CN116825985A - Polymer-assisted nano oxide coated nickel-iron-manganese ternary positive electrode material and preparation method thereof - Google Patents
Polymer-assisted nano oxide coated nickel-iron-manganese ternary positive electrode material and preparation method thereof Download PDFInfo
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- CN116825985A CN116825985A CN202310638624.5A CN202310638624A CN116825985A CN 116825985 A CN116825985 A CN 116825985A CN 202310638624 A CN202310638624 A CN 202310638624A CN 116825985 A CN116825985 A CN 116825985A
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- 239000007774 positive electrode material Substances 0.000 title claims abstract description 44
- URQWOSCGQKPJCM-UHFFFAOYSA-N [Mn].[Fe].[Ni] Chemical compound [Mn].[Fe].[Ni] URQWOSCGQKPJCM-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 229920000642 polymer Polymers 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 39
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000011572 manganese Substances 0.000 claims abstract description 37
- 239000000243 solution Substances 0.000 claims abstract description 30
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract description 19
- 239000002243 precursor Substances 0.000 claims abstract description 18
- 238000005245 sintering Methods 0.000 claims abstract description 18
- 238000010438 heat treatment Methods 0.000 claims abstract description 16
- 238000002156 mixing Methods 0.000 claims abstract description 16
- -1 nickel iron sodium manganate Chemical compound 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 238000001035 drying Methods 0.000 claims abstract description 15
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 14
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 14
- 238000001354 calcination Methods 0.000 claims abstract description 13
- 239000010405 anode material Substances 0.000 claims abstract description 12
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 11
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000012298 atmosphere Substances 0.000 claims abstract description 11
- 239000008139 complexing agent Substances 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims abstract description 8
- 229910052751 metal Inorganic materials 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims abstract description 8
- 238000000975 co-precipitation Methods 0.000 claims abstract description 7
- 239000002184 metal Substances 0.000 claims abstract description 7
- 239000012266 salt solution Substances 0.000 claims abstract description 5
- 230000001590 oxidative effect Effects 0.000 claims abstract description 4
- 239000000843 powder Substances 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 26
- 238000000576 coating method Methods 0.000 claims description 16
- 239000011734 sodium Substances 0.000 claims description 16
- 239000011248 coating agent Substances 0.000 claims description 15
- 238000000498 ball milling Methods 0.000 claims description 13
- 239000010406 cathode material Substances 0.000 claims description 12
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 12
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 11
- 229910052708 sodium Inorganic materials 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 5
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- WFSRWJJESXWWSH-UHFFFAOYSA-N [O-2].[Fe+2].[Mn+2].[Ni+2].[Na+] Chemical compound [O-2].[Fe+2].[Mn+2].[Ni+2].[Na+] WFSRWJJESXWWSH-UHFFFAOYSA-N 0.000 claims description 2
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 2
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000011164 primary particle Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000011163 secondary particle Substances 0.000 claims description 2
- 229910001388 sodium aluminate Inorganic materials 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims 3
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 claims 3
- 150000002505 iron Chemical class 0.000 claims 2
- 150000002696 manganese Chemical class 0.000 claims 2
- 150000002815 nickel Chemical class 0.000 claims 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims 2
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 claims 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims 1
- 239000004280 Sodium formate Substances 0.000 claims 1
- 239000007864 aqueous solution Substances 0.000 claims 1
- 230000001105 regulatory effect Effects 0.000 claims 1
- 239000001632 sodium acetate Substances 0.000 claims 1
- 235000017281 sodium acetate Nutrition 0.000 claims 1
- 235000017550 sodium carbonate Nutrition 0.000 claims 1
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 claims 1
- 235000019254 sodium formate Nutrition 0.000 claims 1
- 235000009518 sodium iodide Nutrition 0.000 claims 1
- 239000004317 sodium nitrate Substances 0.000 claims 1
- 235000010344 sodium nitrate Nutrition 0.000 claims 1
- 239000000126 substance Substances 0.000 claims 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 abstract description 6
- 159000000000 sodium salts Chemical class 0.000 abstract description 2
- 238000003801 milling Methods 0.000 abstract 1
- 239000000463 material Substances 0.000 description 29
- 239000011247 coating layer Substances 0.000 description 12
- 239000003792 electrolyte Substances 0.000 description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
- 241000080590 Niso Species 0.000 description 5
- 239000002033 PVDF binder Substances 0.000 description 5
