CN118712387B - A low-cost manganese-rich iron-based sodium ion battery positive electrode material and its preparation method and application - Google Patents
A low-cost manganese-rich iron-based sodium ion battery positive electrode material and its preparation method and application Download PDFInfo
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- CN118712387B CN118712387B CN202411179076.5A CN202411179076A CN118712387B CN 118712387 B CN118712387 B CN 118712387B CN 202411179076 A CN202411179076 A CN 202411179076A CN 118712387 B CN118712387 B CN 118712387B
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- manganese
- positive electrode
- electrode material
- sodium ion
- ion battery
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 38
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 35
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 239000011572 manganese Substances 0.000 title claims abstract description 25
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 24
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 23
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000011734 sodium Substances 0.000 claims abstract description 23
- DALUDRGQOYMVLD-UHFFFAOYSA-N iron manganese Chemical compound [Mn].[Fe] DALUDRGQOYMVLD-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000011229 interlayer Substances 0.000 claims abstract description 20
- 229910052793 cadmium Inorganic materials 0.000 claims abstract description 15
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 15
- 229910052788 barium Inorganic materials 0.000 claims abstract description 13
- 239000000126 substance Substances 0.000 claims abstract description 4
- 238000005245 sintering Methods 0.000 claims description 30
- 229910000616 Ferromanganese Inorganic materials 0.000 claims description 18
- 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 18
- 229910052708 sodium Inorganic materials 0.000 claims description 18
- 239000010405 anode material Substances 0.000 claims description 17
- 239000002019 doping agent Substances 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 16
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 9
- 239000001301 oxygen Substances 0.000 claims description 9
- 229910052760 oxygen Inorganic materials 0.000 claims description 9
- 239000002243 precursor Substances 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 239000011656 manganese carbonate Substances 0.000 claims description 4
- 229940093474 manganese carbonate Drugs 0.000 claims description 4
- 229910016955 Fe1-xMnx Inorganic materials 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 28
- 239000002245 particle Substances 0.000 abstract description 8
- 238000009792 diffusion process Methods 0.000 abstract description 7
- 229910052791 calcium Inorganic materials 0.000 abstract description 5
- 229910021645 metal ion Inorganic materials 0.000 abstract description 5
- 150000002500 ions Chemical class 0.000 abstract description 4
- 238000003487 electrochemical reaction Methods 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 14
- 239000010410 layer Substances 0.000 description 13
- 230000009286 beneficial effect Effects 0.000 description 8
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 description 8
- 229910000018 strontium carbonate Inorganic materials 0.000 description 8
- 229910052712 strontium Inorganic materials 0.000 description 7
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 229910052727 yttrium Inorganic materials 0.000 description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 6
- CXKCTMHTOKXKQT-UHFFFAOYSA-N cadmium oxide Inorganic materials [Cd]=O CXKCTMHTOKXKQT-UHFFFAOYSA-N 0.000 description 6
- CFEAAQFZALKQPA-UHFFFAOYSA-N cadmium(2+);oxygen(2-) Chemical compound [O-2].[Cd+2] CFEAAQFZALKQPA-UHFFFAOYSA-N 0.000 description 6
- 229910052746 lanthanum Inorganic materials 0.000 description 6
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 5
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- KEBVLXZBNYKBFW-UHFFFAOYSA-J iron(2+);manganese(2+);tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Mn+2].[Fe+2] KEBVLXZBNYKBFW-UHFFFAOYSA-J 0.000 description 5
- 229910052744 lithium Inorganic materials 0.000 description 5
- 239000011591 potassium Substances 0.000 description 5
- 238000007873 sieving Methods 0.000 description 5
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 4
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 4
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 4
- 239000011575 calcium Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 description 4
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 4
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- XBDUTCVQJHJTQZ-UHFFFAOYSA-L iron(2+) sulfate monohydrate Chemical compound O.[Fe+2].[O-]S([O-])(=O)=O XBDUTCVQJHJTQZ-UHFFFAOYSA-L 0.000 description 3
- 150000002696 manganese Chemical class 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- 230000002687 intercalation Effects 0.000 description 2
- 150000002505 iron Chemical class 0.000 description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- ISPYRSDWRDQNSW-UHFFFAOYSA-L manganese(II) sulfate monohydrate Chemical compound O.[Mn+2].[O-]S([O-])(=O)=O ISPYRSDWRDQNSW-UHFFFAOYSA-L 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Chemical compound [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- 239000004277 Ferrous carbonate Substances 0.000 description 1
- 229910017569 La2(CO3)3 Inorganic materials 0.000 description 1
- 229910019398 NaPF6 Inorganic materials 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910000011 cadmium carbonate Inorganic materials 0.000 description 1
- GKDXQAKPHKQZSC-UHFFFAOYSA-L cadmium(2+);carbonate Chemical compound [Cd+2].[O-]C([O-])=O GKDXQAKPHKQZSC-UHFFFAOYSA-L 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 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
- 230000015556 catabolic process Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 235000019268 ferrous carbonate Nutrition 0.000 description 1
- RAQDACVRFCEPDA-UHFFFAOYSA-L ferrous carbonate Chemical compound [Fe+2].[O-]C([O-])=O RAQDACVRFCEPDA-UHFFFAOYSA-L 0.000 description 1
- 229960004652 ferrous carbonate Drugs 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 229910000015 iron(II) carbonate Inorganic materials 0.000 description 1
- NZPIUJUFIFZSPW-UHFFFAOYSA-H lanthanum carbonate Chemical compound [La+3].[La+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O NZPIUJUFIFZSPW-UHFFFAOYSA-H 0.000 description 1
- 229960001633 lanthanum carbonate Drugs 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 235000006748 manganese carbonate Nutrition 0.000 description 1
- 229940099596 manganese sulfate Drugs 0.000 description 1
- 239000011702 manganese sulphate Substances 0.000 description 1
- 235000007079 manganese sulphate Nutrition 0.000 description 1
- 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 1
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 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
- 238000011056 performance test Methods 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000011163 secondary particle Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 125000004436 sodium atom Chemical group 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- QVOIJBIQBYRBCF-UHFFFAOYSA-H yttrium(3+);tricarbonate Chemical compound [Y+3].[Y+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O QVOIJBIQBYRBCF-UHFFFAOYSA-H 0.000 description 1
- 239000011787 zinc oxide Substances 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/0018—Mixed oxides or hydroxides
- C01G49/0072—Mixed oxides or hydroxides containing manganese
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/50—Solid solutions
- C01P2002/52—Solid solutions containing elements as dopants
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
-
- 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)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
本发明涉及一种低成本富锰铁基钠离子电池正极材料及其制备方法与应用，所述正极材料的化学通式为NauFe1‑xMnxMyO2，其中0.98<u≤1.05，0.5≤x≤0.75，0.03≤y≤0.2，掺杂元素M包括A元素、B元素和C元素，其中A元素包括Y和/或La，B元素包括Sr，C元素包括Cd、K、Ca或Ba中的任意一种或者至少两种的组合，所述正极材料的层间距d满足5.45Å≤d≤5.55Å。本发明在富锰铁基二元正极材料中掺杂大粒径的金属离子，这些离子不参与电化学反应，但有助于扩大铁锰材料的层间距，进一步有助于提高钠离子扩散速率，以得到高倍率性能的富锰铁基钠离子电池正极材料。
The present invention relates to a low-cost manganese-rich iron-based sodium ion battery positive electrode material and a preparation method and application thereof. The chemical general formula of the positive electrode material is Na u Fe 1‑x Mn x M y O 2 , wherein 0.98<u≤1.05, 0.5≤x≤0.75, 0.03≤y≤0.2, the doping element M comprises an A element, a B element and a C element, wherein the A element comprises Y and/or La, the B element comprises Sr, and the C element comprises any one or a combination of at least two of Cd, K, Ca or Ba, and the interlayer spacing d of the positive electrode material satisfies 5.45Å≤d≤5.55Å. The present invention dopes large-particle metal ions into the manganese-rich iron-based binary positive electrode material, wherein these ions do not participate in the electrochemical reaction, but help to expand the interlayer spacing of the iron-manganese material, and further help to improve the sodium ion diffusion rate, so as to obtain a manganese-rich iron-based sodium ion battery positive electrode material with high rate performance.
Description
Technical Field
The invention relates to the technical field of sodium ion batteries, in particular to a low-cost manganese-rich iron-based sodium ion battery anode material and a preparation method and application thereof.
Background
Sodium is the second least mass element in the world, and sodium and lithium belong to the same group of elements from the periodic table of elements, and their physicochemical properties are very similar. Although lithium material batteries have advantages over sodium material batteries in energy density, sodium is a much higher storage resource than lithium and its market price is much lower than lithium. Therefore, sodium ion batteries have the advantages of lower cost and rich resources for large-scale applications in the energy storage and electric vehicle industries, and are considered as a new energy storage battery system that is highly likely to replace lithium batteries.
Layered transition metal oxides are the most promising positive electrode materials for sodium ion batteries, and become the current research hot spot due to the characteristics of high theoretical specific capacity, good low-temperature performance, rapid diffusion kinetics and the like. Compared with the traditional nickel-containing material, the sodium-electricity-ferrum-manganese binary positive electrode material has the advantages that the cost is higher, the content of iron in the material is higher in order to ensure higher capacity, iron clusters can be formed due to the fact that the content of iron is increased, the migration energy barrier is reduced, the ferrum can migrate into a sodium layer to be mixed with sodium atoms in the charging and discharging process of the ferrum-manganese binary material, and the multiplying power performance of the material is poor. Its use is severely limited due to its poor rate capability. Therefore, the invention considers that the interlayer spacing is enlarged by doping elements with large grain diameter so as to obtain a novel manganese-rich iron-based binary material with low cost and high multiplying power performance.
Disclosure of Invention
In order to solve the technical problems, the invention provides the manganese-rich iron-based sodium ion battery anode material and the preparation method and application thereof, and the metal additives A, B and C with large particle sizes are selected, so that the interlayer spacing of the manganese-rich iron-based sodium ion battery anode material is enlarged, the diffusion rate of sodium ions is improved, and the multiplying power performance of the anode material is further improved; the preparation method provided by the invention is simple and easy to operate, has low requirements on the production process, and is beneficial to large-scale production.
To achieve the purpose, the invention adopts the following technical scheme:
In a first aspect, the invention provides a low-cost manganese-rich iron-based sodium ion battery positive electrode material, which has a chemical formula of Na uFe1-xMnxMyO2, wherein x is more than or equal to 0.98< 1.05,0.5 > x is more than or equal to 0.75,0.03 > Y is more than or equal to 0.2, a doping element M comprises an element A, an element B and an element C, wherein the element A comprises Y and/or La, the element B comprises Sr, the element C comprises any one or a combination of at least two of Cd, K, ca and Ba, and the sodium layer spacing d of the positive electrode material meets the requirement that d is more than or equal to 5.45A and less than or equal to 5.55A.
Where u may be 0.99, 1, 1.01, 1.02, 1.03, 1.04, or 1.05, but is not limited to the recited values, as are other non-recited values within the range of values; x may be 0.5, 0.55, 0.6, 0.65, 0.7, or 0.75, but is not limited to the recited values, as other non-recited values within the range of values are equally applicable; y may be 0.03, 0.05, 0.1, 0.15, 0.19, or 0.2, but is not limited to the recited values, as other non-recited values within the range of values are equally applicable; d may be 5.45 a, 5.47 a, 5.49 a, 5.51 a, 5.53 a, or 5.55 a, but is not limited to the recited values, as other non-recited values within the range of values are equally applicable.
Typical, but non-limiting, combinations of elements C include combinations of Cd and K, or K, ca and Ba; typical, but non-limiting, combinations of doping elements M include Y, sr and Cd, or La, sr and K, or La, sr, ca and Ba.
The invention takes a manganese-rich iron-based sodium ion battery anode material as a matrix, and selects a large-particle-size metal additive A element, B element and C element with the ion radius of 90 multiplied by 10 -12-140×10-12 m for doping, wherein the A element comprises Y and/or La, the B element comprises Sr, and the C element comprises any one or the combination of at least two of Cd, K, ca and Ba. Wherein La/Y enters the transition metal layer to form a strong La/Y-O bond, which increases the repulsive force between the oxygen of the sodium layers and further increases the interlayer spacing of the sodium layers; sr can enter the Na layer, plays a role in supporting and simultaneously has a melting assisting role, and helps large-particle-diameter atoms to be doped into a material structure; cd. K, ca or Ba will enter the Na layer and act as a "support" because of its larger radius, thus expanding the interlayer spacing of the sodium layer. The large-particle-size metal ions enter the material to play a synergistic effect, so that the interlayer spacing of the positive electrode material is enlarged, the diffusion rate of sodium ions is improved, and the rate capability of the positive electrode material is further improved.
According to the invention, the element A, the element B and the element C are doped, and the interlayer spacing of the sodium layer is effectively enlarged through the synergistic effect of the three elements.
After XRD test, the layer distance d of the positive electrode material prepared by the invention can be calculated by using a Bragg equation 2dsin theta=nλ (d: crystal face distance; theta: diffraction angle; lambda: x-ray wavelength; n is reflection series). The interlayer spacing of the positive electrode material which is not doped with the element A, the element B and the element C is 5.34A, and further shows that the interlayer spacing of the manganese-rich iron-based sodium ion battery positive electrode material is improved after the element A, the element B and the element C are doped together.
The doping elements M in the present invention are preferably a combination of Y, sr and Cd, and further preferably the molar ratio of the three doping elements is (1-2): 1:1, for example, may be 1:1:1, 1.5:1:1, 1.9:1:1 or 2:1:1, but are not limited to the recited values, other non-recited values within the range of values are equally applicable.
In a second aspect, the present invention provides a method for preparing the positive electrode material according to the first aspect, the method comprising the steps of:
Mixing a ferro-manganese source, a sodium source and a doping agent, and sintering to obtain the anode material;
The dopant comprises a doping element M, wherein the M comprises an A element, a B element and a C element, the A element comprises Y and/or La, the B element comprises Sr, and the C element comprises any one or a combination of at least two of Cd, K, ca and Ba.
The preparation method can prepare the anode material of the low-cost ferromanganese-rich sodium ion battery through one-step sintering, is simple and easy to operate, has low requirements on production process, and is beneficial to mass production.
Preferably, the mixing comprises stirring.
Preferably, the rotational speed of the mixture is 300-1300r/min, for example 300r/min, 500r/min, 700r/min, 900r/min or 1300r/min, but not limited to the values recited, other values not recited in the numerical range are equally applicable.
Preferably, the mixing time is 10-30min, for example, 10min, 15min, 20min, 25min or 30min, but not limited to the recited values, and other non-recited values within the range of values are equally applicable.
Preferably, the ferro-manganese source comprises any one or a combination of at least two of a ferro-manganese hydroxide precursor, a ferro-manganese oxide or a ferro-manganese carbonate, typically but not limited to a combination of a ferro-manganese oxide and a ferro-manganese hydroxide precursor, a combination of a ferro-manganese oxide, a ferro-manganese hydroxide precursor and a ferro-manganese carbonate.
Preferably, the iron-manganese hydroxide precursor is prepared by the following preparation method:
Respectively weighing ferric salt and manganese salt according to the molar ratio of iron to manganese, dissolving the ferric salt and the manganese salt in deionized water, and sequentially adding carbon nano tubes, sodium hydroxide solution and ammonia water into the solution to obtain a mixed solution; and drying the mixed solution in an oven to obtain the iron-manganese hydroxide precursor.
Preferably, the chemical formula of the iron manganese hydroxide precursor is Fe 1-xMnx(OH)2, wherein 0.5.ltoreq.x.ltoreq.0.75, for example, 0.5, 0.55, 0.6, 0.65, 0.7 or 0.75, but not limited to the recited values, other non-recited values in the numerical range are equally applicable.
Preferably, the iron salt comprises any one or a combination of at least two of ferrous sulfate heptahydrate, ferrous sulfate monohydrate, or ferrous sulfate anhydrous, and typical but non-limiting combinations include combinations of ferrous sulfate heptahydrate and ferrous sulfate monohydrate, or combinations of ferrous sulfate heptahydrate, ferrous sulfate monohydrate, and ferrous sulfate anhydrous.
Preferably, the manganese salt comprises manganese sulfate monohydrate and/or manganese sulfate anhydrate.
Preferably, the temperature of the drying is 100-140 ℃, for example, 100 ℃, 120 ℃, 130 ℃ or 140 ℃, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
Preferably, the drying time is 8-12h, for example, 8h, 9h, 10h, 11h or 12h, but not limited to the recited values, and other non-recited values in the range are equally applicable.
Preferably, the sodium source comprises sodium carbonate and/or sodium bicarbonate.
Preferably, the mass ratio of the element A, the element B and the element C is (0.5-2): (1-2): 1, for example, may be 0.5:1:1, 1:1:1, 1.5:2:1 or 2:1:1, but is not limited to the recited values, and other non-recited values in the range of values are equally applicable.
Preferably, the a element includes Y, the B element includes Sr, and the C element includes Cd.
Preferably, the dopant includes an a dopant, a B dopant, and a C dopant.
Preferably, the a dopant comprises a yttrium source and/or a lanthanum source, the B dopant comprises a strontium source, and the C dopant comprises any one or a combination of at least two of a cadmium source, a potassium source, a calcium source, or a barium source, typically but not limited to combinations comprising a combination of a cadmium source and a potassium source, or a combination of a potassium source, a calcium source, and a barium source.
Preferably, the a dopant comprises a source of yttrium, the B dopant comprises a source of strontium, and the C dopant comprises a source of cadmium.
Preferably, the yttrium source comprises yttrium oxide and/or yttrium carbonate.
Preferably, the lanthanum source comprises lanthanum oxide and/or lanthanum carbonate.
Preferably, the strontium source comprises strontium oxide and/or strontium carbonate.
Preferably, the cadmium source comprises cadmium oxide and/or cadmium carbonate.
Preferably, the potassium source comprises potassium carbonate.
Preferably, the calcium source comprises calcium oxide and/or calcium carbonate.
Preferably, the barium source comprises barium oxide and/or barium carbonate.
Preferably, the dopant typically, but not limited to, a combination of yttrium, strontium, and cadmium sources, or a combination of lanthanum, strontium, and potassium sources, or a combination of lanthanum, strontium, calcium, and barium sources.
Preferably, the dopant includes a yttrium source, a strontium source, and a cadmium source.
Preferably, the sintering temperature is 940-1200 ℃, for example 940 ℃, 950 ℃, 1000 ℃, 1050 ℃, 1100 ℃, 1150 ℃ or 1200 ℃, but not limited to the values listed, and other values not listed in the numerical range are equally applicable.
Preferably, the sintering time is 10-14h, for example, 10h, 10.5h, 11h, 11.5h, 12h, 13h or 14h, but not limited to the recited values, and other non-recited values within the range of values are equally applicable.
And preparing the anode material within the temperature and sintering time range, wherein the particle size distribution is uniform. When the sintering time is prolonged or the temperature is increased, the particles of the material grow up, on one hand, the specific surface area is reduced along with the growth of the particles, so that the side reaction is reduced, the stability is enhanced, and meanwhile, the sodium reaction sites are reduced because the specific surface area is reduced, so that the capacity is reduced; when the temperature exceeds 1200 ℃, the specific surface area is too small, and the removal and intercalation of sodium ions are seriously affected, so that the rate performance of the anode material is affected; when the sintering time is shortened or the temperature is reduced, insufficient reaction capacity is reduced, crystal faces become coarse, crystal grains are not round, the tips of the crystal grains are easy to deactivate in the reaction process, and the long-term cycle performance of the material is also affected.
Preferably, the atmosphere of sintering comprises an oxygen-containing atmosphere.
Preferably, the oxygen-containing atmosphere comprises air, oxygen or any atmosphere containing oxygen.
Preferably, the temperature rising rate of the sintering is 4-5 min/DEG C, for example, 4 min/DEG C, 4.2 min/DEG C, 4.4 min/DEG C, 4.6 min/DEG C, 4.8 min/DEG C or 5 min/DEG C can be adopted, but the sintering is not limited to the listed values, and other values which are not listed in the numerical range are equally applicable.
The cooling rate of the sintering is 3-5 min/DEG C, for example, 3 min/DEG C, 3.5 min/DEG C, 4 min/DEG C, 4.5 min/DEG C or 5 min/DEG C, but is not limited to the recited values, and other values not recited in the numerical range are applicable.
Preferably, the sintering is further followed by a pulverizing and sieving treatment.
Preferably, after the pulverization and sieving, the particle size D50 of the positive electrode material is 4 to 8. Mu.m, for example, 4 μm, 5 μm, 6 μm, 7 μm or 8 μm, but not limited to the recited values, and other values not recited in the numerical range are equally applicable.
In a third aspect, the invention provides a sodium ion battery, which comprises the positive electrode material of the first aspect or the positive electrode material prepared by the preparation method of the second aspect.
Compared with the prior art, the invention has at least the following beneficial effects:
(1) According to the invention, large-particle-size metal ions are doped in the manganese-rich iron-based sodium ion battery anode material, and the ions do not participate in electrochemical reaction, but are beneficial to expanding the interlayer spacing of the iron-manganese material, and are further beneficial to improving the sodium ion diffusion rate so as to obtain the manganese-rich iron-based sodium ion battery anode material with high rate performance;
(2) The preparation method can prepare the anode material of the low-cost ferromanganese-rich sodium ion battery through one-step sintering, is simple and easy to operate, has low requirements on production process, and is beneficial to mass production.
Drawings
FIG. 1 is an SEM image of the positive electrode material prepared in example 1;
fig. 2 is a charge-discharge curve of the positive electrode material prepared in example 1.
Detailed Description
The technical scheme of the invention is further described below by the specific embodiments with reference to the accompanying drawings. The following examples are merely illustrative of the present invention and are not intended to represent or limit the scope of the invention as defined in the claims.
Example 1
The embodiment provides a positive electrode material of a low-cost manganese-rich iron-based sodium ion battery, and the preparation method of the positive electrode material comprises the following steps:
Weighing 139g of ferrous sulfate heptahydrate and 84.5g of manganese sulfate monohydrate, adding 300ml of deionized water, adding 10g of 14% carbon nanotube solution, uniformly mixing, adding ammonia water with the concentration of 20% to pH=6, adding 0.1mol/L sodium hydroxide to pH=11, and drying at 120 ℃ for 8 hours to prepare an iron-manganese hydroxide precursor Fe0.5Mn0.5 (OH) 2;
Weighing iron-manganese hydroxide precursor Fe0.5Mn0.5 (OH) 2 89.39g, sodium carbonate 53g, yttrium oxide 6.78g, strontium carbonate 8.88g and cadmium oxide 7.68g, stirring for 15min at 300r/min to obtain a mixed material; sintering the mixed material for 12 hours at 1000 ℃ in an oxygen atmosphere, crushing and sieving to obtain Na1Fe0.5Mn0.5Y0.06Sr0.06Cd0.06O2;
FIG. 1 is an SEM image of the positive electrode material prepared in example 1, in which it can be seen that the sintered particles are independent, not secondary particles, and the grain size is mostly between 4-8 μm;
Fig. 2 is a charge-discharge curve of the positive electrode material prepared in example 1, and it can be seen from the graph that the initial charge capacity of the 2-4V material at 0.1C is about 150mAh/g, and the initial charge capacity reaches more than 140mAh/g, and the electrochemical performance is excellent.
Example 2
The embodiment provides a positive electrode material of a low-cost manganese-rich iron-based sodium ion battery, and the preparation method of the positive electrode material comprises the following steps:
Weighing 20g of ferric oxide, 65.21g of manganese dioxide, 88.2g of sodium bicarbonate, 11.3g of yttrium oxide, 7.4g of strontium carbonate and 3.45g of potassium carbonate, and stirring at 800r/min for 25min to obtain a mixed material; sintering the mixed material for 10 hours at 1200 ℃ in air atmosphere, crushing and sieving to obtain Na1.05Fe0.25Mn0.75Y0.1Sr0.05K0.05O2.
Example 3
The embodiment provides a positive electrode material of a low-cost manganese-rich iron-based sodium ion battery, and the preparation method of the positive electrode material comprises the following steps:
46.32g of ferrous carbonate, 69g of manganese carbonate, 52.47g of sodium carbonate, 8.15g of lanthanum oxide, 7.4g of strontium carbonate and 7.67g of barium oxide are weighed and stirred for 20min at 500r/min to obtain a mixed material; sintering the mixed material for 14 hours at 940 ℃ in air atmosphere, crushing and sieving to obtain Na0.99Fe0.4Mn0.6La0.05Sr0.05Ba0.05O2.
Example 4
This example differs from example 1 only in that Na1Fe0.5Mn0.5Y0.01Sr0.01Cd0.01O2 was prepared, except that 1.48g of strontium carbonate, 1.28g of cadmium oxide and 1.13g of yttrium oxide were added, and the same procedure as in example 1 was followed.
Example 5
This example differs from example 1 only in that Na1Fe0.5Mn0.5Y0.06Sr0.01Cd0.06O2 was prepared, except that 1.48g of strontium carbonate was added, and the remainder was the same as in example 1.
Example 6
This example differs from example 1 only in that the sintering temperature was 900℃and the procedure was the same as in example 1.
Example 7
This example differs from example 1 only in that the sintering temperature is 1250℃and the procedure is the same as in example 1.
Example 8
This example differs from example 1 only in that the sintering time is 9.5h, and the rest is the same as example 1.
Example 9
This example differs from example 1 only in that the sintering time is 14.5h, and the rest is the same as example 1.
Comparative example 1
This comparative example differs from example 1 only in that the same procedure as in example 1 was used except that yttrium oxide, strontium carbonate and cadmium oxide were not added.
Comparative example 2
This comparative example differs from example 1 only in that the same procedure was used as in example 1, except that 4.86g of zinc oxide, 4.74g of copper oxide and 4.5g of cobalt oxide were added to prepare Na1Fe0.5Mn0.5Zn0.06Cu0.06Co0.06O2.
Comparative example 3
This comparative example differs from example 1 only in that Na1Fe0.5Mn0.5Y0.06O2 was produced, except that only 6.78g of yttrium oxide was added, and the same as in example 1 was used.
Comparative example 4
This comparative example differs from example 1 only in that Na1Fe0.5Mn0.5Sr0.06O2 was produced, except that only 8.88g of strontium carbonate was added, and the same procedure as in example 1 was followed.
Comparative example 5
This comparative example was different from example 1 only in that Na1Fe0.5Mn0.5Cd0.06O2 was produced, except that only 7.68g of cadmium oxide was added, and the same procedure as in example 1 was repeated.
Comparative example 6
This comparative example differs from example 1 only in that Na1Fe0.5Mn0.5Y0.06Sr0.06O2 was produced, except that cadmium oxide was not added, and the remainder was the same as example 1.
Test method
XRD test and multiplying power test are carried out on the positive electrode materials prepared in the examples 1-9 and the comparative examples 1-6, and the testing method of multiplying power test is as follows: mixing the prepared ferro-manganese binary material with conductive carbon black and polyvinylidene fluoride (PVDF) as a binder according to a mass ratio of 85:10:5, mixing, adding N-methyl pyrrolidone (NMP), stirring uniformly, coating on an aluminum foil, placing in an oven for 8 hours, drying at 100 ℃, cutting to obtain a material electrode plate serving as an anode, taking a metal sodium plate as a cathode, taking an electrolyte as a mixed system containing 1M NaPF6 (DEC: EC: FEC)/(volume ratio is 2:3:5), taking glass fiber (Waterman) as a diaphragm, and assembling in a glove box protected by argon (Ar) to form a 2032 button cell. The battery is tested in the voltage range of 2.0-4.0V, and is respectively charged and discharged for 5 weeks at the temperature of 0.1C/0.5C/1C/2C;
Based on the XRD test results, the sodium interlayer spacing d of the positive electrode material was calculated and recorded in table 1, and the rate performance test results are also recorded in table 1.
TABLE 1
The test results can be seen:
(1) As can be seen from examples 1-9 and comparative examples 1-6, the metal ions of the A element, the B element and the C element are doped, and meanwhile, the A element, the B element and the C element have a synergistic effect, so that the interlayer spacing of the iron-manganese material is enlarged, the sodium ion diffusion rate is improved, and the manganese-rich iron-based sodium ion battery anode material with high rate performance is obtained.
(2) It can be seen from examples 1 and 4 that the present invention can further expand the interlayer spacing of the positive electrode material and improve the rate performance by controlling the doping amount of the doping element. When the doping amount of the doping element is low, the doping element entering the matrix is less, and the further expansion of the interlayer spacing is limited; when the doping amount of the doping element is high, the doping position is limited, the matrix is insufficient to accommodate more doping element, and further expansion of the interlayer spacing is limited.
(3) It can be seen from examples 1 and 5 that the doping ratio of the doping element of the present invention has a preferable range, and when the doping amounts of the three elements are within the preferable range, the interlayer spacing is further enlarged, and the rate performance is further improved. When the doping ratio is larger or smaller, the repulsive force between the oxygen of the sodium layer and the supporting force of the doping element on the sodium layer cannot reach the optimal balance, so that the interlayer spacing cannot be effectively enlarged.
(4) As can be seen from examples 1 and examples 6 to 9, the anode material prepared by the invention has small layer spacing difference and further improved rate performance by further controlling the sintering temperature and sintering time. When the sintering time is prolonged or the temperature is increased, oxygen-deficient compounds are formed, so that the doped elements cannot play a role; on the other hand, the specific surface area of the material is reduced due to the excessively high temperature, which is not beneficial to the removal and intercalation of sodium ions; this results in a decrease in the rate capability of the material. When the sintering time is shortened or the temperature is lowered, insufficient reaction may cause insufficient incorporation of doping elements into the material, which may cause degradation of the rate capability of the material.
In conclusion, the manganese-rich iron-based sodium ion battery anode material is doped with metal ions with large particle sizes, and the ions do not participate in electrochemical reaction, but are beneficial to expanding interlayer spacing of the iron-manganese material and improving sodium ion diffusion rate so as to obtain the manganese-rich iron-based sodium ion battery anode material with high rate performance.
The applicant declares that the above is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be apparent to those skilled in the art that any changes or substitutions that are easily conceivable within the technical scope of the present invention disclosed by the present invention fall within the scope of the present invention and the disclosure.
Claims (10)
1. The positive electrode material of the low-cost manganese-rich iron-based sodium ion battery is characterized by having a chemical general formula of Na uFe1-xMnxMyO2, wherein x is more than or equal to 0.98 and less than or equal to 1.05,0.5 and less than or equal to 0.75,0.03 and Y is more than or equal to 0.2, a doping element M comprises an element A, an element B and an element C, wherein the element A comprises Y and/or La, the element B comprises Sr, the element C comprises any one or a combination of at least two of Cd, K, ca and Ba, and the mass ratio of the element A, the element B and the element C is (0.5-2): (1-2): 1;
The interlayer spacing d of the positive electrode material is more than or equal to 5.45A and less than or equal to 5.55A.
2. A method for preparing the positive electrode material according to claim 1, comprising the steps of:
Mixing a ferro-manganese source, a sodium source and a doping agent, and sintering to obtain the anode material;
The dopant comprises a doping element M, wherein the M comprises an A element, a B element and a C element, the A element comprises Y and/or La, the B element comprises Sr, and the C element comprises any one or a combination of at least two of Cd, K, ca and Ba.
3. The method of claim 2, wherein the source of ferro-manganese comprises any one or a combination of at least two of a ferro-manganese hydroxide precursor, a ferro-manganese oxide, or a ferro-manganese carbonate.
4. The preparation method according to claim 2, wherein the mass ratio of the A element, the B element and the C element is (0.5-2): (1-2): 1.
5. The method according to claim 4, wherein the a element includes Y, the B element includes Sr, and the C element includes Cd.
6. The method of claim 2, wherein the sintering temperature is 940-1200 ℃.
7. The method of claim 2, wherein the sintering time is 10 to 14 hours.
8. The method of manufacturing according to claim 2, wherein the atmosphere of sintering comprises an oxygen-containing atmosphere.
9. The method according to claim 2, wherein the temperature rise rate of the sintering is 4 to 5min/°c, and the temperature decrease rate of the sintering is 3 to 5min/°c.
10. A sodium ion battery, characterized in that the sodium ion battery comprises the positive electrode material of claim 1, or the positive electrode material prepared by the preparation method of any one of claims 2 to 9.
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