CN116986639A - Negative electrode material of sodium ion battery and preparation method and application thereof - Google Patents
Negative electrode material of sodium ion battery and preparation method and application thereof Download PDFInfo
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- CN116986639A CN116986639A CN202311244127.3A CN202311244127A CN116986639A CN 116986639 A CN116986639 A CN 116986639A CN 202311244127 A CN202311244127 A CN 202311244127A CN 116986639 A CN116986639 A CN 116986639A
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- precursor
- sodium ion
- ion battery
- negative electrode
- sodium
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- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 54
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 239000007773 negative electrode material Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000002243 precursor Substances 0.000 claims abstract description 57
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000011259 mixed solution Substances 0.000 claims abstract description 26
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 20
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000004321 preservation Methods 0.000 claims abstract description 17
- 238000005406 washing Methods 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 15
- 238000001354 calcination Methods 0.000 claims abstract description 14
- 229910052742 iron Inorganic materials 0.000 claims abstract description 14
- 239000002253 acid Substances 0.000 claims abstract description 13
- 238000005530 etching Methods 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 239000010405 anode material Substances 0.000 claims abstract description 9
- 239000012716 precipitator Substances 0.000 claims abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 239000007788 liquid Substances 0.000 claims description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 11
- 239000004094 surface-active agent Substances 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 238000000926 separation method Methods 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 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 8
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 8
- 239000008103 glucose Substances 0.000 claims description 8
- 239000002202 Polyethylene glycol Substances 0.000 claims description 7
- 238000005554 pickling Methods 0.000 claims description 7
- 229920001223 polyethylene glycol Polymers 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 239000002077 nanosphere Substances 0.000 claims description 6
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 claims description 6
- -1 alkenyl sulfonate Chemical compound 0.000 claims description 5
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 5
- 239000001632 sodium acetate Substances 0.000 claims description 5
- 235000017281 sodium acetate Nutrition 0.000 claims description 5
- 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 4
- 229930006000 Sucrose Natural products 0.000 claims description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 4
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 4
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 4
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 239000005720 sucrose Substances 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 235000011056 potassium acetate Nutrition 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 229940077386 sodium benzenesulfonate Drugs 0.000 claims description 3
- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical compound [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 claims description 3
- 229940039790 sodium oxalate Drugs 0.000 claims description 3
- MZSDGDXXBZSFTG-UHFFFAOYSA-M sodium;benzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=CC=C1 MZSDGDXXBZSFTG-UHFFFAOYSA-M 0.000 claims description 3
- 229920002472 Starch Polymers 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
- 239000001913 cellulose Substances 0.000 claims description 2
- 229920002678 cellulose Polymers 0.000 claims description 2
- IRXRGVFLQOSHOH-UHFFFAOYSA-L dipotassium;oxalate Chemical compound [K+].[K+].[O-]C(=O)C([O-])=O IRXRGVFLQOSHOH-UHFFFAOYSA-L 0.000 claims description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 2
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 claims description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 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
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 2
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 2
- 239000008107 starch Substances 0.000 claims description 2
- 235000019698 starch Nutrition 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 5
- 230000003139 buffering effect Effects 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 18
- 239000000243 solution Substances 0.000 description 13
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 7
- 239000003792 electrolyte Substances 0.000 description 6
- 238000000227 grinding Methods 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 238000004073 vulcanization Methods 0.000 description 6
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 4
- 239000011258 core-shell material Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000010406 cathode material Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 230000002441 reversible effect Effects 0.000 description 3
