CN108767260B - Carbon-coated FeP hollow nano-electrode material and preparation method and application thereof - Google Patents

Carbon-coated FeP hollow nano-electrode material and preparation method and application thereof Download PDF

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CN108767260B
CN108767260B CN201810575366.XA CN201810575366A CN108767260B CN 108767260 B CN108767260 B CN 108767260B CN 201810575366 A CN201810575366 A CN 201810575366A CN 108767260 B CN108767260 B CN 108767260B
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CN108767260A (en
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夏冬林
李力
李启东
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Wuhan University of Technology WUT
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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
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    • 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
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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
    • 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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    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention discloses a 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

Carbon-coated FeP hollow nano-electrode material and preparation method and application thereof
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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