CN117393745A - High-voltage high-power monocrystal ternary positive electrode material, and preparation method and application thereof - Google Patents
High-voltage high-power monocrystal ternary positive electrode material, and preparation method and application thereof Download PDFInfo
- Publication number
- CN117393745A CN117393745A CN202311281090.1A CN202311281090A CN117393745A CN 117393745 A CN117393745 A CN 117393745A CN 202311281090 A CN202311281090 A CN 202311281090A CN 117393745 A CN117393745 A CN 117393745A
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- China
- Prior art keywords
- lithium
- carbonate
- cobalt
- nickel
- positive electrode
- Prior art date
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Links
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title abstract description 6
- 239000000843 powder Substances 0.000 claims abstract description 36
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 33
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000005056 compaction Methods 0.000 claims abstract description 25
- 239000010405 anode material Substances 0.000 claims abstract description 18
- 239000000126 substance Substances 0.000 claims abstract description 7
- 229910013716 LiNi Inorganic materials 0.000 claims abstract description 4
- 239000011800 void material Substances 0.000 claims abstract description 3
- 239000000463 material Substances 0.000 claims description 55
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 36
- 229910001416 lithium ion Inorganic materials 0.000 claims description 36
- 239000000243 solution Substances 0.000 claims description 32
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 27
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 21
- 238000005245 sintering Methods 0.000 claims description 21
- 239000003292 glue Substances 0.000 claims description 18
- 239000010406 cathode material Substances 0.000 claims description 16
- 239000002245 particle Substances 0.000 claims description 14
- 239000002344 surface layer Substances 0.000 claims description 14
- 239000013078 crystal Substances 0.000 claims description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 12
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 12
- 239000012298 atmosphere Substances 0.000 claims description 12
- IPGANOYOHAODGA-UHFFFAOYSA-N dilithium;dimagnesium;dioxido(oxo)silane Chemical compound [Li+].[Li+].[Mg+2].[Mg+2].[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O IPGANOYOHAODGA-UHFFFAOYSA-N 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 12
- 239000011259 mixed solution Substances 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- 229910052759 nickel Inorganic materials 0.000 claims description 12
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 11
- 229910017052 cobalt Inorganic materials 0.000 claims description 11
- 239000010941 cobalt Substances 0.000 claims description 11
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 11
- 229910021389 graphene Inorganic materials 0.000 claims description 11
- 239000001301 oxygen Substances 0.000 claims description 11
- 229910052760 oxygen Inorganic materials 0.000 claims description 11
- 230000008569 process Effects 0.000 claims description 11
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 239000011572 manganese Substances 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
- 238000004519 manufacturing process Methods 0.000 claims description 7
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 claims description 6
- 238000000576 coating method Methods 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 claims description 6
- 239000011159 matrix material Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 229910000018 strontium carbonate Inorganic materials 0.000 claims description 6
- 238000009210 therapy by ultrasound Methods 0.000 claims description 6
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 5
- 229940044175 cobalt sulfate Drugs 0.000 claims description 5
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 5
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 5
- 229910052748 manganese Inorganic materials 0.000 claims description 5
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 5
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 5
- 229910000484 niobium oxide Inorganic materials 0.000 claims description 5
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical group [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 claims description 5
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 claims description 5
- 229910001936 tantalum oxide Inorganic materials 0.000 claims description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 238000001704 evaporation Methods 0.000 claims description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 4
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 4
- 239000001095 magnesium carbonate Substances 0.000 claims description 4
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 4
- 235000014380 magnesium carbonate Nutrition 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- 238000000967 suction filtration Methods 0.000 claims description 4
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 3
- 230000005540 biological transmission Effects 0.000 claims description 3
- 150000001768 cations Chemical class 0.000 claims description 3
- 229940011182 cobalt acetate Drugs 0.000 claims description 3
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 3
- 229940071125 manganese acetate Drugs 0.000 claims description 3
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 3
- 229940078494 nickel acetate Drugs 0.000 claims description 3
- 239000010955 niobium Substances 0.000 claims description 3
- 238000007789 sealing Methods 0.000 claims description 3
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 2
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 2
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 claims description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 claims description 2
- 239000001099 ammonium carbonate Substances 0.000 claims description 2
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 2
- 229910001429 cobalt ion Inorganic materials 0.000 claims description 2
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims description 2
- MULYSYXKGICWJF-UHFFFAOYSA-L cobalt(2+);oxalate Chemical compound [Co+2].[O-]C(=O)C([O-])=O MULYSYXKGICWJF-UHFFFAOYSA-L 0.000 claims description 2
- 230000008020 evaporation Effects 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 239000010410 layer Substances 0.000 claims description 2
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 2
- 230000014759 maintenance of location Effects 0.000 claims description 2
- 239000011656 manganese carbonate Substances 0.000 claims description 2
- 235000006748 manganese carbonate Nutrition 0.000 claims description 2
- 229940093474 manganese carbonate Drugs 0.000 claims description 2
- 239000011565 manganese chloride Substances 0.000 claims description 2
- 235000002867 manganese chloride Nutrition 0.000 claims description 2
- 229940099607 manganese chloride Drugs 0.000 claims description 2
- 229910001437 manganese ion Inorganic materials 0.000 claims description 2
- RGVLTEMOWXGQOS-UHFFFAOYSA-L manganese(2+);oxalate Chemical compound [Mn+2].[O-]C(=O)C([O-])=O RGVLTEMOWXGQOS-UHFFFAOYSA-L 0.000 claims description 2
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 claims description 2
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- 229910001453 nickel ion Inorganic materials 0.000 claims description 2
