CN114023936B - 氮化物/石墨化碳纳米片包覆三元正极材料及其制备方法 - Google Patents
氮化物/石墨化碳纳米片包覆三元正极材料及其制备方法 Download PDFInfo
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- CN114023936B CN114023936B CN202111271987.7A CN202111271987A CN114023936B CN 114023936 B CN114023936 B CN 114023936B CN 202111271987 A CN202111271987 A CN 202111271987A CN 114023936 B CN114023936 B CN 114023936B
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- nitride
- positive electrode
- electrode material
- graphitized carbon
- ternary positive
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- 239000007774 positive electrode material Substances 0.000 title claims abstract description 76
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 52
- 150000004767 nitrides Chemical class 0.000 title claims abstract description 52
- 239000002135 nanosheet Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000011248 coating agent Substances 0.000 claims abstract description 48
- 238000000576 coating method Methods 0.000 claims abstract description 46
- 239000011159 matrix material Substances 0.000 claims abstract description 34
- 238000002156 mixing Methods 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 19
- 239000011247 coating layer Substances 0.000 claims abstract description 11
- 238000011065 in-situ storage Methods 0.000 claims abstract description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 30
- 238000005245 sintering Methods 0.000 claims description 30
- 239000002904 solvent Substances 0.000 claims description 28
- 239000013067 intermediate product Substances 0.000 claims description 24
- 239000010406 cathode material Substances 0.000 claims description 14
- 229910052782 aluminium Inorganic materials 0.000 claims description 11
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 claims description 10
- 239000012298 atmosphere Substances 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 238000007873 sieving Methods 0.000 claims description 10
- 229920000877 Melamine resin Polymers 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 8
- 238000000926 separation method Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 229910017464 nitrogen compound Inorganic materials 0.000 claims description 5
- 238000004321 preservation Methods 0.000 claims description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 claims description 3
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 2
- 150000004703 alkoxides Chemical group 0.000 claims description 2
- 150000001413 amino acids Chemical class 0.000 claims description 2
- CFJRGWXELQQLSA-UHFFFAOYSA-N azanylidyneniobium Chemical compound [Nb]#N CFJRGWXELQQLSA-UHFFFAOYSA-N 0.000 claims description 2
- 239000004202 carbamide Substances 0.000 claims description 2
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 2
- MZLGASXMSKOWSE-UHFFFAOYSA-N tantalum nitride Chemical compound [Ta]#N MZLGASXMSKOWSE-UHFFFAOYSA-N 0.000 claims description 2
- ZVWKZXLXHLZXLS-UHFFFAOYSA-N zirconium nitride Chemical compound [Zr]#N ZVWKZXLXHLZXLS-UHFFFAOYSA-N 0.000 claims description 2
- 238000009413 insulation Methods 0.000 claims 1
- 239000002064 nanoplatelet Substances 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 24
- 230000008569 process Effects 0.000 abstract description 9
- 239000010410 layer Substances 0.000 abstract description 5
- 238000009776 industrial production Methods 0.000 abstract description 4
- 239000002344 surface layer Substances 0.000 abstract description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 33
- 239000000243 solution Substances 0.000 description 31
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 19
- 238000012360 testing method Methods 0.000 description 17
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 14
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 14
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 14
- 238000003756 stirring Methods 0.000 description 13
- 238000001354 calcination Methods 0.000 description 12
- 239000012065 filter cake Substances 0.000 description 12
- 239000011572 manganese Substances 0.000 description 12
- 239000002243 precursor Substances 0.000 description 12
- 239000012300 argon atmosphere Substances 0.000 description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 9
- 239000001301 oxygen Substances 0.000 description 9
- 229910052760 oxygen Inorganic materials 0.000 description 9
- 229910013716 LiNi Inorganic materials 0.000 description 8
- 239000002033 PVDF binder Substances 0.000 description 6
- 239000006230 acetylene black Substances 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 229910017052 cobalt Inorganic materials 0.000 description 6
- 239000010941 cobalt Substances 0.000 description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 6
- 238000013100 final test Methods 0.000 description 6
- 239000011888 foil Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 230000014759 maintenance of location Effects 0.000 description 6
- IPJKJLXEVHOKSE-UHFFFAOYSA-L manganese dihydroxide Chemical compound [OH-].[OH-].[Mn+2] IPJKJLXEVHOKSE-UHFFFAOYSA-L 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 6
- 229910052759 nickel Inorganic materials 0.000 description 6
- 238000011056 performance test Methods 0.000 description 6
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 6
- 238000011085 pressure filtration Methods 0.000 description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 5
- 229910052744 lithium Inorganic materials 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- -1 nitrogen-containing compound Chemical class 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000002019 doping agent Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000005121 nitriding Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 238000007740 vapor deposition Methods 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 229910018553 Ni—O Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- JPUHCPXFQIXLMW-UHFFFAOYSA-N aluminium triethoxide Chemical compound CCO[Al](OCC)OCC JPUHCPXFQIXLMW-UHFFFAOYSA-N 0.000 description 1
- ACKHWUITNXEGEP-UHFFFAOYSA-N aluminum cobalt(2+) nickel(2+) oxygen(2-) Chemical class [O-2].[Al+3].[Co+2].[Ni+2] ACKHWUITNXEGEP-UHFFFAOYSA-N 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000010261 cell growth Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000010416 ion conductor Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- 229910001947 lithium oxide Inorganic materials 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- ZTILUDNICMILKJ-UHFFFAOYSA-N niobium(v) ethoxide Chemical compound CCO[Nb](OCC)(OCC)(OCC)OCC ZTILUDNICMILKJ-UHFFFAOYSA-N 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- ZGSOBQAJAUGRBK-UHFFFAOYSA-N propan-2-olate;zirconium(4+) Chemical compound [Zr+4].CC(C)[O-].CC(C)[O-].CC(C)[O-].CC(C)[O-] ZGSOBQAJAUGRBK-UHFFFAOYSA-N 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 235000002639 sodium chloride Nutrition 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000002345 surface coating layer Substances 0.000 description 1
- HSXKFDGTKKAEHL-UHFFFAOYSA-N tantalum(v) ethoxide Chemical compound [Ta+5].CC[O-].CC[O-].CC[O-].CC[O-].CC[O-] HSXKFDGTKKAEHL-UHFFFAOYSA-N 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
Classifications
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- H—ELECTRICITY
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- 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
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- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
- C01B21/0615—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron with transition metals other than titanium, zirconium or hafnium
- C01B21/0617—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron with transition metals other than titanium, zirconium or hafnium with vanadium, niobium or tantalum
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
- C01B21/068—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron with silicon
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
- C01B21/072—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron with aluminium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
- C01B21/076—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron with titanium or zirconium or hafnium
-
- 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
- C01B32/20—Graphite
- C01B32/205—Preparation
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/40—Nickelates
- C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
- C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
- C01G53/50—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [MnO2]n-, e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
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- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- 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
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- 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
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
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- H01M4/624—Electric conductive fillers
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Abstract
本发明涉及一种氮化物/石墨化碳纳米片包覆三元正极材料及其制备方法。该氮化物/石墨化碳纳米片包覆三元正极材料,包括三元正极材料基体和包覆层,包覆层由氮化物和石墨化碳组成,且石墨化碳在氮化物的包覆过程中原位形成。本发明在三元正极材料表层包覆氮化物的过程中,原位生成了石墨化碳层结构,相比较物理混合的方法,原位生成的碳层与基体材料连接更加紧密,导电网络更加密集,从而最大限度提升材料倍率性能;该三元正极材料具有优异的倍率性能和循环稳定性,其制备方法工艺流程简单,易于实现工业化生产。
Description
技术领域
本发明涉及锂电池技术领域,尤其涉及一种氮化物/石墨化碳纳米片包覆三元正极材料及其制备方法。
背景技术
锂离子电池作为一种新型的能源储存和转化装置,凭借其工作电压高、能量密度大、库伦效率高、无记忆效应、循环寿命长和对环境影响友好等优点,广泛应用于便携式消费电子设备、新能源汽车和储能电网等领域。锂离子电池的正极材料决定着电池的综合性能,在目前主流正极材料中,三元正极材料LiNixCoyM1-x-yO2(M=Mn或Al)由于具有较高能量/功率密度和低温性能,因此成为了研究重点。
随着三元材料中Ni含量的提高,材料容量上升,但其结构稳定性变差,究其原因是Ni-O键键能较弱,晶体结构稳定性变差,尤其是充放电过程中,高活性的界面和电解液发生氧化还原反应,生成非活性岩盐相结构,造成电解液分解,同时释放大量热量,导致电芯胀气、安全性能下降、放电容量衰减以及循环稳定性恶化等一些列问题。目前解决这一问题的主要技术手段之一是进行包覆,包覆剂不仅能够有效避免高活性正极界面和电解液直接接触,缓解副反应发生,而且还能作为快离子导体,为锂离子扩散传输提供良好的通道,进而提升改善倍率性能。目前包覆剂主要有氧化物,如Al2O3、TiO2、ZrO2、B2O3、SiO2等,尽管该氧化物包覆剂能够改善上述界面稳定性问题,但氧化物大部分属于半导体,电子电导率较低,不能满足大电流充放电要求。相比较氧化物,氮化物具有更好的耐化学腐蚀性,更加优异的电子电导率和热稳定性,作为包覆剂能够更大限度提升三元材料电性能。
目前存在的氮化物包覆技术中,如中国发明专利CN113097459A所公开内容,采用气相沉积包覆方法,该气相反应流程复杂,不易规模化生产。中国发明专利CN112174222A所公开的方法中将待包覆三元正极材料和钛源、含氮化合物进行一步法混合烧结,制备氮化钛包覆三元正极材料,尽管该方法过程简便,便于工业化生产,但在制备过程中,含氮化合物的还原性气体会存在直接与三元材料反应的可能性,从而破坏三元正极主体材料晶格结构,影响材料电性能发挥。
发明内容
有鉴于此,有必要提供一种氮化物/石墨化碳纳米片包覆三元正极材料及其制备方法,用以解决现有技术中气相沉积包覆法工艺流程复杂,一步法混合烧结法容易破坏三元正极主体材料晶格结构、影响材料性能的技术问题。
本发明的第一方面提供一种氮化物/石墨化碳纳米片包覆三元正极材料,包括三元正极材料基体和包覆层,包覆层由氮化物和石墨化碳组成,且石墨化碳在氮化物的包覆过程中原位形成。
本发明的第二方面提供一种氮化物/石墨化碳纳米片包覆三元正极材料的制备方法,包括以下步骤:
提供三元正极材料基体;
通过湿法包覆使包覆元素包覆于三元正极材料基体表面获得中间产物;其中,包覆元素为Al、Si、Ti、Zr、Ta、Nb中的一种或多种;
将中间产物与含碳氮化合物混合均匀,经烧结、粉碎、过筛和除铁,得到氮化物/石墨化碳纳米片包覆三元正极材料。
与现有技术相比,本发明的有益效果为:
本发明在三元正极材料表层包覆氮化物的过程中,原位生成了石墨化碳层结构,相比较物理混合的方法,原位生成的碳层与基体材料连接更加紧密,导电网络更加密集,从而最大限度提升材料倍率性能;该三元正极材料具有优异的倍率性能和循环稳定性,其制备方法工艺流程简单,易于实现工业化生产。
具体实施方式
为了使本发明的目的、技术方案及优点更加清楚明白,以下结合实施例,对本发明进行进一步详细说明。应当理解,此处所描述的具体实施例仅仅用以解释本发明,并不用于限定本发明。
本发明的第一方面提供一种氮化物/石墨化碳纳米片包覆三元正极材料,包括三元正极材料基体和包覆层,包覆层由氮化物和石墨化碳组成,且石墨化碳在氮化物的包覆过程中原位形成。与无定形碳相比,石墨化碳材料的导电性更好,更有利于提高倍率性能。
本发明中,三元正极材料基体为镍钴锰三元正极材料或镍钴铝三元正极材料中的一种或多种,其结构式为LiNixCoyM1-x-yO2(M=Mn或Al)。在本发明的一些具体实施方式中,x≥0.8。
本发明中,氮化物为氮化铝、氮化硅、氮化钛、氮化锆、氮化钽、氮化铌中的一种或多种。
本发明中,包覆层的厚度为1~100nm。
本发明的第二方面提供一种氮化物/石墨化碳纳米片包覆三元正极材料的制备方法,包括以下步骤:
S1、提供三元正极材料基体;
S2、通过湿法包覆使包覆元素包覆于三元正极材料基体表面获得中间产物;其中,包覆元素为Al、Si、Ti、Zr、Ta、Nb中的一种或多种;
S3、将中间产物与含碳氮化合物混合均匀,经烧结、粉碎、过筛和除铁,得到氮化物/石墨化碳纳米片包覆三元正极材料。
本发明通过含碳氮化合物中的氮元素在高温环境中与中间产物表层包覆的过渡金属氧化物反应,生产过渡金属氮化物,同时碳元素在过渡金属的催化石墨化作用下,原位生成石墨化碳纳米片,最终形成了氮化物/石墨化碳纳米片包覆三元正极材料。
本发明中,提供三元正极材料基体的步骤具体为:将三元正极材料前驱体和锂源混合均匀后经煅烧、粉碎、过筛得到三元正极材料基体。
进一步地,三元正极材料前驱体为镍钴锰或镍钴铝的氧化物、氢氧化物、羟基氧化物中的一种或多种;锂源为碳酸锂、氧化锂和氢氧化锂中的一种或几种的混合;三元正极材料前驱体与锂源的摩尔比为1:1~1.15;通过高混机将三元正极材料前驱体和锂源混合均匀;高混机转速为100~1500rpm,进一步为1000rpm,混合处理时间为0.5~5h,进一步为1h;煅烧在氧气气氛下进行,通入氧气气氛的体积浓度≥99%,煅烧温度为500~1200℃,进一步为650~850℃,更进一步为750℃;煅烧时间5~24h,进一步为10~14h,更进一步为12h。
进一步地,三元正极材料基体的制备过程中,还加入掺杂剂以提高正极材料的结构稳定性。例如,掺杂剂可以为二氧化锆、三氧化铝、二氧化钛、氧化镁等,本发明对此不作限制。更进一步地,掺杂剂与三元正极材料前驱体的摩尔比0.0001~0.1:1。
本发明中,包覆元素与三元正极材料基体的质量比为0.0001~0.005:1,进一步为0.0004~0.003:1,更进一步为0.0008~0.001:1。
本发明中,湿法包覆的步骤具体为:
将三元正极材料基体加入到第一溶剂中,形成溶液Ⅰ;
将含包覆元素的化合物加入到第二溶剂中,形成溶液Ⅱ;
将溶液Ⅱ缓慢加入到溶液Ⅰ中,保温反应,经固液分离、烘干获得中间产物。
进一步地,含包覆元素的化合物为含包覆元素的醇盐。在本发明的一些具体实施方式中,含包覆元素的化合物为三乙醇铝、正硅酸乙酯、钛酸四丁酯、异丙醇钛、异丙醇锆、五乙氧基钽、五乙氧基铌中的一种或多种;第一溶剂和第二溶剂为水、甲醇、乙醇、异丙醇、乙二醇中的一种或多种。
进一步地,溶液Ⅰ中,三元正极材料基体与溶剂的用量比为1~20g:100ml,进一步为10~20g:100ml;溶液Ⅱ中,含包覆元素的化合物与溶剂的用量比为0.01~10g:100ml,进一步为0.04~1g:100ml,更进一步为0.1~0.6g:100ml,更进一步为0.2g:100ml。
进一步地,保温反应的温度为30~80℃,进一步为60℃,保温反应的时间0.5~5h,进一步为1~2h;烘干的温度为80~120℃,烘干的时间5~20h。
本发明中,含碳氮化合物为氨基酸、三聚氰胺、尿素中的一种或多种。进一步地,含碳氮化合物与中间产物的质量比为5~20:100,若质量比过高会导致表层包覆层(氮化物和石墨化碳)过多,影响材料容量发挥;过低则包覆层少,达不到包覆的效果;进一步为6~17:100,更进一步为10:100;通过高混机将含碳氮化合物与中间产物混合均匀,高混机转速为1000~4000rpm,进一步为2000rpm,混合处理时间为1~8h,进一步为2h;烧结在惰性气体(如氩气或氮气等)的保护下进行,烧结温度为500~1000℃,进一步为800℃,烧结时间3~12h,进一步为6h。
实施例1
(1)称取500g镍钴锰氢氧化物三元正极材料前驱体Ni0.83Co0.12Mn0.05(OH)2、240g氢氧化锂(LiOH·H2O)和1.5g纳米二氧化锆(ZrO2),转移进高混机中混合,转速1000rpm,混合时间1h后取出,随后将其转移到马弗炉中煅烧,氧气气氛下750℃烧结12h,烧结结束后取出物料,随后进行粉碎和过筛后获得三元正极材料基体;
(2)称取400g三元正极材料基体,转移至3000ml乙醇溶剂中,形成溶液Ⅰ;称取2g异丙醇钛包覆剂转移至1000ml乙醇溶剂中,形成溶液Ⅱ;分别搅拌10min后,将溶液Ⅱ缓慢加入到溶液Ⅰ中,持续进行搅拌,水浴加热至60℃,保温1h,混合溶液进行压滤,固液分离后得到滤饼,随后将其转移至100℃烘箱内部进行烘干,保温10h,获得烘干后的中间产物;
(3)称取300g中间产物和30g三聚氰胺,进行混合后,转入至高混机中高速搅拌,2000rpm转速下搅拌2h,随后转入氩气气氛马弗炉中,氩气气氛下800℃烧结6h,烧结完成后,将所得物料进行粉碎、过筛和除铁,即为最终氮化物/石墨化碳纳米片包覆三元正极材料。
扣式电池测试:将得到的氮化物/石墨化碳纳米片包覆三元正极材料(LiNi0.83Co0.12Mn0.05)、乙炔黑、PVDF按照94:4:4的比例混合,以NMP为溶剂混合均匀后涂覆在铝箔上,制作成2032扣式电池进行电化学性能测试,测试电压范围2.8~4.3V,首周按照0.1C/0.1C充放电,接下来1C/1C循环测试50周。最终测试结果:0.1C放电容量210mAh/g,1C放电容量199mAh/g,50周循环容量保持率98.6%。
实施例2
(1)称取500g镍钴锰氢氧化物三元正极材料前驱体Ni0.83Co0.12Mn0.05(OH)2、240g氢氧化锂(LiOH·H2O)和1.5g纳米二氧化锆(ZrO2),转移进高混机中混合,转速1000rpm,混合时间1h后取出,随后将其转移到马弗炉中煅烧,氧气气氛下750℃烧结12h,烧结结束后取出物料,随后进行粉碎和过筛后获得三元正极材料基体;
(2)称取400g三元正极材料基体,转移至3000ml乙醇溶剂中,形成溶液Ⅰ;称取0.4g异丙醇钛包覆剂转移至1000ml乙醇溶剂中,形成溶液Ⅱ;分别搅拌10min后,将溶液Ⅱ缓慢加入到溶液Ⅰ中,持续进行搅拌,水浴加热至60℃,保温1h,混合溶液进行压滤,固液分离后得到滤饼,随后将其转移至100℃烘箱内部进行烘干,保温10h,获得烘干后的中间产物;
(3)称取300g中间产物、15g三聚氰胺,进行混合后,转入至高混机中高速搅拌,2000rpm转速下搅拌2h,随后转入氩气气氛马弗炉中,氩气气氛下800℃烧结6h,烧结完成后,将所得物料进行粉碎、过筛和除铁,即为最终氮化物/石墨化碳纳米片包覆三元正极材料。
扣式电池测试:将得到的氮化物/石墨化碳纳米片包覆三元正极材料(LiNi0.83Co0.12Mn0.05)、乙炔黑、PVDF按照94:4:4的比例混合,以NMP为溶剂混合均匀后涂覆在铝箔上,制作成2032扣式电池进行电化学性能测试,测试电压范围2.8~4.3V,首周按照0.1C/0.1C充放电,接下来1C/1C循环测试50周。最终测试结果:0.1C放电容量208mAh/g,1C放电容量194mAh/g,50周循环容量保持率93.7%。
实施例3
(1)称取500g镍钴锰氢氧化物三元正极材料前驱体Ni0.83Co0.12Mn0.05(OH)2、240g氢氧化锂(LiOH·H2O)和1.5g纳米二氧化锆(ZrO2),转移进高混机中混合,转速1000rpm,混合时间1h后取出,随后将其转移到马弗炉中煅烧,氧气气氛下750℃烧结12h,烧结结束后取出物料,随后进行粉碎和过筛后获得三元正极材料基体;
(2)称取400g三元正极材料基体,转移至3000ml乙醇溶剂中,形成溶液Ⅰ;称取1g异丙醇钛包覆剂转移至1000ml乙醇溶剂中,形成溶液Ⅱ;分别搅拌10min后,将溶液Ⅱ缓慢加入到溶液Ⅰ中,持续进行搅拌,水浴加热至60℃,保温2h,混合溶液进行压滤,固液分离后得到滤饼,随后将其转移至100℃烘箱内部进行烘干,保温10h,获得烘干后的中间产物;
(3)称取300g中间产物和20g三聚氰胺,进行混合后,转入至高混机中高速搅拌,2000rpm转速下搅拌2h,随后转入氩气气氛马弗炉中,氩气气氛下800℃烧结6h,烧结完成后,将所得物料进行粉碎、过筛和除铁,即为最终氮化物/石墨化碳纳米片包覆三元正极材料。
扣式电池测试:将得到的氮化物/石墨化碳纳米片包覆三元正极材料(LiNi0.83Co0.12Mn0.05)、乙炔黑、PVDF按照94:4:4的比例混合,以NMP为溶剂混合均匀后涂覆在铝箔上,制作成2032扣式电池进行电化学性能测试,测试电压范围2.8~4.3V,首周按照0.1C/0.1C充放电,接下来1C/1C循环测试50周。最终测试结果:0.1C放电容量209mAh/g,1C放电容量196mAh/g,50周循环容量保持率97.9%。
实施例4
(1)称取500g镍钴锰氢氧化物三元正极材料前驱体Ni0.83Co0.12Mn0.05(OH)2、240g氢氧化锂(LiOH·H2O)和1.5g纳米二氧化锆(ZrO2),转移进高混机中混合,转速1000rpm,混合时间1h后取出,随后将其转移到马弗炉中煅烧,氧气气氛下750℃烧结12h,烧结结束后取出物料,随后进行粉碎和过筛后获得三元正极材料基体;
(2)称取400g三元正极材料基体,转移至3000ml乙醇溶剂中,形成溶液Ⅰ;称取6g异丙醇钛包覆剂转移至1000ml乙醇溶剂中,形成溶液Ⅱ;分别搅拌10min后,将溶液Ⅱ缓慢加入到溶液Ⅰ中,持续进行搅拌,水浴加热至60℃,保温2h,混合溶液进行压滤,固液分离后得到滤饼,随后将其转移至100℃烘箱内部进行烘干,保温10h,获得烘干后的中间产物;
(3)称取300g中间产物、50g三聚氰胺,进行混合后,转入至高混机中高速搅拌,2000rpm转速下搅拌2h,随后转入氩气气氛马弗炉中,氩气气氛下800℃烧结6h,烧结完成后,将所得物料进行粉碎、过筛和除铁,即为最终氮化物/石墨化碳纳米片包覆三元正极材料。
扣式电池测试:将得到的氮化物/石墨化碳纳米片包覆三元正极材料(LiNi0.83Co0.12Mn0.05)、乙炔黑、PVDF按照94:4:4的比例混合,以NMP为溶剂混合均匀后涂覆在铝箔上,制作成2032扣式电池进行电化学性能测试,测试电压范围2.8~4.3V,首周按照0.1C/0.1C充放电,接下来1C/1C循环测试50周。最终测试结果:0.1C放电容量207mAh/g,1C放电容量193mAh/g,50周循环容量保持率97.4%。
实施例5
(1)称取500g镍钴锰氢氧化物三元正极材料前驱体Ni0.83Co0.12Mn0.05(OH)2、240g氢氧化锂(LiOH·H2O)和1.5g纳米二氧化锆(ZrO2),转移进高混机中混合,转速1000rpm,混合时间1h后取出,随后将其转移到马弗炉中煅烧,氧气气氛下750℃烧结12h,烧结结束后取出物料,随后进行粉碎和过筛后获得三元正极材料基体;
(2)称取400g三元正极材料基体,转移至3000ml乙醇溶剂中,形成溶液Ⅰ;称取10g异丙醇钛包覆剂转移至1000ml乙醇溶剂中,形成溶液Ⅱ;分别搅拌10min后,将溶液Ⅱ缓慢加入到溶液Ⅰ中,持续进行搅拌,水浴加热至60℃,保温2h,混合溶液进行压滤,固液分离后得到滤饼,随后将其转移至100℃烘箱内部进行烘干,保温10h,获得烘干后的中间产物;
(3)称取300g中间产物和60g三聚氰胺,进行混合后,转入至高混机中高速搅拌,2000rpm转速下搅拌2h,随后转入氩气气氛马弗炉中,氩气气氛下800℃烧结6h,烧结完成后,将所得物料进行粉碎、过筛和除铁,即为最终氮化物/石墨化碳纳米片包覆三元正极材料。
扣式电池测试:将得到的氮化物/石墨化碳纳米片包覆三元正极材料(LiNi0.83Co0.12Mn0.05)、乙炔黑、PVDF按照94:4:4的比例混合,以NMP为溶剂混合均匀后涂覆在铝箔上,制作成2032扣式电池进行电化学性能测试,测试电压范围2.8~4.3V,首周按照0.1C/0.1C充放电,接下来1C/1C循环测试50周。最终测试结果:0.1C放电容量198mAh/g,1C放电容量176mAh/g,50周循环容量保持率97.5%。
对比例1
(1)称取500g镍钴锰氢氧化物三元正极材料前驱体Ni0.83Co0.12Mn0.05(OH)2、240g氢氧化锂(LiOH·H2O)和1.5g纳米二氧化锆(ZrO2),转移进高混机中混合,转速1000rpm,混合时间1h后取出,随后将其转移到马弗炉中煅烧,氧气气氛下750℃烧结12h,烧结结束后取出物料,随后进行粉碎和过筛后获得三元正极材料基体;
(2)称取400g三元正极材料基体,转移至3000ml乙醇溶剂中,形成溶液Ⅰ;称取2g异丙醇钛包覆剂转移至1000ml乙醇溶剂中,形成溶液Ⅱ;分别搅拌10min后,将溶液Ⅱ缓慢加入到溶液Ⅰ中,持续进行搅拌,水浴加热至60℃,保温1h,混合溶液进行压滤,固液分离后得到滤饼,随后将其转移至100℃烘箱内部进行烘干,保温10h,获得烘干后的中间产物;
(3)称取300g中间产物和30g三聚氰胺,进行混合后,转入至高混机中高速搅拌,2000rpm转速下搅拌2h,随后转入氧气气氛马弗炉中,氧气气氛下800℃烧结6h,烧结完成后,将所得物料进行粉碎、过筛和除铁,即为最终氮化物包覆三元正极材料。
扣式电池测试:将得到的氮化物包覆三元正极材料(LiNi0.83Co0.12Mn0.05)、乙炔黑、PVDF按照94:4:4的比例混合,以NMP为溶剂混合均匀后涂覆在铝箔上,制作成2032扣式电池进行电化学性能测试,测试电压范围2.8~4.3V,首周按照0.1C/0.1C充放电,接下来1C/1C循环测试50周。最终测试结果:0.1C放电容量206mAh/g,1C放电容量190mAh/g,50周循环容量保持率97.0%。
与现有技术相比,本发明的有益效果为:
(1)制备方法工艺流程简单,纯固相反应过程,条件便于控制,易于规模化工业生产;
(2)整个包覆过程分为湿法预包覆和后续高温氮化步骤,相比较一次包覆过程,预包覆过程不仅为后续氮化提供了前驱体,而且还能保护三元正极基体材料免遭后续含碳氮还原性气体破坏;
(3)石墨化纳米片在过渡金属催化作用下直接原位生成,相比较物理混合方法,材料之间接触更紧密,导电碳层网络分布更加均匀,从而大幅提升复合材料导电性,较大限度增强三元正极材料倍率性能;
(4)氮化物生成的同时,伴随着石墨化碳包覆层的形成,既增强了离子电导率又增强的电子电导率。
以上所述,仅为本发明较佳的具体实施方式,但本发明的保护范围并不局限于此,任何熟悉本技术领域的技术人员在本发明揭露的技术范围内,可轻易想到的变化或替换,都应涵盖在本发明的保护范围之内。
Claims (8)
1.一种氮化物/石墨化碳纳米片包覆三元正极材料的制备方法,其特征在于,包括以下步骤:
提供三元正极材料基体;
通过湿法包覆使包覆元素包覆于三元正极材料基体表面获得中间产物;其中,所述包覆元素为Al、Si、Ti、Zr、Ta、Nb中的一种或多种;
将所述中间产物与含碳氮化合物混合均匀,经烧结、粉碎、过筛和除铁,得到氮化物/石墨化碳纳米片包覆三元正极材料;其中,烧结的气氛为惰性气体;
所述湿法包覆的步骤具体为:将三元正极材料基体加入到第一溶剂中,形成溶液Ⅰ;将含包覆元素的化合物加入到第二溶剂中,形成溶液Ⅱ;将所述溶液Ⅱ缓慢加入到所述溶液Ⅰ中,保温反应,经固液分离、烘干获得中间产物;
所述含包覆元素的化合物为含包覆元素的醇盐;所述第一溶剂和第二溶剂为水、甲醇、乙醇、异丙醇、乙二醇中的一种或多种。
2.根据权利要求1所述氮化物/石墨化碳纳米片包覆三元正极材料的制备方法,其特征在于,所述包覆元素与三元正极材料基体的质量比为0.0001~0.005:1。
3.根据权利要求1所述氮化物/石墨化碳纳米片包覆三元正极材料的制备方法,其特征在于,所述保温反应的温度为30~80oC,保温反应的时间0.5~5h。
4.根据权利要求1所述氮化物/石墨化碳纳米片包覆三元正极材料的制备方法,其特征在于,所述含碳氮化合物为氨基酸、三聚氰胺、尿素中的一种或多种。
5.根据权利要求1所述氮化物/石墨化碳纳米片包覆三元正极材料的制备方法,其特征在于,所述含碳氮化合物与中间产物的质量比为5~20:100。
6.根据权利要求1所述氮化物/石墨化碳纳米片包覆三元正极材料的制备方法,其特征在于,所述烧结温度为500~1000℃,烧结时间3~12h。
7.一种氮化物/石墨化碳纳米片包覆三元正极材料,其特征在于,包括三元正极材料基体和包覆层,包覆层由氮化物和石墨化碳组成,且石墨化碳在氮化物的包覆过程中原位形成;
所述氮化物/石墨化碳纳米片包覆三元正极材料由权利要求1~6中任一所述氮化物/石墨化碳纳米片包覆三元正极材料的制备方法制得。
8.根据权利要求7所述氮化物/石墨化碳纳米片包覆三元正极材料,其特征在于,所述氮化物为氮化铝、氮化硅、氮化钛、氮化锆、氮化钽、氮化铌中的一种或多种;所述包覆层的厚度为1~100nm。
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CN111952547A (zh) * | 2019-05-16 | 2020-11-17 | 天津国安盟固利新材料科技股份有限公司 | 一种表面包覆改性的锂离子电池正极材料及其制备方法 |
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CN113097459B (zh) | 2021-03-29 | 2022-09-02 | 清华大学 | 一种三元正极材料@氮化钛核壳结构复合材料及制备方法 |
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Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103474635A (zh) * | 2013-09-06 | 2013-12-25 | 广东精进能源有限公司 | 碳包覆氮化硅钛合金高容量负极材料的制备方法及应用 |
CN108039452A (zh) * | 2017-12-12 | 2018-05-15 | 奇瑞汽车股份有限公司 | 一种氮化物包覆的富锂正极材料及其制备方法 |
CN111952547A (zh) * | 2019-05-16 | 2020-11-17 | 天津国安盟固利新材料科技股份有限公司 | 一种表面包覆改性的锂离子电池正极材料及其制备方法 |
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