CN115101738A - Carbon-coated iron-vanadium bimetallic sodium pyrophosphate phosphate composite material and preparation method and application thereof - Google Patents
Carbon-coated iron-vanadium bimetallic sodium pyrophosphate phosphate composite material and preparation method and application thereof Download PDFInfo
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- CN115101738A CN115101738A CN202210876996.7A CN202210876996A CN115101738A CN 115101738 A CN115101738 A CN 115101738A CN 202210876996 A CN202210876996 A CN 202210876996A CN 115101738 A CN115101738 A CN 115101738A
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- 239000002131 composite material Substances 0.000 title claims abstract description 77
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 48
- PNXOJQQRXBVKEX-UHFFFAOYSA-N iron vanadium Chemical compound [V].[Fe] PNXOJQQRXBVKEX-UHFFFAOYSA-N 0.000 title claims abstract description 34
- PZQNFVCVNORNPG-UHFFFAOYSA-M [Na+].OP(O)([O-])=O.OP(O)(=O)OP(O)(O)=O Chemical compound [Na+].OP(O)([O-])=O.OP(O)(=O)OP(O)(O)=O PZQNFVCVNORNPG-UHFFFAOYSA-M 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000011248 coating agent Substances 0.000 claims abstract description 6
- 238000000576 coating method Methods 0.000 claims abstract description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 50
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 42
- 238000010438 heat treatment Methods 0.000 claims description 34
- 239000011734 sodium Substances 0.000 claims description 32
- 239000002243 precursor Substances 0.000 claims description 26
- 229910052720 vanadium Inorganic materials 0.000 claims description 16
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 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
- 238000000498 ball milling Methods 0.000 claims description 15
- 238000005245 sintering Methods 0.000 claims description 15
- 229910052708 sodium Inorganic materials 0.000 claims description 15
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 claims description 15
- 229940048086 sodium pyrophosphate Drugs 0.000 claims description 15
- 235000019818 tetrasodium diphosphate Nutrition 0.000 claims description 15
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims description 15
- 229910052742 iron Inorganic materials 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 13
- 229910052698 phosphorus Inorganic materials 0.000 claims description 13
- 239000011574 phosphorus Substances 0.000 claims description 13
- 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 12
- 238000004108 freeze drying Methods 0.000 claims description 12
- 239000008103 glucose Substances 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 11
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 11
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 11
- 229940062993 ferrous oxalate Drugs 0.000 claims description 11
- OWZIYWAUNZMLRT-UHFFFAOYSA-L iron(2+);oxalate Chemical compound [Fe+2].[O-]C(=O)C([O-])=O OWZIYWAUNZMLRT-UHFFFAOYSA-L 0.000 claims description 11
- OGUCKKLSDGRKSH-UHFFFAOYSA-N oxalic acid oxovanadium Chemical compound [V].[O].C(C(=O)O)(=O)O OGUCKKLSDGRKSH-UHFFFAOYSA-N 0.000 claims description 11
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 10
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 7
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 239000008139 complexing agent Substances 0.000 claims description 6
- 239000007774 positive electrode material Substances 0.000 claims description 5
- 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
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 4
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 3
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 3
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 3
- 239000011790 ferrous sulphate Substances 0.000 claims description 3
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 3
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 3
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 229940010514 ammonium ferrous sulfate Drugs 0.000 claims description 2
- 239000011668 ascorbic acid Substances 0.000 claims description 2
- 235000010323 ascorbic acid Nutrition 0.000 claims description 2
- 229960005070 ascorbic acid Drugs 0.000 claims description 2
- 239000012298 atmosphere Substances 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
- 235000015165 citric acid Nutrition 0.000 claims description 2
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 claims description 2
- 235000019820 disodium diphosphate Nutrition 0.000 claims description 2
- GYQBBRRVRKFJRG-UHFFFAOYSA-L disodium pyrophosphate Chemical compound [Na+].[Na+].OP([O-])(=O)OP(O)([O-])=O GYQBBRRVRKFJRG-UHFFFAOYSA-L 0.000 claims description 2
- IMBKASBLAKCLEM-UHFFFAOYSA-L ferrous ammonium sulfate (anhydrous) Chemical compound [NH4+].[NH4+].[Fe+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O IMBKASBLAKCLEM-UHFFFAOYSA-L 0.000 claims description 2
- 229960001781 ferrous sulfate Drugs 0.000 claims description 2
- 235000001727 glucose Nutrition 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 229940005657 pyrophosphoric acid Drugs 0.000 claims description 2
- 229940001593 sodium carbonate Drugs 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
- 229960001790 sodium citrate Drugs 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