- 239000011230 binding agent Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000006258 conductive agent Substances 0.000 description 5
- 239000011888 foil Substances 0.000 description 5
- 239000003365 glass fiber Substances 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 230000014759 maintenance of location Effects 0.000 description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 5
- 238000011056 performance test Methods 0.000 description 5
- 238000000967 suction filtration Methods 0.000 description 5
- XNDZQQSKSQTQQD-UHFFFAOYSA-N 3-methylcyclohex-2-en-1-ol Chemical compound CC1=CC(O)CCC1 XNDZQQSKSQTQQD-UHFFFAOYSA-N 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 229910021645 metal ion Inorganic materials 0.000 description 4
- 229910044991 metal oxide Inorganic materials 0.000 description 4
- 150000004706 metal oxides Chemical class 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910001415 sodium ion Inorganic materials 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 229910001512 metal fluoride Inorganic materials 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 229910001463 metal phosphate Inorganic materials 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Classifications
-
- 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
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
-
- 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
-
- 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
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
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- Chemical & Material Sciences (AREA)
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- Electrochemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Composite Materials (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a polymer-assisted nano oxide coated nickel-iron-manganese ternary anode material and a preparation method thereof, wherein a nickel-iron-manganese metal salt solution, a sodium hydroxide precipitant solution and a complexing agent solution are added into a reaction kettle filled with base solution for coprecipitation, and a nickel-iron-manganese ternary hydroxide precursor is obtained through reaction; the obtained nickel-iron-manganese ternaryBall-milling and mixing the hydroxide precursor and sodium salt according to a certain proportion, and performing high-temperature sintering under an oxidizing atmosphere after uniformly mixing to obtain the nickel iron sodium manganate anode material; adding the nickel iron sodium manganate positive electrode material obtained in the step, polyvinyl alcohol and an aluminum source into an ethanol water solution, heating and stirring to obtain Al 2 O 3 Sol-gel; the obtained Al 2 O 3 Drying sol-gel under vacuum, and calcining the obtained powder at high temperature to obtain gamma-Al 2 O 3 @NaNi 1/ 3 Fe 1/3 Mn 1/3 O 2 And a positive electrode material.
Description
Technical Field
The invention belongs to the field of battery materials, and particularly relates to a preparation method of a sodium ion battery anode material.
Background
The lithium ion battery is widely applied to industries such as energy storage equipment and electric automobiles by virtue of the advantages of high working voltage, high energy density, long cycle life and the like. However, the lithium resources have the defects of small reserves, uneven distribution, low recovery rate and the like, and the rapidly growing lithium ion battery market must increase the consumption of the lithium resources and lead to continuous rise of the price of the lithium, so that the requirement of large-scale low-cost energy storage is difficult to meet. The content of sodium in the crust is thousands times of that of lithium, and the method has the advantages of rich resources, wide distribution, low price and the like. The O3 type layered anode material is widely focused due to high theoretical capacity, simple synthesis process and high sodium content, and has high application potential.
In the research of the O3 type nickel iron sodium manganate positive electrode material, the defects of complex phase change, interface reaction between the electrode material and electrolyte, slow ion diffusion, low initial coulombic efficiency and the like in the inherent charge and discharge process of the layered transition metal material also limit the further development of the material. In order to improve the electrochemical performance of the O3 type sodium nickel iron manganese oxide anode material, the main method adopted by the current research is to improve the performance of the material from different angles by doping substitution, controlling the micro-morphology, oxide coating and other methods. Common cladding materials include. The coating materials commonly used at present are as follows: metal oxides, hydroxides, phosphates, fluorides, and the like. The proper coating material is selected to inhibit particle cracking and reduce direct contact between the anode material and electrolyte, so that the air stability and the circulation stability of the material are improved and the application value of the material is improved. At present, the thickness controllability and uniformity of a coating layer by a solid phase method are relatively poor, so that the problem of electrolyte erosion or conduction limitation exists in a partial area of the surface of a material, and better electrochemical performance cannot be obtained due to non-uniformity of the surface of the material.
