CN114361425B - Method for directly preparing ferric sodium pyrophosphate composite material from pyrite, ferric sodium pyrophosphate composite material and application of ferric sodium pyrophosphate composite material - Google Patents
Method for directly preparing ferric sodium pyrophosphate composite material from pyrite, ferric sodium pyrophosphate composite material and application of ferric sodium pyrophosphate composite material Download PDFInfo
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- CN114361425B CN114361425B CN202210046186.9A CN202210046186A CN114361425B CN 114361425 B CN114361425 B CN 114361425B CN 202210046186 A CN202210046186 A CN 202210046186A CN 114361425 B CN114361425 B CN 114361425B
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- pyrite
- sodium pyrophosphate
- pyrophosphate
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- 239000002131 composite material Substances 0.000 title claims abstract description 73
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 229910052683 pyrite Inorganic materials 0.000 title claims abstract description 53
- 239000011028 pyrite Substances 0.000 title claims abstract description 53
- 238000000034 method Methods 0.000 title claims abstract description 41
- 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 title claims description 27
- 239000011645 ferric sodium diphosphate Substances 0.000 title claims description 20
- 235000019851 ferric sodium diphosphate Nutrition 0.000 title claims description 20
- 239000000463 material Substances 0.000 claims abstract description 42
- 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 24
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 61
- 238000000498 ball milling Methods 0.000 claims description 49
- 239000000843 powder Substances 0.000 claims description 41
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 40
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 36
- 239000011734 sodium Substances 0.000 claims description 36
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 29
- 239000007787 solid Substances 0.000 claims description 27
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 24
- 229910052799 carbon Inorganic materials 0.000 claims description 23
- 239000007789 gas Substances 0.000 claims description 22
- 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 21
- 229910052742 iron Inorganic materials 0.000 claims description 21
- 229910052708 sodium Inorganic materials 0.000 claims description 21
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 20
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 20
- 238000010438 heat treatment Methods 0.000 claims description 20
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 20
- 239000007774 positive electrode material Substances 0.000 claims description 17
- 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 17
- 229940048086 sodium pyrophosphate Drugs 0.000 claims description 17
- 235000019818 tetrasodium diphosphate Nutrition 0.000 claims description 17
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 239000010941 cobalt Substances 0.000 claims description 14
- 229910017052 cobalt Inorganic materials 0.000 claims description 14
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 14
- 229910052759 nickel Inorganic materials 0.000 claims description 14
- XKRFYHLGVUSROY-UHFFFAOYSA-N argon Substances [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 13
- 229910052786 argon Inorganic materials 0.000 claims description 13
- 239000001257 hydrogen Substances 0.000 claims description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 12
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 12
- 239000011247 coating layer Substances 0.000 claims description 12
- 238000005245 sintering Methods 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 9
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 8
- 229910052698 phosphorus Inorganic materials 0.000 claims description 8
- 239000011574 phosphorus Substances 0.000 claims description 8
- 239000011259 mixed solution Substances 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
- 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 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 4
- 239000003575 carbonaceous material Substances 0.000 claims description 4
- 239000011258 core-shell material Substances 0.000 claims description 4
- 239000008103 glucose Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 239000006012 monoammonium phosphate Substances 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 0.000 claims description 4
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 3
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 3
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 3
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 2
- 239000005696 Diammonium phosphate Substances 0.000 claims description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 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
- 239000006230 acetylene black Substances 0.000 claims description 2
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 2
- ZRIUUUJAJJNDSS-UHFFFAOYSA-N ammonium phosphates Chemical compound [NH4+].[NH4+].[NH4+].[O-]P([O-])([O-])=O ZRIUUUJAJJNDSS-UHFFFAOYSA-N 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
- 239000002041 carbon nanotube Substances 0.000 claims description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 2
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 2
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 2
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 2
- 229910021389 graphene Inorganic materials 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 235000011007 phosphoric acid Nutrition 0.000 claims description 2
- 230000001681 protective effect Effects 0.000 claims description 2
- 229940005657 pyrophosphoric acid Drugs 0.000 claims description 2
- 239000001632 sodium acetate Substances 0.000 claims description 2
- 235000017281 sodium acetate Nutrition 0.000 claims description 2
- 235000010413 sodium alginate Nutrition 0.000 claims description 2
- 239000000661 sodium alginate Substances 0.000 claims description 2
- 229940005550 sodium alginate Drugs 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 235000017550 sodium carbonate 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
- 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
- 239000000126 substance Substances 0.000 claims description 2
- 239000005720 sucrose Substances 0.000 claims description 2
- -1 super P Chemical compound 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 abstract description 10
- 230000008569 process Effects 0.000 abstract description 10
- 229910052500 inorganic mineral Inorganic materials 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 239000011707 mineral Substances 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 229910001415 sodium ion Inorganic materials 0.000 description 21
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 11
