WO2013189109A1 - 高能量密度锂离子电池氧化物正极材料及其制备方法 - Google Patents
高能量密度锂离子电池氧化物正极材料及其制备方法 Download PDFInfo
- Publication number
- WO2013189109A1 WO2013189109A1 PCT/CN2012/078726 CN2012078726W WO2013189109A1 WO 2013189109 A1 WO2013189109 A1 WO 2013189109A1 CN 2012078726 W CN2012078726 W CN 2012078726W WO 2013189109 A1 WO2013189109 A1 WO 2013189109A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- positive electrode
- electrode material
- shell
- core
- hydroxide
- Prior art date
Links
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 12
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 12
- 238000002360 preparation method Methods 0.000 title abstract description 11
- 239000010405 anode material Substances 0.000 title abstract 5
- 239000000203 mixture Substances 0.000 claims abstract description 21
- 239000000463 material Substances 0.000 claims abstract description 19
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 16
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 15
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 14
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 13
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 13
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 12
- 229910052802 copper Inorganic materials 0.000 claims abstract description 12
- 229910052742 iron Inorganic materials 0.000 claims abstract description 12
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 12
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 12
- 239000007774 positive electrode material Substances 0.000 claims description 100
- 239000011257 shell material Substances 0.000 claims description 55
- 239000002243 precursor Substances 0.000 claims description 45
- 239000010410 layer Substances 0.000 claims description 40
- 239000011162 core material Substances 0.000 claims description 34
- 239000011258 core-shell material Substances 0.000 claims description 26
- 239000002245 particle Substances 0.000 claims description 23
- 229910052751 metal Inorganic materials 0.000 claims description 17
- 239000002184 metal Substances 0.000 claims description 17
- 238000005245 sintering Methods 0.000 claims description 17
- 239000007853 buffer solution Substances 0.000 claims description 16
- 239000010406 cathode material Substances 0.000 claims description 16
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 15
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 12
- 229910012851 LiCoO 2 Inorganic materials 0.000 claims description 11
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 10
- 239000011247 coating layer Substances 0.000 claims description 10
- 229910052744 lithium Inorganic materials 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- 238000000151 deposition Methods 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 239000012266 salt solution Substances 0.000 claims description 8
- 229910020599 Co 3 O 4 Inorganic materials 0.000 claims description 7
- 229910052725 zinc Inorganic materials 0.000 claims description 7
- 239000011248 coating agent Substances 0.000 claims description 6
- 238000000576 coating method Methods 0.000 claims description 6
- GCDAQVSLRFIINK-UHFFFAOYSA-M lithium;acetic acid;acetate Chemical compound [Li+].CC(O)=O.CC([O-])=O GCDAQVSLRFIINK-UHFFFAOYSA-M 0.000 claims description 6
- 229910052727 yttrium Inorganic materials 0.000 claims description 6
- 239000013078 crystal Substances 0.000 claims description 5
- 229910021314 NaFeO 2 Inorganic materials 0.000 claims description 4
- ZRBROGSAUIUIJE-UHFFFAOYSA-N azanium;azane;chloride Chemical compound N.[NH4+].[Cl-] ZRBROGSAUIUIJE-UHFFFAOYSA-N 0.000 claims description 4
- FHUOTRMCFQTSOA-UHFFFAOYSA-M potassium;acetic acid;acetate Chemical compound [K+].CC(O)=O.CC([O-])=O FHUOTRMCFQTSOA-UHFFFAOYSA-M 0.000 claims description 4
- BHZOKUMUHVTPBX-UHFFFAOYSA-M sodium acetic acid acetate Chemical compound [Na+].CC(O)=O.CC([O-])=O BHZOKUMUHVTPBX-UHFFFAOYSA-M 0.000 claims description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 3
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910010093 LiAlO Inorganic materials 0.000 claims description 3
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 3
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 3
- WPADUSLPIFNQSF-UHFFFAOYSA-M [NH4+].[Na+].CC([O-])=O.CC([O-])=O Chemical compound [NH4+].[Na+].CC([O-])=O.CC([O-])=O WPADUSLPIFNQSF-UHFFFAOYSA-M 0.000 claims description 3
- 239000008055 phosphate buffer solution Substances 0.000 claims description 3
- NIWMEUWZZDPUEQ-UHFFFAOYSA-M sodium;azane;hydroxide Chemical compound N.[OH-].[Na+] NIWMEUWZZDPUEQ-UHFFFAOYSA-M 0.000 claims description 3
- PRWVAPJXQCMOFT-UHFFFAOYSA-M potassium;azane;hydroxide Chemical compound N.[OH-].[K+] PRWVAPJXQCMOFT-UHFFFAOYSA-M 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 abstract 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 abstract 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 abstract 2
- 229910010092 LiAlO2 Inorganic materials 0.000 abstract 1
- 229910032387 LiCoO2 Inorganic materials 0.000 abstract 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract 1
- 229910052681 coesite Inorganic materials 0.000 abstract 1
- 229910052593 corundum Inorganic materials 0.000 abstract 1
- 229910052906 cristobalite Inorganic materials 0.000 abstract 1
- 238000011031 large-scale manufacturing process Methods 0.000 abstract 1
- 239000000377 silicon dioxide Substances 0.000 abstract 1
- 235000012239 silicon dioxide Nutrition 0.000 abstract 1
- 229910052682 stishovite Inorganic materials 0.000 abstract 1
- 229910052905 tridymite Inorganic materials 0.000 abstract 1
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 1
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 abstract 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 32
- 239000011572 manganese Substances 0.000 description 27
- 238000003756 stirring Methods 0.000 description 21
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 239000000243 solution Substances 0.000 description 14
- 238000001878 scanning electron micrograph Methods 0.000 description 12
- 229910013716 LiNi Inorganic materials 0.000 description 11
- 239000011777 magnesium Substances 0.000 description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 8
- 239000006185 dispersion Substances 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 239000010936 titanium Substances 0.000 description 8
- PQVSTLUFSYVLTO-UHFFFAOYSA-N ethyl n-ethoxycarbonylcarbamate Chemical compound CCOC(=O)NC(=O)OCC PQVSTLUFSYVLTO-UHFFFAOYSA-N 0.000 description 7
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium hydroxide monohydrate Substances [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 description 7
- 229940040692 lithium hydroxide monohydrate Drugs 0.000 description 7
- 239000011159 matrix material Substances 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 239000011701 zinc Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 229910013733 LiCo Inorganic materials 0.000 description 4
- 239000012670 alkaline solution Substances 0.000 description 4
- 238000005253 cladding Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 4
- -1 salt compound Chemical class 0.000 description 4
- 238000001914 filtration Methods 0.000 description 3
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 3
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 3
- 229910052808 lithium carbonate Inorganic materials 0.000 description 3
- 239000012798 spherical particle Substances 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910001228 Li[Ni1/3Co1/3Mn1/3]O2 (NCM 111) Inorganic materials 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- 239000008351 acetate buffer Substances 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000006182 cathode active material Substances 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
- 238000009831 deintercalation Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000000724 energy-dispersive X-ray spectrum Methods 0.000 description 2
- 229910003002 lithium salt Inorganic materials 0.000 description 2
- 159000000002 lithium salts Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- OTYYBJNSLLBAGE-UHFFFAOYSA-N CN1C(CCC1)=O.[N] Chemical compound CN1C(CCC1)=O.[N] OTYYBJNSLLBAGE-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910019440 Mg(OH) Inorganic materials 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 229910015177 Ni1/3Co1/3Mn1/3 Inorganic materials 0.000 description 1
- 229910015150 Ni1/3Co1/3Mn1/3(OH)2 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 239000007771 core particle Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000011268 mixed slurry Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 239000007974 sodium acetate buffer Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
- 235000021419 vinegar Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
- C01G51/40—Cobaltates
- C01G51/42—Cobaltates containing alkali metals, e.g. LiCoO2
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- 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
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Definitions
- the invention belongs to the field of energy materials, and relates to a cathode material for a high energy density lithium ion battery and a preparation method thereof.
- Lithium ion secondary battery is an ideal energy storage system. It has the advantages of high energy density, good cycle, low self-discharge rate and good environmental compatibility. It has been rapidly developed in various fields of consumer electronics, and is used in power tools. The electric vehicle and power generation energy storage fields show great potential.
- High-capacity cathode materials are the basis and key to the development of high-energy-density lithium-ion batteries, and have become the focus of world research in recent years.
- Nickel-based materials have obvious cost advantages. As the nickel content increases, the material capacity can be significantly improved.
