CN115432750A - Porous honeycomb single crystal type high-nickel anode material and preparation method and application thereof - Google Patents
Porous honeycomb single crystal type high-nickel anode material and preparation method and application thereof Download PDFInfo
- Publication number
- CN115432750A CN115432750A CN202211294453.0A CN202211294453A CN115432750A CN 115432750 A CN115432750 A CN 115432750A CN 202211294453 A CN202211294453 A CN 202211294453A CN 115432750 A CN115432750 A CN 115432750A
- Authority
- CN
- China
- Prior art keywords
- lithium
- nickel
- porous honeycomb
- single crystal
- type high
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 216
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 144
- 239000013078 crystal Substances 0.000 title claims abstract description 89
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 239000010405 anode material Substances 0.000 title claims abstract description 30
- 239000000463 material Substances 0.000 claims abstract description 99
- 238000001354 calcination Methods 0.000 claims abstract description 45
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 42
- 238000002156 mixing Methods 0.000 claims abstract description 40
- 239000002243 precursor Substances 0.000 claims abstract description 37
- 150000003839 salts Chemical class 0.000 claims abstract description 35
- 239000012298 atmosphere Substances 0.000 claims abstract description 34
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 34
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 33
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 30
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 30
- 239000007774 positive electrode material Substances 0.000 claims abstract description 29
- 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 17
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000010406 cathode material Substances 0.000 claims description 47
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 45
- 239000002245 particle Substances 0.000 claims description 35
- 238000001035 drying Methods 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 20
- 229910052723 transition metal Inorganic materials 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
- 238000005406 washing Methods 0.000 claims description 11
- 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
- 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
- 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
- 230000002708 enhancing effect Effects 0.000 abstract description 2
- 238000010438 heat treatment Methods 0.000 description 34
- 238000004321 preservation Methods 0.000 description 31
- 235000002639 sodium chloride Nutrition 0.000 description 30
- 230000000052 comparative effect Effects 0.000 description 23
- 239000011572 manganese Substances 0.000 description 22
- 229910013716 LiNi Inorganic materials 0.000 description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 20
- 238000001816 cooling Methods 0.000 description 17
- 239000008367 deionised water Substances 0.000 description 17
- 229910021641 deionized water Inorganic materials 0.000 description 17
- 238000000227 grinding Methods 0.000 description 13
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 12
- 238000006243 chemical reaction Methods 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
- 230000005540 biological transmission Effects 0.000 description 8
- 230000001413 cellular effect Effects 0.000 description 8
- 230000001502 supplementing effect Effects 0.000 description 8
- 229940011182 cobalt acetate Drugs 0.000 description 6
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 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 5
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- 229940071125 manganese acetate Drugs 0.000 description 5
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 5
- 229940078494 nickel acetate Drugs 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000005303 weighing Methods 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
- 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 4
- 238000011161 development Methods 0.000 description 4
- 238000001914 filtration Methods 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
- 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
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000008602 contraction Effects 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 238000000349 field-emission scanning electron micrograph Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229910052748 manganese Inorganic materials 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
- 230000000877 morphologic effect Effects 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-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
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 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 2
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(II) oxide Inorganic materials [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000011056 performance test Methods 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
- 239000013589 supplement Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 208000032953 Device battery issue Diseases 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
- 125000000129 anionic group Chemical group 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application 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
- 230000001351 cycling 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
- 230000002349 favourable effect Effects 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 239000003014 ion exchange membrane Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate 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
- 238000003801 milling Methods 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
- 239000012071 phase Substances 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
- 230000008439 repair process Effects 0.000 description 1
- 238000011160 research Methods 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
- 230000009469 supplementation Effects 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 235000012431 wafers Nutrition 0.000 description 1
Images
Classifications
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- 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
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- 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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
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- 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
Abstract
The invention relates to the technical field of lithium ion batteries, in particular to a porous honeycomb single crystal type high-nickel anode material and a preparation method and application thereof. The preparation method comprises the following steps: after being uniformly mixed with lithium-containing molten salt, the high-nickel precursor material is subjected to first calcination in a low-oxygen atmosphere with the oxygen volume fraction of below 60 percent to obtain a porous honeycomb intermediate material; uniformly mixing the porous honeycomb intermediate material with lithium salt, and then carrying out secondary calcination in pure oxygen atmosphere to obtain a porous honeycomb single crystal type high-nickel positive electrode material; the molar content of nickel element in the high-nickel precursor material is more than or equal to 70 percent; the first calcination includes: preserving heat for 2-6 h at 350-550 ℃, then preserving heat for 8-16 h at 700-850 ℃, and then preserving heat for 1-5 h at 900-1000 ℃. The preparation method can form a porous honeycomb structure, thereby enhancing the structural stability of the material, improving the electrochemical performance of the anode material, and particularly improving the capacity and the cycle stability.
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 anode material and a preparation method and application thereof.
Background
The urgent need of human society for portable quick charging equipment and high-endurance pure electric vehicles provides challenges for the development of high-energy and high-power-density lithium ion power batteries. The traditional high-nickel cathode material is easy to generate morphological and structural damage under the condition of large current due to the inherent polycrystalline spherical structure, so that the lithium ion transmission kinetics of the traditional high-nickel cathode material is slow. The existing research reports that the stability of the material is improved through anion/cation doping, surface coating, a concentration gradient structure and morphology regulation. These strategies have a significant effect on extending cycle life, but do not significantly improve performance under high current conditions.