- 159000000000 sodium salts Chemical class 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical group COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229940040526 anhydrous sodium acetate Drugs 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229940095991 ferrous disulfide Drugs 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 229920001542 oligosaccharide Polymers 0.000 description 2
- 150000002482 oligosaccharides Chemical class 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000006183 anode active material Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000006182 cathode active material Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229910001448 ferrous ion Inorganic materials 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000011534 incubation Methods 0.000 description 1
- 229910000358 iron sulfate Inorganic materials 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 150000003346 selenoethers Chemical class 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- XGPOMXSYOKFBHS-UHFFFAOYSA-M sodium;trifluoromethanesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C(F)(F)F XGPOMXSYOKFBHS-UHFFFAOYSA-M 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 230000002459 sustained effect Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/12—Sulfides
-
- 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
- H01M4/581—Chalcogenides or intercalation compounds thereof
- H01M4/5815—Sulfides
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
Abstract
The invention provides a negative electrode material of a sodium ion battery, a preparation method and application thereof, and relates to the technical field of sodium ion batteries. Specifically comprises the following steps: 1) Carrying out first heat preservation on the mixed solution of the iron source, the precipitator and the surfactantTreating and obtaining a first precursor; 2) Carrying out heat preservation treatment on the mixed solution of the first precursor and the carbon source for the second time to obtain a second precursor; 3) Carrying out acid washing etching treatment on the second precursor to obtain a third precursor; 4) And mixing the third precursor with the reduced sulfur powder, and calcining at high temperature under vacuum condition to obtain the sodium ion battery anode material. The carbon layer structure of the invention is FeS 2 The volume expansion of the electrode is used for providing elastic buffering, so that the stability of the electrode structure and the sodium ion shuttle property in the circulation process can be obviously improved; meanwhile, the highly graphitized porous carbon has excellent conductivity, realizes stronger electric property enhancement, and has good application prospect.
Description
Technical Field
The invention relates to the technical field of sodium ion batteries, in particular to a sodium ion battery negative electrode material, a preparation method of the sodium ion battery negative electrode material and a sodium ion battery.
Background
The sodium ion battery is a secondary battery, and mainly works by virtue of sodium ions moving between a positive electrode and a negative electrode, and is similar to the working principle of a lithium ion battery; because of the limited lithium resources and the high cost that severely affect the further applications of lithium ion batteries in the energy storage field, sodium ion batteries are currently considered as a promising alternative due to their low cost, high reserves and environmental friendliness. Compared with a lithium ion battery, the sodium ion battery has at least the following advantages: the sodium salt raw material is rich in reserve and low in price; (2) Due to the characteristic of sodium salt, low-concentration electrolyte (the electrolyte with the same concentration, the conductivity of sodium salt is about 20 percent higher than that of lithium electrolyte) is allowed to be used, so that the cost is reduced; (3) The sodium ions do not form alloy with aluminum, and the negative electrode can adopt aluminum foil as a current collector, so that the cost and the weight can be further reduced; (4) Since the sodium ion battery has no overdischarge characteristic, the sodium ion battery is allowed to discharge to zero volt; in addition, the energy density of the sodium ion battery is more than 100Wh/kg, which is comparable with that of a lithium iron phosphate battery, but the cost advantage is obvious, and the sodium ion battery is expected to replace the traditional lead-acid battery in large-scale energy storage.
The current sodium ion negative electrode materials mainly comprise carbonaceous materials, organic compounds, transition metal oxides/sulfides/selenides and the like. Wherein the transition metal sulfide is FeS, feS 2 、Co 9 S 8 、MoS 2 The method has received extensive attention due to the advantages of high theoretical capacity, low cost, environmental protection and the like; feS according to the invention 2 For example, CN201811203277.9 discloses a selenium-doped ferrous disulfide carbon-coated composite, and CN202210778000.9 discloses a phosphorus-doped FeS 2 A negative electrode material of @ C; however, when elemental doping such as sulfur and phosphorus is not present, feS 2 Is not high in electron conductivity and FeS 2 The conversion reaction occurs in the continuous discharge process, which causes volume expansion change, reduces electrochemical circulation stability and seriously affects FeS 2 Reversible discharge capacity and practical application of the cathode material.
In view of this, the present invention has been made.
