CN116177499B - Preparation method and application of double-carbon strategy optimized iron diselenide - Google Patents
Preparation method and application of double-carbon strategy optimized iron diselenide Download PDFInfo
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- JZUAITAPPPWUSR-UHFFFAOYSA-N bis(selanylidene)iron Chemical compound [Fe](=[Se])=[Se] JZUAITAPPPWUSR-UHFFFAOYSA-N 0.000 title claims abstract description 127
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 91
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 101
- 229910001415 sodium ion Inorganic materials 0.000 claims abstract description 44
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims abstract description 43
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 39
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 39
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 27
- 239000007788 liquid Substances 0.000 claims abstract description 22
- 238000003756 stirring Methods 0.000 claims abstract description 22
- 239000006185 dispersion Substances 0.000 claims abstract description 19
- IMBKASBLAKCLEM-UHFFFAOYSA-L ferrous ammonium sulfate (anhydrous) Chemical compound [NH4+].[NH4+].[Fe+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O IMBKASBLAKCLEM-UHFFFAOYSA-L 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 16
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims abstract description 14
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims abstract description 14
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000007773 negative electrode material Substances 0.000 claims abstract description 8
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 24
- 239000013543 active substance Substances 0.000 claims description 22
- 239000007795 chemical reaction product Substances 0.000 claims description 21
- 239000008367 deionised water Substances 0.000 claims description 21
- 229910021641 deionized water Inorganic materials 0.000 claims description 21
- 239000011259 mixed solution Substances 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 239000002002 slurry Substances 0.000 claims description 19
- 239000010405 anode material Substances 0.000 claims description 17
- 238000001035 drying Methods 0.000 claims description 17
- 230000009977 dual effect Effects 0.000 claims description 11
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 10
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 10
- 239000002033 PVDF binder Substances 0.000 claims description 10
- 239000006230 acetylene black Substances 0.000 claims description 10
- 238000004140 cleaning Methods 0.000 claims description 10
- 239000011889 copper foil Substances 0.000 claims description 10
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 10
- 239000011230 binding agent Substances 0.000 claims description 5
- 239000006258 conductive agent Substances 0.000 claims description 5
- 229920001661 Chitosan Polymers 0.000 claims description 4
- 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
- 239000008103 glucose Substances 0.000 claims description 4
- OWEGMIWEEQEYGQ-UHFFFAOYSA-N 100676-05-9 Natural products OC1C(O)C(O)C(CO)OC1OCC1C(O)C(O)C(O)C(OC2C(OC(O)C(O)C2O)CO)O1 OWEGMIWEEQEYGQ-UHFFFAOYSA-N 0.000 claims description 3
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 claims description 3
- GUBGYTABKSRVRQ-PICCSMPSSA-N Maltose Natural products O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@@H]1O[C@@H]1[C@@H](CO)OC(O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-PICCSMPSSA-N 0.000 claims description 3
- 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 3
- 229930006000 Sucrose Natural products 0.000 claims description 3
- 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 3
- GUBGYTABKSRVRQ-QUYVBRFLSA-N beta-maltose Chemical compound OC[C@H]1O[C@H](O[C@H]2[C@H](O)[C@@H](O)[C@H](O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@@H]1O GUBGYTABKSRVRQ-QUYVBRFLSA-N 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 239000001863 hydroxypropyl cellulose Substances 0.000 claims description 3
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 239000005720 sucrose Substances 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 8
- 230000008859 change Effects 0.000 abstract description 6
- 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 abstract description 4
- 239000000463 material Substances 0.000 abstract description 4
- 229910052708 sodium Inorganic materials 0.000 abstract description 4
- 239000011734 sodium Substances 0.000 abstract description 4
- 238000003860 storage Methods 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 20
- 229910003481 amorphous carbon Inorganic materials 0.000 description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 8
- 239000010406 cathode material Substances 0.000 description 8
- 239000003792 electrolyte Substances 0.000 description 8
- 239000003365 glass fiber Substances 0.000 description 8
- 239000003960 organic solvent Substances 0.000 description 8
- XGPOMXSYOKFBHS-UHFFFAOYSA-M sodium;trifluoromethanesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C(F)(F)F XGPOMXSYOKFBHS-UHFFFAOYSA-M 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 239000004005 microsphere Substances 0.000 description 6
- 239000000956 alloy Substances 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 238000001000 micrograph Methods 0.000 description 4
- 238000004626 scanning electron microscopy Methods 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 3
- 230000001351 cycling effect Effects 0.000 description 3
- 239000011164 primary particle Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 238000001237 Raman spectrum Methods 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 238000009831 deintercalation Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- 230000002687 intercalation Effects 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- -1 polytetrafluoroethylene Polymers 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 239000011669 selenium Substances 0.000 description 2
- 150000003346 selenoethers Chemical class 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- ZAKAOZUIEHSPGA-UHFFFAOYSA-N [Se].[Se].[Cu] Chemical compound [Se].[Se].[Cu] ZAKAOZUIEHSPGA-UHFFFAOYSA-N 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- INPLXZPZQSLHBR-UHFFFAOYSA-N cobalt(2+);sulfide Chemical compound [S-2].[Co+2] INPLXZPZQSLHBR-UHFFFAOYSA-N 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- XIMIGUBYDJDCKI-UHFFFAOYSA-N diselenium Chemical compound [Se]=[Se] XIMIGUBYDJDCKI-UHFFFAOYSA-N 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910021385 hard carbon 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
