CN114976019B - Sodium ion positive electrode material, preparation method thereof and battery - Google Patents
Sodium ion positive electrode material, preparation method thereof and battery Download PDFInfo
- Publication number
- CN114976019B CN114976019B CN202210832813.1A CN202210832813A CN114976019B CN 114976019 B CN114976019 B CN 114976019B CN 202210832813 A CN202210832813 A CN 202210832813A CN 114976019 B CN114976019 B CN 114976019B
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- Prior art keywords
- containing compound
- sodium
- positive electrode
- manganese
- copper
- Prior art date
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- 239000007774 positive electrode material Substances 0.000 title claims abstract description 75
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title abstract description 19
- 239000000463 material Substances 0.000 claims abstract description 95
- 239000011734 sodium Substances 0.000 claims abstract description 61
- 239000002585 base Substances 0.000 claims abstract description 35
- 239000011247 coating layer Substances 0.000 claims abstract description 31
- 229910052742 iron Inorganic materials 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910014248 MzO2 Inorganic materials 0.000 claims abstract description 10
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 10
- 239000003513 alkali Substances 0.000 claims abstract description 7
- 150000001875 compounds Chemical class 0.000 claims description 84
- 239000010949 copper Substances 0.000 claims description 58
- 239000011572 manganese Substances 0.000 claims description 50
- 238000002156 mixing Methods 0.000 claims description 44
- 238000005245 sintering Methods 0.000 claims description 42
- 239000011248 coating agent Substances 0.000 claims description 38
- 238000000576 coating method Methods 0.000 claims description 38
- 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 27
- 238000000034 method Methods 0.000 claims description 27
- 229910052708 sodium Inorganic materials 0.000 claims description 27
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 24
- 229910052802 copper Inorganic materials 0.000 claims description 24
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 22
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 22
- 238000007580 dry-mixing Methods 0.000 claims description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 229910052748 manganese Inorganic materials 0.000 claims description 21
- 230000008569 process Effects 0.000 claims description 21
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 20
- 239000012452 mother liquor Substances 0.000 claims description 19
- 239000000758 substrate Substances 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 17
- 238000010025 steaming Methods 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 238000000975 co-precipitation Methods 0.000 claims description 13
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 11
- 239000005751 Copper oxide Substances 0.000 claims description 11
- 229910000431 copper oxide Inorganic materials 0.000 claims description 11
- 150000003839 salts Chemical class 0.000 claims description 11
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 11
- YQCJRBZJRYWSPK-UHFFFAOYSA-J copper;manganese(2+);tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Mn+2].[Cu+2] YQCJRBZJRYWSPK-UHFFFAOYSA-J 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 9
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 9
- 229940099596 manganese sulfate Drugs 0.000 claims description 9
- 239000011702 manganese sulphate Substances 0.000 claims description 9
- 235000007079 manganese sulphate Nutrition 0.000 claims description 9
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 9
- BNBLBRISEAQIHU-UHFFFAOYSA-N disodium dioxido(dioxo)manganese Chemical compound [Na+].[Na+].[O-][Mn]([O-])(=O)=O BNBLBRISEAQIHU-UHFFFAOYSA-N 0.000 claims description 8
- VASIZKWUTCETSD-UHFFFAOYSA-N oxomanganese Chemical compound [Mn]=O VASIZKWUTCETSD-UHFFFAOYSA-N 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- 239000002243 precursor Substances 0.000 claims description 8
- ZNYJCXSTUQBQIC-UHFFFAOYSA-J copper manganese(2+) dicarbonate Chemical compound C([O-])([O-])=O.[Mn+2].C([O-])([O-])=O.[Cu+2] ZNYJCXSTUQBQIC-UHFFFAOYSA-J 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 6
- 239000010413 mother solution Substances 0.000 claims description 6
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 5
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 5
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 5
- 229940071125 manganese acetate Drugs 0.000 claims description 5
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 5
- GEYXPJBPASPPLI-UHFFFAOYSA-N manganese(III) oxide Inorganic materials O=[Mn]O[Mn]=O GEYXPJBPASPPLI-UHFFFAOYSA-N 0.000 claims description 5
- 239000001632 sodium acetate Substances 0.000 claims description 5
- 235000017281 sodium acetate Nutrition 0.000 claims description 5
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 5
- 235000011152 sodium sulphate Nutrition 0.000 claims description 5
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims description 4
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 claims description 4
- 229940112669 cuprous oxide Drugs 0.000 claims description 4
- 239000001509 sodium citrate Substances 0.000 claims description 4
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- TYTHZVVGVFAQHF-UHFFFAOYSA-N manganese(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Mn+3].[Mn+3] TYTHZVVGVFAQHF-UHFFFAOYSA-N 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- PPNAOCWZXJOHFK-UHFFFAOYSA-N manganese(2+);oxygen(2-) Chemical compound [O-2].[Mn+2] PPNAOCWZXJOHFK-UHFFFAOYSA-N 0.000 claims description 2
- 239000002994 raw material Substances 0.000 description 35
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 16
- 238000001816 cooling Methods 0.000 description 12
- 239000000126 substance Substances 0.000 description 8
- 238000000498 ball milling Methods 0.000 description 7
- 238000004321 preservation Methods 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 239000012856 weighed raw material Substances 0.000 description 6
- 239000010405 anode material Substances 0.000 description 5
- 239000010406 cathode material Substances 0.000 description 5
- 238000001878 scanning electron micrograph Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 239000004814 polyurethane Substances 0.000 description 3
- 229920002635 polyurethane Polymers 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- JJAQWVYNFRYENB-UHFFFAOYSA-N [Mn].[Cu].[Na] Chemical compound [Mn].[Cu].[Na] JJAQWVYNFRYENB-UHFFFAOYSA-N 0.000 description 2
- 239000012670 alkaline solution Substances 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 2
- 239000000347 magnesium hydroxide Substances 0.000 description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 2
- LQKOJSSIKZIEJC-UHFFFAOYSA-N manganese(2+) oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Mn+2].[Mn+2].[Mn+2].[Mn+2] LQKOJSSIKZIEJC-UHFFFAOYSA-N 0.000 description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000003801 milling Methods 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- -1 polypropylene Polymers 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- 239000013077 target material Substances 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004115 Sodium Silicate Substances 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
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 150000005323 carbonate salts Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical compound [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
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 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
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 229920000447 polyanionic polymer Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000013225 prussian blue Substances 0.000 description 1
- 229960003351 prussian blue Drugs 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 229910000018 strontium carbonate Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 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
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Composite Materials (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention relates to the technical field of sodium ion secondary batteries, in particular to a sodium ion positive electrode material, a preparation method thereof and a battery. The sodium ion positive electrode material provided by the invention takes Na 1+aCuxMnyMzO2 (beta phase) with a zig-zag layered structure as a base material, takes Na 2/3+bCu1/3+mMn2/3+nAcO2 of a P2 phase as a coating layer, and M and A respectively comprise at least one of Fe, co, ni, mg, al, ti, cr, li, ca, zn, sr, Y, zr, la, F, si, P and B. The positive electrode material has higher charge-discharge gram specific capacity, higher structural stability, air stability and water stability, lower residual alkali, lower pH value and excellent cycle stability and rate capability.
Description
Technical Field
The invention relates to the technical field of batteries, in particular to a sodium ion positive electrode material, a preparation method thereof and a battery.
Background
In recent years, as the shortage of lithium ion battery cathode material resources increases and the price of raw materials continues to rise, the market price of lithium ion batteries increases. In contrast, the main materials of the positive electrode material of the sodium ion battery are relatively rich in sodium, copper, iron and manganese, the cost is low, the cost of the sodium ion battery is effectively reduced by the low-cost positive electrode material, and particularly the sodium ion battery with low cost and high safety performance is attractive compared with the lithium ion with high price in the energy storage field with more strict cost requirements.
The sodium ion positive electrode materials which are widely studied at present mainly comprise oxide positive electrode materials, polyanion positive electrode materials and Prussian blue positive electrode materials. Among the oxide positive electrode materials, the most promising application prospect is mainly O3 type layered oxide and P2 type layered oxide, and O3 type layered oxide and P2 type layered oxide often have higher specific capacity, P2 often has more stable physicochemical properties, such as better cycle and rate performance, but P2 material often has lower specific capacity.
NaMnO 2 with a special zig-zag corrugated lamellar structure is similar to an O3 lamellar structure, has higher specific capacity, but has poorer stability, and the zig-zag sodium-copper-manganese anode material prepared by doping a small amount of copper on the basis of the material can stabilize the structure of the material to a certain extent, and nevertheless, the circulation, multiplying power, stability and the like of the material still have larger room for improvement. In view of this, the present invention has been made.
Disclosure of Invention
The invention aims to provide a sodium ion positive electrode material to solve the technical problems that a multi-element positive electrode material in the prior art cannot fundamentally solve the problems of poor circulation and multiplying power performance, high pH value, poor air stability and poor slurry stability of an O3 material.
The invention also aims to provide a preparation method of the sodium ion positive electrode material, which is simple and feasible and can be produced in a large scale.
Another object of the present invention is to provide a battery comprising the above-mentioned sodium ion 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:
a sodium ion positive electrode material comprises a base material and a coating layer coated on at least part of the surface of the base material;
The substrate comprises Na 1+aCuxMnyMzO2 with a zig-zag layered structure, wherein M is a first doping element, a is more than or equal to 0.05 and less than or equal to 0.05,0.05, x is more than or equal to 0.15,0.85 and less than or equal to y is more than or equal to 0.95, z is more than or equal to 0 and x+y+z=1;
The coating layer comprises Na 2/3+bCu1/3+mMn2/3+nAcO2 with a P2 phase, wherein A is a second doping element, b is more than or equal to-0.06 and less than or equal to-0.06, m is more than or equal to-0.03 and less than or equal to-0.03, n is more than or equal to-0.03, c is more than or equal to 0 and m+n+c=0;
The first doping element and the second doping element include at least one of Fe, co, ni, mg, al, ti, cr, li, ca, zn, sr, Y, zr, la, F, si, P and B, respectively.
In some embodiments, the coating layer comprises 0.5% to 30% by mass of the total mass of the substrate and the coating layer.
In some embodiments, the coating layer comprises 0.5% to 20% by mass of the total mass of the substrate and the coating layer.
In some embodiments, the first doping element and the second doping element are different elements.
In some embodiments, the first doping element is selected from at least one of Ti, mg, al, ca and Cr and the second doping element is selected from at least one of Fe, co, ni, sr, si and B.
In some embodiments, the first doping element is selected from at least one of Li, Y, la, and Zn, and the second doping element is selected from at least one of F, P, si and B.
In some embodiments, the shape of the sodium ion positive electrode material includes at least one of rod-like, sheet-like, and particulate.
The preparation method of the sodium ion positive electrode material comprises the following steps:
(a) Carrying out first treatment or direct dry mixing on a first copper-containing compound, a first sodium-containing compound, a first manganese-containing compound and an M-containing compound to obtain a first material, wherein the first treatment comprises coprecipitation and dry mixing; performing first sintering treatment on the first material to obtain a base material;
(b) Dry mixing or wet mixing the substrate in step (a) with a second copper-containing compound, a second sodium-containing compound, a second manganese-containing compound and an a-containing compound to obtain a second material; and performing second sintering treatment on the second material.
In some embodiments, the first and second copper-containing compounds each include at least one of copper oxide, copper acetate, copper sulfate, copper manganese carbonate, and copper manganese hydroxide.
In some embodiments, the first sodium-containing compound and the second sodium-containing compound each comprise at least one of sodium hydroxide, sodium carbonate, sodium sulfate, sodium acetate, sodium citrate, and sodium manganate.
In some embodiments, the first and second manganese-containing compounds each include at least one of manganese monoxide, manganese dioxide, manganese sesquioxide, manganese tetraoxide, manganese acetate, manganese sulfate and sodium manganate, copper manganese carbonate, and copper manganese hydroxide.
In some embodiments, the M-containing compound comprises at least one of an M-containing oxide, an M-containing hydroxide, and an M-containing soluble salt; the M includes at least one of Fe, co, ni, mg, al, ti, cr, li, ca, zn, sr, Y, zr, la, F, si, P and B.
In some embodiments, the a-containing compound comprises at least one of an a-containing oxide, an a-containing hydroxide, and an a-containing soluble salt; the A includes at least one of Fe, co, ni, mg, al, ti, cr, li, ca, zn, sr, Y, zr, la, F, si, P and B.
In some embodiments, the first process specifically includes: mixing a soluble first copper-containing compound, a soluble first manganese-containing compound and a soluble M-containing compound with an acid solution to obtain a mother solution, wherein the pH value of the mother solution is less than or equal to 4; adding alkali liquor into the mother liquor for reaction, and drying to obtain a precursor material; dry mixing the precursor material with a first sodium-containing compound to obtain a first material; in the coprecipitation process, the temperature of the reaction system is controlled to be 20-80 ℃, and the pH value of the reaction system is more than 4 and less than 12.
In some embodiments, the wet mixing specifically includes: mixing a mixture of a soluble second copper-containing compound, a soluble second sodium-containing compound, a soluble second manganese-containing compound and a soluble A-containing compound with water or an alcohol solvent to obtain a coating solution; and coating the substrate by using the coating solution in a rotary steaming mode.
In some embodiments, in step (a), the mixing speed of the direct dry mixing and the dry mixing is 500 to 5000r/min, respectively, and the mixing time is 3 to 20min, respectively.
In some embodiments, in step (b), the dry mixing is performed at a mixing speed of 500 to 5000r/min for a mixing time of 3 to 20min.
In some embodiments, the temperature of the first sintering process is 850 to 1000 ℃ and the time of the first sintering process is 8 to 20 hours.
In some embodiments, the temperature of the second sintering process is 800 to 950 ℃ and the time of the second sintering process is 8 to 20 hours.
A battery comprising the sodium ion positive electrode material.
In some embodiments, the D50 particle size of the sodium ion positive electrode material is 3 to 40 μm.
In some embodiments, the pH of the sodium ion positive electrode material is 10.0 to 13.0.
Compared with the prior art, the invention has the beneficial effects that:
(1) According to the sodium ion positive electrode material, the base material Na 1+aCuxMnyMzO2 has higher gram specific capacity, and the coating layer Na 2/3+bCu1/3+mMn2/3+nMcO2 has good structural stability, air stability, water stability, lower residual alkali and lower pH value; the positive electrode material obtained by combining the base material and the coating layer has higher gram specific capacity and excellent cycle stability and rate capability.
(2) The raw material cost is low, and the production cost is low; the used metal resources are rich; the positive electrode material has lower pH value, and does not need additional pH lowering processes such as water washing, acid washing and the like, so that the positive electrode material has better slurry processing performance.
(3) The coating layer and the base material comprise the same main element sodium copper manganese, and the coating layer and the base material have better compatibility, so the preparation method of the positive electrode material is simple and easy to realize, the large-scale production is easy to realize, and the consistency and the stability of the product are good.
(4) The battery provided by the invention adopts the sodium ion positive electrode material, and has excellent electrochemical performance.
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 an X-ray diffraction (XRD) pattern of a sodium ion positive electrode material in example 1 of the present invention;
FIG. 2 is a Scanning Electron Microscope (SEM) image of a sodium ion positive electrode material according to example 2 of the present invention;
FIG. 3 is a graph showing the charge and discharge of the sodium ion positive electrode material in example 3 of the present invention;
FIG. 4 is an XRD pattern of a sodium ion positive electrode material in example 4 of the present invention;
FIG. 5 is an SEM image of a sodium ion positive electrode material according to example 5 of the present invention;
FIG. 6 is a graph showing the charge and discharge of the sodium ion positive electrode material of example 6 of the present invention;
FIG. 7 is an SEM image of a sodium ion positive electrode material of example 7 of the present invention;
Fig. 8 is an XRD pattern of the sodium ion positive electrode material in example 8 of the present invention.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present 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.
According to one aspect of the invention, the invention relates to a sodium ion positive electrode material, which comprises a substrate and a coating layer coated on at least part of the surface of the substrate;
The substrate comprises Na 1+aCuxMnyMzO2 with a zig-zag layered structure, wherein M is a first doping element, a is more than or equal to 0.05 and less than or equal to 0.05,0.05, x is more than or equal to 0.15,0.85 and less than or equal to y is more than or equal to 0.95, z is more than or equal to 0 and x+y+z=1;
The coating layer comprises Na 2/3+bCu1/3+mMn2/3+nAcO2 with a P2 phase, wherein A is a second doping element, b is more than or equal to-0.06 and less than or equal to-0.06, m is more than or equal to-0.03 and less than or equal to-0.03, n is more than or equal to-0.03, c is more than or equal to 0 and m+n+c=0;
The first doping element and the second doping element include at least one of Fe, co, ni, mg, al, ti, cr, li, ca, zn, sr, Y, zr, la, F, si, P and B, respectively.
In the invention, the Na 1+aCuxMnyMzO2 material has similar high sodium proportion with the O3 type layered oxide, has higher charge and discharge capacity, but also has the inherent defects of most O3 materials, such as relatively poorer multiplying power, cycle performance, higher pH, poorer air stability, water stability and the like, because the Mn 3+ element has stronger ginger-Taylor effect, the performance of the material alone cannot meet the actual use requirement. The Na 2/3+bCu1/3+ mMn2/3+nAcO2 with the P2 phase is adopted as the coating layer of the Na 1+aCuxMnyMzO2 material, so that the defects of the material can be improved, and the material has better compatibility with the Na 1+ aCuxMnyMzO2 material, so that a more stable coating layer can be formed.
The coating material and the base material are the same in that the two have the same main element, the difference is the proportion of sodium element, copper element and manganese element, and meanwhile, the first doping element and the second doping element are mutually independent and are not influenced. In the positive electrode material, the transition metal of the base material and the coating layer is mainly copper and manganese, and the mol content of the transition metal meets Cu+Mn which is more than or equal to 90 percent. The base material has low Cu content, and Mn element has two valence states of +3 and +4; the coating layer has higher Cu content, and Mn element is mainly +4 valence.
In some embodiments, the X-ray diffraction (XRD) pattern of the positive electrode material shows that the structure space group of the surface layer of the coated material is P6 3/mmc, and belongs to the 6-square crystal system, as shown in fig. 1, fig. 4 and fig. 8, there is a strong characteristic peak at the position of 16 °±0.5°, which indicates that the positive electrode material is Na 2/3+bCumMnnMcO2 with the surface layer being P2 phase.
The positive electrode material has good air stability, low residual alkali on the surface of the material, pH value of 10.0-13.0, and no obvious change in pH value after long-time exposure to air environment. And the anode material has good water stability, and still keeps low moisture content and good electrochemical performance after being exposed in a humid environment for 24 hours.
In some embodiments, the value of a includes, but is not limited to, -0.05, -0.04, -0.03, -0.01, 0, 0.1, 0.2, 0.3, 0.4, or 0.5. In some embodiments, the value of x includes, but is not limited to, 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, 0.11, 0.12, 0.13, 0.14, or 0.15. In some embodiments, y has a value of, but is not limited to, 0.85, 0.86, 0.87, 0.88, 0.89, 0.9, 0.91, 0.92, 0.93, 0.94, or 0.95. In some embodiments, z has a value of, but is not limited to, 0, 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, or 0.1.
In some embodiments, the range of values for b includes, but is not limited to, -0.06, -0.05, -0.04, -0.03, -0.02, -0.01, 0, 0.01, 0.02, 0.03, 0.04, 0.05, or 0.06. In some embodiments, the range of values for m includes, but is not limited to, -0.03, -0.02, -0.01, 0, 0.01, 0.02, or 0.03. In some embodiments, n ranges from, but is not limited to, -0.03, -0.02, -0.01, 0, 0.01, 0.02, or 0.03. In some embodiments, the value of c includes, but is not limited to, 0, 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, or 0.09.
In one embodiment, the coating layer comprises 0.5 to 30% by mass of the total mass of the substrate and the coating layer. In one embodiment, the mass of the coating layer is 0.8%, 1%, 1.5%, 2%, 3%, 5%, 6%, 8%, 10%, 12%, 15%, 18%, 20%, 22%, 25%, 27%, 29% or 30% of the total mass of the substrate and the coating layer, and other values within the above range may be selected, without specific limitation. The invention can better improve the defects of Na 1+aCuxMnyMzO2 materials and ensure the stability of the coating layer by setting the proper mass content of the coating layer.
In one embodiment, the coating layer comprises 2% to 20% by mass of the total mass of the substrate and the coating layer. The battery prepared from the positive electrode material obtained in the range has more excellent cycle performance.
In one embodiment, the first doping element and the second doping element are the same element.
In one embodiment, the first doping element and the second doping element are different elements.
In one embodiment, the first doping element is selected from at least one of Ti, mg, al, ca and Cr, and the second doping element is selected from at least one of Fe, co, ni, sr, si and B. In some embodiments, the first doping element is Ti and the second doping element is selected from Fe, co, ni, sr or B. In some embodiments, the first doping element is Mg and the second doping element is selected from Fe, co, ni, sr or B. In some embodiments, the first doping element is Cr and the second doping element is selected from Fe, co, ni, sr or B. In some embodiments, the first doping element is Ca and the second doping element is selected from Fe, co, ni, sr or B. In some embodiments, the first doping element is Al and the second doping element is selected from Fe, co, ni, sr or B.
In one embodiment, the first doping element is selected from at least one of Li, Y, la, and Zn, and the second doping element is selected from at least one of F, P, si and B. In some embodiments, the first doping element is La and the second doping element is selected from P, si and B. In some embodiments, the first doping element is Y and the second doping element is selected from Si and B. In some embodiments, the first doping element is Zn and the second doping element is selected from F and P.
It should be noted that the first doping element and the second doping element given above are exemplary but not limiting embodiments.
In one embodiment, the shape of the sodium ion positive electrode material includes at least one of a rod shape, a sheet shape, and a particle shape. The shape of the positive electrode material in the invention comprises various shapes, and the specific shape is related to the coating amount of the material, the sintering process and the pretreatment mode of the raw material.
According to another aspect of the invention, the invention also relates to a preparation method of the positive electrode material, which comprises the following steps:
(a) First treating or directly dry-mixing a first copper-containing compound, a first sodium-containing compound, a first manganese-containing compound and an M-containing compound to obtain a first material, wherein the first treatment comprises coprecipitation and dry mixing; performing first sintering treatment on the first material to obtain a base material;
(b) Dry mixing or wet mixing the substrate in step (a) with a second copper-containing compound, a second sodium-containing compound, a second manganese-containing compound and an a-containing compound to obtain a second material; and performing second sintering treatment on the second material.
In some embodiments, the first process specifically includes: mixing a soluble first copper-containing compound, a soluble first manganese-containing compound and a soluble M-containing compound with an acid solution to obtain a mother solution, wherein the pH value of the mother solution is less than or equal to 4; adding alkali liquor into the mother liquor for reaction, and drying to obtain a precursor material; dry mixing the precursor material with a first sodium-containing compound to obtain a first material; in the coprecipitation process, the temperature of the reaction system is controlled to be 20-80 ℃, and the pH value of the reaction system is more than 4 and less than 12.
In some embodiments, a method of co-precipitation comprises: dissolving a first copper-containing compound, a first manganese-containing compound and an M-containing compound with dilute sulfuric acid according to a proper proportion to prepare mother liquor, and injecting the mother liquor into a reaction kettle (preferably, the mother liquor is prepared by adding a small amount of acid into soluble copper sulfate, sodium sulfate and manganese sulfate, wherein the pH value of the mother liquor is less than or equal to 4), slowly adding alkaline solution such as ammonia water and sodium hydroxide with a certain concentration into the synthesis reaction kettle according to a certain flow rate, slowly stirring in the reaction process, and continuously and gradually injecting the alkaline solution. The temperature is controlled at 20-80 ℃, such as 22 ℃, 50 ℃, 78 ℃, and the like, the pH value in the coprecipitation process is 4 < 12, finally, the target precursor is obtained by washing in alkali liquor and drying, and the target precursor and the first sodium-containing compound are fully mixed and sintered to obtain the base material (the coprecipitation is the preferred scheme, and other feasible schemes such as carbonate precipitation technology can also be adopted).
In some embodiments, step (a): ball milling or direct dry mixing is carried out on a mixture of the first copper-containing compound, the first sodium-containing compound, the first manganese-containing compound and the M-containing compound to obtain a first material; and performing first sintering treatment on the first material to obtain a base material. The dry-mixed raw materials are oxide raw materials and/or soluble salt and insoluble salt raw materials of the raw materials. In view of improving the efficiency, the ball milling time is 2 to 8 hours, such as 3 hours, 4 hours, 5 hours, 7 hours, and the like, and the proper parameters of the ball milling and sand milling can be set to be the particle size D50 of less than 2 microns after the ball milling and sand milling, so that excessive requirements are not required. In some embodiments, the mixing speed of the direct dry blend is 500to 5000r/min, e.g., 1000r/min, 1500r/min, 2000r/min, 3000r/min, etc.; the time is 3-20 min, such as 5min, 10min, 12min, 15min, 20min, etc. The mixing effect can be achieved without excessive requirements.
In some embodiments, step (b): dry mixing the substrate in step (a) with a second copper-containing compound, a second sodium-containing compound, a second manganese-containing compound and an a-containing compound to obtain a second material; and performing second sintering treatment on the second material. The dry-mixed starting material is selected from the group consisting of oxide starting materials and/or soluble, insoluble salt starting materials. The dry mixing is carried out by a high-speed mixer at a rotation speed of 500-5000 r/min, for example, 1000r/min, 1500r/min, 2000r/min, 3000r/min, etc., and for a period of 3-20 min, for example, 5min, 10min, 12min, 15min, 20min, etc. The dry mixing can achieve the mixing effect.
In some embodiments, step (b): wet mixing the substrate in step (a) with a second copper-containing compound, a second sodium-containing compound, a second manganese-containing compound and an a-containing compound to obtain a second material; and performing second sintering treatment on the second material. The raw materials involved in the wet mixing are preferably soluble raw materials, and may be nano water-insoluble oxide, inorganic salt raw materials, and the like.
The specific steps of the wet mixing method comprise:
(a) Mixing a mixture of a soluble second copper-containing compound, a soluble second sodium-containing compound, a soluble second manganese-containing compound and a soluble A-containing compound with water or an alcohol solvent to obtain a coating solution; (b) And placing the substrate to be coated in rotary steaming equipment (a rotary steaming bottle or a rotary steaming furnace), and carrying out rotary evaporation coating until a dry coating material is finally obtained.
The spin-steaming temperature of the aqueous solution is slightly higher than 100deg.C, such as 101 deg.C, 105 deg.C, 110, etc. The set temperature of the ethanol solution is higher than 70 ℃, such as 71 ℃, 75 ℃, 80 ℃ and the like, and the mass ratio of the use amount of the ethanol solution to the use amount of the solution is controlled within the range of 0.5-2.0.
In some embodiments, the first and second copper-containing compounds each include at least one of copper oxide, copper acetate, copper sulfate, copper manganese carbonate, and copper manganese hydroxide.
In some embodiments, the first sodium-containing compound and the second sodium-containing compound each comprise at least one of sodium hydroxide, sodium carbonate, sodium sulfate, sodium acetate, sodium citrate, and sodium manganate.
In some embodiments, the first and second manganese-containing compounds each include at least one of manganese monoxide, manganese dioxide, manganese sesquioxide, manganese tetraoxide, manganese acetate, manganese sulfate and sodium manganate, copper manganese carbonate, and copper manganese hydroxide.
In some embodiments, the M-containing compound comprises at least one of an M-containing oxide, an M-containing hydroxide, and an M-containing soluble salt; the M includes at least one of Fe, co, ni, mg, al, ti, cr, li, ca, zn, sr, Y, zr, la, F, si, P and B. In some embodiments, the M-containing soluble salt comprises an M-containing carbonate salt.
In some embodiments, the a-containing compound comprises at least one of an a-containing oxide, an a-containing hydroxide, and an a-containing soluble salt; the A includes at least one of Fe, co, ni, mg, al, ti, cr, li, ca, zn, sr, Y, zr, la, F, si, P and B. In some embodiments, the a-containing soluble salt comprises an a-containing carbonate.
In some embodiments, the temperature of the first sintering process is 850 to 1000 ℃ and the time of the first sintering process is 8 to 20 hours. In some embodiments, the temperature of the first sintering process includes, but is not limited to 860 ℃, 870 ℃, 890 ℃, 900 ℃, 910 ℃, 920 ℃, 930 ℃, 950 ℃, 970 ℃, 990 ℃, or ℃ in temperature. In some embodiments, the time of the first sintering process includes, but is not limited to, 8h, 9h, 10h, 11h, 12h, 3h, 14h, 15h, 16h, 17h, 18h, 19h, or 20h.
In some embodiments, the temperature of the second sintering process is 800 to 950 ℃ and the time of the second sintering process is 8 to 20 hours. In some embodiments, the temperature of the second sintering process includes, but is not limited to 810 ℃, 820 ℃, 830 ℃, 840 ℃, 850 ℃, 860 ℃, 870 ℃, 880 ℃, 890 ℃, 900 ℃, 910 ℃, 920 ℃, 930 ℃, 940 ℃, or 950 ℃. In some embodiments, the time of the second sintering process includes, but is not limited to, 8h, 9h, 10h, 11h, 12h, 3h, 14h, 15h, 16h, 17h, 18h, 19h, or 20h.
In another aspect, the invention relates to a battery comprising the sodium ion positive electrode material.
In some embodiments, the D50 particle size of the sodium ion positive electrode material is 3 μm to 40 μm.
Further description will be provided below in connection with specific examples.
Example 1
The preparation method of the sodium ion positive electrode material comprises the following steps:
(a) Raw materials required by raw materials are calculated according to a chemical formula Na 0.95Cu0.05Mn0.95O2, raw materials of sodium carbonate, copper oxide and manganous oxide are weighed according to a proportion, high-speed mixer equipment with the specification of 20L is adopted for fully mixing, the rotating speed is 2000r/min, the mixing time is 10min, the obtained mixed materials are placed in an air atmosphere furnace for sintering and heat preservation at 1000 ℃ for 8h, the materials are cooled and taken out, and the materials are crushed to obtain a base material;
(b) According to the molecular formula Na 0.6Cu0.3Mn0.7O2 and the coating amount of 0.5%, the weighed sodium carbonate, nano copper oxide, nano manganese dioxide and the base material are subjected to dry coating according to the calculated proportion (the ball milling tank and the polyurethane steel balls are adopted for fully mixing and coating, the rotating speed is 20r/min, the time is 10 h), the obtained material is subjected to heat preservation and sintering for 16h at the temperature of 850 ℃ in the air atmosphere, the material is cooled and taken out, and the material is taken out after being crushed, so that the sodium ion anode material is obtained.
Example 2
The preparation method of the sodium ion positive electrode material comprises the following steps:
(a) Calculating powdery sodium hydroxide, cuprous oxide and manganese dioxide required by raw materials according to a chemical formula Na 1.00Cu0.10Mn0.90O2, fully mixing the raw materials, placing the mixture in an air atmosphere furnace, sintering at 950 ℃ for 12 hours, cooling, taking out, and crushing to obtain a base material;
(b) And (3) according to the molecular formula Na 0.66Cu0.33Mn0.67O2 and the coating amount of 1%, calculating the required sodium carbonate, nano copper oxide and nano manganese dioxide for coating, carrying out dry coating on the weighed raw materials and the base material according to the calculated proportion (adopting a 20L high-speed mixer, the rotating speed is 2000r/min, the mixing time is 10 min), carrying out heat preservation and sintering for 16h at the temperature of 850 ℃ in air atmosphere, cooling, taking out, crushing, and taking out to obtain the sodium ion anode material.
An SEM image of the sodium ion cathode material in this example is shown in fig. 2.
Example 3
The preparation method of the sodium ion positive electrode material comprises the following steps:
(a) Calculating copper sulfate and manganese sulfate required by raw materials according to a chemical formula Na 1.05Cu0.15Mn0.85O2, dissolving the copper sulfate and manganese sulfate raw materials in dilute sulfuric acid according to a proportion to prepare mother liquor, injecting the mother liquor into a reaction kettle, slowly stirring at room temperature, injecting 2mol/L ammonia water solution, and finally washing and drying to obtain copper-manganese hydroxide coprecipitation; fully mixing copper-manganese hydroxide coprecipitation with powdery sodium hydroxide, placing the mixture in an air atmosphere furnace, sintering at 900 ℃ and preserving heat for 16 hours, cooling and taking out the mixture, and crushing the mixture to obtain a base material;
(b) According to the molecular formula Na 0.72Cu0.36Mn0.64O2 and coating raw materials required by 2 percent coating amount, wet coating is carried out on the weighed sodium acetate, copper acetate and manganese acetate raw materials and the base material according to the calculated proportion, and the specific operation is as follows: the preparation method comprises the steps of firstly, fully decomposing raw materials into ethanol to prepare coating mother liquor, then adding the calculated matrix to be coated and diluted mother liquor into a rotary steaming bottle according to the mass ratio of 1:1, vacuumizing and rotary steaming at the water bath temperature of 80 ℃, finally obtaining coated powder, carrying out heat preservation and sintering for 8 hours at the temperature of 950 ℃ in air atmosphere, cooling, taking out, crushing, and taking out to obtain the sodium ion positive electrode material.
The charge-discharge curve of the sodium ion positive electrode material in this example is shown in fig. 3.
Example 4
The preparation method of the sodium ion positive electrode material comprises the following steps:
(a) Calculating copper sulfate and manganese sulfate required by raw materials according to a chemical formula Na 0.95Cu0.05Mn0.85Ti0.1O2, dissolving the copper sulfate and manganese sulfate raw materials in dilute sulfuric acid according to a proportion to prepare mother liquor, injecting the mother liquor into a reaction kettle, slowly stirring at room temperature, injecting 2mol/L ammonia water solution, and finally washing and drying to obtain copper-manganese hydroxide coprecipitation; fully mixing the obtained copper-manganese hydroxide coprecipitation, sodium carbonate and titanium dioxide by adopting high-speed mixer equipment with the specification of 20L, and mixing for 10min at the rotating speed of 2000 r/min; placing the mixed materials in an air atmosphere furnace, sintering at 850 ℃ for 20 hours, cooling, taking out, and crushing to obtain a base material;
(b) According to the molecular formula Na 0.66Cu0.30Mn0.64Fe0.06O2 and 5% coating amount, calculating the required sodium citrate, nano copper oxide, nano manganese trioxide and nano ferric oxide, carrying out wet coating on the weighed raw materials and the base material according to the calculated proportion, wherein the specific operation is as follows: the preparation method comprises the steps of firstly, fully decomposing raw materials into ethanol to prepare coating mother liquor, then adding a calculated matrix to be coated and diluted mother liquor into a rotary steaming bottle according to a mass ratio of 1:1, vacuumizing and rotary steaming at a water bath temperature of 80 ℃ to finally obtain coated powder, carrying out heat preservation and sintering for 13h at 900 ℃ in an air atmosphere, cooling, taking out, crushing, and taking out to obtain the sodium ion positive electrode material.
Example 5
The preparation method of the sodium ion positive electrode material comprises the following steps:
(a) Calculating sodium sulfate, copper sulfate, manganese sulfate and magnesium carbonate required by raw materials according to a chemical formula Na 0.98Cu0.07Mn0.88Mg0.05O2, fully mixing the raw materials by adopting high-speed mixer equipment with the specification of 20L, wherein the rotating speed is 2000r/min, and the mixing time is 10min; placing the obtained mixed materials in an air atmosphere furnace, sintering at 800 ℃ for 24 hours, cooling, taking out, and crushing to obtain a base material;
(b) According to the molecular formula Na 0.68Cu0.33Mn0.65Co0.02O2 and the coating amount of 10%, the required coated sodium hydroxide, nano copper oxide, nano manganic oxide and nano cobaltosic oxide are calculated, the weighed raw materials and the base material are subjected to dry coating according to the calculated proportion (a ball milling tank and polyurethane steel balls are adopted for fully mixing and coating, the rotating speed is 20r/min, the time is 10 h), the temperature is kept for sintering for 16h under the condition of 850 ℃ in the air atmosphere, the temperature is reduced, the raw materials are taken out, and the sodium ion anode material is obtained after crushing.
An SEM image of the sodium ion cathode material in this example is shown in fig. 5.
Example 6
The preparation method of the sodium ion positive electrode material comprises the following steps:
(a) Calculating sodium manganate (sodium manganate is used as a reagent grade material, all sodium sources and part of manganese sources are provided), copper oxide and manganese oxide, and aluminum oxide according to a chemical formula Na 1.00Cu0.09Mn0.89Al0.02O2, fully mixing the raw materials by using high-speed mixer equipment with the specification of 20L, wherein the rotating speed is 2000r/min, the mixing time is 10min, placing the obtained mixed materials in an air atmosphere furnace, sintering at 1000 ℃ for 8h, cooling, taking out, and crushing to obtain a base material;
(b) According to the molecular formula Na 0.67Cu0.32Mn0.65Ni0.03O2 and 15% coating amount, the required coating sodium acetate, copper acetate, manganese acetate and nickel sulfate are calculated, and the weighed raw materials and the base material are subjected to wet coating according to the calculated proportion, and the specific operation is as follows: dispersing raw materials in pure water to prepare coating mother liquor, adding the calculated matrix to be coated and the diluted mother liquor into a rotary steaming bottle according to the mass ratio of 1:1, vacuumizing and rotary steaming at the temperature of an oil bath of 100 ℃ to finally obtain coated powder, carrying out heat preservation and sintering for 16 hours at the temperature of 850 ℃ in an air atmosphere, cooling, taking out, crushing, and taking out to obtain the sodium ion positive electrode material.
The charge-discharge curve of the sodium ion positive electrode material in this example is shown in fig. 6.
Example 7
The preparation method of the sodium ion positive electrode material comprises the following steps:
(a) Calculating sodium carbonate, copper oxide, manganese dioxide and calcium oxide required by raw materials according to a chemical formula Na 1.02Cu0.13Mn0.86Ca0.01O2, fully mixing the raw materials by adopting high-speed mixer equipment with the specification of 20L, wherein the rotating speed is 2000r/min, the mixing time is 10min, placing the obtained mixed materials in an air atmosphere furnace, sintering at 950 ℃ for 12h, cooling, taking out, and crushing to obtain a base material;
(b) According to the molecular formula Na 0.72Cu0.35Mn0.65Sr0.01Si0.01O2 and the coating amount of 20%, the required coating raw materials of sodium carbonate, copper oxide, manganese dioxide, strontium carbonate and sodium silicate are calculated, and the weighed raw materials and the base material are subjected to wet coating according to the calculated proportion, and the specific operation is as follows: the preparation method comprises the steps of firstly, fully decomposing raw materials into ethanol to prepare cladding mother liquor, then adding the calculated matrix to be clad and diluted mother liquor into a rotary steaming bottle according to the mass ratio of 1:1, vacuumizing and rotary steaming at the water bath temperature of 80 ℃, finally obtaining clad powder, carrying out heat preservation and sintering for 8 hours at the temperature of 950 ℃ in air atmosphere, cooling, taking out, crushing, and taking out to obtain the target material.
An SEM image of the sodium ion cathode material in this example is shown in fig. 7.
Example 8
The preparation method of the sodium ion positive electrode material comprises the following steps:
(a) Calculating sodium carbonate, cuprous oxide, magnesium hydroxide, manganese dioxide and zirconium oxide required by raw materials according to a chemical formula Na 1.05Cu0.05Mn0.91Ni0.02Zr0.02O2, fully mixing the raw materials by adopting high-speed mixer equipment with the specification of 20L, wherein the rotating speed is 2000r/min, the mixing time is 10min, placing the obtained mixed materials in an air atmosphere furnace, sintering at 900 ℃, preserving heat for 16h, cooling, taking out, and crushing to obtain a base material;
(b) According to the molecular formula Na 0.69Cu0.34Mn0.65B0.01O2 and the coating amount of 30 percent, the required sodium carbonate, cuprous oxide, magnesium hydroxide, manganese dioxide and boric acid are calculated, the weighed raw materials and the base material are subjected to dry coating according to the calculated proportion (a ball milling tank and polyurethane steel balls are adopted for fully mixing and coating, the rotating speed is 20r/min, the time is 10 h), the temperature is kept for sintering for 8h under the condition of 950 ℃ in the air atmosphere, the temperature is reduced, the raw materials are taken out, and the target material is obtained after crushing.
Experimental example
The sodium ion positive electrode material of the present invention was subjected to tests of pH, particle size, first week capacity and 100 week capacity retention, and the results are shown in table 1.
Button cell equipment and test includes: the prepared cathode material, conductive carbon black SP, and polyvinylidene fluoride (PVDF) were prepared in the following amounts of 90:5:5, uniformly mixing and grinding, coating the mixture on an aluminum foil to serve as an anode plate, taking a metal sodium plate as a cathode plate, taking a microporous polypropylene film as a diaphragm, taking 1mol/L sodium hexafluorophosphate solution as electrolyte, and assembling the anode plate, the cathode plate, the diaphragm, the cathode electrode and the cathode shell into a button half cell according to the sequence of the anode shell, the cathode plate, the diaphragm, the cathode electrode and the cathode shell, wherein the testing system is as follows: first-round discharge capacity of 0.1C at 2.5-4.0V, and capacity retention rate of 100 weeks in cycle.
TABLE 1 test results of pH, particle size, first week Capacity and 100 week Capacity Retention of Positive electrode Material
From the above, the present invention uses the zig-zag layered structure Na 1+aCuxMnyMzO2 (beta phase) as the coated material and the P2 phase Na 2/3+bCu1/3+mMn2/3+nMcO2 as the coated material, and the obtained positive electrode material has the advantages of high specific discharge capacity, excellent cycle performance and excellent physicochemical processing 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 (8)
1. The sodium ion positive electrode material is characterized by comprising a base material and a coating layer coated on at least part of the surface of the base material;
the substrate comprises Na 1+aCuxMnyMzO2 with a zig-zag layered structure, wherein M is a first doping element, a is more than or equal to 0.05 and less than or equal to 0.05,0.05, x is more than or equal to 0.15,0.85 and less than or equal to y is more than or equal to 0.95, z is more than or equal to 0 and x+y+z=1;
The coating layer comprises Na 2/3+bCu1/3+mMn2/3+nAcO2 with a P2 phase, wherein A is a second doping element, b is more than or equal to-0.06 and less than or equal to-0.06, m is more than or equal to-0.03 and less than or equal to-0.03, n is more than or equal to-0.03, c is more than or equal to 0 and m+n+c=0;
The first doping element and the second doping element respectively comprise at least one of Fe, co, ni, mg, al, ti, cr, li, ca, zn, sr, Y, zr, la, F, si, P and B;
The mass of the coating layer accounts for 0.5% -30% of the total mass of the base material and the coating layer;
The D50 particle size of the sodium ion positive electrode material is 3-40 mu m;
The pH of the sodium ion positive electrode material is 10.0-13.0.
2. The sodium ion positive electrode material according to claim 1, wherein the mass of the coating layer is 0.5 to 20% of the total mass of the base material and the coating layer.
3. The sodium ion positive electrode material according to claim 1, wherein the first doping element and the second doping element are different elements.
4. The sodium ion positive electrode material according to claim 1, comprising any one of the following features (1) to (3):
(1) The first doping element is selected from at least one of Ti, mg, al, ca and Cr, and the second doping element is selected from at least one of Fe, co, ni, sr, si and B;
(2) The first doping element is selected from at least one of Li, Y, la and Zn, and the second doping element is selected from at least one of F, P, si and B;
(3) The shape of the sodium ion positive electrode material includes at least one of a rod shape, a sheet shape, and a particle shape.
5. The method for preparing a sodium ion positive electrode material according to any one of claims 1 to 4, comprising the steps of:
(a) Carrying out first treatment or direct dry mixing on a first copper-containing compound, a first sodium-containing compound, a first manganese-containing compound and an M-containing compound to obtain a first material, wherein the first treatment comprises coprecipitation and dry mixing; performing first sintering treatment on the first material to obtain a base material;
(b) Dry mixing or wet mixing the substrate in step (a) with a second copper-containing compound, a second sodium-containing compound, a second manganese-containing compound and an a-containing compound to obtain a second material; and performing second sintering treatment on the second material.
6. The method for preparing a sodium ion positive electrode material according to claim 5, comprising at least one of the following features (1) to (5):
(1) The first copper-containing compound and the second copper-containing compound respectively comprise at least one of copper oxide, cuprous oxide, copper acetate, copper sulfate, copper manganese carbonate and copper manganese hydroxide;
(2) The first sodium-containing compound and the second sodium-containing compound respectively comprise at least one of sodium hydroxide, sodium carbonate, sodium sulfate, sodium acetate, sodium citrate and sodium manganate;
(3) The first manganese-containing compound and the second manganese-containing compound respectively comprise at least one of manganese monoxide, manganese dioxide, manganese sesquioxide, manganous oxide, manganese acetate, manganese sulfate and sodium manganate, copper manganese carbonate and copper manganese hydroxide;
(4) The M-containing compound comprises at least one of an M-containing oxide, an M-containing hydroxide, and an M-containing soluble salt; the M comprises at least one of Fe, co, ni, mg, al, ti, cr, li, ca, zn, sr, Y, zr, la, F, si, P and B;
(5) The a-containing compound includes at least one of an a-containing oxide, an a-containing hydroxide, and an a-containing soluble salt; the A includes at least one of Fe, co, ni, mg, al, ti, cr, li, ca, zn, sr, Y, zr, la, F, si, P and B.
7. The method for preparing a sodium ion positive electrode material according to claim 5, characterized by comprising any one of the following characteristics (1) to (6):
(1) The first process specifically includes: mixing a soluble first copper-containing compound, a soluble first manganese-containing compound and a soluble M-containing compound with an acid solution to obtain a mother solution, wherein the pH value of the mother solution is less than or equal to 4; adding alkali liquor into the mother liquor for reaction, and drying to obtain a precursor material; dry mixing the precursor material with a first sodium-containing compound to obtain a first material; in the coprecipitation process, the temperature of a reaction system is controlled to be 20-80 ℃, and the pH of the reaction system is more than 4 and less than 12;
(2) The wet mixing method specifically comprises the following steps: mixing a mixture of a soluble second copper-containing compound, a soluble second sodium-containing compound, a soluble second manganese-containing compound and a soluble A-containing compound with water or an alcohol solvent to obtain a coating solution; coating the substrate with the coating solution by spin steaming;
(3) In the step (a), the mixing rotational speeds of the direct dry mixing and the dry mixing are respectively 500-5000 r/min, and the mixing time is respectively 3-20 min;
(4) In the step (b), the mixing speed of the dry mixing is 500-5000 r/min, and the mixing time is 3-20 min;
(5) The temperature of the first sintering treatment is 850-1000 ℃, and the time of the first sintering treatment is 8-20 hours;
(6) The temperature of the second sintering treatment is 800-950 ℃, and the time of the second sintering treatment is 8-20 h.
8. A battery comprising the sodium ion positive electrode material according to any one of claims 1 to 4.
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| CN116282228A (en) * | 2023-03-27 | 2023-06-23 | 荆门市格林美新材料有限公司 | Sodium ion precursor material and preparation method and application thereof |
| CN116207248B (en) * | 2023-05-04 | 2023-09-01 | 溧阳中科海钠科技有限责任公司 | Sodium-rich layered oxide positive electrode material, preparation method thereof and sodium ion battery |
| CN116387494B (en) * | 2023-05-29 | 2023-09-01 | 宜宾锂宝新材料有限公司 | Positive electrode material, preparation method thereof and sodium ion battery |
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