- NCA can reach 180 mAh/g at 4.25 V, but the high nickel cathode material has high surface activity and is easy to react with the electrolyte. The reaction causes the battery to swell, so it is necessary to modify these cathode materials.
- the core-shell structure is an effective modification treatment method to form a shell layer which is more stable than the matrix outside the core particles to improve the overall performance of the material. When the particles are coated, the safety performance is greatly improved.
- the main research of core-shell structure cathode materials is limited to high manganese materials in the shell layer, and a new type of cathode material is still needed in the field. Summary of the invention
- a positive electrode material comprising a positive electrode material body and a coating layer on a surface of the positive electrode material body,
- the coating material is one of Al 2 O 3 , ZrO 2 , MgO, SiO 2 , ZnO 2 , TiO 2 , Y 2 O 3 , LiAlO 2 or a combination thereof;
- the cathode material body includes a shell layer and a core located in the shell layer, wherein the core material is
- Lii +x [Ni 1-yz Co y Mn z ]O 2 where -0 ⁇ 1 ⁇ 0 ⁇ 2, 0 ⁇ y ⁇ 0.5, 0 ⁇ 0 ⁇ 5, 0 ⁇ y+z ⁇ 0.7
- the shell material is Li 1+a [Co 1-b X b ]O 2 , where -0.1 ⁇ a ⁇ 0.2, 0 ⁇ b ⁇ 0.5, X is Al, Mg, Cu, Zr, Ti, Cr, V , one or a combination of Fe, Mn, Ni; or
- the main body of the positive electrode material is a mixture of LUNii ⁇ COyMi ⁇ and LiCoO 2 , wherein -0.1 ⁇ x ⁇ 0.2, 0 ⁇ y ⁇ 0.5, 0 ⁇ 0 ⁇ 5, 0 ⁇ y+z ⁇ 0.7.
- the shell material is Li 1+a [Co 1-b X b ]O 2 , -0.1 ⁇ a ⁇ 0.2, and X is Al, Mg, Cu, Zr, Ti, Cr, V, Fe.
- each b is independently: 0 ⁇ b ⁇ 0.5.
- x 0.
- a 0.
- the core material and the shell material have a lattice structure of a-NaFeO 2 type, and the space group is R-3m.
- both the core material and the shell material have ionic deintercalation capabilities.
- the ratio of the thickness of the shell layer to the radius of the positive electrode material particles is 0.005-0.5;
- the coating layer has a thickness of 0.2 to 50 nm.
- the Ni content in the core material is greater than the Ni content in the shell material, and the Co content in the core material is less than the Co content in the shell material.
- the core is composed of 0.1 to 5 ⁇ m of crystal grains
- the shell layer is composed of crystal grains of 0.1 to 5 ⁇ m.
- 0 ⁇ y ⁇ 1.0, 0 ⁇ z ⁇ 1.0, 0 ⁇ y+z ⁇ l; 0 ⁇ b ⁇ 1.0, X, M are independently selected from Al, Mg, One of Cu, Zr, Ti, Cr, V, Fe, Mn, Ni, Y, Zn or a combination thereof.
- the sintered sample is placed in a buffer solution, the salt solution of the metal M is added, and the pH is adjusted to be alkaline, on the surface of the sintered sample.
- the hydroxide of the metal M is precipitated.
- the buffer solution is acetic acid-sodium acetate, acetic acid-potassium acetate, acetic acid-lithium acetate, ammonia-ammonium chloride, ammonia water, ammonium acetate-sodium acetate, acetic acid, ammonia-sodium hydroxide, ammonia.
- potassium hydroxide, a phosphate buffer solution, a borate buffer solution having a pH of from 4.0 to 14.0 A third aspect of the invention provides the method for preparing a positive electrode material according to the first aspect, comprising the steps of:
- 0 ⁇ y ⁇ 1.0, 0 ⁇ z ⁇ 1.0, 0 ⁇ y+z ⁇ l; 0 ⁇ b ⁇ 1.0, X, M are independently selected from Al, Mg, Cu, Zr, Ti, Cr, V, One of Fe, Mn, Ni, Y, Zn or a combination thereof.
- the mass ratio of NiLy.zCOyMn ⁇ OH to Co 3 O 4 is from 0.1:0.9 to 0.9:0.1.
- the lithium source is one of lithium carbonate, lithium hydroxide monohydrate, lithium acetate, lithium nitrate, or a combination thereof.
- the Co 3 O 4 has a particle size of 0.1 to 5 ⁇ m.
- the sintered sample in the step (c), is placed in a buffer solution, the salt solution of the metal ruthenium is added, and the pH is adjusted to be alkaline, on the surface of the sintered sample.
- the hydroxide of the metal ruthenium is precipitated.
- the buffer solution is acetic acid-sodium acetate, acetic acid-potassium acetate, acetic acid-lithium acetate, ammonia-ammonium chloride, ammonia water, ammonium acetate-sodium acetate, acetic acid, ammonia-sodium hydroxide, ammonia.
- potassium hydroxide, a phosphate buffer solution, a borate buffer solution having a pH of from 4.0 to 14.0 a lithium ion battery comprising the positive electrode material of the first aspect is provided.
- Figure 1 is a scanning electron micrograph of a core-shell precursor prepared in Example 1.
- Fig. 2 is a scanning electron micrograph of the positive electrode material prepared in Example 1.
- Figure 3 is a scanning electron micrograph of the core-shell precursor prepared in Example 2.
- Fig. 4 is a scanning electron micrograph of the positive electrode material prepared in Example 2.
- Figure 5 is a scanning electron micrograph of the core-shell precursor prepared in Example 3.
- Fig. 6 is a scanning electron micrograph of the positive electrode material prepared in Example 3.
- Fig. 7 is a view showing the internal appearance of particles of the positive electrode material prepared in Example 3.
- Figure 8 is a shell EDS spectrum of Example 3.
- Figure 9 is a core EDS spectrum of Example 3.
- Figure 10 is a scanning electron micrograph of the positive electrode material prepared in Example 4.
- Figure 11 is a scanning electron micrograph of the core-shell precursor prepared in Example 5.
- Figure 12 is a scanning electron micrograph of the positive electrode material prepared in Example 5.
- Figure 13 is a scanning electron micrograph of the positive electrode material prepared in Example 6.
- Figure 14 is a scanning electron micrograph of the positive electrode material prepared in Example 7.
- Figure 15 is an XRD chart of the positive electrode material prepared in Examples 8 and 9.
- Figure 16 is a scanning electron micrograph of the positive electrode material prepared in Example 10.
- Fig. 17 is a graph showing the results of the refinement of the positive electrode material prepared in Example 3.
- Figure 18 is a discharge curve of the positive electrode material prepared in Examples 1-4.
- Figure 19 is a discharge curve of the positive electrode materials prepared in Examples 5, 6, and 10.
- Figure 20 is a discharge curve of the positive electrode material prepared in Examples 7-9.
- Figure 21 is a charge and discharge cycle diagram of the positive electrode material prepared in Example 3 and Example 4.
- Fig. 22 is a charge and discharge cycle diagram of the positive electrode material prepared in Example 5 and Example 6.
- Example 23 is a charge and discharge cycle diagram of the positive electrode material prepared in Example 7 and Example 8. detailed description
- the inventors of the present application have extensively and intensively studied and accidentally developed a novel positive electrode material, and deposited an amorphous oxide coating layer on the outside of the positive electrode material body, which can further improve the comprehensive performance of the positive electrode material and can be used for A lithium ion secondary battery is fabricated. On the basis of this, the present invention has been completed.
- Cathode material
- the positive electrode material of the present invention comprises a positive electrode material body and a coating layer on the surface of the positive electrode material body, wherein the cladding layer material is Al 2 O 3 , ZrO 2 , MgO, SiO 2 , ZnO 2 , TiO 2 , Y 2 O 3 Or one or a combination of LiAlO 2 ;
- the cathode material body comprises a shell layer and a core located in the shell layer, wherein the core material is Li 1+x [Ni 1-yz Co y Mn z ]O 2 , wherein -0 ⁇ 1 ⁇ 0 ⁇ 2 , 0 ⁇ y ⁇ 0.5, 0 ⁇ 0 ⁇ 5, 0 ⁇ y+z ⁇ 0.7;
- the shell material is Li 1+a [Co 1-b X b ]O 2 , where -0.1 ⁇ a ⁇ 0.2 , 0 ⁇ b ⁇ 0.5, X is one of Al, Mg, Cu, Zr, Ti, Cr, V, Fe, Mn, Ni or a combination thereof; or
- the main body of the positive electrode material is a mixture of Li ⁇ Ni ⁇ COyMigOs and LiCoO 2 , wherein -0.1 ⁇ x ⁇ 0.2, 0 ⁇ y ⁇ 0.5, 0 ⁇ 0 ⁇ 5, 0 ⁇ y+z ⁇ 0.7.