- DOLZKNFSRCEOFV-UHFFFAOYSA-L nickel(2+);oxalate Chemical compound [Ni+2].[O-]C(=O)C([O-])=O DOLZKNFSRCEOFV-UHFFFAOYSA-L 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- 238000002604 ultrasonography Methods 0.000 claims description 2
- 238000009423 ventilation Methods 0.000 claims description 2
- 239000011667 zinc carbonate Substances 0.000 claims description 2
- 235000004416 zinc carbonate Nutrition 0.000 claims description 2
- 229910000010 zinc carbonate Inorganic materials 0.000 claims description 2
- 239000003792 electrolyte Substances 0.000 abstract description 20
- 230000000694 effects Effects 0.000 abstract description 8
- 230000008595 infiltration Effects 0.000 abstract description 6
- 238000001764 infiltration Methods 0.000 abstract description 6
- 238000007086 side reaction Methods 0.000 abstract description 6
- 230000000052 comparative effect Effects 0.000 description 15
- 238000012360 testing method Methods 0.000 description 13
- 229910021645 metal ion Inorganic materials 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000003513 alkali Substances 0.000 description 7
- 239000011148 porous material Substances 0.000 description 7
- 230000006872 improvement Effects 0.000 description 5
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 description 4
- 238000007600 charging Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- PQVSTLUFSYVLTO-UHFFFAOYSA-N ethyl n-ethoxycarbonylcarbamate Chemical compound CCOC(=O)NC(=O)OCC PQVSTLUFSYVLTO-UHFFFAOYSA-N 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 229940040692 lithium hydroxide monohydrate Drugs 0.000 description 4
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium hydroxide monohydrate Substances [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 description 4
- 229940053662 nickel sulfate Drugs 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 238000004321 preservation Methods 0.000 description 4
- WSMQKESQZFQMFW-UHFFFAOYSA-N 5-methyl-pyrazole-3-carboxylic acid Chemical compound CC1=CC(C(O)=O)=NN1 WSMQKESQZFQMFW-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 239000008157 edible vegetable oil Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- GQYHUHYESMUTHG-UHFFFAOYSA-N lithium niobate Chemical compound [Li+].[O-][Nb](=O)=O GQYHUHYESMUTHG-UHFFFAOYSA-N 0.000 description 3
- 229940099596 manganese sulfate Drugs 0.000 description 3
- 239000011702 manganese sulphate Substances 0.000 description 3
- 235000007079 manganese sulphate Nutrition 0.000 description 3
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 239000002033 PVDF binder Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000010280 constant potential charging Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 238000012827 research and development Methods 0.000 description 2
- 238000004513 sizing Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 208000032953 Device battery issue Diseases 0.000 description 1
- 229910001290 LiPF6 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
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 1
- 238000002479 acid--base titration Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 230000006399 behavior Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000010351 charge transfer process Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010277 constant-current charging Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000005213 imbibition Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 239000010416 ion conductor Substances 0.000 description 1
- 238000010884 ion-beam technique Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 150000002642 lithium compounds Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B5/00—Single-crystal growth from gels
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G33/00—Compounds of niobium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G35/00—Compounds of tantalum
-
- 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
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
- C30B29/16—Oxides
- C30B29/22—Complex oxides
-
- 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
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—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
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Abstract
The invention discloses a high-voltage high-power monocrystal ternary anode material, and a preparation method and application thereof. The chemical formula of the monocrystal ternary anode material provided by the invention is rGO@LiM' O 3 @LiNi x Co y Mn 1‑x‑y O 2 The lithium battery has an evenly distributed internal void structure, higher powder compaction density and good electrolyte infiltration effect, so that the power performance and the cycle performance of the battery are improved, and the problems of side reaction between the positive electrode active material and the electrolyte, poor electrochemical performance, poor quick charge performance and poor cycle performance of the lithium battery under high voltage and the like are solved.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and relates to a high-voltage high-power monocrystal ternary positive electrode material, and a preparation method and application thereof.
Background
Along with the continuous innovation of new energy material research and development technology, a lithium ion battery which is composed of a lithium ion positive electrode material and has the advantages of low carbon, environment friendliness, high energy density, wide working temperature range and the like is paid attention to. Based on the problems of poor cruising ability and low charging speed of the existing electric automobile, the power battery is more and more urgent in demand for a power type lithium ion battery.
The current quick-charge type lithium ion battery, namely the multiplying power type lithium ion battery, is mainly realized by adopting a quick-charge type electrolyte, multiplying power type anode and cathode materials, a pole piece surface density reduction method and the like. The discharge capacity of the nickel-cobalt-manganese ternary material can be improved by improving the nickel content in the ternary material or improving the charging voltage of the ternary material. The improvement of the nickel content brings about the improvement of the capacity, but the circularity and the safety become poor, so the development of the high-voltage nickel-cobalt-manganese ternary material is a method for improving the capacity and the energy density.
However, when the ternary positive electrode material is charged and discharged under the conditions of high voltage and high temperature, the ternary positive electrode material particles are easily broken due to the fact that the quantity of lithium ions for intercalation and deintercalation is large, the reaction is severe and the generated anisotropic stress is strong, so that more side reactions are generated, and finally the cycle performance and the safety performance of the battery are affected. Although the capacity of the ternary material is increased by increasing the charging voltage of the ternary material, the capacity is increased by 10-15 mAh/g every 0.1V, and the energy density of the positive electrode material is greatly increased, the ternary material is irreversibly transformed after the voltage is increased, the exposed electrode surface is further reacted with electrolyte, the formed SEI film is continuously grown, the capacity and the cycle performance of the material are also reduced, and the layered structure of the ternary material is collapsed due to the increase of the voltage.