To develop high power density lithium ion batteries, commonly employed methods include electrode design and morphology engineering. In terms of electrode design, electron transport and lithium ion passage are generally shortened by reducing the thickness of the electrode, modifying the current collector, or adjusting the addition amount and morphology of the conductive agent. Meanwhile, from the particle level, the rapid charging and discharging capacity of the anode material can be improved by regulating the appearance and the size of the anode material. For example, the positive electrode material particles are designed to have a hollow or porous honeycomb structure or a small particle structure through morphological engineering, so that the large specific surface area of the active material can be fully utilized, the contact with the electrolyte is enhanced, and the mobility of lithium ions is improved, which has attracted great interest. However, this method is usually carried out by additionally introducing a surfactant/etchant/complex ion-forming agent. Moreover, what is easily overlooked is that these methods cannot ensure structural stability under severe operating conditions, and the high-nickel positive electrode material may still have particle breakage and serious irreversible phase change, resulting in battery failure.
Single crystal type high nickel cathode materials are gaining favor due to their excellent thermal stability and cycling performance, and more stable structures. However, the conventional single crystal type particles have a dense structure inside, so that the capacity under a high current condition is relatively low, the full exertion of electrochemical performance is limited, and the further commercial development of the single crystal large-particle high-nickel cathode material is hindered.
Therefore, the development of a novel morphological engineering technology applied to the synthesis and preparation of the porous cellular single-crystal high-nickel anode material with micron-sized particles and higher nickel content has important significance for the development of lithium ion batteries.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The first purpose of the invention is to provide a preparation method of a porous honeycomb single crystal type high-nickel cathode material, which can form a special porous honeycomb structure, wherein the structure can enhance the structural stability of the material, improve the electrochemical performance of the cathode material, and particularly improve the capacity and the cycle stability of the cathode material.
The second purpose of the invention is to provide a porous honeycomb single crystal type high-nickel cathode material.
The third purpose of the invention is to provide a positive pole piece.
A fourth object of the present invention is to provide a lithium ion battery.
In order to achieve the above purpose of the present invention, the following technical solutions are adopted:
in a first aspect, the invention provides a preparation method of a porous honeycomb single crystal type high-nickel anode material, which comprises the following steps:
(a) After being uniformly mixed with the lithium-containing molten salt, the high-nickel precursor material is subjected to first calcination in a low-oxygen atmosphere with an oxygen volume fraction of 60% or less (including but not limited to the point value of any one of 55%, 50%, 45%, 40%, 35%, 30%, 25%, 20% and 15% or the range value between any two), so as to obtain the porous honeycomb intermediate material. The porous honeycomb intermediate material prepared at this time is a lithium-deficient material with a defective structure.
In some specific embodiments of the present invention, in step (a), the low-oxygen atmosphere with an oxygen volume fraction of 60% or less includes, but is not limited to, air, or a low-oxygen atmosphere gas obtained by adjusting a ratio of oxygen to other gases, wherein the other gases include, but are not limited to, nitrogen or argon.
After the lithium-containing molten salt is added in the step (a), the first calcination is carried out in a low-oxygen atmosphere, and the high-nickel precursor material can form large single crystal particles in a molten salt environment. The first two stages of calcination in the first calcination are to form large single crystal particles with a layered structure, and the third stage of calcination can partially decompose the large single crystal particles, so that internal lithium ions are extracted, an obvious defect structure can be formed, and a porous structure (a pore structure) can be formed.
By combining three-stage heating high-temperature calcination reaction in a molten salt environment, the precursor material can be converted into micron-sized single crystal large particles, and a porous honeycomb special structure can be formed on a single crystal particle main body, so that the electrolyte can be permeated, the lithium ion movement path can be shortened, the rapid transmission of lithium ions in the single crystal large particles can be promoted, the electrochemical performance of the single crystal high-nickel anode material under high current density can be improved, and the problem of low electrochemical performance caused by long lithium ion output path in the single crystal anode material particles can be effectively solved. And the advantage of ion transmission speed makes the electrochemical performance of the ion-exchange membrane more outstanding.
(b) And (b) uniformly mixing the porous honeycomb intermediate material obtained in the step (a) with lithium salt, and then carrying out secondary calcination in a pure oxygen atmosphere to supplement lithium, thereby obtaining the porous honeycomb single-crystal type high-nickel cathode material with complete components and a complete laminated structure.
In the step (b), the porous honeycomb intermediate material and the lithium salt are subjected to secondary calcination in a pure oxygen atmosphere to supplement lithium, so that a positive electrode material with a good structure can be formed, and the performance of the positive electrode material is improved.
In the step (a), the molar content of nickel element in the high-nickel precursor material is more than or equal to 70 percent; including but not limited to, dot values of any one of 71%, 72%, 73%, 75%, 78%, 80%, 83%, 85%, 90%, 95%, 98%, 99%, or range values between any two. The molar content of the nickel element in the high-nickel precursor material refers to the molar percentage of the nickel element in the high-nickel precursor material in the transition metal elements (the sum of the molar contents of the transition metal elements) in the high-nickel precursor material.
The high nickel precursor material with the nickel content is favorable for forming a hole structure.