Disclosure of Invention
The first object of the present invention is to provide a carbon-coated FeS 2 Preparation method of nanosphere sodium ion battery anode material for solving FeS 2 Volume expansion during sustained discharge due to switching reactions, and FeS 2 Negative effects in terms of electrical properties such as low electron conductivity, reduced electrochemical stability, reduced reversible discharge capacity of the negative electrode, etc.
The second aim of the invention is to provide a sodium-ion battery anode material prepared by the preparation method of the sodium-ion battery anode material; the anode material has a unique core-shell nano structure, takes an ordered carbon structure as a cladding shell layer and ferrous disulfide as an anode active material, effectively improves the electrical property and avoids FeS 2 Electrical properties are lost due to volume expansion.
The third object of the present invention is to provide a sodium ion battery, which comprises the negative electrode material of the sodium ion battery.
In order to achieve the above object of the present invention, the following technical solutions are specifically adopted:
the preparation method of the negative electrode material of the sodium ion battery comprises the following steps:
firstly, carrying out heat preservation treatment on a mixed solution of an iron source, a precipitator and a surfactant for the first time, and then carrying out solid-liquid separation to obtain a first precursor;
performing heat preservation treatment on the mixed solution of the first precursor and the carbon source for the second time, and then performing solid-liquid separation to obtain a second precursor;
step three, carrying out acid washing etching treatment on the second precursor, and obtaining a third precursor;
step four, mixing the third precursor with the reduced sulfur powder, and calcining for 4-6 hours at 400-600 ℃ under vacuum condition to obtain the carbon-coated FeS 2 The negative electrode material of the sodium ion battery of the nanospheres.
The sodium ion battery negative electrode material is prepared by adopting the preparation method of the sodium ion battery negative electrode material.
A sodium ion battery comprises the sodium ion battery anode material. Further, the sodium ion battery cathode material, and optionally other cathode active materials or electrode auxiliary materials are prepared to obtain a sodium ion battery cathode, and then the battery cathode is assembled with any battery anode, diaphragm or electrolyte to obtain the sodium ion battery. The materials such as the battery positive electrode, separator, and electrolyte are not limited in the present invention.
Compared with the prior art, the invention has the beneficial effects that: the invention discloses a preparation method of a negative electrode material of a sodium ion battery, which adopts Fe 3 O 4 The @ C template is prepared based on a brand new vacuum vulcanization method to obtain core-shell carbon coated FeS 2 A @ C nanostructure; wherein the carbon layer structure is FeS 2 The volume expansion of the electrode is used for providing elastic buffering, so that the stability of the electrode structure and the sodium ion shuttle property in the circulation process can be obviously improved; meanwhile, the highly graphitized porous carbon has excellent conductivity, thereby realizing electrons of the anode materialThe conductivity is increased, the electrochemical stability is enhanced, the reversible discharge capacity is increased, and the like.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are needed in the description of the embodiments or the prior art will be briefly described, and it is obvious that the drawings in the description below are some embodiments of the present invention, and other drawings can be obtained according to the drawings without inventive effort for a person skilled in the art.
FIG. 1 provides XRD contrast plots for inventive example 1 and comparative example (where PDF#42-1340 represents FeS 2 A standard PDF card);
fig. 2 provides an SEM scan of example 1 of the present invention.
Detailed Description
The technical solution of the present invention will be clearly and completely described below with reference to the accompanying drawings and detailed description, but it will be understood by those skilled in the art that the examples described below are some, but not all, examples of the present invention, and are intended to be illustrative of the present invention only and should not be construed as limiting the scope of the present invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
The invention is carried out by the following specific embodiments: the preparation method of the negative electrode material of the sodium ion battery comprises the following steps: firstly, carrying out heat preservation treatment on a mixed solution of an iron source, a precipitator and a surfactant for the first time, and then carrying out solid-liquid separation to obtain a first precursor; performing heat preservation treatment on the mixed solution of the first precursor and the carbon source for the second time, and then performing solid-liquid separation to obtain a second precursor; step three, the second precursor is subjected to acid treatmentWashing and etching treatment to obtain a third precursor; step four, mixing the third precursor with the reduced sulfur powder, and calcining for 4-6 hours at 400-600 ℃ under vacuum condition to obtain the carbon-coated FeS 2 The negative electrode material of the sodium ion battery of the nanospheres.
The following explanation exists for the method steps of the present invention: in the first step of the invention, fe with uniform spherical structure is obtained by mixing and reacting an iron source, a precipitator and a surfactant 3 O 4 And (3) nanoparticles. Wherein, the precipitant provides alkaline environment on one hand, realizes the precipitation of iron source, realizes static stabilization on the other hand, and prevents particle agglomeration; at the same time, the surfactant can also have the effect of additionally preventing particle agglomeration.
In the second step of the invention, the first precursor and the carbon source are mixed for hydrothermal reaction to obtain the oligosaccharide coated Fe 3 O 4 A sphere of structure; the oligosaccharides are further converted into carbonaceous shells in the subsequent calcination of step four.
In the third step of the invention, part of Fe is realized by etching the second precursor by acid washing 3 O 4 The core is dissolved and removed (Fe 3 O 4 +8HCl==2FeCl 3 +FeCl 2 +4H 2 O) to achieve the effect of relieving the volume expansion of the subsequent vacuum vulcanization step and the volume expansion of the final material during charging and discharging.
In step four of the present invention, the vulcanization of iron oxide (Fe 3 O 4 +8S(g)==3FeS 2 +2SO 2 ) By carrying out the vulcanization reaction in a vacuum environment and at a specific calcination temperature, the sulfur dosage is effectively reduced, and compared with the conventional vulcanization, the sulfur is not required to be particularly excessive, so that the raw material cost is saved; in the second aspect, through a closed vacuum environment, more sufficient reaction between the third precursor and sulfur can be realized, and the vulcanization efficiency is greatly improved; in the third aspect, the sulfur dioxide gas of the reaction byproducts can be effectively post-treated, and the sulfur dioxide gas can be collected and sold in the mass production process, so that the cost is further reduced.
As a preferred embodiment, there is at least one of the following features 1) to 4) for the kind of raw material involved in the present invention:
1) The iron source comprises at least one of ferric trichloride, ferric nitrate, ferric sulfate or ferric acetate;
2) The precipitant comprises at least one of sodium acetate, potassium acetate, sodium oxalate, potassium oxalate, sodium sulfide or sodium citrate;
3) The surfactant comprises at least one of ethylene glycol, polyvinylpyrrolidone (PVP), sodium benzenesulfonate or alpha-sodium alkenyl sulfonate;
4) The carbon source comprises at least one of glucose, sucrose, starch or cellulose.
As a preferred embodiment, in the mixed solution of the first step, the concentration of the iron source is 0.15mol/L to 0.3mol/L, the concentration of the precipitant is 1.0mol/L to 2.0mol/L, and the concentration of the surfactant is 10g/L to 50g/L, based on the amount of the substance of the iron atoms;
as a more preferred embodiment, in the mixed solution of step one, the concentration of the iron source includes, but is not limited to, 0.15, 0.16, 0.17, 0.18, 0.19, 0.2, 0.22, 0.24, 0.26, 0.28, 0.3 (mol/L), the concentration of the precipitant includes, but is not limited to, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0 (mol/L), and the concentration of the surfactant includes, but is not limited to, 10, 15, 20, 25, 30, 35, 40, 45, 50 (g/L), based on the amount of the iron atom substance.
As a preferred embodiment, for the mixed solution of step one, the solvent includes at least one of ethylene glycol, glycerol or propanol. The solvent selected by the invention has a certain reducibility, and can reduce part of iron ions into ferrous ions, so that the component Fe is obtained after subsequent heat preservation treatment 3 O 4 Is a particle of (2).
