CN117525391A - Polyanion positive electrode material of sodium ion battery and preparation method thereof - Google Patents
Polyanion positive electrode material of sodium ion battery and preparation method thereof Download PDFInfo
- Publication number
- CN117525391A CN117525391A CN202311511667.3A CN202311511667A CN117525391A CN 117525391 A CN117525391 A CN 117525391A CN 202311511667 A CN202311511667 A CN 202311511667A CN 117525391 A CN117525391 A CN 117525391A
- Authority
- CN
- China
- Prior art keywords
- sodium
- potassium
- ruthenium
- source
- doped carbon
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 25
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 25
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 229920000447 polyanionic polymer Polymers 0.000 title claims abstract description 6
- 238000002360 preparation method Methods 0.000 title abstract description 11
- 239000000463 material Substances 0.000 claims abstract description 56
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 49
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 46
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 46
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 41
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 39
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000011591 potassium Substances 0.000 claims abstract description 37
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 37
- BYTVRGSKFNKHHE-UHFFFAOYSA-K sodium;[hydroxy(oxido)phosphoryl] phosphate;iron(2+) Chemical compound [Na+].[Fe+2].OP([O-])(=O)OP([O-])([O-])=O BYTVRGSKFNKHHE-UHFFFAOYSA-K 0.000 claims abstract description 13
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 51
- 239000011734 sodium Substances 0.000 claims description 45
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 32
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 24
- XWQGIDJIEPIQBD-UHFFFAOYSA-J sodium;iron(3+);phosphonato phosphate Chemical compound [Na+].[Fe+3].[O-]P([O-])(=O)OP([O-])([O-])=O XWQGIDJIEPIQBD-UHFFFAOYSA-J 0.000 claims description 23
- 238000003756 stirring Methods 0.000 claims description 23
- 238000000227 grinding Methods 0.000 claims description 19
- 239000011259 mixed solution Substances 0.000 claims description 16
- 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 15
- 229910052708 sodium Inorganic materials 0.000 claims description 15
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 14
- 239000011812 mixed powder Substances 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 229910052742 iron Inorganic materials 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 9
- 229910052698 phosphorus Inorganic materials 0.000 claims description 9
- 239000011574 phosphorus Substances 0.000 claims description 9
- 239000013543 active substance Substances 0.000 claims description 7
- 229910052786 argon Inorganic materials 0.000 claims description 7
- 238000001354 calcination Methods 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- 239000011645 ferric sodium diphosphate Substances 0.000 claims description 7
- 235000019851 ferric sodium diphosphate Nutrition 0.000 claims description 7
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 7
- 238000001291 vacuum drying Methods 0.000 claims description 7
- 239000011261 inert gas Substances 0.000 claims description 6
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 4
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 4
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 4
- 238000003837 high-temperature calcination Methods 0.000 claims description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 230000000630 rising effect Effects 0.000 claims description 4
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 claims description 4
- 238000005245 sintering Methods 0.000 claims description 4
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 4
- 239000004254 Ammonium phosphate Substances 0.000 claims description 2
- 239000005696 Diammonium phosphate Substances 0.000 claims description 2
- 239000005955 Ferric phosphate Substances 0.000 claims description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 2
- 239000004471 Glycine Substances 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 2
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 2
- 229930006000 Sucrose Natural products 0.000 claims description 2
- MCDLETWIOVSGJT-UHFFFAOYSA-N acetic acid;iron Chemical compound [Fe].CC(O)=O.CC(O)=O MCDLETWIOVSGJT-UHFFFAOYSA-N 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 2
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 2
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 2
- 235000010323 ascorbic acid Nutrition 0.000 claims description 2
- 239000011668 ascorbic acid Substances 0.000 claims description 2
- 229960005070 ascorbic acid Drugs 0.000 claims description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- 150000001722 carbon compounds Chemical class 0.000 claims description 2
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 2
- 229940032958 ferric phosphate Drugs 0.000 claims description 2
- 229940062993 ferrous oxalate Drugs 0.000 claims description 2
- 239000008103 glucose Substances 0.000 claims description 2
- OWZIYWAUNZMLRT-UHFFFAOYSA-L iron(2+);oxalate Chemical compound [Fe+2].[O-]C(=O)C([O-])=O OWZIYWAUNZMLRT-UHFFFAOYSA-L 0.000 claims description 2
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 claims description 2
- 229910000399 iron(III) phosphate Inorganic materials 0.000 claims description 2
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 2
- 239000006012 monoammonium phosphate Substances 0.000 claims description 2
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 2
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 2
- 235000011007 phosphoric acid Nutrition 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 235000011181 potassium carbonates Nutrition 0.000 claims description 2