In addition, the mass fraction of nickel element in the porous honeycomb single crystal type high-nickel anode material prepared in the step (b) is more than or equal to 70 percent; including but not limited to, dot values of any one of 71%, 72%, 73%, 75%, 78%, 80%, 83%, 85%, 90%, 95%, 98%, 99%, or range values between any two. The molar content of the nickel element in the porous honeycomb single-crystal-type high-nickel cathode material refers to the molar weight percentage of the nickel element in the porous honeycomb single-crystal-type high-nickel cathode material in the transition metal elements (the 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: the method comprises the steps of preserving heat for 2-6 h (including but not limited to the point value of any one of 3h, 4h and 5h or the range value between any two) at 350-550 ℃ (including but not limited to the point value of 370 ℃, 390 ℃, 400 ℃, 420 ℃, 450 ℃, 480 ℃, 500 ℃ and 530 ℃ or the range value between any two), then preserving heat for 8-16 h (including but not limited to the point value of any one of 9h, 10h, 12h, 14h and 15h or the range value between any two) at 700-850 ℃ (including but not limited to the point value of any one of 720 ℃, 740 ℃, 750 ℃, 780 ℃, 800 ℃ and 830 ℃ or the range value between any two) and preserving heat for 1-5 h (including but not limited to the point value of any one of 900-1000 ℃ (including but not limited to 920 ℃, 940 ℃, 950 ℃, 970 ℃, 990 ℃ or the range value between any two) at 900-1000 ℃ (including but not limited to the point value of any one of 2h, 3h and 4h or the range value between any two).
According to the preparation method provided by the invention, the porous honeycomb-shaped 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 of the micron-sized single crystal anode material are solved. Due to the special appearance of the prepared honeycomb single crystal particles, the honeycomb single crystal high-nickel anode material has the characteristic that the single crystal particles relieve the stress generated by expansion and contraction in the charging and discharging processes; meanwhile, the honeycomb structure has abundant space channels, so that the size of micron-sized single crystal particles is kept, the contact surface with electrolyte is promoted, the lithium ion transmission speed is increased, and the disadvantage that the electrochemical performance of the single crystal particles is poor due to the fact that the lithium ion transmission speed is low is improved.
The honeycomb monocrystal high-nickel anode material (namely the porous honeycomb monocrystal type high-nickel anode 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 anode material and enhancing the structural stability of the material.
Moreover, the high-nickel cathode material with the nickel content exceeding (more than or equal to) 70% can exert the high-capacity characteristic of the high-nickel cathode material to a greater extent, and simultaneously the electrochemical performance of the high-nickel cathode material is further improved by combining with the special porous honeycomb structure.
In addition, the first calcination is performed 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 preserved for 3 to 5 hours at 400 to 500 ℃, then preserved for 10 to 15 hours at 750 to 840 ℃ and preserved for 2 to 4 hours at 910 to 960 ℃.
Preferably, in step (a), during the first calcination, the molar ratio of the lithium element in the lithium-containing molten salt to the transition metal element in the high-nickel precursor material is ≧ 1.5, including but not limited to the point of any one of 2, 3, 4, 5, 6, 7, 8, 9, 10, 13, 15, 18, 20 or a range of values between any two; the preferred molar ratio is 2 to 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 plural kinds, the molar amount of the transition metal element in the above molar ratio is the sum of the molar amounts of all the transition metal elements.
Preferably, in step (a), the lithium-containing molten salt comprises a lithium salt, or a molten salt formed by mixing the lithium salt with an inorganic salt. That is, the molten lithium-containing salt may be a lithium salt as it is, or a molten salt obtained by mixing a lithium salt and an inorganic salt at an arbitrary molar ratio.
The molten lithium-containing salt added in step (b) is used for forming large single-crystal grains and forming a porous honeycomb 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 of them 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 comprises at least one of potassium carbonate, potassium nitrate, potassium chloride and potassium sulfate.
Preferably, the molten lithium-containing salt consists essentially of, in a molar ratio of 4 to 8:1, lithium hydroxide and lithium sulfate; wherein the molar ratio includes, but is not limited to, the following values of any one of 5, 6, 1, 7, or a range between any two.
The use of the molten lithium-containing salt of the above-specified composition is advantageous in promoting the formation of a porous honeycomb structure.
In some specific embodiments of the present invention, in the step (a), the high nickel precursor material may be prepared by any conventional preparation method, such as physical or chemical methods, including but not limited to solid phase method, coprecipitation method, sol-gel method, spray drying method, combustion method, and the like. Wherein. Meanwhile, the particle morphology of the high nickel precursor material may be any and 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 (a). In addition, anionic, cationic substitution or doping is also included.
In some specific embodiments of the present invention, in step (a), the temperature increase rate of the first calcination is 2-10 ℃/min, including but not limited to the point value of any one of 3 ℃/min, 4 ℃/min, 5 ℃/min, 6 ℃/min, 7 ℃/min, 8 ℃/min, 9 ℃/min or the range value between any two.
In some embodiments of the invention, in step (a), the first calcination is performed in a crucible furnace.
In some embodiments of the invention, in step (a), the method of mixing uniformly comprises mixing and grinding; preferably, the time of milling is 10 to 20min, including but not limited to a point value of any one of 12min, 14min, 15min, 18min or a range value between any two.
In some specific embodiments of the present invention, in step (a), the particle size of the high nickel precursor material is 50 to 800nm, including but not limited to values in the range of any one of 70nm, 90nm, 100nm, 130nm, 150nm, 200nm, 250nm, 300nm, 400nm, 500nm, 600nm, 700nm, 750nm, or any range therebetween.
Preferably, in the step (b), 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 (c) adding lithium salt in the step (b) for supplementing lithium, thereby forming the cathode material with a good structure.
