CN116504954A - Positive electrode material, preparation method thereof and sodium ion battery - Google Patents
Positive electrode material, preparation method thereof and sodium ion battery Download PDFInfo
- Publication number
- CN116504954A CN116504954A CN202310786687.5A CN202310786687A CN116504954A CN 116504954 A CN116504954 A CN 116504954A CN 202310786687 A CN202310786687 A CN 202310786687A CN 116504954 A CN116504954 A CN 116504954A
- Authority
- CN
- China
- Prior art keywords
- positive electrode
- copper
- layered
- sodium
- electrode material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 60
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 23
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title abstract description 22
- 239000000463 material Substances 0.000 claims abstract description 93
- 229910052751 metal Inorganic materials 0.000 claims abstract description 47
- 239000011734 sodium Substances 0.000 claims abstract description 41
- 239000002184 metal Substances 0.000 claims abstract description 39
- 239000011247 coating layer Substances 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 24
- MJEPCYMIBBLUCJ-UHFFFAOYSA-K sodium titanium(4+) phosphate Chemical compound P(=O)([O-])([O-])[O-].[Ti+4].[Na+] MJEPCYMIBBLUCJ-UHFFFAOYSA-K 0.000 claims abstract description 14
- 239000000126 substance Substances 0.000 claims abstract description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 51
- 238000001354 calcination Methods 0.000 claims description 36
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 34
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 claims description 32
- 239000010949 copper Substances 0.000 claims description 30
- 239000002243 precursor Substances 0.000 claims description 28
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 26
- 239000005751 Copper oxide Substances 0.000 claims description 25
- 229910000431 copper oxide Inorganic materials 0.000 claims description 25
- 239000013084 copper-based metal-organic framework Substances 0.000 claims description 23
- 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 20
- 229910052708 sodium Inorganic materials 0.000 claims description 20
- 238000005245 sintering Methods 0.000 claims description 19
- 239000012266 salt solution Substances 0.000 claims description 18
- 239000005639 Lauric acid Substances 0.000 claims description 16
- 239000010405 anode material Substances 0.000 claims description 16
- 229910052802 copper Inorganic materials 0.000 claims description 16
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 14
- 239000010936 titanium Substances 0.000 claims description 13
- 150000001879 copper Chemical class 0.000 claims description 12
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 12
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 12
- 238000004729 solvothermal method Methods 0.000 claims description 8
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 7
- 229910052748 manganese Inorganic materials 0.000 claims description 7
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 7
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 6
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 5
- 159000000000 sodium salts Chemical class 0.000 claims description 5
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- 229910019142 PO4 Inorganic materials 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 4
- 239000010452 phosphate Substances 0.000 claims description 4
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 239000011780 sodium chloride Substances 0.000 claims description 3
- 239000004317 sodium nitrate Substances 0.000 claims description 3
- 235000010344 sodium nitrate Nutrition 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 3
- 239000002245 particle Substances 0.000 abstract description 13
- 239000003792 electrolyte Substances 0.000 abstract description 5
- 230000009286 beneficial effect Effects 0.000 abstract description 4
- 230000005540 biological transmission Effects 0.000 abstract description 4
- 238000005336 cracking Methods 0.000 abstract description 4
- 239000011259 mixed solution Substances 0.000 description 26
- 239000011572 manganese Substances 0.000 description 22
- 238000002156 mixing Methods 0.000 description 18
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 18
- 239000000243 solution Substances 0.000 description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 14
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 14
- 238000007873 sieving Methods 0.000 description 14
- 238000003756 stirring Methods 0.000 description 13
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 10
- 239000011777 magnesium Substances 0.000 description 9
- 238000000498 ball milling Methods 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- 229910052786 argon Inorganic materials 0.000 description 7
- 229910000388 diammonium phosphate Inorganic materials 0.000 description 7
- 235000019838 diammonium phosphate Nutrition 0.000 description 7
- 239000004408 titanium dioxide Substances 0.000 description 7
- 239000012298 atmosphere Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- BBMHARZCALWXSL-UHFFFAOYSA-M sodium dihydrogenphosphate monohydrate Chemical compound O.[Na+].OP(O)([O-])=O BBMHARZCALWXSL-UHFFFAOYSA-M 0.000 description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- 229910021529 ammonia Inorganic materials 0.000 description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000000395 magnesium oxide Substances 0.000 description 5
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 5
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 5
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical group O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 4
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 4
- 229940099596 manganese sulfate Drugs 0.000 description 4
- 239000011702 manganese sulphate Substances 0.000 description 4
- 235000007079 manganese sulphate Nutrition 0.000 description 4
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 4
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 4
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 229910001928 zirconium oxide Inorganic materials 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 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 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000012716 precipitator Substances 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- IVORCBKUUYGUOL-UHFFFAOYSA-N 1-ethynyl-2,4-dimethoxybenzene Chemical compound COC1=CC=C(C#C)C(OC)=C1 IVORCBKUUYGUOL-UHFFFAOYSA-N 0.000 description 1
- IRPGOXJVTQTAAN-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanal Chemical compound FC(F)(F)C(F)(F)C=O IRPGOXJVTQTAAN-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminum fluoride Inorganic materials F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- 239000004254 Ammonium phosphate Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 239000005696 Diammonium phosphate Substances 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 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
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 1
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 1
- 235000019289 ammonium phosphates Nutrition 0.000 description 1
- 239000012300 argon atmosphere Substances 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
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- DEIVNMVWRDMSMJ-UHFFFAOYSA-N hydrogen peroxide;oxotitanium Chemical compound OO.[Ti]=O DEIVNMVWRDMSMJ-UHFFFAOYSA-N 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical class [Fe+2].[Fe+2].[Fe+2].[Fe+3].[Fe+3].[Fe+3].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCYOBGZUOMKFPA-UHFFFAOYSA-N 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 150000002696 manganese Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 235000019837 monoammonium phosphate Nutrition 0.000 description 1
- 239000006012 monoammonium phosphate Substances 0.000 description 1
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 1
- 235000019799 monosodium phosphate Nutrition 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229920000447 polyanionic polymer Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 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
-
- 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
- H01M4/36—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
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
-
- 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
-
- 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
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
-
- 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
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Composite Materials (AREA)
- Engineering & Computer Science (AREA)
- Crystallography & Structural Chemistry (AREA)
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Abstract
The invention relates to the technical field of sodium ion batteries, in particular to a positive electrode material, a preparation method thereof and a sodium ion battery. The positive electrode material of the present invention comprises: a layered O3-type oxide and a coating layer coated on the surface of the layered O3-type oxide; the chemical formula of the layered O3 type oxide is Na 1‑x Cu y Ni 1/3‑y Fe 1/ 3 Mn 1/3 O 2 The method comprises the steps of carrying out a first treatment on the surface of the In the formula, x is more than or equal to-0.04 and less than or equal to 0.03,0.04, and y is more than or equal to-0.11; the saidThe layered O3-type oxide has a porous structure; the coating layer comprises sodium titanium phosphate and/or metal doped sodium titanium phosphate. The hole structure in the positive electrode material can relieve particle breakage caused by charge and discharge deformation, and is beneficial to Na ion transmission; the coating layer can prevent the internal material from directly contacting with the electrolyte, stabilize the surface interface and further prevent the particles from cracking; the positive electrode material has excellent structural stability, cycle performance and rate performance under high pressure.