- 239000001103 potassium chloride Substances 0.000 claims description 2
- 235000011164 potassium chloride Nutrition 0.000 claims description 2
- 239000004323 potassium nitrate Substances 0.000 claims description 2
- 235000010333 potassium nitrate Nutrition 0.000 claims description 2
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 2
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 2
- 235000011151 potassium sulphates Nutrition 0.000 claims description 2
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- 239000011780 sodium chloride Substances 0.000 claims description 2
- 235000002639 sodium chloride Nutrition 0.000 claims description 2
- 239000001509 sodium citrate Substances 0.000 claims description 2
- 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 2
- 235000011083 sodium citrates Nutrition 0.000 claims description 2
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 2
- 235000010344 sodium nitrate Nutrition 0.000 claims description 2
- 239000004317 sodium nitrate Substances 0.000 claims description 2
- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical compound [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 claims description 2
- 229940039790 sodium oxalate Drugs 0.000 claims description 2
- 239000001488 sodium phosphate Substances 0.000 claims description 2
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 2
- 235000011008 sodium phosphates Nutrition 0.000 claims description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 2
- 235000011152 sodium sulphate Nutrition 0.000 claims description 2
- 239000005720 sucrose Substances 0.000 claims description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims 6
- 238000010304 firing Methods 0.000 claims 1
- 238000010438 heat treatment Methods 0.000 abstract description 12
- -1 ruthenium ions Chemical class 0.000 abstract description 7
- 239000002245 particle Substances 0.000 abstract description 6
- 239000011247 coating layer Substances 0.000 abstract description 4
- 239000013078 crystal Substances 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 230000007547 defect Effects 0.000 abstract description 2
- 238000009831 deintercalation Methods 0.000 abstract description 2
- 238000009792 diffusion process Methods 0.000 abstract description 2
- 230000002349 favourable effect Effects 0.000 abstract description 2
- 238000009830 intercalation Methods 0.000 abstract description 2
- 230000002687 intercalation Effects 0.000 abstract description 2
- 239000010410 layer Substances 0.000 abstract description 2
- 229910001414 potassium ion Inorganic materials 0.000 abstract description 2
- 230000000087 stabilizing effect Effects 0.000 abstract description 2
- 238000012546 transfer Methods 0.000 abstract description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 20
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 10
- 239000002002 slurry Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 5
- 239000002033 PVDF binder Substances 0.000 description 5
- 239000004743 Polypropylene Substances 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 239000011230 binding agent Substances 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 239000006258 conductive agent Substances 0.000 description 5
- 239000002270 dispersing agent Substances 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- 239000011888 foil Substances 0.000 description 5
- 229910052744 lithium Inorganic materials 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000012982 microporous membrane Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 238000011056 performance test Methods 0.000 description 5
- 229920001155 polypropylene Polymers 0.000 description 5
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 239000010405 anode material Substances 0.000 description 3
- 239000010406 cathode material Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- YFARFNIESOHDHO-UHFFFAOYSA-N [Ru].[K] Chemical compound [Ru].[K] YFARFNIESOHDHO-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
- H01M4/04—Processes of manufacture in general
- H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
-
- 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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
Abstract
The invention discloses a polyanion positive electrode material of a sodium ion battery and a preparation method thereof. Potassium ions and ruthenium ions are doped in the sodium iron pyrophosphate material at the same time, and carbon is coated outside the sodium iron pyrophosphate material. The carbon coating layer is used as a conductive layer to improve the conductivity of the particle surface, and meanwhile, the carbon coating layer can inhibit the growth of crystal grains to obtain particles with smaller particle sizes; moreover, the reducibility of carbon can effectively prevent Fe during the heat treatment 2+ OxidationAnd obtaining the positive electrode material with higher purity. The proper amount of ruthenium doping plays a role in stabilizing the crystal structure of the material and reducing the charge transfer resistance of the material, and the ruthenium doping enables the material to generate lattice defects and is favorable for the deintercalation and intercalation of sodium ions, so that the first discharge capacity and the cycle performance of the material are improved. The doped potassium can increase and shorten the sodium ion diffusion channel of the material, thereby being beneficial to the storage of sodium ions and improving the capacity of the material.
Description
Technical Field
The invention belongs to the technical field of sodium ion battery positive electrode materials, and particularly relates to a sodium ion battery polyanion positive electrode material and a preparation method thereof.
