CN108767260B - A carbon-coated FeP hollow nano-electrode material and its preparation method and application - Google Patents
A carbon-coated FeP hollow nano-electrode material and its preparation method and application Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 87
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 85
- 239000007772 electrode material Substances 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000002105 nanoparticle Substances 0.000 claims abstract description 39
- 229910001415 sodium ion Inorganic materials 0.000 claims abstract description 25
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- 239000010406 cathode material Substances 0.000 claims abstract description 12
- 238000011065 in-situ storage Methods 0.000 claims abstract description 6
- 239000002344 surface layer Substances 0.000 claims abstract description 6
- 239000010410 layer Substances 0.000 claims abstract description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 48
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 41
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 40
- 239000000203 mixture Substances 0.000 claims description 37
- 229910001868 water Inorganic materials 0.000 claims description 26
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 25
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 24
- 238000001035 drying Methods 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 24
- 238000005406 washing Methods 0.000 claims description 24
- 239000000843 powder Substances 0.000 claims description 22
- 238000001816 cooling Methods 0.000 claims description 21
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 20
- 239000000243 solution Substances 0.000 claims description 19
- 238000001354 calcination Methods 0.000 claims description 18
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 16
- 239000002243 precursor Substances 0.000 claims description 16
- 239000008367 deionised water Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 14
- 239000011248 coating agent Substances 0.000 claims description 12
- 238000000576 coating method Methods 0.000 claims description 12
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 12
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims description 10
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 10
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 10
- 238000005530 etching Methods 0.000 claims description 10
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 8
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 8
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 6
- 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 claims description 6
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- 239000000463 material Substances 0.000 abstract description 13
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- 239000002131 composite material Substances 0.000 abstract 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 9
- 238000000137 annealing Methods 0.000 description 8
- 235000019441 ethanol Nutrition 0.000 description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 6
- QZRHHEURPZONJU-UHFFFAOYSA-N iron(2+) dinitrate nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QZRHHEURPZONJU-UHFFFAOYSA-N 0.000 description 6
- 229910052744 lithium Inorganic materials 0.000 description 6
- 239000005416 organic matter Substances 0.000 description 6
- 229910052723 transition metal Inorganic materials 0.000 description 6
- 150000003624 transition metals Chemical class 0.000 description 6
- 239000011149 active material Substances 0.000 description 4
- 238000003487 electrochemical reaction Methods 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000002086 nanomaterial Substances 0.000 description 4
- 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 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000001768 carboxy methyl cellulose Substances 0.000 description 3
- 230000001351 cycling effect Effects 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 239000007773 negative electrode material Substances 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 2
- 238000009831 deintercalation Methods 0.000 description 2
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- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 238000004080 punching Methods 0.000 description 2
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- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 2
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
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- 239000006258 conductive agent Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
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- 239000008187 granular material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 238000005381 potential energy Methods 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 description 1
- 229910001488 sodium perchlorate Inorganic materials 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
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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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- 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
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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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a carbon-coated FeP hollow nano-electrode material and a preparation method and application thereof. The composite material is formed by assembling an FeP nano particle inner core with the diameter of 200-300 nanometers and a carbon shell surface layer; wherein a middle layer gap is formed between the nanoparticle inner core and the carbon shell surface layer, and the diameter of the nano electrode material is 300-400 nanometers. The carbon-coated FeP hollow nano-electrode material is prepared by a simple hydrothermal-coating-calcining-etching-high-temperature in-situ reaction five-step method, the process is simple and easy to operate, the cost is greatly reduced, the preparation process is green and environment-friendly, and the carbon-coated FeP hollow nano-electrode material has potential large-scale market application value; when the material is used as a sodium ion battery cathode material, the charge-discharge specific capacity can reach 582mA/g for the first time under a charge-discharge test under a high current density of 200mA/g, the charge-discharge specific capacity is 566.7mA/g after 500 times of long circulation, and the capacity retention rate is 97.4%.
Description
Technical Field
The invention belongs to the technical field of nano materials and electrochemistry, and particularly relates to a carbon-coated FeP hollow nano electrode material as well as a preparation method and application thereof.