- the core portion of the positive electrode material has an ion deintercalation ability with the shell portion, and the structures of the two are the same, but the element composition is different.
- the shell layer is a high-cobalt material with better electrochemical performance.
- a layer of amorphous oxide coating is deposited outside the shell layer to further improve the overall performance of the material.
- both the core and the shell material have a-NaFeO 2 structure, and the space group is R-3m. Li occupies the 3a position, Ni, Co, and Mn occupy the 3b position, and O occupies the 3c position.
- the material is further characterized in that the core and the shell layer constitute spherical particles, and the spherical particles are composed of 0.1-2 ⁇ m of crystal particles having a size of 2 to 50 ⁇ m.
- the quality of the coating material is 0.001-10% of the total mass of the active cathode material, and the thickness of the coating layer is 0.2-50 nm.
- the ratio of the thickness of the shell layer to the particle size of the spherical particles of the entire positive electrode material is 0.005-0.5.
- 0 ⁇ y ⁇ 1.0, 0 ⁇ z ⁇ 1.0, 0 ⁇ y+z ⁇ l; 0 ⁇ b ⁇ 1.0, X, M are independently selected from Al, Mg, Cu, Zr, Ti, Cr, V, One of Fe, Mn, Ni, Y, Zn or a combination thereof.
- the precursor prepared has a core-shell structure, and after sintering, the particles form a shell layer having a concentration gradient.
- the coating material can be uniformly attached to the surface of the core-shell material.
- the positive electrode material of the present invention can be prepared by the following method: a. precursor ⁇ ⁇ ⁇ ) ⁇ ⁇ ⁇ ( ⁇ ) 2 , 0 ⁇ y ⁇ 1.0, 0 ⁇ z ⁇ 1.0 , 0 ⁇ y+z ⁇ l, added to the solvent S, and stirred to form a dispersion S1.
- the solvent S may be one or a mixture of water, ethanol, and ethylene glycol.
- the salt solution of Co or the salt solution of Co and X is added to the SI.
- the concentration of the Co and X salt solution is 0 to 10 mol/L.
- the operating atmosphere may be one or more of air, nitrogen, and argon.
- X is one or more of Al, Mg, Cu, Zr, Ti, Cr, V, Fe, Mn which are soluble in the solvent S I .
- alkaline solution E to completely precipitate metal ions Co or Co and X.
- the alkaline solution may be one or more of ammonia water, lithium hydroxide, sodium hydroxide, or potassium hydroxide solution.
- the lithium salt is one or more selected from the group consisting of lithium carbonate, lithium hydroxide monohydrate, lithium acetate, and lithium nitrate.
- the sintered sample is added to a buffer solution and stirred to form a dispersion.
- the buffer solution can be vinegar One or more of acid-sodium acetate, acetic acid-potassium acetate, acetic acid-lithium acetate, ammonia-ammonium chloride, ammonia water, ammonium chloride.
- the pH of the buffer solution ranges from 4.0 to 14.0.
- the metal M salt compound must be soluble in solvent S, which may be aluminum, magnesium, zirconium, silicon, zinc, titanium chloride, nitrate, sulfate, acetate One or several.
- the solvent S may be one or a mixture of water, ethanol, and ethylene glycol.
- concentration of the M salt solution is 0.01 to 10 mol/L.
- alkaline solution E to completely precipitate metal M.
- the alkaline solution may be one or more of ammonia water, lithium hydroxide, sodium hydroxide, and potassium hydroxide solution.
- the preparation method of the positive electrode material of the invention comprises the steps of:
- 0 ⁇ y ⁇ 1.0, 0 ⁇ z ⁇ 1.0, 0 ⁇ y+z ⁇ l; 0 ⁇ b ⁇ 1.0, X, M are independently selected from the group consisting of Al, Mg, Cu, Zr, Ti, Cr, One of V, Fe, Mn, Ni, Y, Zn or a combination thereof.
- the invention is advantageous in that:
- the present invention provides a positive electrode material of a novel structure and composition.
- the positive electrode material of the present invention has a uniform shell layer and a controllable thickness.
- the positive electrode material has the outermost coating layer, which has a good protective effect on the main body of the positive electrode material.
- the positive electrode material of the present invention has the advantages of high capacity, good cycleability, low surface activity, high pressure resistance, and good safety.
- a positive electrode material having a core of LiNi 1/3 Co 1/3 Mn 1/3 O 2 and a shell layer of Li[( 1/3 Co 1/3 Mn 1/3 ) 99 Al aQ1 ]O 2 was prepared.
- lithium hydroxide monohydrate and the dried precursor were uniformly mixed at a molar ratio of 1.10, and the mixture was calcined at 450 ° C for 5 hours in the air, then heated to 900 ° C for 12 hours, and naturally cooled to room temperature.
- a positive active material having a surface of Li[(Ni 1/3 Co 1/3 Mn 1/3 )a 99 Ala Q1 ]O 2 and an internal matrix of LiNi 1/3 Co 1/3 Mn 1/3 O 2 is obtained, The morphology is shown in Fig. 2, the particle size is 1-21 ⁇ , and the shell thickness is 0.2 ⁇ .
- Example 2 Example 2
- a positive electrode material having a core of LiNi 5 Co 2 Mn a3 O 2 and a shell layer of Li[( a 5 Coa 2 Mn 3 ) a99 Al a() 1 ]O 2 was prepared.
- lithium hydroxide monohydrate and the dried precursor were uniformly mixed at a molar ratio of 1.10, and the mixture was calcined at 900 ° C for 12 hours in an oxygen atmosphere, and naturally cooled to room temperature.
- a positive electrode active material having a shell layer of I ⁇ iNi sCo ⁇ Mna ⁇ Al ⁇ ]O 2 and a core of LiNia 5 Co a2 Mno. 3 O 2 was obtained, and its morphology was as shown in Fig. 4, and the particle size was 1-25 ⁇ m.
- the thickness of the shell layer is 0.5 ⁇ m.
- a positive electrode material having a core of LiNi 5 Co 2 Mna 3 O 2 and a shell layer of LiCoO 2 was prepared.
- Ni a5 Co a2 Mn 3 (OH) 2 10.0200g forming a dispersion of the precursor, adding 1% ammonia water, adjusting the pH to about 9.0, continuing to adjust the pH to 11 with concentrated ammonia water, stirring for 60 minutes, stopping the stirring After filtration, washed twice, the coated precursor was dried at 120 ° C for 12 hours, its morphology is shown in Figure 5, the particle size is 1-20 ⁇ , then the lithium hydroxide monohydrate and the dried precursor The mixture was uniformly mixed at a molar ratio of 1.10, and the mixture was calcined at 900 ° C for 12 hours in an oxygen atmosphere, and naturally cooled to room temperature.
- a positive active material having a surface of LiCoO 2 and an internal matrix of LiNi 5 Co 2 Mn 3 O 2 was obtained, and its morphology was as shown in Fig. 6, and the particle diameter was 1 to 25 ⁇ m.
- the thickness of the shell layer is 0.5 ⁇ m.
- Figure 7 is a diagram showing the internal shape of the particles of the positive electrode material.
- the shell and core of the core-shell material consist of 0.1-2 ⁇ small grains.
- the shell and core were analyzed by energy spectrum EDS. The results are shown in Figure 8, Figure 9 and Table 1.
- the content of Ni in the core is larger than the content of Ni in the shell, and the content of Co in the core is smaller than the content of Co in the shell.
- Shell and core part EDS element analysis results are shown in Figure 8, Figure 9 and Table 1.
- the content of Ni in the core is larger than the content of Ni in the shell, and the content of Co in the core is smaller than the content of Co in the shell.
- Shell and core part EDS element analysis results are shown in Figure 8, Figure 9 and Table 1.
- the preparation is a core material of LiNi Q . 5 Co 2 Mna 3 O 2 , the shell layer is LiCoO 2 , and the coating layer is ⁇ 1 2 ⁇ 3 .
- the positive electrode material prepared in Example 2 weighed 5 g, added to a 100 mL acetic acid-lithium acetate buffer solution having a pH of 6.0, and gradually added a 0.1 mol/L solution of ⁇ 1( ⁇ 3 ) 3 , and stirred for 30 minutes.