Description
Technical Field
The invention relates to the technical field of sodium ion batteries, in particular to a positive electrode material, a preparation method thereof and a sodium ion battery.
Background
The sodium ion battery has wide application prospect in the energy storage field due to the cost advantage, the working principle is similar to that of a lithium ion battery, and the reversible intercalation and deintercalation of sodium ions between the anode and the cathode are utilized to realize the storage and release of energy.
Currently, positive electrode materials of sodium ion batteries mainly include polyanion compounds, prussian blue compounds and layered oxides, wherein layered oxides are receiving attention due to their high specific capacity and structure similar to that of positive electrode materials of lithium ion batteries.
Layered Na 1-x Cu y Ni 1/3-y Fe 1/3 Mn 1/3 O 2 The positive electrode material has the advantages of high gram capacity, high compacted density, excellent cycle performance and the like. Synthetic layered Na 1-x Cu y Ni 1/3-y Fe 1/3 Mn 1/3 O 2 In the process of the positive electrode material, cu (OH) is used for 2 The pH of the precipitate is about 4.2 to 6.7, and Ni (OH) 2 、Fe(OH) 2 、Mn(OH) 2 The pH of the precipitate is about 7-10, so that the Cu is easy to separate out a large amount of irregular crystal nuclei by using a coprecipitation method to synthesize CuNiFeMn. Thus, the precursor stage requires separate synthesis of Ni, fe, mn and Cu. Layered Na 1- x Cu y Ni 1/3-y Fe 1/3 Mn 1/3 O 2 The working voltage of the battery of the positive electrode material is more below 4.0V, and the higher voltage can lead sodium ions to be excessively separated and embeddedAnd breakage of material particles occurs, so that the cycle performance is poor at high voltage.
In view of this, the present invention has been made.
Disclosure of Invention
The first object of the present invention is to provide a positive electrode material for solving the problem of layered Na existing in the prior art 1- x Cu y Ni 1/3-y Fe 1/3 Mn 1/3 O 2 The positive electrode material has unstable structure, is easy to crack under high pressure and has poor cycle performance under high pressure.
The second aim of the invention is to provide a preparation method of the positive electrode material, which is simple and feasible and is suitable for large-scale production; the prepared positive electrode material has stable structure and excellent cycle performance and multiplying power performance under high voltage.
A third object of the present invention is to provide a sodium ion battery comprising the above positive electrode material, which has excellent electrochemical properties.
In order to achieve the above object of the present invention, the following technical solutions are specifically adopted:
in a first aspect, the present invention provides a positive electrode material comprising: a layered O3-type oxide and a coating layer coated on the surface of the layered O3-type oxide;
the chemical formula of the layered O3 type oxide is Na 1-x Cu y Ni 1/3-y Fe 1/3 Mn 1/3 O 2 The method comprises the steps of carrying out a first treatment on the surface of the In the formula, x is more than or equal to-0.04 and less than or equal to 0.03,0.04, and y is more than or equal to-0.11;
the layered O3-type oxide has a porous structure;
the coating layer comprises sodium titanium phosphate and/or metal doped sodium titanium phosphate.
Further, the chemical formula of the metal doped sodium titanium phosphate is Na 1+a M a Ti 2-a (PO 4 ) 3 The method comprises the steps of carrying out a first treatment on the surface of the Wherein a is 0.0001 to 0.5; m is doped metal, and the average valence state of M is +3;
and/or M comprises at least one of Zr, al and Mg.
Further, the mass ratio of the layered O3 oxide to the coating layer is (250-1000): 1.
in a second aspect, the present invention also provides a method for preparing the positive electrode material as described above, including the steps of:
s1, calcining a copper-based metal organic framework material to obtain porous copper oxide;
s2, reacting the porous copper oxide, the mixed metal salt solution and the precipitant to obtain a precursor material; the metal elements in the mixed metal salt solution comprise Cu, ni, fe and Mn;
s3, sintering the precursor material and a sodium source to obtain a layered O3 oxide;
s4, grinding and calcining the mixture containing the sodium salt, the titanium source and the phosphate and the layered O3 type oxide in sequence to obtain the anode material;
and/or the mixed material further comprises a doped metal source.
Further, in step S1, the preparation method of the copper-based metal organic framework material includes the following steps:
and (3) copper salt, lauric acid, 1,3, 5-trimesic acid and an organic solvent react to obtain the copper-based metal organic framework material.