The problems faced by the current high-voltage nickel cobalt lithium manganate mainly comprise five aspects: bulk phase structure change, surface structure change, interface side reaction, O participating in charge transfer process and high voltage matching. These five problems in turn lead to a series of macroscopic battery failure behaviors such as rapid material capacity decay, increased internal resistance, electrolyte consumption, interface film thickening, and reduced safety performance, respectively. As the charging voltage increases, the surface of the nickel cobalt lithium manganate positive electrode is enriched with a large amount of Ni 3+ Has stronger oxidability, is easy to generate side reaction with electrolyte, causes electrolyte corrosion, dissolves out metal cations, even releases oxygen, and greatly influences the cycle performance and the safety performance of the material under the high-voltage condition.
The prior commercial high-power lithium ion batteries all use a lithium ion battery positive electrode material with a cut-off voltage of 4.2V as a positive electrode active material, and the low energy density of the lithium ion battery always restricts the further development of the battery technology although the rate performance and the cycle life are excellent. If the cut-off voltage of the anode material of the conventional high-power lithium ion battery is increased to 4.35V, the specific surface area of the material is larger due to the characteristics of secondary agglomerated particles, and the anode material is extremely easy to generate side reaction with electrolyte in the high-potential charge and discharge process, so that the electrochemical performance is lost. Therefore, in order to ensure that the material has higher high-current discharge performance and higher cycle life and energy density, the current commercial secondary particle high-power lithium ion battery anode material cannot meet the requirements. Meanwhile, the commercial high-voltage lithium ion battery anode material has a large central granularity and a small specific surface, so that the anode material is difficult to show good high-current discharge performance under high voltage. Therefore, in order to meet the energy density requirement of the market for the positive electrode material of the high-power lithium ion battery, the positive electrode material of the lithium ion battery is also required to be greatly improved.
The main problems of the current positive electrode materials of the power battery include: (1) The power type material is mainly secondary agglomerated balls, and is easy to generate structural stripping and collapse from grain boundaries under the condition of high voltage or larger current charge and discharge, so that the capacity of the battery is greatly attenuated in the high-temperature circulation process; (2) The power performance is poor, and the requirements of the development of the existing battery cells cannot be met; (3) The aim of improving the multiplying power performance of the material is achieved by adding a large amount of cobalt element, so that the cost of the anode material is greatly increased. Due to the price of cobalt and other factors, the decoobalization of the cathode material has become a definite trend. And the reduction of the cobalt content can bring negative effects such as reduction of the rate performance, so that the cobalt content of the high-power ternary positive electrode material is difficult to reduce.
The positive electrode material plays a decisive role in energy density, safety and service life. Among the numerous positive electrode materials, ternary positive electrode materials, particularly high nickel NCM, have been widely studied. However, nickel-rich layered oxide positive electrodes have many surface side effects and microstructural defects, such as residual lithium compounds, HF attack, structural degradation, inter/intra-crystalline cracking, and low electrical conductivity during cycling, ultimately resulting in reduced battery cycle life. In the cobalt-free layered cathode material, due to the lack of cobalt, the electron conductivity of the material is poor, the lithium ion migration speed is slow, the lithium and nickel mixed discharge is serious, the layered structure is poor, and the effect on the rate capability and the cycle life in the cobalt-free nickel-rich layered cathode material is particularly great. Thus, there is a need to provide a method for improving the power performance of low to no cobalt, nickel-rich layered oxide anodes at high voltages.
At present, the main factors of the compaction density of the positive electrode plate mainly comprise the following four points: (1) true density of the material; (2) material morphology; (3) material particle size distribution; (4) and (5) pole piece technology. The compaction density of the positive electrode material has a great influence on the battery performance, and although the energy density of a ternary material battery used in a new energy automobile is high, a cooling system is needed in the use process, so that the available energy of the ternary material accounts for only 47 percent. It is believed that at certain process conditions, the greater the compacted density, the more energy is available to the ternary material and the higher the initial capacity of the battery, but an excessively high unconditioned compacted density can cause particle breakage and severely shorten battery life. Therefore, the prepared high-compaction-resistant material can properly improve the compaction density of the anode, so that the discharge capacity of the battery can be effectively increased, the internal resistance can be reduced, the polarization loss can be reduced, the cycle life of the battery can be considered, and the utilization rate of the lithium ion battery can be improved.
In summary, on the premise of ensuring that the electrical performance of the positive electrode material meets the requirement, the improvement of the compaction density must be paid attention to so as to improve the competitiveness of the product. However, the current conventional ternary positive electrode material has a pole piece compaction density of 3.4-3.6g/cm 3 The volume energy density of the battery is effectively improved, the endurance mileage of the electric vehicle is improved, and the requirements of consumers are met.
Disclosure of Invention
The invention aims to provide a high-voltage high-power monocrystal ternary positive electrode material which has a pore structure with uniform distribution and enlarged pore diameter, higher compaction density and good electrolyte infiltration effect, so that the power performance and the cycle performance of a battery are improved, and the problems of poor electrochemical performance, poor quick charge performance and poor cycle performance of a lithium battery under high voltage and the like caused by side reaction between a positive electrode active material and the electrolyte are solved.
In order to achieve the above purpose, the present invention provides the following technical solutions:
in a first aspect, the invention provides a single crystal ternary cathode material comprising the following components: a nickel cobalt manganese particle matrix and a graphene coating the surface of the nickel cobalt manganese particle matrix;
the chemical formula of the monocrystal ternary anode material is rGO@LiM' O3@LiNi x Co y Mn 1-x-y O 2 Wherein x is more than or equal to 0.6 and less than 1, y is more than 0 and less than 0.1, and M' is a pentavalent cation selected from Nb and/or Ta;
the monocrystal ternary anode material has an internal void structure which is uniformly distributed, and the powder compaction density of the monocrystal ternary anode material is more than 3.7 g/cc;
the monocrystal ternary positive electrode material is a high-voltage material, the 1C multiplying power 50-week cycle capacity retention rate is more than 97% up to the working voltage of 4.5V, and the discharge capacity under different multiplying powers is as follows: the value of 5C/1C is greater than 0.87, and the value of 3C/0.33C is greater than 0.90.