- 229910001415 sodium ion Inorganic materials 0.000 abstract description 19
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 abstract description 14
- 238000009792 diffusion process Methods 0.000 abstract description 8
- 230000009286 beneficial effect Effects 0.000 abstract description 4
- 230000005540 biological transmission Effects 0.000 abstract description 4
- 239000010405 anode material Substances 0.000 abstract description 3
- 230000001351 cycling effect Effects 0.000 abstract description 3
- 230000002349 favourable effect Effects 0.000 abstract description 3
- 239000011247 coating layer Substances 0.000 abstract 1
- 239000008187 granular material Substances 0.000 abstract 1
- 239000010410 layer Substances 0.000 abstract 1
- 238000001308 synthesis method Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 15
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 239000012300 argon atmosphere Substances 0.000 description 10
- 238000001816 cooling Methods 0.000 description 10
- 239000013078 crystal Substances 0.000 description 10
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 6
- 239000000084 colloidal system Substances 0.000 description 6
- 239000011645 ferric sodium diphosphate Substances 0.000 description 6
- 235000019851 ferric sodium diphosphate Nutrition 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 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 description 6
- 238000007599 discharging Methods 0.000 description 5
- 239000011149 active material Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 230000007547 defect Effects 0.000 description 3
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 description 3
- 235000011180 diphosphates Nutrition 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 229940048084 pyrophosphate Drugs 0.000 description 3
- -1 vanadium sodium pyrophosphate Chemical compound 0.000 description 3
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910001448 ferrous ion Inorganic materials 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000010416 ion conductor Substances 0.000 description 2
- 229910021506 iron(II) hydroxide Inorganic materials 0.000 description 2
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000009827 uniform distribution Methods 0.000 description 2
- 229910001456 vanadium ion Inorganic materials 0.000 description 2
- 229910001935 vanadium oxide Inorganic materials 0.000 description 2
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- 229910000628 Ferrovanadium Inorganic materials 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229960004887 ferric hydroxide Drugs 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 238000004770 highest occupied molecular orbital Methods 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000004776 molecular orbital Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 235000011837 pasties Nutrition 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- 229920000447 polyanionic polymer Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/38—Condensed phosphates
- C01B25/42—Pyrophosphates
- C01B25/425—Pyrophosphates of alkali metals
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/45—Phosphates containing plural metal, or metal and ammonium
- C01B25/451—Phosphates containing plural metal, or metal and ammonium containing metal and ammonium
-
- 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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
Abstract
The invention relates to the technical field of sodium ion batteries, in particular to a carbon-coated iron-vanadium bimetallic sodium pyrophosphate phosphate composite material and a preparation method and application thereof 4 Fe 1.5‑1.5x V 1+x (PO 4 ) 2 P 2 O 7 Granules anda composite material formed by a surface carbon coating layer; the grain diameter is 100 nm-2 μm, the carbon content is 3% -10%, and the thickness of the carbon layer is 3-15 nm. The iron-vanadium bimetallic sodium pyrophosphate phosphate composite material is favorable for accelerating the diffusion rate of sodium ions, and the carbon coating is favorable for improving the electron transmission rate. The synthesis method is simple, the conditions are mild, the yield is high, and the prepared composite material has high specific capacity, high working voltage and excellent cycling stability when being used as a sodium ion anode material, and is beneficial to industrial large-scale popularization.
Description
Technical Field
The invention relates to the technical field of sodium ion batteries, in particular to a carbon-coated iron-vanadium bimetallic sodium pyrophosphate phosphate composite material as well as a preparation method and application thereof.
Background
The sodium ion battery is considered to be an ideal large-scale energy storage application technology due to abundant sodium resource storage and environmental friendliness; the large size of sodium ions leads to the relative difficulty in embedding and diffusion in the anode material, and the structural change of the embedded material is larger, so that the specific capacity, the dynamic performance, the cycle performance and the like of the electrode material are correspondingly deteriorated, and the sodium ion battery with high capacity, long cycle and high stability is constructed and a simple and efficient preparation process is researched and developed, which is required by researchers.