Disclosure of Invention
The invention aims to overcome the defects and the shortcomings in the background art, and provides a preparation method of a spherical nickel iron sodium manganate positive electrode material with high specific capacity and high multiplying power. In order to solve the technical problems, the technical scheme provided by the invention is as follows:
a polymer-assisted nano oxide coated nickel-iron-manganese ternary positive electrode material and a preparation method thereof comprise the following steps:
(1) Adding the nickel-iron-manganese metal salt solution, the sodium hydroxide precipitant solution and the complexing agent solution into a reaction kettle filled with base solution for coprecipitation reaction to obtain the nickel-iron-manganese ternary hydroxide precursor.
(2) Ball-milling and mixing the nickel-iron-manganese ternary hydroxide precursor obtained in the step (1) and sodium salt according to a certain proportion, and performing high-temperature sintering under an oxidizing atmosphere after uniformly mixing to obtain the nickel-iron-manganese positive electrode material.
(3) Adding the nickel iron sodium manganate positive electrode material obtained in the step (2), polyvinyl alcohol and an aluminum source into an ethanol water solution, heating and stirring to obtain Al 2 O 3 Sol-gel.
(4) The Al obtained in the step (3) is reacted with 2 O 3 Drying sol-gel under vacuum, and calcining the obtained powder at high temperature to obtain gamma-Al 2 O 3 @NaNi 1/3 Fe 1/3 Mn 1/3 O 2 And a positive electrode material.
In the above preparation method, preferably, the specific process in the coprecipitation reaction in the step (1) is as follows: adding nickel-iron-manganese metal salt solution, sodium hydroxide precipitant solution and complexing agent solution into the base solution drop by drop, controlling the reaction conditions to carry out coprecipitation reaction, and aging, filtering, washing and drying the mixture after the reaction is completed to obtain the solid-structure nickel-iron-manganese ternary hydroxide precursor.
Preferably, the metal salt of nickel, iron and manganese in the step (1) is one or more of soluble nitrate, acetate, sulfate and oxalate; the concentration of the NaOH precipitant is 2-6mol L -1 The method comprises the steps of carrying out a first treatment on the surface of the The NH is 3 ·H 2 The concentration of the O complexing agent is 10-40wt%; the pH value of the solution is 10-12, and the coprecipitation reaction time is 10-30h.
Preferably, the ball milling rotation speed required in the ball milling process in the step (2) is 100-700 r/min, and the ball milling time is 2-10 h.
Preferably, the sodium source used in the high-temperature sintering process in the step (2) is one or more of sodium carbonate, sodium hydroxide and sodium bicarbonate, and the hydroxide precursor: sodium source: the molar ratio of the metal elements in the nano oxidation is 1: (0.9-1.05): (0.01-0.1).
Preferably, the presintering temperature in the high-temperature sintering process in the step (2) is 300-600 ℃, and the presintering time is 4-10h; the re-calcination is carried out at 800-950 ℃ for 6-15h.
Preferably, the oxygen content in the atmosphere during the sintering in step (2) is more than 50%, water and CO 2 The content is lower than 0.1%.
Preferably, in the step (3), the aluminum source is one or more of aluminum nitrate, sodium aluminate, aluminum isopropoxide and aluminum chloride.
Preferably, in the dissolving process in the step (3), the heating temperature is 100-200 ℃, and the stirring time is 2-6 hours.
Preferably, in the step (4), the vacuum drying temperature is 60-120 ℃ and the drying time is 6-20 h.
Preferably, the temperature in the high-temperature sintering process in the step (4) is 400-700 ℃, and the sintering time is 4-12 hours.
The invention adopts a polymer-assisted sol-gel method to prepare the nano oxide coated nickel iron sodium manganate anode material. The primary particles of the positive electrode material are granular with the particle size of 100-200 nm, the secondary particles are spherical with the particle size of 4-10 mu m, and the size of the coating is 1-20 nm. Dispersing a positive electrode material and an aluminum source in a solution containing polyvinyl alcohol, and forming an aluminum oxide coating layer on the surface of the positive electrode material by utilizing aluminum nitrate decomposition in a high-temperature sintering process after vacuum drying; meanwhile, the mixed solution entering the gap of the positive electrode material is decomposed at high temperature, and the metal oxide is reserved in the bulk phase, so that the contact between the material and the electrolyte is further reduced, the occurrence of side reaction at an interface is reduced, the cycling stability of the material is improved, the effect of reducing residual alkali on the surface of the material is simultaneously played, the processability of the material is improved, and the requirements of the material on storage and use environments are reduced.
Compared with the prior art, the invention has the beneficial effects that:
(1) The nickel iron sodium manganate anode material coated by the metal oxide can inhibit particle cracking and reduce direct contact between the anode material and electrolyte. The invention uses a polymer auxiliary sol-gel method to prepare gamma-Al in the nickel-iron-manganese ternary anode material 2 O 3 As above, the selected polyvinyl alcohol (PVA) polymer may promoteAnd forming a film, so that the metal oxide coating layer and the positive electrode material are better combined together. The method can form an ultrathin and uniform coating layer on the surface of irregular particles by a simple sol-gel coating method. The thickness of the coating layer is controlled below 10nm, which benefits from the polymer/gamma-Al 2 O 3 Excellent film forming ability of sol gel. Ultra-thin gamma-Al 2 O 3 The coating layer not only realizes the high-efficiency transmission of sodium ions, but also enhances the electrochemical performance of the positive electrode material under high pressure.
(2) The coulomb efficiency of the nano oxide coated nickel iron sodium manganate anode material prepared by the method is obviously improved, and the first coulomb efficiency of the material under the 1C current multiplying power can reach more than 90% in a voltage interval of 2-4.0V.
(3) The preparation method has the advantages of low synthesis cost, easily available raw materials, simple synthesis method, easy operation, short synthesis period, safe and effective battery and suitability for large-scale production.
(4) The invention adds polyvinyl alcohol to assist the coating of nano alumina, thereby ensuring Al 3 + is uniformly dispersed, and the formed coating layer is more loose, porous and uniform; polyvinyl alcohol is a good dispersant, can form sol-gel with uniform composition when added into solution, and aluminum nitrate is decomposed into Al in the subsequent high-temperature sintering process 2 O 3 Simultaneously, polyvinyl alcohol is decomposed into water and carbon dioxide, and the polyvinyl alcohol is decomposed to form gas, so that Al 2 O 3 The coating layer is porous, so that the coating layer is prevented from being too thick, and uniform porous Al is finally formed 2 O 3 The purpose of the coating layer is to inhibit the growth of the coating layer and prevent the coating layer from being too thick.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 shows gamma-Al prepared in example 1 2 O 3 @NaNi 1/3 Fe 1/3 Mn 1/3 O 2 SEM image of positive electrode material.
FIG. 2 shows gamma-Al prepared in example 1 2 O 3 @NaNi 1/3 Fe 1/3 Mn 1/3 O 2 Cathode material and comparative example 1NaNi 1/3 Fe 1/ 3 Mn 1/3 O 2 Cycling performance graph of the material assembled coin cell at 1C discharge rate.
FIG. 3 shows gamma-Al prepared in example 1 2 O 3 @NaNi 1/3 Fe 1/3 Mn 1/3 O 2 And a first charge-discharge curve of the button cell assembled by the materials under the discharge multiplying power of 1C.
FIG. 4 is a NaNi prepared in comparative example 1 1/3 Fe 1/3 Mn 1/3 O 2 SEM image of positive electrode material.
FIG. 5 is a NaNi prepared in comparative example 1 1/3 Fe 1/3 Mn 1/3 O 2 And a first charge-discharge curve of the button cell assembled by the materials under the discharge multiplying power of 1C.
Description of the embodiments
The present invention will be described more fully hereinafter with reference to the accompanying drawings, in which preferred embodiments are shown, for the purpose of illustrating the invention, but the scope of the invention is not limited to the specific embodiments shown.
Unless defined otherwise, all technical and scientific terms used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the scope of the present invention.
Example 1
A polymer-assisted nano oxide coated nickel-iron-manganese ternary positive electrode material and a preparation method thereof comprise the following steps:
NiSO is carried out 4 ·7H 2 O，FeSO 4 ·7H 2 O，MnSO 4 ·H 2 O is dissolved in deionized water according to the mol ratio of 1:1:1 to prepare 2mol L -1 Then under nitrogen gasAdding the mixture into a continuous stirred tank reactor under the protection of atmosphere, and adding 4mol L -1 NaOH precipitant and 20wt% NH 3 ·H 2 After O complexing agent, the pH value of the solution is kept within 10-11, after full reaction, suction filtration, repeated washing, impurity removal and drying are carried out, ni is obtained 1/3 Fe 1/3 Mn 1/3 (OH) 2 A precursor. Taking 1mol Ni 1/ 3 Fe 1/3 Mn 1/3 (OH) 2 Precursor and 0.500mol Na 2 CO 3 Fully ball milling and mixing, heating to 500 ℃ at 5 ℃/min in an atmosphere furnace, presintering for 4 hours, heating to 890 ℃ and sintering for 12 hours to obtain NaNi 1/3 Fe 1/3 Mn 1/3 O 2 And a positive electrode material. Dissolving 1mol of positive electrode material, 0.001mol of aluminum nitrate nonahydrate and 0.030mol of polyvinyl alcohol in ethanol water solution, and stirring at 150 ℃ for 4 hours to obtain Al 2 O 3 Drying the sol-gel in a vacuum environment at 85 ℃ for 12 hours, and calcining at 600 ℃ for 6 hours to obtain gamma-Al 2 O 3 @NaNi 1/3 Fe 1/3 Mn 1/3 O 2 And a positive electrode material.
FIG. 1 shows gamma-Al prepared in example 1 2 O 3 @NaNi 1/3 Fe 1/3 Mn 1/3 O 2 SEM of material, coating particle size of about 15nm, and holes at the edges of the coating, indicating successful gamma-Al incorporation 2 O 3 Material coated NaNi 1/3 Fe 1/3 Mn 1/3 O 2 A surface.
Assembling a battery: 0.2000g of gamma-Al obtained in this example was weighed out 2 O 3 @NaNi 1/3 Fe 1/3 Mn 1/3 O 2 The positive electrode material is prepared by adding 0.0250g of conductive carbon black as a conductive agent and 0.0250g of PVDF (polyvinylidene fluoride) as a binder, uniformly mixing, coating on an aluminum foil to prepare a positive electrode plate, taking a sodium plate as a negative electrode in a vacuum glove box, taking a battery diaphragm as a glass fiber diaphragm of Whatman GF/D, and taking 1mol/LNaClO as electrolyte 4 (EC: dmc=1:1 (volume ratio) +5% fec), assembled into a coin cell of CR 2025.
After the materials are assembled into a half cell, electrochemical performance test is carried out in a 2-4.0V interval, as shown in figure 3, the initial coulombic efficiency is 90.54% under the current multiplying power of 1C, the specific discharge capacity can reach 120.72mAh/g, and the capacity retention rate after 100 times of circulation is 91.74% as shown in figure 2.
Example 2
A polymer-assisted nano oxide coated nickel-iron-manganese ternary positive electrode material and a preparation method thereof comprise the following steps:
NiSO is carried out 4 ·7H 2 O，FeSO 4 ·7H 2 O，MnSO 4 ·H 2 O is dissolved in deionized water according to the mol ratio of 2:4:4 to prepare 2mol L -1 Then adding the metal ion solution into a continuous stirred tank reactor under the protection of nitrogen atmosphere, and adding 4mol L -1 NaOH precipitant and 20wt% NH 3 ·H 2 After O complexing agent, the pH value of the solution is kept within 10-11, after full reaction, suction filtration, repeated washing, impurity removal and drying are carried out, ni is obtained 1/3 Fe 1/3 Mn 1/3 (OH) 2 A precursor. Taking 1mol Ni 1/ 3 Fe 1/3 Mn 1/3 (OH) 2 Precursor and 0.500mol Na 2 CO 3 Fully ball milling and mixing, heating to 500 ℃ at 5 ℃/min in an atmosphere furnace, presintering for 4 hours, heating to 890 ℃ and sintering for 12 hours to obtain NaNi 1/3 Fe 1/3 Mn 1/3 O 2 And a positive electrode material. Dissolving 1mol of positive electrode material, 0.001mol of aluminum nitrate nonahydrate and 0.030mol of polyvinyl alcohol in ethanol water solution, and stirring at 150 ℃ for 4 hours to obtain Al 2 O 3 Drying the sol-gel in a vacuum environment at 85 ℃ for 12 hours, and calcining at 600 ℃ for 6 hours to obtain gamma-Al 2 O 3 @NaNi 1/3 Fe 1/3 Mn 1/3 O 2 And a positive electrode material.
Assembling a battery: 0.2000g of gamma-Al obtained in this example was weighed out 2 O 3 @NaNi 1/3 Fe 1/3 Mn 1/3 O 2 Adding 0.0250g of conductive carbon black as a conductive agent and 0.0250g of PVDF (polyvinylidene fluoride) as a binder into the positive electrode material, uniformly mixing, coating the mixture on an aluminum foil to prepare a positive electrode plate, taking a sodium plate as a negative electrode in a vacuum glove box, and taking a battery diaphragm as glass fiber of Whatman GF/DDiaphragm, electrolyte is 1mol/LNaClO 4 (EC: dmc=1:1 (volume ratio) +5% fec), assembled into a coin cell of CR 2025.
After the materials are assembled into a half battery, electrochemical performance test is carried out in a 2-4.0V interval, the initial coulombic efficiency is 93.27% under the current multiplying power of 1C, the specific discharge capacity can reach 122.7mAh/g, and the capacity retention rate after 100 times of circulation is 88.93%.
Example 3
A polymer-assisted nano oxide coated nickel-iron-manganese ternary positive electrode material and a preparation method thereof comprise the following steps:
NiSO is carried out 4 ·7H 2 O，FeSO 4 ·7H 2 O，MnSO 4 ·H 2 O is dissolved in deionized water according to the mol ratio of 1:1:1 to prepare 2mol L -1 Then adding the metal ion solution into a continuous stirred tank reactor under the protection of nitrogen atmosphere, and adding 4mol L -1 NaOH precipitant and 20wt% NH 3 ·H 2 After O complexing agent, the pH value of the solution is kept within 10-11, after full reaction, suction filtration, repeated washing, impurity removal and drying are carried out, ni is obtained 1/3 Fe 1/3 Mn 1/3 (OH) 2 A precursor. Taking 1mol Ni 1/ 3 Fe 1/3 Mn 1/3 (OH) 2 Precursor and 0.500mol Na 2 CO 3 Fully ball milling and mixing, heating to 500 ℃ at 5 ℃/min in an atmosphere furnace, presintering for 4 hours, heating to 890 ℃ and sintering for 12 hours to obtain NaNi 1/3 Fe 1/3 Mn 1/3 O 2 And a positive electrode material. Dissolving 1mol of positive electrode material, 0.002mol of aluminum nitrate nonahydrate and 0.030mol of polyvinyl alcohol in ethanol water solution, and stirring at 150 ℃ for 4 hours to obtain Al 2 O 3 Drying the sol-gel in a vacuum environment at 85 ℃ for 12 hours, and calcining at 600 ℃ for 6 hours to obtain gamma-Al 2 O 3 @NaNi 1/3 Fe 1/3 Mn 1/3 O 2 And a positive electrode material.
Assembling a battery: 0.2000g of gamma-Al obtained in this example was weighed out 2 O 3 @NaNi 1/3 Fe 1/3 Mn 1/3 O 2 Positive electrode material, add 0.0250g of conductive carbon black as a conductive agent and 0.0250g of PVDF (polyvinylidene fluoride) as a binder, uniformly mixing, coating on an aluminum foil to prepare a positive plate, taking a metal sodium plate as a negative electrode in a vacuum glove box, taking a battery diaphragm as a glass fiber diaphragm of Whatman GF/D, and taking 1mol/LNaClO as electrolyte 4 (EC: dmc=1:1 (volume ratio) +5% fec), assembled into a coin cell of CR 2025.
After the materials are assembled into a half battery, electrochemical performance test is carried out in a 2-4.0V interval, the initial coulomb efficiency is 90.19% under the current multiplying power of 1C, the specific discharge capacity can reach 121.8mAh/g, and the capacity retention rate is 89.53% after 100 times of circulation.
Example 4
A polymer-assisted nano oxide coated nickel-iron-manganese ternary positive electrode material and a preparation method thereof comprise the following steps:
NiSO is carried out 4 ·7H 2 O，FeSO 4 ·7H 2 O，MnSO 4 ·H 2 O is dissolved in deionized water according to the mol ratio of 1:1:1 to prepare 2mol L -1 Then adding the metal ion solution into a continuous stirred tank reactor under the protection of nitrogen atmosphere, and adding 4mol L -1 NaOH precipitant and 20wt% NH 3 ·H 2 After O complexing agent, the pH value of the solution is kept within 10-11, after full reaction, suction filtration, repeated washing, impurity removal and drying are carried out, ni is obtained 1/3 Fe 1/3 Mn 1/3 (OH) 2 A precursor. Taking 1mol Ni 1/ 3 Fe 1/3 Mn 1/3 (OH) 2 Precursor and 0.500mol Na 2 CO 3 Fully ball milling and mixing, heating to 500 ℃ at 5 ℃/min in an atmosphere furnace, presintering for 4 hours, heating to 890 ℃ and sintering for 12 hours to obtain NaNi 1/3 Fe 1/3 Mn 1/3 O 2 And a positive electrode material. Dissolving 1mol of positive electrode material, 0.001mol of aluminum nitrate nonahydrate and 0.030mol of polyvinyl alcohol in ethanol water solution, and stirring at 150 ℃ for 4 hours to obtain Al 2 O 3 Drying the sol-gel in a vacuum environment at 85 ℃ for 12 hours, and calcining the sol-gel at a high temperature of 500 ℃ for 6 hours to obtain gamma-Al 2 O 3 @NaNi 1/3 Fe 1/3 Mn 1/3 O 2 Positive electrode materialAnd (5) material.
Assembling a battery: 0.2000g of gamma-Al obtained in this example was weighed out 2 O 3 @NaNi 1/3 Fe 1/3 Mn 1/3 O 2 The positive electrode material is prepared by adding 0.0250g of conductive carbon black as a conductive agent and 0.0250g of PVDF (polyvinylidene fluoride) as a binder, uniformly mixing, coating on an aluminum foil to prepare a positive electrode plate, taking a sodium plate as a negative electrode in a vacuum glove box, taking a battery diaphragm as a glass fiber diaphragm of Whatman GF/D, and taking 1mol/LNaClO as electrolyte 4 (EC: dmc=1:1 (volume ratio) +5% fec), assembled into a coin cell of CR 2025.
After the materials are assembled into a half battery, electrochemical performance test is carried out in a 2-4.0V interval, the initial coulomb efficiency is 94.46% under the current multiplying power of 1C, the specific discharge capacity can reach 127.42mAh/g, and the capacity retention rate is 90.03% after 100 times of circulation.
Comparative example 1
The preparation method of the nickel-iron-manganese ternary positive electrode material comprises the following steps of:
NiSO is carried out 4 ·7H 2 O，FeSO 4 ·7H 2 O，MnSO 4 ·H 2 O is dissolved in deionized water according to the mol ratio of 1:1:1 to prepare 2mol L -1 Then adding the metal ion solution into a continuous stirred tank reactor under the protection of nitrogen atmosphere, and adding 4mol L -1 NaOH precipitant and 20wt% NH 3 ·H 2 After O complexing agent, the pH value of the solution is kept within 10-11, after full reaction, suction filtration, repeated washing, impurity removal and drying are carried out, ni is obtained 1/3 Fe 1/3 Mn 1/3 (OH) 2 A precursor. Taking 1mol Ni 1/ 3 Fe 1/3 Mn 1/3 (OH) 2 Precursor and 0.5mol Na 2 CO 3 Fully ball milling and mixing, heating to 500 ℃ at 5 ℃/min in an atmosphere furnace, presintering for 4 hours, heating to 890 ℃ and sintering for 12 hours to obtain NaNi 1/3 Fe 1/3 Mn 1/3 O 2 An active material.
Material FIG. 4 is an SEM image of an uncoated sodium nickel iron manganate positive electrode material prepared in comparative example 1, the material surface was smooth, and no apparent coating was present.
Assembling a battery: 0.2000g of pure NaNi obtained in this example was weighed out 1/3 Fe 1/3 Mn 1/3 O 2 The positive electrode material is prepared by adding 0.0250g of conductive carbon black as a conductive agent and 0.0250g of PVDF (polyvinylidene fluoride) as a binder, uniformly mixing, coating on an aluminum foil to prepare a positive electrode plate, taking a sodium plate as a negative electrode in a vacuum glove box, taking a battery diaphragm as a glass fiber diaphragm of Whatman GF/D, and taking 1mol/LNaClO as electrolyte 4 (EC: dmc=1:1 (volume ratio) +5% fec), assembled into a coin cell of CR 2025.
After the materials are assembled into a half cell, electrochemical performance test is carried out in a 2-4.0V interval, as shown in figure 5, the initial coulombic efficiency is 93.66% under the current multiplying power of 1C, the specific discharge capacity can reach 127.26mAh/g, and the capacity retention rate after 100 times of circulation is 84.9% as shown in figure 4.
Claims (10)
1. The polymer-assisted nano oxide coated nickel-iron-manganese ternary positive electrode material is characterized in that the chemical formula of the coated nickel-iron-sodium manganate ternary positive electrode material is as follows: gamma-Al 2 O 3 @NaNi y Fe z Mn 1-y-z O 2 Wherein x is more than or equal to 0 and less than or equal to 0.1, y is more than or equal to 0 and less than or equal to 1/3, and z is more than or equal to 0 and less than or equal to 1/3.
2. The polymer-assisted nano-oxide coated nickel-iron-manganese ternary cathode material according to claim 1, wherein the coating is not only on the surface of the particles, but also in the bulk phase.
3. The polymer-assisted nano oxide coated nickel-iron-manganese ternary cathode material according to any one of claims 1-2, wherein primary particles of the cathode material are granular with a particle size of 100-200 nm, secondary particles of the cathode material are spherical with a particle size of 4-10 μm, and the size of a coating is 1-20 nm.
4. A method for preparing a polymer-assisted nano-oxide coated nickel-iron-manganese ternary cathode material according to any one of claims 1-2, comprising the steps of:
(1) Dissolving stoichiometric ratio of nickel salt, iron salt and manganese salt in deionized water to prepare metal salt solution, adding the metal salt solution into a continuous stirred tank reactor under the protection of nitrogen atmosphere, and adding NaOH precipitant and NH 3 ·H 2 O complexing agent, pH value of the solution is regulated, and after coprecipitation reaction for a certain time, hydroxide precursor is prepared after water washing, alcohol washing and drying;
(2) Ball-milling and mixing the hydroxide precursor and a sodium source according to a certain proportion, and performing high-temperature sintering under an oxidizing atmosphere after uniformly mixing to obtain a sodium nickel iron manganese oxide anode material;
(3) Adding a nickel iron sodium manganate positive electrode material, polyvinyl alcohol and an aluminum source into an ethanol aqueous solution, heating and stirring to obtain Al 2 O 3 Sol-gel;
(4) Al is added with 2 O 3 Drying sol-gel under vacuum, and calcining the obtained powder at high temperature to obtain gamma-Al 2 O 3 @NaNi 1/3 Fe 1/3 Mn 1/3 O 2 And a positive electrode material.
5. The method for preparing the polymer-assisted nano oxide coated nickel-iron-manganese ternary cathode material according to claim 4, wherein the manganese salt, the nickel salt and the iron salt in the step (1) are one or more of soluble sulfate, nitrate, formate and acetate; the concentration of the NaOH precipitant is 2-6mol L -1 The method comprises the steps of carrying out a first treatment on the surface of the The NH is 3 ·H 2 The concentration of the O complexing agent is 10-40wt%; the pH value of the solution is 10-12, and the coprecipitation reaction time is 10-30h.
6. The method for preparing the polymer-assisted nano-oxide-coated nickel-iron-manganese ternary cathode material according to claim 4, wherein the sodium source in the high-temperature sintering process in the step (2) is one or more of sodium carbonate, sodium hydroxide, sodium acetate, sodium nitrate, sodium formate and sodium iodide.
7. The preparation method of the polymer-assisted nano oxide coated nickel-iron-manganese ternary cathode material is characterized in that the ball milling rotation speed in the ball milling process in the step (2) is 100-700 r/min, and the ball milling time is 2-10 h.
8. The method for preparing the polymer-assisted nano-oxide-coated nickel-iron-manganese ternary cathode material according to claim 4, wherein in the step (2), the high-temperature sintering process comprises pre-calcination and re-calcination, wherein the pre-calcination is performed by raising the temperature from room temperature to 300-600 ℃ at a heating rate of 1-10 ℃/min, and presintering for 4-10h; and the re-calcination is to heat to 800-950 ℃ at a heating rate of 1-10 ℃/min, and calcination is carried out for 6-15h.
9. The method for preparing a polymer-assisted nano-oxide-coated nickel-iron-manganese ternary cathode material according to claim 4, wherein in step (2), the oxygen content in the oxidizing sintering atmosphere exceeds 50%, and water and CO are mixed 2 The content is lower than 0.1%.
10. The method for preparing the polymer-assisted nano oxide coated nickel-iron-manganese ternary cathode material according to claim 4, wherein in the step (3), the aluminum source is one or more of aluminum nitrate, sodium aluminate, aluminum isopropoxide and aluminum chloride.
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