Preferably, in step (b), the porous honeycomb intermediate material and the lithium salt further comprise the step of washing and drying the porous honeycomb intermediate material obtained in step (a) before said mixing.
In some embodiments of the present invention, the washing is performed with water (e.g., deionized water), and the number of washing is 2 to 5, and optionally 3 or 4.
The porous honeycomb intermediate material prepared in step (a) is a mixture of single crystal particles and lithium salt, and the soluble lithium salt in the mixture can be removed by washing. Meanwhile, the washing causes the crystal structure on the surface of the porous honeycomb intermediate material to be damaged, so that lithium is supplemented and re-calcination (i.e., second calcination) is performed to repair the structure.
In some specific embodiments of the present invention, the temperature of the drying is 40 to 120 ℃, including but not limited to the point value of any one of 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃, 110 ℃ or the 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 between any two.
In some specific embodiments of the present invention, in the 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 calculated and added according to the molar content ratio of lithium element to (all) transition metal elements in the prepared porous honeycomb single crystal type high nickel cathode material being 1.
Preferably, in step (b), the temperature of the second calcination is 500 to 800 ℃, including but not limited to the values of any one of 550 ℃, 600 ℃, 650 ℃, 700 ℃, 750 ℃ or the range values between any two; the holding time of the second calcination is 3-15 h, including but not limited to the value of any one of 5h, 8h, 10h, 12h and 14h or the range value between any two.
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 the 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 present invention, in step (b), the temperature increase rate of the second calcination is 2-10 ℃/min, including but not limited to the point value of any one of 3 ℃/min, 4 ℃/min, 5 ℃/min, 6 ℃/min, 7 ℃/min, 8 ℃/min, 9 ℃/min or the range value between any two of them.
In some specific embodiments of the invention, in step (a), the second calcination is performed in a tube furnace.
Preferably, the particle size of the porous honeycomb single crystal type high nickel cathode material obtained in the step (b) is 1-8 μm.
In a second aspect, the invention provides the 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 anode material provided by the invention has a high-capacity characteristic, wherein the porous honeycomb structure can relieve stress generated by expansion and contraction in the charging and discharging processes, and the honeycomb structure has abundant space channels, so that the contact surface with an electrolyte is increased while the size of micron-sized single crystal particles is maintained, and the lithium ion transmission speed is increased.
The porous honeycomb monocrystal type high-nickel anode material has excellent electrochemical performance, particularly higher charge-discharge specific capacity and stable long cycle performance.
In a third aspect, the invention provides a positive pole piece, which is mainly prepared from the porous honeycomb single-crystal type high-nickel positive pole material.
In a fourth aspect, the present invention provides a lithium ion battery, including the positive electrode plate described above.
The lithium ion battery has excellent electrochemical performance, and particularly has high 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 anode material provided by the invention can form a porous honeycomb structure, and the porous honeycomb special structure has rich space channels, so that the permeation of electrolyte is facilitated, the movement path of lithium ions is shortened, the rapid transmission of the lithium ions in large single crystal particles is promoted, and the electrochemical performance of the single crystal high-nickel anode material under high current density is improved. 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 type high-nickel anode material provided by the invention can improve the electrochemical performance of the anode material and enhance the structural stability of the material.
(3) The preparation method of the porous honeycomb single crystal type high-nickel cathode material provided by the invention can be used for preparing the high-nickel cathode material with the nickel content exceeding 70%, and is beneficial to exerting the high-capacity characteristic of the high-nickel cathode material to a greater extent.
(4) The porous honeycomb monocrystal type high-nickel anode material provided by the invention has excellent electrochemical performance, and particularly has high 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 used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is a view showing a non-porous single crystal type LiNi obtained in comparative example 1 0.6 Co 0.2 Mn 0.2 O 2 FESEM image of 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 is a porous honeycomb single crystal type high nickel LiNi prepared in example 1 0.75 Co 0.10 Mn 0.15 O 2 FESEM images of positive electrode materials; 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 type high nickel LiNi prepared in example 2 0.92 Co 0.03 Mn 0.05 O 2 FESEM images of positive electrode materials; 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; wherein, FIG. 4 (a) shows porous honeycomb single crystal type high nickel LiNi prepared in example 1 0.75 Co 0.10 Mn 0.15 O 2 XRD pattern of the positive electrode material; FIG. 4 (b) shows LiNi of high nickel of porous honeycomb single crystal type 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 the charge and discharge cycle performance at 2C current density for the assembled battery of example 1;
fig. 6 is a graph of the charge and discharge cycle performance at 2C current density for the assembled cell of example 2.
Detailed Description
The technical solutions of the present invention will be clearly and completely described below with reference to the accompanying drawings and the detailed description, but those skilled in the art will understand that the following described embodiments are some, not all, of the embodiments of the present invention, and are only used for illustrating the present invention, and should not be construed as limiting the scope of the present invention. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
Example 1
The preparation method of the porous honeycomb single-crystal type high-nickel cathode material provided by the embodiment comprises the following steps:
(1) 100mmol oxalic acid was dissolved in 100mL deionized water to prepare solution A. Then according to the proportion of nickel element: cobalt element: manganese element =75:10:15, 32.5mmol of nickel acetate, 5mmol of cobalt acetate and 7.5mmol of manganese acetate are weighed out and dissolved in 100mL of deionized water to prepare a solution B. And then, quickly pouring the solution A into the solution B, stirring for reaction for 2 hours, and filtering and drying to obtain the nickel-cobalt-manganese oxalate precursor material (the molar content of the 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 by mixing lithium hydroxide and lithium sulfate in a molar ratio of 6: 4.2 mixing and grinding for 10min, heating and calcining in a crucible furnace in an air atmosphere by a three-section heating program (namely first calcining), firstly heating to 480 ℃ at the speed of 4 ℃/min for heat preservation treatment for 3h, then heating to 850 ℃ at the speed of 4 ℃/min for continuous heat preservation treatment for 10h, then heating to 950 ℃ at the speed of 4 ℃/min for continuous heat preservation treatment for 2h, and finally cooling to room temperature along with the furnace to obtain the porous honeycomb intermediate material.