Therefore, taking phosphate and pyrophosphate as an example, it contains special pyrophosphate and phosphate units with strong covalent bond, and the relative separation of valence electrons and polyanion, and this special three-dimensional framework structure, accompanied by multiple electron mechanism, the energy transition between the highest occupied molecular orbital and the lowest occupied molecular orbital is small, which is very beneficial to the rapid extraction and intercalation of sodium ions, and pyrophosphate material is favored more and more due to abundant cheap iron resource, three-dimensional ion diffusion channel, good safety performance.
Chinese patent CN107195886B discloses a vanadium sodium pyrophosphate @ carbon composite anode material, preparation and application, vanadium oxide coated with a carbon layer in advance is prepared from a vanadium source and a carbon source through hydrothermal and presintering, then ball milling is carried out on the vanadium oxide and a sodium source and a phosphorus source, a microspherical precursor is obtained through spray granulation, the precursor is calcined, washed and dried to obtain carbon-coated vanadium sodium pyrophosphate with a microspherical structure, the discharge capacity of the first ring of the prepared battery is nearly 70mAh/g, and the specific capacity of 50 rings under the 2C multiplying power is more than 60 mAh/g; the rate performance and cycling stability of the battery have yet to be further improved.
Disclosure of Invention
Aiming at the condition that the rate performance and the cycle stability of the existing carbon-coated sodium pyrophosphate ion battery are not ideal enough, the invention provides a carbon-coated iron-vanadium bimetallic sodium pyrophosphate phosphate composite material, and the prepared sodium ion battery has better rate performance and cycle stability; the invention also provides a preparation method of the carbon-coated iron-vanadium bimetallic sodium pyrophosphate phosphate composite material, and the sodium ion battery prepared from the iron-vanadium bimetallic sodium pyrophosphate phosphate composite material has excellent rate performance and cycle stability; the invention also provides a positive electrode material prepared from the carbon-coated iron-vanadium bimetallic sodium pyrophosphate phosphate composite material, and the sodium ion battery prepared from the positive electrode material has better rate capability and cycling stability.
The invention is realized by the following technical scheme:
a carbon-coated Fe-V bimetal sodium pyrophosphate phosphate composite material is prepared from Fe-V bimetal sodium pyrophosphate Na 4 Fe 1.5-1.5x V 1+x (PO 4 ) 2 P 2 O 7 Composite material formed by particles and surface carbon coating; -1<x<1；
The particle size of the composite material is 100 nm-2 mu m, the carbon content is 3% -10%, and the thickness of the carbon layer is 3-15 nm.
The vanadium is added with iron to form the bimetallic sodium pyrophosphate phosphate composite material, the crystal structure defect of a local area is made in the doping process, a sodium ion diffusion channel is widened, the diffusion rate of sodium ions is accelerated, the electron transmission rate is improved by carbon coating, the cycle stability and the multiplying power performance of the sodium ion battery prepared in such a way are remarkably improved, the sufficient dispersibility of the composite material is maintained by the micron-sized and submicron-sized particle sizes, and the sodium ion diffusion path is shortened.
A preparation method of a carbon-coated iron-vanadium bimetallic sodium pyrophosphate phosphate composite material comprises the following steps:
s1, sequentially adding a sodium source, an iron source, a vanadium source, a phosphorus source and a complexing agent into an ethanol solution, uniformly stirring, ultrasonically dispersing, mechanically ball-milling, and freeze-drying to obtain a precursor;
and S2, placing the precursor in an inert atmosphere, preheating, heating and sintering to obtain the carbon-coated iron-vanadium bimetallic sodium pyrophosphate phosphate composite material.
Preferably, in step S1, the sodium source includes at least one of disodium dihydrogen pyrophosphate, sodium carbonate, sodium oxalate, and sodium citrate;
the iron source comprises at least one of ferrous oxalate, ferrous sulfate and ammonium ferrous sulfate;
the vanadium source comprises at least one of vanadyl oxalate, ammonium metavanadate and vanadium pentoxide;
the phosphorus source comprises at least one of ammonium dihydrogen phosphate, diammonium hydrogen phosphate, pyrophosphoric acid and sodium pyrophosphate;
the complexing agent is at least one of citric acid, glucose, oxalic acid or ascorbic acid, and is a carbon source.
Preferably, in step S1, all raw materials are sufficiently dispersed and stirred to promote the reaction to form the required sodium pyrophosphate doped with iron and vanadium uniformly, so as to keep the battery performance of the composite material stable.
Preferably, in step S1, the volume ratio of ethanol to deionized water in the ethanol solution is 1: 2-3; the solid-to-liquid ratio of the sodium source, the iron source, the vanadium source, the phosphorus source, the complexing agent and the dispersing solvent is 100-300 g/L.
The ethanol can effectively reduce ferrous hydroxide colloid generated by hydrolysis of ferrous ions in the solution and further oxidize the ferrous hydroxide colloid into ferric hydroxide colloid, the ultrasonic ball milling process is favorable for uniform mixing of the ferrous ions and vanadium ions, the crystal defects are favorably and uniformly distributed, and the excellent electrochemical performance of the obtained composite material is ensured.
Preferably, in step S1, the molar ratio of sodium element, iron element, vanadium element and phosphorus element in the sodium source, iron source, vanadium source and phosphorus source is 4.0 to 4.2: 1.5-1.5 x: 1+ x: 3.9 to 4.1.
Preferably, in step S1, the freeze-drying is carried out at-40 to-20 ℃ for 2 to 10 hours. Preferably, in step S2, the temperature is increased to 300-400 ℃ at a rate of 3-10 ℃/min for preheating for 2-5 h, and then increased to 500-650 ℃ at a rate of 3-10 ℃/min for sintering for 3-10 h, so as to obtain the carbon-coated iron-vanadium bimetallic sodium pyrophosphate phosphate composite material.
A positive electrode material prepared from the composite material or the composite material prepared by the preparation method.
A positive plate prepared from the composite material or the composite material prepared by the preparation method.
A battery prepared by using the composite material or the positive plate prepared by the preparation method.
The invention has the beneficial effects that:
(1) the carbon-coated iron-vanadium bimetallic composite material has the advantages of increasing the uniform distribution of crystal structure defects by utilizing ferrovanadium doping, along with micron and submicron particles, short sodium ion diffusion distance, high transmission rate, high specific surface area, high conductivity, high ion transmission speed and the like, moderate voltage, stable platform, and excellent battery rate performance and cycle stability.
(2) In the preparation process, ethanol and water are mixed as a dispersing solvent, and vanadium and iron ions are fully mixed by an ultrasonic ball milling dispersing means, so that the fast ionic conductor is synthesized in a pure phase, and the fast ionic conductor has the advantages of large specific surface area, high electrochemical activity, higher voltage platform and specific capacity and excellent electrochemical performance.
(3) The carbon wraps the surfaces of the iron-vanadium bimetallic sodium pyrophosphate particles, so that the diffusion rate of sodium ions on the surface interface of the active material is accelerated, the corrosion of electrolyte to an electrolytic material is inhibited, the growth of the active material particles is limited by the coating, the particle size of the active material particles is effectively reduced, the dispersity and the stability are greatly increased, the utilization rate of the active material particles is improved, the active sites are increased, and the electrochemical activity is improved.
(4) The sodium source, the iron source, the vanadium source, the phosphorus source and the carbon source are wide in source and low in price, and the actual production cost can be effectively reduced.
(5) The preparation process is simple, the energy consumption is low, the calcination temperature is low, the production cost is further reduced, and the large-scale industrial popularization is facilitated.
Drawings
FIG. 1 is an SEM photograph of example 1.
Figure 2 is the XRD pattern of example 1.
FIG. 3 is a specific capacity-voltage curve during charging and discharging of the battery made of the composite material of example 1.
Fig. 4 is a graph of the charge and discharge efficiency at 1C rate for 100 cycles of a battery made from the composite material of example 1.
Detailed Description
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein, but rather should be construed as broadly as the present invention is capable of modification in various respects, all without departing from the spirit and scope of the present invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
Example 1
Carbon-coated phosphoric acid ferric sodium pyrophosphate Na 4 Fe 1.5-1.5x V 1+x (PO 4 ) 2 P 2 O 7 The preparation method of the @ C composite material comprises the following steps:
s1, adding 0.03mol of sodium pyrophosphate, 0.045mol of ferrous oxalate, 0.03mol of vanadyl oxalate, 0.06mol of diammonium hydrogen phosphate and 0.5g of glucose into 50mL of alcohol-water in a volume ratio of 1: 3, stirring and uniformly mixing the mixture in the ethanol solution, performing ultrasonic dispersion, performing mechanical ball milling for 10 hours, and performing-30 freeze drying for 10 hours to obtain a precursor of the iron-vanadium bimetallic sodium pyrophosphate phosphate composite material;
s2, placing the precursor obtained in the step S1 under the protection of argon atmosphere, heating to 350 ℃, preheating for 3h, heating to 550 ℃, sintering for 3h, wherein the heating speed is 5 ℃/min, and thenFurnace cooling to obtain Na 4 Fe 1.5-1.5x V 1+x (PO 4 ) 2 P 2 O 7 @ C composite.
Example 2
Carbon-coated phosphoric acid ferric sodium pyrophosphate Na 4 Fe 1.5-1.5x V 1+x (PO 4 ) 2 P 2 O 7 The preparation method of the @ C composite material comprises the following steps:
s1, 0.03mol of sodium carbonate, 0.0225mol of ferrous sulfate, 0.045mol of ammonium metavanadate, 0.06mol of ammonium dihydrogen phosphate, and 0.5g of glucose are added to 50mL of a solution of glucose in a volume ratio of 1: 3, stirring and uniformly mixing the mixture in an ethanol solution (ethanol: deionized water), performing ultrasonic dispersion, performing mechanical ball milling for 10 hours, and performing-30 freeze drying for 10 hours to obtain a precursor of the iron-vanadium bimetallic sodium pyrophosphate phosphate composite material;
s2, placing the precursor obtained in the step S1 under the protection of argon atmosphere, heating to 350 ℃, preheating for 3h, heating to 550 ℃, sintering for 3h, heating at the speed of 5 ℃/min, and furnace cooling to obtain Na 4 Fe 1.5-1.5x V 1+x (PO 4 ) 2 P 2 O 7 @ C composite material.
Example 3
Carbon-coated phosphoric acid ferric sodium pyrophosphate Na 4 Fe 1.5-1.5x V 1+x (PO 4 ) 2 P 2 O 7 The preparation method of the @ C composite material comprises the following steps:
s1, adding 0.03mol of sodium pyrophosphate, 0.0225mol of ferrous oxalate, 0.045mol of vanadyl oxalate, 0.06mol of diammonium hydrogen phosphate and 0.5g of citric acid into 50mL of solution with a volume ratio of 1: 3 (ethanol: deionized water), stirring and mixing uniformly, performing ultrasonic dispersion, performing mechanical ball milling for 10 hours, and performing-30 freeze drying for 10 hours to obtain a precursor of the iron-vanadium bimetallic sodium pyrophosphate phosphate composite material;
s2, placing the precursor obtained in the step S1 under the protection of argon atmosphere, heating to 350 ℃, preheating for 3h, heating to 550 ℃, sintering for 3h, heating at the speed of 5 ℃/min, and furnace cooling to obtain Na 4 Fe 1.5-1.5x V 1+x (PO 4 ) 2 P 2 O 7 @ C composite material.
Example 4
Carbon-coated phosphoric acid ferric sodium pyrophosphate Na 4 Fe 1.5-1.5x V 1+x (PO 4 ) 2 P 2 O 7 The preparation method of the @ C composite material comprises the following steps:
s1, adding 0.03mol of sodium pyrophosphate, 0.0225mol of ferrous oxalate, 0.045mol of vanadyl oxalate, 0.06mol of diammonium hydrogen phosphate and 0.5g of glucose into 50mL of solution with a volume ratio of 1: 3 (ethanol: deionized water), stirring and uniformly mixing, performing ultrasonic dispersion, performing mechanical ball milling for 3 hours, and performing-20 freeze drying for 3 hours to obtain a precursor of the iron-vanadium bimetallic sodium pyrophosphate phosphate composite material;
s2, placing the precursor obtained in the step S1 under the protection of argon atmosphere, heating to 350 ℃, preheating for 3h, heating to 550 ℃, sintering for 3h, heating at the speed of 5 ℃/min, and furnace cooling to obtain Na 4 Fe 1.5-1.5x V 1+x (PO 4 ) 2 P 2 O 7 @ C composite material.
Example 5
Carbon-coated phosphoric acid ferric sodium pyrophosphate Na 4 Fe 1.5-1.5x V 1+x (PO 4 ) 2 P 2 O 7 The preparation method of the @ C composite material comprises the following steps:
s1, 0.03mol of sodium pyrophosphate, 0.045mol of ferrous oxalate, 0.03mol of vanadyl oxalate, 0.06mol of diammonium hydrogen phosphate and 0.5g of glucose are added into 50mL of a mixed solution of glucose in sequence, wherein the volume ratio of the mixed solution is 1: 3, stirring and uniformly mixing the mixture in an ethanol solution (ethanol: deionized water), performing ultrasonic dispersion, performing mechanical ball milling for 10 hours, and performing-30 freeze drying for 10 hours to obtain a precursor of the iron-vanadium bimetallic sodium pyrophosphate phosphate composite material;
s2, placing the precursor obtained in the step S1 under the protection of argon atmosphere, heating to 400 ℃, preheating for 2h, heating to 650 ℃, sintering for 6h, heating at a speed of 3 ℃/min, and furnace cooling to obtain Na 4 Fe 1.5-1.5x V 1+x (PO 4 ) 2 P 2 O 7 @ C composite material.
Example 6
Carbon-coated phosphoric acid ferric sodium pyrophosphate Na 4 Fe 1.5-1.5x V 1+x (PO 4 ) 2 P 2 O 7 The preparation method of the @ C composite material comprises the following steps:
s1, adding 0.03mol of sodium pyrophosphate, 0.09mol of ferrous oxalate, 0.003mol of vanadyl oxalate, 0.06mol of diammonium hydrogen phosphate and 0.5g of glucose into 50mL of alcohol-water in a volume ratio of 1: 3, stirring and uniformly mixing the mixture in the ethanol solution, performing ultrasonic dispersion, performing mechanical ball milling for 10 hours, and performing-30 freeze drying for 10 hours to obtain a precursor of the iron-vanadium bimetallic sodium pyrophosphate phosphate composite material;
s2, placing the precursor obtained in the step S1 under the protection of argon atmosphere, heating to 350 ℃, preheating for 3h, heating to 550 ℃, sintering for 3h, heating at the speed of 5 ℃/min, and furnace cooling to obtain Na 4 Fe 1.5-1.5x V 1+x (PO 4 ) 2 P 2 O 7 @ C composite material.
Comparative example 1
A method of making a composite material comprising the steps of:
s1, adding 0.02mol of sodium pyrophosphate, 0.045mol of ferrous oxalate, 0.03mol of vanadyl oxalate, 0.08mol of diammonium hydrogen phosphate and 0.5g of glucose into 50mL of solution with a volume ratio of 1: 3 (ethanol: deionized water), stirring and mixing uniformly, performing ultrasonic dispersion, performing mechanical ball milling for 10 hours, and performing-30 freeze drying for 10 hours to obtain a precursor;
and S2, placing the precursor obtained in the step S1 under the protection of argon atmosphere, heating to 350 ℃, preheating for 3 hours, heating to 550 ℃, sintering for 3 hours at the heating speed of 5 ℃/min, and furnace cooling to obtain the composite material.
Comparative example 2
A method of making a composite material comprising the steps of:
s1, sequentially adding 0.03mol of sodium pyrophosphate, 0.045mol of ferrous oxalate, 0.03mol of vanadyl oxalate and 0.06mol of diammonium hydrogen phosphate into 50mL of solution with the volume ratio of 1: 3, stirring and uniformly mixing the mixture in an ethanol solution (ethanol: deionized water), performing ultrasonic dispersion, performing mechanical ball milling for 10 hours, and performing-30 freeze drying for 10 hours to obtain a precursor of the iron-vanadium bimetallic sodium pyrophosphate phosphate composite material;
s2, placing the precursor obtained in the step S1 under the protection of argon atmosphere, heating to 350 ℃, preheating for 3h, heating to 550 ℃, sintering for 3h, heating at the speed of 5 ℃/min, and furnace cooling to obtain Na 4 Fe 1.5-1.5x V 1+x (PO 4 ) 2 P 2 O 7 @ C composite material.
Comparative example 3
A method of making a composite material comprising the steps of:
s1, adding 0.03mol of sodium pyrophosphate, 0.045mol of ferrous oxalate, 0.03mol of vanadyl oxalate, 0.06mol of diammonium hydrogen phosphate and 0.5g of glucose into 50mL of solution with a volume ratio of 1: 3, stirring and uniformly mixing the mixture in an ethanol solution (ethanol: deionized water), performing ultrasonic dispersion, performing mechanical ball milling for 10 hours, and performing-30 freeze drying for 10 hours to obtain a precursor of the iron-vanadium bimetallic sodium pyrophosphate phosphate composite material;
s2, placing the precursor obtained in the step S1 under the protection of argon atmosphere, heating to 300 ℃, preheating for 3h, heating to 450 ℃, sintering for 3h, heating at a speed of 5 ℃/min, and furnace cooling to obtain Na 4 Fe 1.5-1.5x V 1+x (PO 4 ) 2 P 2 O 7 @ C composite material.
Comparative example 4
A method of making a composite material comprising the steps of:
s1, adding 0.03mol of sodium pyrophosphate, 0.045mol of ferrous oxalate, 0.03mol of vanadyl oxalate, 0.06mol of diammonium hydrogen phosphate and 0.5g of glucose into 50mL of deionized water, stirring and uniformly mixing, and drying at 60 ℃ for 10 hours to obtain a precursor of the iron-vanadium bimetallic sodium pyrophosphate phosphate composite material;
s2, placing the precursor in the protection of argon atmosphere, heating to 350 ℃, preheating for 3h, heating to 550 ℃, sintering for 3h, heating at a speed of 5 ℃/min, furnace cooling to obtain Na 4 Fe 1.5-1.5x V 1+x (PO 4 ) 2 P 2 O 7 @ C composite material.
The composite materials prepared in the above examples and comparative examples are used as positive active materials for preparing positive electrodes of sodium-ion batteries, and then are appliedIn a sodium ion battery; more specifically, the carbon-coated iron-vanadium bimetallic sodium pyrophosphate phosphate composite material is weighed, 15 wt.% of acetylene black serving as a conductive agent and 15 wt.% of PVDF serving as a binder are added, a proper amount of N-methyl pyrrolidone (NMP) is added after the materials are fully ground and mixed to form uniform black pasty slurry, the slurry is coated on a carbon-coated aluminum foil current collector to serve as a test electrode, a metal sodium sheet serves as a contrast electrode to be assembled into a button cell, and an electrolytic liquid system is adopted to be 1MNaClO 4 EC: DMC: EMC (1: 1: 1), and the electrochemical performance of the battery is detected by a blue test system.
Table 1 below shows the first charge specific capacity, the discharge specific capacity and the charge-discharge efficiency detection data of 100 cycles at 1C rate of the button cell prepared in each example and the comparative example:
TABLE 1 electrochemical data for each example and comparative example
As can be seen from the data in table 1, the parameters of examples 1 to 5 are within the protection range, fig. 1 shows that the particles manufactured in example 1 are in the nanometer scale, the (011) crystal surface corresponding to 15.9 °, the (210) crystal surface corresponding to 16.7 °, the (222) crystal surface corresponding to 33.7 °, the (602) crystal surface corresponding to 34.3 °, and the (104) crystal surface corresponding to 34.4 ° in fig. 2 are all very sharp, and have a high degree of coincidence with a standard card, which indicates that the crystallinity is high, fig. 3 shows that the charging and discharging coulombic efficiency is high, the charging and discharging platform is stable and close to 100%, which is beneficial to improving the energy density and the power density and the cycle stability, fig. 4 shows that the charging and discharging efficiency of 100 cycles under the 1C rate is kept above 90%, and the first charging and discharging specific capacity of the batteries obtained in examples 1 to 5 exceeds 89.5mAh g -1 The charge-discharge efficiency of 100 cycles at 1C rate exceeds 94%; in example 6, the doping amount of vanadium is reduced by ten times, but the uniform distribution of vanadium ions in iron ions is not influenced, and electrochemical performance is realizedThe chemical performance is not affected; the sodium source and the phosphorus source of the comparative example 1 are too little, the crystal structures of the sintered composite material are not correct, the impurities are more, and the first charge-discharge specific capacity data is obviously reduced; the comparative example 2 has no carbon coating, and the influence of the first charge-discharge specific capacity data is small because the crystal structure is not influenced, but the conductivity is reduced, the capacity protection rate is low, the cycle stability is poor, and the charge-discharge efficiency of 100 cycles under the 1C multiplying power is obviously reduced; the sintering temperature of the comparative example 3 is too low, which seriously affects the crystallinity of the product and has too high impurity content, thus causing the performance of the whole battery to be reduced; comparative example 4 Fe due to the dispersant only deionized water lacking organic solvent 2+ Hydrolysis takes place to Fe (OH) 2 Colloid, Fe (OH) 2 Is easy to be oxidized to generate Fe 3+ And Fe (OH) 3 The colloid and ferric iron impurity phase are generated in the product, and the generated colloid cannot be fully dispersed and mixed with other ions due to the lack of the ball milling process, so that the product phase is impure due to the insufficient dispersion process of the raw materials, and the electrochemical performance is poor.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent should be subject to the appended claims.
Claims (10)
1. The carbon-coated iron-vanadium bimetallic sodium pyrophosphate phosphate composite material is characterized by being prepared from iron-vanadium bimetallic sodium pyrophosphate phosphate Na 4 Fe 1.5-1.5x V 1+x (PO 4 ) 2 P 2 O 7 Composite material formed by particles and surface carbon coating; -1<x<1；
The particle size of the composite material is 100 nm-2 mu m, the carbon content is 3% -10%, and the thickness of the carbon layer is 3-15 nm.
2. The preparation method of the carbon-coated iron-vanadium bimetallic sodium pyrophosphate phosphate composite material as claimed in claim 1, characterized by comprising the following steps:
s1, sequentially adding a sodium source, an iron source, a vanadium source, a phosphorus source and a complexing agent into an ethanol solution, stirring and uniformly mixing, performing ultrasonic dispersion, performing mechanical ball milling, and performing freeze drying to obtain a precursor;
and S2, placing the precursor of S1 in an inert atmosphere, preheating, heating and sintering to obtain the carbon-coated iron-vanadium bimetallic sodium pyrophosphate phosphate composite material.
3. The method of claim 2, wherein in step S1, the sodium source comprises at least one of disodium dihydrogen pyrophosphate, sodium carbonate, sodium oxalate, and sodium citrate; the iron source comprises at least one of ferrous oxalate, ferrous sulfate and ammonium ferrous sulfate;
the vanadium source comprises at least one of vanadyl oxalate, ammonium metavanadate and vanadium pentoxide;
the phosphorus source comprises at least one of ammonium dihydrogen phosphate, diammonium hydrogen phosphate, pyrophosphoric acid and sodium pyrophosphate;
the complexing agent is at least one of citric acid, glucose, oxalic acid or ascorbic acid.
4. The method for preparing the carbon-coated iron-vanadium bimetallic sodium pyrophosphate phosphate composite material as claimed in claim 2, wherein in the step S1, the volume ratio of ethanol to deionized water in the ethanol solution is 1: 2-3; the solid-to-liquid ratio of the sodium source, the iron source, the vanadium source, the phosphorus source, the complexing agent and the dispersing solvent is 100-300 g/L.
5. The method for preparing the carbon-coated iron-vanadium bimetallic sodium pyrophosphate phosphate composite material as claimed in claim 2, wherein in the step S1, the molar ratio of sodium element, iron element, vanadium element and phosphorus element in the sodium source, the iron source, the vanadium source and the phosphorus source is 4.0-4.2: 1.5-1.5 x: 1+ x: 3.9 to 4.1.
6. The method for preparing the carbon-coated iron-vanadium bimetallic sodium pyrophosphate phosphate composite material according to claim 2, wherein in the step S1, the composite material is freeze-dried at the temperature of-40 to-20 ℃ for 2 to 10 hours.
7. The method for preparing the carbon-coated iron-vanadium bimetallic sodium pyrophosphate phosphate composite material according to claim 2, wherein in step S2, the temperature is raised to 300-400 ℃ at a heating rate of 3-10 ℃/min for preheating for 2-5 h, and then raised to 500-650 ℃ at a heating rate of 3-10 ℃/min for sintering for 3-10 h, so as to obtain the carbon-coated iron-vanadium bimetallic sodium pyrophosphate phosphate composite material.
8. A positive electrode material prepared from the composite material according to claim 1 or the composite material prepared by the preparation method according to claims 2 to 7.
9. A positive electrode sheet produced from the composite material according to claim 1 or the composite material produced by the production method according to claims 2 to 7.
10. A battery prepared using the positive electrode sheet of claim 9.
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| CN116443836A (en) * | 2023-03-27 | 2023-07-18 | 江苏大学 | Method for synthesizing sodium ion battery anode material sodium ferric pyrophosphate/carbon |
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| CN116443836A (en) * | 2023-03-27 | 2023-07-18 | 江苏大学 | Method for synthesizing sodium ion battery anode material sodium ferric pyrophosphate/carbon |
| CN116344772A (en) * | 2023-04-18 | 2023-06-27 | 广东广钠新材科技有限公司 | Spherical ferric sodium pyrophosphate positive electrode material and preparation method thereof |
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