In a second aspect, the present invention further provides a method for preparing the single crystal ternary cathode material, comprising the steps of:
s1, mixing a nickel source, a cobalt source, a manganese source and a lithium source, adding carbonate into the mixed solution, and evaporating to form gel A;
s2, sintering the gel A for the first time, crushing, carrying out surface layer lithium-rich treatment on the obtained powder B in a treatment liquid, and carrying out suction filtration and drying to obtain powder C;
s3, dissolving lithium magnesium silicate and graphene oxide in water, adding nano oxide, and performing ultrasonic treatment to obtain a glue solution D;
s4, placing the powder C into the glue solution D, stirring, and sealing the surface layer by using an oily substance to obtain a sample;
s5, performing secondary sintering on the sample to obtain the monocrystal ternary anode material.
In the step S1, the total concentration of nickel ions, cobalt ions, manganese ions and lithium ions in the mixed solution is 10-100g/L, preferably 50-70g/L.
The nickel source is at least one of nickel chloride, nickel acetate, nickel sulfate and nickel oxalate.
The cobalt source is at least one of cobalt chloride, cobalt acetate, cobalt sulfate and cobalt oxalate.
The manganese source is at least one of manganese chloride, manganese carbonate, manganese acetate and manganese oxalate.
The lithium source is at least one of lithium chloride, lithium acetate, lithium hydroxide and lithium carbonate.
The carbonate is at least one of sodium carbonate, sodium bicarbonate, ammonium carbonate, magnesium carbonate, strontium carbonate, potassium carbonate and zinc carbonate.
The carbonate is used in an amount of 1 to 5wt%, preferably 2.5 to 3.5wt% based on the mass of the lithium source.
The evaporation conditions are as follows: under the water bath condition, the temperature is 40-70 ℃, preferably 50-60 ℃ for 10-36 hours, preferably 18-24 hours.
In step S2, the conditions of the primary sintering are as follows: the temperature is 800-1000 ℃, preferably 850-950 ℃, for 10-30 hours, preferably 15-20 hours, in an atmosphere with an oxygen content > 40%.
The treatment solution is an aqueous solution composed of the lithium source, a hydrogen peroxide solution and citric acid.
The concentration of lithium ions in the treatment liquid is 0.5-2 wt%, preferably 1-1.5 wt%; the concentration of hydrogen peroxide is 5-30wt%, preferably 15-20wt%; the mass volume ratio of the citric acid to the hydrogen peroxide is as follows: (0.1-2) g:10mL, preferably (0.5-1) g:10mL.
The surface lithium enrichment treatment process comprises the following steps: ozone is introduced into the solution under the critical micro-positive pressure condition; the critical micro-positive pressure is micro-positive pressure formed after ozone overcomes the water pressure, the introducing time is 0.5-2h, preferably 1-1.5h, and the ventilation amount of the ozone is 0.1-0.5 m 3 Preferably 0.2-0.3m 3 /h。
Under the condition of critical micro-positive pressure, ozone has high diffusivity, permeability and solubility, and has the oxidation effect on the powder B to be treated by combining the unique oxidability and corrosiveness of hydrogen peroxide.
Under the condition of critical micro-positive pressure, ozone forms a bubble film on the surface of the particles in the rapid expansion process, surrounds the whole particles, and diffuses into the particles, not just limited to the surface layer; and the lithium content is in a gradient type with gradually decreasing concentration from the surface layer to the inside; in addition, the gas diffuses in the liquid phase environment, and has uniformity in all directions, so that the orientation is avoided, the internal stress of the material lattice is reduced, and the stability of the product is improved.
The conditions of suction filtration and drying are as follows: filtering under inert gas protection, and drying at 60-100deg.C, preferably 70-90deg.C for 5-20 hr, preferably 10-15 hr.
In step S3, the amount of the lithium magnesium silicate is 5 to 20wt%, preferably 10 to 15wt% based on the water mass.
The graphene oxide is used in an amount of 0.5 to 5wt%, preferably 2 to 3wt% based on the mass of the lithium magnesium silicate.
The nano oxide is niobium oxide and/or tantalum oxide.
The nano-oxide is used in an amount of 1 to 10wt%, preferably 5 to 8wt% based on the mass of the lithium magnesium silicate.
The conditions of the ultrasound are: the ultrasonic frequency is 20-60Hz, preferably 30-40Hz, the ultrasonic energy transmission efficiency is 1-10w/g, preferably 4-7w/g, the ultrasonic time is 5-40min, preferably 15-30min, the ultrasonic temperature is 20-50 ℃, preferably 30-45 ℃.
In the step S4, the amount of the powder C is 30-60wt%, preferably 40-50wt%, of the mass of the glue solution D.
The oily substance is oil with density less than that of water.
The thickness of the oil layer of the seal is 1-10cm, preferably 4-7cm.
In step S5, the conditions of the secondary sintering are as follows: the temperature is 300-600 ℃, preferably 400-500 ℃ for 1-3 hours, preferably 1.5-2.5 hours under inert atmosphere.
In a third aspect, the present invention further provides a lithium ion battery comprising the following composition: a positive electrode and a negative electrode; the material of the positive electrode is the monocrystal ternary positive electrode material.
The beneficial effects obtained by the invention are as follows:
1. according to the invention, carbonate is introduced in the mixing stage, so that the carbonate is ensured to be uniformly distributed, and a pore structure is left in the material after the carbonate is decomposed in the sintering process and is uniformly distributed, so that the pores in the material are increased and the distribution is more uniform; the pores not only shorten the diffusion path of lithium ions and improve the power performance, but also can relieve the internal stress when being used under high compaction density, thereby effectively improving the mechanical stability of the monocrystal ternary material. In addition, the pores can also improve the electrolyte wettability of the material under high compaction density, realize good infiltration effect, effectively reduce the impedance of the battery and achieve the purpose of improving the power performance and the cycle performance of the battery.
2. According to the invention, citric acid and hydrogen peroxide solution are adopted to oxidize the surface of the matrix material, and a 'lithium-rich' interface is formed on the surface of the material, so that more lithium is provided, and the charge and discharge capacity of the material is improved.
3. According to the invention, through graphene oxide coating, the corrosion of HF in the electrolyte to the matrix material is reduced, the high-voltage safety, the cycle performance and the overcharge resistance of the electrolyte are improved, the electrochemical polarization of the positive electrode material in the charge and discharge process is reduced, and the rate performance and the cycle performance are obviously improved.
4. The invention further adds nano oxide to form a coating layer of lithium niobate and lithium tantalate on the surface of the ternary positive electrode material, thereby playing roles of stabilizing the surface structure of the material and reducing residual alkali; the lithium tantalate and the lithium niobate are lithium ion conductors, so that the lithium ion diffusion coefficient of the surface of the material can be improved; in addition, lithium tantalate and lithium niobate are piezoelectric materials, and under the external mechanical action, generated polarized charges and an electric field changing along with time can drive electrons to flow in an external circuit, so that the power performance of the materials is improved.
5. The ternary material prepared by the method has large-particle monocrystalline morphology, improves the crystal structure stability of the material under high voltage, and achieves the purposes of improving the cycle stability and the thermal stability of the material.
6. The ternary material prepared by the method has high compaction density which can reach more than 3.7g/cc, and is beneficial to improving the energy density of the lithium ion battery. The method has universality and is suitable for ternary materials consisting of different nickel, cobalt and manganese.
Drawings
Fig. 1 is an SEM image of a sample obtained in example one.
FIG. 2 is the EDS of the sample obtained in example one.
FIG. 3 is a cross-sectional electron microscope topography of the sample obtained in example one.
Fig. 4 is XRD of the sample obtained in example one.
Detailed Description
The invention will be further illustrated with reference to the following specific examples, but the invention is not limited to the following examples.
The experimental methods used in the following examples are conventional methods unless otherwise specified.
Reagents, materials, instruments and the like used in the examples described below are commercially available unless otherwise specified.
Example 1
S1, mixing nickel sulfate, cobalt sulfate and manganese sulfate according to a metal ion molar ratio of 70:10:20, preparing a mixed solution with a metal ion concentration of 17g/L according to a metal ion content and lithium hydroxide monohydrate molar ratio of 1:1.02, adding strontium carbonate (3 wt% of the mass of the lithium hydroxide monohydrate), uniformly mixing, and heating for 12 hours under a water bath condition at 50 ℃ to evaporate until the liquid forms gel A;
s2, performing primary sintering on the gel A, wherein the sintering condition is 880 ℃, the heat preservation time is 15 hours, the industrial oxygen atmosphere with the oxygen content being more than 93 percent is obtained after crushing, and the powder B is subjected to surface layer lithium-rich treatment in a treatment liquid;
the lithium ion concentration of the lithium-rich treatment solution was 1wt%. The using amount of citric acid is (wt): h 2 O 2 (V) = (0.2 g): 10mL, hydrogen peroxide concentration 10wt%, during which 0.3m was introduced 3 Ozone treatment per hour for 1 hour. Vacuum filtering at 90 ℃ in nitrogen protection atmosphere, and drying for 10 hours to obtain powder C;
s3, preparing a solution according to the mass ratio of the lithium magnesium silicate to the water of 10wt%, adding 1wt% of graphene oxide into the water, adding 6wt% of nano niobium oxide, and performing ultrasonic treatment on the mixed solution to obtain a glue solution D;
s4, placing the powder C into the glue solution D, uniformly stirring (the powder C is 50wt% of the mass of the glue solution D), and protecting the surface layer by using an edible oil seal with the thickness of 1 cm;
s5, sintering the sample obtained in the step S4, and keeping the temperature at 400 ℃ for 1 hour in a nitrogen atmosphere to obtain the high-voltage high-power monocrystal ternary material E.
XRD, SEM-EDS and other tests were performed on the samples obtained in this example.
The compaction density of the sample is 3.76g/cm by adopting a powder compaction density instrument 3 。
Example two
S1, mixing nickel sulfate, cobalt sulfate and manganese sulfate according to a molar ratio of metal ions (65:07:28), preparing a mixed solution with a metal ion concentration of 33g/L by using the metal ion content and lithium hydroxide monohydrate according to a molar ratio of (1:1.06), adding strontium carbonate (5 wt% of the mass of the lithium hydroxide monohydrate), uniformly mixing, and heating for 36 hours under a water bath condition at 40 ℃ to evaporate until the liquid forms gel A;
s2, performing primary sintering on the gel A, wherein the sintering condition is 897 ℃, the heat preservation time is 18 hours, compressed air with the oxygen content being more than 45% is mixed with industrial oxygen atmosphere, powder B is obtained after crushing, and surface layer lithium enrichment treatment is performed on the powder B in a treatment liquid.
