CN115432750B - Porous honeycomb single-crystal high-nickel positive electrode material, and preparation method and application thereof - Google Patents
Porous honeycomb single-crystal high-nickel positive electrode material, and preparation method and application thereof Download PDFInfo
- Publication number
- CN115432750B CN115432750B CN202211294453.0A CN202211294453A CN115432750B CN 115432750 B CN115432750 B CN 115432750B CN 202211294453 A CN202211294453 A CN 202211294453A CN 115432750 B CN115432750 B CN 115432750B
- Authority
- CN
- China
- Prior art keywords
- lithium
- nickel
- porous honeycomb
- positive electrode
- electrode material
- 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.)
- Active
Links
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 207
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 141
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 90
- 239000013078 crystal Substances 0.000 title claims abstract description 83
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 239000000463 material Substances 0.000 claims abstract description 98
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 52
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 51
- 238000001354 calcination Methods 0.000 claims abstract description 47
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000002243 precursor Substances 0.000 claims abstract description 44
- 150000003839 salts Chemical class 0.000 claims abstract description 42
- 238000002156 mixing Methods 0.000 claims abstract description 40
- 239000012298 atmosphere Substances 0.000 claims abstract description 34
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 32
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 27
- 239000001301 oxygen Substances 0.000 claims abstract description 26
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 20
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000010405 anode material Substances 0.000 claims abstract description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 45
- 238000004321 preservation Methods 0.000 claims description 39
- 239000002245 particle Substances 0.000 claims description 37
- 229910052723 transition metal Inorganic materials 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 17
- 239000010406 cathode material Substances 0.000 claims description 13
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 12
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 claims description 12
- 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 12
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 8
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 7
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 5
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 5
- HQRPHMAXFVUBJX-UHFFFAOYSA-M lithium;hydrogen carbonate Chemical compound [Li+].OC([O-])=O HQRPHMAXFVUBJX-UHFFFAOYSA-M 0.000 claims description 5
- YNQRWVCLAIUHHI-UHFFFAOYSA-L dilithium;oxalate Chemical compound [Li+].[Li+].[O-]C(=O)C([O-])=O YNQRWVCLAIUHHI-UHFFFAOYSA-L 0.000 claims description 4
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims description 4
- 229910001947 lithium oxide Inorganic materials 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims description 3
- 159000000000 sodium salts Chemical class 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims 6
- 229910003002 lithium salt Inorganic materials 0.000 abstract description 24
- 159000000002 lithium salts Chemical class 0.000 abstract description 24
- 235000002639 sodium chloride Nutrition 0.000 description 36
- 238000010438 heat treatment Methods 0.000 description 33
- 239000011572 manganese Substances 0.000 description 30
- 238000001035 drying Methods 0.000 description 26
- 230000000052 comparative effect Effects 0.000 description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 22
- 229910013716 LiNi Inorganic materials 0.000 description 20
- 239000008367 deionised water Substances 0.000 description 17
- 229910021641 deionized water Inorganic materials 0.000 description 17
- 238000001816 cooling Methods 0.000 description 16
- 238000000227 grinding Methods 0.000 description 14
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 12
- 229910017052 cobalt Inorganic materials 0.000 description 12
- 239000010941 cobalt Substances 0.000 description 12
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 12
- 229910052748 manganese Inorganic materials 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 10
- 230000001502 supplementing effect Effects 0.000 description 10
- 238000005406 washing Methods 0.000 description 9
- 230000005540 biological transmission Effects 0.000 description 8
- 229940011182 cobalt acetate Drugs 0.000 description 8
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 8
- BEDNMLJNVASDSN-UHFFFAOYSA-H [Mn++].[Co++].[Ni++].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O Chemical compound [Mn++].[Co++].[Ni++].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O BEDNMLJNVASDSN-UHFFFAOYSA-H 0.000 description 7
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 6
- DDXROPFGVVLFNZ-UHFFFAOYSA-H cobalt(2+) manganese(2+) nickel(2+) tricarbonate Chemical compound [Mn+2].[Co+2].C([O-])([O-])=O.[Ni+2].C([O-])([O-])=O.C([O-])([O-])=O DDXROPFGVVLFNZ-UHFFFAOYSA-H 0.000 description 6
- 229940071125 manganese acetate Drugs 0.000 description 6
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 6
- 229940078494 nickel acetate Drugs 0.000 description 6
- 229910000480 nickel oxide Inorganic materials 0.000 description 6
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 210000004027 cell Anatomy 0.000 description 4
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 4
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(II) oxide Inorganic materials [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 4
- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 4
- 239000004570 mortar (masonry) Substances 0.000 description 4
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 230000009469 supplementation Effects 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 230000008602 contraction Effects 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000011790 ferrous sulphate Substances 0.000 description 2
- 235000003891 ferrous sulphate Nutrition 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 230000000877 morphologic effect Effects 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 235000017550 sodium carbonate Nutrition 0.000 description 2
- 239000004317 sodium nitrate Substances 0.000 description 2
- 235000010344 sodium nitrate Nutrition 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 208000032953 Device battery issue Diseases 0.000 description 1
- 102000004310 Ion Channels Human genes 0.000 description 1
- 229910011628 LiNi0.7Co0.15Mn0.15O2 Inorganic materials 0.000 description 1
- 229910011695 LiNi0.7Co0.3O2 Inorganic materials 0.000 description 1
- 229910011729 LiNi0.7Mn0.3O2 Inorganic materials 0.000 description 1
- 229910002995 LiNi0.8Co0.15Al0.05O2 Inorganic materials 0.000 description 1
- 229910015872 LiNi0.8Co0.1Mn0.1O2 Inorganic materials 0.000 description 1
- 229910016222 LiNi0.9Co0.1O2 Inorganic materials 0.000 description 1
- 229910013290 LiNiO 2 Inorganic materials 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 229910021314 NaFeO 2 Inorganic materials 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 210000003850 cellular structure Anatomy 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 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
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 1
- 229940044175 cobalt sulfate Drugs 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
- 238000009841 combustion method Methods 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 238000011534 incubation Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- RSNHXDVSISOZOB-UHFFFAOYSA-N lithium nickel Chemical compound [Li].[Ni] RSNHXDVSISOZOB-UHFFFAOYSA-N 0.000 description 1
- 229940099596 manganese sulfate Drugs 0.000 description 1
- 239000011702 manganese sulphate Substances 0.000 description 1
- 235000007079 manganese sulphate Nutrition 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical compound [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 description 1
- 229940039790 sodium oxalate Drugs 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/40—Nickelates
- C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
- C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
- C01G53/50—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [MnO2]n-, e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/40—Nickelates
- C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
-
- 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
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/30—Three-dimensional structures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
-
- 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
-
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to the technical field of lithium ion batteries, in particular to a porous honeycomb single-crystal type high-nickel positive electrode material, a preparation method and application thereof. The preparation method comprises the following steps: uniformly mixing a high-nickel precursor material and lithium-containing molten salt, and then performing first calcination in a low-oxygen atmosphere with the oxygen volume fraction of less than 60% to obtain a porous honeycomb-shaped intermediate material; uniformly mixing the porous honeycomb intermediate material with lithium salt, and then performing second calcination in pure oxygen atmosphere to obtain a porous honeycomb single-crystal high-nickel anode material; the molar content of nickel element in the high-nickel precursor material is more than or equal to 70%; the first calcination includes: preserving heat for 2-6 h at 350-550 ℃, preserving heat for 8-16 h at 700-850 ℃ and preserving heat for 1-5 h at 900-1000 ℃. The preparation method can form a porous honeycomb structure, so that the structural stability of the material is enhanced, the electrochemical performance of the positive electrode material is improved, and particularly the capacity and the circulation stability are improved.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a porous honeycomb single-crystal type high-nickel positive electrode material, a preparation method and application thereof.
Background
The urgent need for portable fast charging devices and high endurance pure electric vehicles by human society presents challenges for developing high energy, high power density lithium ion power batteries. The conventional high-nickel positive electrode material is easy to generate morphological and structural damage under the condition of high current due to the inherent polycrystalline spherical structure, so that the lithium ion transmission kinetics is slow. The prior researches report that the stability of the material is improved through anion/cation doping, surface coating, concentration gradient structure and morphology regulation. These strategies have significant effects on cycle life extension but do not have significant improvements in performance under high current conditions.