- 230000014759 maintenance of location Effects 0.000 description 11
- 229910052573 porcelain Inorganic materials 0.000 description 11
- 238000001291 vacuum drying Methods 0.000 description 8
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 7
- 238000009792 diffusion process Methods 0.000 description 7
- 229910001416 lithium ion Inorganic materials 0.000 description 7
- 230000007704 transition Effects 0.000 description 7
- 239000002245 particle Substances 0.000 description 6
- 239000007772 electrode material Substances 0.000 description 5
- 238000005086 pumping Methods 0.000 description 5
- 238000004146 energy storage Methods 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 235000010755 mineral Nutrition 0.000 description 4
- 230000008859 change Effects 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000011573 trace mineral Substances 0.000 description 3
- 235000013619 trace mineral Nutrition 0.000 description 3
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229940062993 ferrous oxalate Drugs 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- 230000002687 intercalation Effects 0.000 description 2
- OWZIYWAUNZMLRT-UHFFFAOYSA-L iron(2+);oxalate Chemical compound [Fe+2].[O-]C(=O)C([O-])=O OWZIYWAUNZMLRT-UHFFFAOYSA-L 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000009777 vacuum freeze-drying Methods 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 235000011180 diphosphates Nutrition 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000011056 performance test Methods 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
- 229920000447 polyanionic polymer Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 229940048084 pyrophosphate Drugs 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
-
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a method for directly preparing a sodium iron pyrophosphate composite material from pyrite, the sodium iron pyrophosphate composite material and application thereof. The invention realizes the direct synthesis from the mineral material to the battery material, effectively reduces the production cost, shortens the process flow, has the characteristics of simple preparation method, low raw material cost, high theoretical capacity, ideal voltage and stable circulation, and has good commercialization prospect.
Description
Technical Field
The invention relates to the technical field of preparation of positive electrode materials, in particular to the field of sodium ion battery materials, and more particularly relates to a method for directly preparing a sodium iron pyrophosphate composite material from pyrite, the sodium iron pyrophosphate composite material and application thereof.
Background
Due to the limitation of factors such as the aggravation of the traditional fossil energy consumption and the energy safety, and the enhancement of ecological environment protection concept by people, the sustainable development, the utilization and the storage of energy are highly valued in all countries of the world. Electrochemical energy storage has the characteristics of high efficiency, low cost, safety, convenience and the like compared with mechanical energy storage, electromagnetic energy storage and phase change energy storage, and has been developed into a current main energy storage technology. The lithium ion battery is a storage battery with advantages in energy density and power density, and can be used in various fields of electronic products, aerospace, military and military industry and the like. With the wide application of lithium ion batteries, particularly the rapid development of the electric automobile market, lithium resources are consumed in a large amount. According to the principle of a lithium ion 'rocking chair type' battery, a sodium ion-rich compound is similar to a lithium ion positive electrode material, and provides removable sodium ions and a structure, so that the sodium ion battery has become a hot research problem in recent years, and various sodium storage materials have been widely researched.
Sodium ions are about 55% larger than lithium ions, the intercalation and diffusion of sodium ions in the same structural material are often relatively difficult, and the structural change of the intercalated material is larger, so that the specific capacity, the dynamic performance, the cycle performance and the like of the electrode material are correspondingly deteriorated. Compared with lithium ion batteries, the sodium ion battery field has a plurality of technical problems to be overcome, and the technical maturity of the sodium ion battery is seriously delayed from that of the lithium ion battery. Over the last several decades, scientific researchers have conducted extensive research into the positive electrode materials of sodium ion batteries. In the existing cathode material system, researchers are pursuing high capacity, long cycle, high stability, and wide sources of raw materials.
Among the numerous positive electrode materials for sodium ion batteries, polyanionic compounds are considered as a type of electrode material with the most promising application prospect due to their excellent structural stability, safety and suitable voltage plateau. Taking the phosphate as an example, it contains a specific tetrahedral PO with a strong covalent bond 4 Unit, relative separation of valence electrons from polyanions. The special three-dimensional framework structure is accompanied by a multi-electron mechanism, and the energy transition between the highest occupied molecular orbit and the lowest occupied molecular orbit is smaller, so that the rapid extraction and intercalation of sodium ions are very facilitated. Sodium ferric pyrophosphate materials are increasingly favored due to the abundance of inexpensive iron resources, three-dimensional ion diffusion channels, and good safety performance. Nevertheless, poor electronic conductivity, slow ion diffusion rate, and difficult control of high temperature sintered structure still is a phase transition problem of pyrophosphate iron-based materials, which affects its practical application.
Disclosure of Invention
In order to solve the problems, the invention provides the method for directly preparing the carbon-coated sodium ferric pyrophosphate composite material from pyrite, which can directly prepare the sodium ferric pyrophosphate composite material from the mineral material to the electrode material by taking pyrite as an iron source and providing doping elements, has the advantages of simple process, stable product and easy mass production, and the prepared sodium ferric pyrophosphate has a carbon coating layer, good crystallization and uniform size, improves the electronic conductivity and the sodium ion diffusion rate of the material by doping trace elements cobalt and nickel in the pyrite, solves the problem of unstable phase transition in the charging and discharging process, greatly improves the electrochemical performance of the material, and has wide application prospect.