The lithium ion concentration of the lithium-rich treatment solution was 0.5wt%. The using amount of citric acid is (wt): h 2 O 2 (V) = (0.1 g): 10mL of hydrogen peroxide was introduced at a concentration of 30wt% during which time 0.5m was introduced 3 Ozone treatment per hour for 1 hour. Vacuum filtering at 100deg.C under nitrogen protection for 5 hr to obtain powder C;
s3, preparing a solution by taking the mass ratio of lithium magnesium silicate to water as 10wt%, adding 5wt% of graphene oxide into water, adding 7wt% of nano tantalum oxide, and carrying out ultrasonic treatment on the mixed solution to obtain a glue solution D;
s4, placing the powder C into the glue solution D, uniformly stirring (the powder C is 40wt% of the mass of the glue solution D), and protecting the surface layer by using an edible oil seal with the thickness of 1 cm;
s5, sintering the sample obtained in the step S4, and maintaining the temperature at 600 ℃ for 1 hour in a nitrogen atmosphere to obtain the high-voltage high-power monocrystal ternary material E.
The compaction density of the sample is 3.81g/cm by adopting a powder compaction density instrument 3 。
Example III
S1, mixing nickel acetate, cobalt acetate and manganese acetate according to a molar ratio of metal ions (60:05:35), preparing a mixed solution with the metal ion concentration of 100g/L by the metal ion content and lithium carbonate according to a molar ratio (1:1.08), adding magnesium carbonate (5 wt% of the mass of the lithium carbonate), uniformly mixing, and heating for 12 hours under the water bath condition of 50 ℃ to evaporate until the liquid forms gel A;
s2, performing primary sintering on the gel A, wherein the sintering condition is 950 ℃, the heat preservation time is 15 hours, the oxygen content is more than 30% in the compressed air industrial oxygen mixed gas atmosphere, the powder B is obtained after crushing, and the surface layer lithium-rich treatment is performed on the powder B in the treatment liquid;
the lithium ion concentration of the lithium-rich treatment solution was 2wt%. The using amount of citric acid is (wt): h 2 O 2 (V) = (0.2 g): 10mL, hydrogen peroxide concentration 10wt%, during which 0.5m was introduced 3 Ozone treatment per hour for 1 hour. Vacuum filtering at 90 ℃ in nitrogen protection atmosphere, and drying for 10 hours to obtain powder C;
s3, preparing a solution by taking the mass ratio of lithium magnesium silicate to water as 10wt%, adding 1wt% of graphene oxide into water, adding 6wt% of nano niobium oxide, and carrying out ultrasonic treatment on the mixed solution to obtain a glue solution D;
s4, placing the powder C into the glue solution D, uniformly stirring (the powder C is 50wt% of the mass of the glue solution D), and protecting the surface layer by using an edible oil seal with the thickness of 1 cm;
s5, sintering the sample obtained in the step S4, and keeping the temperature at 400 ℃ for 1 hour in a nitrogen atmosphere to obtain the high-voltage high-power monocrystal ternary material E.
The compaction density of the sample is 3.79g/cm by adopting a powder compaction density meter 3 。
Example IV
S1, mixing nickel sulfate, cobalt sulfate and manganese sulfate according to a molar ratio of metal ions (80:10:10), preparing a mixed solution with the metal ion concentration of 100g/L by the metal ion content and lithium carbonate according to a molar ratio (1:1.08), adding magnesium carbonate (5 wt% of the mass of the lithium carbonate), uniformly mixing, and heating for 12 hours under the water bath condition of 50 ℃ to evaporate until the liquid forms gel A;
s2, performing primary sintering on the gel A, wherein the sintering condition is 950 ℃, the heat preservation time is 15 hours, the oxygen content is more than 30% in the compressed air industrial oxygen mixed gas atmosphere, the powder B is obtained after crushing, and the surface layer lithium-rich treatment is performed on the powder B in the treatment liquid;
the lithium ion concentration of the lithium-rich treatment solution was 2wt%. The using amount of citric acid is (wt): h 2 O 2 (V) = (0.2 g): 10mL, hydrogen peroxide concentration of 10wt%During which 0.5m is introduced 3 Ozone treatment per hour for 1 hour. Vacuum filtering at 90 ℃ in nitrogen protection atmosphere, and drying for 10 hours to obtain powder C;
s3, preparing a solution by taking the mass ratio of lithium magnesium silicate to water as 10wt%, adding 1wt% of graphene oxide into water, adding 6wt% of nano niobium oxide, and carrying out ultrasonic treatment on the mixed solution to obtain a glue solution D;
s4, placing the powder C into the glue solution D, uniformly stirring (the powder C is 50wt% of the mass of the glue solution D), and sealing the surface layer by using gasoline;
s5, sintering the sample obtained in the step S4, and maintaining the temperature at 600 ℃ for 1 hour in a nitrogen atmosphere to obtain the high-voltage high-power monocrystal ternary material E.
The compaction density of the sample is 3.781g/cm by adopting a powder compaction density instrument 3 。
Comparative example one
The strontium carbonate application is omitted compared to the second step S1 of the embodiment. The rest steps are consistent.
Comparative example two
The lithium enrichment treatment step is omitted compared with the second step S2 of the embodiment. The rest steps are consistent.
Comparative example three
The tantalum oxide application is omitted compared to step S3 of embodiment two. The rest steps are consistent.
Comparative example four
Commercially available LiNi 0.65 Co 0.07 Mn 0.28 O 2 . The compaction density of the sample is 3.65g/cm by adopting a powder compaction density instrument 3 。
And (3) effect verification:
1. structural characterization
Taking the material obtained in the first embodiment as an example, SEM and EDS characterization were performed on the product obtained in the first embodiment, and the results are shown in fig. 1 and fig. 2, respectively.
As can be seen from fig. 1, the product prepared in the first embodiment has a single crystal morphology, and the surface of the sample can be observed to be coated with the coating and uniformly dispersed.