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- MHWZQNGIEIYAQJ-UHFFFAOYSA-N molybdenum diselenide Chemical compound [Se]=[Mo]=[Se] MHWZQNGIEIYAQJ-UHFFFAOYSA-N 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B19/00—Selenium; Tellurium; Compounds thereof
- C01B19/007—Tellurides or selenides of metals
-
- 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
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- 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
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
- C01B32/168—After-treatment
-
- 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
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- 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
- H01M4/621—Binders
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- 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
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- 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
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- H01M2004/027—Negative electrodes
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Abstract
A preparation method and application of double-carbon strategy optimized iron diselenide relate to a preparation method and application of iron diselenide. The invention aims to solve the problems that the structure is unstable and the internal conductivity of the material is poor due to unavoidable volume change of iron diselenide in the reaction process, so that the sodium storage performance cannot be fully exerted. The method comprises the following steps: adding ferrous ammonium sulfate and an organic carbon source into the dispersion liquid of the carbon nano tube, stirring and dispersing uniformly by ultrasonic waves, adding selenium powder and hydrazine hydrate, and performing hydrothermal reaction to obtain the iron diselenide with optimized double carbon strategy. The double-carbon strategy optimized iron diselenide is used for preparing a negative electrode material of a sodium ion battery. When the prepared double-carbon strategy-optimized iron diselenide is used as a negative electrode of a sodium ion battery, better rate capability and cycle stability can be shown. The invention can obtain the iron diselenide with optimized double-carbon strategy.
Description
Technical Field
The invention relates to a preparation method and application of iron diselenide.
Background
The development of lithium ion batteries has encountered bottlenecks due to the reduction of lithium resources and the surge of lithium metal prices. Sodium Ion Batteries (SIBs) are considered a promising alternative to lithium ion batteries because of their rocking chair-like energy storage mechanism and abundant sodium resources. Carbon materials (hard carbon, graphite), metal oxides (iron oxide, copper oxide, molybdenum oxide), metal sulfides (molybdenum sulfide, cobalt sulfide), metal selenides (iron diselenide, molybdenum diselenide, copper diselenide), and alloy materials (metallic tin) are used as the negative electrode of sodium ion batteries, and a great deal of research has been conducted. Among them, iron diselenide is considered to be the most promising negative electrode material in sodium ion batteries due to small volume changes, high specific capacity, and weak shuttle effect of the polyselenide.
However, insufficient conductivity and unavoidable volume expansion/contraction in repeated cycling have prevented the pace of commercial use of iron diselenide. Morphology adjustment and addition of carbon materials are the main methods for improving the chemical properties of diselenide ferroelectric materials. However, the single carbon coating does not improve the internal conductivity and nanoparticle aggregation problems still prevent the development of iron diselenide.
Disclosure of Invention
The invention aims to solve the problem that the sodium storage performance cannot be fully exerted due to unstable structure and poor conductivity inside a material caused by unavoidable volume change of iron diselenide in the reaction process, and provides a preparation method and application of the iron diselenide with optimized double-carbon strategy.
The preparation method of the double-carbon strategy optimized iron diselenide is specifically completed according to the following steps:
1. Dispersing the carbon nano tube into deionized water to obtain a dispersion liquid of the carbon nano tube;
2. Adding ferrous ammonium sulfate and an organic carbon source into the dispersion liquid of the carbon nano tube, stirring and uniformly dispersing by ultrasonic waves, adding selenium powder and hydrazine hydrate, and continuously stirring to form uniform mixed liquid;
the organic carbon source in the second step is one or a mixture of more than one of glucose, sucrose, chitosan, maltose, citric acid and hydroxypropyl cellulose;
3. pouring the mixed solution into a hydrothermal reaction kettle, and performing hydrothermal reaction at high temperature and high pressure to obtain a reaction product;
4. And (3) cleaning and drying the reaction product to obtain the iron diselenide with optimized double-carbon strategy.
The double-carbon strategy optimized iron diselenide is used for preparing a negative electrode material of a sodium ion battery.
The principle of the invention is as follows:
The iron diselenide has the advantages of high theoretical specific capacity, weak shuttle effect of the polyselenide, rich reserves and the like. However, iron diselenide inevitably undergoes a volume change during intercalation/deintercalation of sodium ions, resulting in a decrease in structural stability thereof. And the poor electronic conductivity in the iron diselenide can not fully exert the sodium storage performance of the iron diselenide; according to the carbon nano tube with positive charges, the carbon-coated nano iron diselenide particles with negative charges are combined into the microsphere, and the amorphous carbon coated on the surface of the primary iron diselenide particles not only improves the conductivity, but also serves as a buffer layer to relieve the volume change in the sodium ion embedding/extracting process, so that the excellent long cycle life is obtained; in addition, the carbon nanotubes interspersed within the microspheres may improve internal conductivity, thereby improving rate performance. The criss-cross carbon nanotube structure is similar to a 'reinforcement cage', while the iron diselenide nano-particles can be analogous to 'concrete' in the building field; the results show that the dual-carbon strategy is an effective approach for internal and external optimization, and provides a new idea for optimizing the metal selenide used as the negative electrode of the high-performance sodium ion battery.