Background
With the widespread use of large lithium batteries, the demand for lithium resources has increased gradually, resulting in a gradual increase in the prices of lithium resources and lithium ion batteries. Therefore, in order to alleviate the problems of reserve and supply of lithium ion battery raw materials, development of a novel energy storage battery system with low cost, long service life and safety is imperative. Compared with the limited lithium resources, the sodium resources are rich, the price is far lower than that of the lithium resources, and the sodium ion battery has a charge-discharge mechanism similar to that of the lithium ion battery, so that the sodium ion battery is expected to replace the lithium ion battery to meet the large-scale energy storage requirement. But face the challenge of being due to Na + Is larger (with Li) + Compared to) higher mass and lower redox potential, and therefore the structural adjustment of sodium ion cells in conventional electrode materials is more difficult, resulting in lower overall energy density. The positive electrode material is a key component of the sodium ion battery, is a main place for storing sodium ions, and has decisive influence on whether the battery is safe and reliable in use, excellent in electrochemical performance and development prospect.
The materials of the iron-based system become a sodium ion battery anode material system with great commercial value due to the characteristics of easily available raw materials and wide sources. The preparation method of the sodium ferric pyrophosphate material is simple and convenient, and has better cycle performance, but the electron conductivity and the ion mobility of the sodium ferric pyrophosphate material are lower than those of other sodium ion positive electrode materials.
Disclosure of Invention
The invention provides a potassium and ruthenium co-doped carbon coated sodium iron pyrophosphate material and a preparation method thereof, aiming at improving the first discharge capacity and the cycle performance of the existing sodium iron pyrophosphate material.
The potassium and ruthenium co-doped carbon coated ferric sodium pyrophosphate material provided by the invention is characterized in that potassium ions and ruthenium ions are doped in the ferric sodium pyrophosphate material at the same time, and carbon is coated outside the ferric sodium pyrophosphate material.
The structural formula of the potassium and ruthenium co-doped carbon coated sodium ferric pyrophosphate material is as follows: na (Na) 4-x K x Fe 3-1.5y Ru y (PO 4 ) 2 P 2 O 7 /C，
In the structural formula, x is more than 0 and less than or equal to 0.4, and y is more than 0 and less than or equal to 0.4.
The potassium and ruthenium co-doped carbon coated sodium ferric pyrophosphate material is prepared by a method comprising the following steps:
(1) Weighing a sodium source, an iron source, a phosphorus source, a potassium source, a ruthenium source and a carbon source according to the molar ratio in the structural formula;
(2) Dissolving a carbon source and an iron source in water, stirring until the carbon source and the iron source are completely dissolved, adding a phosphorus source, a sodium source, a potassium source and a ruthenium source, and stirring to form a mixed solution; adding glycol into the mixed solution, and stirring until gel is formed; vacuum drying the gel, and grinding to obtain mixed powder;
(3) The mixed powder is subjected to low-temperature primary burning in an inert gas atmosphere; taking out the obtained product, grinding again, calcining at high temperature in inert gas atmosphere, and cooling along with a furnace to obtain the potassium and ruthenium co-doped carbon coated sodium ferric pyrophosphate material.
In the step (1) of the method, the sodium source is at least one of sodium oxalate, sodium citrate, sodium carbonate, sodium phosphate, sodium dihydrogen phosphate, sodium chloride, sodium sulfate, sodium nitrate and sodium bicarbonate.
The iron source is at least one of iron powder, ferric phosphate, ferrous oxalate, ferrous acetate and ferric nitrate.
The phosphorus source is at least one of monoammonium phosphate, diammonium phosphate, phosphoric acid and ammonium phosphate.
The ruthenium source is at least one of ruthenium chloride or ruthenium dioxide.
The potassium source is at least one of potassium chloride, potassium nitrate, potassium carbonate and potassium sulfate.
The carbon source is at least one of citric acid, glucose, glycine, sucrose, ascorbic acid and polyvinyl alcohol.
The ratio of the amount of sodium to the amount of potassium, the amount of iron, the amount of ruthenium, the amount of phosphorus, and the amount of carbon compounds in all raw materials may be 4-x: x:3-1.5y: y:4:3-6; wherein x is 0< 0.4, y is 0< 0.4;
in the step (2), a carbon source and an iron source are dissolved in water, and the mixture is stirred at 60-100 ℃ until the mixture is completely dissolved;
adding a phosphorus source and a sodium source, and magnetically stirring for 1-2 hours in a water bath environment at 70-100 ℃ to form a mixed solution;
adding a potassium source, a ruthenium source and ethylene glycol into the mixed solution, and magnetically stirring for 1-3 hours under the oil bath condition of 100-140 ℃ until gel is formed;
in the step (3), the temperature of the low-temperature primary combustion can be 350-400 ℃ and the time can be 3.5-4.5 h;
the high-temperature calcination temperature can be 550-650 ℃ and the high-temperature calcination time can be 10-12 h.