As can be seen from FIG. 2, the presence of Nb element on the surface of the positive electrode material proves thatThe surface of the positive electrode material is provided with LiNbO 2 And (5) coating.
As can be seen from fig. 3, the cross section of the sample prepared in the first embodiment has a hole structure with uniformly distributed pore sizes, the particles of the positive electrode material are cut by an ion beam mill (CP), a sample with a cross section of the particles being observable is obtained, and a Scanning Electron Microscope (SEM) is used to photograph the cross section image.
As can be seen from FIG. 4, the material prepared in example one is single alpha-NaFeO 2 A layered structure; (006) The/(102) and (108)/(110) peaks are obviously split, indicating that the material has a better lamellar structure.
2. PH and residual alkali detection
The testing method comprises the following steps: see Hunan He Ministry of technology, inc. 'Nickel cobalt lithium manganate analysis determination method', specifically as follows:
(1) pH test: the lithium ion battery anode material and distilled water are mixed according to a solid-liquid ratio of 1:10, testing by a pH meter, wherein the specific reference can be made to the 4 th part of the analysis and determination method of lithium nickel cobalt manganate;
(2) Residual alkali determination: the acid-base titration method is adopted, and the specific reference can be seen in the section 5 of the analysis and determination method of lithium nickel cobalt manganate;
(3) The free lithium content in table 1 is the sum of the lithium ion content in the residual alkali (lithium carbonate and lithium hydroxide).
TABLE 1 residual alkali content of cathode materials of different examples
| Project | pH | LiOH(wt％) | Li 2 CO 3 (wt％) | Free lithium (ppm) |
| Example 1 | 11.67 | 0.11 | 0.07 | 447.16 |
| Example two | 11.51 | 0.08 | 0.05 | 309.75 |
| Example III | 11.68 | 0.12 | 0.05 | 426.14 |
| Example IV | 11.65 | 0.11 | 0.10 | 491.61 |
| Comparative example one | 11.94 | 0.21 | 0.46 | 1469.80 |
| Comparative example two | 11.96 | 0.21 | 0.40 | 1377.394 |
| Comparative example three | 11.96 | 0.22 | 0.45 | 1483.49 |
| Comparative example four | 11.72 | 0.13 | 0.24 | 825.56 |
As can be seen from the test results in table 1, the pH and residual alkali content of the samples prepared by the preparation method of the present invention are lower than those of the comparative examples, which indicates that the ternary positive electrode material with low residual alkali content can be prepared by the preparation method of the present invention.
3. Electrical performance detection method
The positive electrode materials of the lithium ion batteries in the first-4 and the comparative examples are respectively assembled into 2016 button batteries, wherein the positive electrode is an active material: SP: polyvinylidene fluoride is dissolved in N-methyl pyrrolidone in a mass ratio of 90:5:5, and the mixture is stirred to obtain evenly dispersed slurry, and the slurry is evenly smeared on an aluminum foil and dried for 12 hours at 120 ℃ to prepare the polyvinylidene fluoride composite material; the negative electrode is a lithium sheet; the diaphragm is Celgard 2400; the electrolyte was 1M LiPF6 dissolved in EC/DMC/DEC (1:1:1 inwt.%). The battery assembly process is completed in a glove box.
The test conditions were as follows: testing on a blue electric tester in a constant temperature box at 25 ℃; test current: constant current and constant voltage charging of 0.2C, 0.33C, 1C, 2C, 3C and 5C, constant current and constant voltage discharging of 0.2C, 0.33C, 1C, 2C, 3C and 5C, and constant voltage charging stage cut-off condition: cut-off current 0.05C; test voltage range: 2.8-4.5V. The cycle test was a 1C rate cycle of 50 times.
TABLE 2 electrochemical Properties of cathode materials of different examples
As can be seen from the test results in Table 2, the specific discharge capacity of 0.2C of the second example reaches 195.28mAh/g, and the first efficiency is 87.24%. The discharge specific capacity of 0.2C of comparative example 1 reaches 187.65mAh/g, the first turn capacity of example two is significantly better than comparative example 1, and the ratio of 5C/1C to 1C/0.33C is lower than example two. From this, it is known that strontium carbonate is advantageous for improving the rate performance, particularly the capacity exertion at high rate, and has an important influence on the first-time efficiency. As can be seen from the comparison of the second comparative example and the second example, the gram capacity of the sample after the lithium-rich treatment plays a significant role in improving. From the comparison of the third comparative example and the second comparative example, the tantalum oxide plays an important role in improving the first efficiency and gram capacity of the material. In a word, the monocrystal ternary material prepared by the method has the advantages of high capacity, high first coulombic efficiency and good cycle performance.
4. Pole piece wettability testing method
The electrolyte is a core part of the research and development of the lithium ion battery, is an important medium for ensuring ion transmission, and is also an important foundation for obtaining high voltage and high specific energy of the battery. The wetting condition of the electrolyte in the pole piece has an important influence on the electrochemical performance. As a positive electrode material of one of the main materials of the lithium ion battery, the positive electrode material is good and bad for the electrolyte infiltration condition, and is also a key index for influencing the battery performance.
After uniformly coating the sizing agent under the same process formula condition (adopting an electrochemical test pole piece sizing agent mixing scheme), pole pieces with the same compaction density (3.7) are respectively prepared, and pole pieces with the same length and width dimensions (25 x 3 cm) are cut. And immersing the bottom in electrolyte, and collecting the imbibition height of the pole piece in the same immersion time (60 s). The results are shown in the following table.
TABLE 3 electrolyte infiltration results for different examples of anodes at the same time
As can be seen from the test results in table 3, under the same pole piece manufacturing process conditions and the same pole piece compaction density, the positive electrode material prepared by the method disclosed by the invention has better electrolyte wettability, and the higher the pole piece infiltration height is under the same time.