To develop high power density lithium ion batteries, methods commonly employed include electrode design and morphology engineering. In the aspect of electrode design, the electron transfer and the lithium ion channel are generally shortened by reducing the thickness of the electrode, modifying the current collector or adjusting the addition amount and the form of the conductive agent. Meanwhile, from the particle level, the appearance and the size of the positive electrode material are regulated and controlled, so that the rapid charge and discharge capability of the positive electrode material can be improved. For example, the positive electrode material particles are designed to have a hollow or porous honeycomb structure and small particles by morphology engineering, and the large specific surface area of the active material can be fully utilized to enhance the contact with the electrolyte, so that great interest is brought to the improvement of the mobility of lithium ions. However, this approach is typically accomplished by the additional introduction of a surfactant/etchant/complexing ion former. Moreover, it is easily neglected that these methods do not guarantee structural stability under severe operating conditions, and the high nickel positive electrode material may still have particle breakage and severe irreversible phase change, resulting in battery failure.
Single-crystal type high-nickel positive electrode materials are increasingly favored because of their excellent thermal stability and cycle performance, and more stable structure. However, the conventional monocrystal type particles have compact structures, so that the capacity of the monocrystal type particles under the condition of large current is low, the full play of electrochemical performance is limited, and the further commercialized development of monocrystal large-particle high-nickel cathode materials is hindered.
Therefore, developing a novel morphological engineering technology to be applied to the synthesis and preparation of the single crystal high nickel anode material with porous honeycomb shape, micron-sized particle size and higher nickel content has important significance for the development of lithium ion batteries.
In view of this, the present invention has been made.
Disclosure of Invention
The first object of the present invention is to provide a preparation method of a porous honeycomb single-crystal type high nickel positive electrode material, which can form a porous honeycomb special structure, and the structure can enhance the structural stability of the material, improve the electrochemical performance of the positive electrode material, and especially improve the capacity and the cycle stability of the positive electrode material.
The second object of the invention is to provide a porous honeycomb single-crystal type high nickel cathode material.
A third object of the present invention is to provide a positive electrode sheet.
A fourth object of the present invention is to provide a lithium ion battery.
In order to achieve the above object of the present invention, the following technical solutions are specifically adopted:
in a first aspect, the invention provides a preparation method of a porous honeycomb single-crystal type high-nickel positive electrode material, which comprises the following steps:
(a) And uniformly mixing the high-nickel precursor material and the lithium-containing molten salt, and then performing first calcination in a low-oxygen atmosphere with the oxygen volume fraction of less than 60% (including but not limited to any one of point values or range values between any two of 55%, 50%, 45%, 40%, 35%, 30%, 25%, 20% and 15%) to obtain the porous honeycomb intermediate material. The porous honeycomb intermediate material prepared at this time is a lithium-deficient material having a defective structure.
In some specific embodiments of the present invention, in the step (a), the low oxygen atmosphere with the oxygen volume fraction of 60% or less includes, but is not limited to, air, or a low oxygen atmosphere gas obtained by adjusting the ratio of oxygen to other gases, wherein the other gases include, but are not limited to, nitrogen or argon.
After adding lithium-containing molten salt in the step (a), performing first calcination in a low-oxygen atmosphere, wherein the high-nickel precursor material can form single crystal large particles in the molten salt environment. The first two sections of calcination in the first calcination are used for forming monocrystal large particles with a layered structure, the third section of calcination can enable the monocrystal large particles to be partially decomposed, internal lithium ions are extracted, obvious defect structures can be formed, and the formation of a porous structure (hole structure) is facilitated.
The precursor material can be converted into micron-sized monocrystal large particles by combining with a three-stage heating high-temperature calcination reaction in a molten salt environment, and a porous honeycomb special structure can be formed on the monocrystal particle main body, so that the infiltration of electrolyte is facilitated, the lithium ion movement path is shortened, the rapid transmission of lithium ions in the monocrystal large particles is promoted, the electrochemical performance of the monocrystal high-nickel positive electrode material under high current density is improved, and the problem of lower electrochemical performance caused by long lithium ion output path in the monocrystal positive electrode material particles is effectively solved. And the advantage of ion transmission speed makes it have more outstanding electrochemical performance.
(b) And (c) uniformly mixing the porous honeycomb intermediate material obtained in the step (a) with lithium salt, then performing second calcination in pure oxygen atmosphere, and supplementing lithium to obtain the porous honeycomb single-crystal high-nickel anode material with complete components and a complete layered structure.
And (b) calcining the porous honeycomb intermediate material and lithium salt in a pure oxygen atmosphere for second calcination and supplementing lithium to form the positive electrode material with a perfect structure, thereby improving the performance of the positive electrode material.
In the step (a), the molar content of nickel element in the high-nickel precursor material is more than or equal to 70%; including but not limited to a point value of any one of, or a range value between any two of, 71%, 72%, 73%, 75%, 78%, 80%, 83%, 85%, 90%, 95%, 98%, 99%. Wherein, the molar content of the nickel element in the high-nickel precursor material refers to the mole percentage of the nickel element in the high-nickel precursor material in the transition metal element (sum of the molar contents of the transition metal elements) in the high-nickel precursor material.
The adoption of the nickel precursor material with high nickel content is beneficial to forming a hole structure.
In addition, the mass fraction of nickel element in the porous honeycomb single-crystal type high-nickel positive electrode material prepared in the step (b) is more than or equal to 70%; including but not limited to a point value of any one of, or a range value between any two of, 71%, 72%, 73%, 75%, 78%, 80%, 83%, 85%, 90%, 95%, 98%, 99%. The molar content of the nickel element in the porous honeycomb single-crystal type high-nickel cathode material refers to the molar percentage of the nickel element in the porous honeycomb single-crystal type high-nickel cathode material in the transition metal element (sum of the molar contents of the transition metal elements) in the porous honeycomb single-crystal type high-nickel cathode material.
In step (a), the first calcining comprises: prior to the incubation for between 350 and 550 ℃ (including but not limited to any one of the point values of 370 ℃, 390 ℃, 400 ℃, 420 ℃, 450 ℃, 480 ℃, 500 ℃ and 530 ℃ or any range between the two) for between 2 and 6 hours (including but not limited to any one of the point values of 3 hours, 4 hours and 5 hours or any range between the two), then the temperature is kept for 8 to 16 hours (including but not limited to 9 hours) at 700 to 850 ℃ (including but not limited to 720 ℃, 740 ℃, 750 ℃, 780 ℃, 800 ℃, 830 ℃ or a range between any two point values) a point value of any one of 10h, 12h, 14h, 15h or a range value between any two), then preserving the temperature for 1 to 5 hours (including but not limited to any one point value or any range value between any two of 2 hours, 3 hours and 4 hours) at 900 to 1000 ℃ (including but not limited to any one point value or any range value between any two of 920 ℃, 940 ℃, 950 ℃, 970 ℃ and 990 ℃).
According to the preparation method provided by the invention, the porous honeycomb single crystal material is synthesized by carrying out three-stage high-temperature molten salt reaction in a low-oxygen atmosphere, so that the problems of slow lithium ion transmission and insufficient performance exertion of the micron-sized single crystal positive electrode material are solved. Thanks to the special morphology of the prepared honeycomb monocrystal particles, the honeycomb monocrystal high-nickel positive electrode material has the characteristic that the monocrystal particles relieve stress generated by expansion and shrinkage in the charge and discharge process; meanwhile, the honeycomb structure has rich space channels, so that the contact surface with electrolyte is improved while the size of micron-sized monocrystalline particles is maintained, the lithium ion transmission speed is enhanced, and the disadvantage of poor electrochemical performance of the monocrystalline particles due to low lithium ion transmission speed is overcome.
The honeycomb single crystal high nickel positive electrode material (namely the porous honeycomb single crystal high nickel positive electrode material) prepared by the low oxygen atmosphere (air) assisted molten salt method has excellent electrochemical performance, and an effective synthesis route is provided for improving the electrochemical performance of the positive electrode material and enhancing the structural stability of the material.
And the high-nickel positive electrode material with the nickel content exceeding (more than or equal to) 70 percent can exert the high capacity characteristic of the high-nickel positive electrode material to a greater extent, and simultaneously, the electrochemical performance of the high-nickel positive electrode material is further improved by combining the porous honeycomb special structure.
In addition, the first calcination is carried out in the low-oxygen atmosphere in the step (a), so that the use cost of oxygen can be greatly reduced; the preparation method has the advantages of simple operation, low cost, short process flow, suitability for mass production and the like.
Preferably, in step (a), the first calcination comprises: the temperature is kept for 3 to 5 hours at 400 to 500 ℃, then kept for 10 to 15 hours at 750 to 840 ℃ and then kept for 2 to 4 hours at 910 to 960 ℃.
Preferably, in step (a), during the first calcination, the molar ratio of lithium element in the lithium-containing molten salt to transition metal element in the high nickel precursor material is ≡1.5, including but not limited to point values of any one of 2, 3, 4, 5, 6, 7, 8, 9, 10, 13, 15, 18, 20 or range values between any two; the preferred molar ratio is 2-10: 1. wherein the transition metal element includes, but is not limited to, at least one of Ni, co, mn, fe, ti, W, and Al; when the transition metal element includes a plurality of transition metal elements, the molar amount of the transition metal element in the above molar ratio is the sum of the molar amounts of all transition metal elements.
Preferably, in step (a), the lithium-containing molten salt comprises a lithium salt, or a molten salt formed after mixing the lithium salt with an inorganic salt. That is, the lithium-containing molten salt may be a lithium salt as it is, or a molten salt formed by mixing a lithium salt and an inorganic salt in an arbitrary molar ratio.
The lithium-containing molten salt added in step (b) is used to form single crystal large particles and to form a porous honeycomb-like special structure.
Preferably, the lithium salt includes at least one of lithium oxide, lithium hydroxide, lithium bicarbonate, lithium carbonate, lithium sulfate, lithium nitrate, lithium acetate, lithium oxalate, and lithium chloride, and two or three kinds may be selected.
Preferably, the inorganic salt comprises a sodium salt and/or a potassium salt.
In some specific embodiments of the invention, the sodium salt comprises at least one of sodium carbonate, sodium bicarbonate, sodium nitrate, sodium chloride, sodium sulfate, sodium acetate, and sodium oxalate. The potassium salt includes at least one of potassium carbonate, potassium nitrate, potassium chloride and potassium sulfate.
Preferably, the lithium-containing molten salt consists essentially of a molar ratio of 4 to 8:1, lithium hydroxide and lithium sulfate; wherein the molar ratio includes, but is not limited to, a point value of any one of 5:1, 6:1, 7:1, or a range value between any two.
The use of lithium-containing molten salts of the above specific composition is advantageous in promoting the formation of porous cellular structures.
In some specific embodiments of the present invention, in step (a), the preparation method of the high nickel precursor material may employ any conventional preparation method, such as a physical method or a chemical method, including, but not limited to, a solid phase method, a coprecipitation method, a sol gel method, a spray drying method, a combustion method, and the like. Wherein. Meanwhile, the particle morphology of the high nickel precursor material may be any, conventional morphology including, but not limited to, at least one of spherical, rod-like, needle-like, flake-like, and irregular shapes.
In some specific embodiments of the present invention, in step (a), the element contained in the high nickel precursor material includes, but is not limited to, at least one of Li, ni, co, mn, fe, ti, mg, W, sr, ca, al and O. Preferably, the high nickel precursor material includes, but is not limited to, liNi 0.7 Co 0.15 Mn 0.15 O 2 、LiNi 0.7 Mn 0.3 O 2 、LiNi 0.7 Co 0.3 O 2 、LiNi 0.8 Co 0.1 Mn 0.1 O 2 、LiNi 0.8 Co 0.15 Al 0.05 O 2 、LiNi 0.9 Mn 0.1 O 2 、LiNi 0.9 Co 0.1 O 2 And LiNiO 2 At least one of them. In addition, the case of substitution or doping of anions and cations is also included.
In some specific embodiments of the invention, in step (a), the first calcination is at a temperature rise rate of 2-10 ℃/min, including but not limited to a point value of any one of 3 ℃/min, 4 ℃/min, 5 ℃/min, 6 ℃/min, 7 ℃/min, 8 ℃/min, 9 ℃/min, or a range value between any two.
In some specific embodiments of the invention, in step (a), the first calcination is performed in a crucible furnace.
In some specific embodiments of the invention, in step (a), the method of homogenizing comprises mixing and grinding; preferably, the grinding time is 10-20 min, including but not limited to any one of 12min, 14min, 15min, 18min or range between any two.
In some specific embodiments of the invention, in step (a), the high nickel precursor material has a particle size of 50 to 800nm, including but not limited to a point value of any one of 70nm, 90nm, 100nm, 130nm, 150nm, 200nm, 250nm, 300nm, 400nm, 500nm, 600nm, 700nm, 750nm, or a range value between any two.
Preferably, in step (b), the lithium salt comprises at least one of lithium oxide, lithium hydroxide, lithium bicarbonate, lithium carbonate, lithium sulfate, lithium nitrate, lithium acetate, lithium oxalate, and lithium chloride. The lithium salt added in step (b) is used for lithium supplementation, thereby forming a positive electrode material with a perfect structure.
Preferably, in step (b), the porous honeycomb intermediate material and the lithium salt further comprise a step of washing and drying the porous honeycomb intermediate material obtained in step (a) before the mixing.
In some embodiments of the invention, the washing is performed with water (e.g., deionized water) for a number of times ranging from 2 to 5, and optionally 3 or 4 times.
The porous cellular intermediate material produced in step (a) is a mixture of monocrystalline particles and lithium salt, and the soluble lithium salt in the mixture can be removed by washing. Meanwhile, washing causes damage to the crystal structure of the surface of the porous honeycomb intermediate material, so that lithium supplementation and re-calcination (i.e., second calcination) of the repaired structure are required.
In some specific embodiments of the invention, the drying temperature is 40-120 ℃, including but not limited to, a point value of any one of 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃, 110 ℃ or a range value between any two; the drying time is 6-48 h, including but not limited to any one of 8h, 10h, 12h, 15h, 18h, 20h, 25h, 30h, 35h, 40h, 45h or a range of values therebetween.
In some specific embodiments of the present invention, in step (b), the amount of the lithium salt is determined according to the content of lithium element in the washed porous honeycomb intermediate material, and the lithium salt is added according to the molar content ratio of lithium element to (total) transition metal element in the prepared porous honeycomb single-crystal type high-nickel cathode material being 1:1.
Preferably, in step (b), the temperature of the second calcination is 500-800 ℃, including but not limited to a point value of any one of 550 ℃, 600 ℃, 650 ℃, 700 ℃, 750 ℃ or a range value between any two; the heat preservation time of the second calcination is 3-15 h, including but not limited to any one of the point values or the range values between any two of 5h, 8h, 10h, 12h and 14 h.
In some specific embodiments of the present invention, in step (b), the volume fraction of oxygen in the pure oxygen atmosphere is greater than 99%, including but not limited to a point value of any one of 99.1%, 99.3%, 99.5%, 99.7%, 99.9%, or a range value between any two.
In some specific embodiments of the invention, in step (b), the second calcination is at a rate of temperature rise of 2-10 ℃/min, including but not limited to a point value of any one of 3 ℃/min, 4 ℃/min, 5 ℃/min, 6 ℃/min, 7 ℃/min, 8 ℃/min, 9 ℃/min, or a range value between any two.
In some specific embodiments of the invention, in step (a), the second calcination is performed in a tube furnace.
Preferably, the porous honeycomb single-crystal type high nickel cathode material obtained in step (b) has a particle size of 1 to 8 μm.
In a second aspect, the invention provides a porous honeycomb single-crystal type high-nickel cathode material prepared by the preparation method of the porous honeycomb single-crystal type high-nickel cathode material.
The porous honeycomb single-crystal type high-nickel positive electrode material provided by the invention has high capacity, wherein the porous honeycomb structure can relieve stress generated by expansion and contraction in the charge and discharge process, and has rich space channels, so that the contact surface with electrolyte is increased while the size of micron-sized single-crystal particles is maintained, and the lithium ion transmission speed is improved.
The porous honeycomb single-crystal type high-nickel positive electrode material has excellent electrochemical performance, and particularly has higher charge-discharge specific capacity and stable long-cycle performance.
In a third aspect, the invention provides a positive electrode sheet, which is mainly prepared from the porous honeycomb single-crystal high-nickel positive electrode material.
In a fourth aspect, the present invention provides a lithium ion battery comprising a positive electrode sheet as described above.
The lithium ion battery has excellent electrochemical performance, and particularly has higher charge-discharge specific capacity and stable long-cycle performance.
Compared with the prior art, the invention has the beneficial effects that:
(1) The preparation method of the porous honeycomb single-crystal type high-nickel positive electrode material provided by the invention can form a porous honeycomb structure, and the porous honeycomb special structure has rich space channels, is favorable for the permeation of electrolyte, shortens the movement path of lithium ions, promotes the rapid transmission of lithium ions in large single-crystal particles, and improves the electrochemical performance of the single-crystal high-nickel positive electrode material under high current density. In addition, the porous honeycomb structure can effectively relieve stress generated by expansion and contraction in the charge and discharge process.
(2) The preparation method of the porous honeycomb single-crystal high-nickel positive electrode material provided by the invention can improve the electrochemical performance of the positive electrode material and enhance the structural stability of the material.
(3) The preparation method of the porous honeycomb single-crystal type high-nickel positive electrode material provided by the invention can prepare the high-nickel positive electrode material with the nickel content exceeding 70%, and is beneficial to exerting the high capacity characteristic of the high-nickel positive electrode material to a greater extent.
(4) The porous honeycomb single-crystal high-nickel positive electrode material provided by the invention has excellent electrochemical performance, and particularly has higher charge-discharge specific capacity and stable long-cycle performance.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are needed in the description of the embodiments or the prior art will be briefly described, and it is obvious that the drawings in the description below are some embodiments of the present invention, and other drawings can be obtained according to the drawings without inventive effort for a person skilled in the art.
FIG. 1 shows a non-porous single-crystal type LiNi obtained in comparative example 1 0.6 Co 0.2 Mn 0.2 O 2 FESEM of the positive electrode material; wherein, the magnification of FIG. 1 (a) is 5000 times, and the magnification of FIG. 1 (b) is 18000 times;
FIG. 2 shows a porous honeycomb single-crystal type high nickel LiNi obtained in example 1 0.75 Co 0.10 Mn 0.15 O 2 FESEM of the positive electrode material; wherein, the magnification of fig. 2 (a) is 2200 times, and the magnification of fig. 2 (b) is 5000 times;
FIG. 3 is a porous honeycomb single-crystal high-nickel LiNi obtained in example 2 0.92 Co 0.03 Mn 0.05 O 2 FESEM of the positive electrode material; wherein, the magnification of fig. 3 (a) is 4500 times, and the magnification of fig. 3 (b) is 10000 times;
fig. 4 is an XRD pattern of the positive electrode materials prepared in example 1 and example 2; FIG. 4 (a) shows a porous honeycomb single-crystal type high nickel LiNi obtained in example 1 0.75 Co 0.10 Mn 0.15 O 2 XRD pattern of the positive electrode material; FIG. 4 (b) shows a porous honeycomb single-crystal type high nickel LiNi obtained in example 2 0.92 Co 0.03 Mn 0.05 O 2 XRD pattern of the positive electrode material;
FIG. 5 is a graph of charge and discharge cycle performance at a current density of 2C for the assembled battery of example 1;
fig. 6 is a graph showing charge and discharge cycle performance at a current density of 2C for the assembled battery of example 2.
Detailed Description
The technical solution of the present invention will be clearly and completely described below with reference to the accompanying drawings and detailed description, but it will be understood by those skilled in the art that the examples described below are some, but not all, examples of the present invention, and are intended to be illustrative of the present invention only and should not be construed as limiting the scope of the present invention. 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. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
Example 1
The preparation method of the porous honeycomb single-crystal high-nickel positive electrode material provided by the embodiment comprises the following steps:
(1) 100mmol of oxalic acid was dissolved in 100mL of deionized water to prepare solution A. Then according to the nickel element: cobalt element: elemental manganese = 75:10: the molar ratios of 15 were weighed out respectively 32.5mmol of nickel acetate, 5mmol of cobalt acetate and 7.5mmol of manganese acetate, and were dissolved together in 100mL of deionized water to prepare solution B. And then rapidly pouring the solution A into the solution B, stirring and reacting for 2 hours, filtering and drying to obtain the nickel cobalt manganese oxalate precursor material (the molar content of nickel element is 75%).
(2) Mixing the nickel cobalt manganese oxalate precursor material obtained in the step (1) with lithium-containing molten salt (molten salt formed after mixing lithium hydroxide and lithium sulfate in a molar ratio of 6:1) according to the molar ratio of transition metal elements in the nickel cobalt manganese oxalate precursor material to lithium elements in the lithium-containing molten salt of 1:4.2, mixing and grinding for 10min, heating and calcining (namely, first calcining) in a crucible furnace in an air atmosphere according to a three-stage heating program, firstly heating to 480 ℃ at the speed of 4 ℃/min for 3h, then heating to 850 ℃ at the speed of 4 ℃/min for 10h, then heating to 950 ℃ at the speed of 4 ℃/min for 2h, and finally cooling to room temperature along with the furnace to obtain the porous honeycomb intermediate material.
After the reaction is completed (i.e., the first calcination and cooling are completed), the soluble lithium salt in the porous honeycomb intermediate material is washed clean with deionized water, and then dried in an oven. Wherein the drying temperature is 80 ℃ and the drying time is 10 hours.
(3) Determining the amount of the dried porous honeycomb intermediate material and lithium carbonate (the amount of lithium salt is determined according to the content of lithium element in the washed porous honeycomb intermediate material in the step (2), calculating and adding according to the molar content ratio of the lithium element to the transition metal element in the prepared porous honeycomb single-crystal type high-nickel positive electrode material of 1:1, and performing the following examples and steps The same way as in each comparative example), and carrying out heat preservation treatment for 6 hours (namely second calcination) at 720 ℃ in a tube furnace under an oxygen atmosphere (namely pure oxygen atmosphere) for supplementing lithium ions, and then cooling to room temperature along with the furnace to obtain the porous honeycomb single-crystal high-nickel LiNi with complete components and perfect structure 0.75 Co 0.10 Mn 0.15 O 2 Positive electrode material (nickel element molar content 75%).
Example 2
The preparation method of the porous honeycomb single-crystal high-nickel positive electrode material provided by the embodiment comprises the following steps:
(1) 100mmol of ammonium oxalate was dissolved in 100mL of deionized water to prepare solution A. Then according to the nickel element: cobalt element: elemental manganese = 92:3:5 molar ratios 46mmol of nickel acetate, 1.5mmol of cobalt acetate and 2.5mmol of manganese acetate were weighed out respectively and dissolved together in 100mL of deionized water to prepare solution B. And then rapidly pouring the solution A into the solution B, stirring and reacting for 2 hours, filtering and drying to obtain the nickel cobalt manganese oxalate precursor material (the molar content of nickel element is 92%).
(2) Mixing the nickel cobalt manganese oxalate precursor material obtained in the step (1) with lithium-containing molten salt (molten salt formed after mixing lithium hydroxide and lithium sulfate in a molar ratio of 6:1) according to the molar ratio of transition metal elements in the nickel cobalt manganese oxalate precursor material to lithium elements in the lithium-containing molten salt of 1:4.2, mixing and grinding for 10min, heating and calcining in a crucible furnace in an air atmosphere in a three-stage heating program, firstly heating to 480 ℃ at a speed of 4 ℃/min, carrying out heat preservation for 3h, then heating to 830 ℃ at a speed of 4 ℃/min, continuously carrying out heat preservation for 10h, heating to 900 ℃ at a speed of 4 ℃/min, continuously carrying out heat preservation for 2h, and finally cooling to room temperature along with the furnace to obtain the porous honeycomb-shaped intermediate material.
After the reaction is finished, the soluble lithium salt in the porous honeycomb intermediate material is washed by deionized water and then is dried in an oven. Wherein the drying temperature is 80 ℃ and the drying time is 10 hours.
(3) Mixing the porous honeycomb intermediate material dried in the step (2) with lithium hydroxide, and carrying out heat preservation treatment for 6 hours at 620 ℃ in a tube furnace under an oxygen atmosphere for supplementing lithium ions, and then followingCooling the furnace to room temperature to obtain the porous honeycomb single-crystal high-nickel LiNi with complete components and complete structures 0.92 Co 0.03 Mn 0.05 O 2 Positive electrode material (92% mole content of nickel element).
Example 3
The preparation method of the porous honeycomb single-crystal high-nickel positive electrode material provided by the embodiment comprises the following steps:
(1) 100mmol of sodium carbonate was dissolved in 100mL of deionized water to prepare solution A. Then according to the nickel element: cobalt element: elemental manganese = 70:10: the molar ratio of 20 was measured for 35mmol nickel nitrate, 5mmol cobalt nitrate and 10mmol manganese nitrate, respectively, and the solution was prepared as solution B by dissolving together in 100mL deionized water. And then rapidly pouring the solution A into the solution B, stirring and reacting for 2 hours, filtering and drying to obtain the nickel cobalt manganese carbonate precursor material (the molar content of nickel element is 70%).
(2) Mixing the nickel cobalt manganese carbonate precursor material obtained in the step (1) with lithium-containing molten salt (molten salt formed after the molar ratio of lithium hydroxide to lithium sulfate is 6:1) according to the molar ratio of transition metal elements in the nickel cobalt manganese carbonate precursor material to lithium elements in the lithium-containing molten salt of 1:4.2, mixing and grinding for 10min, heating and calcining in a crucible furnace in an air atmosphere in a three-stage heating program, firstly heating to 480 ℃ at a speed of 4 ℃/min, carrying out heat preservation treatment for 3h, then heating to 840 ℃ at a speed of 4 ℃/min, carrying out heat preservation treatment for 10h, heating to 960 ℃ at a speed of 4 ℃/min, carrying out heat preservation treatment for 2h, and finally cooling to room temperature along with the furnace to obtain the porous honeycomb-shaped intermediate material.
After the reaction is finished, the soluble lithium salt in the porous honeycomb intermediate material is washed by deionized water and then is dried in an oven. Wherein the drying temperature is 80 ℃ and the drying time is 10 hours.
(3) Mixing the porous honeycomb intermediate material dried in the step (2) with lithium carbonate, performing heat preservation treatment for 6 hours at 730 ℃ in a tube furnace under oxygen atmosphere for supplementing lithium ions, and then cooling to room temperature along with the furnace to obtain porous honeycomb single-crystal high-nickel LiNi with complete components and complete structures 0.70 Co 0.10 Mn 0.20 O 2 Positive electrode material(the molar content of nickel element is 70%).
Example 4
The preparation method of the porous honeycomb single-crystal high-nickel positive electrode material provided by the embodiment comprises the following steps:
(1) 100mmol sodium bicarbonate is dissolved in 100mL deionized water to prepare solution A. According to the nickel element: cobalt element: elemental manganese = 80:10: the molar ratio of 10 was measured for 40mmol nickel sulfate, 5mmol cobalt sulfate and 5mmol manganese sulfate, respectively, and the solution was prepared as solution B by dissolving together in 100mL deionized water. And then rapidly pouring the solution A into the solution B, stirring and reacting for 2 hours, filtering and drying to obtain the nickel cobalt manganese carbonate precursor material (the molar content of nickel element is 80%).
(2) Mixing the nickel cobalt manganese carbonate precursor material obtained in the step (1) with lithium-containing molten salt (molten salt formed after the molar ratio of lithium hydroxide to lithium sulfate is 6:1) according to the molar ratio of transition metal elements in the nickel cobalt manganese carbonate precursor material to lithium elements in the lithium-containing molten salt of 1:4.2, mixing and grinding for 10min, heating and calcining in a crucible furnace in an air atmosphere in a three-stage heating program, firstly heating to 480 ℃ at a speed of 4 ℃/min, carrying out heat preservation for 3h, then heating to 850 ℃ at a speed of 4 ℃/min, continuously carrying out heat preservation for 10h, heating to 930 ℃ at a speed of 4 ℃/min, continuously carrying out heat preservation for 2h, and finally cooling to room temperature along with the furnace to obtain the porous honeycomb-shaped intermediate material.
After the reaction is finished, the soluble lithium salt in the porous honeycomb intermediate material is washed by deionized water and then is dried in an oven. Wherein the drying temperature is 80 ℃ and the drying time is 10 hours.
(3) Mixing the porous honeycomb intermediate material dried in the step (2) with lithium hydroxide, carrying out heat preservation treatment for 6 hours at 710 ℃ in a tube furnace under an oxygen atmosphere for supplementing lithium ions, and then cooling to room temperature along with the furnace to obtain porous honeycomb single-crystal high-nickel LiNi with complete components and complete structures 0.80 Co 0.10 Mn 0.10 O 2 Positive electrode material (nickel element molar content 80%).
Example 5
The preparation method of the porous honeycomb single-crystal high-nickel positive electrode material provided by the embodiment comprises the following steps:
(1) According to the nickel element: cobalt element: elemental manganese = 83:7:10, respectively weighing nickel acetate, cobalt acetate and manganese acetate, putting the nickel acetate, cobalt acetate and manganese acetate in a mortar together, and grinding for 1h to obtain an acetate precursor material (the molar content of nickel element is 83%).
(2) The acetate precursor material obtained in the step (1) and lithium-containing molten salt (the molar ratio of lithium hydroxide to lithium sulfate is 6:1) are mixed according to the molar ratio of transition metal element in the acetate precursor material to lithium element in the lithium-containing molten salt of 1:4.2, mixing and grinding for 10min, heating and calcining in a crucible furnace in an air atmosphere in a three-stage heating program, firstly heating to 480 ℃ at a speed of 4 ℃/min, carrying out heat preservation for 3h, then heating to 830 ℃ at a speed of 4 ℃/min, continuously carrying out heat preservation for 10h, heating to 900 ℃ at a speed of 4 ℃/min, continuously carrying out heat preservation for 2h, and finally cooling to room temperature along with the furnace to obtain the porous honeycomb-shaped intermediate material.
After the reaction is finished, the soluble lithium salt in the porous honeycomb intermediate material is washed by deionized water and then is dried in an oven. Wherein the drying temperature is 80 ℃ and the drying time is 10 hours.
(3) Mixing the porous honeycomb intermediate material dried in the step (2) with lithium hydroxide, performing heat preservation treatment for 7 hours at 650 ℃ in a tubular furnace under an oxygen atmosphere to supplement lithium ions, and then cooling to room temperature along with the furnace to obtain porous honeycomb single-crystal high-nickel LiNi with complete components and complete structures 0.83 Co 0.07 Mn 0.10 O 2 Positive electrode material (molar content of nickel element 83%).
Example 6
The preparation method of the porous honeycomb single-crystal high-nickel positive electrode material provided by the embodiment comprises the following steps:
(1) According to the nickel element: cobalt element: elemental manganese = 97:0.333:2, respectively weighing nickel oxide, cobaltosic oxide and manganese dioxide in a molar ratio, putting the nickel oxide, the cobaltosic oxide and the manganese dioxide in a mortar together, and grinding for 1.5h to obtain an oxide precursor material (the molar content of nickel element is 97%).