In order to achieve the above object, the technical scheme of the present invention is as follows:
a method for directly preparing ferric sodium pyrophosphate composite material from pyrite comprises the following steps:
s1, respectively dispersing pyrite, a phosphorus source, a sodium source and a carbon source in absolute ethyl alcohol, mixing to obtain a mixed solution, adjusting the pH value of the mixed solution to 2-6, vacuumizing, ball milling, filtering and drying to obtain solid powder;
s2, heating the solid powder to 300-450 ℃ under the protection atmosphere containing hydrogen, preheating, and then heating to 500-700 ℃ for sintering to obtain a composite material;
the pyrite contains Fe and S with the content more than 99.9 percent and contains associated elements of cobalt and nickel.
In some embodiments, the composite material is a core-shell structure, the inner core is a nickel and cobalt doped ferric sodium pyrophosphate material, and the coating layer is a carbon material; the thickness of the coating layer is 3-10 nm, and the carbon content is 3-10% of the mass of the composite material.
In some embodiments, in step S1, the pyrite is ball-milled to obtain a powder material, then the pyrite powder, the phosphorus source, the sodium source and the carbon source are respectively dispersed in absolute ethyl alcohol, then mixed, stirred uniformly at a stirring rate of 100-800 r/min to obtain a mixed solution, then the pH of the mixed solution is adjusted to 2-6, and then the mixed solution is subjected to vacuum ball-milling, filtration and drying to obtain solid powder. More preferably, the stirring rate is 500-800 r/min; stirring time is 0.5-2 h.
In some embodiments, the vacuum ball milling speed is 100-600 r/min, and the ball milling time is 5-24 h; more preferably, the ball milling rotation speed is 500-800 r/min; ball milling time is 20-24 h;
in some embodiments, the vacuum freeze-drying mode is adopted for drying, wherein the vacuum freeze-drying temperature is between minus 30 ℃ and minus 10 ℃ and the drying time is between 5 and 24 and h; more preferably, the temperature is-20 to-15 ℃; the drying time is 10-12 h.
In some embodiments, the preheat time is from 1 to 3 h; the sintering time is 2-8 hours.
In some embodiments, the pyrite, the phosphorus source, and the sodium source are in a molar ratio of 2.9-3.1: 3.9 to 4.1: 3.9-4.1; the molar ratio of iron element to carbon of pyrite to carbon source is 1: and 2-5, mixing. More preferably, mixing iron element, phosphorus element and sodium element in the sodium iron pyrophosphate composite material according to stoichiometric ratio; the molar ratio of iron element to carbon of pyrite to carbon source is 1: 2-3.
In some embodiments, the phosphorus source comprises at least one of diammonium phosphate, monoammonium phosphate, phosphoric acid, triammonium phosphate, sodium dihydrogen phosphate, disodium hydrogen phosphate, pyrophosphoric acid, sodium pyrophosphate.
In some embodiments, the sodium source comprises at least one of sodium pyrophosphate, sodium carbonate, sodium bicarbonate, sodium acetate, sodium oxalate, sodium bicarbonate, sodium alginate, sodium citrate. Preferably, the sodium source is sodium pyrophosphate and/or sodium bicarbonate.
In some embodiments, the carbon source comprises at least one of citric acid, glucose, sucrose, acetylene black, super P, graphene, carbon nanotubes, oxalic acid. Preferably, the carbon source is citric acid and/or glucose.
In some embodiments, the protective atmosphere is a hydrogen-argon mixed atmosphere or a hydrogen-nitrogen mixed atmosphere. Specifically, the volume ratio of hydrogen in the mixed gas is 5-10%. The hydrogen gas is used for removing sulfur element in pyrite particles.
The invention also provides a sodium iron pyrophosphate composite material, which is prepared by the method in any embodiment, and the composite material has a core-shell structure, wherein the inner core is nickel and cobalt doped sodium iron pyrophosphate material, the coating layer is carbon material, and the chemical formula is as follows: na (Na) 4 Fe 3-x-y Co x Ni y (PO 4 ) 2 P 2 O 7 And @ C, wherein 0 < x+y < 0.1 and x > 0 and y > 0.
In some embodiments, the particle size of the ferric sodium pyrophosphate composite material is 100 nm-100 μm, preferably 100-300 nm; the coating layer is an amorphous carbon coating layer, and the thickness of the coating layer is 3-10 nm, preferably 5-7 nm.
The invention also provides a positive electrode material, which comprises the ferric sodium pyrophosphate composite material.
Compared with the prior art, the invention has the following beneficial effects:
(1) The invention prepares the carbon-coated sodium ferric pyrophosphate composite material by adopting pyrite as an iron source, wherein the pyrite is taken as a typical iron ore, and the main component is FeS 2 The method has the advantages that the ore grade is high, the impurity content is low, the Fe and S content in the ore is more than 99.9 percent, the ore contains half-raw trace elements of cobalt and nickel (less than 0.1 percent by weight), pyrite is used as an iron source, the one-step preparation from mineral materials to electrode materials can be realized, the half-raw nickel and cobalt elements in pyrite are effectively utilized, and the half-raw nickel and cobalt elements can directly dope iron sites in the generated composite material, so that the steps of removing impurities and doping in the later period are saved, the technological process is shortened, and the production cost is reduced.
(2) According to the invention, the pyrite is used for directly preparing the sodium ferric pyrophosphate composite material, and trace associated elements contained in the pyrite obviously improve the phase transition stability in the charge-discharge process, and the nano-scale carbon layer on the surface of the doped sodium ferric pyrophosphate active material particles is uniformly coated, so that the direct contact between the active material and the electrolyte is avoided, and the interface side reaction and the metal ion dissolution are obviously inhibited.
(3) According to the invention, the pyrite is used for directly preparing the sodium iron pyrophosphate composite material, so that the direct preparation from the mineral material to the electrode material is realized, the utilization rate of the mineral material is greatly improved, and the production process flow is effectively shortened.
(4) The trace elements associated with pyrite are mainly cobalt and nickel, and the content is extremely low, so that adverse effects are not caused in the process of preparing sodium iron pyrophosphate, and a key effect is played on improving the electrochemical performance of the material. Trace amounts of cobalt and nickel enter the sodium iron pyrophosphate phase, more specifically the iron metal sites, during the preparation process by ball milling and calcination to form Na 4 Fe 3-x-y Co x Ni y (PO 4 ) 2 P 2 O 7 Material (x+y < 0.1). Compared with pure phase Na 4 Fe 3 (PO 4 ) 2 P 2 O 7 Materials, na 4 Fe 3-x-y Co x Ni y (PO 4 ) 2 P 2 O 7 The doping of cobalt and nickel improves the ion diffusion rate and the electron conductivity, improves the circulation stability and the thermal stability of the material, effectively solves the problem of unstable structure in the phase transition process due to the existence of the nickel and the cobalt, and obviously improves the electrochemical performance of the material.
(5) The addition amount of the carbon source is changed in the precursor synthesis stage, so that the particle size and the thickness of the carbon coating layer are regulated and controlled, microscopic particle aggregation is reduced, a carbon coating layer with compact structure and uniform dispersion is formed on the surface of the active substance particles, the conductivity of the material is improved, the damage of the water phase coating to the structure of the composite material can be avoided, the structural stability of the composite material can be improved, the structural phase change and interface side reaction of the material in the high-voltage and high-temperature circulation process are inhibited, the overcharging performance of the material is improved, and meanwhile, the voltage application range of the composite material can be expanded.
(6) The composite material prepared by the method is used as the positive electrode active material in the battery, so that the cycle performance and the multiplying power performance of the battery can be greatly improved, the technical problems of high production cost, low electronic conductivity, low ion diffusion rate, unstable phase transition and the like of the conventional iron-based positive electrode material are effectively solved, and the synthesis method is simple and easy and suitable for industrialization, is environment-friendly, has abundant raw material resources, is low in cost and has wide industrial application prospect.
Drawings
FIG. 1 is a process flow diagram of the pyrite of the present invention for preparing sodium iron pyrophosphate;
FIG. 2 is an SEM image of sodium iron pyrophosphate prepared in example 1 of the invention;
FIG. 3 is an XRD pattern of sodium iron pyrophosphate prepared in example 1 of the present invention;
FIG. 4 is a charge-discharge curve of sodium iron pyrophosphate prepared in example 1 of the present invention;
FIG. 5 is a charge-discharge cycle chart of sodium iron pyrophosphate prepared in example 1 of the present invention.
Detailed Description
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention. The invention may be embodied in many other forms than described herein and similarly modified by those skilled in the art without departing from the spirit or scope of the invention, which is therefore not limited to the specific embodiments disclosed below.
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 herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
Example 1
As shown in fig. 1, a method for directly preparing a sodium iron pyrophosphate composite material from pyrite comprises the following steps:
s1, taking 4 g pyrite, performing ball milling, adjusting the rotating speed to 600 r/min and the ball milling time to 20 h, dispersing powder obtained by ball milling in absolute ethyl alcohol, adding 0.04 mol of sodium pyrophosphate, 0.02 mol of ammonium dihydrogen phosphate and 0.06 mol of citric acid (the molar ratio of the ammonium dihydrogen phosphate to the iron element is 2:1), and adjusting the pH value to be 3 by utilizing phosphoric acid; vacuumizing and ball milling at a speed of 500 r/min for 12 h, and then drying at-20 ℃ for 5 h to obtain solid powder;
s2, placing the obtained solid powder into a porcelain boat, preheating and preserving heat at a speed of 5 ℃/min to 300 ℃ under the atmosphere of hydrogen-argon mixed gas (the hydrogen flow accounts for 10% of the total gas flow), and then continuously heating at a speed of 5 ℃/min to 600 ℃ to sinter 6 h to obtain the carbon-coated sodium iron pyrophosphate composite material (Na 4 Fe 3-x-y Co x Ni y (PO 4 ) 2 P 2 O 7 And @ C, wherein 0 < x+y < 0.1) the obtained composite material was subjected to SEM and XRD analyses, and the analysis results are shown in FIG. 2 and FIG. 3, respectively.
And preparing a battery by taking the obtained composite material as a positive electrode material, and performing electrochemical performance test, wherein the test results are shown in fig. 4 and 5. The method comprises the following steps:
the composite material prepared by the embodiment and the sodium sheet are assembled into a button cell, and the voltage of the material can reach 3.1V; at the 1C multiplying power, the specific discharge capacity of 100 circles in a circulation way reaches 118 mAh/g, and the capacity retention rate reaches more than 93%.
Example 2
As shown in fig. 1, a method for directly preparing a sodium iron pyrophosphate composite material from pyrite comprises the following steps:
s1, taking 4 g pyrite, performing ball milling, adjusting the rotating speed to 600 r/min and the ball milling time to 20 h, dispersing powder obtained by ball milling in absolute ethyl alcohol, adding 0.04 mol of sodium pyrophosphate, 0.03 mol of sodium dihydrogen phosphate and 0.06 mol of citric acid (the molar ratio to iron is 2:1), and adjusting the pH=6 by utilizing phosphoric acid; then ball milling for 12 h under vacuum of 500 r/min, and drying for 5 h under vacuum at-20deg.C to obtain solid powder
S2, placing the obtained solid powder into a porcelain boat, preheating and preserving heat at a speed of 3 ℃/min to 350 ℃ under the atmosphere of hydrogen-argon mixed gas (the hydrogen flow is 5% of the total gas flow) for 1 h, and then continuously heating at a speed of 3 ℃/min to 600 ℃ for 6 h sintering to obtain Na 4 Fe 3-x-y Co x Ni y (PO 4 ) 2 P 2 O 7 @C composite material, wherein 0 < x+y < 0.1。
The composite positive electrode material of the sodium ion battery prepared by the embodiment and the sodium sheet are assembled into a button battery, and the voltage of the material can reach 3.1V; at the 1C multiplying power, the specific discharge capacity of 100 circles in a circulation way reaches 115 mAh/g, and the capacity retention rate reaches more than 90%.
Example 3
As shown in fig. 1, a method for directly preparing a sodium iron pyrophosphate composite material from pyrite comprises the following steps:
s1, taking 4 g pyrite, performing ball milling, adjusting the rotating speed to 600 r/min, performing ball milling for 20 h, dispersing powder obtained by ball milling in absolute ethyl alcohol, adding 0.04 mol of sodium pyrophosphate, 0.02 mol of ammonium dihydrogen phosphate and 0.06 mol of glucose (the molar ratio of the ammonium dihydrogen phosphate to iron is 2:1), adjusting the pH value to 4 by utilizing phosphoric acid, performing vacuum pumping to 500 r/min, performing ball milling to 12 h, and performing vacuum drying at-20 ℃ to 5 h to obtain solid powder;
s2, placing the obtained solid powder into a porcelain boat, heating to 350 ℃ at a speed of 8sheshidu/min under the atmosphere of hydrogen-argon mixed gas (the hydrogen flow is 10% of the total gas flow), preheating and preserving heat for 1 h, and then continuously heating to 600 ℃ at a speed of 8 ℃/min for sintering for 6 h; thus obtaining Na 4 Fe 3-x-y Co x Ni y (PO 4 ) 2 P 2 O 7 And @ C composite material, wherein 0 < x+y < 0.1.
The composite positive electrode material of the sodium ion battery prepared by the embodiment and the sodium sheet are assembled into a button battery, and the voltage of the material can reach 3.1V; at the 1C multiplying power, the specific discharge capacity of 100 circles in a circulation way reaches 115 mAh/g, and the capacity retention rate reaches more than 90%.
Example 4
As shown in fig. 1, a method for directly preparing a sodium iron pyrophosphate composite material from pyrite comprises the following steps:
s1, taking 4 g pyrite, performing ball milling, adjusting the rotating speed to 600 r/min, performing ball milling for 20 h, dispersing powder obtained by ball milling in absolute ethyl alcohol, adding 0.04 mol of sodium pyrophosphate, 0.02 mol of ammonium dihydrogen phosphate and 0.06 mol of citric acid (the molar ratio of the ammonium dihydrogen phosphate to iron is 2:1), adjusting the pH value to 4 by utilizing phosphoric acid, performing vacuum pumping to 300 r/min, performing ball milling to 6 h, and performing vacuum drying at-20 ℃ to 10 h to obtain solid powder;
s2, placing the obtained solid powder into a porcelain boat, preheating and preserving heat at a speed of 10 ℃/min to 350 ℃ under the atmosphere of hydrogen-argon mixed gas (the hydrogen flow is 5% of the total gas flow) for 1 h, and then continuously heating at a speed of 10 ℃/min to 600 ℃ for 6 h sintering to obtain Na 4 Fe 3-x-y Co x Ni y (PO 4 ) 2 P 2 O 7 And @ C composite material, wherein 0 < x+y < 0.1.
The composite positive electrode material of the sodium ion battery prepared by the embodiment and the sodium sheet are assembled into a button battery, and the voltage of the material can reach 3.1V; and under the 1C multiplying power, the specific discharge capacity of 100 circles is 113 mAh/g, and the capacity retention rate is more than 89%.
Example 5
As shown in fig. 1, a method for directly preparing a sodium iron pyrophosphate composite material from pyrite comprises the following steps:
s1, taking 4 g pyrite, performing ball milling, adjusting the rotating speed to 600 r/min, performing ball milling for 20 h, dispersing powder obtained by ball milling in absolute ethyl alcohol, adding 0.04 mol of sodium pyrophosphate, 0.02 mol of ammonium dihydrogen phosphate and 0.06 mol of citric acid (the molar ratio of the ammonium dihydrogen phosphate to iron is 2:1), adjusting the pH value to 3 by utilizing phosphoric acid, performing vacuum pumping to 500 r/min, performing ball milling to 12 h, and performing vacuum drying at-20 ℃ to 5 h to obtain solid powder;
s2, placing the obtained solid powder into a porcelain boat, preheating and preserving heat at a speed of 3 ℃/min to 350 ℃ under the atmosphere of hydrogen-argon mixed gas (the hydrogen flow is 8% of the total gas flow), and then continuously heating at a speed of 3 ℃/min to 600 ℃ to sinter 6 h to obtain Na 4 Fe 3-x-y Co x Ni y (PO 4 ) 2 P 2 O 7 And @ C composite material, wherein 0 < x+y < 0.1.
The composite positive electrode material of the sodium ion battery prepared by the embodiment and the sodium sheet are assembled into a button battery, and the voltage of the material can reach 3.1V; at the 1C multiplying power, the specific discharge capacity of 100 circles is 117 mAh/g, and the capacity retention rate is more than 92%.
Example 6
As shown in fig. 1, a method for directly preparing a sodium iron pyrophosphate composite material from pyrite comprises the following steps:
s1, taking 4 g pyrite, performing ball milling, adjusting the rotating speed to 600 r/min, performing ball milling for 20 h, dispersing powder obtained by ball milling in absolute ethyl alcohol, adding 0.04 mol of sodium pyrophosphate, 0.02 mol of ammonium dihydrogen phosphate and 0.06 mol of citric acid (the molar ratio of the ammonium dihydrogen phosphate to iron is 2:1), adjusting the pH value to 4 by utilizing phosphoric acid, vacuumizing, performing ball milling at a rate of 500 r/min to 12 h, and performing vacuum drying at a temperature of-20 ℃ to 5 h to obtain solid powder;
s2, placing the obtained solid powder into a porcelain boat, preheating and preserving heat at a speed of 5 ℃/min to 350 ℃ under the atmosphere of hydrogen-argon mixed gas (the hydrogen flow is 7% of the total gas flow) for 1 h, and then continuously heating at a speed of 5 ℃/min to 550 ℃ for 3 h sintering to obtain Na 4 Fe 3-x-y Co x Ni y (PO 4 ) 2 P 2 O 7 And @ C composite material, wherein 0 < x+y < 0.1.
The composite positive electrode material of the sodium ion battery prepared by the embodiment and the sodium sheet are assembled into a button battery, and the voltage of the material can reach 3.05V; at the 1C multiplying power, the specific discharge capacity of 100 circles in a circulation way reaches 108 mAh/g, and the capacity retention rate reaches more than 87%.
Comparative example 1
The method of this comparative example is identical to the preparation method of example 1, except that ferrous oxalate is used as the iron source, and the specific steps are:
s1, dispersing 0.03 mol of ferrous oxalate in absolute ethyl alcohol, adding 0.04 mol of sodium pyrophosphate, 0.02 mol of ammonium dihydrogen phosphate and 0.06 mol of citric acid (the molar ratio of the ammonium dihydrogen phosphate to the iron is 2:1), adjusting pH to be 3 by utilizing phosphoric acid, carrying out ball milling for 20 h by vacuum pumping for 600 r/min, and then carrying out vacuum drying for 5 h at the temperature of-20 ℃ to obtain solid powder;
s2, placing the obtained solid powder into a porcelain boat, heating to 350 ℃ under the atmosphere of hydrogen-argon mixed gas (the hydrogen flow is 10% of the total gas flow), preheating and preserving heat for 1 h, continuously heating to 600 ℃ and sintering for 6 h to obtain Na 4 Fe 3 (PO 4 ) 2 P 2 O 7 @ C composite.
The composite positive electrode material of the sodium ion battery prepared by the comparative example and the sodium sheet are assembled into a button battery, and the voltage of the material can reach 3.0V; at the 1C multiplying power, the specific discharge capacity of 100 circles is 103 mAh/g, the capacity retention rate is lower than 85%, the specific discharge capacity of the material is reduced, and the circulation stability is reduced.