While the invention has been described in detail in the foregoing general description and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that modifications and improvements can be made thereto. Accordingly, such modifications or improvements may be made without departing from the spirit of the invention and are intended to be within the scope of the invention as claimed.
Claims (10)
1. A single crystal ternary positive electrode material comprising the following composition: a nickel cobalt manganese particle matrix and a graphene coating the surface of the nickel cobalt manganese particle matrix;
the chemical formula of the monocrystal ternary anode material is rGO@LiM' O3@LiNi x Co y Mn 1-x-y O 2 Wherein x is more than or equal to 0.6 and less than 1, y is more than 0 and less than 0.1, and M' is a pentavalent cation selected from Nb and/or Ta;
the monocrystal ternary anode material has an internal void structure which is uniformly distributed, and the powder compaction density of the monocrystal ternary anode material is more than 3.7 g/cc;
the monocrystal ternary positive electrode material is a high-voltage material, the working voltage is 4.5V, the 1C multiplying power 50-week cycle capacity retention rate is more than 97%, and the discharge capacity under different multiplying powers is as follows: the value of 5C/1C is greater than 0.87, and the value of 3C/0.33C is greater than 0.90.
2. The method for preparing the single crystal ternary cathode material of claim 1, comprising the following steps:
s1, mixing a nickel source, a cobalt source, a manganese source and a lithium source, adding carbonate into the mixed solution, and evaporating to form gel A;
s2, sintering the gel A for the first time, crushing, carrying out surface layer lithium-rich treatment on the obtained powder B in a treatment liquid, and carrying out suction filtration and drying to obtain powder C;
s3, dissolving lithium magnesium silicate and graphene oxide in water, adding nano oxide, and performing ultrasonic treatment to obtain a glue solution D;
s4, placing the powder C into the glue solution D, stirring, and sealing the surface layer by using an oily substance to obtain a sample;
s5, performing secondary sintering on the sample to obtain the monocrystal ternary anode material.
3. The method for preparing a single crystal ternary cathode material according to claim 2, wherein the method comprises the following steps: in the step S1, the total concentration of nickel ions, cobalt ions, manganese ions and lithium ions in the mixed solution is 10-100g/L;
the nickel source is at least one of nickel chloride, nickel acetate, nickel sulfate and nickel oxalate;
the cobalt source is at least one of cobalt chloride, cobalt acetate, cobalt sulfate and cobalt oxalate;
the manganese source is at least one of manganese chloride, manganese carbonate, manganese acetate and manganese oxalate;
the lithium source is at least one of lithium chloride, lithium acetate, lithium hydroxide and lithium carbonate.
4. A method for producing a single crystal ternary cathode material according to claim 2 or 3, characterized in that: in the step S1, the carbonate is at least one of sodium carbonate, sodium bicarbonate, ammonium carbonate, magnesium carbonate, strontium carbonate, potassium carbonate and zinc carbonate;
the carbonate is used in an amount of 1-5wt% of the mass of the lithium source;
the evaporation conditions are as follows: under the water bath condition, the temperature is 40-70 ℃ and the time is 10-36h.
5. The method for producing a single crystal ternary cathode material according to any one of claims 2 to 4, wherein: in step S2, the conditions of the primary sintering are as follows: the temperature is 800-1000 ℃ and the time is 10-30h under the atmosphere with the oxygen content of more than 40 percent.
6. The method for producing a single crystal ternary cathode material according to any one of claims 2 to 5, characterized in that: in step S2, the treatment solution is an aqueous solution composed of the lithium source, a hydrogen peroxide solution and citric acid;
in the treatment solution, the concentration of lithium ions is 0.5-2 wt%, the concentration of hydrogen peroxide is 5-30wt%, and the mass volume ratio of the citric acid to the hydrogen peroxide is as follows: (0.1-2) g:10mL;
the surface lithium enrichment treatment process comprises the following steps: ozone is introduced into the solution under the critical micro-positive pressure condition;
the critical micro-positive pressure is micro-positive pressure formed after ozone overcomes the water pressure;
the introducing time is 0.5-2h;
the ventilation of the ozone is 0.1-0.5 m 3 /h；
The conditions of suction filtration and drying are as follows: filtering under inert gas protection atmosphere, and drying at 60-100deg.C for 5-20 hr.
7. The method for producing a single crystal ternary cathode material according to any one of claims 2 to 6, characterized in that: in the step S3, the dosage of the lithium magnesium silicate is 5-20wt% of the water mass;
the dosage of the graphene oxide is 0.5-5wt% of the mass of the lithium magnesium silicate;
the nano oxide is niobium oxide and/or tantalum oxide;
the dosage of the nano oxide is 1-10wt% of the mass of the lithium magnesium silicate;
the conditions of the ultrasound are: the ultrasonic frequency is 20-60Hz, the ultrasonic energy transmission efficiency is 1-10w/g, the ultrasonic time is 5-40min, and the ultrasonic temperature is 20-50 ℃.
8. The method for producing a single crystal ternary cathode material according to any one of claims 2 to 7, characterized in that: in the step S4, the dosage of the powder C is 30-60wt% of the mass of the glue solution D;
the oily substance is oil with density less than that of water;
the thickness of the oil layer of the seal is 1-10cm.
9. The method for producing a single crystal ternary cathode material according to any one of claims 2 to 8, wherein: in step S5, the conditions of the secondary sintering are as follows: under inert atmosphere, the temperature is 300-600 ℃ and the time is 1-3h.
10. A lithium ion battery comprising the following composition: a positive electrode and a negative electrode; the material of the positive electrode is the monocrystal ternary positive electrode material of claim 1.
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