Preferably, the temperature rising rate of the low-temperature primary sintering is 1-5 ℃/min, and the temperature rising rate of the high-temperature sintering is 1-2 ℃/min.
The inert gas may be argon or nitrogen.
The application of the potassium and ruthenium co-doped carbon coated sodium ferric pyrophosphate material in sodium ion batteries also belongs to the protection scope of the invention.
In the application, the potassium and ruthenium co-doped carbon coated sodium ferric pyrophosphate material is used as a polyanion positive electrode material of a sodium ion battery.
The invention also provides a sodium ion battery, which takes the potassium and ruthenium co-doped carbon coated ferric sodium pyrophosphate material as an anode active substance.
Compared with the prior art, the invention has the beneficial effects that:
1. the carbon coating layer can be used as a conductive layer to improve the conductivity of the particle surface, and meanwhile, the carbon coating layer can inhibit the growth of crystal grains to obtain particles with smaller particle sizes; moreover, the reducibility of carbon can effectively prevent Fe during the heat treatment 2+ Oxidizing to obtain the positive electrode material with higher purity.
2. The proper amount of ruthenium doping plays a role in stabilizing the crystal structure of the material and reducing the charge transfer resistance of the material, and the ruthenium doping enables the material to generate lattice defects and is favorable for the deintercalation and intercalation of sodium ions, so that the first discharge capacity and the cycle performance of the material are improved. And the doped potassium can increase and shorten the sodium ion diffusion channel of the material, thereby being beneficial to the storage of sodium ions and improving the capacity of the material.
Drawings
FIG. 1 shows a positive electrode material Na prepared in example 1 of the present invention 3.8 K 0.2 Fe 2.7 Ru 0.2 (PO 4 ) 2 P 2 O 7 SEM image of/C.
FIG. 2 shows the positive electrode materials Na prepared in comparative examples 1, 2 and 3 of the present invention 4-x K x Fe 3 (PO 4 ) 2 P 2 O 7 First-turn charge-discharge plot of/C (x= 0,0.2,0.4).
FIG. 3 shows the positive electrode material Na prepared in comparative example 2, example 1, example 2 of the present invention 3.8 K 0.2 Fe 3-1.5y Ru y (PO 4 ) 2 P 2 O 7 First-turn charge-discharge plot of/C (y= 0,0.2,0.4).
Detailed Description
The following detailed description of the invention is provided in connection with the accompanying drawings that are presented to illustrate the invention and not to limit the scope thereof. The examples provided below are intended as guidelines for further modifications by one of ordinary skill in the art and are not to be construed as limiting the invention in any way.
The experimental methods in the following examples, unless otherwise specified, are conventional methods, and are carried out according to techniques or conditions described in the literature in the field or according to the product specifications. Materials, reagents and the like used in the examples described below are commercially available unless otherwise specified.
Comparative example 1, preparation of Na 4 Fe 3 (PO 4 ) 2 P 2 O 7 Material/C
According to Na: fe: p: citric acid = 4:3:4:4.5 molar ratio 0.04mol Na 2 CO 3 0.06mol of iron powder, 0.08mol of H 3 PO 4 0.09mol of citric acid, and then 0.06mol of ethylene glycol is weighed; dissolving citric acid and iron powder in water, stirring at 80deg.C until completely dissolved, and adding H 3 PO 4 And Na (Na) 2 CO 3 Magnetically stirring for 2 hours in a water bath environment at 80 ℃ to form a mixed solution; adding glycol into the mixed solution, and magnetically stirring for 1h under the oil bath condition of 120 ℃ until gel is formed; vacuum drying the gel and grinding to obtain mixed powder; heating the mixed powder to 350 ℃ at a speed of 2 ℃/min in a tube furnace filled with nitrogen, and performing low-temperature primary burning for 4.5 hours; taking out the obtained product, grinding the product again uniformly, heating the product to 600 ℃ in a tube furnace filled with nitrogen at a speed of 2 ℃/min, calcining the product for 12 hours at a high temperature, cooling the product along with the furnace, and grinding the product to obtain the carbon-coated sodium ferric pyrophosphate cathode material.
The prepared carbon-coated sodium ferric pyrophosphate positive electrode material is used as an active substance, SP is used as a conductive agent, PVDF is used as a binder, N-methyl-2-pyrrolidone (NMP) is used as a dispersing agent, and the following positive electrode materials are prepared: SP: pvdf=8: 1: mixing the slurry according to the mass ratio of 1, and coating the slurry on an aluminum foil to prepare the positive plate. Then NaClO with metal sodium sheet as negative electrode, polypropylene microporous membrane as diaphragm and 1mol/L 4 As an electrolyte, a CR2032 type battery was fabricated in a glove box filled with argon.