Further, the preparation method of the copper-based metal organic framework material comprises at least one of the following technical characteristics (1) - (4);
(1) The copper salt comprises at least one of copper sulfate, copper nitrate, copper chloride and copper acetate;
(2) The organic solvent comprises the following components in percentage by volume (0.5-2): 1 methanol and butanol;
(3) The molar ratio of the copper salt to the lauric acid to the 1,3, 5-trimesic acid is (4-6): (200-220): (2-4);
(4) The temperature of the solvothermal reaction is 110-150 ℃, and the time of the solvothermal reaction is 2-8 hours.
Further, in the step S1, the calcination temperature is 270-320 ℃, and the calcination time is 4-8 hours.
Further, in step S3, the sodium source includes at least one of sodium carbonate, sodium nitrate, and sodium chloride;
and/or the sintering temperature is 850-950 ℃, and the sintering time is 10-20 h.
Further, in step S4, the doped metal source includes at least one of a Zr source, an Al source, and a Mg source;
and/or the calcination temperature is 600-850 ℃, and the calcination time is 3-6 hours.
In a third aspect, the invention also provides a sodium ion battery comprising the positive electrode material as described above.
Compared with the prior art, the invention has the beneficial effects that:
1. the positive electrode material of the invention comprises porous layered O3 type Na 1-x Cu y Ni 1/3-y Fe 1/3 Mn 1/3 O 2 A sodium titanium phosphate material coating layer coated on the surface of the material; the porous structure in the positive electrode material can relieve particle breakage caused by charge and discharge deformation of the material, and is beneficial to rapid transmission of Na ions; the coating layer can prevent the surface of the internal material from directly contacting with the electrolyte, inhibit side reactions and formation of a resistive surface film, stabilize the surface interface, and further prevent particles from cracking under high pressure, thereby exhibiting more excellent cycle performance and rate performance under high pressure.
2. According to the preparation method of the positive electrode material, the copper-based metal organic framework material is adopted as a base material, and is sintered to form the porous copper oxide, the porous copper oxide can form a better solid solution with other metals, and a large number of pore structures are formed in the material, so that the performance of the positive electrode material under high pressure is improved, and the phenomenon of breakage of particles of the positive electrode material under high pressure is relieved.
3. The positive electrode material can be used as the positive electrode material of a sodium ion battery, and can improve the cycle performance and the multiplying power performance of the sodium ion battery.
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 needed in the description of the embodiments or the prior art will be briefly described, and it is obvious that the drawings in the description below are some embodiments of the present invention, and other drawings can be obtained according to the drawings without inventive effort for a person skilled in the art.
FIG. 1 is a scanning electron microscope image of the positive electrode material prepared in example 1 of the present invention.
Detailed Description
The technical solution of the present invention will be clearly and completely described below with reference to the accompanying drawings and detailed description, but it will be understood by those skilled in the art that the examples described below are some, but not all, examples of the present invention, and are intended to be illustrative of the present invention only and should not be construed as limiting the scope of the present invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
In a first aspect, some embodiments of the present invention provide a positive electrode material comprising: a layered O3-type oxide and a coating layer coated on the surface of the layered O3-type oxide;
the chemical formula of the layered O3 type oxide is Na 1-x Cu y Ni 1/3-y Fe 1/3 Mn 1/3 O 2 The method comprises the steps of carrying out a first treatment on the surface of the In the formula, x is more than or equal to-0.04 and less than or equal to 0.03,0.04, and y is more than or equal to-0.11;
the layered O3-type oxide has a porous structure;
the coating layer comprises sodium titanium phosphate (NaTi) 2 (PO 4 ) 3 ) And/or metal doped sodium titanium phosphate.
The anode material of the invention has a core-shell structure and comprises porous layered O3 type Na 1-x Cu y Ni 1/3-y Fe 1/3 Mn 1/3 O 2 Sodium titanium phosphate and/or metal doped sodium titanium phosphate coating coated on the surface of the inner core.
Internal Na of the cathode material of the invention 1-x Cu y Ni 1/3-y Fe 1/3 Mn 1/3 O 2 The material has a large number of hole structures, so that particle breakage caused by charge and discharge deformation of the material can be relieved, and rapid transmission of Na ions is facilitated; the coating layer can prevent Na inside 1-x Cu y Ni 1/3-y Fe 1/3 Mn 1/3 O 2 The surface of the material is directly contacted with the electrolyte, so that side reactions and formation of a resistive surface film are inhibited, and the surface interface is stabilized, so that the material has better interface stability, and particles are further prevented from being broken under high pressure, so that more excellent cycle performance and rate performance are shown under high pressure.
In some embodiments, the metal-doped sodium titanium phosphate has the formula Na 1+a M a Ti 2-a (PO 4 ) 3 The method comprises the steps of carrying out a first treatment on the surface of the Wherein a is 0.0001 to 0.5; m is doped metal, and the average valence state of M is +3; preferably, M comprises at least one of Zr, al and Mg.
In some embodiments, the mass ratio of the layered O3-type oxide to the coating layer is (250-1000): 1, a step of; typical, but not limiting, for example, the mass ratio of layered O3-type oxide to coating layer may be 250:1. 350: 1. 450: 1. 550). 1. 650: 1. 750: 1. 850: 1. 950: 1. 1000:1. or a range value consisting of any two thereof; preferably, the mass ratio of the layered O3-type oxide to the coating layer is (500-750): 1.
the coating layer of the invention is used as a protective layer of the internal porous layered oxide, so that the contact area of the internal porous layered oxide exposed to electrolyte can be reduced, and the occurrence of interface side reaction can be reduced. By setting the proper mass ratio of the layered oxide and the coating layer, the internal material can be better protected, the stability of the coating layer is improved, and the anode material has more excellent cycle performance and rate capability.
In some embodiments, the particle size D50 of the particles of the layered O3-type oxide is 3-10 μm, and the thickness of the coating layer is 10-50 nm; typically, but not by way of limitation, the thickness of the cladding layer may be, for example, 10nm, 20nm, 30nm, 40nm, 50nm or a range of any two of these.
In a second aspect, some embodiments of the present invention provide a method for preparing the above positive electrode material, including the steps of:
s1, calcining a copper-based metal organic framework material to obtain porous copper oxide;
s2, reacting the porous copper oxide, the mixed metal salt solution and the precipitant to obtain a precursor material; the metal elements in the mixed metal salt solution comprise Cu, ni, fe and Mn;
s3, sintering the precursor material and a sodium source to obtain a layered O3 oxide;
s4, grinding and calcining the mixture containing the sodium salt, the titanium source and the phosphate and the layered O3 type oxide in sequence to obtain the anode material.
In some embodiments, the mixed material further includes a dopant metal source.
The invention adopts copper-based metal organic framework material as a base material, porous copper oxide is formed after sintering, then mixed metal salt solution containing Ni, fe, mn, cu and precipitant are added for reaction to form Cu, ni, fe, mn hydroxide coated porous copper oxide precursor material, and then the precursor material and sodium source are sintered to obtain layered O3 type Na with a large amount of pore structures inside 1-x Cu y Ni 1/3-y Fe 1/3 Mn 1/3 O 2 The method comprises the steps of carrying out a first treatment on the surface of the Due to the fluxing action of CuO, the synthesized material can be uniformly distributed on the surface of copper oxide, and after high-temperature calcination, ni, fe, mn and Cu form a better solid solution, and a large number of holes are formed in the material, so that the cracking of spherical particles caused by charge-discharge deformation of the material can be relieved, and the rapid transmission of Na ions is facilitated; and finally, calcining the mixture of the layered O3 type oxide and the mixture containing the sodium salt, the titanium source and the phosphate, and coating the surface of the layered O3 type oxide to further prevent particle breakage and improve the performance of the anode material under high pressure.
The preparation method of the positive electrode material disclosed by the invention is simple in process, suitable for large-scale production, and the prepared positive electrode material has the advantages of good structural stability, difficulty in cracking, excellent cycle performance and rate performance and the like under high pressure.
When copper elements in the porous copper oxide cannot meet the requirements, the proportion of the elements is regulated by adding Cu.
In some embodiments, in step S1, a method for preparing a copper-based metal organic framework material includes the steps of:
copper salt, lauric acid, 1,3, 5-trimesic acid and organic solvent react to obtain the copper-based metal organic framework material.
The copper-based metal organic framework material prepared by the preparation method can provide structural support, is easy for sodium source to enter during sintering of a large number of holes, and is beneficial to improving the multiplying power performance of the material.
In some embodiments, the copper salt comprises at least one of copper sulfate, copper nitrate, copper chloride, and copper acetate.
In some embodiments, the organic solvent comprises (0.5-2) by volume: 1 methanol and butanol.
In some embodiments, the molar ratio of copper salt, lauric acid, and 1,3, 5-trimesic acid is (4-6): (200-220): (2-4); preferably 5:210:3.
in some embodiments, the temperature of the solvothermal reaction is 110-150 ℃ and the time of the solvothermal reaction is 2-8 hours; typical, but not limiting, for example, the temperature of the solvothermal reaction may be 110 ℃, 120 ℃, 130 ℃, 140 ℃, 150 ℃ or a range of any two of them, and the time of the solvothermal reaction may be 2h, 3h, 4h, 5h, 6h, 7h, 8h or a range of any two of them.
In some embodiments, the method for preparing the copper-based metal organic framework material specifically includes the following steps:
copper salt, lauric acid, methanol and butanol are mixed to obtain a mixed solution I; in the mixed solution I, the concentration of copper salt is 0.01-0.04 mol/L, and the concentration of lauric acid is 0.42-1.68 mol/L;
mixing 1,3, 5-trimesic acid, methanol and butanol to obtain a mixed solution II; in the mixed solution II, the concentration of the 1,3, 5-trimesic acid is 0.006-0.024 mol/L;
the volume ratio is 1:1, adding the mixed solution I into the mixed solution II at a rate of 0.5-2 mL/min, reacting for 2-8 h at 110-150 ℃, and sequentially centrifuging, washing and drying to obtain the copper-based metal-organic framework material. Preferably, the drying temperature is 35-60 ℃, and the drying time is 12-24 hours.
In some embodiments, in the step S1, the calcination temperature is 270-320 ℃, and the calcination time is 4-8 hours; typically, but not by way of limitation, the temperature of calcination may be 270 ℃, 280 ℃, 290 ℃, 300 ℃, 310 ℃, 320 ℃ or any two of these ranges, and the time of calcination may be 4 hours, 5 hours, 6 hours, 7 hours, 8 hours or any two of these ranges. Preferably, the calcination is carried out in an inert atmosphere, preferably N 2 Or Ar.
In some embodiments, in the step S2, the molar ratio of the porous copper oxide to the copper in the mixed metal salt is (7-9) to (1-3); preferably 8:2.
in some embodiments, in step S2, the concentration of the mixed metal salt solution is 1-2 mol/L; preferably, the mixed metal salt solution comprises copper salt, ferric salt, nickel salt and manganese salt; more preferably, the mixed metal salt includes at least one of nitrate, chloride, acetate and sulfate.
In some embodiments, in step S2, the precipitant includes sodium hydroxide solution with a concentration of 3-5 mol/L and/or ammonia solution with a concentration of 5-9 mol/L.
In some embodiments, in step S2, during the reaction, the pH of the system is 10.5-11.5, and the ammonia value is 2.8-3.2 g/L; preferably, the pH of the system is 10.9-11.1.
In some embodiments, in step S2, the reaction temperature is 40-60 ℃; preferably, the reaction is stopped until the particles reach the target particle size.
The prepared porous copper oxide is added into a mixed metal salt solution, a precipitator is slowly added in the stirring process, cu, ni, fe, mn is deposited in a hydroxide form, and Cu, ni, fe, mn hydroxide coated copper oxide material is formed by precipitation through controlling the stirring speed and the feeding amount of the precipitator.
In some embodiments, in step S3, the sodium source comprises at least one of sodium carbonate, sodium chloride, and sodium nitrate.
In some embodiments, in step S3, the ratio of the number of moles of sodium element in the sodium source to the total number of moles of metal elements in the precursor material is (0.97-1.04): 1.
in some embodiments, in step S3, the sintering temperature is 850-950 ℃ and the sintering time is 10-20 hours; typically, but not by way of limitation, the sintering temperature may be 850 ℃, 860 ℃, 870 ℃, 880 ℃, 890 ℃, 900 ℃, 910 ℃, 920 ℃, 930 ℃, 940 ℃, 950 ℃ or any two of these ranges, and the sintering time may be 10h, 12h, 14h, 16h, 18h, 20h or any two of these ranges. Preferably, the sintering is performed under air; preferably, the flow rate of air is 10-20 mL/min.
In some embodiments, in step S3, crushing and sieving are further included after sintering; preferably, the crushing comprises crushing the roller (1-1.5 mm) by using a jaw crusher (gap 3.5-4.5 mm); the sieving includes sieving with 250-400 mesh sieve.
In some embodiments, in step S4, the mixture further includes at least one of a Zr source, an Al source, and a Mg source; preferably, the Zr source comprises at least one of zirconia, zirconium hydroxide and zirconium chloride; the Al source comprises at least one of aluminum oxide, aluminum hydroxide, sodium metaaluminate, aluminum chloride, aluminum nitrate and aluminum fluoride; the Mg source includes at least one of magnesium oxide, magnesium hydroxide, magnesium chloride, aluminum nitrate, and magnesium chloride.
In some embodiments, in step S4, the sodium salt comprises sodium dihydrogen phosphate; the titanium source comprises at least one of titanium dioxide, titanium trioxide and tetrabutyl titanate; the phosphate salt includes at least one of diammonium phosphate, monoammonium phosphate, and ammonium phosphate.
In some embodiments, in step S4, milling comprises ball milling; preferably, the grinding comprises ball milling for 1-3 hours at a rotational speed of 300-600 r/min.
In some embodiments, in the step S4, the calcination temperature is 600-850 ℃, and the calcination time is 3-6 hours; typically, but not by way of limitation, the temperature of calcination may be, for example, 600 ℃, 650 ℃, 700 ℃, 750 ℃, 800 ℃, or a range of any two of these; the time of calcination may be 3h, 4h, 5h, 6h, or a range of any two of these. Preferably, the calcination is carried out under an inert atmosphere; more preferably, under an argon atmosphere.
In a third aspect, some embodiments of the present invention provide a sodium ion battery comprising the above-described positive electrode material.
The positive electrode material can be used in sodium ion batteries, and can improve the cycle performance and the multiplying power performance of the sodium ion batteries.
Further description will be provided below in connection with specific examples.
Example 1
The preparation method of the positive electrode material provided by the embodiment comprises the following steps:
s1, mixing copper sulfate, lauric acid, methanol and butanol to obtain a mixed solution I; mixing 1,3, 5-trimesic acid, methanol and butanol to obtain a mixed solution II; the volume ratio is 1:1, adding the mixed solution I into the mixed solution II at a rate of 0.5-2 mL/min, reacting at 130 ℃ for 5 hours, and sequentially centrifuging, washing and drying at 50 ℃ for 20 hours to obtain a copper-based metal-organic framework material; wherein, the volume ratio of methanol to butanol is 1:1, the concentration of copper sulfate in the mixed solution I is 0.025M, and the molar ratio of the copper sulfate, lauric acid and 1,3, 5-trimesic acid is 5:210:3, a step of;
and calcining the copper-based metal organic framework material at 300 ℃ for 6 hours in a nitrogen atmosphere to obtain the porous copper oxide.
S2, according to the mol ratio of Cu, ni, fe and Mn of 1.5:25.8:33.3:33.3 weighing copper chloride, nickel sulfate, ferric chloride and manganese sulfate, and then mixing with water to prepare a mixed metal salt solution with the concentration of 1.5 mol/L;
adding the porous copper oxide into the mixed metal salt solution, adding a sodium hydroxide solution with the concentration of 4mol/L and an ammonia water solution with the concentration of 7mol/L in the stirring process, keeping the pH value of the solution at 60 ℃ to be 11.0+/-0.2, and the ammonia value to be 2.8-3.2 g/L, and obtaining a precursor material with the D50 approximately equal to 4.5+/-0.5 mu m after the reaction; the molar ratio of the porous copper oxide to the copper in the mixed metal salt is 8:2.
s3, in an air atmosphere, the air flow rate is 10-20 mL/min, and the precursor material and sodium carbonate (the mole of sodium element in a sodium source)The ratio of the number to the total number of moles of metal elements in the precursor material was 1.01: 1) Sintering at 900 deg.c for 15 hr, crushing with jaw crusher (gap 3.5-4.5 mm) and roller (1-1.5 mm), and sieving with 250-400 mesh sieve to obtain layered O3 oxide (with chemical formula of NaCu) 0.075 Ni 0.258 Fe 1/3 Mn 1/3 O 2 ）。
S4, sodium dihydrogen phosphate monohydrate, zirconium oxide, magnesium oxide, aluminum oxide, titanium dioxide and diammonium hydrogen phosphate according to a molar ratio of 30:4:4:1:30:30, uniformly mixing to obtain a mixed material;
ball milling the mixed material and the layered O3 oxide for 2 hours at the rotating speed of 300-600 r/min by adopting a stirring ball mill, placing the mixed material and the layered O3 oxide in a tubular furnace, heating to 750 ℃ at the speed of 3 ℃/min under the argon environment, calcining for 5 hours, and sieving to obtain the anode material, wherein the coating layer of the anode material is Na 1.5 Mg 0.2 Zr 0.2 Al 0.1 Ti 1.5 (PO 4 ) 3 The mass ratio of the layered O3-type oxide to the coating layer is 625:1.
example 2
The preparation method of the positive electrode material provided by the embodiment comprises the following steps:
s1, mixing copper sulfate, lauric acid, methanol and butanol to obtain a mixed solution I; mixing 1,3, 5-trimesic acid, methanol and butanol to obtain a mixed solution II; the volume ratio is 1:1, adding the mixed solution I into the mixed solution II at a rate of 0.5-2 mL/min, reacting at 130 ℃ for 5 hours, and sequentially centrifuging, washing and drying at 50 ℃ for 20 hours to obtain a copper-based metal-organic framework material; wherein, the volume ratio of methanol to butanol is 1:1, the concentration of copper sulfate in the mixed solution I is 0.025M, and the molar ratio of the copper sulfate, lauric acid and 1,3, 5-trimesic acid is 5:210:3, a step of;
and calcining the copper-based metal organic framework material at 300 ℃ for 6 hours in a nitrogen atmosphere to obtain the porous copper oxide.
S2, the mol ratio of Cu, ni, fe and Mn is 0.8:29.3:33.3:33.3 weighing copper chloride, nickel sulfate, ferric chloride and manganese sulfate, and then mixing with water to prepare a mixed metal salt solution with the concentration of 1.5 mol/L;
adding the porous copper oxide into the mixed metal salt solution, adding a sodium hydroxide solution with the concentration of 4mol/L and an ammonia water solution with the concentration of 7mol/L in the stirring process, keeping the pH value of the solution at 60 ℃ to be 11.0+/-0.2, and the ammonia value to be 2.8-3.2 g/L, and obtaining a precursor material with the D50 approximately equal to 4.5+/-0.5 mu m after the reaction; the molar ratio of the porous copper oxide to the copper in the mixed metal salt is 8:2.
s3, sintering the precursor material and sodium carbonate (the ratio of the mole number of sodium elements in a sodium source to the total mole number of metal elements in the precursor material is 1.01:1) for 15 hours at 900 ℃ in an air atmosphere at the air flow rate of 10-20 mL/min, crushing the precursor material by a jaw crusher (gap 3.5-4.5 mm) pair roller (1-1.5 mm), and sieving the precursor material by a 250-400-mesh sieve to obtain the layered O3 oxide (the chemical formula is NaCu) 0.04 Ni 0.293 Fe 1/3 Mn 1/3 O 2 ）。
S4, sodium dihydrogen phosphate monohydrate, zirconium oxide, magnesium oxide, aluminum oxide, titanium dioxide and diammonium hydrogen phosphate according to a molar ratio of 30:4:4:1:30:30, uniformly mixing to obtain a mixed material;
ball milling the mixed material and the layered O3 oxide for 2 hours at the rotating speed of 300-600 r/min by adopting a stirring ball mill, placing the mixed material and the layered O3 oxide in a tubular furnace, heating to 750 ℃ at the speed of 3 ℃/min under the argon environment, calcining for 5 hours, and sieving to obtain the anode material, wherein the coating layer of the anode material is Na 1.5 Mg 0.2 Zr 0.2 Al 0.1 Ti 1.5 (PO 4 ) 3 The mass ratio of the layered O3-type oxide to the coating layer is 625:1.
example 3
The preparation method of the positive electrode material provided by the embodiment comprises the following steps:
s1, mixing copper sulfate, lauric acid, methanol and butanol to obtain a mixed solution I; mixing 1,3, 5-trimesic acid, methanol and butanol to obtain a mixed solution II; the volume ratio is 1:1, adding the mixed solution I into the mixed solution II at a rate of 0.5-2 mL/min, reacting at 130 ℃ for 5 hours, and sequentially centrifuging, washing and drying at 50 ℃ for 20 hours to obtain a copper-based metal-organic framework material; wherein, the volume ratio of methanol to butanol is 1:1, the concentration of copper sulfate in the mixed solution I is 0.025M, and the molar ratio of the copper sulfate, lauric acid and 1,3, 5-trimesic acid is 5:210:3, a step of;
and calcining the copper-based metal organic framework material at 300 ℃ for 6 hours in a nitrogen atmosphere to obtain the porous copper oxide.
S2, according to the mol ratio of Cu, ni, fe and Mn of 2.2:22.3:33.3:33.3 weighing copper chloride, nickel sulfate, ferric chloride and manganese sulfate, and then mixing with water to prepare a mixed metal salt solution with the concentration of 1.5 mol/L;
adding the porous copper oxide into the mixed metal salt solution, adding a sodium hydroxide solution with the concentration of 4mol/L and an ammonia water solution with the concentration of 7mol/L in the stirring process, keeping the pH value of the solution at 60 ℃ to be 11.0+/-0.2, and the ammonia value to be 2.8-3.2 g/L, and obtaining a precursor material with the D50 approximately equal to 4.5+/-0.5 mu m after the reaction; the molar ratio of the porous copper oxide to the copper in the mixed metal salt is 8:2.
s3, sintering the precursor material and sodium carbonate (the ratio of the mole number of sodium elements in a sodium source to the total mole number of metal elements in the precursor material is 1.01:1) for 15 hours at 900 ℃ in an air atmosphere at the air flow rate of 10-20 mL/min, crushing the precursor material by a jaw crusher (gap 3.5-4.5 mm) pair roller (1-1.5 mm), and sieving the precursor material by a 250-400-mesh sieve to obtain the layered O3 oxide (the chemical formula is NaCu) 0.11 Ni 0.223 Fe 1/3 Mn 1/3 O 2 ）。
S4, sodium dihydrogen phosphate monohydrate, zirconium oxide, magnesium oxide, aluminum oxide, titanium dioxide and diammonium hydrogen phosphate according to a molar ratio of 30:4:4:1:30:30, uniformly mixing to obtain a mixed material;
ball milling the mixed material and the layered O3 oxide for 2 hours at the rotating speed of 300-600 r/min by adopting a stirring ball mill, placing the mixed material and the layered O3 oxide in a tubular furnace, heating to 750 ℃ at the speed of 3 ℃/min under the argon environment, calcining for 5 hours, and sieving to obtain the anode material, wherein the coating layer of the anode material is Na 1.5 Mg 0.2 Zr 0.2 Al 0.1 Ti 1.5 (PO 4 ) 3 The mass ratio of the layered O3-type oxide to the coating layer is 625:1.
example 4
The preparation method of the positive electrode material provided in this embodiment refers to embodiment 1, and is different in that in step S4, the mass ratio of the mixed material to the layered O3-type oxide is 250:1.
example 5
The preparation method of the positive electrode material provided in this embodiment refers to embodiment 1, and is different in that in step S4, the mass ratio of the mixed material to the layered O3-type oxide is 1000:1.
example 6
The preparation method of the positive electrode material provided in this embodiment refers to embodiment 1, and is different in that in step S4, sodium dihydrogen phosphate monohydrate, alumina, titanium dioxide, and diammonium hydrogen phosphate are mixed according to a molar ratio of 3:1:3:3, uniformly mixing to obtain a mixed material.
Ball milling the mixed material and the layered O3 oxide for 2 hours at the rotating speed of 300-600 r/min by adopting a stirring ball mill, placing the mixed material and the layered O3 oxide in a tubular furnace, heating to 750 ℃ at the speed of 3 ℃/min under the argon environment, calcining for 5 hours, and sieving to obtain the anode material, wherein the coating layer of the anode material is Na 1.5 Al 0.5 Ti 1.5 (PO 4 ) 3 The mass ratio of the layered O3-type oxide to the coating layer is 625:1.
example 7
The preparation method of the positive electrode material provided in this embodiment refers to embodiment 1, and is different in that in step S4, sodium dihydrogen phosphate monohydrate, titanium dioxide, and diammonium hydrogen phosphate are mixed according to a molar ratio of 1:2:2, uniformly mixing to obtain a mixed material.
Ball milling the mixed material and the layered O3 oxide for 2 hours at the rotating speed of 300-600 r/min by adopting a stirring ball mill, placing the mixed material and the layered O3 oxide in a tubular furnace, heating to 750 ℃ at the speed of 3 ℃/min under the argon environment, calcining for 5 hours, and sieving to obtain the anode material, wherein the coating layer of the anode material is NaTi 2 (PO 4 ) 3 The mass ratio of the layered O3-type oxide to the coating layer is 625:1.
example 8
The reference example of the preparation method of the positive electrode material provided in this example is different in that in step S1, copper nitrate, lauric acid, methanol and butanol are mixed to obtain a mixed solution I; mixing 1,3, 5-trimesic acid, methanol and butanol to obtain a mixed solution II; the volume ratio is 1:1, adding the mixed solution I into the mixed solution II at a rate of 0.5-2 mL/min, reacting for 8 hours at 150 ℃, and sequentially centrifuging, washing and drying for 20 hours at 50 ℃ to obtain a copper-based metal organic framework material; wherein, the volume ratio of methanol to butanol is 1.5:1, the concentration of copper nitrate in the mixed solution I is 0.015M, and the molar ratio of copper nitrate, lauric acid and 1,3, 5-trimesic acid is 5:210:3, a step of;
and calcining the copper-based metal organic framework material at 320 ℃ for 8 hours in a nitrogen atmosphere to obtain the porous copper oxide.
Comparative example 1
The preparation method of the positive electrode material provided by the comparative example comprises the following steps:
s1, the mol ratio of Cu, ni, fe and Mn is 7.5:25.8:33.3:33.3 weighing copper chloride, nickel sulfate, ferric chloride and manganese sulfate, and then mixing with water to prepare a mixed metal salt solution with the concentration of 1.5 mol/L;
s2, adding a sodium hydroxide solution with the concentration of 4mol/L and an ammonia water solution with the concentration of 7mol/L in the stirring process of the mixed metal salt solution, keeping the pH value of the solution at 60 ℃ to be 11.0+/-0.2 and the ammonia value to be 2.8-3.2 g/L, and obtaining the precursor material with the D50 approximately equal to 4.5+/-0.5 mu m after the reaction.
S3, sintering the precursor material and sodium carbonate (the ratio of the mole number of sodium elements in a sodium source to the total mole number of metal elements in the precursor material is 1.01:1) for 15 hours at 900 ℃ in an air atmosphere at the air flow rate of 10-20 mL/min, crushing the precursor material by a jaw crusher (gap 3.5-4.5 mm) pair roller (1-1.5 mm), and sieving the precursor material by a 250-400-mesh sieve to obtain the layered O3 oxide (the chemical formula is NaCu) 0.075 Ni 0.258 Fe 1/3 Mn 1/3 O 2 ）。
S4, sodium dihydrogen phosphate monohydrate, zirconium oxide, magnesium oxide, aluminum oxide, titanium dioxide and diammonium hydrogen phosphate according to a molar ratio of 30:4:4:1:30:30, uniformly mixing to obtain a mixed material;
ball milling the mixed material and the layered O3 oxide for 2 hours at the rotating speed of 300-600 r/min by adopting a stirring ball mill, placing the mixed material and the layered O3 oxide in a tubular furnace, heating to 750 ℃ at the speed of 3 ℃/min under the argon environment, calcining for 5 hours, and sieving to obtain the anode materialThe coating layer of the material is Na 1.5 Mg 0.2 Zr 0.2 Al 0.1 Ti 1.5 (PO 4 ) 3 The mass ratio of the layered O3-type oxide to the coating layer is 625:1.
comparative example 2
The preparation method of the positive electrode material provided by the comparative example is characterized in that in the step S4, the layered O3-type oxide is ball-milled for 2 hours by adopting a stirring ball mill at the rotating speed of 300-600 r/min, then the layered O3-type oxide is placed in a tube furnace, the temperature is increased to 750 ℃ at the speed of 3 ℃/min in an argon environment, the calcination is carried out for 5 hours, the positive electrode material is obtained after sieving, and the positive electrode material has no coating layer.
Test example 1
The positive electrode material obtained in example 1 was subjected to a scan test, and the results are shown in fig. 1.
From fig. 1, it can be seen that the preparation method of the present invention successfully synthesizes a positive electrode material with a single crystal morphology with good dispersibility, and the single crystal morphology has good air stability and battery cycle performance.
The positive electrode materials prepared in examples 1 to 8 and comparative examples 1 to 2 were assembled into sodium ion batteries, and each battery was tested, and the results are shown in table 1.
And (3) assembling a button cell:
positive electrode material, conductive agent Super P and adhesive PVDF according to the mass ratio of 90:5:5 preparing positive electrode material slurry by using a deaeration machine, regulating the solid content of the slurry to 39% by adopting N-methyl pyrrolidone (NMP), coating the regulated slurry on aluminum foil by using an automatic coating machine, drying at 120 ℃ in a vacuum drying oven, rolling by a roll squeezer, performing button 2032 battery assembly in a glove box after punching by a slicer, and adopting NaPF with electrolyte of 1.2mol/L 6 Wherein the solvent is EC: PC: emc=1: 1:1 (volume ratio), 2wt% of FEC is additionally added, the diaphragm is a glass fiber diaphragm, and a metal sodium sheet is adopted as a counter electrode.
And carrying out charge and discharge test on the button half battery in a voltage interval of 2.5-4.2V on a blue electric tester. 0.1C was charged and discharged 2 times, and the capacity retention after 50 cycles of 1C and the rate capability of 1C/0.1C were tested. The test results are recorded in table 1.
The rate performance in table 1 is a ratio of the capacity under 1C to the capacity under 0.1C.
TABLE 1
From table 1, it can be seen that the cathode material prepared by the preparation method of the invention can not only improve the cycle performance at high voltage, but also has good high-current multiplying power performance.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.
Claims (10)
1. A positive electrode material, characterized by comprising: a layered O3-type oxide and a coating layer coated on the surface of the layered O3-type oxide;
the chemical formula of the layered O3 type oxide is Na 1-x Cu y Ni 1/3-y Fe 1/3 Mn 1/3 O 2 The method comprises the steps of carrying out a first treatment on the surface of the In the formula, x is more than or equal to-0.04 and less than or equal to 0.03,0.04, and y is more than or equal to-0.11;
the layered O3-type oxide has a porous structure;
the coating layer comprises sodium titanium phosphate and/or metal doped sodium titanium phosphate.
2. The positive electrode material according to claim 1, wherein the metal-doped sodium titanium phosphate has a chemical formula of Na 1+a M a Ti 2-a (PO 4 ) 3 The method comprises the steps of carrying out a first treatment on the surface of the Wherein a is 0.0001 to 0.5; m is doped metal, and the average valence state of M is +3;
and/or M comprises at least one of Zr, al and Mg.
3. The positive electrode material according to claim 1, wherein the mass ratio of the layered O3-type oxide to the coating layer is (250 to 1000): 1.
4. a method for preparing a positive electrode material according to any one of claims 1 to 3, comprising the steps of:
s1, calcining a copper-based metal organic framework material to obtain porous copper oxide;
s2, reacting the porous copper oxide, the mixed metal salt solution and the precipitant to obtain a precursor material; the metal elements in the mixed metal salt solution comprise Cu, ni, fe and Mn;
s3, sintering the precursor material and a sodium source to obtain a layered O3 oxide;
s4, grinding and calcining the mixture containing the sodium salt, the titanium source and the phosphate and the layered O3 type oxide in sequence to obtain the anode material;
and/or the mixed material further comprises a doped metal source.
5. The method for producing a positive electrode material according to claim 4, wherein in step S1, the method for producing a copper-based metal-organic framework material comprises the steps of:
and (3) copper salt, lauric acid, 1,3, 5-trimesic acid and an organic solvent react to obtain the copper-based metal organic framework material.
6. The method for producing a positive electrode material according to claim 5, comprising at least one of the following technical features (1) to (4);
(1) The copper salt comprises at least one of copper sulfate, copper nitrate, copper chloride and copper acetate;
(2) The organic solvent comprises the following components in percentage by volume (0.5-2): 1 methanol and butanol;
(3) The molar ratio of the copper salt to the lauric acid to the 1,3, 5-trimesic acid is (4-6): (200-220): (2-4);
(4) The temperature of the solvothermal reaction is 110-150 ℃, and the time of the solvothermal reaction is 2-8 hours.
7. The method according to claim 4, wherein in the step S1, the calcination temperature is 270 to 320 ℃, and the calcination time is 4 to 8 hours.
8. The method of producing a positive electrode material according to claim 4, wherein in step S3, the sodium source includes at least one of sodium carbonate, sodium nitrate, and sodium chloride;
and/or the sintering temperature is 850-950 ℃, and the sintering time is 10-20 h.
9. The method of producing a positive electrode material according to claim 4, wherein in step S4, the doped metal source includes at least one of a Zr source, an Al source, and a Mg source;
and/or the calcination temperature is 600-850 ℃, and the calcination time is 3-6 hours.
10. A sodium ion battery comprising the positive electrode material of any one of claims 1 to 3.
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| CN117594778A (en) * | 2024-01-18 | 2024-02-23 | 深圳为方能源科技有限公司 | Sodium ion battery positive electrode material and preparation method and application thereof |
| CN117613516A (en) * | 2024-01-11 | 2024-02-27 | 溧阳中科海钠科技有限责任公司 | Diaphragm and preparation method and application thereof |
| CN117638051A (en) * | 2023-12-31 | 2024-03-01 | 江门市科恒实业股份有限公司 | Coated O3 type manganese-based sodium ion battery positive electrode material and preparation method thereof |
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| CN116093326A (en) * | 2023-02-01 | 2023-05-09 | 天津市捷威动力工业有限公司 | Sodium ion battery positive electrode material and preparation method and application thereof |
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| CN117613516A (en) * | 2024-01-11 | 2024-02-27 | 溧阳中科海钠科技有限责任公司 | Diaphragm and preparation method and application thereof |
| CN117613516B (en) * | 2024-01-11 | 2024-04-16 | 溧阳中科海钠科技有限责任公司 | Diaphragm and preparation method and application thereof |
| CN117594778A (en) * | 2024-01-18 | 2024-02-23 | 深圳为方能源科技有限公司 | Sodium ion battery positive electrode material and preparation method and application thereof |
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