Comparative example 2
The method of this comparative example is the same as the preparation method of example 1, except that the pH is not controlled, and the specific steps are:
s1, taking 4 g pyrite, performing ball milling, adjusting the rotating speed to 600 r/min and the ball milling time to 20 h, dispersing powder obtained by ball milling in absolute ethyl alcohol, adding 0.04 mol of sodium pyrophosphate, 0.02 mol of ammonium dihydrogen phosphate and 0.06 mol of citric acid (the molar ratio of the sodium pyrophosphate to the iron is 2:1), performing ball milling to 12 h by vacuumizing to 500 r/min, and then performing vacuum drying to 5 h at the temperature of-20 ℃ to obtain solid powder;
s2, placing the obtained solid powder into a porcelain boat, heating to 350 ℃ under the atmosphere of hydrogen-argon mixed gas (the hydrogen flow is 10% of the total gas flow), preheating and preserving heat for 1 h, continuously heating to 600 ℃ and sintering for 6 h to obtain Na 4 Fe 3-x-y Co x Ni y (PO 4 ) 2 P 2 O 7 And @ C composite material, wherein 0 < x+y < 0.1.
The composite positive electrode material of the sodium ion battery prepared by the embodiment and the sodium sheet are assembled into a button battery, and the voltage of the material can reach 3.0V; at 1C multiplying power, the specific discharge capacity of 100 circles in circulation reaches 110 mAh/g, and the capacity retention rate is less than 85%.
Comparative example 3
The method of this comparative example was the same as the preparation method of example 1, except that no carbon source was added, and the specific steps were as follows:
s1, taking 4 g pyrite, performing ball milling, adjusting the rotating speed to 600 r/min and the ball milling time to 20 h, dispersing powder obtained by ball milling in absolute ethyl alcohol, adding 0.04 mol of sodium pyrophosphate and 0.02 mol of ammonium dihydrogen phosphate, adjusting the pH to be=3 by utilizing phosphoric acid, performing ball milling to 12 h by vacuumizing to 500 r/min, and then performing vacuum drying to 5 h at the temperature of minus 20 ℃ to obtain solid powder;
s2, putting the obtained solid powder into a porcelain boatHeating to 350deg.C under hydrogen-argon mixed gas atmosphere (hydrogen flow is 10% of total gas flow), preheating and maintaining 1 h, continuously heating to 600deg.C, sintering 6 h to obtain Na 4 Fe 3-x-y Co x Ni y (PO 4 ) 2 P 2 O 7 A composite material, wherein 0 < x+y < 0.1.
The composite positive electrode material of the sodium ion battery prepared by the embodiment and the sodium sheet are assembled into a button battery, and the voltage of the material can reach 3.0V; at 1C multiplying power, the specific discharge capacity of 100 circles in circulation reaches 105 mAh/g, and the capacity retention rate is lower than 82%.
Comparative example 4
The method of this comparative example was identical to the preparation method of example 1, except that the firing temperature was outside the required range of the present invention, and specifically, the following was adopted:
s1, taking 4 g pyrite, performing ball milling, adjusting the rotating speed to 600 r/min, performing ball milling for 20 h, dispersing powder obtained by ball milling in absolute ethyl alcohol, adding 0.04 mol of sodium pyrophosphate, 0.02 mol of monoammonium phosphate and 0.06 mol of citric acid (the molar ratio of the monoammonium phosphate to iron is 2:1), adjusting the pH value to be 3 by utilizing phosphoric acid, vacuumizing to 500 r/min, performing ball milling to 12 h, drying at the temperature of minus 20 ℃ to 5 h to obtain black powder, placing the black powder into a porcelain boat, heating to 350 ℃ under the atmosphere of hydrogen-argon mixed gas, preheating and preserving heat to 1 h, continuously heating to 800 ℃ and sintering to 6 h, and obtaining Na 4 Fe 3 (PO 4 ) 2 P 2 O 7 A composite material.
The solid powder material prepared by the embodiment and the sodium sheet are assembled into a button cell, and the voltage of the material can be lower than 2.6V; at the 1C multiplying power, the discharge specific capacity of 100 circles is 70 mAh/g, and the capacity retention rate is less than 70%.
Comparative example 5
The method of this comparative example was identical to the preparation method of example 1, except that the calcination time was less than the required range of the present invention, and specifically, the following was adopted:
s1, taking 4 g pyrite, performing ball milling, adjusting the rotating speed to 600 r/min, performing ball milling for 20 h, dispersing powder obtained by ball milling in absolute ethyl alcohol, adding 0.04 mol of sodium pyrophosphate, 0.02 mol of ammonium dihydrogen phosphate and 0.06 mol of citric acid (the molar ratio of the ammonium dihydrogen phosphate to iron is 2:1), adjusting the pH value to 3 by utilizing phosphoric acid, performing vacuum pumping to 500 r/min, performing ball milling to 12 h, and performing vacuum drying at-20 ℃ to 5 h to obtain solid powder;
s2, placing the obtained solid powder into a porcelain boat, heating to 350 ℃ in a hydrogen-argon mixed gas atmosphere, preheating and preserving heat for 1 h, continuously heating to 400 ℃ and sintering for 6 h, and obtaining Na 4 Fe 3 (PO 4 ) 2 P 2 O 7 ) A composite material.
The solid powder material prepared by the embodiment and the sodium sheet are assembled into a button cell, and the voltage of the material can be lower than 2.6V; at the 1C multiplying power, the discharge specific capacity of 100 circles is 53 mAh/g, the capacity retention rate is less than 61%, the material capacity is reduced, and the cycle performance is obviously reduced.
In conclusion, by the method, the process conditions are strictly controlled, the composite material with good crystallization and stable phase transition can be obtained, the electronic conductivity and the sodium ion diffusion rate of the material can be effectively improved, and the electrochemical performance is excellent.
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The above examples illustrate only a few embodiments of the invention, which are described in detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.
Claims (10)
1. The method for directly preparing the ferric sodium pyrophosphate composite material from pyrite is characterized by comprising the following steps of:
s1, respectively dispersing pyrite, a phosphorus source, a sodium source and a carbon source in absolute ethyl alcohol to obtain a mixed solution, adjusting the pH value of the mixed solution to 2-6, carrying out vacuum ball milling, filtering and drying to obtain solid powder;
s2, heating the solid powder to 300-400 ℃ under the protection atmosphere containing hydrogen, preheating, and then heating to 500-700 ℃ for sintering to obtain a composite material;
the pyrite contains Fe and S with the content more than 99.9 percent and contains associated elements of cobalt and nickel.
2. The method for directly preparing the ferric sodium pyrophosphate composite material from pyrite according to claim 1, wherein the composite material has a core-shell structure, the inner core is nickel and cobalt doped ferric sodium pyrophosphate material, and the coating layer is carbon material; the thickness of the coating layer is 3-10 nm, and the carbon content is 3-10% of the mass of the composite material.
3. The method for directly preparing ferric sodium pyrophosphate composite material from pyrite according to claim 1, wherein the molar ratio of pyrite, phosphorus source and sodium source is 2.9-3.1: 3.9 to 4.1: 3.9-4.1; the molar ratio of iron element to carbon of pyrite to carbon source is 1: and 2-5, mixing.
4. The method for directly preparing ferric sodium pyrophosphate composite material from pyrite according to claim 1, wherein the phosphorus source comprises at least one of diammonium phosphate, monoammonium phosphate, phosphoric acid, triammonium phosphate, sodium dihydrogen phosphate, disodium hydrogen phosphate, pyrophosphoric acid, sodium pyrophosphate.
5. The method for directly preparing ferric sodium pyrophosphate composite material from pyrite according to claim 1, wherein the sodium source comprises at least one of sodium pyrophosphate, sodium carbonate, sodium bicarbonate, sodium acetate, sodium oxalate, sodium bicarbonate, sodium alginate, sodium citrate.
6. The method for directly preparing ferric sodium pyrophosphate composite material from pyrite according to claim 1, wherein the carbon source comprises at least one of citric acid, glucose, sucrose, acetylene black, super P, graphene, carbon nanotubes and oxalic acid.
7. The method for directly preparing ferric sodium pyrophosphate composite material from pyrite according to claim 1, wherein the protective atmosphere is a hydrogen-argon mixed atmosphere or a hydrogen-nitrogen mixed atmosphere.
8. The method for directly preparing ferric sodium pyrophosphate composite material from pyrite according to claim 7, wherein the hydrogen volume ratio in the mixed gas is 5-10%.
9. A sodium iron pyrophosphate composite material, characterized in that the composite material is made by the method of any one of claims 1-8, the composite material is in a core-shell structure, the inner core is nickel and cobalt doped sodium iron pyrophosphate material, the coating layer is carbon material, and the chemical formula is: na (Na) 4 Fe 3-x-y Co x Ni y (PO 4 ) 2 P 2 O 7 And @ C, wherein 0 < x+y < 0.1.
10. A positive electrode material comprising the ferric sodium pyrophosphate composite material of claim 9.
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| CN103746115A (en) * | 2013-12-13 | 2014-04-23 | 灵宝金源矿业股份有限公司 | Method for preparing cell-grade lithium iron phosphate from pyrite slag |
| CN107507978A (en) * | 2017-07-28 | 2017-12-22 | 齐鲁工业大学 | A kind of sodium-ion battery FeS2/Fe3O4/ C negative materials and preparation method thereof |
| CN107902633A (en) * | 2017-11-06 | 2018-04-13 | 郑州大学 | A kind of selenizing pyrite material and its battery of preparation |
| CN109786715A (en) * | 2019-01-28 | 2019-05-21 | 中南大学 | A method of copper-based rich sodium layered oxide material is prepared based on chalcopyrite |
| CN112909244A (en) * | 2019-12-04 | 2021-06-04 | 中南大学 | Pyrite-based composite material and preparation method and application thereof |
| CN111196600A (en) * | 2020-01-09 | 2020-05-26 | 深圳第三代半导体研究院 | Iron phosphate material with hollow spherical structure and preparation method thereof |
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