The assembled battery is subjected to charge-discharge cycle performance test at room temperature, the voltage range is 1.5-4.0V, and the first charge-discharge curve is shown in figure 2. The first charge capacity of the material at 0.1C is 73.2mAh/g, and the first discharge capacity is 72.9mAh/g.
Comparative example 2 preparation of Na 3.8 K 0.2 Fe 3 (PO 4 ) 2 P 2 O 7 Material/C
According to Na: k: fe: p: citric acid = 3.8:0.2:3:4:4.5 molar ratio 0.038mol Na 2 CO 3 、0.002mol K 2 CO 3 0.06mol of iron powder, 0.08mol of H 3 PO 4 0.09mol of citric acid, and then 0.06mol of ethylene glycol is weighed; dissolving citric acid and iron powder in water, stirring at 80deg.C until completely dissolved, and adding H 3 PO 4 、K 2 CO 3 And Na (Na) 2 CO 3 Magnetically stirring for 2 hours in a water bath environment at 80 ℃ to form a mixed solution; adding glycol into the mixed solution, and magnetically stirring for 1h under the oil bath condition of 120 ℃ until gel is formed; vacuum drying the gel and grinding to obtain mixed powder; heating the mixed powder to 350 ℃ at a speed of 2 ℃/min in a tube furnace filled with nitrogen, and performing low-temperature primary burning for 4.5 hours; taking out the obtained product, grinding the product again uniformly, heating the product to 600 ℃ in a tube furnace filled with nitrogen at a speed of 2 ℃/min, calcining the product for 12 hours at a high temperature, cooling the product along with the furnace, and grinding the product to obtain the potassium-doped carbon-coated sodium ferric pyrophosphate cathode material.
The prepared positive electrode material is taken as an active substance, SP is taken as a conductive agent, PVDF is taken as a binder, N-methyl-2-pyrrolidone (NMP) is taken as a dispersing agent, and the positive electrode material is prepared by the following steps: SP: pvdf=8: 1: mixing the slurry according to the mass ratio of 1, and coating the slurry on an aluminum foil to prepare the positive plate. Then NaClO with metal sodium sheet as negative electrode, polypropylene microporous membrane as diaphragm and 1mol/L 4 As an electrolyte, a CR2032 type battery was fabricated in a glove box filled with argon.
The assembled battery is subjected to charge-discharge cycle performance test at room temperature, the voltage range is 1.5-4.0V, and the first charge-discharge curve is shown in figure 2. The first charge capacity of the material at 0.1C is 95.6mAh/g, the first discharge capacity is 79.9mAh/g, and the first discharge capacity and the capacity retention rate after potassium doping are improved.
Comparative example3. Preparation of Na 3.6 K 0.4 Fe 3 (PO 4 ) 2 P 2 O 7 Material/C
According to Na: k: fe: p: citric acid = 3.6:0.4:3:4:4.5 molar ratio 0.036mol Na 2 CO 3 、0.004mol K 2 CO 3 0.06mol of iron powder, 0.08mol of H 3 PO 4 0.09mol of citric acid, and then 0.06mol of ethylene glycol is weighed; dissolving citric acid and iron powder in water, stirring at 80deg.C until completely dissolved, and adding H 3 PO 4 、K 2 CO 3 And Na (Na) 2 CO 3 Magnetically stirring for 2 hours in a water bath environment at 80 ℃ to form a mixed solution; subsequently adding glycol into the mixed solution, magnetically stirring for 1h under the oil bath condition of 120 ℃ until gel is formed; vacuum drying the gel and grinding to obtain mixed powder; heating the mixed powder to 350 ℃ at a speed of 2 ℃/min in a tube furnace filled with nitrogen, and performing low-temperature primary burning for 4.5 hours; taking out the obtained product, grinding the product again uniformly, heating the product to 600 ℃ in a tube furnace filled with nitrogen at a speed of 2 ℃/min, calcining the product for 12 hours at a high temperature, cooling the product along with the furnace, and grinding the product to obtain the potassium-doped carbon-coated sodium ferric pyrophosphate cathode material.
The prepared positive electrode material is taken as an active substance, SP is taken as a conductive agent, PVDF is taken as a binder, N-methyl-2-pyrrolidone (NMP) is taken as a dispersing agent, and the positive electrode material is prepared by the following steps: SP: pvdf=8: 1: mixing the slurry according to the mass ratio of 1, and coating the slurry on an aluminum foil to prepare the positive plate. Then NaClO with metal sodium sheet as negative electrode, polypropylene microporous membrane as diaphragm and 1mol/L 4 As an electrolyte, a CR2032 type battery was fabricated in a glove box filled with argon.