- the positive electrode active material having a surface of ⁇ 1 3 ⁇ 2 , a shell layer of LiCoO 2 and an inner matrix of LiNi 5 Co Q . 2 Mno. 3 O 2 was obtained, and its morphology was as shown in Fig. 10, and the particle diameter was 1-25 ⁇ m.
- the thickness of the cladding layer was 25 nm.
- a positive electrode material having a core of LiNi 5 Co 2 Mna 3 O 2 and a shell layer of LiCo 95 Ala() 5 O 2 was prepared.
- the particle size was 1-25 ⁇ m, and then the lithium hydroxide monohydrate and the dried precursor were uniformly mixed at a molar ratio of 1.10, and the mixture was mixed in oxygen.
- the mixture was calcined at 900 ° C for 12 hours in the atmosphere and naturally cooled to room temperature.
- a positive electrode active material having a surface of LiCoO 2 and an internal matrix of LiNi 5 Coa 2 M 3 ⁇ 43 O 2 was obtained, and its morphology was as shown in Fig. 12, and the particle diameter was 1 to 25 ⁇ m.
- the thickness of the shell layer is 0.6 ⁇ m.
- a positive electrode material having a core of LiNi 5 Co 2 Mna 3 O 2 , a shell layer of LiCo 95 Ala() 5 O 2 and a cladding layer of MgO was prepared.
- Example 7 Using the positive electrode material prepared in Example 5, weighed 5.0204 g, added to 100 mL of water, stirred to form a dispersion, and added a concentration of 0.1 mol/L of MgSO 4 solution, and adjusted the pH with a 1 mol/L NaOH solution. After stirring for 120 minutes, the mixture was filtered and washed with water to obtain a positive electrode material coated with Mg(OH) 2 . The positive electrode material was dried at 120 ° C for 10 hours, and then calcined at 500 ° C for 12 hours to obtain a surface. It is MgO, the shell layer is LiCo Q. 95 Al ()5 O 2 , and the internal matrix is LiNi Q . 5 Co 2 Mn a3 O 2 cathode active material, its morphology is shown in Figure 13, the particle size is 1-25 ⁇ . The thickness of the cladding layer was 30 nm. Example 7
- the Co 3 O 4 and Ni 5 Coa 2 Mn a3 (OH) 2 precursors were uniformly mixed at a molar ratio of 1:4, and the uniformly mixed precursor was uniformly mixed with lithium carbonate in a molar ratio of 1.0:1.1 at 900 ° C.
- the sintering atmosphere was oxygen to obtain a positive electrode material, which was a mixture of LiCoO 2 and Li[Ni 5 Co 2 Mna 3 ]O 2 .
- the morphology of the positive electrode material is shown in Fig. 14, and the particle diameter is 0.5 to 25 ⁇ m.
- Example 9 5 g of the positive electrode material in Example 7 was added to a 100 mL acetic acid-lithium acetate buffer solution having a pH of 6.0, and a 0.1 mol/L solution of ⁇ 1( ⁇ 3 ) 3 was gradually added, and after stirring for 30 minutes, 5% was added dropwise. Ammonia water, adjusted to pH 8.0, stirred for 30 minutes, stopped stirring, filtered, washed twice with water, and the coated precursor was dried at 120 ° C for 8 hours and then calcined at 450 ° C for 15 hours. A positive electrode material having a surface of ⁇ 1 2 ⁇ 3 and a positive electrode material body of a mixture of LiCoO 2 and Li[Ni 5 Co 2 Mna 3 ]O 2 was obtained.
- Example 9 5 g of the positive electrode material in Example 7 was added to a 100 mL acetic acid-lithium acetate buffer solution having a pH of 6.0, and a 0.1 mol/L solution of ⁇ 1( ⁇ 3 )
- the Co 3 O 4 and Ni 5 Co a2 Mn a3 (OH) 2 precursors were uniformly mixed at a molar ratio of 1:3, and the uniformly mixed precursor was uniformly mixed with lithium acetate in a molar ratio of 1.0:1.1 at 950 ° C. After sintering for 12 hours, the sintering atmosphere was oxygen.
- the sintered cathode material is added to a 100 mL acetic acid-sodium acetate buffer solution having a pH of 6.0, and a 0.1 mol/L solution of ⁇ 1( ⁇ 3 ) 3 is gradually added.
- a positive electrode material having a surface of ⁇ 1 2 ⁇ 3 and a positive electrode material body of a mixture of LiCoO 2 and Li[Ni Q . 5 Co 2 Mna 3 ]O 2 was obtained.
- Figure 15 is an XRD chart of the positive electrode material prepared in Examples 8 and 9. The results show that the intensity of the diffraction peak of lithium cobaltate in the positive electrode material increases as the proportion of tricobalt tetroxide in the precursor increases.
- Example 10
- the core material was prepared as LiNi Q . 5 Co 2 Mna 3 O 2
- the shell layer was a positive electrode material of LiCo 95 Ala Q5 O 2
- the coating layer was a positive electrode material of ZrO 2 .
- lithium hydroxide monohydrate and the dried precursor were uniformly mixed at a molar ratio of 1.10, and the mixture was baked at 900 ° C for 12 hours in an oxygen atmosphere, and naturally cooled to room temperature.
- a positive active material having a shell layer of LiCoo.95Alo.05O2 and an inner matrix of LiNi 5 Co 2 Mna 3 O 2 was obtained, and its morphology was as shown in Fig. 16, and the particle diameter was 1-25 ⁇ m.
- the thickness of the shell layer is 0.5 ⁇ m.
- the positive electrode material has an a-NaFeO 2 type structure, and the space group is R-3m. Li occupies the 3a position, Ni, Co, and Mn occupy the 3b position, and O occupies the 3c position.
- the positive electrode materials prepared in Examples ⁇ to ⁇ were separately mixed with the conductive agent acetylene black and the binder polyvinylidene fluoride (PVDF) in a solution of nitrogen methylpyrrolidone (NMP), a positive electrode material, acetylene black and a binder.
- NMP nitrogen methylpyrrolidone
- the mass ratio of the agents was 90:5:5, respectively, and then the uniformly mixed slurry was coated on an aluminum foil, and vacuum-dried at 120 ° C for 12 hours to obtain a positive electrode of a lithium ion battery.
- the above-mentioned pole piece is used as a positive electrode, metal lithium is used as a negative electrode, the electrolyte is made of a solution of 1 mol/L lithium hexafluorophosphate of ethylene carbonate and dimethyl carbonate, and 20 ⁇ m thick polyethylene is used as a separator, and assembled into a CR2032 type button lithium ion battery. .
- the assembled button battery was tested on a blue electric charge and discharge tester with a voltage range of 2.8-4.3 volts and a charge and discharge current density of 16 mA/g.