After the reaction is finished (i.e., the first calcination and cooling is 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 10h.
(3) Mixing the porous honeycomb intermediate material dried in the step (2) with lithium carbonate (the amount of lithium salt is determined according to the content of lithium element in the washed porous honeycomb intermediate material, 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 being 1, and the same for each pair of proportions in the following examples), carrying out heat preservation treatment at 720 ℃ in an oxygen atmosphere (namely pure oxygen atmosphere) in a tubular furnace for 6h (namely second calcination) for supplementing lithium ions, and then cooling to room temperature along with the furnace to obtain the porous honeycomb single crystal type high-nickel LiNi with complete components and complete structure 0.75 Co 0.10 Mn 0.15 O 2 The cathode material (the molar content of nickel element is 75%).
Example 2
The preparation method of the porous honeycomb single-crystal type high-nickel cathode 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: manganese element =92:3:5, respectively weighing 46mmol of nickel acetate, 1.5mmol of cobalt acetate and 2.5mmol of manganese acetate, and dissolving the components in 100mL of deionized water to prepare a solution B. And then, quickly pouring the solution A into the solution B, stirring for reaction for 2 hours, and filtering and drying to obtain the nickel-cobalt-manganese oxalate precursor material (the molar content of the 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 by mixing lithium hydroxide and lithium sulfate in a molar ratio of 6: 4.2 mixing and grinding for 10min, heating and calcining in a crucible furnace in an air atmosphere by a three-section heating program, heating to 480 ℃ at the speed of 4 ℃/min for 3h, heating to 830 ℃ at the speed of 4 ℃/min for 10h, continuously heating to 900 ℃ at the speed of 4 ℃/min for 2h, and 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 cellular intermediate material is washed clean by deionized water and then is dried in an oven. Wherein the drying temperature is 80 ℃ and the drying time is 10h.
(3) Mixing the porous honeycomb intermediate material dried in the step (2) with lithium hydroxide, carrying out heat preservation treatment for 6 hours in a tubular furnace at 620 ℃ in an oxygen atmosphere for supplementing lithium ions, and then cooling to room temperature along with the furnace to obtain porous honeycomb single crystal type high nickel LiNi with complete components and complete structure 0.92 Co 0.03 Mn 0.05 O 2 The cathode material (the molar content of nickel element is 92%).
Example 3
The preparation method of the porous honeycomb single crystal type high-nickel cathode 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: manganese element =70:10: the molar ratios of 20 are respectively weighed as 35mmol of nickel nitrate, 5mmol of cobalt nitrate and 10mmol of manganese nitrate, and the components are dissolved in 100mL of deionized water together to prepare a solution B. And then quickly 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 the 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 by mixing lithium hydroxide and lithium sulfate in a molar ratio of 6: 4.2 mixing and grinding for 10min, heating and calcining in a crucible furnace in an air atmosphere by a three-section heating program, heating to 480 ℃ at the speed of 4 ℃/min for 3h, heating to 840 ℃ at the speed of 4 ℃/min for 10h, heating to 960 ℃ at the speed of 4 ℃/min for 2h, and 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 cellular intermediate material is washed clean by deionized water and then is dried in an oven. Wherein the drying temperature is 80 ℃ and the drying time is 10h.
(3) Mixing the porous cellular intermediate material dried in the step (2) with lithium carbonate, performing heat preservation treatment at 730 ℃ for 6h in a tubular furnace in an oxygen atmosphere for supplementing lithium ions, and then cooling to room temperature along with the furnace to obtain porous cellular single crystal type high-nickel LiNi with complete components and complete structure 0.70 Co 0.10 Mn 0.20 O 2 The cathode material (the molar content of the nickel element is 70%).
Example 4
The preparation method of the porous honeycomb single crystal type high-nickel cathode material provided by the embodiment comprises the following steps:
(1) Dissolving 100mmol of sodium bicarbonate in 100mL of deionized water to prepare a solution A, and then adding nickel: cobalt element: manganese element =80:10: the molar ratio of 10 is respectively weighed as 40mmol nickel sulfate, 5mmol cobalt sulfate and 5mmol manganese sulfate, and the components are dissolved in 100mL deionized water together to prepare a solution B. And then, quickly pouring the solution A into the solution B, stirring and reacting for 2 hours, and filtering and drying to obtain the nickel-cobalt-manganese carbonate precursor material (the molar content of the 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 by mixing lithium hydroxide and lithium sulfate in a molar ratio of 6: 4.2 mixing and grinding for 10min, heating and calcining in a crucible furnace in an air atmosphere by a three-section heating program, heating to 480 ℃ at the speed of 4 ℃/min for heat preservation treatment for 3h, heating to 850 ℃ at the speed of 4 ℃/min for heat preservation treatment for 10h, heating to 930 ℃ at the speed of 4 ℃/min for heat preservation treatment for 2h, 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 cellular intermediate material is washed clean by deionized water and then is dried in an oven. Wherein the drying temperature is 80 ℃ and the drying time is 10h.
(3) The porous honeycomb-shaped intermediate material dried in the step (2) is treatedMixing with lithium hydroxide, carrying out heat preservation treatment at 710 ℃ for 6h in a tube furnace in an oxygen atmosphere for supplementing lithium ions, and then cooling to room temperature along with the furnace to obtain porous honeycomb single crystal type high nickel LiNi with complete components and complete structure 0.80 Co 0.10 Mn 0.10 O 2 The cathode material (the molar content of the nickel element is 80%).
Example 5
The preparation method of the porous honeycomb single crystal type high-nickel cathode material provided by the embodiment comprises the following steps:
(1) According to the nickel element: cobalt element: manganese element =83:7: respectively weighing nickel acetate, cobalt acetate and manganese acetate according to the molar ratio of 10, placing the materials in a mortar together, and grinding for 1 hour to obtain an acetate precursor material (the molar content of the nickel element is 83%).
(2) Mixing the acetate precursor material obtained in the step (1) with a molten lithium-containing salt (the molar ratio of lithium hydroxide to lithium sulfate is 6): 4.2 mixing and grinding for 10min, heating and calcining in a crucible furnace in an air atmosphere by a three-section heating program, heating to 480 ℃ at the speed of 4 ℃/min for 3h, heating to 830 ℃ at the speed of 4 ℃/min for 10h, continuously heating to 900 ℃ at the speed of 4 ℃/min for 2h, and 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 cellular intermediate material is washed clean by deionized water and then is dried in an oven. Wherein the drying temperature is 80 ℃ and the drying time is 10h.
(3) Mixing the porous honeycomb intermediate material dried in the step (2) with lithium hydroxide, then carrying out heat preservation treatment for 7 hours in a tubular furnace at 650 ℃ 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 type high nickel LiNi with complete components and complete structure 0.83 Co 0.07 Mn 0.10 O 2 The cathode material (the molar content of the nickel element is 83%).
Example 6
The preparation method of the porous honeycomb single crystal type high-nickel cathode material provided by the embodiment comprises the following steps:
(1) According to the nickel element: cobalt element: manganese element =97:0.333:2, respectively weighing nickel protoxide, cobaltosic oxide and manganese dioxide, putting the materials in a mortar together, and grinding the materials for 1.5 hours to obtain an oxide precursor material (the molar content of the nickel element is 97%).
(2) Mixing the oxide precursor material obtained in the step (1) with a lithium-containing molten salt (molten salt formed by mixing lithium hydroxide and lithium sulfate at a molar ratio of 6: 4.2 mixing and grinding for 10min, heating and calcining in a crucible furnace in an air atmosphere by a three-section heating program, heating to 480 ℃ at the speed of 4 ℃/min for 3h, heating to 830 ℃ at the speed of 4 ℃/min for 10h, continuously heating to 900 ℃ at the speed of 4 ℃/min for 2h, and 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 clean by deionized water and then is dried in an oven. Wherein the drying temperature is 80 ℃ and the drying time is 10h.
(3) Mixing the porous honeycomb intermediate material dried in the step (2) with lithium hydroxide, carrying out heat preservation treatment for 6 hours in a tube furnace at 620 ℃ 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 type high-nickel LiNi with complete components and complete structure 0.97 Co 0.01 Mn 0.02 O 2 The cathode material (the molar content of nickel element is 97%).
Example 7
The preparation method of the porous honeycomb single-crystal type high-nickel cathode material provided by the embodiment comprises the following steps:
(1) According to the nickel element: manganese element: iron element =83:15:2, respectively weighing nickel protoxide, cobalt acetate and ferrous sulfate, placing the materials in a mortar together, and grinding for 1.5 hours to obtain the mixed precursor material (the molar content of the 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 the transition metal element in the mixed precursor material to the lithium element in the lithium-containing molten salt being 1:2, mixing and grinding for 15min, heating and calcining in a crucible furnace in an air atmosphere by a three-section heating program, heating to 500 ℃ at a speed of 4 ℃/min for heat preservation treatment for 3h, heating to 800 ℃ at a speed of 5 ℃/min for heat preservation treatment for 12h, heating to 1000 ℃ at a speed of 6 ℃/min for heat preservation treatment 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 cellular intermediate material is washed clean 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 at 800 ℃ for 3h in a tubular furnace 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 type high-nickel LiNi with complete components and complete structure 0.83 Mn 0.15 Fe 0.02 O 2 The cathode material (the molar content of the nickel element is 83%).
Example 8
The preparation method of the porous honeycomb single crystal type high-nickel cathode material provided by the embodiment comprises the following steps:
(1) According to the proportion of nickel element: cobalt element: titanium element =90:8:2, respectively weighing nickel protoxide, cobalt monoxide and titanium dioxide, putting the materials in a mortar together, and grinding for 1.5h to finally obtain the oxide precursor material (the molar content of the nickel element is 90%).
(2) Mixing the oxide precursor material obtained in the step (1) with a lithium-containing molten salt (a molten salt formed by mixing lithium nitrate and sodium nitrate at a molar ratio of 5: 8, mixing and grinding for 15min, heating and calcining in a crucible furnace in an air atmosphere by a three-section heating program, heating to 400 ℃ at the speed of 3 ℃/min for heat preservation for 5h, heating to 750 ℃ at the speed of 6 ℃/min for continuous heat preservation for 15h, heating to 910 ℃ at the speed of 8 ℃/min for continuous heat preservation for 4h, and 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 clean by deionized water and then is dried in an oven. Wherein the drying temperature is 100 ℃ and the drying time is 6h.
(3) Mixing the porous honeycomb intermediate material dried in the step (2) with lithium nitrate in a tube furnace, carrying out heat preservation treatment at 600 ℃ for 10 hours in an oxygen atmosphere for replenishing lithium ions, and then cooling to room temperature along with the furnace to obtain the porous honeycomb single crystal type high-nickel LiNi with complete components and complete structure 0.90 Co 0.08 Ti 0.02 O 2 The cathode material (the molar content of the nickel element is 90%).
Comparative example 1
The preparation method of the nonporous single crystal type positive electrode material provided in this comparative example is basically the same as that of example 1, except that:
firstly, in the step (1), according to the nickel element: cobalt element: manganese element =60:20: the molar ratios of 20 are respectively weighed 30mmol of nickel acetate, 10mmol of cobalt acetate and 10mmol of manganese acetate. And (2) in the nickel-cobalt-manganese oxalate precursor material obtained in the step (1), the molar content of the nickel element is 60%.
Secondly, in the step (2), the temperature is firstly increased to 480 ℃ at the speed of 4 ℃/min for heat preservation treatment for 3h, then the temperature is increased to 830 ℃ at the speed of 4 ℃/min for heat preservation treatment for 10h, and then the temperature is increased to 970 ℃ at the speed of 4 ℃/min for heat preservation treatment for 2h.
Thirdly, in the step (3), the material which is washed and dried is directly subjected to heat preservation treatment (heat preservation treatment at 750 ℃ for 7 hours) without adding lithium carbonate. 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 in the oxygen atmosphere, and then is cooled to room temperature along with the furnace to obtain the nonporous single crystal LiNi with complete components and complete structure 0.60 Co 0.20 Mn 0.20 O 2 The cathode material (the molar content of the nickel element is 60%).
Comparative example 2
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, in step (2), the temperature is first raised to 480 ℃ at a rate of 4 ℃/min for a heat preservation treatment of 4 hours, and then raised to 830 ℃ at a rate of 4 ℃/min for a heat preservation treatment of 11 hours (i.e., two-stage temperature raising is performed).
Comparative example 3
The preparation method of the non-porous single crystal type cathode material provided in this comparative example is basically the same as that in example 1, except that, in step (2), the temperature is first raised to 600 ℃ at a rate of 4 ℃/min for heat preservation treatment for 3 hours, then raised to 900 ℃ at a rate of 4 ℃/min for heat preservation treatment for 10 hours, and then raised to 800 ℃ at a rate of 4 ℃/min for heat preservation treatment for 2 hours.
Comparative example 4
The method for producing 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 the step (2) is performed by heating and calcining in an oxygen atmosphere (pure oxygen atmosphere) (i.e., first calcining).
Comparative example 5
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 in step (1), the ratio of nickel element: cobalt element: manganese element =65:15: the molar ratios of 20 are called nickel acetate, cobalt acetate and manganese acetate, respectively.
Experimental example 1
ICP detection was performed on the intermediate material obtained after the washing in step (2) in examples 1 to 6 and comparative example 1 and the positive electrode material obtained after the second calcination in step (3), respectively, and the atomic ratios of lithium, nickel, cobalt, and manganese were calculated, and the results are shown in table 1.
TABLE 1 atomic ratio results for lithium, nickel, cobalt, manganese for each group of materials
As can be seen from table 1, the nickel molar content of the product of comparative example 1 =60%, and the lithium element content in the intermediate material after washing is close to the stoichiometric ratio, so no additional lithium ions need to be added in the subsequent calcination process.
The nickel mole content of the products of the examples 1 to 6 is more than or equal to 70 percent, and the lithium element content of the intermediate materials after washing is far less than the stoichiometric ratio, so that the components of the intermediate materials need to be further supplemented with lithium.
The atomic ratios of lithium to nickel, cobalt and manganese in the products of comparative example 1 and examples 1 to 6 after washing with water and re-calcination (i.e. the second calcination) were all close to theoretical values in the tests, which indicates that the component contents of the products of examples 1 to 6 were complete after lithium supplementation.
Experimental example 2
The positive electrode materials obtained in comparative example 1, example 1 and example 2 were subjected to FESEM examination, and the results are shown in fig. 1, fig. 2 and fig. 3, respectively.
As can be seen from FIG. 1, the nonporous single crystal type LiNi obtained in comparative example 1 was 0.6 Co 0.2 Mn 0.2 O 2 The particle size of the anode material reaches the micron level, the particle surface is smooth, the existence of holes cannot be observed, and the anode material belongs to the conventional single crystal particle appearance.
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 anode material achieves the micron-sized particle size, the particle surface is rough, and the existence of a fine pore structure can be observed, which is different from the conventional single crystal particle appearance in figure 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 anode material reaches micron level, the particle surface is very rough, and the particle surface is distributed with a plurality of larger hole structures, which is obviously different from the conventional single crystal particle shape in fig. 1.
Meanwhile, XRD detection was performed on the positive electrode materials obtained in example 1 and example 2 of the present invention, respectively, and the results are shown in fig. 4. Wherein FIG. 4 (a) shows LiNi in the form of porous honeycomb single crystal of example 1 0.75 Co 0.10 Mn 0.15 O 2 XRD pattern of the positive electrode material; FIG. 4 (b) is a view showing porous honeycomb single crystal type high nickel LiNi prepared in example 2 0.92 Co 0.03 Mn 0.05 O 2 XRD pattern of the positive electrode material.
As is clear from FIG. 4, the diffraction peaks of the positive electrode materials obtained in examples 1 and 2 are the same as those of hexagonal system α -NaFeO 2 The layered structures are corresponding, and the two pairs of diffraction peaks (006)/(012) and (018)/(110) are obviously separated, which shows that the two cathode materials have perfect layered structures, and the I (003)/I (104) peak intensity ratios of the two cathode materials are greater than 1.2, which shows that the lithium-supplementing calcined materials have low lithium-nickel mixed-exclusion degree.
Experimental example 3
The positive electrode materials prepared in the above examples and comparative examples were mixed with a conductive agent and a binder at a mass ratio of 9:0.4:0.6 proportion is dispersed in 1-methyl-2-pyrrolidone organic solvent for size mixing, then the size is coated on aluminum foil, and after drying and rolling, the aluminum foil is cut into electrode wafers which are used as positive plates. And assembling the positive plate, the counter electrode lithium plate and the diaphragm into a 2016 type button cell in a glove box under the protection of argon. Then, electrochemical performance tests (first discharge capacity at a current density of 2C and capacity after 100 cycles) were performed on each cell using a cell electrochemical tester, and the results are shown in table 2.
Table 2 electrochemical performance test results of each battery group
| Group of | First discharge capacity (mAh/g) | Capacity after 100 cycles (mAh/g) | Capacity retention ratio (%) |
| 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 is superior to that of each comparative example.
In example 2, the first discharge capacity at the current density of 2C was 189.6mAh/g, the capacity after 100 cycles was 170.1mAh/g, and the capacity retention rate was 89.7%.
Therefore, the porous honeycomb monocrystal type high-nickel monocrystal 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.
Fig. 5 shows a charge-discharge cycle performance chart at a current density of 2C in example 1. Fig. 6 shows the charge/discharge cycle characteristics at a current density of 2C in example 2.
While particular embodiments of the present invention have been illustrated and described, it will be appreciated that the above embodiments are only intended to illustrate the technical solution of the present invention and not to limit it; those of ordinary skill in the art will understand that: modifications may be made to the above-described embodiments, or equivalents may be substituted for some or all of the features thereof without departing from the spirit and scope of the present invention; the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention; it is therefore intended to cover in the appended claims all such changes and modifications that are within the scope of this invention.
Claims (10)
1. The preparation method of the porous honeycomb single crystal type high-nickel anode material is characterized by comprising the following steps of:
(a) After being uniformly mixed with lithium-containing molten salt, the high-nickel precursor material is subjected to first calcination in a low-oxygen atmosphere with the oxygen volume fraction of below 60% to obtain a porous honeycomb intermediate material;
(b) Uniformly mixing the porous honeycomb intermediate material obtained in the step (a) with lithium salt, and then carrying out secondary calcination in pure oxygen atmosphere to obtain the porous honeycomb single crystal type 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 percent;
in step (a), the first calcining comprises: the temperature is preserved for 2 to 6 hours at the temperature of 350 to 550 ℃, then is preserved for 8 to 16 hours at the temperature of 700 to 850 ℃, and then is preserved for 1 to 5 hours at the temperature of 900 to 1000 ℃.
2. The method for preparing a porous honeycomb single-crystal type high-nickel cathode material according to claim 1, wherein in the step (a), the first calcination includes: the temperature is preserved for 3 to 5 hours at 400 to 500 ℃, then preserved for 10 to 15 hours at 750 to 840 ℃ and preserved for 2 to 4 hours at 910 to 960 ℃.
3. The preparation method of the porous honeycomb single-crystal high-nickel positive electrode material according to claim 1, wherein in the 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 not less than 1.5, preferably 2-10: 1.
4. the method for preparing the porous honeycomb single-crystal high-nickel positive electrode material according to claim 1, wherein in the step (a), the lithium-containing molten salt comprises a lithium salt or a molten salt formed by mixing the lithium salt with an inorganic salt;
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;
preferably, the inorganic salt comprises a sodium salt and/or a potassium salt;
preferably, the molten lithium-containing salt consists essentially of lithium ions in a molar ratio of 4 to 8:1, and lithium sulfate.
5. The method for preparing a porous honeycomb single crystal type high nickel positive electrode material according to claim 1, wherein in the step (b), 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;
preferably, said porous honeycomb intermediate material and said lithium salt further comprise, before said mixing, the step of washing and drying said porous honeycomb intermediate material obtained in step (a).
6. The method for preparing a porous honeycomb single-crystal-type high-nickel cathode material according to claim 1, wherein in the step (b), the temperature of the second calcination is 500-800 ℃, and the holding time is 3-15 h.
7. The method for preparing the porous honeycomb single crystal type high nickel cathode material according to claim 1, wherein the particle size of the porous honeycomb single crystal type high nickel cathode material obtained in the step (b) is 1 to 8 μm.
8. The porous honeycomb single crystal type high nickel positive electrode material prepared by the method for preparing the porous honeycomb single crystal type high nickel positive electrode material according to any one of claims 1 to 7.
9. The positive pole piece is mainly prepared from the porous honeycomb single-crystal type high-nickel positive pole material in claim 8.
10. A lithium ion battery comprising the positive electrode tab of claim 9.
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