The assembled battery is subjected to charge-discharge cycle performance test at room temperature, the voltage range is 1.5-4.0V, and the first charge-discharge curve is shown in figure 2. The first charge capacity of the material at 0.1C is 84.2mAh/g, and the first discharge capacity is 75.4mAh/g. As is clear from comparison with comparative example 2, increasing the doping amount of K in a proper amount effectively improves the first discharge capacity and the capacity retention.
Example 1 preparation of Na 3.8 K 0.2 Fe 2.7 Ru 0.2 (PO 4 ) 2 P 2 O 7 Material/C
According to Na: k: fe: ru: p: citric acid = 3.8:0.2:2.7:0.2:4:4.5 molar ratio 0.038mol Na 2 CO 3 、0.02mol K 2 CO 3 0.054mol of iron powder, 0.004mol of RuCl 3 、0.08mol H 3 PO 4 0.09mol of citric acid, and then 0.06mol of ethylene glycol is weighed; dissolving citric acid and iron powder in water, stirring at 80deg.C until completely dissolved, and adding H 3 PO 4 、K 2 CO 3 、Na 2 CO 3 And RuCl 3 Magnetically stirring for 2 hours in a water bath environment at 80 ℃ to form a mixed solution; adding glycol into the mixed solution, and magnetically stirring for 1h under the oil bath condition of 120 ℃ until gel is formed; vacuum drying the gel and grinding to obtain mixed powder; heating the mixed powder to 350 ℃ at a speed of 2 ℃/min in a tube furnace filled with nitrogen, and performing low-temperature primary burning for 4.5 hours; taking out the obtained product, grinding the product again uniformly, heating the product to 600 ℃ in a tube furnace filled with nitrogen at a speed of 2 ℃/min, calcining the product for 12 hours at a high temperature, cooling the product along with the furnace, and grinding the product to obtain the potassium and ruthenium co-doped carbon coated sodium ferric pyrophosphate anode material. FIG. 1 shows Na of the prepared potassium-ruthenium co-doped carbon-coated sodium iron pyrophosphate positive electrode material 3.8 K 0.2 Fe 2.7 Ru 0.2 (PO 4 ) 2 P 2 O 7 SEM image of/C.
The prepared positive electrode material is taken as an active substance, SP is taken as a conductive agent, PVDF is taken as a binder, N-methyl-2-pyrrolidone (NMP) is taken as a dispersing agent, and the positive electrode material is prepared by the following steps: SP: pvdf=8: 1: mixing the slurry according to the mass ratio of 1, and coating the slurry on an aluminum foil to prepare the positive plate. Then NaClO with metal sodium sheet as negative electrode, polypropylene microporous membrane as diaphragm and 1mol/L 4 As an electrolyte, a CR2032 type battery was fabricated in a glove box filled with argon.
The assembled battery is subjected to charge-discharge cycle performance test at room temperature, the voltage range is 1.5-4.0V, and the first charge-discharge curve is shown in figure 3. The first charge capacity of the material at 0.1C is 101.4mAh/g, the first discharge capacity is 93.4mAh/g, and the first-cycle charge-discharge specific capacity of the material can be greatly improved by co-doping potassium and ruthenium.
EXAMPLE 2 preparation of Na 3.8 K 0.2 Fe 2.4 Ru 0.4 (PO 4 ) 2 P 2 O 7 Material/C
According to Na: k: fe: ru: p: citric acid = 3.8:0.2:2.4:0.4:4:4.5 molar ratio 0.038mol Na 2 CO 3 、0.002mol K 2 CO 3 0.048mol of iron powder, 0.008mol of RuCl 3 、0.08mol H 3 PO 4 0.09mol of citric acid, and then 0.06mol of ethylene glycol is weighed; dissolving citric acid and iron powder in water, stirring at 80deg.C until completely dissolved, and adding H 3 PO 4 、K 2 CO 3 、Na 2 CO 3 And RuCl 3 Magnetically stirring for 2 hours in a water bath environment at 80 ℃ to form a mixed solution; adding glycol into the mixed solution, and magnetically stirring for 1h under the oil bath condition of 120 ℃ until gel is formed; vacuum drying the gel and grinding to obtain mixed powder; heating the mixed powder to 350 ℃ at a speed of 2 ℃/min in a tube furnace filled with nitrogen, and performing low-temperature primary burning for 4.5 hours; taking out the obtained product, grinding the product again uniformly, heating the product to 600 ℃ in a tube furnace filled with nitrogen at a speed of 2 ℃/min, calcining the product for 12 hours at a high temperature, cooling the product along with the furnace, and grinding the product to obtain the potassium and ruthenium co-doped carbon coated sodium ferric pyrophosphate anode material.