Compared with the prior art, the technical scheme of the invention has the following advantages:
1. According to the invention, the double-carbon strategy is adopted to optimize the iron diselenide by a one-step hydrothermal method, the amorphous carbon derived from an organic carbon source is coated on the surface of primary particles of the iron diselenide, so that the volume change of the iron diselenide in the sodium ion embedding/extracting process can be relieved, and the carbon nano tube is inserted into the iron diselenide microsphere, so that the electronic conductivity of the iron diselenide microsphere can be improved, and therefore, when the iron diselenide optimized by the double-carbon strategy is used as a negative electrode of a sodium ion battery, better multiplying power performance and circulation stability can be shown;
2. According to the invention, the double-carbon strategy is adopted to optimize the iron diselenide, the amorphous carbon derived from the organic carbon source is coated on the surface of the primary particle of the iron diselenide to relieve the volume change of the primary particle of the iron diselenide in the sodium ion intercalation/deintercalation process, and the carbon nano tube is inserted in the iron diselenide, so that the electronic conductivity in the iron diselenide can be improved;
3. The invention provides a simple one-step hydrothermal method for optimizing the structure of iron diselenide; meanwhile, the problems of poor conductivity and poor structural stability are solved, and the operation is simple and the repeatability is high;
4. The method takes the iron diselenide optimized by the double-carbon strategy as an active substance, and prepares the negative electrode of the sodium ion battery by mixing and grinding the active substance, the conductive agent and the binder, and has the advantages of good conductivity, high structural stability and the like; the material is used for sodium ion batteries, and has good rate performance and excellent cycle stability.
Drawings
FIG. 1 is a scanning electron microscope image, in which (a) is a scanning electron microscope image of pure iron diselenide prepared in comparative example 2; (b) Scanning electron microscopy images of amorphous carbon coated iron diselenide prepared for comparative example 1; (c) Scanning electron microscopy images of iron diselenide optimized for the two-carbon strategy prepared in example 1;
FIG. 2 is an XRD spectrum of pure iron diselenide prepared in comparative example 2, amorphous carbon coated iron diselenide prepared in comparative example 1, and dual carbon policy optimized iron diselenide prepared in example 1;
FIG. 3 is a Raman spectrum of pure iron diselenide prepared in comparative example 2, amorphous carbon coated iron diselenide prepared in comparative example 1, and dual carbon strategy optimized iron diselenide prepared in example 1;
FIG. 4 is a graph of the rate performance, wherein 1 is pure iron diselenide prepared in comparative example 2, 2 is amorphous carbon coated iron diselenide prepared in comparative example 1, and 3 is dual carbon policy optimized iron diselenide prepared in example 1;
Fig. 5 is a graph of the cycling performance of the dual carbon policy optimized iron diselenide prepared in example 1.
Detailed Description
The first embodiment is as follows: the preparation method of the double-carbon strategy optimized iron diselenide is specifically completed according to the following steps:
1. Dispersing the carbon nano tube into deionized water to obtain a dispersion liquid of the carbon nano tube;
2. Adding ferrous ammonium sulfate and an organic carbon source into the dispersion liquid of the carbon nano tube, stirring and uniformly dispersing by ultrasonic waves, adding selenium powder and hydrazine hydrate, and continuously stirring to form uniform mixed liquid;
the organic carbon source in the second step is one or a mixture of more than one of glucose, sucrose, chitosan, maltose, citric acid and hydroxypropyl cellulose;
3. pouring the mixed solution into a hydrothermal reaction kettle, and performing hydrothermal reaction at high temperature and high pressure to obtain a reaction product;
4. And (3) cleaning and drying the reaction product to obtain the iron diselenide with optimized double-carbon strategy.
The second embodiment is as follows: the present embodiment differs from the specific embodiment in that: the volume ratio of the mass of the carbon nano tube to the deionized water in the first step is (100 mg-200 mg) (50 mL-100 mL). The other steps are the same as in the first embodiment.
And a third specific embodiment: this embodiment differs from the first or second embodiment in that: the molar ratio of the ferrous ammonium sulfate to the selenium powder in the second step is 1:2. The other steps are the same as those of the first or second embodiment.
The specific embodiment IV is as follows: one difference between this embodiment and the first to third embodiments is that: the mass ratio of the substance of the ferrous ammonium sulfate to the organic carbon source in the second step is (2 mmol-6 mmol) (0.2 g-2 g). The other steps are the same as those of the first to third embodiments.
Fifth embodiment: one to four differences between the present embodiment and the specific embodiment are: the mass ratio of the organic carbon source to the carbon nano tube in the second step is (0.2 g-2 g) (100 mg-200 mg). Other steps are the same as those of the first to fourth embodiments.