(2) Mixing the oxide precursor material obtained in the step (1) with lithium-containing molten salt (molten salt formed after mixing lithium hydroxide and lithium sulfate in a molar ratio of 6:1) according to a molar ratio of transition metal element in the oxide precursor material to lithium element in the lithium-containing molten salt of 1:4.2, mixing and grinding for 10min, heating and calcining in a crucible furnace in an air atmosphere in a three-stage heating program, firstly heating to 480 ℃ at a speed of 4 ℃/min, carrying out heat preservation for 3h, then heating to 830 ℃ at a speed of 4 ℃/min, continuously carrying out heat preservation for 10h, heating to 900 ℃ at a speed of 4 ℃/min, continuously carrying out heat preservation for 2h, and finally cooling to room temperature along with the furnace to obtain the porous honeycomb-shaped intermediate material.
After the reaction is finished, the soluble lithium salt in the porous honeycomb intermediate material is washed by deionized water and then is dried in an oven. Wherein the drying temperature is 80 ℃ and the drying time is 10 hours.
(3) Mixing the porous honeycomb intermediate material dried in the step (2) with lithium hydroxide, performing heat preservation treatment for 6 hours at 620 ℃ in a tubular furnace under an oxygen atmosphere for supplementing lithium ions, and then cooling to room temperature along with the furnace to obtain porous honeycomb single-crystal high-nickel LiNi with complete components and complete structures 0.97 Co 0.01 Mn 0.02 O 2 Positive electrode material (nickel element molar content 97%).
Example 7
The preparation method of the porous honeycomb single-crystal high-nickel positive electrode material provided by the embodiment comprises the following steps:
(1) According to the nickel element: manganese element: elemental iron = 83:15:2, respectively weighing nickel oxide, cobalt acetate and ferrous sulfate in a molar ratio, putting the nickel oxide, cobalt acetate and ferrous sulfate in a mortar together, and grinding for 1.5h to obtain a mixed precursor material (the molar content of nickel element is 83%).
(2) Mixing the mixed precursor material obtained in the step (1) with lithium-containing molten salt (lithium bicarbonate) according to the molar ratio of transition metal element in the mixed precursor material to lithium element in the lithium-containing molten salt of 1:2, after mixing and grinding for 15min, heating and calcining in a crucible furnace in an air atmosphere in a three-stage heating program, firstly heating to 500 ℃ at a speed of 4 ℃/min, carrying out heat preservation for 3h, then heating to 800 ℃ at a speed of 5 ℃/min, continuously carrying out heat preservation for 12h, heating to 1000 ℃ at a speed of 6 ℃/min, continuously carrying out heat preservation for 1h, and finally cooling to room temperature along with the furnace to obtain the porous honeycomb intermediate material.
After the reaction is finished, the soluble lithium salt in the porous honeycomb intermediate material is washed by deionized water and then is dried in an oven. Wherein the drying temperature is 60 ℃ and the drying time is 15h.
(3) Mixing the porous honeycomb intermediate material dried in the step (2) with lithium acetate, carrying out heat preservation treatment for 3 hours at 800 ℃ in a tubular furnace under the oxygen atmosphere for supplementing lithium ions, and then cooling to room temperature along with the furnace to obtain the porous honeycomb single-crystal high-nickel LiNi with complete components and complete structures 0.83 Mn 0.15 Fe 0.02 O 2 Positive electrode material (molar content of nickel element 83%).
Example 8
The preparation method of the porous honeycomb single-crystal high-nickel positive electrode material provided by the embodiment comprises the following steps:
(1) According to the nickel element: cobalt element: elemental titanium = 90:8:2, respectively weighing nickel oxide, cobalt monoxide and titanium dioxide according to the molar ratio, putting the nickel oxide, the cobalt monoxide and the titanium dioxide in a mortar together, and grinding for 1.5 hours to finally obtain an oxide precursor material (the molar content of nickel element is 90%).
(2) Mixing the oxide precursor material obtained in the step (1) with a lithium-containing molten salt (molten salt formed after mixing lithium nitrate and sodium nitrate in a molar ratio of 5:1) according to a molar ratio of 1:8, mixing and grinding for 15min, heating and calcining in a crucible furnace in an air atmosphere in a three-stage heating program, firstly heating to 400 ℃ at a speed of 3 ℃/min, carrying out heat preservation treatment for 5h, then heating to 750 ℃ at a speed of 6 ℃/min, continuously carrying out heat preservation treatment for 15h, heating to 910 ℃ at a speed of 8 ℃/min, continuously carrying out heat preservation treatment for 4h, and finally cooling to room temperature along with the furnace to obtain the porous honeycomb intermediate material.
After the reaction is finished, the soluble lithium salt in the porous honeycomb intermediate material is washed by deionized water and then is dried in an oven. Wherein the drying temperature is 100 ℃ and the drying time is 6 hours.
(3) Drying the porous material in the step (2)Mixing the honeycomb intermediate material and lithium nitrate in a tube furnace, performing heat preservation treatment at 600 ℃ for 10 hours in an oxygen atmosphere for supplementing lithium ions, and then cooling to room temperature along with the furnace to obtain the porous honeycomb single-crystal high-nickel LiNi with complete components and complete structures 0.90 Co 0.08 Ti 0.02 O 2 Positive electrode material (nickel element molar content 90%).
Comparative example 1
The preparation method of the non-porous single crystal type positive electrode material provided in this comparative example is substantially the same as that of example 1, except that:
first, in step (1), according to the nickel element: cobalt element: elemental manganese = 60:20: the molar ratios of 20 were weighed out respectively 30mmol of nickel acetate, 10mmol of cobalt acetate and 10mmol of manganese acetate. The nickel cobalt manganese oxalate precursor material obtained in the step (1) has a molar content of nickel element of 60%.
Secondly, in the step (2), firstly, the temperature is raised to 480 ℃ at the speed of 4 ℃/min for heat preservation for 3 hours, then the temperature is raised to 830 ℃ at the speed of 4 ℃/min for heat preservation for 10 hours, and then the temperature is raised to 970 ℃ at the speed of 4 ℃/min for heat preservation for 2 hours.
Thirdly, in the step (3), lithium carbonate is not added, but the material after washing and drying is directly subjected to heat preservation treatment (heat preservation treatment at 750 ℃ for 7 h). Because the test result shows that the lithium ion content in the sample is close to the theoretical value after water washing, the dried material is directly subjected to heat preservation treatment for 7 hours at 750 ℃ in a tube furnace under the oxygen atmosphere, and then is cooled to room temperature along with the furnace, thus obtaining the non-porous single crystal LiNi with complete components and complete structures 0.60 Co 0.20 Mn 0.20 O 2 Positive electrode material (molar content of nickel element 60%).
Comparative example 2
The preparation method of the non-porous single-crystal type cathode material provided in the present comparative example is basically the same as that of example 1, except that in the step (2), the temperature is first raised to 480 ℃ at a speed of 4 ℃/min for heat preservation treatment for 4 hours, and then raised to 830 ℃ at a speed of 4 ℃/min for heat preservation treatment for 11 hours (i.e., two-stage temperature rise is performed).
Comparative example 3
The preparation method of the non-porous single crystal type positive electrode material provided in the comparative example is basically the same as that of example 1, except that in the step (2), the temperature is firstly raised to 600 ℃ at the speed of 4 ℃/min for 3 hours, then the temperature is raised to 900 ℃ at the speed of 4 ℃/min for 10 hours, and then the temperature is raised to 800 ℃ at the speed of 4 ℃/min for 2 hours.
Comparative example 4
The method for producing a non-porous single-crystal type positive electrode material provided in this comparative example is substantially the same as in example 1, except that the step (2) is a heat calcination (i.e., first calcination) in an oxygen atmosphere (pure oxygen atmosphere).
Comparative example 5
The preparation method of the non-porous single-crystal cathode material provided in this comparative example is substantially the same as that of example 1, except that in step (1), the following nickel element: cobalt element: elemental manganese = 65:15: the molar ratio of 20 is respectively weighed nickel acetate, cobalt acetate and manganese acetate.
Experimental example 1
The results of ICP detection of the water-washed intermediate materials obtained in step (2) and the positive electrode materials obtained in step (3) in examples 1 to 6 and comparative example 1, respectively, and the atomic ratios of lithium, nickel, cobalt, and manganese were calculated, are shown in table 1.