The prepared positive electrode material is taken as an active substance, SP is taken as a conductive agent, PVDF is taken as a binder, N-methyl-2-pyrrolidone (NMP) is taken as a dispersing agent, and the positive electrode material is prepared by the following steps: SP: pvdf=8: 1: mixing the slurry according to the mass ratio of 1, and coating the slurry on an aluminum foil to prepare the positive plate. Then NaClO with metal sodium sheet as negative electrode, polypropylene microporous membrane as diaphragm and 1mol/L 4 As an electrolyte, a CR2032 type battery was fabricated in a glove box filled with argon.
The assembled battery is subjected to charge-discharge cycle performance test at room temperature, the voltage range is 1.5-4.0V, and the first charge-discharge curve is shown in figure 3. The first charge capacity of the material at 0.1C is 92.9mAh/g, the first discharge capacity is 85.8mAh/g, and the capacity is reduced compared with that of the material in example 1, which shows that the charging and discharging specific capacity of the material can be improved by doping a proper amount of ruthenium.
The present invention is described in detail above. It will be apparent to those skilled in the art that the present invention can be practiced in a wide range of equivalent parameters, concentrations, and conditions without departing from the spirit and scope of the invention and without undue experimentation. While the invention has been described with respect to specific embodiments, it will be appreciated that the invention may be further modified. In general, this application is intended to cover any variations, uses, or adaptations of the invention following, in general, the principles of the invention and including such departures from the present disclosure as come within known or customary practice within the art to which the invention pertains.
Claims (10)
1. A potassium and ruthenium co-doped carbon coated sodium ferric pyrophosphate material has a structural formula: na (Na) 4-x K x Fe 3-1.5y Ru y (PO 4 ) 2 P 2 O 7 C, wherein 0<x≤0.4，0<y≤0.4。
2. A method for preparing the potassium and ruthenium co-doped carbon coated sodium iron pyrophosphate material of claim 1, comprising the steps of:
(1) Weighing a sodium source, an iron source, a phosphorus source, a potassium source, a ruthenium source and a carbon source according to the molar ratio in the structural formula;
(2) Dissolving a carbon source and an iron source in water, stirring until the carbon source and the iron source are completely dissolved, adding a phosphorus source, a sodium source, a potassium source and a ruthenium source, and stirring to form a mixed solution; adding glycol into the mixed solution, and stirring until gel is formed; vacuum drying the gel, and grinding to obtain mixed powder;
(3) The mixed powder is subjected to low-temperature primary burning in an inert gas atmosphere; taking out the obtained product, grinding again, calcining at high temperature in inert gas atmosphere, and cooling along with a furnace to obtain the potassium and ruthenium co-doped carbon coated sodium ferric pyrophosphate material.
3. The method for preparing the potassium and ruthenium co-doped carbon coated sodium iron pyrophosphate material according to claim 2, which is characterized in that: in the step (1), the sodium source is at least one of sodium oxalate, sodium citrate, sodium carbonate, sodium phosphate, sodium dihydrogen phosphate, sodium chloride, sodium sulfate, sodium nitrate and sodium bicarbonate;
the iron source is at least one of iron powder, ferric phosphate, ferrous oxalate, ferrous acetate and ferric nitrate;
the phosphorus source is at least one of monoammonium phosphate, diammonium phosphate, phosphoric acid and ammonium phosphate;
the ruthenium source is at least one of ruthenium chloride or ruthenium dioxide;
the potassium source is at least one of potassium chloride, potassium nitrate, potassium carbonate and potassium sulfate;
the carbon source is at least one of citric acid, glucose, glycine, sucrose, ascorbic acid and polyvinyl alcohol.
4. The method for preparing the potassium and ruthenium co-doped carbon coated sodium iron pyrophosphate material according to claim 2, which is characterized in that: in all the raw materials, the ratio of the amount of sodium substance to the amount of potassium substance, the amount of iron substance, the amount of ruthenium substance, the amount of phosphorus substance and the amount of carbon compound substance is in turn 4-x: x:3-1.5y: y:4:3-6; wherein x is 0< 0.4 and y is 0< 0.4.
5. The method for preparing the potassium and ruthenium co-doped carbon coated sodium iron pyrophosphate material according to claim 2, which is characterized in that: in the step (3), the low-temperature initial firing temperature is 350-400 ℃ and the time is 3.5-4.5 h.
6. The method for preparing the potassium and ruthenium co-doped carbon coated sodium iron pyrophosphate material according to claim 2, which is characterized in that: the high-temperature calcination temperature is 550-650 ℃ and the high-temperature calcination time is 10-12 h.