As a preferred embodiment, in preparing the mixed solution of the first step, the iron source, the precipitant and the surfactant are dissolved in a solvent and then stirred to achieve sufficient mixing; as a more preferable embodiment, stirring is performed at a speed of 400rpm to 800rpm for 1h to 3h, and then the mixed solution of the step one is obtained.
As a preferable implementation mode, the temperature of the first heat preservation treatment is 200-240 ℃, and the time of the first heat preservation treatment is 6-24 hours;
as a more preferred embodiment, the temperature of the first soak process includes, but is not limited to, 200, 205, 210, 215, 220, 225, 230, 235, 240 (°c), and the time of the first soak process includes, but is not limited to, 6, 7, 8, 9, 10, 12, 14, 16, 18, 20, 22, 24 (h).
As a preferred embodiment, the first heat-retaining treatment is performed in a closed reaction vessel such as a reaction kettle, a reaction tank, or a closed reactor; the closed reaction vessel can better provide high-pressure reaction conditions of high temperature and 2-3 mpa.
As a preferred embodiment, after the first heat-preserving treatment is completed, solid-liquid separation is performed, and the obtained solid matter is sufficiently washed to obtain the first precursor; as a more preferable embodiment, the washing can be performed by adopting a mixed solution of ethanol and deionized water as a washing liquid, or can be independently performed by adopting ethanol and deionized water respectively; the washing may be performed several times until the first precursor is cleaned.
As a preferred embodiment, in the mixed solution in the second step, the concentration of the first precursor is 1g/L to 5g/L, and the concentration of the carbon source is 10g/L to 50g/L;
as a more preferred embodiment, in the mixed solution of step two, the concentration of the first precursor includes, but is not limited to, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5 (g/L), and the concentration of the carbon source includes, but is not limited to, 10, 15, 20, 25, 30, 35, 40, 45, 50 (g/L).
As a preferred embodiment, for the mixed solution in the second step, water and ethanol are used as the solvent, and the volume ratio of water to ethanol is (1-4): 1, including but not limited to 1: 1. 2:1. 3: 1. 4:1, etc.
In a preferred embodiment, the first precursor and the carbon source are dissolved in a solvent and stirred to achieve sufficient mixing when the mixed solution of the second step is prepared; as a more preferable embodiment, stirring is carried out at a speed of 400rpm to 800rpm for 1h to 3h, and then the mixed solution of the step two is obtained.
As a preferable implementation mode, the temperature of the second heat preservation treatment is 160-200 ℃, and the time of the second heat preservation treatment is 8-10 hours;
as a more preferred embodiment, the temperature of the second soak treatment includes, but is not limited to, 160, 165, 170, 175, 180, 185, 190, 195, 200 (°c), and the time of the second soak treatment includes, but is not limited to, 8, 8.5, 9, 9.5, 10 (h).
As a preferred embodiment, the second incubation treatment is performed in a closed reaction vessel, such as a reaction kettle, a reaction tank, or a closed reactor; the reaction conditions of high temperature and high pressure can be better provided by the closed reaction vessel.
As a preferred embodiment, after the second heat-preserving treatment is completed, solid-liquid separation is performed, and the obtained solid matter is sufficiently washed to obtain the second precursor; as a more preferable embodiment, the washing can be performed by adopting a mixed solution of ethanol and deionized water as a washing liquid, or can be independently performed by adopting ethanol and deionized water respectively; the washing may be performed several times until the second precursor is cleaned.
As a preferred embodiment, the acid used for the acid etching treatment includes at least one of hydrochloric acid, sulfuric acid, acetic acid, or phosphoric acid; the concentration of the acid is 1mol/L to 4mol/L based on the mass of the hydrogen ions;
as a more preferred embodiment, the concentration of the acid includes, but is not limited to, 1, 1.5, 2, 2.5, 3, 3.5, 4 (mol/L); meanwhile, the content of the second precursor in the pickling solution is 5 g/L-50 g/L.
As a preferable embodiment, the pickling and etching treatment is performed for 5min to 30min, and the pickling treatment is performed in a stirring state;
in a more preferred embodiment, the stirring speed of the acid etching treatment is 300rpm to 500rpm, and the stirring time is 5min to 30min.
As a preferred embodiment, after the pickling and etching treatment is finished, performing solid-liquid separation, and sufficiently washing the obtained solid substance to obtain the third precursor; as a more preferable embodiment, the washing can be performed by adopting a mixed solution of ethanol and deionized water as a washing liquid, or can be independently performed by adopting ethanol and deionized water respectively; the washing may be performed several times until the third precursor is cleaned.
As a preferred embodiment, before performing the fourth step, the method further includes: grinding the third precursor and the reduced sulfur powder, or synchronously mixing and grinding the third precursor and the reduced sulfur powder; as a more preferred embodiment, the grinding is carried out to a particle size > 300 mesh.
As a preferred embodiment, the mass ratio of the third precursor to the reduced sulfur powder is 1: (3-5); as a more preferred embodiment, the mass ratio of the third precursor to the reduced sulfur powder includes, but is not limited to, 1:3. 1:3.5, 1:4. 1:4.5, 1:5.
as a preferred embodiment, the temperature is raised to the calcination temperature at a rate of 1 ℃/min to 3 ℃/min, and then the calcination is performed.
As a preferred embodiment, the temperature of the calcination includes, but is not limited to, 400, 410, 420, 430, 440, 450, 460, 470, 480, 490, 500, 510, 520, 530, 540, 550, 560, 570, 580, 590, 600 (°c), and the time of the calcination includes, but is not limited to, 4, 4.5, 5, 5.5, 6 (h).
Example 1
(1) Ferric trichloride hexahydrate, anhydrous sodium acetate and polyethylene glycol are dissolved in ethylene glycol, and stirred for 2 hours under the condition of stirring speed of 600r/min to obtain solution A. Wherein, the concentration of ferric chloride is 0.2mol/L, the concentration of sodium acetate is 1.5mol/L, and the concentration of polyethylene glycol is 30g/L.
(2) Adding the solution A into a reaction kettle, preserving heat for 15 hours at 220 ℃, centrifuging the solution in the reaction kettle to obtain a precipitate, and repeatedly washing with ethanol and deionized water respectively, or obtaining a precursor A.
(3) Precursor oxide A and analytically pure glucose solid were dissolved in a mixed solution of water and ethanol and stirred for 2h at a stirring speed of 600r/min to give solution B. Wherein the concentration of the precursor oxide A is 3g/L, the concentration of glucose is 30g/L, and the volume ratio of water to ethanol is 2:1.
(4) Adding the solution B into a reaction kettle, and preserving heat for 9 hours at 180 ℃; centrifuging the solution in the reaction kettle to obtain a precipitate, and repeatedly washing with ethanol and deionized water sequentially, or obtaining the precursor oxide B.
(5) The precursor oxide B was added to the HCl solution and stirred for 15min at a stirring speed of 400 r/min. Wherein the amount of the oxide B is 30g/L, and the concentration of HCl is 2mol/L; repeatedly washing the precipitate with ethanol and deionized water, or obtaining the precursor oxide C.
(6) Fully grinding and mixing the precursor oxide C and the reduced sulfur powder, wherein the mass ratio of the precursor oxide C to the reduced sulfur powder is 1:4; then adding the mixed solid into a vacuum sealing tube, heating to 500 ℃ at the speed of 2 ℃/min, and preserving heat and calcining for 5 hours to obtain the core-shell carbon-coated FeS of the embodiment 2 The negative electrode material of the sodium ion battery of the nanospheres.
Example 2
Substantially the same as in example 1, the only difference is that: in the step (6), the temperature is raised to 450 ℃ at a speed of 1 ℃/min, and the calcination is carried out for 6 hours.
Example 3
Substantially the same as in example 1, the only difference is that: in the step (6), the temperature is raised to 600 ℃ at a rate of 3 ℃/min, and the calcination is carried out for 4 hours.
Example 4
Substantially the same as in example 1, the only difference is that:
iron trichloride hexahydrate, sodium acetate anhydrous and polyethylene glycol in step (1) are respectively replaced by ferric nitrate nonahydrate, sodium oxalate anhydrous and polyvinylpyrrolidone;
the glucose in step (3) is replaced by sucrose;
the HCl in step (5) is replaced with sulfuric acid.
Example 5
Substantially the same as in example 1, the only difference is that:
iron trichloride hexahydrate, anhydrous sodium acetate and polyethylene glycol in the step (1) are respectively replaced by iron sulfate, anhydrous potassium acetate and sodium benzenesulfonate correspondingly;
the glucose in step (3) is replaced by sucrose;
the HCl in step (5) is replaced with phosphoric acid.
Example 6
Substantially the same as in example 1, the only difference is that:
in the step (1), the concentration of ferric chloride is 0.15mol/L, the concentration of sodium acetate is 1.0mol/L, and the concentration of polyethylene glycol is 10g/L;
the concentration of the precursor oxide A in the step (3) is 1g/L, and the concentration of glucose is 10g/L;
the amount of the oxide B in the step (5) is 5g/L, and the concentration of HCl is 1mol/L;
in the step (6), the mass ratio of the precursor oxide C to the reduced sulfur powder is 1:3.
example 7
Substantially the same as in example 1, the only difference is that:
in the step (1), the concentration of ferric chloride is 0.3mol/L, the concentration of sodium acetate is 2.0mol/L, and the concentration of polyethylene glycol is 50g/L;
the concentration of the precursor oxide A in the step (3) is 5g/L, and the concentration of glucose is 50g/L;
the amount of the oxide B in the step (5) is 50g/L, and the concentration of HCl is 4mol/L;
in the step (6), the mass ratio of the precursor oxide C to the reduced sulfur powder is 1:5.
comparative example
Substantially the same as in example 1, the only difference is that:
in step (6): fully grinding and mixing the precursor oxide C and the reduced sulfur powder, wherein the mass ratio of the precursor oxide C to the reduced sulfur powder is 1:4; then placing the mixed solid in a tube furnace, heating to 500 ℃, and calcining for 5 hours at a temperature of kept constant to obtain the core-shell carbon-coated FeS of the comparative example 2 The negative electrode material of the sodium ion battery of the nanospheres.
FIG. 1 shows XRD contrast patterns of example 1 and comparative example, and FeS is additionally given in addition to XRD patterns of example 1 and comparative example 2 Standard PDF cards (PDF # 42-1340) for control; fig. 2 shows an SEM scan of example 1.
Test examples
The negative electrode materials for sodium ion batteries obtained in examples 1 to 7 and comparative examples are prepared to obtain a negative electrode for a battery, and the specific steps include: the electrode raw materials comprise the sodium ion battery cathode materials prepared in each example and comparative example, a conductive agent (acetylene black) and an adhesive (CMC), wherein the mass ratio is 8:1:1, a step of; adding proper amount of water, grinding into slurry, and coating on copper foil. And drying in a vacuum oven at 80 ℃ to obtain the electrode negative electrode. And in addition, metal sodium is taken as an anode, electrolyte is ethylene glycol dimethyl ether dissolved with 1mol of sodium triflate, a diaphragm is glass fiber, and the CR2025 button cell is assembled in a glove box filled with argon. The performance of the resulting series of button cells was tested and the test results are shown in table 1.
All sample materials were tested by constant current charge and discharge tests (voltage interval 0.01V-3.0V) on a CT3002AU battery test system manufactured by Wuhan City blue electric electronics Co., ltd.) in a constant temperature environment at 25 ℃. The cycle performance was 1C (1c=1000 mA g -1 ) The test was conducted at a current density, and the test results are shown in Table 1.
TABLE 1
While the invention has been illustrated and described with reference to specific embodiments, it is to be understood that the above embodiments are merely illustrative of the technical aspects of the invention and not restrictive thereof; those of ordinary skill in the art will appreciate that: modifications may be made to the technical solutions described in the foregoing embodiments, or equivalents may be substituted for some or all of the technical features thereof, without departing from the spirit and scope of the present invention; such modifications and substitutions do not depart from the spirit of the corresponding technical solutions; it is therefore intended to cover in the appended claims all such alternatives and modifications as fall within the scope of the invention.
Claims (10)
1. The preparation method of the sodium ion battery anode material is characterized by comprising the following steps of:
firstly, carrying out heat preservation treatment on a mixed solution of an iron source, a precipitator and a surfactant for the first time, and then carrying out solid-liquid separation to obtain a first precursor;
performing heat preservation treatment on the mixed solution of the first precursor and the carbon source for the second time, and then performing solid-liquid separation to obtain a second precursor;
step three, carrying out acid washing etching treatment on the second precursor, and obtaining a third precursor;
step four, mixing the third precursor with the reduced sulfur powder, and calcining for 4-6 hours at 400-600 ℃ under vacuum condition to obtain the carbon-coated FeS 2 The negative electrode material of the sodium ion battery of the nanospheres.
2. The method for preparing a negative electrode material of a sodium ion battery according to claim 1, wherein the preparation method comprises at least one of the following features (a) - (d):
(a) The iron source comprises at least one of ferric trichloride, ferric nitrate, ferric sulfate or ferric acetate;
(b) The precipitant comprises at least one of sodium acetate, potassium acetate, sodium oxalate, potassium oxalate, sodium sulfide or sodium citrate;
(c) The surfactant comprises at least one of polyethylene glycol, polyvinylpyrrolidone, sodium benzenesulfonate or alpha-sodium alkenyl sulfonate;
(d) The carbon source comprises at least one of glucose, sucrose, starch or cellulose.
3. The method for producing a negative electrode material for a sodium ion battery according to claim 1, wherein in the mixed solution of the first step, the concentration of the iron source is 0.15mol/L to 0.3mol/L, the concentration of the precipitant is 1.0mol/L to 2.0mol/L, and the concentration of the surfactant is 10g/L to 50g/L, based on the amount of the substance of iron atoms;
wherein, for the mixed solution of the first step, the solvent comprises at least one of glycol, glycerol or propanol.
4. The method for preparing the negative electrode material of the sodium ion battery according to claim 1, wherein the temperature of the first heat preservation treatment is 200-240 ℃, and the time of the first heat preservation treatment is 6-24 hours.
5. The method for preparing a negative electrode material of a sodium ion battery according to claim 1, wherein in the mixed solution of the second step, the concentration of the first precursor is 1g/L to 5g/L, and the concentration of the carbon source is 10g/L to 50g/L;
wherein, for the mixed solution in the second step, water and ethanol are adopted as solvents, and the volume ratio is (1-4): 1.
6. the method for preparing the negative electrode material of the sodium ion battery according to claim 1, wherein the temperature of the second heat preservation treatment is 160-200 ℃, and the time of the second heat preservation treatment is 8-10 h.
7. The method for preparing the sodium ion battery anode material according to claim 1, wherein the acid used in the pickling etching treatment comprises at least one of hydrochloric acid, sulfuric acid, acetic acid or phosphoric acid, and the concentration of the acid is 1 mol/L-4 mol/L;
the pickling and etching treatment time is 5 min-30 min, and the pickling and etching treatment is carried out in a stirring state.
8. The method for preparing a negative electrode material of a sodium ion battery according to claim 1, wherein the mass ratio of the third precursor to the reduced sulfur powder is 1: (3-5).
9. The negative electrode material for sodium ion battery according to any one of claims 1 to 8.
10. A sodium ion battery comprising the sodium ion battery anode material of claim 9.
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