Table 1 results of atomic ratios of lithium, nickel, cobalt, manganese for the materials of the groups
As can be seen from table 1, the molar content of nickel in the product of comparative example 1=60%, and the content of lithium element in the intermediate material after washing with water is close to the stoichiometric ratio, so that no additional lithium ions need to be added in the subsequent calcination process.
The molar content of nickel in the products of the examples 1 to 6 is more than or equal to 70 percent, and the content of lithium element in the intermediate materials after water washing is far less than the stoichiometric ratio, so that further lithium supplementation is needed to perfect the components.
After washing with water and re-calcining (i.e. second calcining), the atomic ratios of lithium, nickel, cobalt and manganese in the products of comparative example 1 and examples 1 to 6 are all close to theoretical values, which indicates that the component contents of the products of examples 1 to 6 are improved after lithium supplementation.
Experimental example 2
The positive electrode materials prepared in comparative example 1, example 1 and example 2 were subjected to FESEM detection, respectively, and the results are shown in fig. 1, fig. 2 and fig. 3, respectively.
As can be seen from FIG. 1, the non-porous single-crystal LiNi obtained in comparative example 1 0.6 Co 0.2 Mn 0.2 O 2 The particle size of the positive electrode material reaches the micron level, the particle surface is smooth, the existence of holes cannot be observed, and the positive electrode material belongs to the conventional single crystal particle morphology.
As can be seen from FIG. 2, the porous honeycomb single-crystal type high nickel LiNi prepared in example 1 0.75 Co 0.10 Mn 0.15 O 2 The positive electrode material reached micron-sized particles with a rough particle surface, and the presence of fine pore structures was observed, unlike the conventional single crystal particle morphology of fig. 1.
As can be seen from FIG. 3, the porous honeycomb single-crystal type high nickel LiNi prepared in example 2 0.92 Co 0.03 Mn 0.05 O 2 The particle size of the positive electrode material reaches the micron level, the particle surface is very rough, and a plurality of larger hole structures are distributed on the particle surface, which is obviously different from the conventional single crystal particle morphology in fig. 1.
Meanwhile, XRD detection was performed on the positive electrode materials prepared in examples 1 and 2 of the present invention, respectively, and the results are shown in fig. 4. FIG. 4 (a) shows a porous honeycomb single-crystal type high nickel LiNi obtained in example 1 0.75 Co 0.10 Mn 0.15 O 2 XRD pattern of the positive electrode material; FIG. 4 (b) shows a porous honeycomb single-crystal type high nickel LiNi obtained in example 2 0.92 Co 0.03 Mn 0.05 O 2 XRD pattern of the positive electrode material.
As can be seen from FIG. 4, the positive electrode materials prepared in example 1 and example 2 have diffraction peaks both of which are equal to those of hexagonal alpha-NaFeO 2 The layered structure corresponds, the two pairs of diffraction peaks (006)/(012) and (018)/(110) are separated significantly,the positive electrode materials have good lamellar structures, and the ratio of the I (003)/I (104) peak intensity of the positive electrode materials to the I (003)/I (104) peak intensity of the positive electrode materials is larger than 1.2, which indicates that the lithium nickel mixing degree of the two materials after the lithium supplementing calcination is lower.
Experimental example 3
The positive electrode materials prepared in each example and each comparative example are respectively mixed with a conductive agent and a binder according to the mass ratio of 9:0.4: and 0.6 proportion of the aluminum foil is dispersed in a 1-methyl-2-pyrrolidone organic solvent for size mixing, then the size is coated on the aluminum foil, and after drying and rolling, a Cheng Dianji wafer is cut and used as a positive plate. And assembling the positive electrode sheet, the counter electrode lithium sheet and the diaphragm into the 2016-type button cell in a glove box protected by argon. Each cell was then subjected to electrochemical performance testing (first discharge capacity at 2C current density and capacity after 100 cycles) using a cell electrochemical tester, and the results are shown in table 2.
Table 2 results of electrochemical performance test of each group of cells
| Group of | First discharge capacity (mAh/g) | Capacity after 100 cycles (mAh/g) | Capacity retention (%) |
| Example 1 | 166.7 | 145.5 | 87.3％ |
| Example 2 | 189.6 | 170.1 | 89.7％ |
| Example 3 | 161.3 | 143.5 | 88.96％ |
| Example 4 | 170.2 | 149.9 | 88.07％ |
| Example 5 | 174.8 | 152.8 | 87.41％ |
| Example 6 | 199.5 | 178.6 | 89.52％ |
| Example 7 | 173.7 | 157.7 | 90.79％ |
| Example 8 | 185.9 | 169.6 | 91.23％ |
| Comparative example 1 | 148.7 | 125.8 | 84.60％ |
| Comparative example 2 | 161.4 | 148.2 | 79.43％ |
| Comparative example 3 | 160.5 | 138.7 | 84.55％ |
| Comparative example 4 | 159.8 | 133.2 | 83.35％ |
| Comparative example 5 | 152.1 | 129.6 | 85.21％ |
As can be seen from table 2, the electrochemical performance of each example was superior to each comparative example.
Wherein, the first discharge capacity of example 2 at 2C current density is 189.6mAh/g, the capacity after 100 circles is 170.1mAh/g, and the capacity retention rate is 89.7%.
Therefore, the porous honeycomb single-crystal type high-nickel single-crystal positive electrode material prepared by the preparation method provided by the invention has a porous structure, higher charge-discharge specific capacity and stable long-cycle performance.
The charge-discharge cycle performance chart of example 1 at a current density of 2C is shown in fig. 5. The charge-discharge cycle performance chart of example 2 at a current density of 2C is shown in fig. 6.
While the invention has been illustrated and described with reference to specific embodiments, it is to be understood that the above embodiments are merely illustrative of the technical aspects of the invention and not restrictive thereof; those of ordinary skill in the art will appreciate that: modifications may be made to the technical solutions described in the foregoing embodiments, or equivalents may be substituted for some or all of the technical features thereof, without departing from the spirit and scope of the present invention; such modifications and substitutions do not depart from the spirit of the corresponding technical solutions; it is therefore intended to cover in the appended claims all such alternatives and modifications as fall within the scope of the invention.
Claims (9)
1. The preparation method of the porous honeycomb single-crystal high-nickel positive electrode material is characterized by comprising the following steps of:
(a) Uniformly mixing the high-nickel precursor material and lithium-containing molten salt, and then performing first calcination in a low-oxygen atmosphere with the oxygen volume fraction of less than 60% to obtain a porous honeycomb intermediate material;
(b) Uniformly mixing the porous honeycomb intermediate material obtained in the step (a) with a lithium-containing compound, and then performing second calcination in a pure oxygen atmosphere to obtain the porous honeycomb single-crystal high-nickel anode material;
in the step (a), the molar content of nickel element in the high-nickel precursor material is more than or equal to 70%;
in step (a), the first calcining comprises: firstly, preserving heat for 2-6 hours at 350-550 ℃, then preserving heat for 8-16 hours at 700-850 ℃, and further preserving heat for 1-5 hours at 900-1000 ℃;
in the step (a), in the first calcination process, the molar ratio of lithium element in the lithium-containing molten salt to transition metal element in the high-nickel precursor material is more than or equal to 1.5;
in step (a), the lithium-containing molten salt comprises a lithium-containing compound or a molten salt formed after mixing the lithium-containing compound with an inorganic salt; the lithium-containing compound is at least one of lithium oxide, lithium hydroxide, lithium bicarbonate, lithium carbonate, lithium sulfate, lithium nitrate, lithium acetate, lithium oxalate and lithium chloride; the inorganic salt comprises sodium salt and/or potassium salt;
In the step (b), the temperature of the second calcination is 500-800 ℃, and the heat preservation time is 3-15 h;
in the step (b), the lithium-containing compound is at least one of lithium oxide, lithium hydroxide, lithium bicarbonate, lithium carbonate, lithium sulfate, lithium nitrate, lithium acetate, lithium oxalate, and lithium chloride.
2. The method of preparing a porous honeycomb single-crystal-form high-nickel positive electrode material according to claim 1, wherein in step (a), the first calcination comprises: the temperature is kept for 3-5 hours at 400-500 ℃, then kept for 10-15 hours at 750-840 ℃, and then kept for 2-4 hours at 910-960 ℃.
3. The method of preparing a porous honeycomb single-crystal type high-nickel positive electrode material according to claim 1, wherein in the step (a), in the first calcination process, a molar ratio of lithium element in the lithium-containing molten salt to transition metal element in the high-nickel precursor material is 2 to 10:1.
4. the method for preparing a porous honeycomb single-crystal type high-nickel positive electrode material according to claim 1, wherein the lithium-containing molten salt mainly comprises the following components in a molar ratio of 4-8: 1 and lithium sulfate.
5. The method for producing a porous honeycomb single-crystal-form high-nickel positive electrode material according to claim 1, wherein in the step (b), the porous honeycomb intermediate material and the lithium-containing compound are washed and dried before the mixing is performed, and the porous honeycomb intermediate material obtained in the step (a) is further washed and dried.
6. The method for producing a porous honeycomb single-crystal type high-nickel positive electrode material according to claim 1, wherein the porous honeycomb single-crystal type high-nickel positive electrode material obtained in the step (b) has a particle size of 1 to 8 μm.
7. The porous honeycomb single-crystal high-nickel cathode material prepared by the preparation method of the porous honeycomb single-crystal high-nickel cathode material according to any one of claims 1-6.
8. The positive electrode plate is characterized by being mainly prepared from the porous honeycomb single-crystal type high-nickel positive electrode material of claim 7.
9. A lithium ion battery comprising the positive electrode sheet of claim 8.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211294453.0A CN115432750B (en) | 2022-10-21 | 2022-10-21 | Porous honeycomb single-crystal high-nickel positive electrode material, and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211294453.0A CN115432750B (en) | 2022-10-21 | 2022-10-21 | Porous honeycomb single-crystal high-nickel positive electrode material, and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115432750A CN115432750A (en) | 2022-12-06 |
| CN115432750B true CN115432750B (en) | 2023-11-21 |
Family
ID=84252185
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211294453.0A Active CN115432750B (en) | 2022-10-21 | 2022-10-21 | Porous honeycomb single-crystal high-nickel positive electrode material, and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115432750B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117276532B (en) * | 2023-11-21 | 2024-03-29 | 宜宾锂宝新材料有限公司 | High-tap-density positive electrode material, preparation method thereof and lithium battery |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09320584A (en) * | 1996-03-26 | 1997-12-12 | Sharp Corp | Manufacture of positive electrode active material and nonaqueous secondary battery |
| CN107528064A (en) * | 2017-08-10 | 2017-12-29 | 广东邦普循环科技有限公司 | A kind of high voltage type class monocrystalline tertiary cathode material and preparation method thereof |
| KR20180114412A (en) * | 2017-04-10 | 2018-10-18 | 주식회사 엘지화학 | Positive electrode active material for secondary battery, method for producing the same, positive electrode and secondary battery comprising the same |
| CN109301186A (en) * | 2018-09-10 | 2019-02-01 | 清远佳致新材料研究院有限公司 | A kind of tertiary cathode material and preparation method thereof of cladded type porous structure |
| CN110137488A (en) * | 2019-05-28 | 2019-08-16 | 郑州中科新兴产业技术研究院 | A kind of nickelic positive electrode of secondary lithium batteries and preparation method thereof |
| CN114551839A (en) * | 2022-02-25 | 2022-05-27 | 中南大学 | Pre-lithiation of single crystal type cobalt-free high-nickel positive electrode material and preparation method thereof |
| CN114940519A (en) * | 2022-06-20 | 2022-08-26 | 泾河新城陕煤技术研究院新能源材料有限公司 | Preparation method of high-nickel monocrystal nickel cobalt lithium manganate ternary cathode material |
-
2022
- 2022-10-21 CN CN202211294453.0A patent/CN115432750B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09320584A (en) * | 1996-03-26 | 1997-12-12 | Sharp Corp | Manufacture of positive electrode active material and nonaqueous secondary battery |
| KR20180114412A (en) * | 2017-04-10 | 2018-10-18 | 주식회사 엘지화학 | Positive electrode active material for secondary battery, method for producing the same, positive electrode and secondary battery comprising the same |
| CN107528064A (en) * | 2017-08-10 | 2017-12-29 | 广东邦普循环科技有限公司 | A kind of high voltage type class monocrystalline tertiary cathode material and preparation method thereof |
| CN109301186A (en) * | 2018-09-10 | 2019-02-01 | 清远佳致新材料研究院有限公司 | A kind of tertiary cathode material and preparation method thereof of cladded type porous structure |
| CN110137488A (en) * | 2019-05-28 | 2019-08-16 | 郑州中科新兴产业技术研究院 | A kind of nickelic positive electrode of secondary lithium batteries and preparation method thereof |
| CN114551839A (en) * | 2022-02-25 | 2022-05-27 | 中南大学 | Pre-lithiation of single crystal type cobalt-free high-nickel positive electrode material and preparation method thereof |
| CN114940519A (en) * | 2022-06-20 | 2022-08-26 | 泾河新城陕煤技术研究院新能源材料有限公司 | Preparation method of high-nickel monocrystal nickel cobalt lithium manganate ternary cathode material |
Non-Patent Citations (1)
| Title |
|---|
| LiNi_(0.8)Co_(0.2)O_2正极材料的空气气氛烧结合成与电化学性能;陈凯;刘兴泉;马慎思;寇丹;张峥;;储能科学与技术(06);603-609 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115432750A (en) | 2022-12-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP7241875B2 (en) | Cathode material for high-power lithium-ion battery and method for producing the same | |
| CN107275633B (en) | Gradient fluorine-doped ternary cathode material with low lattice stress and preparation method thereof | |
| CN102694167B (en) | Modified lithium manganate positive pole material and preparation method thereof | |
| US7645542B2 (en) | Active material for positive electrode in non-aqueous electrolyte secondary battery having SO4 ions | |
| CN106340638B (en) | A kind of high-rate lithium-rich manganese-based anode material of double layer hollow structure and preparation method thereof | |
| JP7204049B2 (en) | Lithium manganese rich material, method of making and use thereof | |
| CN106784790B (en) | A kind of preparation method of nickle cobalt lithium manganate tertiary cathode material | |
| CN110911687A (en) | Rare earth element modified lithium ion battery positive electrode material, and preparation method and application thereof | |
| CN103606663B (en) | A kind of Multiplying-power lithium-rich composite anode material and preparation method thereof | |
| WO2015039490A1 (en) | Lithium-rich anode material and preparation method thereof | |
| CN105514373A (en) | Positive electrode material of high-capacity lithium ion battery and preparation method of positive electrode material | |
| CN110233250A (en) | A kind of preparation method of single crystal grain tertiary cathode material | |
| CN105024067B (en) | Lithium ion battery, composite doped modified positive active material thereof and preparation method | |
| CN108448109A (en) | A kind of stratiform lithium-rich manganese-based anode material and preparation method thereof | |
| CN109888225A (en) | Positive electrode and preparation method thereof and lithium ion battery | |
| CN115432750B (en) | Porous honeycomb single-crystal high-nickel positive electrode material, and preparation method and application thereof | |
| CN102361074A (en) | Lithium ion battery anode nano material with ultrahigh rate and preparation method for same | |
| CN106450283A (en) | Preparing method of lithium-rich ternary anode material with high power capacity | |
| CN110867577A (en) | 811NCM ternary cathode material with three-dimensional nanowire array structure and preparation method thereof | |
| CN115010190A (en) | High-entropy oxide cathode material and preparation method and application thereof | |
| CN115395007A (en) | Layered-spinel composite phase monocrystal lithium-rich manganese-based positive electrode material and application thereof | |
| CN105185981B (en) | A kind of LiNixMn2-xO4The preparation method of positive electrode | |
| CN110350171A (en) | A kind of preparation method of the high ni-type tertiary cathode material of rubidium element doping | |
| CN112635750A (en) | Phosphorus-doped ternary lithium ion positive electrode material, preparation method thereof and lithium ion battery | |
| CN110112371A (en) | A kind of method of surface coating modification Spinel positive electrode |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |