CN117096308A - Coated layered oxide positive electrode material and preparation method and application thereof - Google Patents
Coated layered oxide positive electrode material and preparation method and application thereof Download PDFInfo
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- CN117096308A CN117096308A CN202311125473.XA CN202311125473A CN117096308A CN 117096308 A CN117096308 A CN 117096308A CN 202311125473 A CN202311125473 A CN 202311125473A CN 117096308 A CN117096308 A CN 117096308A
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- layered oxide
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- 239000007774 positive electrode material Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title abstract description 26
- 229910001415 sodium ion Inorganic materials 0.000 claims abstract description 59
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 48
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims abstract description 47
- 239000000463 material Substances 0.000 claims abstract description 34
- 239000011247 coating layer Substances 0.000 claims abstract description 32
- 239000010406 cathode material Substances 0.000 claims description 38
- 239000011734 sodium Substances 0.000 claims description 35
- 239000000126 substance Substances 0.000 claims description 29
- 239000011572 manganese Substances 0.000 claims description 25
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 25
- 238000002156 mixing Methods 0.000 claims description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- 239000011575 calcium Substances 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 238000000498 ball milling Methods 0.000 claims description 15
- 238000005245 sintering Methods 0.000 claims description 13
- 238000001291 vacuum drying Methods 0.000 claims description 13
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 12
- 229910052796 boron Inorganic materials 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
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 11
- 229910052742 iron Inorganic materials 0.000 claims description 11
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 11
- 229910052708 sodium Inorganic materials 0.000 claims description 11
- 239000001488 sodium phosphate Substances 0.000 claims description 11
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 11
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 10
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 6
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 229910052791 calcium Inorganic materials 0.000 claims description 6
- 239000011737 fluorine Substances 0.000 claims description 6
- 229910052731 fluorine Inorganic materials 0.000 claims description 6
- 229910052748 manganese Inorganic materials 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 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
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 4
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 4
- 150000002505 iron Chemical class 0.000 claims description 4
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 claims description 4
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 4
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims description 4
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 3
- 239000010452 phosphate Substances 0.000 claims description 3
- 239000004254 Ammonium phosphate Substances 0.000 claims description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 2
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 2
- 239000004327 boric acid Substances 0.000 claims description 2
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims description 2
- 229910001634 calcium fluoride Inorganic materials 0.000 claims description 2
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 2
- 229910000398 iron phosphate Inorganic materials 0.000 claims description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 2
- IPJKJLXEVHOKSE-UHFFFAOYSA-L manganese dihydroxide Chemical compound [OH-].[OH-].[Mn+2] IPJKJLXEVHOKSE-UHFFFAOYSA-L 0.000 claims description 2
- 229940099596 manganese sulfate Drugs 0.000 claims description 2
- 239000011702 manganese sulphate Substances 0.000 claims description 2
- 235000007079 manganese sulphate Nutrition 0.000 claims description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 2
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 2
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 claims description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 2
- 229910000160 potassium phosphate Inorganic materials 0.000 claims description 2
- 235000011009 potassium phosphates Nutrition 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
- 239000001632 sodium acetate Substances 0.000 claims description 2
- 235000017281 sodium acetate Nutrition 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 239000011780 sodium chloride Substances 0.000 claims description 2
- 239000004317 sodium nitrate Substances 0.000 claims description 2
- 235000010344 sodium nitrate Nutrition 0.000 claims description 2
- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical compound [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 claims description 2
- 229940039790 sodium oxalate Drugs 0.000 claims description 2
- 235000011008 sodium phosphates Nutrition 0.000 claims description 2
- 125000000129 anionic group Chemical group 0.000 claims 1
- 125000002091 cationic group Chemical group 0.000 claims 1
- 150000001450 anions Chemical class 0.000 abstract description 14
- 150000001768 cations Chemical class 0.000 abstract description 12
- 239000003792 electrolyte Substances 0.000 abstract description 10
- 238000007086 side reaction Methods 0.000 abstract description 6
- 239000000243 solution Substances 0.000 description 22
- 230000000052 comparative effect Effects 0.000 description 10
- 239000010405 anode material Substances 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000002243 precursor Substances 0.000 description 5
- 229910004261 CaF 2 Inorganic materials 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 238000009831 deintercalation Methods 0.000 description 4
- 230000002427 irreversible effect Effects 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 230000004888 barrier function Effects 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000005955 Ferric phosphate Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910052810 boron oxide Inorganic materials 0.000 description 2
- ZDVYABSQRRRIOJ-UHFFFAOYSA-N boron;iron Chemical compound [Fe]#B ZDVYABSQRRRIOJ-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 239000011267 electrode slurry Substances 0.000 description 2
- 229940032958 ferric phosphate Drugs 0.000 description 2
- 230000036571 hydration Effects 0.000 description 2
- 238000006703 hydration reaction Methods 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- 230000002687 intercalation Effects 0.000 description 2
- 229910000399 iron(III) phosphate Inorganic materials 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910014507 Na0.67Ni0.33Mn0.67O2 Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- -1 cation salt Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 239000007771 core particle Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910021385 hard carbon Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000011229 interlayer Substances 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
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920000447 polyanionic polymer Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 230000007704 transition Effects 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
-
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
Landscapes
- 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)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a coated layered oxide positive electrode material, a preparation method and application thereof, wherein the coated layered oxide positive electrode material comprises a P2 type anion-cation co-doped layered oxide and a coating layer arranged on the surface of the P2 type anion-cation co-doped layered oxide, and the material of the coating layer contains iron element; the P2 type layered oxide is co-doped by adopting anions and cations, so that the cycle performance and the multiplying power performance of the sodium ion battery are effectively improved, and meanwhile, the surface of the sodium ion battery is provided with the coating layer containing the iron element, so that the direct contact between the P2 type anion and cation co-doped layered oxide and electrolyte can be effectively avoided, the occurrence of side reaction is further reduced, the cycle stability of the sodium ion battery is further improved, and the finally obtained coated layered oxide positive electrode material is used as the positive electrode material of the sodium ion battery, so that the sodium ion battery has high discharge capacity, excellent cycle performance and multiplying power performance.
Description
Technical Field
The invention belongs to the technical field of sodium ion batteries, and particularly relates to a coated layered oxide positive electrode material, a preparation method and application thereof.
Background
The working principle of the sodium ion battery is similar to that of a lithium ion battery, sodium ions are separated from a positive electrode and are embedded into a negative electrode through electrolyte when the lithium ion battery is charged, electrons move from an external circuit to the negative electrode for balancing charges, and the sodium ions are completely opposite when the lithium ion battery is discharged; in an ideal case, sodium ions can be completely reversibly extracted and intercalated without causing damage to the crystal structure.
The electrode material is critical to the sodium ion battery, the positive electrode material of the sodium ion battery is one of important components of the sodium ion battery, and the development of the ideal positive electrode material of the sodium ion battery is the key for pushing the sodium ion battery. Currently, the studied positive electrode materials of sodium ion batteries are mainly crystalline materials, including transition metal oxides, polyanion compounds and Prussian blue compounds. Since the intercalation and deintercalation reaction kinetics of sodium ions in the electrode material are closely related to the crystal structure of the material, the diffusion barrier for sodium ions to migrate in the layered material is lower than that of lithium ions, so that the layered compound is very advantageous as a sodium storage material; on the one hand, layered transition metal oxides are often preferred in the study of sodium ion battery cathode materials because the interlayer spacing perpendicular to the c-axis is often adjustable during intercalation and deintercalation of sodium ions; on the other hand, layered oxides have been widely studied for their characteristics of easy synthesis, high energy/power density, environmental friendliness, and the like.
Currently, layered oxides can be classified into the following categories by the coordination environment of sodium ions and the way of stacking oxygen: o3, P2, O2, etc., generally, O3 and P2 structures are most frequently present, and P3 type structures can be constructed under certain specific synthesis conditions. In the charging process, the O3 type structure can be changed into a P3 type structure, and the P2 type structure can be changed into an O2 type structure, so that the phase change of the structure can influence the diffusion of sodium ions and increase polarization; on the other hand, the phase transition also causes the change of lattice constant to induce the generation of stress, so that cracks are generated in particles, the materials are crushed, and finally the energy efficiency and the cycle performance of the battery are influenced, therefore, the O3 type and the P2 type have respective advantages, but the O3 type has higher sodium content than the P2 type, so that the initial capacity can be higher, sodium ions undergo a narrow tetrahedral center position during the migration of the O3 type structure, so that the diffusion energy barrier is larger, in contrast, the sodium ions in the P2 type structure undergo a relatively wide planar quadrilateral center position, the energy barrier is lower, so that the P2 type can show higher multiplying power performance, but the sodium deficiency structure of the P2 type positive electrode material and the irreversible phase change of P2-O2 under the high voltage state can lead to the rapid attenuation of the material capacity, so that the application of the sodium ion in the sodium ion battery is severely limited.
A common modification to these problems is doping and cladding. CN110336010a discloses a preparation method of a P2 layered anode material of an anion-cation co-doped nanoscale sodium ion battery with strong interaction; wherein the anions doped in the anion salt solution are Cl - 、Br - 、I - 、S 2- Or Se 2- The doped cation in the doped cation salt is Mg 2+ 、Zn 2+ 、Ag + 、Cu 2+ 、Ti 4+ 、Al 3+ 、Cr 4+ Or Fe (Fe) 3+ One or more of the following; according to the scheme, an anion doped nanoscale precursor is prepared through a wet method, and then cations are doped to obtain the cathode material of the anion co-doped nanoscale sodium ion battery. Although the sodium ion material prepared by the method combines the synergistic effect of anions and cations, the precursor prepared by the method has very strict conditions, the morphology of the precursor is not well controlled, the precursor is not easy to produce in large scale, and the prepared precursor is easy to have side reaction with electrolyte, so that the performance is fast attenuated.
CN111697210a discloses a P2 type sodium ion battery multi-element layered positive electrode material and a preparation method thereof, wherein the positive ion doped sodium ion positive electrode material is prepared by a sol-gel method, the positive ion positive electrode material prepared by the method is simple, but has low capacity, and meanwhile, side reaction of electrolyte is easy to occur, and the preparation cost is high, the process stability is poor, so that the positive ion positive electrode material is not beneficial to industrial production.
Therefore, in view of the above technical problems, there is an urgent need to develop a coated layered oxide cathode material having low preparation cost, high rate performance and stable structure.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a coated layered oxide positive electrode material, a preparation method and application thereof, wherein the coated layered oxide positive electrode material takes P2 type anion-cation co-doped layered oxide as a core, and a coating layer containing iron element is coated on the surface of the coated layered oxide positive electrode material, the preparation process is simple, the crystal structure is quite stable, and when the coated layered oxide positive electrode material is used as a positive electrode material of a sodium ion battery, the capacity, the cycle performance and the multiplying power performance of the sodium ion battery can be effectively improved.
To achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a coated layered oxide cathode material, which comprises a P2 type anion-cation co-doped layered oxide and a coating layer arranged on the surface of the P2 type anion-cation co-doped layered oxide;
the material of the coating layer contains iron element.
The coated layered oxide anode material provided by the invention takes P2 type anion-cation co-doped layered oxide as a core, and a coating layer containing iron element is arranged on the surface of the material; on one hand, the layered oxide is co-doped by adopting anions and cations, so that the phase change of a P2-O2 irreversible structure generated during circulation can be inhibited to a certain extent, the layered oxide has excellent circulation performance, and meanwhile, the electronic and ionic conductivity of the layered oxide is improved, and the multiplying power performance of the layered oxide is greatly improved; on the other hand, the surface of the P2 type anion-cation co-doped layered oxide is provided with the coating layer containing the iron source, so that cracking and falling of core particles can be further prevented, direct contact between the P2 type anion-cation co-doped layered oxide and electrolyte is effectively avoided, side reaction is reduced, the cycling stability of the material is further improved, and the boron element in the P2 type anion-cation co-doped layered oxide and the iron element of the coating layer can form a powerful chemical bond to enable the coating layer to be more stable, and the conductivity of the coating layer can be improved after the formed iron boride is diffused into the coating layer;
in conclusion, the special limitation of the core P2 type anion-cation co-doped layered oxide and the arrangement of the coating layer enable the finally obtained coated layered oxide positive electrode material to have higher structural stability, and when the coated layered oxide positive electrode material is used as a positive electrode material of a sodium ion battery, the cycle performance and the multiplying power performance of the sodium ion battery can be effectively improved.
Preferably, the chemical formula of the P2 type anion-cation co-doped layered oxide is Na 0.67-x Ca x Ni 0.33 Mn 0.67- y O 2-2x-3y (BO 3 ) y F 2x Wherein x is more than 0.005 and less than or equal to 0.2,0.005, and y is more than or equal to 0.2.
Where x may be 0.01, 0.03, 0.05, 0.07, 0.09, 0.11, 0.13, 0.15, 0.17, or 0.19, etc., and y may be 0.01, 0.03, 0.05, 0.07, 0.09, 0.11, 0.13, 0.15, 0.17, or 0.19, etc.
As a preferable technical scheme of the invention, the chemical formula of the P2 type anion-cation co-doped layered oxide provided by the invention is Na 0.67-x Ca x Ni 0.33 Mn 0.67-y O 2-2x-3y (BO 3 ) y F 2x Doped with B element, ca element, F element, mn element and Co element;
for the B element, on the one hand, the B element is more energetically favorable to enter into the oxygen layer at the tetrahedral interstitial sites and form BO in the P2 phase material 3 Is a planar triangular structure of the BO 3 The plane triangle structure can play a role of a wedge, can better support the whole structure in the Na ion deintercalation process, and increasesThe sliding energy of the transition metal layer is added, so that the sliding of the transition metal layer is restrained, the irreversible structural evolution of P2-O2 generated by P2-type anion-cation co-doped layered oxide during circulation is effectively restrained, and the structural stability of the material is further effectively improved; at the same time the BO 3 The formation of the configuration can also effectively regulate the ratio of Nae/Naf sites, thereby disturbing the ordered arrangement of Na/vacancies common in P2 phase materials, namely BO 3 The configuration can generate electrostatic repulsive force on surrounding Na while supporting the P2 structure, and the Na occupying Naf site is repelled to Nae to occupy, so that the electrochemical performance of the material is improved; in addition, the doping of the B element can also improve the hydration energy of the P2 type layered oxide and prevent the formation of a hydration phase; on the other hand, the melting point of the boron oxide is lower, the boron oxide can be uniformly diffused into the interior and the surface of the coated layered oxide anode material in the calcining process, the boron on the interior can improve the stability and the conductivity of the material, the boron on the surface of the material can further react with the iron element in the coating layer to form a chemical bond in the calcining process, so that the bonding strength of the coating layer is improved, the cycling stability of the sodium ion battery is further improved, the boron on the surface of the material can be diffused into the coating layer in the calcining process, reacts with the iron element of the coating layer to form iron boride, and the conductivity of the coating layer is improved;
for Ca element and F element, wherein Ca 2+ Similar to Na+ radius, F - With O 2- Has higher electronegativity than that of Ca, therefore 2+ F (F) - The co-doping of anions and cations of the layered oxide greatly improves the electrochemical performance of the layered oxide, and the non-active Ca 2+ Can reduce Na + The vacancy ordering inhibits the c-axis expansion in the charging process, thereby being beneficial to improving the electronic and ionic conductivity and leading the P2 type anion-cation co-doped layered oxide to have higher multiplying power performance; meanwhile, the strength of M-F bond is greater than that of M-O bond (M represents metal element), so that MO 2 The sliding of the layer becomes more difficult, and the irreversible structural evolution of the layered oxide from P2 to O2 is restrained, so that the cycle performance of the material is improved to a great extent;
for Mn element and Co element, the Co-doping of the Mn element and the Co element can obviously improve the structural stability of the P2 type anion-cation Co-doped layered oxide and provide capacity.
Preferably, x is more than or equal to 0.01 and less than or equal to 0.15, and if the value of x is lower than 0.15, the sodium content is too low, and the gram capacity of the P2 type anion-cation co-doped layered oxide is low.
Preferably, y is equal to or greater than 0.01 and equal to or less than 0.15.
Preferably, the chemical formula of the P2 type anion-cation co-doped layered oxide is Na 0.57 Ca 0.1 Ni 0.33 Mn 0.57 O 1.5 (BO 3 ) 0.1 F 0.2 Or Na (or) 0.52 Ca 0.15 Ni 0.33 Mn 0.52 O 1.25 (BO 3 ) 0.15 F 0.3 。
Preferably, the material of the coating layer comprises iron phosphate and/or iron oxide.
Preferably, the mass percentage of the iron element in the coated layered oxide cathode material is 0.5-1.5%, for example 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.1%, 1.2%, 1.3% or 1.4%, etc.
As a preferable technical scheme of the invention, the invention further limits the mass percentage of the iron element in the coated layered oxide positive electrode material to be 0.5-1.5%, if the mass percentage of the iron element is higher than 1.5%, the thickness of the coating layer is too high, thereby preventing the deintercalation of sodium ions, and the gram capacity of the positive electrode material is sacrificed, so that the multiplying power performance of the material is influenced; if the mass percentage of the iron element is less than 0.5%, the coating difficulty is increased, the coating uniformity is reduced, and further the side reaction between the layered oxide and the electrolyte cannot be effectively prevented.
In a second aspect, the present invention provides a method for preparing the coated layered oxide cathode material according to the first aspect, the method comprising the steps of:
(1) Mixing a sodium source, a nickel source, a manganese source, a boron source, a calcium source and a fluorine source in a solvent, and sintering to obtain a P2 type anion-cation co-doped layered oxide;
(2) Mixing the P2 type anion-cation co-doped layered oxide obtained in the step (1), an iron source and a displacer in a solvent, and performing heat treatment to obtain the coated layered oxide cathode material.
It should be noted that, in the step (1), the amounts of the nickel source, the manganese source, the boron source, the calcium source and the fluorine source are limited according to the stoichiometric ratio in the structural formula of the P2 type anion-cation co-doped layered oxide, and the molar amount of the sodium source is 5-9% more than the theoretical molar amount according to the stoichiometric ratio, so as to supplement the volatilization of sodium element in the sintering process;
similarly, the ratio of the amount of the iron source and the amount of the displacer added in the step (2) may be defined according to the chemical formula of the material of the coating layer to be prepared, and the total amount of the iron source and the displacer is determined according to the mass ratio of the iron element in the coated layered oxide cathode material.
Preferably, the mixing of step (1) is performed under ball milling conditions.
Preferably, the rotational speed of the ball mill is 100 to 600rpm, for example 150rpm, 200rpm, 300rpm, 400rpm, 500rpm, or the like.
Preferably, the mixing time of step (1) is 0.5 to 10 hours, such as 1, 2, 3, 4, 5, 6, 7, 8 or 9 hours, etc.
Preferably, the step (1) further comprises a step of drying before sintering.
Preferably, the drying is vacuum drying.
Preferably, the temperature of the vacuum drying is 80 to 200 ℃, for example, 100 ℃, 120 ℃, 140 ℃, 160 ℃, 180 ℃, or the like.
Preferably, the time of the vacuum drying is 5 to 20 hours, for example, 7 hours, 9 hours, 11 hours, 13 hours, 15 hours, 17 hours, 19 hours, or the like,
preferably, the sintering temperature in step (1) is 600 to 1300 ℃, for example 700 ℃, 800 ℃, 900 ℃, 1000 ℃, 1100 ℃, 1200 ℃, etc.
Preferably, the sintering time in step (1) is 8 to 20 hours, for example 10 hours, 12 hours, 14 hours, 16 hours or 18 hours, etc.
Preferably, the solvent of step (1) comprises ethanol.
Preferably, the sodium source of step (1) comprises any one or a combination of at least two of sodium chloride, sodium acetate, sodium carbonate, sodium hydroxide, sodium nitrate or sodium oxalate.
Preferably, the nickel source of step (1) comprises any one or a combination of at least two of nickel oxide, nickel sulfate, nickel nitrate, nickel hydroxide or nickel chloride.
Preferably, the manganese source of step (1) comprises any one or a combination of at least two of manganese oxide, manganese sulfate, manganese nitrate or manganese hydroxide.
Preferably, the boron source of step (1) comprises any one or a combination of at least two of boric acid, a borate or an oxide of boron.
Preferably, the calcium source and the fluorine source of step (1) each comprise calcium fluoride.
Preferably, the solvent of step (2) is a mixture of water and an organic solvent.
Preferably, the organic solvent comprises any one or a combination of at least two of ethanol, ethylene glycol or propanol.
Preferably, the iron source is a soluble iron salt.
Preferably, the soluble iron salt comprises any one or a combination of at least two of ferric nitrate, ferric sulfate or ferric chloride.
Preferably, the displacer includes a soluble phosphate or base.
Preferably, the soluble phosphate salt comprises any one or a combination of at least two of sodium phosphate, potassium phosphate or ammonium phosphate.
Preferably, the base comprises any one or a combination of at least two of sodium hydroxide, potassium hydroxide or ammonia.
Preferably, the mixing of step (2) is performed under ball milling conditions.
Preferably, the rotational speed of the ball mill is 100 to 600rpm, for example 150rpm, 200rpm, 300rpm, 400rpm, 500rpm, or the like.
Preferably, the mixing time of step (2) is 0.5 to 10 hours, such as 1, 2, 3, 4, 5, 6, 7, 8 or 9 hours, etc.
Preferably, the temperature of the heat treatment in step (2) is 300 to 900 ℃, for example 400 ℃, 500 ℃, 600 ℃, 700 ℃, 800 ℃, or the like.
Preferably, the time of the heat treatment in the step (2) is 2-10 h, 4h, 5h, 6h, 7h, 8h or 9h, etc.
As a preferable technical scheme of the invention, the preparation method comprises the following steps:
(1) Mixing a sodium source, a nickel source, a manganese source, a boron source, a calcium source, a fluorine source and a solvent for 0.5-10 h under the ball milling condition of 100-600 rpm, vacuum drying for 5-20 h at 80-200 ℃, and sintering for 8-20 h at 600-1300 ℃ to obtain the P2 type anion-cation co-doped layered oxide;
(2) Dissolving an iron source in an organic solvent to obtain an iron source solution; dissolving a displacer in water to obtain a displacer solution;
(3) Mixing the P2 type anion-cation co-doped layered oxide obtained in the step (1), the iron source solution obtained in the step (2) and the displacer solution for 0.5-10 h under the ball milling with the rotating speed of 100-600 rpm, and then carrying out heat treatment for 2-10 h at 300-900 ℃ after drying to obtain the coated layered oxide anode material.
In a third aspect, the present invention provides a sodium ion battery comprising a coated layered oxide cathode material as described in the first aspect.
Compared with the prior art, the invention has the following beneficial effects:
the coated layered oxide anode material provided by the invention comprises a P2 type anion-cation co-doped layered oxide and a coating layer arranged on the surface of the P2 type anion-cation co-doped layered oxide, wherein the material of the coating layer contains iron element; the P2 type layered oxide is co-doped by adopting anions and cations, so that the cycle performance and the multiplying power performance of the sodium ion battery are effectively improved, and meanwhile, the surface of the sodium ion battery is coated with the coating layer containing the iron element, so that the direct contact between the P2 type anion and cation co-doped layered oxide and electrolyte can be effectively avoided, the occurrence of side reaction is further reduced, the cycle stability of the sodium ion battery is further improved, and the finally obtained coated layered oxide positive electrode material is used as the positive electrode material of the sodium ion battery, so that the sodium ion battery has high discharge capacity, excellent cycle performance and multiplying power performance.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
Example 1
The coated layered oxide positive electrode material comprises a P2 type anion-cation co-doped layered oxide, wherein the surface of the P2 type anion-cation co-doped layered oxide is coated with ferric phosphate;
wherein the chemical formula of the P2 type anion-cation co-doped layered oxide is Na 0.57 Ca 0.1 Ni 0.33 Mn 0.57 O 1.5 (BO 3 ) 0.1 F 0.2 The mass percentage of iron element in the coated layered oxide cathode material is 0.5%;
the preparation method of the coated layered oxide cathode material provided by the embodiment comprises the following steps:
(1) Na is added according to the total molar ratio of each element in the chemical formula of the P2 type anion-cation co-doped layered oxide 2 CO 3 、Mn 2 O 3 、NiO、CaF 2 And B 2 O 3 Mixing (wherein Na 2 CO 3 The molar usage amount of the catalyst is 5 percent higher than the theoretical molar usage amount), ethanol is added, the mixture is subjected to wet ball milling for 5 hours in a planetary ball mill with the rotating speed of 300rpm, then the mixture is dried in vacuum for 12 hours at the temperature of 100 ℃, finally the mixture is added into a muffle furnace, sintered for 12 hours at the temperature of 1050 ℃ in air atmosphere, cooled and taken out, and the P2 type anion-cation co-doped layered oxide is obtained;
(2) Dissolving ferric chloride in ethanol to obtain ferric chloride solution with the mass concentration of 4%; dissolving sodium phosphate in water to obtain sodium phosphate solution with mass concentration of 2%;
(3) Mixing the P2 type anion-cation co-doped layered oxide obtained in the step (1), the ferric chloride solution obtained in the step (2) and the sodium phosphate solution (the ferric chloride solution and the sodium phosphate solution are added according to the total molar metering ratio of each element in the chemical formula of the material of the coating layer), performing wet ball milling for 5 hours in a planetary ball mill with the rotating speed of 300rpm, then performing vacuum drying for 12 hours at 100 ℃, and performing heat treatment for 8 hours at 800 ℃ to obtain the coated layered oxide cathode material.
Example 2
A coated layered oxide positive electrode material comprises a P2 type anion-cation co-doped layered oxide, wherein the surface of the P2 type anion-cation co-doped layered oxide is coated with ferric oxide;
wherein the chemical formula of the P2 type anion-cation co-doped layered oxide is Na 0.57 Ca 0.1 Ni 0.33 Mn 0.57 O 1.5 (BO 3 ) 0.1 F 0.2 The mass percentage of iron element in the coated layered oxide cathode material is 0.5%;
the preparation method of the coated layered oxide cathode material provided by the embodiment comprises the following steps:
(1) Na is added according to the total molar ratio of each element in the chemical formula of the P2 type anion-cation co-doped layered oxide 2 CO 3 、Mn 2 O 3 、NiO、CaF 2 And B 2 O 3 Mixing (wherein Na 2 CO 3 Adding ethanol, performing wet ball milling for 2 hours in a planetary ball mill with the rotation speed of 200rpm, then performing vacuum drying for 10 hours at 150 ℃, finally adding the mixture into a muffle furnace, sintering for 20 hours at 600 ℃ in an air atmosphere, cooling, and taking out to obtain the P2 type anion-cation co-doped layered oxide;
(2) Dissolving ferric nitrate into ethanol to obtain a ferric nitrate solution with the mass concentration of 4.0%; dissolving sodium hydroxide in water to obtain sodium hydroxide solution with the mass concentration of 3.0%;
(3) Mixing the P2 type anion-cation co-doped layered oxide obtained in the step (1), the ferric nitrate solution obtained in the step (2) and the sodium hydroxide solution (ferric chloride solution and sodium phosphate solution are added according to the total molar metering ratio of each element in the chemical formula of the material of the coating layer), performing wet ball milling for 2 hours in a planetary ball mill with the rotating speed of 600rpm, then performing vacuum drying for 12 hours at 100 ℃, and performing heat treatment for 10 hours at 300 ℃ to obtain the coated layered oxide anode material.
Example 3
A coated layered oxide positive electrode material comprises a P2 type anion-cation co-doped layered oxide, wherein the surface of the P2 type anion-cation co-doped layered oxide is coated with ferric phosphate;
wherein the chemical formula of the P2 type anion-cation co-doped layered oxide is Na 0.52 Ca 0.15 Ni 0.33 Mn 0.52 O 1.25 (BO 3 ) 0.15 F 0.3 The mass percentage of iron element in the coated layered oxide cathode material is 0.5%;
the preparation method of the coated layered oxide cathode material provided by the embodiment comprises the following steps:
(1) Na is added according to the total molar ratio of each element in the chemical formula of the P2 type anion-cation co-doped layered oxide 2 CO 3 、Mn 2 O 3 、NiO、CaF 2 And B 2 O 3 Mixing (wherein Na 2 CO 3 Adding ethanol, performing wet ball milling for 10 hours in a planetary ball mill with the rotating speed of 100rpm, then performing vacuum drying for 10 hours at 120 ℃, finally adding the mixture into a muffle furnace, sintering for 8 hours at 1300 ℃ in an air atmosphere, cooling, and taking out to obtain the P2 type anion-cation co-doped layered oxide;
(2) Dissolving ferric chloride in ethanol to obtain ferric chloride solution with the mass concentration of 4.0%; dissolving sodium phosphate in water to obtain sodium phosphate solution with the mass concentration of 2.0%;
(3) Mixing the P2 type anion-cation co-doped layered oxide obtained in the step (1), the ferric chloride solution obtained in the step (2) and the sodium phosphate solution (the ferric chloride solution and the sodium phosphate solution are added according to the total molar metering ratio of each element in the chemical formula of the material of the coating layer), performing wet ball milling for 10 hours in a planetary ball mill with the rotating speed of 100rpm, then performing vacuum drying for 10 hours at 200 ℃, and performing heat treatment for 5 hours at 900 ℃ to obtain the coated layered oxide cathode material.
Example 4
The coated layered oxide cathode material differs from example 1 only in that the mass percentage of iron element in the coated layered oxide cathode material is 1%, and other structures, substances and preparation methods are the same as example 1.
Example 5
The coated layered oxide cathode material differs from example 1 only in that the mass percentage of iron element in the coated layered oxide cathode material is 1.5%, and other structures, substances and preparation methods are the same as example 1.
Example 6
The coated layered oxide cathode material differs from example 1 only in that the mass percentage of iron element in the coated layered oxide cathode material is 0.2%, and other structures, substances and preparation methods are the same as example 1.
Example 7
The coated layered oxide cathode material differs from example 1 only in that the mass percentage of iron element in the coated layered oxide cathode material is 2%, and other structures, substances and preparation methods are the same as example 1.
Example 8
A coated layered oxide cathode material is different from example 1 in that the P2 type anion and cation co-doped layered oxide has a chemical formula of Na 0.67 Ni 0.33 Mn 0.57 O 1.7 (BO 3 ) 0.1 And CaF is not added in the step (1) of the preparation method 2 Other structures, materials and steps were the same as in example 1.
Example 9
A coated layered oxide cathode material is different from example 1 in that the P2 type anion and cation co-doped layered oxide has a chemical formula of Na 0.57 Ca 0.1 Ni 0.33 Mn 0.67 O 1.8 F 0.2 And B is not added in the step (1) of the preparation method 2 O 3 Other structures, materials and steps were the same as in example 1.
Comparative example 1
A coated layered oxide cathode material is different from example 1 in that a layered oxide (the chemical formula is Na 0.67 Ni 0.33 Mn 0.67 O 2 ) Replace P2 type anion-cation co-doped layered oxide, and CaF is not added in the step (1) of the preparation method 2 And B 2 O 3 Other structures, materials and steps were the same as in example 1.
Comparative example 2
A P2 type anion-cation co-doped layered oxide positive electrode material has a chemical formula of Na 0.52 Ca 0.15 Ni 0.33 Mn 0.52 O 1.25 (BO 3 ) 0.15 F 0.3 ；
The preparation method of the P2 type anion-cation co-doped layered oxide positive electrode material provided by the comparative example comprises the following steps: na is added according to the total molar metering ratio of each element in the chemical formula of the P2 type anion-cation co-doped layered oxide anode material 2 CO 3 、Mn 2 O 3 、NiO、CaF 2 And B 2 O 3 Mixing (wherein Na 2 CO 3 The molar usage amount of the catalyst is 5% higher than the theoretical molar usage amount), ethanol is added, wet ball milling is carried out for 10 hours in a planetary ball mill with the rotating speed of 100rpm, then vacuum drying is carried out for 10 hours at the temperature of 120 ℃, finally a muffle furnace is added, sintering is carried out for 8 hours at the temperature of 1300 ℃ in air atmosphere, cooling is carried out, and the P2 type anion-cation co-doped layered oxide anode material is obtained.
Application example 1
A sodium ion battery comprising a positive electrode, a negative electrode, a separator and an electrolyte;
wherein the materials of the positive electrode comprise 90%, 5%, 2.5% and 2.5% of coated layered oxide positive electrode materials (example 1), PVDF, multi-wall carbon tubes and SP;
the material of the negative electrode comprises hard carbon, SBR, CMC and SP with the mass percentage of 95.5%, 1.4%, 1.1% and 2% respectively;
the electrolyte comprises EC, DMC and EMC with the mass ratio of 5:2:3, and then NaPF is added 6 So that NaPF is 6 The concentration of (2) is 0.5mol/L;
the preparation process of the sodium ion battery provided by the application example comprises the following steps:
(1) Mixing a material of the positive electrode with NMP to obtain positive electrode slurry with the solid content of 55%, and performing coating, rolling and die cutting to obtain a positive electrode plate;
mixing the material of the negative electrode with water to obtain negative electrode slurry with the solid content of 48%, and performing coating, rolling and die cutting to obtain a negative electrode plate;
(2) And (3) assembling the positive electrode plate, the negative electrode plate and the diaphragm obtained in the step (1), injecting electrolyte, and carrying out capacity division and formation to obtain the sodium ion battery.
Application examples 2 to 9
A sodium ion battery was different from application example 1 only in that the coated layered oxide cathode materials obtained in examples 2 to 9 were used in place of the coated layered oxide cathode material obtained in example 1, respectively, and other substances, amounts and preparation methods were the same as those of application example 1.
Comparative application example 1
A sodium ion battery differing from application example 1 only in that the coated layered oxide cathode material obtained in comparative example 1 was used instead of the coated layered oxide cathode material obtained in example 1, and other substances, amounts and preparation methods were the same as those of application example 1.
Comparative application example 2
A sodium ion battery is different from application example 1 only in that the P2 type anion-cation co-doped layered oxide positive electrode material obtained in comparative example 2 is used for replacing the coated layered oxide positive electrode material obtained in example 1, and other substances, the use amount and the preparation method are the same as application example 1.
Performance test:
(1) Gram capacity for first discharge: testing under the current of 0.2 ℃ and the normal temperature of 25 ℃ and the voltage range of 2.0-4.5V;
(2) Cycle performance: capacity retention after 200 weeks of 0.2C cycle was tested at 25 ℃;
(3) Rate capability: at 25 ℃, after 1C charging, discharging is carried out by adopting different multiplying powers (1C/3C/5C).
The sodium ion batteries provided in application examples 1 to 9 and comparative application examples 1 to 2 were tested according to the above test methods, and the test results are shown in table 1:
TABLE 1
From the data in table 1, it can be seen that:
(1) The first discharge gram capacity of the sodium ion battery provided by application examples 1-5 is 145.2-147.9 mAh/g, the capacity retention rate of 200 weeks of circulation is as high as 89.9-92.1%, and the rate performance test shows that the 3C capacity retention rate is 97.5-99.3%, and the 5C capacity retention rate is 91.5-94.2%;
(2) Comparing the data of application example 1 and comparative application example 1, it can be found that, by adopting the layered oxide without doping anions and cations as the positive electrode material, not only the gram capacity of the sodium ion battery for the first time is greatly reduced, but also the multiplying power and the cycle performance of the sodium ion battery are simultaneously reduced;
(3) As can be seen from comparing the data of application example 1 and comparative application example 2, the use of the P2-type anion-cation co-doped layered oxide without the coating layer as the positive electrode material also results in the decrease of the first discharge gram capacity, the cycle performance and the rate capability of the sodium ion battery;
(4) Further, according to the data of application example 1 and application examples 6 to 7, it was found that too much or too little iron content in the material of the coating layer also causes a decrease in the cycle and rate performance of the finally obtained sodium ion battery;
(5) Finally, it can be seen from the data of application example 1 and application examples 8 to 9 that the kind of doping element in the layered oxide also has an influence on the cycle and the rate performance of the final sodium ion battery.