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Abstract
提供一种高能量密度锂离子电池氧化物正极材料、其制备方法及用途。所述正极材料包括正极材料主体和包覆层。所述主体包括壳层和位于壳层内的核心,所述核心的材料为Li1+x[Ni1-y-zCoyMnz]O2其中,-0.1≤x≤0.2,0≤y≤0.5,0≤z≤0.5,0≤y+z≤0.7;所述壳层的材料为Li1+a[Co1-bXb]O2,其中,-0.1≤a≤0.2,0≤b≤0.5,X为Al、Mg、Cu、Zr、Ti、Cr、V、Fe、Mn、Ni中的一种或其组合。或者所述主体为Li1+x[Ni1-y-zCoyMnz]O2和LiCoO2的混合物,其中,-0.1≤x≤0.2,0≤y≤0.5,0≤z≤0.5,0≤y+z≤0.7。所述包覆层的材料为Al2O3、ZrO2、MgO、SiO2、ZnO、TiO2、Y2O3、LiAlO2中的一种或其组合。所述正极材料具有容量高、循环性好、表面活性低、耐高压、安全性好的优点。制备工艺简单,适合大规模生产应用。
Description
高能量密度锂离子电池氧化物正极材料及其制备方法
技术领域
本发明属于能源材料领域, 涉及一种高能量密度锂离子电池用正极材料及其 制备方法。 技术背景
锂离子二次电池是一种理想的储能系统, 具有能量密度高、 循环性好、 自放 电率低和环境兼容性好等优点, 在各类消费电子产品领域获得迅速发展, 并在电 动工具、 电动汽车和发电储能领域显示出巨大的潜力。
高容量正极材料是开发高能量密度锂离子电池的基础与关键, 近年来成为了 世界研究的焦点。 镍基材料具有明显的成本优势, 随着镍含量的增加, 材料容量 能够明显提高, 如 NCA在 4.25V能够达到 180mAh/g, 但高镍正极材料的表面活 性较高, 容易与电解液发生副反应造成电池胀气, 因此需要对这些正极材料进行 改性处理。
核壳结构是一种有效的改性处理方法, 在核心颗粒外形成一层比基体更稳定 的壳层, 提高材料整体性能。 在颗粒在加上包覆层, 安全性能得到大幅提高。 目 前, 核壳结构正极材料的主要研究局限于壳层为高锰材料, 本领域尚需研制新型 的正极材料。 发明内容
本发明的目的在于, 提供一种新型的高能量密度锂离子电池氧化物正极材料 及其制备方法。 本发明的第一方面, 提供一种正极材料, 所述正极材料包括正极材料主体和 位于正极材料主体表面的包覆层,
其中, 包覆层材料为 Al2O3、 ZrO2、 MgO、 SiO2、 ZnO2、 TiO2、 Y2O3、 LiAlO2 中的一种或其组合;
所述正极材料主体包括壳层和位于壳层内的核心, 其中, 核心材料为
Lii+x[Ni1-y-zCoyMnz]O2, 其中, -0· 1≤χ≤0·2, 0≤y≤0.5, 0≤ζ≤0·5, 0<y+z<0.7 ; 壳层 材料为 Li1+a[Co1-bXb]O2, 其中, -0.1≤a≤0.2, 0≤b≤0.5, X为 Al、 Mg、 Cu、 Zr、 Ti、 Cr、 V、 Fe、 Mn、 Ni中的一种或其组合; 或
所述正极材料主体为 LUNii^COyMi ^和 LiCoO2 的混合物, 其中 -0.1<x<0.2, 0≤y≤0.5, 0≤ζ≤0·5, 0≤y+z≤0.7。
在另一优选例中, 壳层材料为 Li1+a[Co1-bXb]O2, -0.1≤a≤0.2, X为 Al、 Mg、 Cu、 Zr、 Ti、 Cr、 V、 Fe、 Mn、 Ni中两种以上的组合时, 各 b独立地为: 0<b≤0.5。
在另一优选例中, x=0。
在另一优选例中, a=0。
在另一优选例中, 所述核心材料和所述壳层材料的晶格结构均为 a-NaFeO2 型, 空间群均为 R-3m。
在另一优选例中, 所述核心材料和所述壳层材料均具有离子脱嵌能力。
在另一优选例中, 所述壳层厚度与所述正极材料颗粒半径的比例为 0.005-0.5; 和 /或
所述包覆层的厚度为 0.2〜50nm。
在另一优选例中, 所述核心材料中 Ni含量大于所述壳层材料中 Ni含量, 所 述核心材料中 Co含量小于所述壳层材料中 Co含量。
在另一优选例中, 所述核心由 0.1-5μιη的晶粒构成, 所述壳层由 0.1〜5μιη的 晶粒构成。 本发明的第二方面, 提供第一方面所述的正极材料的制备方法, 包括步骤:
(a) 在 Ni1-y-zCoyMnz(OH)2表面沉降 Co的氢氧化物, 或 X和 Co的氢氧化物, 得到核壳前驱体 P;
(b) 将所述核壳前驱体 P与锂源按照 Li/P=l-1.2的摩尔比混合后烧结;
(c) 在烧结后的样品的表面沉降金属 M的氢氧化物;
(d) 在 200- 1000 °C烧结 0.5-24小时, 得到所述正极材料,
其中, 0≤y≤1.0, 0≤z≤1.0, 0<y+z<l ; 0≤b≤1.0, X、 M独立地选自为 Al、 Mg、
Cu、 Zr、 Ti、 Cr、 V、 Fe、 Mn、 Ni、 Y、 Zn中的一种或其组合。
在另一优选例中, 所述步骤 (c)中, 将烧结后的样品置于缓冲溶液中, 加入所 述金属 M的盐溶液, 调节 pH至碱性, 在所述烧结后的样品的表面沉降金属 M 的氢氧化物。
在另一优选例中,所述缓冲溶液为醋酸-醋酸钠、醋酸-醋酸钾、醋酸-醋酸锂、 氨-氯化铵、 氨水、 醋酸铵-醋酸钠、 醋酸、 氨 -氢氧化钠、 氨 -氢氧化钾、 磷酸盐缓 冲溶液、 硼酸盐缓冲溶液中的一种或其组合, 所述缓冲溶液的 pH为 4.0-14.0。 本发明的第三方面, 提供第一方面所述的正极材料的制备方法, 包括步骤:
(a) 在 Ni1-y-zCoyMnz(OH)2与 Co3O4混合, 得到核壳前驱体 P;
(b) 将所述核壳前驱体 P与锂源按照 Li/P=l-1.2的摩尔比混合后烧结;
(c) 在烧结后的样品的表面沉降金属 M的氢氧化物;
(d) 在 200- 1000 °C烧结 0.5-24小时, 得到所述正极材料,
其中, 0≤y≤1.0, 0≤z≤1.0, 0<y+z<l ; 0≤b≤1.0, X、 M独立地选自为 Al、 Mg、 Cu、 Zr、 Ti、 Cr、 V、 Fe、 Mn、 Ni、 Y、 Zn中的一种或其组合。
在另一优选例中, NiLy.zCOyMn^OH 与 Co3O4的质量比为 0.1 : 0.9至 0.9:0.1。 在另一优选例中, 锂源采用碳酸锂、 一水氢氧化锂、 醋酸锂、 硝酸锂中的一 种或其组合。
在另一优选例中, 所述 Co3O4的颗粒尺寸为 0.1-5μιη。
在另一优选例中, 所述步骤 (c)中, 将烧结后的样品置于缓冲溶液中, 加入所 述金属 Μ的盐溶液, 调节 pH至碱性, 在所述烧结后的样品的表面沉降金属 Μ 的氢氧化物。
在另一优选例中,所述缓冲溶液为醋酸-醋酸钠、醋酸-醋酸钾、醋酸-醋酸锂、 氨-氯化铵、 氨水、 醋酸铵-醋酸钠、 醋酸、 氨 -氢氧化钠、 氨 -氢氧化钾、 磷酸盐缓 冲溶液、 硼酸盐缓冲溶液中的一种或其组合, 所述缓冲溶液的 pH为 4.0-14.0。 本发明的第四方面, 提供一种锂离子电池, 包括第一方面所述的正极材料。
应理解, 在本发明范围内中, 本发明的上述各技术特征和在下文 (如实施例) 中具体描述的各技术特征之间都可以互相组合, 从而构成新的或优选的技术方 案。 限于篇幅, 在此不再一一累述。 附图说明
图 1为实施例 1制备的核壳前驱体的扫描电镜图。
图 2为实施例 1制备的正极材料的扫描电镜图。
图 3为实施例 2制备的核壳前驱体的扫描电镜图。
图 4为实施例 2制备的正极材料的扫描电镜图。
图 5为实施例 3制备的核壳前驱体的扫描电镜图。
图 6为实施例 3制备的正极材料的扫描电镜图。
图 7为实施例 3制备的正极材料的颗粒内部形貌图。
图 8为实施例 3壳层 EDS谱图。
图 9为实施例 3核心 EDS谱图。
图 10为实施例 4制备的正极材料的扫描电镜图。
图 11为实施例 5制备的核壳前驱体的扫描电镜图。
图 12为实施例 5制备的正极材料的扫描电镜图。
图 13为实施例 6制备的正极材料的扫描电镜图。
图 14实施例 7制备的正极材料的扫描电镜图。
图 15为实施例 8、 9制备的正极材料的 XRD谱图。
图 16实施例 10制备的正极材料的扫描电镜图。
图 17为实施例 3制备的正极材料谱图精修后的结果图。
图 18为实施例 1-4制备的正极材料的放电曲线。
图 19为实施例 5、 6、 10制备的正极材料的放电曲线。
图 20为实施例 7-9制备的正极材料的放电曲线。
图 21为实施例 3、 实施例 4制备的正极材料充放电循环图。
图 22为实施例 5、 实施例 6制备的正极材料充放电循环图。
图 23为实施例 7、 实施例 8制备的正极材料充放电循环图。
具体实施方式
本申请的发明人经过广泛而深入地研究, 意外研发出一种新型的正极材料, 在正极材料主体外沉积一层无定形氧化物包覆层, 可进一步提高正极材料的综合 性能, 能够用于制作锂离子二次电池。 在此基础上, 完成了本发明。 正极材料
本发明的正极材料包括正极材料主体和位于正极材料主体表面的包覆层, 其中, 包覆层材料为 Al2O3、 ZrO2、 MgO、 SiO2、 ZnO2、 TiO2、 Y2O3、 LiAlO2 中的一种或其组合;
所述正极材料主体包括壳层和位于壳层内的核心, 其中, 核心材料为 Li1+x[Ni1-y-zCoyMnz]O2, 其中, -0· 1≤χ≤0·2, 0≤y≤0.5, 0≤ζ≤0·5, 0<y+z<0.7 ; 壳层 材料为 Li1+a[Co1-bXb]O2, 其中, -0.1≤a≤0.2, 0≤b≤0.5, X为 Al、 Mg、 Cu、 Zr、 Ti、 Cr、 V、 Fe、 Mn、 Ni中的一种或其组合; 或
所述正极材料主体为 Li ^Ni^^COyMigOs和 LiCoO2 的混合物, 其中 -0.1<x<0.2, 0≤y≤0.5, 0≤ζ≤0·5, 0≤y+z≤0.7。
该正极材料核心部分组成与壳层部分都有离子脱嵌能力, 两者的结构相同, 但元素组成不同。 壳层为高钴材料, 具有更好的电化学性能, 在壳层外沉积一层 无定形氧化物包覆层, 可进一步提高材料的综合性能。
从壳层至核心, Ni的浓度逐渐增加, Co的浓度逐渐减小。 根据合成的正极 材料 XRD谱图解析, 核心和壳层材料均具有 a-NaFeO2结构, 空间群为 R-3m。 Li占据 3a位置, Ni、 Co、 Mn占据 3b位置, O占据 3c位置。
该材料的特征还在于, 核心和壳层组成球形颗粒, 球形颗粒由 0.1-2μιη的晶 粒构成, 该球形颗粒的尺寸为 2-50μιη。
包覆层材料的质量占活性正极材料总质量的 0.001-10%, 包覆层厚度为 0.2-50nm。 壳层厚度与整个正极材料球形颗粒粒径的比值为 0.005-0.5。 制备方法
本发明的的正极材料的制备方法, 包括步骤:
(a) 在 Ni1-y-zCoyMnz(OH)2表面沉降 Co的氢氧化物, 或 X和 Co的氢氧化物, 得到核壳前驱体 P;
(b) 将所述核壳前驱体 P与锂源按照 Li/P=l-1.2的摩尔比混合后烧结;
(c) 在烧结后的样品的表面沉降金属 M的氢氧化物;
(d) 在 200- 1000 °C烧结 0.5-24小时, 得到所述正极材料,
其中, 0≤y≤1.0, 0≤z≤1.0, 0<y+z<l ; 0≤b≤1.0, X、 M独立地选自为 Al、 Mg、 Cu、 Zr、 Ti、 Cr、 V、 Fe、 Mn、 Ni、 Y、 Zn中的一种或其组合。
本发明中, Li/P=l-1.2的摩尔比是指 Li的摩尔数与核壳前驱体的摩尔数之比 为 1-1.2。
本发明的方法, 制备的前驱体具有核壳结构, 烧结后, 颗粒形成一个具有浓 度梯度的壳层。 采用本制备方法, 能够使包覆层物质均匀附着在核壳材料表面。
在一优选实施方式中, 本发明的正极材料可以通过以下方法制备: a. 将前驱体 Νί^ζΟ)γΜηζ(ΟΗ)2, 0<y<1.0, 0<z<1.0 , 0<y+z<l , 加入到溶剂 S中, 搅拌形成分散液 S l。 溶剂 S可以是水、 乙醇、 乙二醇中的一种或几种的混 合物。
b. 将 Co的盐溶液或 Co、 X的盐溶液加入到 SI中。 Co、 X盐溶液的浓度为 0〜10 mol/L。 操作气氛可以是空气、 氮气、 氩气中的一种或几种。 X为 Al、 Mg、 Cu、 Zr、 Ti、 Cr、 V、 Fe、 Mn中的一种或几种能溶于溶剂 S I的盐。
c. 在 b步骤操作的同时, 加入碱性溶液 E, 使金属离子 Co或 Co和 X完全 沉淀。 碱性溶液可以是氨水、 氢氧化锂、 氢氧化钠、 氢氧化钾溶液中的一种或几 种。
d. 过滤、 干燥得核壳前驱体 Pl。 干燥温度为 50-200 °C。
e. 将包覆前驱体 PI与锂盐按摩尔比 Li/Pl=1.0〜 1.2进行混合。 锂盐采用碳 酸锂、 一水氢氧化锂、 醋酸锂、 硝酸锂中的一种或几种。
f. 高温煅烧。化合物在 T 1温度下预烧 0-20小时,然后在 T2温度下保温 5-50 小时, 其中 T1=100-1000°C, T2=400-1000°C o
g. 烧结后的样品加入到缓冲溶液中, 搅拌形成分散液。该缓冲溶液可以是醋
酸-醋酸钠、 醋酸-醋酸钾、 醋酸-醋酸锂、 氨-氯化铵、 氨水、 氯化铵中的一种或几 种。 缓冲溶液 pH范围在 4.0- 14.0之内。
h. 加入包覆金属 M的盐溶液, 金属 M盐类化合物必须能溶于溶剂 S, 可以 是铝、 镁、 锆、 硅、 锌、 钛的氯化物、 硝酸盐、 硫酸盐、 醋酸盐中的一种或几种。 溶剂 S 可以是水、 乙醇、 乙二醇中的一种或几种的混合物。 M盐溶液的浓度为 0.01〜10 mol/L。
i. 加入碱性溶液 E, 使金属 M完全沉淀。 碱性溶液可以是氨水、 氢氧化锂、 氢氧化钠、 氢氧化钾溶液中的一种或几种。
j . 过滤后干燥, 干燥温度为 50-200 °C。
k. 高温焙烧, 焙烧温度为 300- 100°C, 焙烧时间为 1 -24小时。 包覆金属盐化 合物的重量为含锂活性物质重量的 0.5- 10%。 本发明的正极材料的制备方法, 包括步骤:
(a) 在 Ni1-y-zCoyMnz(OH)2与 Co3O4混合, 得到核壳前驱体 P ;
(b) 将所述核壳前驱体 P与锂源按照 Li/P=l - 1.2的摩尔比混合后烧结;
(c) 在烧结后的样品的表面沉降金属 M的氢氧化物;
(d) 在 200- 1000 °C烧结 0.5-24小时, 得到所述正极材料,
其中, 0≤y≤1.0, 0≤z≤1.0, 0<y+z<l ; 0≤b≤1 .0, X、 M独立地选自为 Al、 Mg、 Cu、 Zr、 Ti、 Cr、 V、 Fe、 Mn、 Ni、 Y、 Zn中的一种或其组合。 本发明的有益之处在于:
(1) 本发明提供了一种新型结构和组成的正极材料。
(2) 本发明的正极材料壳层均匀, 厚度可控。
(3) 正极材料具有最外层的包覆层, 对正极材料主体起到良好的保护作用。
(4) 本发明的正极材料具有容量高、 循环性好、 表面活性低、 耐高压、 安全 性好等优点。
(5) 本发明的制备工艺简单, 适合大规模应用。
下面结合具体实施例, 进一步阐述本发明。 应理解, 这些实施例仅用于说明 本发明而不用于限制本发明的范围。 下列实施例中未注明具体条件的实验方法, 通常按照常规条件或按照制造厂商所建议的条件。 除非另行定义, 文中所使用的所有专业与科学用语与本领域熟练人员所熟悉 的意义相同。 此外, 任何与所记载内容相似或均等的方法及材料皆可应用于本发 明方法中。 文中所述的较佳实施方法与材料仅作示范之用。 实施例 1
制备核心为 LiNi1/3Co1/3Mn1/3O2,壳层为 Li[( 1/3Co1/3Mn1/3) 99AlaQ1]O2的正极 材料。
称取 13.3234g Al2(SO4)3-18H2O, 加入到 100g 水中完全溶解, 加入前驱体 Ni1/3Co1/3Mn1/3(OH)2 18.3083g , 搅拌形成前驱体的分散液, 加入浓度为 2%的 ΝΗ3·Η2Ο, 使 Α1(ΟΗ)3完全沉淀出来, 终点 pH值在 9左右, 滴加完后, 继续搅 拌 60分钟, 停止搅拌后过滤, 水洗两次, 将被包覆的前驱体在 120°C下干燥 12 小时, 其形貌如图 1 所示, 粒径为 1-20μιη。 然后将一水氢氧化锂与干燥的前驱 体按照摩尔比 1.10混合均匀, 将混合物在空气中 450°C预烧 5 小时后, 升温至 900°C焙烧 12小时, 自然冷却至室温。得到表面为 Li[(Ni1/3Co1/3Mn1/3)a99AlaQ1]O2, 内部基体为 LiNi1/3Co1/3Mn1/3O2的正极活性材料, 其形貌如图 2 所示, 粒径为 1-21 μιη, 壳层厚度为 0.2μιη。 实施例 2
制备核心为 LiNi 5Co 2Mna3O2,壳层为 Li[( a5Coa2Mn 3)a99Ala()1]O2的正极 材料。
称取 Α1(ΝΟ3)3·9Η2Ο L4450g, 溶于 100 mL水中, 加入 Nio.5CoQ.2MnQ.3(OH)2 10.0420g, 形成前驱体的分散液, 滴加浓度为 1%氨水, 调节 pH值至 9.0左右, 继续用浓氨水调节 pH至 11, 搅拌 60分钟, 停止搅拌后过滤, 水洗两次, 将被 包覆的前驱体在 120°C下干燥 12小时, 其形貌如图 3所示, 粒径为 1-20μιη。 然
后将一水氢氧化锂与干燥的前驱体按照摩尔比 1.10混合均匀,将混合物在氧气气 氛中 900°C焙烧 12小时,自然冷却至室温。得到壳层为 I^iNi sCo^Mna^^Al ^ ]O2, 核心为 LiNia5Coa2Mno.3O2的正极活性材料, 其形貌如图 4 所示, 粒径为 1-25μιη。 壳层厚度为 0.5μιη。 实施例 3
制备核心为 LiNi 5Co 2Mna3O2, 壳层为 LiCoO2的正极材料。
称取 Co(CH3COO)2*4H2O 1.4411g , 溶于 100 mL 水 中 , 力口 入
Nia5Coa2Mn 3(OH)2 10.0200g, 形成前驱体的分散液, 滴加浓度为 1%氨水, 调节 pH值至 9.0左右, 继续用浓氨水调节 pH至 11, 搅拌 60分钟, 停止搅拌后过滤, 水洗两次, 将被包覆的前驱体在 120°C下干燥 12小时, 其形貌如图 5所示, 粒径 为 1-20μιη, 然后将一水氢氧化锂与干燥的前驱体按照摩尔比 1.10混合均匀, 将 混合物在氧气气氛中 900°C焙烧 12小时, 自然冷却至室温。 得到表面为 LiCoO2, 内部基体为 LiNi 5Co 2Mn 3O2的正极活性材料, 其形貌如图 6 所示, 粒径为 1-25μιη。 壳层厚度为 0.5μιη。
图 7为正极材料的颗粒内部形貌图。核壳材料的壳层和核心部分均由 0.1-2μιη 小晶粒组成。
采用能谱 EDS分别对壳层、 核心进行分析, 结果如图 8、 图 9和表 1所示。 核心中 Ni含量大于壳层中 Ni含量, 核心中 Co含量小于壳层中 Co含量。 壳层和核心部分 EDS元素分析结果
实施例 4
制备核心为 LiNiQ.5Co 2Mna3O2,壳层为 LiCoO2,包覆层为 Α12Ο3的正极材料。
采用实施例 2中制备的正极材料, 称取 5g, 加入到 pH为 6.0的 lOOmL醋酸 -醋酸锂缓冲溶液中, 逐渐加入 O.lmol/L的 Α1(ΝΟ3)3溶液, 搅拌 30分钟后, 滴加 5%氨水, 调节 pH至 8.0, 搅拌 30分钟, 停止搅拌后过滤, 水洗两次, 将被包覆 的前驱体在 120°C下干燥 12小时,然后在 550°C下焙烧 8小时。得到表面为 Α13Ο2, 壳层为 LiCoO2, 内部基体为 LiNi 5CoQ.2Mno.3O2的正极活性材料, 其形貌如图 10 所示, 粒径为 1-25μιη。 包覆层的厚度 25nm。 实施例 5
制备核心为 LiNi 5Co 2Mna3O2, 壳层为 LiCo 95Ala()5O2的正极材料。
称取 Co(CH3COO)2*4H2O 5.4360g, Α1(ΝΟ3)3·9Η2Ο 0.9097g, 溶于 lOOmL水 中, 加入 NiQ.5Co 2Mn 3(OH)2 20.0100g, 搅拌形成前驱体的分散液, 滴加浓度 为 5%氨水,调节 pH至 9.0左右,然后用 lmol/L的 NaOH溶液调节 pH值至 11.0, 搅拌 30分钟, 停止搅拌后过来, 水洗两次, 将此前驱体在 120°C下干燥 12小时, 其形貌如图 11所示,粒径为 1-25μιη然后将一水氢氧化锂与干燥的前驱体按照摩 尔比 1.10混合均匀, 将混合物在氧气气氛中 900°C焙烧 12小时, 自然冷却至室 温。 得到表面为 LiCoO2, 内部基体为 LiNi 5Coa2M¾3O2的正极活性材料, 其形 貌如图 12所示, 粒径为 1-25μιη。 壳层厚度为 0.6μιη。 实施例 6
制备核心为 LiNi 5Co 2Mna3O2, 壳层为 LiCo 95Ala()5O2, 包覆层为 MgO的 正极材料。
采用实施例 5中制备的正极材料, 称取 5.0204g, 加入到 lOOmL水中, 搅拌 后形成分散液, 加入浓度为 O.lmol/L的 MgSO4溶液, 用 1 mol/L的 NaOH溶液 调节 pH值至 12, 搅拌 120min后, 过滤、 水洗, 得到表面包覆有 Mg(OH)2的正 极材料, 将该正极材料在 120°C下干燥 10小时, 然后在 500°C下焙烧 12小时, 得到表面为 MgO,壳层为 LiCoQ.95Al ()5O2, 内部基体为 LiNiQ.5Co 2Mna3O2的正极 活性材料, 其形貌如图 13所示, 粒径为 1-25μιη。 包覆层的厚度 30nm。
实施例 7
将 Co3O4与 Ni 5Coa2Mna3(OH)2前驱体按照摩尔比 1:4混合均匀, 混合均匀 的前驱体与碳酸锂按照摩尔比 1.0: 1.1的比例混合均匀, 在 900°C下烧结 12小时, 烧结气氛为氧气, 得到正极材料, 为 LiCoO2和 Li[Ni 5Co 2Mna3]O2的混合物。 正极材料的形貌如图 14所示, 粒径为 0.5-25μιη。 实施例 8
将实施例 7中的正极材料 5g, 加入到 pH为 6.0的 100mL醋酸 -醋酸锂缓冲 溶液中, 逐渐加入 O.lmol/L的 Α1(ΝΟ3)3溶液, 搅拌 30分钟后, 滴加 5%氨水, 调节 pH至 8.0, 搅拌 30分钟, 停止搅拌后过滤, 水洗两次, 将被包覆的前驱体 在 120°C下干燥 8小时, 然后在 450°C下焙烧 15小时。 得到表面为 Α12Ο3, 正极 材料主体为 LiCoO2和 Li[Ni 5Co 2Mna3]O2的混合物的正极材料。 实施例 9
将 Co3O4与 Ni 5Coa2Mna3(OH)2前驱体按照摩尔比 1:3混合均匀, 混合均匀 的前驱体与醋酸锂按照摩尔比 1.0: 1.1的比例混合均匀, 在 950°C下烧结 12小时, 烧结气氛为氧气。烧结后的正极材料加入到 pH为 6.0的 lOOmL醋酸 -醋酸钠缓冲 溶液中, 逐渐加入 O.lmol/L的 Α1(ΝΟ3)3溶液, 搅拌 60分钟后, 滴加 1%氨水, 调节 pH至 8.0, 搅拌 50分钟, 停止搅拌后过滤, 水洗两次, 将被包覆的前驱体 在 120°C下干燥 8小时, 然后在 450°C下焙烧 12小时。 得到表面为 Α12Ο3, 正极 材料主体为 LiCoO2和 Li[NiQ.5Co 2Mna3]O2的混合物的正极材料。
图 15为实施例 8、 9制备的正极材料的 XRD谱图。 结果表明, 正极材料中 钴酸锂的衍射峰强度随前驱体中四氧化三钴的比例增加而增加。 实施例 10
制备核心为 LiNiQ.5Co 2Mna3O2, 壳层为 LiCo 95AlaQ5O2的正极材料, 包覆层 为 ZrO2的正极材料。
称取 Co(CH3COO)2*4H2O 5.4380g, Α1(ΝΟ3)3·9Η2Ο 0.9085g, 溶于 lOOmL水
中, 加入 Ni 5Co 2Mn 3(OH)2 20.0120g, 搅拌形成前驱体的分散液, 滴加浓度 为 5%氨水,调节 pH至 9.0左右,然后用 lmol/L的 NaOH溶液调节 pH值至 11.0, 搅拌 30分钟,停止搅拌后过滤,水洗两次,将此前驱体在 120°C下干燥 12小时,, 粒径为 1-20μιη。然后将一水氢氧化锂与干燥的前驱体按照摩尔比 1.10混合均匀, 将混合物在氧气气氛中 900 °C焙烧 12 小时, 自然冷却至室温。 得到壳层为 LiCoo.95Alo.05O2 , 内部基体为 LiNi 5Co 2Mna3O2的正极活性材料, 其形貌如图 16 所示, 粒径为 1-25μιη。 壳层厚度为 0.5μιη。
配制 ρΗ=5.5的 HAc-NaAc缓冲溶液 50mL,上述合成的正极材料加入缓冲溶 液中, 然后将 0.1 mol/L的 Zr(Ac)4溶液加入到缓冲溶液中, 逐渐沉降 Zr(OH)4, 搅拌 60分钟后过滤, 水洗三次。 在干燥箱中 110°C下, 干燥 5个小时, 然后在 550°C煅烧 6小时, 冷却到室温, 得到三层结构的正极材料。 颗粒直径 1-25μιη, 壳层厚度为 0.5μιη。 结构表征及性能测试:
以实施例 3制备的正极材料为例, 对其 XRD图谱进行解析, 结果如图 17所 示。 根据解析结果可知, 该正极材料具有 a-NaFeO2型结构, 空间群为 R-3m。 Li 占据 3a位置, Ni、 Co、 Mn占据 3b位置, O占据 3c位置。 解析的晶胞参数为, a=b=2.8662, c=14.2302, 精修结果中 Rp=0.99%, wp=1.36%, GOF=1.32%。
将实施例 ι〜ιο 制备的正极材料分别与导电剂乙炔黑、 粘结剂聚偏氟乙烯 (PVDF) 在氮甲基吡咯垸酮 (NMP) 溶液中混合均匀, 正极材料、 乙炔黑和粘 结剂的质量比分别为 90: 5: 5, 然后将混合均匀的料浆涂覆在铝箔上, 120°C下 真空干燥 12小时, 制得锂离子电池正极。
使用上述极片为正极, 以金属锂为负极, 电解液采用 1 mol/L六氟磷酸锂的 碳酸乙烯酯和碳酸二甲酯的溶液, 20微米厚的聚乙烯为隔膜, 组装成 CR2032型 纽扣锂离子电池。
组装成的纽扣电池在蓝电充放电测试仪上, 进行充放电测试, 电压范围为 2.8-4.3伏, 充放电电流密度采用 16 mA/g。
图 18、 19、 20为实施例 1〜10制备的正极材料的放电曲线。
表 2显示各实施例制备的正极材料的初始放电容量。
结果表明, 核壳正极材料容量与核心材料容量基本一致, 核壳材料表面包覆 氧化物后, 容量较包覆之前略有减小。 表 2初始放电容量对比
以实施例 3〜8制备正极材料为例, 对表面未包覆氧化物的正极材料和表面包 覆氧化物的正极材料的充放电循环结果进行比较, 如图 21-23所示。 结果表明, 表面包覆氧化物的核壳正极材料较未包覆的正极材料容量保持率高, 循环性较 好。 在本发明提及的所有文献都在本申请中引用作为参考, 就如同每一篇文献被 单独引用作为参考那样。 此外应理解, 在阅读了本发明的上述讲授内容之后, 本 领域技术人员可以对本发明作各种改动或修改, 这些等价形式同样落于本申请所 附权利要求书所限定的范围。
Claims
1.一种正极材料, 其特征在于, 所述正极材料包括正极材料主体和位于正极 材料主体表面的包覆层,
其中, 包覆层材料为 Al2O3、 ZrO2、 MgO、 SiO2、 ZnO2、 TiO2、 Y2O3、 LiAlO2 中的一种或其组合;
所述正极材料主体包括壳层和位于壳层内的核心, 其中, 核心材料为 Lii+x[Ni1-y-zCoyMnz]O2, 其中, -0.1<x<0.2 , 0≤y≤0.5, 0≤ζ≤0·5, 0<y+z<0.7 ; 壳层 材料为 Li1+a[Co1-bXb]O2, 其中, -0.1≤a≤0.2, 0≤b≤0.5, X为 Al、 Mg、 Cu、 Zr、 Ti、 Cr、 V、 Fe、 Mn、 Ni中的一种或其组合; 或
所述正极材料主体为 LUNii^COyMi ^和 LiCoO2 的混合物, 其中 -0.1<x<0.2, 0≤y≤0.5, 0≤ζ≤0·5, 0≤y+z≤0.7。
2. 如权利要求 1所述的正极材料, 其特征在于, 所述核心材料和所述壳层材 料的晶格结构均为 a-NaFeO2型, 空间群均为 R-3m。
3. 如权利要求 1所述的正极材料, 其特征在于, 所述壳层厚度与所述正极材 料颗粒半径的比例为 0.005-0.5 ; 和 /或
所述包覆层的厚度为 0.2〜50nm。
4. 如权利要求 1所述的正极材料, 其特征在于, 所述核心材料中 Ni含量大 于所述壳层材料中 Ni含量, 所述核心材料中 Co含量小于所述壳层材料中 Co含
5. 如权利要求 1所述的正极材料, 其特征在于, 所述核心由 0.1-5μιη的晶粒 构成, 所述壳层由 0.1〜5μιη的晶粒构成。
6. 如权利要求 1〜5任一项所述的正极材料的制备方法,其特征在于,包括步 骤:
(a) 在 Ni1-y-zCoyMnz(OH)2表面沉降 Co的氢氧化物, 或 X和 Co的氢氧化物, 得到核壳前驱体 P;
(b) 将所述核壳前驱体 P与锂源按照 Li/P=l-1.2的摩尔比混合后烧结;
(c) 在烧结后的样品的表面沉降金属 M的氢氧化物;
(d) 在 200- 1000 °C烧结 0.5-24小时, 得到所述正极材料,
其中, 0≤y≤1.0, 0≤z≤1.0, 0<y+z<l ; 0≤b≤1.0, X、 M独立地选自为 Al、 Mg、 Cu、 Zr、 Ti、 Cr、 V、 Fe、 Mn、 Ni、 Y、 Zn中的一种或其组合。
7. 如权利要求 1所述的正极材料的制备方法, 其特征在于, 包括步骤:
(a) 在 Ni1-y-zCoyMnz(OH)2与 Co3O4混合, 得到核壳前驱体 P;
(b) 将所述核壳前驱体 P与锂源按照 Li/P=l-1.2的摩尔比混合后烧结;
(c) 在烧结后的样品的表面沉降金属 M的氢氧化物;
(d) 在 200- 1000 °C烧结 0.5-24小时, 得到所述正极材料,
其中, 0≤y≤1.0, 0≤z≤1.0, 0<y+z<l ; 0≤b≤1.0, X、 M独立地选自为 Al、 Mg、 Cu、 Zr、 Ti、 Cr、 V、 Fe、 Mn、 Ni、 Y、 Zn中的一种或其组合。
8. 如权利要求 6或 7所述的方法, 其特征在于, 所述步骤 (c)中, 将烧结后的 样品置于缓冲溶液中, 加入所述金属 M的盐溶液, 调节 pH至碱性, 在所述烧结 后的样品的表面沉降金属 M的氢氧化物。
9. 如权利要求 8所述的方法, 其特征在于, 所述缓冲溶液为醋酸-醋酸钠、 醋酸-醋酸钾、 醋酸-醋酸锂、 氨-氯化铵、 氨水、 醋酸铵-醋酸钠、 醋酸、 氨 -氢氧 化钠、 氨 -氢氧化钾、 磷酸盐缓冲溶液、 硼酸盐缓冲溶液中的一种或其组合, 所述 缓冲溶液的 pH为 4.0-14.0。
10. 一种锂离子电池, 其特征在于, 包括权利要求 1〜5任一项所述的正极材
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CN110921786B (zh) * | 2019-11-23 | 2021-11-09 | 同济大学 | 一种去除邻苯二甲酸酯类的光电催化阳极材料及处理方法 |
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CN103515606B (zh) | 2016-09-14 |
US20150104708A1 (en) | 2015-04-16 |
CN103515606A (zh) | 2014-01-15 |
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