile, under the condition of high-rate charging, the whole battery core generates heat due to violent reaction of components in the battery, so that the temperature of the battery core is increased, and the safety risk of fire failure is caused, so that the lithium ion battery core with high safety and quick charging is provided, and the development trend is reached.
Lithium cobaltate is used as a main positive active substance with high energy density, and the improvement of the upper limit working voltage and gram capacity is considered as a way of effectively improving the energy density, but when the lithium cobaltate is applied to a quick-charging cell, the safety performance caused by temperature rise increases the failure risk, so that the lithium cobaltate cannot be directly used as a positive material of a quick-charging system.
Disclosure of Invention
Research finds that in order to improve the overall energy density and the quick charge performance of the battery from the perspective of the positive electrode active material, the temperature rise of the battery under higher voltage needs to be reduced, for the positive electrode active material, certain coating doping modification is carried out, the structural stability and the cycling stability of the positive electrode active material under a high voltage system can be effectively improved, meanwhile, the particle size of lithium cobaltate is controlled through different synthesis processes, the size effect is formed by reducing the particle size, the polarization problem of the lithium cobaltate generated in the charge and discharge use process of a quick charge core is reduced, the temperature rise is reduced, and the use requirement of the high voltage quick charge core is met. The invention relates to a high-voltage lithium cobaltate positive active material, a preparation method and application thereof. Meanwhile, compared with the temperature rise difference of a conventional positive active material (such as untreated conventional lithium cobaltate purchased from a commercial way) and the positive active material of the invention in the charging process, a test result shows that after the circulation of 3.0V-4.48V (for a graphite electrode), the temperature rise of the conventional positive active material in a 5C fast charging cell is 16-17 ℃, which shows that under the condition of high-rate charging, the polarization of the conventional positive active material in the charging process is large, while the temperature rise of the positive active material in the 5C fast charging cell of the invention is 10-12 ℃, which shows that by the modification means of the invention, the charging capacity of the positive active material is obviously improved, the polarization generated in the using process is reduced, and further, the temperature rise of the cell in the high-rate charging use is obviously reduced.
The term "fast charge system" refers to an electrical core system that can be used under high rate charging conditions, such as 2C-10C, e.g., 2C, 3C, 5C, 10C, etc.
The term "high voltage system" refers to an electrical core system having a cutoff voltage of 4.45V or more, such as 4.45-4.48V, e.g., 4.45V, 4.46V, 4.47V, 4.48V, etc.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a positive active material comprises at least one core material and at least one shell material, wherein the at least one shell material is coated on the surface of the at least one core material to form at least one particle with a core-shell structure;
the raw materials for preparing the at least one nuclear material at least comprise Me 3 O 4 Which is a precursor of cobalt doped with Al and Z, wherein Me ═ Co 1-a-b Al a Z b Z is one or more of Y, La, Mg, Ti, Zr, Ni and MnSeed growing; 0<a≤0.2，0<b≤0.1；
The at least one core material is compounded from large and small particles and has a bimodal particle size distribution, wherein the particle diameter D of the large-particle core material 50 Particle size D of core material of small particles of 10-25 μm 50 Is 3-8 μm.
In the invention, the bimodal particle size distribution means that a particle size volume distribution curve tested by a laser particle sizer has two convex curve peaks.
According to the invention, the core material is selected from Li x Me 1-y M y O 2 Wherein Me is Co 1-a-b Al a Z b M is one or more of Al, Mg, Ti, Zr, Co, Ni, Mn, Y, La, Sr, W and Sc, and Z is one or more of Y, La, Mg, Ti, Zr, Ni, Mn and Ce; x is more than or equal to 0.95 and less than or equal to 1.07, y is more than or equal to 0 and less than or equal to 0.1, 0<a≤0.2，0<b≤0.1。
According to the invention, the raw materials for the preparation of the at least one shell material, which are identical or different, are selected independently of one another from one or more of the group consisting of metal fluorides, metal oxides, metal borate compounds and metal phosphate compounds.
According to the present invention, the at least one shell material is the same or different and is selected independently from each other from a calcined product of one or more of the above-mentioned metal fluorides, metal oxides, metal borate compounds, and metal phosphate compounds, for example, metal oxides, metal alloy-based compounds, and the like.
According to the invention, said Al and Z-doped cobalt precursors Me 3 O 4 Is prepared by the following method:
1) preparing a cobalt source, a compound containing an Al element and a compound containing a Z element into an aqueous solution;
2) mixing the aqueous solution, the complex and a precipitator, and reacting to obtain the carbonate MeCO containing Al and Z-doped cobalt 3 ；
3) Carbonate MeCO containing Al and Z-doped cobalt 3 Calcining to obtain a precursor Me containing Al and Z-doped cobalt 3 O 4 。
Specifically, the positive active material comprises at least one core material and at least one shell material, wherein the at least one shell material is coated on the surface of the at least one core material to form at least one particle with a core-shell structure; the at least one core material is compounded from large and small particles and has a bimodal particle size distribution; that is, the formed positive electrode active material may be defined as (An1+ An2) × Bn, where An1 and An2 respectively represent at least one core material different in particle size, and Bn represents at least one shell material.
Specifically, the mass ratio of the large-particle core material to the small-particle core material is, for example, 1 to 5:5:9, illustratively 1:9, 2:8, 3:7, 4:6, or 5: 5.
Specifically, the particle diameter D of the core material of the large particles 50 10 μm, 11 μm, 12 μm, 14 μm, 15 μm, 16 μm, 17 μm, 18 μm, 19 μm, 20 μm, 21 μm, 22 μm, 23 μm, 24 μm or 25 μm, particle diameter D of the core material of the small particles 50 3 μm, 4 μm, 5 μm, 6 μm, 7 μm or 8 μm.
Specifically, the particle diameter D of the positive electrode active material 50 Is less than 9 μm, for example, 4 μm or more and less than 9 μm, such as 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 8.5 μm.
Specifically, the thickness of the shell material in the positive electrode active material is less than or equal to 40nm, such as 5-30nm, such as 5nm, 6nm, 8nm, 10nm, 12nm, 15nm, 18nm, 20nm, 22nm, 23nm, 25nm, 28nm, 30nm, 35nm, 38nm, and 40 nm.
Specifically, the mass of the shell material in the positive electrode active material accounts for 0.03-1% of the total mass of the positive electrode active material, such as 0.03%, 0.04%, 0.05%, 0.06%, 0.07%, 0.08%, 0.09%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%.
Specifically, the temperature change of the cell of the lithium ion secondary battery assembled by the positive electrode active material before and after 2C-10C (such as 5C-10C) charging is tested. Compared with the temperature change of the positive plate of the lithium ion secondary battery assembled by the conventional positive active material and the positive plate of the invention before and after charging and discharging, the test result shows that the temperature of the battery core body prepared by the conventional positive active material is obviously increased after 2C-10C (such as 5C-10C) quick charging, which shows that under the condition of high-rate charging, the polarization generated by the conventional positive active material in the charging process is large, while the temperature rise amplitude generated by the positive active material of the invention when the 2C-10C (such as 5C-10C) is charged is smaller than that of the conventional positive active material, which shows that the charging capacity of the positive active material is improved by the modification means of the invention.
In particular, the metal fluoride is selected from AlF 3 、Li 3 F. One or more of MgF.
Specifically, the metal oxide is selected from Al 2 O 3 、TiO 2 、ZrO 2 、MgO 2 One or more of (a).
In particular, the metal borate compound is selected from AlBO 3 。
In particular, the metal phosphate compound is selected from AlPO 4 、Li 3 PO 4 And the like.
The invention also provides a preparation method of the positive active material, which comprises the following steps:
a) at least one core material is prepared, and the raw materials for preparing the core material comprise a precursor Me containing Al and Z-doped cobalt 3 O 4 ；
b) Preparing at least one raw material for preparing the shell material;
c) mixing the preparation raw material of the at least one shell material in the step b) with the at least one core material in the step a), and calcining to prepare the positive electrode active substance; and the at least one core material is compounded from large and small particles and has a bimodal particle size distribution, wherein the particle diameter D of the large-particle core material 50 Particle size D of core material of small particles of 10-25 μm 50 Is 3-8 μm.
According to the invention, the core material in step a) is prepared by the following method:
1) preparing a cobalt source, a compound containing an Al element and a compound containing a Z element into an aqueous solution;
2) mixing the above aqueous solutionMixing the complex and a precipitator, and reacting to obtain the carbonate MeCO containing Al and Z-doped cobalt 3 ；
3) Carbonate MeCO containing Al and Z-doped cobalt 3 Calcining to obtain a precursor Me containing Al and Z-doped cobalt 3 O 4 ；
4) A lithium source, a compound optionally containing an M element, a precursor Me containing Al and Z-doped cobalt 3 O 4 And calcining to obtain the core material.
In the step 1), the step (A) is carried out,
specifically, the cobalt source is at least one selected from cobalt acetate, cobalt oxalate, cobalt nitrate, cobalt sulfate, cobalt chloride and cobalt hydroxide.
Specifically, the compound containing the Al element is at least one selected from an oxide, a chloride, a hydroxide, a carbonate, a sulfate, a nitrate, an oxalate and an acetate containing the Al element.
Specifically, the compound containing the Z element is at least one selected from oxides, chlorides, hydroxides, carbonates, sulfates, nitrates, oxalates and acetates containing the Z element.
Specifically, the molar ratio of the cobalt source, the compound containing the Al element and the compound containing the Z element is such that the molar ratio of Co, Al and Z is 1-a-b: a: b, wherein a is more than 0 and less than or equal to 0.2, and b is more than 0 and less than or equal to 0.1.
Specifically, the concentration of the cobalt source in the aqueous solution is 0.8-3.8 mol/L.
In the step 2), the step (c) is carried out,
specifically, the complexing agent is selected from ammonia water, and the concentration of the ammonia water is 20% -25%.
Specifically, the precipitating agent is selected from soluble alkali, and the soluble alkali is selected from Na 2 CO 3 、NH 4 HCO 3 、(NH 4 ) 2 CO 3 And the like.
Specifically, the mass ratio of the complex to the precipitant is 2:1-1: 1.
Specifically, in the mixed system, the concentration of the precipitant is 0.8-3.8 mol/L.
Specifically, the reaction temperature is 30-80 ℃, and the reaction time is 10-20 hours.
Specifically, the aqueous solution, the complex solution and the precipitant solution may undergo a complex precipitation reaction after being mixed.
In the step 3), the step (c),
specifically, the calcination temperature is 920-1000 ℃, and the calcination time is 8-12 hours. The calcination is carried out under an air atmosphere.
In the step 4), the step (c) is carried out,
specifically, the compound containing the M element is at least one selected from oxide, chloride, hydroxide, carbonate, sulfate, nitrate, oxalate and acetate of M.
Specifically, the lithium source is at least one selected from the group consisting of lithium hydroxide, lithium nitrate, lithium carbonate, lithium oxalate, lithium acetate, lithium oxide, and lithium citrate.
In particular, the lithium source, the compound containing M element, the precursor Me containing Al and Z-doped cobalt 3 O 4 Such that the molar ratio of Li, Me, M is x: 1-y: y, wherein x is more than or equal to 0.95 and less than or equal to 1.05, and y is more than or equal to 0 and less than or equal to 0.1.
Specifically, the calcination temperature is 900-1070 ℃, and the calcination time is 8-12 hours. The calcination is carried out under an air atmosphere.
According to the invention, the core material in step a) is prepared by the following method:
1') preparing a cobalt source into an aqueous solution;
2') mixing the aqueous solution, the complex and a precipitator, and reacting to obtain cobalt carbonate CoCO 3 ；
3') the carbonate CoCO of cobalt 3 Calcining to obtain a precursor Co of the cobalt 3 O 4 ；
4') a lithium source, a compound containing an Al element, a compound containing an Z element, optionally a compound containing an M element, a precursor of cobalt Co 3 O 4 And calcining to obtain the core material.
According to the invention, in step b), the raw material for preparing the shell material is selected from one or more of metal oxide, metal fluoride, metal borate compound and metal phosphate compound.
According to the invention, said step c) comprises the following steps:
physically mixing at least one core material and at least one shell material preparation raw material, and calcining to obtain at least one core-shell structure particle with at least one shell material coated on the surface of at least one core material, namely the positive electrode active substance; and the at least one core material is compounded from large and small particles and has a bimodal particle size distribution, wherein the particle diameter D of the large-particle core material 50 Particle size D of core material of small particles of 10-25 μm 50 Is 3-8 μm.
Specifically, the physical mixing time is 2-4 h; the physical mixing is at least one of stirring, ball milling and grinding, for example; the calcination temperature is 800-1000 ℃, the calcination time is 6-9h, and the calcination is carried out in an air atmosphere.
The invention also provides a positive plate which comprises the positive active material.
According to the present invention, the positive electrode sheet includes a conductive agent and a binder.
Specifically, the positive plate comprises the following components in percentage by mass:
70-99 wt% of positive electrode active material, 0.5-15 wt% of conductive agent and 0.5-15 wt% of binder.
Specifically, the positive plate comprises the following components in percentage by mass:
80-98 wt% of positive electrode active material, 1-10 wt% of conductive agent and 1-10 wt% of binder.
Specifically, the conductive agent is at least one selected from conductive carbon black, acetylene black, ketjen black, conductive graphite, conductive carbon fiber, carbon nanotube, metal powder, and carbon fiber.
Specifically, the binder is at least one selected from polyvinylidene fluoride (PVDF), Polytetrafluoroethylene (PTFE), and lithium Polyacrylate (PAALi).
The invention also provides a lithium ion battery which comprises the positive plate.
According to the invention, the lithium ion battery is a 2C-10C (such as 5C-10C) fast-charging system lithium ion battery.
According to the present invention, the lithium ion battery is a high-voltage system lithium ion battery having a cutoff voltage of 4.45V or more (e.g., 4.45V to 4.48V).
According to the invention, the lithium ion battery further comprises a negative plate, a diaphragm and electrolyte.
Specifically, the electrolyte comprises a non-aqueous solvent, a conductive lithium salt and an additive, wherein the additive comprises a nitrile compound, vinylene carbonate and 1, 3-propylene sulfonic acid lactone.
Specifically, the non-aqueous organic solvent is selected from a mixture in which at least one of cyclic carbonates and at least one of linear carbonates and linear carboxylates are mixed in an arbitrary ratio.
Specifically, the cyclic carbonate is selected from at least one of ethylene carbonate and propylene carbonate, the linear carbonate is selected from at least one of dimethyl carbonate, diethyl carbonate and ethyl methyl carbonate, and the linear carboxylate is selected from at least one of ethyl propionate, propyl propionate and propyl acetate.
Specifically, the nonaqueous organic solvent is calculated by taking the total volume as 100 vol%, wherein the volume fraction of the cyclic carbonate is 20-40 vol%, and the volume fraction of the linear carbonate and/or the linear carboxylic ester is 60-80 vol%.
Specifically, the conductive lithium salt is at least one selected from lithium hexafluorophosphate, lithium bis (fluorosulfonyl) imide and lithium bis (trifluoromethanesulfonyl) imide.
Specifically, the nitrile compound is at least one selected from adiponitrile, succinonitrile and 1, 2-bis (cyanoethoxy) ethane.
Specifically, the negative electrode sheet includes a negative electrode active material, a conductive agent, and a binder.
Specifically, the negative plate comprises the following components in percentage by mass:
70-99 wt% of negative electrode active material, 0.5-15 wt% of conductive agent and 0.5-15 wt% of binder.
Specifically, the negative plate comprises the following components in percentage by mass:
80-98 wt% of negative electrode active material, 1-10 wt% of conductive agent and 1-10 wt% of binder.
Specifically, the negative active material is selected from one or a combination of several of artificial graphite, natural graphite, hard carbon, mesocarbon microbeads, lithium titanate, silicon carbon and silicon monoxide.
Specifically, the used diaphragm is a material taking polypropylene as a base material, or a gummed diaphragm coated with ceramic on one side or two sides on the basis of the material.
The invention also provides the application of the positive active material, which is used for a lithium ion battery of a 2C-10C (such as 5C-10C) fast charge system and/or a lithium ion battery of a high voltage system with a cut-off voltage of more than or equal to 4.45V (such as 4.45V-4.48V).
According to the invention, the positive electrode active material is used for the positive electrode active material in the positive electrode sheet of the lithium ion battery of a 2C-10C (such as 5C-10C) quick-charging system.
According to the present invention, the positive electrode active material is used for a positive electrode sheet of a high-voltage system lithium ion battery having a cut-off voltage of 4.45V or more (e.g., 4.45V to 4.48V).
Preferably, the positive electrode active material is used for the positive electrode active material in the positive electrode sheet of the lithium ion battery of a 2C-10C (such as 5C-10C) quick-charging system and a high-voltage system with a cut-off voltage of more than or equal to 4.45V (such as 4.45V-4.48V).
The present invention also provides a method for reducing the temperature rise and the impedance of a battery under a 2C-10C (e.g., 5C-10C) rapid charging system and/or a high voltage system having a cut-off voltage of 4.45V or more (e.g., 4.45V-4.48V), the method comprising using the above-mentioned positive electrode active material.
Has the advantages that:
lithium cobaltate is a positive electrode active material with a layered structure, wherein oxygen ions form a close-packed layer, and a cobalt layer and a lithium layer are alternately distributed on two sides of the close-packed layer formed by the oxygen ions; due to the pursuit of high energy density of lithium ion batteries, the charge cut-off voltage of lithium cobaltate is continuously improved, and the voltage is developed from 4.2V and 4.35V to more than 4.4V nowadays. Along with the increase of the working voltage, the discharge capacity of lithium cobaltate is also improved, and meanwhile, local lattice structure collapse and irreversible phase change are caused due to the instability of the layered lithium cobaltate structure (the change of the lithium concentration generates structural change, so that stress causes microcrack generation) and the instability of the surface (the cobalt is dissolved by reaction with an electrolyte), wherein the irreversible phase change comprises the conversion of the layered structure to the spinel structure. Simultaneously, because lithium ion battery is to the pursuit of fast charge ability, along with the promotion of the multiplying power that charges, the polarization that lithium cobaltate produced in the charging process increases thereupon, can arouse that electric core heat production is too big in the quick charge in-process, and then arouses the problem that electric core body temperature rose, has great potential safety hazard in the use. Therefore, the key to developing high-voltage fast-charging lithium cobalt oxide is to solve the problems that the lithium cobalt oxide with a layered structure undergoes a frequent phase change process and the material is damaged by stress generated in the phase change process when the lithium cobalt oxide is in a high-voltage and deep delithiation state; and in a deep lithium removal state, the thermal stability of the lithium cobaltate is improved, the polarization problem of the lithium cobaltate generated in the rapid charging process is reduced, and the use safety of the lithium cobaltate under high voltage is improved.
The invention provides a high-voltage quick-charge lithium cobaltate positive active material, a preparation method and application thereof 3 O 4 The material is Al and Z to replace Co ion, so as to ensure the stability of layered structure in the charging and discharging process and avoid frequent transition of lithium cobaltate in the charging and discharging process between layered hexagonal system and spinel monoclinic system. The particle size of the lithium cobaltate is further controlled by adjusting the synthesis process of the lithium cobaltate, the polarization generated by the size effect in the charging and discharging process is reduced, meanwhile, the direct contact between the electrolyte and the high-concentration tetravalent cobalt ions on the surface of the anode is avoided by a shell coating means formed on the surface to cause decomposition reaction and dissolve out the cobalt ions in the electrolyte and release gas, and the dissolution of the cobalt ions along with the dissolution of the cobalt ions on the surface layer and the dissolution of the tetravalent cobalt ions on the surface of the anodeThe amount is increased, and the local structure of the surface layer of the particles collapses, so that potential safety hazards are brought to the safety performance; and the corrosion of HF generated by the reaction of the electrolyte and a small amount of water in the lithium cobaltate core structure to the positive electrode active material can be avoided. The high-voltage positive active substance with the core-shell structure can keep a stable structure under a high-voltage system, and meanwhile, the lithium cobaltate matrix is isolated from the electrolyte through the shell coating substance, so that a stable positive active substance/electrolyte interface can be formed, and Co oxidation and dissolution are delayed, so that the lithium cobaltate structure is stabilized, the structural deterioration and collapse are inhibited, and the quick charging capability is improved while the performance is ensured; meanwhile, the charging capacity and the cycling stability of the battery can be effectively improved by introducing the high-voltage lithium cobaltate positive active substance into the lithium ion secondary battery, the temperature rise of the battery cell in the 2C-10C (such as 5C-10C) charging use is reduced, and the use safety performance of the battery cell is improved.
In conclusion, compared with the prior art, the lithium ion battery provided by the invention has good charging capability and cycling stability under the charging use condition of 2C-10C (such as 5C-10C) due to the use of the high-voltage quick-charging lithium cobaltate positive electrode active material. Meanwhile, the temperature rise generated by charging the lithium ion battery under 2C-10C (such as 5C-10C) is obviously reduced compared with the conventional lithium cobaltate, and the lithium ion battery can meet the use requirements of high-end digital products on lightness, thinness, high charging and high safety.
Detailed Description
The preparation method of the present invention will be described in further detail with reference to specific examples. It is to be understood that the following examples are only illustrative and explanatory of the present invention and should not be construed as limiting the scope of the present invention. All the techniques realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.
The experimental methods used in the following examples are all conventional methods unless otherwise specified; reagents, materials and the like used in the following examples are commercially available unless otherwise specified.
Example 1
The positive active substance has a core-shell structure and comprises a core material and a shell material,wherein the chemical composition of the core material is Li 1.03 Co 0.986 Al 0.01 Mg 0.002 Y 0.002 O 2 Is prepared by compounding large and small particles according to the ratio of 3:7, wherein the large particles D 50 D of 15 μm, small particles 50 Is 3-4 μm; the shell material is TiO 2 ；
The preparation method of the positive active material comprises the following steps:
(1) dissolving CoSO in deionized water 4 、Al 2 (SO 4 ) 3 Mixed salt solution with a molar ratio of Co to Al of 98.6 to 1 is prepared, and Co in the mixed salt solution 2+ The concentration of (A) is 1.25 mol/L; preparing a complexing agent solution from concentrated ammonia water and distilled water according to a volume ratio of 1: 10; selecting a 1.2mol/L sodium carbonate solution as a precipitator solution; injecting a precipitator solution of a solvent 1/3 into the reaction kettle, under the action of strong stirring and the protection of inert gas, continuously injecting the mixed salt solution, the complexing agent solution and the precipitator solution into the reaction kettle in a parallel flow control flow manner to react, controlling the flow rate to be not more than 200L/h, stirring at the same time, controlling the stirring speed to be not more than 300rpm, controlling the pH value of a reaction system to be 8-12, and controlling the temperature of the reaction kettle to be 70-80 ℃ in the reaction process; monitoring the concentration of liquid phase ions of doping elements Al and Co in a reaction system in real time in the reaction process; carrying out continuous reaction, repeated crystallization for 4 times, and then carrying out centrifugal filtration to obtain a precursor cobalt salt doped with Al;
(2) weighing yttrium oxide according to a molar ratio of Co to Y of 98.6 to 0.2, uniformly stirring and mixing the yttrium oxide with the Al-doped precursor cobalt salt in the step (1), placing the mixture in a muffle furnace at 900 ℃ for 8 hours, and then crushing a sintered product to obtain Al and Y Co-doped Co with uniform particle distribution 3 O 4 A precursor;
(3) weighing lithium carbonate according to a molar ratio of Li to Co of 103 to 99.5, weighing magnesium oxide according to a molar ratio of Co to Mg of 98.6 to 0.2, and weighing Co Co-doped with Al and Y in the step (2) 3 O 4 The precursor is stirred and mixed evenly, placed in a muffle furnace at 1030 ℃ for 12h of sintering time, and then the sintered product is crushed to obtain D 50 Al, Y and Mg with 15 mu m uniformly distributed particlesCo-doped large-particle lithium cobaltate Li 1.03 Co 0.986 Al 0.01 Mg 0.002 Y 0.002 O 2 ；
(4) The preparation process of the small-particle lithium cobaltate is the same as that of the large particle, the difference is that the sintering temperature of the small particle is 950 ℃, and the small particle is crushed after sintering to obtain D 50 Is 3-4 mu m of small Al, Y and Mg co-doped lithium cobaltate Li with uniformly distributed particles 1.03 Co 0.98 6 Al 0.01 Mg 0.002 Y 0.002 O 2 ；
(5) Uniformly mixing the large particles and the small particles according to the mass ratio of 3:7 (large particles: small particles), weighing titanium dioxide and the mixed lithium cobaltate according to the molar ratio of Co to Ti of 98.4:0.2, uniformly stirring and mixing, placing the mixture in a muffle furnace at 950 ℃, sintering for 12 hours, and then crushing the sintered product to obtain D 50 6 mu m positive electrode active material Li with core-shell structure 1.03 Co 0.984 Al 0.01 Mg 0.002 Y 0.002 Ti 0.002 O 2 。
Example 2
The preparation process is the same as that of example 1, except that the mass ratio of the mixed particles of the large and small particles is adjusted from 3:7 to 2:8 to obtain D 50 5 mu m positive active material Li with core-shell structure 1.03 Co 0.984 Al 0.01 Mg 0.002 Y 0.002 Ti 0.002 O 2 。
Example 3
The preparation process is the same as that of example 1, except that the mass ratio of the mixed large and small particles is adjusted from 3:7 to 1:9 to obtain D 50 Positive electrode active material Li with core-shell structure of 4 μm 1.03 Co 0.984 Al 0.01 Mg 0.002 Y 0.002 Ti 0.002 O 2 。
Comparative example 1
The preparation process is the same as that of example 1, except that the mass ratio of the mixed particles of the large and small particles is adjusted from 3:7 to 8:2 to obtain D 50 13.5 mu m positive electrode active material Li with core-shell structure 1.03 Co 0.984 Al 0.01 Mg 0.002 Y 0.002 Ti 0.002 O 2 。
Comparative example 2
The positive active material has a core-shell structure and comprises a core material and a shell material, wherein the chemical composition of the core material is Li 1.03 Co 0.982 Al 0.015 Mg 0.002 Y 0.001 O 2 Is formed by compounding large and small particles according to the ratio of 8:2, wherein the large particles D 50 18 μm, small particle D 50 Is 4.5 μm; the shell material is Al 2 O 3 ；
The preparation method of the positive active material comprises the following steps:
(1) dissolving CoSO in deionized water 4 、Al 2 (SO 4 ) 3 Preparing a mixed salt solution with a molar ratio of Co to Al of 98.2 to 1.5 to prepare an Al-doped precursor cobalt salt, wherein the specific method is shown in step (1) of example 1;
(2) placing the Al-doped precursor cobalt salt obtained in the step (1) in a muffle furnace at 900 ℃ for 8h, and then crushing the sintered product to obtain Al-doped Co with uniformly distributed particles 3 O 4 A precursor;
(3) weighing lithium carbonate according to a molar ratio of Li to Co of 103:99.5, weighing magnesium oxide and yttrium oxide according to a molar ratio of Co to Mg to Y of 98.2:0.2:0.1, and weighing Al-doped Co in the step (2) 3 O 4 Stirring and mixing the precursor uniformly, placing the precursor in a muffle furnace at 1050 ℃ for 12h of sintering time, and then crushing a sintered product to obtain Al, Mg and Y co-doped large-particle lithium cobaltate Li with uniform particle size distribution 1.03 Co 0.982 Al 0.015 Mg 0.002 Y 0.001 O 2 Large particles D 50 18 mu m, the preparation method of the small-particle lithium cobaltate is the same as that of the large particle, the component is the same as that of the large particle, and the small particle D 50 The particle size of the lithium cobaltate is 4.5 mu m, and then the large and small particle lithium cobaltate is uniformly mixed according to the mass ratio of 8:2 to obtain a core particle lithium cobaltate material;
(4) weighing Al according to a molar ratio of Co to Al of 98:0.2 2 O 3 Mixing with the above nuclear particle lithium cobaltate, placing in muffle furnace at 950 deg.C for 12h, and pulverizing to obtain D 50 Positive electrode active material Li having a core-shell structure of 16 μm 1.03 Co 0.98 Al 0.017 Mg 0.002 Y 0.001 O 2 。
The lithium ion batteries provided in examples 1 to 3 and comparative examples 1 to 2 include a positive electrode sheet, a negative electrode sheet, a separator interposed between the positive electrode sheet and the negative electrode sheet, and an electrolyte, wherein the positive electrode sheet includes a positive electrode current collector and a positive electrode active material layer disposed on the positive electrode current collector, the positive electrode active material layer includes a positive electrode active material, a binder, and a conductive agent, and the battery of the present invention employs a graphite negative electrode having a charge cut-off voltage of 4.45 to 4.48V.
The lithium ion batteries described in examples 1-3 and comparative examples 1-2 were prepared as follows:
mixing artificial graphite, styrene diene rubber (SBR), sodium carboxymethylcellulose and conductive carbon black in a weight ratio of 94% to 3% to 2% to 1%, dispersing the mixture in water, and mixing by double planets to obtain negative electrode slurry. And coating the slurry on a copper current collector, and then rolling and drying to obtain the negative plate.
The lithium cobaltate positive electrode active material prepared in examples 1 to 3 and comparative examples 1 to 2 was mixed with conductive carbon black and PVDF in a weight ratio of 96%: 2%: 2%, and dispersed to obtain a positive electrode slurry. Coating the slurry on an aluminum foil current collector, rolling to prepare a positive plate, assembling the positive plate, a negative plate and a diaphragm into a lithium ion battery, and injecting a non-aqueous electrolyte.
Among them, the nonaqueous electrolytic solution used is a conventional electrolytic solution known in the art, and the solvent contains Ethylene Carbonate (EC), diethyl carbonate (DEC), Propylene Carbonate (PC), fluoroethylene carbonate (FEC) and the like. The membranes used are commercially available membranes known in the art.
TABLE 1 Performance test results of the lithium ion batteries of examples and comparative examples under a 4.45V system
TABLE 2 Performance test results of the lithium ion batteries of examples and comparative examples under a 4.48V system
The following tests were performed on the lithium ion batteries of examples 1 to 3 and comparative examples 1 to 2, and the results are shown in tables 1 and 2.
The first efficiency test procedure used was:
charging to 4.45V/4.48V at a constant current at a charging and discharging rate of 0.2C, charging to 4.45V/4.48V at a constant voltage at a charging rate of 0.05C, and discharging to 3.0V at a discharging rate of 0.2C at 25 ℃, and counting the first charging and discharging capacity, wherein the first efficiency is (first discharging capacity)/(first charging capacity) × 100%.
The gram volume test procedure used was:
at 25 ℃, the material was charged at a constant current to 4.45V/4.48V at a charge/discharge rate of 0.2C, then charged at a constant voltage to 4.45V/4.48V at a charge rate of 0.05C, and then discharged to 3.0V at a discharge rate of 0.2C, and the discharge capacity was counted, and the gram capacity was (discharge capacity)/(weight of positive electrode active material).
The cycle performance test procedure used was:
the lithium ion batteries of examples 1 to 3 and comparative examples 1 to 2 were charged at 25 ℃ at a constant current at a charge rate of 5C to 4.45V/4.48V, further charged at a constant voltage at a charge rate of 0.05C to 4.45V/4.48V, and then discharged at a discharge rate of 1C to 3.0V, and the charge and discharge cycles were repeated 500 times, and the discharge capacity at the first cycle and the discharge capacity at the 500 th cycle were measured to determine the capacity retention rate after the cycles, i.e., the capacity retention rate after the cycles (discharge capacity at the 500 th cycle)/(discharge capacity at the first cycle) × 100%.
The temperature rise test procedure used was:
for the lithium ion batteries of examples 1 to 3 and comparative examples 1 to 2, at 25 ℃, the battery was charged at a constant current of 5 ℃ to 4.45V/4.48V, then charged at a constant voltage of 0.05C to 4.45V/4.48V, and then discharged at a discharge rate of 1C to 3.0V, a thermocouple was placed in the middle of the battery, the change in the bulk temperature during charging and discharging was synchronously detected, the initial temperature was T1, the maximum temperature during charging and discharging was T2, and the statistical data of temperature rise was T2 to T1.
As can be seen by comparing tables 1 and 2, from the test results of examples 1-3 and comparative examples 1-2: when the high-voltage lithium cobaltate positive active material is used as the positive active material of the lithium ion battery, the cycle performance of the battery core under a high-voltage system is equivalent to that of the conventional particle size design (the particle size range of commercial lithium cobaltate is 15-16 mu m), the capacity retention rate after 500 cycles is at least more than 80%, the cycle performance under high voltage is excellent, and the temperature rise of the battery core adopting the lithium cobaltate as the positive active material is 4-5 ℃ lower than that of the battery core adopting the lithium cobaltate as the positive active material. The method mainly adopts Co modified by double doping of Al and rare earth elements 3 O 4 As a precursor, Al element plays a role in stabilizing the structure of a lithium cobaltate nuclear matrix material and inhibiting the local structural collapse of lithium cobaltate caused by excessive phase change in the circulation process, while rare earth element has larger atomic radius and can form local defects when being doped into the lithium cobaltate body and simultaneously improve ionic conductivity and electronic conductivity, and meanwhile, a shell coating layer is formed on the surface of the nuclear matrix material by adopting a coating means, so that the conductivity cannot be greatly reduced when the material is blocked from being in direct contact with electrolyte, the side reaction of a lithium cobaltate positive electrode active substance and the electrolyte interface under a high-voltage system is reduced, the electrochemical polarization is further reduced by doping the rare earth element, the circulation performance of the material is ensured, and the size of lithium cobaltate particles is reduced by adjusting a synthesis process, so that the electrochemical polarization generated by a scale effect in the charge-discharge process is reduced, the heat accumulation amplitude of the battery cell is reduced in the charging and discharging use process, so that the charging and discharging temperature rise of the battery cell is reduced, and the use safety performance of the quick charging cell is improved.
In a word, the lithium ion battery with the high-voltage lithium ion battery anode active material prepared by the invention can give consideration to both the cycle performance and the quick-charging safety performance under high voltage, and simultaneously, due to charging, the battery has higher volume energy density and can meet the requirement of people on thinning of the lithium ion battery.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A positive active material comprises at least one core material and at least one shell material, wherein the at least one shell material is coated on the surface of the at least one core material to form at least one particle with a core-shell structure;
the raw materials for preparing the at least one nuclear material at least comprise Me 3 O 4 Which is a precursor of cobalt doped with Al and Z, wherein Me ═ Co 1-a-b Al a Z b Z is one or more of Y, La, Mg, Ti, Zr, Ni and Mn; 0<a≤0.2，0<b≤0.1；
The at least one core material is compounded from large and small particles and has a bimodal particle size distribution, wherein the particle diameter D of the large-particle core material 50 Particle size D of core material of small particles of 10-25 μm 50 Is 3-8 μm.
2. The positive electrode active material according to claim 1, wherein the core material is selected from Li x Me 1-y M y O 2 Wherein Me is Co 1-a-b Al a Z b M is one or more of Al, Mg, Ti, Zr, Co, Ni, Mn, Y, La, Sr, W and Sc, and Z is one or more of Y, La, Mg, Ti, Zr, Ni, Mn and Ce; x is more than or equal to 0.95 and less than or equal to 1.07, y is more than or equal to 0 and less than or equal to 0.1, 0<a≤0.2，0<b≤0.1。
3. The positive active material according to claim 1 or 2, wherein the raw materials for preparing the at least one shell material are the same or different and are independently selected from one or more of metal fluorides, metal oxides, metal borate compounds, and metal phosphate compounds.
4. The positive electrode active material according to any one of claims 1 to 3, wherein the positive electrode active material comprises at least one core material and at least one shell material, and the at least one shell material is coated on the surface of the at least one core material to form at least one particle having a core-shell structure; the at least one core material is compounded from large and small particles and has a bimodal particle size distribution; that is, the formed positive electrode active material is defined as (An1+ An2) × Bn, where An1 and An2 respectively represent at least one core material different in particle size, and Bn represents at least one shell material.
5. The positive electrode active material according to any one of claims 1 to 4, wherein the mass ratio of the core material of the large particles to the core material of the small particles is, for example, 1 to 5:5: 9.
6. The positive electrode active material according to any one of claims 1 to 5, wherein the particle diameter D of the positive electrode active material 50 Less than 9 μm, for example, 4 μm or more and less than 9 μm; and/or the presence of a gas in the atmosphere,
the thickness of the shell material in the positive active material is less than or equal to 40 nm; and/or the presence of a gas in the gas,
the mass of the shell material in the positive active material accounts for 0.03-1% of the total mass of the positive active material.
7. A positive electrode sheet comprising the positive electrode active material according to any one of claims 1 to 6, a conductive agent, and a binder; the positive plate comprises the following components in percentage by mass:
70-99 wt% of positive electrode active material, 0.5-15 wt% of conductive agent and 0.5-15 wt% of binder.
8. A lithium ion battery comprising the positive electrode sheet of claim 7.
Preferably, the lithium ion battery is a 2C-10C quick-charging system lithium ion battery.
Preferably, the lithium ion battery is a high-voltage system lithium ion battery with a cut-off voltage of 4.45V or more.
9. Use of the positive active material according to any one of claims 1 to 6 for a lithium ion battery of a 2C-10C fast charge system and/or for a lithium ion battery of a high voltage system having a cut-off voltage of 4.45V or more.
10. A method for reducing temperature rise and impedance of a battery under a 2C-10C rapid charging system and/or under a high voltage system for a cut-off voltage of 4.45V or more, the method comprising using the positive electrode active material according to any one of claims 1 to 6.
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