The applicant states that the present invention is described by way of the above examples as a coated layered oxide positive electrode material, and a method of preparing and using the same, but the present invention is not limited to the above examples, i.e., it is not meant that the present invention must be practiced in dependence upon the above examples. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of raw materials for the product of the present invention, addition of auxiliary components, selection of specific modes, etc., falls within the scope of the present invention and the scope of disclosure.
Claims (10)
1. The coated layered oxide positive electrode material is characterized by comprising a P2 type anion-cation co-doped layered oxide and a coating layer arranged on the surface of the P2 type anion-cation co-doped layered oxide;
the material of the coating layer contains iron element.
2. The coated layered oxide cathode material according to claim 1, wherein the P2-type anionic and cationic co-doped layered oxide has a chemical formula Na 0.67-x Ca x Ni 0.33 Mn 0.67-y O 2-2x-3y (BO 3 ) y F 2x The method comprises the steps of carrying out a first treatment on the surface of the Wherein x is more than 0.005 and less than or equal to 0.2,0.005, and y is more than or equal to 0.2;
preferably, x is equal to or more than 0.01 and equal to or less than 0.15;
preferably, y is equal to or greater than 0.01 and equal to or less than 0.15;
preferably, the chemical formula of the P2 type anion-cation co-doped layered oxide is Na 0.57 Ca 0.1 Ni 0.33 Mn 0.57 O 1.5 (BO 3 ) 0.1 F 0.2 Or Na (or) 0.52 Ca 0.15 Ni 0.33 Mn 0.52 O 1.25 (BO 3 ) 0.15 F 0.3 。
3. The coated layered oxide cathode material according to claim 1 or 2, wherein the material of the coating layer comprises iron phosphate and/or iron oxide;
preferably, the mass percentage of the iron element in the coated layered oxide cathode material is 0.5-1.5%.
4. A method for preparing the coated layered oxide cathode material according to any one of claims 1 to 3, comprising the steps of:
(1) Mixing a sodium source, a nickel source, a manganese source, a boron source, a calcium source and a fluorine source in a solvent, and sintering to obtain a P2 type anion-cation co-doped layered oxide;
(2) Mixing the P2 type anion-cation co-doped layered oxide obtained in the step (1), an iron source and a displacer in a solvent, and performing heat treatment to obtain the coated layered oxide cathode material.
5. The method of claim 4, wherein the mixing in step (1) is performed under ball milling conditions;
preferably, the rotation speed of the ball milling is 100-600 rpm;
preferably, the mixing time in the step (1) is 0.5-10 h;
preferably, the step (1) further comprises a step of drying before sintering;
preferably, the drying is vacuum drying;
preferably, the temperature of the vacuum drying is 80-200 ℃;
preferably, the time of the vacuum drying is 5-20 hours.
6. The method of claim 4 or 5, wherein the sintering temperature in step (1) is 600-1300 ℃;
preferably, the sintering time in the step (1) is 8-20 h.
7. The process according to any one of claims 4 to 6, wherein the solvent of step (1) comprises ethanol;
preferably, the sodium source of step (1) comprises any one or a combination of at least two of sodium chloride, sodium acetate, sodium carbonate, sodium hydroxide, sodium nitrate or sodium oxalate;
preferably, the nickel source of step (1) comprises any one or a combination of at least two of nickel oxide, nickel sulfate, nickel nitrate, nickel hydroxide or nickel chloride;
preferably, the manganese source of step (1) comprises any one or a combination of at least two of manganese oxide, manganese sulfate, manganese nitrate or manganese hydroxide;
preferably, the boron source of step (1) comprises any one or a combination of at least two of boric acid, a borate or an oxide of boron;
preferably, the calcium source and the fluorine source of step (1) each comprise calcium fluoride.
8. The method according to any one of claims 4 to 7, wherein the solvent in step (2) is a mixture of water and an organic solvent;
preferably, the organic solvent comprises any one or a combination of at least two of ethanol, ethylene glycol or propanol;
preferably, the iron source is a soluble iron salt;
preferably, the soluble iron salt comprises any one or a combination of at least two of ferric nitrate, ferric sulfate or ferric chloride;
preferably, the displacer includes a soluble phosphate or base;
preferably, the soluble phosphate comprises any one or a combination of at least two of sodium phosphate, potassium phosphate or ammonium phosphate;
preferably, the base comprises any one or a combination of at least two of sodium hydroxide, potassium hydroxide or ammonia.
9. The method according to any one of claims 4 to 8, wherein the mixing in step (2) is performed under ball milling conditions;
preferably, the rotation speed of the ball milling is 100-600 rpm;
preferably, the mixing time in the step (2) is 0.5-10 h;
preferably, the temperature of the heat treatment in the step (2) is 300-900 ℃;
preferably, the time of the heat treatment in the step (2) is 2-10 h.
10. A sodium ion battery comprising the coated layered oxide cathode material of any one of claims 1 to 3.
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