Background
In recent years, environmental pollution has become more serious with the development of industry and the heavy use of fossil fuels. The search for new green clean energy is a problem to be solved urgently, and the energy storage system is a bottleneck for developing clean energy all the time. Portable electronic equipment, flexible wearable electronic devices, electric vehicles, power grid-connected power generation and the like all put higher demands on energy storage systems. The key to realizing energy conversion and green application is to prepare an energy storage system with high power and large capacity. Lithium ion batteries are one of the most potential energy storage systems, with relatively mature technology. However, with the large-scale application of lithium ion batteries, the metal lithium resource is rapidly declining. Statistically, at the current consumption rate, the existing lithium resources can only support 30 years of use. How to search for a novel battery material for replacing metal lithium becomes a research hotspot in the current energy field.
As a metal element of the same main group, sodium has similar chemical properties and extremely abundant reserves as metallic lithium, and has capacity contribution comparable to lithium and better reaction kinetics in electrochemical reactions, and is the most potential metal to replace lithium. The sodium ion battery has excellent rate performance, higher capacity and good cycling stability. The nano material has higher specific surface area and better activity, has large contact area with electrolyte and short sodium ion deintercalation distance when being used as a sodium ion battery electrode material, can effectively improve the electrochemical activity of the material, and has remarkable advantages when being used as a high-capacity long-life sodium ion battery electrode material. The nano material has high specific surface area and good contact with electrolyte to promote the diffusion of sodium ions, so that structural stress existing in the polarization and charge-discharge processes is reduced, the electrochemical window and the cycling stability of the battery are improved, and the nano material with the hierarchical porous structure has great advantages.
As a potential cathode material, the transition metal phosphide has the characteristics of cheap raw materials, abundant reserves, simple synthesis, high theoretical capacity and the like, so that the transition metal phosphide is widely researched. However, the transition metal phosphide electrode material has two fatal defects, namely, the relatively poor conductivity causes the rate capability and the power density of the electrode material to be lower; secondly, the material is irreversibly changed in phase due to the electrochemical conversion reaction, the problem of volume expansion is serious, the structure is difficult to maintain, and capacity attenuation and cycle life reduction are caused. In recent years, how to improve the conductivity and electrochemical cycling stability of transition metal phosphide in electrochemical reaction becomes a research hotspot, the main strategy is to synthesize a porous hierarchical structure and construct an electrode material of a core-shell mechanism, but the general synthesis method has the problems of complicated synthesis steps, low yield of synthesized products and the like.
Disclosure of Invention
The invention aims to solve the problems of the existing transition metal phosphide electrode material, and provides a carbon-coated FeP hollow nano-electrode material and a preparation method thereof.
In order to achieve the purpose, the technical scheme is as follows:
a carbon-coated FeP hollow nano-electrode material is formed by assembling a FeP nano-particle inner core with the diameter of 200-300 nanometers and a carbon shell surface layer; wherein a middle layer gap is formed between the nanoparticle inner core and the carbon shell surface layer, and the diameter of the nano electrode material is 300-400 nanometers.
The preparation method of the carbon-coated FeP hollow nano-electrode material comprises the following steps:
1) adding ferric nitrate nonahydrate into deionized water, and stirring to fully dissolve the ferric nitrate nonahydrate; adding sodium hydroxide solution, and stirring to mix thoroughly;
2) putting the mixture into a reaction kettle for hydrothermal reaction, centrifugally filtering the obtained product, washing and drying to obtain precursor red powder;
3) dispersing the obtained precursor red powder in a mixed solution of ethanol and water, performing ultrasonic dispersion, sequentially adding ammonia water, resorcinol and formaldehyde, stirring to fully mix, washing and drying to obtain red powder;
4) calcining the obtained red powder in a tubular furnace in the nitrogen atmosphere, and naturally cooling to room temperature to obtain carbon-coated Fe3O4A nanoparticle;
5) coating carbon with Fe3O4Mixing the nano particles with a hydrochloric acid solution, etching by using hydrochloric acid, washing and drying to obtain the carbon-coated Fe3O4Hollow nanoparticles;
6) coating carbon with Fe3O4And placing the hollow nano particles and sodium hypophosphite in a tubular furnace to perform high-temperature in-situ reaction in a nitrogen atmosphere, and naturally cooling to room temperature to obtain the carbon-coated FeP hollow nano electrode material.
According to the scheme, the molar ratio of the ferric nitrate nonahydrate to the sodium hydroxide in the step 1 is 1: 1.
According to the scheme, the hydrothermal reaction temperature in the step 2 is 80-140 ℃, and the hydrothermal reaction time is 72-144 h.
According to the scheme, the mass ratio of the precursor red powder, ammonia water, resorcinol and formaldehyde in the step 3 is 2: 30: 1: 2.
according to the scheme, in the step 4, the calcining temperature is 400-600 ℃, the heating rate is 2-5 ℃/min, and the calcining time is 4-6 h.
According to the scheme, the concentration of the hydrochloric acid solution in the step 5 is 1-4 mol/L, and the etching time is 20-60 min.
According to the scheme, the carbon in the step 6 is coated with Fe3O4The mass ratio of the hollow nano particles to the sodium hypophosphite is 1: (10-20); the high-temperature in-situ reaction temperature is 300-500 ℃; the heating rate is 2-5 ℃/min, and the reaction time is 3-5 h.
The carbon-coated FeP hollow nano-electrode material is applied as a negative electrode material of a sodium ion battery.
The invention solves the problem of low conductivity of the transition metal phosphide in the electrochemical reaction, shortens the diffusion path of sodium ions in the electrochemical reaction, improves the specific surface area and the electrochemical active sites of the active material, ensures the structure and the electrochemical stability of the active material by buffering the abrupt change of the volume of the material in the process of sodium ion deintercalation, and effectively improves the electrochemical performance of the material by constructing the carbon-coated FeP hollow nano-electrode material. When the material is used as a sodium ion battery cathode material, the charge-discharge specific capacity can reach 582mA/g for the first time under a charge-discharge test under a high current density of 200mA/g, the charge-discharge specific capacity is 566.7mA/g after 500 times of long circulation, and the capacity retention rate is 97.4%. The result shows that the carbon-coated FeP hollow nano-electrode material has higher capacity and excellent cycle stability, and is a potential application material of a high-capacity long-life sodium ion battery.
The invention has the following beneficial effects:
the carbon-coated FeP hollow nano-electrode material is prepared by a simple hydrothermal-coating-calcining-etching-high-temperature in-situ reaction five-step method, the preparation process is simple and easy to operate, the preparation cost of the electrode material is greatly reduced, the preparation process is green and environment-friendly, and the potential large-scale market application value is realized;
the carbon-coated FeP hollow nano-electrode material synthesized by the method has the characteristics of high dispersion, uniform size and high phase purity, and is convenient for preparing high-quality electrode materials;
when the carbon-coated FeP hollow nano-electrode material is used as a sodium ion battery cathode material, the carbon-coated FeP hollow nano-electrode material shows excellent electrochemical conductivity, higher capacity and excellent cycle stability, and is a potential application material of a high-capacity long-life sodium ion battery.
Drawings
FIG. 1: the invention relates to a flow chart for preparing a carbon-coated FeP hollow nano electrode material;
FIG. 2: example 1 XRD pattern of carbon-coated FeP hollow nano-electrode material precursor;
FIG. 3: example 1 SEM image of carbon-coated FeP hollow nano-electrode material precursor;
FIG. 4: XRD pattern of carbon-coated FeP hollow nano-electrode material of example 1;
FIG. 5: SEM image of carbon-coated FeP hollow nano-electrode material of example 1;
FIG. 6: the battery cycle performance curve diagram of the carbon-coated FeP hollow nano-electrode material of example 1.
Detailed Description
The following examples further illustrate the technical solutions of the present invention, but should not be construed as limiting the scope of the present invention.
Example 1
The preparation method of the carbon-coated FeP hollow nano-electrode material comprises the synthesis steps as shown in figure 1,
1) 0.1mol of iron nitrate nonahydrate (Fe (NO)3)3·9H2O) putting the mixture into a beaker, adding 100mL of deionized water, and stirring for 30min to fully dissolve the mixture; adding 100mL of 1mol/L sodium hydroxide solution (NaOH), and stirring for 30min to fully mix;
2) putting the solution obtained in the step 1) into a reaction kettle, carrying out hydrothermal reaction at 100 ℃ for 96 hours, taking out the reaction kettle, and naturally cooling to room temperature; centrifuging and filtering the obtained product, washing the product for 6 times by using water and absolute ethyl alcohol, and drying the product in an oven at 80 ℃ for 12 hours to obtain precursor red powder; as shown in fig. 2, the X-ray diffraction pattern (XRD) showed that the precursor was cubic and free of impurities. As shown in FIG. 3, a Field Emission Scanning Electron Microscope (FESEM) test result shows that the precursor has good dispersibility, is basically in a monodisperse distribution and has a cubic structure with the particle size of 200-300 nanometers.
3) Dispersing the product obtained in the step 2) in a mixed solution of 70mL of ethanol and 10mL of deionized water, performing ultrasonic dispersion for 30min, sequentially adding 3mL of ammonia water, 0.1g of resorcinol and 0.14mL of formaldehyde, stirring for 2h to fully mix the mixture, washing the product for 6 times with water and absolute ethanol, and drying in an oven at 80 ℃ for 12h to obtain red powder;
4) heating the organic matter coated nano-particles obtained in the step 3) in a tubular furnace at the temperature of 550 ℃ at 2 ℃/min in a nitrogen atmosphere; the calcination time is 4h, the annealing treatment is carried out, and the carbon-coated Fe can be obtained after the natural cooling to the room temperature3O4A nanoparticle;
5) putting the product obtained in the step 4) into a beaker, adding 2mol/L hydrochloric acid for etching for 30min, washing the product with water and absolute ethyl alcohol for 6 times, and drying in an oven at 80 ℃ for 12h to obtain carbon-coated Fe3O4Hollow nanoparticles;
6) coating the carbon obtained in the step 5) with Fe3O4Hollow nanoparticles and sodium hypophosphite (NaH)2PO2·H2O) is mixed with the following components in a mass ratio of 1: 20 heating the mixture in a tubular furnace at the temperature of 400 ℃ at 2 ℃/min in the nitrogen atmosphere; the calcination time is 4h, the annealing treatment is carried out, and the carbon-coated FeP hollow nano-electrode material can be obtained after the natural cooling to the room temperature.
As shown in FIG. 4, an X-ray diffraction pattern (XRD) shows that the carbon-coated FeP hollow nano-electrode material is in a cubic phase and has no other impurity phases. As shown in fig. 5, the SEM shows that the carbon-coated FeP hollow nano-electrode material is prepared in this example, and the carbon is coated and forms a structure of the middle layer void. The conductivity of the electrode material is improved, the volume expansion and shrinkage of the electrode material in the charging and discharging process can be effectively buffered when the electrode material is used as a cathode material of a sodium-ion battery, the structural stability of the material is improved, and meanwhile, the contact area of the material and electrolyte is effectively increased, so that the electrochemical performance with long service life and high capacity is obtained.
The carbon-coated FeP hollow nano-electrode material prepared by the invention is taken as sodium ionsThe battery negative electrode material and the sodium ion battery are prepared by the same method as the common method. The preparation method of the negative plate comprises the following steps: the method is characterized in that a carbon-coated FeP hollow nano-electrode material is used as an active material, acetylene black is used as a conductive agent, sodium carboxymethylcellulose (CMC) is used as a binder, and the mass ratio of the active material to the acetylene black to the sodium carboxymethylcellulose is 80: 15: 5; mixing them according to a certain proportion, ultrasonic treating to make them uniform, coating them on the copper foil, vacuum drying, then making sheet-punching by about 1cm on sheet-punching machine2Size; with sodium perchlorate (NaClO)4) And as an electrolyte, a sodium sheet is used as a counter electrode, Celgard2325 is used as a diaphragm, and CR2025 type stainless steel is used as a battery shell to assemble the button type sodium-ion battery.
Taking the carbon-coated FeP hollow nano-electrode material as an example, when the material is used as a negative electrode material of a sodium ion battery, a battery cycle performance curve graph at a current density of 200mA/g is shown in FIG. 6. According to a charge-discharge test under a high current density of 500mA/g, the first charge-discharge specific capacity can reach 582mA/g, after 500 long cycles, the first charge-discharge specific capacity is 566.7mA/g, and the capacity retention rate is 97.4%. The result shows that the carbon-coated FeP hollow nano-electrode material has higher capacity and excellent cycle stability, and is a potential application material of a high-capacity long-life sodium ion battery.
Example 2
The preparation method of the carbon-coated FeP hollow nano-electrode material comprises the following steps:
1) 0.2mol of iron nitrate nonahydrate (Fe (NO)3)3·9H2O) putting the mixture into a beaker, adding 200mL of deionized water, and stirring for 30min to fully dissolve the mixture; adding 200mL of 1mol/L sodium hydroxide solution (NaOH), and stirring for 30min to fully mix;
2) putting the solution obtained in the step 1) into a reaction kettle, carrying out hydrothermal reaction at 80 ℃ for 120h, taking out the reaction kettle, and naturally cooling to room temperature; centrifuging and filtering the obtained product, washing the product for 6 times by using water and absolute ethyl alcohol, and drying the product in an oven at 80 ℃ for 24 hours to obtain precursor red powder;
3) dispersing the product obtained in the step 2) in a mixed solution of 70mL of ethanol and 10mL of deionized water, performing ultrasonic dispersion for 40min, sequentially adding 3mL of ammonia water, 0.15g of resorcinol and 0.21mL of formaldehyde, stirring for 2h to fully mix, washing the product with water and absolute ethyl alcohol for 4 times, and drying in an oven at 80 ℃ for 12h to obtain red powder;
4) heating the organic matter coated nano-particles obtained in the step 3) in a tubular furnace at 3 ℃/min in a nitrogen atmosphere, and keeping the temperature at 550 ℃; the calcination time is 4h, the annealing treatment is carried out, and the carbon-coated Fe can be obtained after the natural cooling to the room temperature3O4A nanoparticle;
5) putting the product obtained in the step 4) into a beaker, adding 1mol/L hydrochloric acid for etching for 30min, washing the product with water and absolute ethyl alcohol for 6 times, and drying in an oven at 60 ℃ for 12h to obtain carbon-coated Fe3O4Hollow nanoparticles;
6) coating the carbon obtained in the step 5) with Fe3O4Hollow nanoparticles and sodium hypophosphite (NaH)2PO2·H2O) is mixed with the following components in a mass ratio of 1: 10 heating the mixture in a tubular furnace at the temperature of 350 ℃ in the nitrogen atmosphere at the speed of 2 ℃/min; the calcination time is 4h, the annealing treatment is carried out, and the carbon-coated FeP hollow nano-electrode material can be obtained after the natural cooling to the room temperature.
Example 3
The preparation method of the carbon-coated FeP hollow nano-electrode material comprises the following steps:
1) 0.2mol of iron nitrate nonahydrate (Fe (NO)3)3·9H2O) putting the mixture into a beaker, adding 100mL of deionized water, and stirring for 30min to fully dissolve the mixture; adding 100mL of 2mol/L sodium hydroxide solution (NaOH), and stirring for 60min to fully mix;
2) putting the solution obtained in the step 1) into a reaction kettle, carrying out hydrothermal reaction at 100 ℃ for 96 hours, taking out the reaction kettle, and naturally cooling to room temperature; centrifuging and filtering the obtained product, washing the product for 6 times by using water and absolute ethyl alcohol, and drying the product in an oven at 80 ℃ for 24 hours to obtain precursor red powder;
3) dispersing the product obtained in the step 2) in a mixed solution of 60mL of ethanol and 8mL of deionized water, ultrasonically dispersing for 30min, sequentially adding 2.4mL of ammonia water, 0.1g of resorcinol and 0.14mL of formaldehyde, stirring for 2h to fully mix the mixture, washing the product with water and absolute ethanol for 6 times, and drying in an oven at 80 ℃ for 12h to obtain red powder;
4) heating the organic matter coated nano-particles obtained in the step 3) in a tubular furnace at the temperature of 500 ℃ at 2 ℃/min in the nitrogen atmosphere; the calcination time is 4h, the annealing treatment is carried out, and the carbon-coated Fe can be obtained after the natural cooling to the room temperature3O4A nanoparticle;
5) putting the product obtained in the step 4) into a beaker, adding 1mol/L hydrochloric acid for etching for 30min, washing the product with water and absolute ethyl alcohol for 6 times, and drying in an oven at 80 ℃ for 12h to obtain carbon-coated Fe3O4Hollow nanoparticles;
6) coating the carbon obtained in the step 5) with Fe3O4Hollow nanoparticles and sodium hypophosphite (NaH)2PO2·H2O) is mixed with the following components in a mass ratio of 1: 20 heating the mixture in a tubular furnace at the temperature of 400 ℃ at 2 ℃/min in the nitrogen atmosphere; the calcination time is 6h, the annealing treatment is carried out, and the carbon-coated FeP hollow nano-electrode material can be obtained after the natural cooling to the room temperature;
example 4
The preparation method of the carbon-coated FeP hollow nano-electrode material comprises the following steps:
1) 0.15mol of iron nitrate nonahydrate (Fe (NO)3)3·9H2O) putting the mixture into a beaker, adding 100mL of deionized water, and stirring for 30min to fully dissolve the mixture; adding 100mL of 1.5mol/L sodium hydroxide solution (NaOH), and stirring for 60min to mix thoroughly;
2) putting the solution obtained in the step 1) into a reaction kettle, carrying out hydrothermal reaction at 100 ℃ for 120h, taking out the reaction kettle, and naturally cooling to room temperature; centrifuging and filtering the obtained product, washing the product for 6 times by using water and absolute ethyl alcohol, and drying the product in an oven at 80 ℃ for 12 hours to obtain precursor red powder;
3) dispersing the product obtained in the step 2) in a mixed solution of 70mL of ethanol and 10mL of deionized water, performing ultrasonic dispersion for 30min, sequentially adding 3mL of ammonia water, 0.2g of resorcinol and 0.28mL of formaldehyde, stirring for 2h to fully mix the mixture, washing the product for 6 times with water and absolute ethanol, and drying in an oven at 60 ℃ for 12h to obtain red powder;
4) coating the organic matter obtained in the step 3) with nano particlesHeating the granules in a tubular furnace at 2 ℃/min in the nitrogen atmosphere, and keeping the temperature at 600 ℃; calcining for 4h, and naturally cooling to room temperature to obtain carbon-coated Fe3O4A nanoparticle;
5) putting the product obtained in the step 4) into a beaker, adding 2mol/L hydrochloric acid for etching for 30min, washing the product with water and absolute ethyl alcohol for 6 times, and drying in an oven at 80 ℃ for 12h to obtain carbon-coated Fe3O4Hollow nanoparticles;
6) coating the carbon obtained in the step 5) with Fe3O4Hollow nanoparticles and sodium hypophosphite (NaH)2PO2·H2O) is mixed with the following components in a mass ratio of 1: 10 heating the mixture in a tubular furnace at the temperature of 400 ℃ in the nitrogen atmosphere at the speed of 2 ℃/min; the calcination time is 4h, the annealing treatment is carried out, and the carbon-coated FeP hollow nano-electrode material can be obtained after the natural cooling to the room temperature;
example 5
The preparation method of the carbon-coated FeP hollow nano-electrode material comprises the following steps:
1) 0.2mol of iron nitrate nonahydrate (Fe (NO)3)3·9H2O) putting the mixture into a beaker, adding 100mL of deionized water, and stirring for 30min to fully dissolve the mixture; adding 100mL of 2mol/L sodium hydroxide solution (NaOH), and stirring for 60min to fully mix;
2) putting the solution obtained in the step 1) into a reaction kettle, carrying out hydrothermal reaction at 100 ℃ for 96 hours, taking out the reaction kettle, and naturally cooling to room temperature; centrifuging and filtering the obtained product, washing the product for 6 times by using water and absolute ethyl alcohol, and drying the product in an oven at 80 ℃ for 24 hours to obtain precursor red powder;
3) dispersing the product obtained in the step 2) in a mixed solution of 70mL of ethanol and 10mL of deionized water, performing ultrasonic dispersion for 30min, sequentially adding 3mL of ammonia water, 0.1g of resorcinol and 0.14mL of formaldehyde, stirring for 2h to fully mix the mixture, washing the product with water and absolute ethanol for 6 times, and drying in an oven at 60 ℃ for 24h to obtain red powder;
4) heating the organic matter coated nano-particles obtained in the step 3) in a tubular furnace at the temperature of 500 ℃ at 2 ℃/min in the nitrogen atmosphere; the calcination time is 6h, the annealing treatment is carried out, and the mixture is naturally cooled to the room temperatureThus obtaining carbon-coated Fe3O4A nanoparticle;
5) putting the product obtained in the step 4) into a beaker, adding 3mol/L hydrochloric acid for etching for 30min, washing the product with water and absolute ethyl alcohol for 6 times, and drying in an oven at 80 ℃ for 12h to obtain carbon-coated Fe3O4Hollow nanoparticles;
6) coating the carbon obtained in the step 5) with Fe3O4Hollow nanoparticles and sodium hypophosphite (NaH)2PO2·H2O) is mixed with the following components in a mass ratio of 1: 20 heating the mixture in a tubular furnace at the temperature of 400 ℃ at 2 ℃/min in the nitrogen atmosphere; the calcination time is 4h, and the carbon-coated FeP hollow nano-electrode material can be obtained after natural cooling to the room temperature.
Example 6
The preparation method of the carbon-coated FeP hollow nano-electrode material comprises the following steps:
1) 0.2mol of iron nitrate nonahydrate (Fe (NO)3)3·9H2O) putting the mixture into a beaker, adding 100mL of deionized water, and stirring for 60min to fully dissolve the mixture; adding 100mL of 2mol/L sodium hydroxide solution (NaOH), and stirring for 30min to fully mix;
2) putting the solution obtained in the step 1) into a reaction kettle, carrying out hydrothermal reaction at 100 ℃ for 120h, taking out the reaction kettle, and naturally cooling to room temperature; centrifuging and filtering the obtained product, washing the product for 6 times by using water and absolute ethyl alcohol, and drying the product in an oven at 80 ℃ for 24 hours to obtain precursor red powder;
3) dispersing the product obtained in the step 2) in a mixed solution of 70mL of ethanol and 10mL of deionized water, ultrasonically dispersing for 60min, sequentially adding 3mL of ammonia water, 0.1g of resorcinol and 0.14mL of formaldehyde, stirring for 2h to fully mix, washing the product with water and absolute ethyl alcohol for 6 times, and drying in an oven at 60 ℃ for 24h to obtain red powder;
4) heating the organic matter coated nano-particles obtained in the step 3) in a tubular furnace at the temperature of 550 ℃ at 2 ℃/min in a nitrogen atmosphere; calcining for 6h, and naturally cooling to room temperature to obtain carbon-coated Fe3O4A nanoparticle;
5) putting the product obtained in the step 4) into a beakerAdding 2mol/L hydrochloric acid for etching for 30min, washing the product with water and absolute ethyl alcohol for 6 times, and drying in an oven at 80 ℃ for 12h to obtain carbon-coated Fe3O4Hollow nanoparticles;
6) coating the carbon obtained in the step 5) with Fe3O4Hollow nanoparticles and sodium hypophosphite (NaH)2PO2·H2O) is mixed with the following components in a mass ratio of 1: 20 heating in a tubular furnace at 3 ℃/min in nitrogen atmosphere, and keeping the temperature at 400 ℃; the calcination time is 4h, and the carbon-coated FeP hollow nano-electrode material can be obtained after natural cooling to the room temperature.
Claims (7)
1. A preparation method of a carbon-coated FeP hollow nano sodium ion battery cathode material is characterized by comprising the following steps:
1) adding ferric nitrate nonahydrate into deionized water, and stirring to fully dissolve the ferric nitrate nonahydrate; adding sodium hydroxide solution, and stirring to mix thoroughly;
2) putting the mixture into a reaction kettle for hydrothermal reaction, centrifugally filtering the obtained product, washing and drying to obtain precursor red powder;
3) dispersing the obtained precursor red powder in a mixed solution of ethanol and water, performing ultrasonic dispersion, sequentially adding ammonia water, resorcinol and formaldehyde, stirring to fully mix, washing and drying to obtain red powder;
4) calcining the obtained red powder in a tubular furnace in the nitrogen atmosphere, and naturally cooling to room temperature to obtain carbon-coated Fe3O4A nanoparticle;
5) coating carbon with Fe3O4Mixing the nano particles with a hydrochloric acid solution, etching by using hydrochloric acid, washing and drying to obtain the carbon-coated Fe3O4Hollow nanoparticles;
6) coating carbon with Fe3O4Placing the hollow nano particles and sodium hypophosphite in a tubular furnace to perform high-temperature in-situ reaction in a nitrogen atmosphere, and naturally cooling to room temperature to obtain a carbon-coated FeP hollow nano electrode material;
the carbon-coated FeP hollow nano-electrode material is formed by assembling a FeP nano-particle inner core with the diameter of 200-300 nanometers and a carbon shell surface layer; wherein a middle layer gap is formed between the nanoparticle inner core and the carbon shell surface layer, and the diameter of the nano electrode material is 300-400 nanometers.
2. The preparation method of the carbon-coated FeP hollow nano sodium ion battery cathode material as claimed in claim 1, wherein the molar ratio of ferric nitrate nonahydrate to sodium hydroxide in step 1 is 1: 1.
3. The preparation method of the carbon-coated FeP hollow nano sodium ion battery cathode material as claimed in claim 1, wherein the hydrothermal reaction temperature in the step 2 is 80-140 ℃ and the hydrothermal reaction time is 72-144 h.
4. The preparation method of the carbon-coated FeP hollow nano sodium ion battery cathode material as claimed in claim 1, wherein the mass ratio of the precursor red powder, ammonia water, resorcinol and formaldehyde in step 3 is 2: 30: 1: 2.
5. the preparation method of the carbon-coated FeP hollow nano sodium ion battery cathode material as claimed in claim 1, wherein the calcination temperature in step 4 is 400-600 ℃, the temperature rise rate is 2-5 ℃/min, and the calcination time is 4-6 h.
6. The preparation method of the carbon-coated FeP hollow nano sodium ion battery cathode material as claimed in claim 1, wherein the concentration of the hydrochloric acid solution in the step 5 is 1-4 mol/L, and the etching time is 20-60 min.
7. The preparation method of the carbon-coated FeP hollow nano sodium ion battery cathode material as claimed in claim 1, wherein the carbon in step 6 is coated with Fe3O4The mass ratio of the hollow nano particles to the sodium hypophosphite is 1: (10-20); the high-temperature in-situ reaction temperature is 300-500 ℃; the heating rate is 2-5 ℃/min, and the reaction time is 3-5 h.
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| CN110165156B (en) * | 2019-04-12 | 2021-02-19 | 淮阴工学院 | FeP/FeC double-layer heterogeneous interface electrode material in carbon confinement space and preparation method and application thereof |
| CN110304614A (en) * | 2019-07-11 | 2019-10-08 | 中南大学 | A kind of transition metal phosphide iron phosphide negative electrode material |
| CN110459768A (en) * | 2019-08-14 | 2019-11-15 | 中南大学 | A kind of iron phosphide/carbon composite material with octahedral structure and its preparation method and application |
| CN111987315A (en) * | 2020-09-02 | 2020-11-24 | 扬州大学 | Preparation method of carbon nano-box encapsulated NiCoP nano-particle composite material and lithium ion battery cathode material thereof |
| CN114628668B (en) * | 2020-12-10 | 2023-11-03 | 中国科学院大连化学物理研究所 | FeP@NC with nitrogen-doped carbon as carrier and its preparation and application |
| CN113135588A (en) * | 2021-04-19 | 2021-07-20 | 合肥工业大学 | Carbon-coated SnO2Preparation method of hollow nanosphere |
| CN114551832A (en) * | 2022-02-23 | 2022-05-27 | 扬州大学 | Preparation method of nano composite material and lithium ion electrode negative electrode material thereof |
| CN114639815A (en) * | 2022-04-08 | 2022-06-17 | 东莞市沃泰通新能源有限公司 | Preparation method of sodium ion battery negative electrode material, negative electrode sheet and sodium ion battery |
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