Specific embodiment six: the present embodiment differs from the first to fifth embodiments in that: the volume ratio of the mass of the organic carbon source to the hydrazine hydrate in the second step is (0.2 g-2 g) (10 mL-20 mL). Other steps are the same as those of the first to fifth embodiments.
Seventh embodiment: one difference between the present embodiment and the first to sixth embodiments is that: the temperature of the hydrothermal reaction in the third step is 120-240 ℃, and the time of the hydrothermal reaction is 6-48 h. Other steps are the same as those of embodiments one to six.
Eighth embodiment: the embodiment is a double-carbon strategy optimized iron diselenide for preparing a sodium ion battery anode material.
Detailed description nine: one of the differences between this embodiment and the first to eighth embodiments is: the preparation of the sodium ion battery anode material by using the double-carbon strategy optimized iron diselenide is specifically completed according to the following steps: the iron diselenide optimized by the double-carbon strategy is taken as an active substance, and is added into N-methyl pyrrolidone according to the mass ratio of (7-8.5) (0.5-2) (0.5-1) of the active substance, the conductive agent and the binder, ground to uniform slurry, and then coated on a copper foil to obtain the negative electrode material of the sodium ion battery. Other steps are the same as those of embodiments one to eight.
Detailed description ten: the present embodiment differs from the first to ninth embodiments in that: the conductive agent is acetylene black; the binder is polyvinylidene fluoride. The other steps are the same as those of embodiments one to nine.
The following examples are used to verify the benefits of the present invention:
example 1: the preparation method of the double-carbon strategy optimized iron diselenide is specifically completed according to the following steps:
1. Dispersing 100mg of carbon nanotubes into 50mL of deionized water to obtain a carbon nanotube dispersion;
2. adding 4mmol of ferrous ammonium sulfate and 1g of citric acid into the dispersion liquid of the carbon nano tube, stirring and dispersing for 2 hours by ultrasonic wave, adding 8mmol of selenium powder and 20mL of hydrazine hydrate, and continuously stirring for 2 hours to form a uniform mixed liquid;
3. Pouring the mixed solution into a 100mL hydrothermal reaction kettle, placing the mixed solution into a blast drying box, and performing hydrothermal reaction at a high temperature and a high pressure of 200 ℃ for 18 hours to obtain a reaction product;
4. And (3) respectively cleaning the reaction products for 3 times by using deionized water and absolute ethyl alcohol in sequence, and drying to obtain the iron diselenide (CNT@FeSe 2 -C) with optimized double carbon strategy.
The iron diselenide with optimized double carbon strategy prepared in the example 1 is used as an active substance, and is mixed and ground into uniform slurry in an N-methyl pyrrolidone organic solvent according to the mass ratio of the active substance, acetylene black and polyvinylidene fluoride of 8:1:1, and the uniform slurry is coated on a copper foil to prepare the sodium ion battery anode material; the prepared sodium ion battery cathode material is used as a working electrode, sodium metal is used as a counter electrode, glass fiber is used as a diaphragm, sodium trifluoromethane sulfonate is used as electrolyte, a CR2032 button battery is assembled, and the specific capacity of the CR2032 button battery is tested under the current density of 0.1 A.g -1; the rate performance of the cells was tested at different current densities of 0.1, 0.2, 0.5, 1.0, 2.0, 5, 10, 15a·g -1, etc.; cycle performance was tested at a current density of 10a·g -1; the test results obtained showed that: the sodium ion battery anode material prepared by the method has good electrochemical performance: has a high specific capacity of 514.8 mAh-g -1 at a current density of 0.1A-g -1; at a large current density of 15 A.g -1, the ceramic material has a specific capacity of 306 mAh.g -1; after 10000 circles of circulation, the specific capacity of 237 mAh.g -1 can still be maintained under the current density of 10 A.g -1, and the capacity retention rate is as high as 72.2%.
Example 2: the preparation method of the double-carbon strategy optimized iron diselenide is specifically completed according to the following steps:
1. Dispersing 100mg of carbon nanotubes into 50mL of deionized water to obtain a carbon nanotube dispersion;
2. adding 4mmol of ferrous ammonium sulfate and 1.5g of citric acid into the dispersion liquid of the carbon nano tube, stirring and dispersing for 2 hours by ultrasonic wave, adding 8mmol of selenium powder and 20mL of hydrazine hydrate, and continuously stirring for 2 hours to form uniform mixed liquid;
3. Pouring the mixed solution into a 100mL hydrothermal reaction kettle, placing the mixed solution into a blast drying box, and performing hydrothermal reaction at a high temperature and a high pressure of 200 ℃ for 18 hours to obtain a reaction product;
4. And (3) respectively cleaning the reaction products for 3 times by using deionized water and absolute ethyl alcohol in sequence, and drying to obtain the iron diselenide (CNT@FeSe 2 -C) with optimized double carbon strategy.
The iron diselenide with optimized double carbon strategy prepared in the example 2 is used as an active substance, and is mixed and ground into uniform slurry in an N-methyl pyrrolidone organic solvent according to the mass ratio of the active substance, acetylene black and polyvinylidene fluoride of 8:1:1, and the uniform slurry is coated on a copper foil to prepare the sodium ion battery anode material; the prepared sodium ion battery cathode material is used as a working electrode, sodium metal is used as a counter electrode, glass fiber is used as a diaphragm, sodium trifluoromethane sulfonate is used as electrolyte, and the CR2032 button battery is assembled, and the specific capacity is tested under the current density of 0.1 A.g -1; the rate performance of the cells was tested at different current densities of 0.1,0.2, 0.5, 1.0, 2.0, 5, 10, 15a·g -1, etc.; cycle performance was tested at a current density of 10a·g -1; the test results obtained showed that: the sodium ion battery anode material prepared by the method has good electrochemical performance: a high specific capacity of 504.3 mAh-g -1 at a current density of 0.1A-g -1; at a high current density of 15 A.g -1, a specific capacity of 297.7 mAh.g -1 is possessed; after 10000 cycles of circulation under the current density of 10 A.g -1, the specific capacity of 214.4 mAh.g -1 can be still maintained.
Example 3: the preparation method of the double-carbon strategy optimized iron diselenide is specifically completed according to the following steps:
1. dispersing 150mg of carbon nanotubes into 50mL of deionized water to obtain a carbon nanotube dispersion;
2. adding 4mmol of ferrous ammonium sulfate and 1g of citric acid into the dispersion liquid of the carbon nano tube, stirring and dispersing for 2 hours by ultrasonic wave, adding 8mmol of selenium powder and 20mL of hydrazine hydrate, and continuously stirring for 2 hours to form a uniform mixed liquid;
3. Pouring the mixed solution into a 100mL hydrothermal reaction kettle, placing the mixed solution into a blast drying box, and performing hydrothermal reaction at a high temperature and a high pressure of 200 ℃ for 18 hours to obtain a reaction product;
4. And (3) respectively cleaning the reaction products for 3 times by using deionized water and absolute ethyl alcohol in sequence, and drying to obtain the iron diselenide (CNT@FeSe 2 -C) with optimized double carbon strategy.
The iron diselenide with optimized double carbon strategy prepared in the example 3 is used as an active substance, and is mixed and ground into uniform slurry in an N-methyl pyrrolidone organic solvent according to the mass ratio of the active substance, acetylene black and polyvinylidene fluoride of 8:1:1, and the uniform slurry is coated on a copper foil to prepare the sodium ion battery anode material; the prepared sodium ion battery cathode material is used as a working electrode, sodium metal is used as a counter electrode, glass fiber is used as a diaphragm, sodium trifluoromethane sulfonate is used as electrolyte, and the CR2032 button battery is assembled, and the specific capacity is tested under the current density of 0.1 A.g -1; the rate performance of the cells was tested at different current densities of 0.1,0.2, 0.5, 1.0, 2.0, 5, 10, 15a·g -1, etc.; cycle performance was tested at a current density of 10a·g -1; the test results obtained showed that: the sodium ion battery anode material prepared by the method has good electrochemical performance: has a high specific capacity of 486.1 mAh-g -1 at a current density of 0.1A-g -1; at a large current density of 15 A.g -1, the alloy has a specific capacity of 284.2 mAh.g -1; after 10000 cycles of circulation under the current density of 10 A.g -1, the specific capacity of 202.9 mAh.g -1 can be still maintained.
Example 4: the preparation method of the double-carbon strategy optimized iron diselenide is specifically completed according to the following steps:
1. Dispersing 100mg of carbon nanotubes into 50mL of deionized water to obtain a carbon nanotube dispersion;
2. Adding 4mmol of ferrous ammonium sulfate and 2g of citric acid into the dispersion liquid of the carbon nano tube, stirring and dispersing for 2 hours by ultrasonic wave, adding 8mmol of selenium powder and 20mL of hydrazine hydrate, and continuously stirring for 2 hours to form uniform mixed liquid;
3. Pouring the mixed solution into a 100mL hydrothermal reaction kettle, placing the mixed solution into a blast drying box, and performing hydrothermal reaction at a high temperature and a high pressure of 200 ℃ for 18 hours to obtain a reaction product;
4. And (3) respectively cleaning the reaction products for 3 times by using deionized water and absolute ethyl alcohol in sequence, and drying to obtain the iron diselenide (CNT@FeSe 2 -C) with optimized double carbon strategy.
The iron diselenide with optimized double carbon strategy prepared in the example 4 is used as an active substance, and is mixed and ground into uniform slurry in an N-methyl pyrrolidone organic solvent according to the mass ratio of the active substance, acetylene black and polyvinylidene fluoride of 8:1:1, and the uniform slurry is coated on a copper foil to prepare the sodium ion battery anode material; the prepared sodium ion battery cathode material is used as a working electrode, sodium metal is used as a counter electrode, glass fiber is used as a diaphragm, sodium trifluoromethane sulfonate is used as electrolyte, and the CR2032 button battery is assembled, and the specific capacity is tested under the current density of 0.1 A.g -1; the rate performance of the cells was tested at different current densities of 0.1,0.2, 0.5, 1.0, 2.0, 5, 10, 15a·g -1, etc.; cycle performance was tested at a current density of 10a·g -1; the test results obtained showed that: the sodium ion battery anode material prepared by the method has good electrochemical performance: has a high specific capacity of 475.3 mAh-g -1 at a current density of 0.1A-g -1; at a large current density of 15 A.g -1, the specific capacity of 265.5 mAh.g -1 is possessed; after 10000 cycles of circulation under the current density of 10 A.g -1, the specific capacity of 198.1 mAh.g -1 can still be maintained.
Example 5: the preparation method of the double-carbon strategy optimized iron diselenide is specifically completed according to the following steps:
1. Dispersing 100mg of carbon nanotubes into 50mL of deionized water to obtain a carbon nanotube dispersion;
2. Adding 4mmol of ferrous ammonium sulfate and 1.0g of glucose into the dispersion liquid of the carbon nano tube, stirring and dispersing for 2 hours by ultrasonic wave, adding 8mmol of selenium powder and 20mL of hydrazine hydrate, and continuously stirring for 2 hours to form a uniform mixed liquid;
3. Pouring the mixed solution into a 100mL hydrothermal reaction kettle, placing the mixed solution into a blast drying box, and performing hydrothermal reaction at a high temperature and a high pressure of 180 ℃ for 12 hours to obtain a reaction product;
4. And (3) respectively cleaning the reaction products for 3 times by using deionized water and absolute ethyl alcohol in sequence, and drying to obtain the iron diselenide (CNT@FeSe 2 -C) with optimized double carbon strategy.
The iron diselenide with optimized double carbon strategy prepared in the example 5 is used as an active substance, and is mixed and ground into uniform slurry in an N-methyl pyrrolidone organic solvent according to the mass ratio of the active substance, acetylene black and polyvinylidene fluoride of 8:1:1, and the uniform slurry is coated on a copper foil to prepare the sodium ion battery anode material; the prepared sodium ion battery cathode material is used as a working electrode, sodium metal is used as a counter electrode, glass fiber is used as a diaphragm, sodium trifluoromethane sulfonate is used as electrolyte, and the CR2032 button battery is assembled, and the specific capacity is tested under the current density of 0.1 A.g -1; the rate performance of the cells was tested at different current densities of 0.1,0.2, 0.5, 1.0, 2.0, 5, 10, 15a·g -1, etc.; cycle performance was tested at a current density of 10a·g -1; the test results obtained showed that: the sodium ion battery anode material prepared by the method has good electrochemical performance: a high specific capacity of 504.0 mAh-g -1 at a current density of 0.1A-g -1; at a large current density of 15 A.g -1, the alloy has a specific capacity of 291.5 mAh.g -1; after 10000 cycles of circulation under the current density of 10 A.g -1, the specific capacity of 203.8 mAh.g -1 can be still maintained.
Example 6: the preparation method of the double-carbon strategy optimized iron diselenide is specifically completed according to the following steps:
1. Dispersing 100mg of carbon nanotubes into 50mL of deionized water to obtain a carbon nanotube dispersion;
2. Adding 4mmol of ferrous ammonium sulfate and 1g of chitosan into the dispersion liquid of the carbon nano tube, stirring and dispersing for 2 hours by ultrasonic wave, adding 8mmol of selenium powder and 20mL of hydrazine hydrate, and continuously stirring for 2 hours to form uniform mixed liquid;
3. Pouring the mixed solution into a 100mL hydrothermal reaction kettle, placing the mixed solution into a blast drying box, and performing hydrothermal reaction at a high temperature and a high pressure of 180 ℃ for 24 hours to obtain a reaction product;
4. And (3) respectively cleaning the reaction products for 3 times by using deionized water and absolute ethyl alcohol in sequence, and drying to obtain the iron diselenide (CNT@FeSe 2 -C) with optimized double carbon strategy.
The iron diselenide with optimized double carbon strategy prepared in the example 6 is used as an active substance, and is mixed and ground into uniform slurry in an N-methyl pyrrolidone organic solvent according to the mass ratio of the active substance, acetylene black and polyvinylidene fluoride of 8:1:1, and the uniform slurry is coated on a copper foil to prepare the sodium ion battery anode material; the prepared sodium ion battery cathode material is used as a working electrode, sodium metal is used as a counter electrode, glass fiber is used as a diaphragm, sodium trifluoromethane sulfonate is used as electrolyte, and the CR2032 button battery is assembled, and the specific capacity is tested under the current density of 0.1 A.g -1; the rate performance of the cells was tested at different current densities of 0.1,0.2, 0.5, 1.0, 2.0, 5, 10, 15a·g -1, etc.; cycle performance was tested at a current density of 10a·g -1; the test results obtained showed that: the sodium ion battery anode material prepared by the method has good electrochemical performance: has a high specific capacity of 488.5 mAh-g -1 at a current density of 0.1A-g -1; at a large current density of 15 A.g -1, the alloy has a specific capacity of 284.8 mAh.g -1; after 10000 cycles of circulation, the specific capacity of 199.6 mAh.g -1 can be still maintained under the current density of 10 A.g -1.
Comparative example 1: the preparation method of amorphous carbon coated iron diselenide is completed according to the following steps:
Adding 4mmol of ferrous sulfate and 0.5g of citric acid into 50mL of deionized water, performing ultrasonic dispersion for 2h, adding 8mmol of selenium powder and 20mL of hydrazine hydrate, and fully stirring for 2h to form a uniform mixed solution; pouring the obtained mixed solution into a 100mL polytetrafluoroethylene reaction kettle, and placing the mixed solution into a blast drying box for hydrothermal reaction for 18h at the temperature of 200 ℃; and after the reaction is finished, the reaction kettle is cooled to room temperature, deionized water and absolute ethyl alcohol are sequentially used for respectively cleaning the reaction products for 3 times, and amorphous carbon coated iron diselenide (FeSe 2 -C) is obtained.
The amorphous carbon coated iron diselenide prepared in the comparative example 1 is used as an active substance, and is mixed and ground into uniform slurry in an N-methyl pyrrolidone organic solvent according to the mass ratio of the active substance, acetylene black and polyvinylidene fluoride of 8:1:1, and the uniform slurry is coated on a copper foil to prepare the sodium ion battery anode material; the prepared sodium ion battery cathode material is used as a working electrode, sodium metal is used as a counter electrode, glass fiber is used as a diaphragm, sodium trifluoromethane sulfonate is used as electrolyte, and the CR2032 button battery is assembled, and the specific capacity is tested under the current density of 0.1 A.g -1; the rate performance of the cells was tested at different current densities of 0.1, 0.2, 0.5, 1.0, 2.0, 5, 10, 15a·g -1, etc.; the test results obtained showed that: the sodium ion battery anode material prepared by the method has poor electrochemical performance: has a high specific capacity of 428.1 mAh.g -1 at a current density of 0.1 A.g -1; at a large current density of 15 A.g -1, it has a specific capacity of 90.4 mAh.g -1.
Comparative example 2: the preparation method of the pure iron diselenide is completed according to the following steps:
firstly, adding 4mmol of ferrous ammonium sulfate into 50mL of deionized water, stirring until the ferrous ammonium sulfate is completely dissolved, then adding 8mmol of selenium powder and 20mL of hydrazine hydrate, and fully stirring for 2h to form a uniform mixed solution; pouring the obtained mixed solution into a polytetrafluoroethylene reaction kettle with the volume of 100mL, placing the mixed solution into a blast drying box, performing hydrothermal reaction for 18h at the temperature of 200 ℃, and cooling the reaction kettle to the room temperature after the reaction is finished to obtain a reaction product; and (3) washing the reaction product for 3 times by using deionized water and absolute ethyl alcohol in sequence to obtain pure iron diselenide (FeSe 2).
The pure iron diselenide prepared in the comparative example 2 is taken as an active substance, and is mixed and ground into uniform slurry in an N-methyl pyrrolidone organic solvent according to the mass ratio of the active substance, acetylene black and polyvinylidene fluoride of 8:1:1, and the uniform slurry is coated on a copper foil to prepare the negative electrode material of the sodium ion battery; the prepared sodium ion battery cathode material is used as a working electrode, sodium metal is used as a counter electrode, glass fiber is used as a diaphragm, sodium trifluoromethane sulfonate is used as electrolyte, and the CR2032 button battery is assembled, and the specific capacity is tested under the current density of 0.1 A.g -1; the rate performance of the cells was tested at different current densities of 0.1, 0.2, 0.5, 1.0, 2.0, 5, 10, 15a·g -1, etc.; the test results obtained showed that: the electrochemical performance of the negative electrode material of the sodium ion battery prepared by the method is very poor: has a specific capacity of 396.2mAh/g at a current density of 0.1 A.g -1; at a large current density of 15 A.g -1, the specific capacity is only 8.4 mAh.g -1.
FIG. 1 is a scanning electron microscope image, in which (a) is a scanning electron microscope image of pure iron diselenide prepared in comparative example 2; (b) Scanning electron microscopy images of amorphous carbon coated iron diselenide prepared for comparative example 1; (c) Scanning electron microscopy images of iron diselenide optimized for the two-carbon strategy prepared in example 1;
As can be seen from fig. 1, (a) pure iron diselenide exhibits an irregularly sized, disordered grain structure; (b) Amorphous carbon coated iron diselenide exhibits a clustered structure; (c) The dual carbon strategy optimized iron diselenide exhibits a uniform size microsphere morphology.
FIG. 2 is an XRD spectrum of pure iron diselenide prepared in comparative example 2, amorphous carbon coated iron diselenide prepared in comparative example 1, and dual carbon policy optimized iron diselenide prepared in example 1;
As can be seen from fig. 2: the characteristic diffraction peaks in XRD spectra of pure iron diselenide, amorphous carbon coated iron diselenide and double carbon strategy optimized iron diselenide are basically consistent, which indicates that the carbon coating and double carbon optimization operation cannot influence the crystal structure of the iron diselenide, and the characteristic peaks of carbon nano tubes are arranged on the double carbon strategy optimized iron diselenide XRD spectrum, which indicates that the carbon nano tubes are successfully introduced into the iron diselenide microsphere.
FIG. 3 is a Raman spectrum of pure iron diselenide prepared in comparative example 2, amorphous carbon coated iron diselenide prepared in comparative example 1, and dual carbon strategy optimized iron diselenide prepared in example 1;
As can be seen from fig. 3: in the Raman spectrograms of pure iron diselenide, amorphous carbon coated iron diselenide and double carbon strategy optimized iron diselenide, obvious characteristic peaks are respectively arranged at 180.5cm -1 and 216.3cm -1, the corresponding characteristic peaks are the telescopic vibration of Fe-Se bonds and Se-Se bonds in the iron diselenide, and the weak characteristic peaks of the carbon coated iron diselenide at 1320cm -1 and 1560cm -1 are the corresponding amorphous carbon; the strong diffraction peaks of the iron diselenide optimized by the double-carbon strategy at 1350cm -1 and 1650cm -1 correspond to characteristic peaks of the carbon nanotubes.
FIG. 4 is a graph of the rate performance, wherein 1 is pure iron diselenide prepared in comparative example 2, 2 is amorphous carbon coated iron diselenide prepared in comparative example 1, and 3 is dual carbon policy optimized iron diselenide prepared in example 1;
As can be seen from fig. 4, the dual carbon strategy optimized iron diselenide exhibits far superior iron diselenide and carbon coated iron diselenide rate capability as the current increases. At a current density of 15 A.g -1, the capacity is as high as 306 mAh.g -1.
Fig. 5 is a graph of the cycling performance of the dual carbon policy optimized iron diselenide prepared in example 1.
As can be seen from fig. 5, the iron diselenide optimized by the two-carbon strategy exhibits excellent cycle performance, and the capacity retention rate after 10000 cycles is still up to 72.2% at a current density of 10a·g -1.
Claims (10)
1. The preparation method of the double-carbon strategy optimized iron diselenide is characterized by comprising the following steps of:
1. Dispersing the carbon nano tube into deionized water to obtain a dispersion liquid of the carbon nano tube;
2. Adding ferrous ammonium sulfate and an organic carbon source into the dispersion liquid of the carbon nano tube, stirring and uniformly dispersing by ultrasonic waves, adding selenium powder and hydrazine hydrate, and continuously stirring to form uniform mixed liquid;
the organic carbon source in the second step is one or a mixture of more than one of glucose, sucrose, chitosan, maltose, citric acid and hydroxypropyl cellulose;
3. pouring the mixed solution into a hydrothermal reaction kettle, and performing hydrothermal reaction at high temperature and high pressure to obtain a reaction product;
4. And (3) cleaning and drying the reaction product to obtain the iron diselenide with optimized double-carbon strategy.
2. The method for preparing the iron diselenide optimized by the two-carbon strategy according to claim 1, wherein the volume ratio of the mass of the carbon nano tube to the deionized water in the first step is (100 mg-200 mg) (50 mL-100 mL).
3. The method for preparing iron diselenide optimized by a two-carbon strategy according to claim 1, wherein the molar ratio of ferrous ammonium sulfate to selenium powder in the second step is 1:2.
4. The preparation method of the double-carbon strategy-optimized iron diselenide is characterized in that the mass ratio of the substance amount of ferrous ammonium sulfate to the organic carbon source in the second step is (2 mmol-6 mmol) (0.2 g-2 g).
5. The preparation method of the double-carbon strategy-optimized iron diselenide, which is characterized in that the mass ratio of the organic carbon source to the carbon nano tube in the second step is (0.2 g-2 g) (100 mg-200 mg).
6. The preparation method of the double-carbon strategy optimized iron diselenide, which is characterized in that the volume ratio of the mass of the organic carbon source to the hydrazine hydrate in the second step is (0.2 g-2 g) (10 mL-20 mL).
7. The preparation method of the double-carbon strategy optimized iron diselenide, which is characterized in that the temperature of the hydrothermal reaction in the step three is 120-240 ℃ and the time of the hydrothermal reaction is 6-48 h.
8. The use of a double-carbon strategy-optimized iron diselenide prepared by the preparation method according to any one of claims 1-7, wherein the double-carbon strategy-optimized iron diselenide is used for preparing a sodium ion battery anode material.
9. The use of a double carbon strategy optimized iron diselenide according to claim 8, characterized in that the double carbon strategy optimized iron diselenide is used for preparing a negative electrode material of a sodium ion battery, which is specifically accomplished by the following steps: and adding (7-8.5) (0.5-2) (0.5-1) of iron diselenide optimized by a double-carbon strategy as an active substance into N-methylpyrrolidone according to the mass ratio of the active substance to the conductive agent to the binder, grinding to obtain uniform slurry, and then coating the uniform slurry on a copper foil to obtain the negative electrode material of the sodium ion battery.
10. The use of a dual carbon policy optimized iron diselenide according to claim 9, wherein said conductive agent is acetylene black; the binder is polyvinylidene fluoride.
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