7. The method for preparing the potassium and ruthenium co-doped carbon coated sodium iron pyrophosphate material according to claim 2, which is characterized in that: the temperature rising rate of the low-temperature primary sintering is 1-5 ℃/min, and the temperature rising rate of the high-temperature sintering is 1-2 ℃/min;
the inert gas is argon or nitrogen.
8. Use of the potassium, ruthenium co-doped carbon coated sodium iron pyrophosphate material of claim 1 or prepared by the method for preparing the potassium, ruthenium co-doped carbon coated sodium iron pyrophosphate material of claims 2-7 in sodium ion batteries.
9. The use according to claim 8, characterized in that: in the application, the potassium and ruthenium co-doped carbon coated sodium ferric pyrophosphate material is used as a polyanion positive electrode material of a sodium ion battery.
10. A sodium ion battery characterized by: the sodium ion battery takes the potassium and ruthenium co-doped carbon-coated ferric sodium pyrophosphate material as claimed in claim 1 or the potassium and ruthenium co-doped carbon-coated ferric sodium pyrophosphate material prepared by the method for preparing the potassium and ruthenium co-doped carbon-coated ferric sodium pyrophosphate material as claimed in claims 2-7 as an anode active substance.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311511667.3A CN117525391A (en) | 2023-11-14 | 2023-11-14 | Polyanion positive electrode material of sodium ion battery and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311511667.3A CN117525391A (en) | 2023-11-14 | 2023-11-14 | Polyanion positive electrode material of sodium ion battery and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117525391A true CN117525391A (en) | 2024-02-06 |
Family
ID=89760188
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311511667.3A Pending CN117525391A (en) | 2023-11-14 | 2023-11-14 | Polyanion positive electrode material of sodium ion battery and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117525391A (en) |
-
2023
- 2023-11-14 CN CN202311511667.3A patent/CN117525391A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108046231B (en) | Sodium ion battery positive electrode material and preparation method thereof | |
| CN103956485B (en) | Lithium iron phosphate electrode material of a kind of three-dimensional hierarchical structure and preparation method thereof | |
| CN111180709B (en) | Carbon nano tube and metal copper co-doped ferrous oxalate lithium battery composite negative electrode material and preparation method thereof | |
| CN113659141B (en) | SiO@Mg/C composite material and preparation method and application thereof | |
| CN111162256A (en) | Mixed polyanion type sodium ion battery positive electrode material and preparation thereof | |
| CN113929069B (en) | Manganese-rich phosphate positive electrode material and preparation method and application thereof | |
| CN111029560A (en) | Spinel structure positive active material doped with sodium ions in gradient manner and preparation method thereof | |
| CN113651303A (en) | Preparation method of nano flaky iron phosphate and LiFePO prepared by using same4Positive electrode active material/C | |
| CN114512649A (en) | Composite lithium manganese iron phosphate cathode material, preparation method and application thereof | |
| CN115642257A (en) | Lithium supplement agent, preparation method thereof, positive electrode material and lithium ion battery | |
| CN114975990A (en) | Lithium manganese iron phosphate-based positive electrode material, positive electrode, lithium ion battery and preparation method | |
| CN115064665A (en) | Doped modified carbon-coated sodium titanium phosphate composite material and preparation method and application thereof | |
| CN110649263A (en) | Nickel-ion battery lithium vanadium phosphate positive electrode material, sol-gel preparation method and application | |
| CN114094089A (en) | Positive electrode lithium supplement additive, preparation thereof and application thereof in lithium supplement of positive electrode of lithium ion battery | |
| CN107834054B (en) | Preparation method of lithium nickel manganese oxide-graphene composite material for lithium ion battery | |
| CN108172813B (en) | Composite cathode material and preparation method thereof | |
| CN116682946A (en) | Doped modified ferric sodium pyrophosphate positive electrode material and preparation method thereof | |
| CN114249312B (en) | Rod-shaped sodium ion positive electrode material and preparation method and application thereof | |
| CN115275168A (en) | High-rate lithium ion battery negative electrode material and preparation method thereof | |
| CN112072084B (en) | Composite electrode material and preparation method and application thereof | |
| CN104332628A (en) | Preparation method and lithium ion battery of lithium ion battery positive material | |
| CN113991103A (en) | Aqueous lithium ion battery NaTi2(PO4)3Preparation method of/C negative electrode material | |
| CN113764671A (en) | Anode material of lithium ion battery | |
| CN117525391A (en) | Polyanion positive electrode material of sodium ion battery and preparation method thereof | |
| CN117438554B (en) | High-first-efficiency silicon oxide negative electrode material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |