CN114784243B - Nitrogen-doped reduced graphene oxide loaded nickel phosphide composite material and preparation method thereof - Google Patents

Nitrogen-doped reduced graphene oxide loaded nickel phosphide composite material and preparation method thereof Download PDF

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CN114784243B
CN114784243B CN202210406575.8A CN202210406575A CN114784243B CN 114784243 B CN114784243 B CN 114784243B CN 202210406575 A CN202210406575 A CN 202210406575A CN 114784243 B CN114784243 B CN 114784243B
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graphene oxide
composite material
nitrogen
reduced graphene
nickel
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CN114784243A (en
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徐亚利
唐仲丰
马强
张向丹
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Henan Institute of Engineering
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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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5805—Phosphides
    • 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
    • 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
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

Abstract

The invention belongs to the field of sodium ion battery electrode materials, and particularly relates to a nitrogen-doped reduced graphene oxide loaded nickel phosphide composite material and a preparation method thereof. According to the preparation method, the amino trimethylene phosphonic acid is used as a phosphorus source and a nitrogen source at the same time, and the graphene oxide is used as a carbon source, and the nitrogen-doped reduced graphene oxide loaded nickel phosphide composite material is prepared through simple and efficient two-step heat treatment. The preparation method has the advantages of simple preparation process, mild synthesis conditions, suitability for large-scale batch production and good industrial application prospect. Meanwhile, in the composite material prepared by the method, the reduced graphene oxide is used as coated carbon, and nitrogen element doping is performed, so that not only can the conductivity and sodium ion storage capacity of the composite material be improved, but also the pulverization of nickel phosphide in the electrochemical charge and discharge process can be relieved, the multiplying power performance of the composite material is effectively improved, and the composite material is very suitable for being used as a sodium ion battery electrode material.

Description

Nitrogen-doped reduced graphene oxide loaded nickel phosphide composite material and preparation method thereof
Technical Field
The invention belongs to the field of sodium ion battery electrode materials, and particularly relates to a nitrogen-doped reduced graphene oxide loaded nickel phosphide composite material and a preparation method thereof.
Background
In recent years, lithium ion batteries have been the most promising secondary batteries due to high energy density and long cycle life, and have been successfully used in the fields of mobile phones, electric vehicles, and the like. However, with the widespread use of lithium, the shortage of lithium resources and the problem of cost become bottlenecks limiting the future development of lithium resources, and at the same time, sodium Ion Batteries (SIBs) with abundant resources and low cost are getting more and more attention from researchers, and are expected to become high-performance energy storage batteries for the next generation and large-scale use.
At present, a plurality of sodium storage anode materials are researched, wherein the sodium storage anode materials comprise carbon-based materials, transition metal compounds, alloy materials and the like. Among them, transition metal compounds include oxides, sulfides, phosphides, and the like, and transition metal phosphides have attracted attention in sodium ion batteries because of their high theoretical specific capacity and low storage potential. However, the poor rate capability of phosphide is caused by the problems of poor conductivity and volume expansion, which requires the synthesis of nanoscale materials and the assistance of conductive material coating technology to improve the conductivity and alleviate the volume expansion.
The common coating method in the prior art has more research on the core-shell structure coated by carbon. Carbon coating currently developed includes MOF carbon coating, hard carbon coating, 3D graphene foam, and other coating methods. The invention patent application with the publication number of CN107331851A discloses a nickel phosphide/3D graphene composite material of a sodium ion battery nano-sheet array and a preparation method thereof, wherein 3D graphene is prepared on foam nickel by a CVD method, and Ni (OH) is grown by a hydrothermal method 2 The nickel phosphide/3D graphene composite material of the nano-sheet array is obtained by high-temperature phosphating, and the cyclic stability of the composite material is improved to a certain extent, but the improvement of the multiplying power performance of the material is not involved, and the used method has complicated steps, high operation difficulty and expensive equipment, and is not suitable for large-scale popularization.
Disclosure of Invention
Aiming at the problems in the prior art, one of the purposes of the invention is to provide a preparation method of a nitrogen-doped reduced graphene oxide loaded nickel phosphide composite material, which has simpler preparation process, mild synthesis conditions, is suitable for large-scale batch production, and can endow the composite material with good multiplying power performance.
The invention further aims to provide the nitrogen-doped reduced graphene oxide loaded nickel phosphide composite material, which can improve the conductivity of the composite material, relieve the pulverization of nickel phosphide in the electrochemical charging and discharging process, improve the rate capability of the composite material and is suitable for being used as a sodium ion battery electrode material.
In order to achieve the above purpose, the technical scheme adopted by the preparation method of the nitrogen-doped reduced graphene oxide loaded nickel phosphide composite material is as follows:
the preparation method of the nitrogen-doped reduced graphene oxide loaded nickel phosphide composite material comprises the following steps:
1) Mixing graphene oxide with water, and performing ultrasonic dispersion to obtain graphene oxide dispersion liquid; dissolving nickel salt in water to obtain nickel salt solution;
2) Dropwise adding the amino trimethylene phosphonic acid into the graphene oxide dispersion liquid obtained in the step 1), and stirring to obtain a mixed liquid A;
3) Dropwise adding the nickel salt solution obtained in the step 1) into the mixed solution A, reacting at 70-80 ℃, and drying to obtain a precursor;
4) And (3) carrying out heat treatment on the precursor in an inert atmosphere at 500-800 ℃ and cooling to obtain the catalyst.
According to the preparation method of the composite material, the amino trimethylene phosphonic acid is used as a phosphorus source and a nitrogen source at the same time, and the graphene oxide is used as a carbon source, so that the nitrogen-doped reduced graphene oxide loaded nickel phosphide composite material is prepared through simple and efficient two-step heat treatment. The preparation method has the advantages of simple preparation process, mild synthesis condition, no need of configuring expensive equipment, suitability for large-scale batch production and good industrial application prospect.
Meanwhile, in the composite material prepared by the method, the reduced graphene oxide is used as coated carbon, and nitrogen element doping is performed, so that not only can the conductivity and sodium ion storage capacity of the composite material be improved, but also the pulverization of nickel phosphide in the electrochemical charge and discharge process can be relieved, the rate capability of the composite material is effectively improved, and the use requirement of the sodium ion battery electrode material is greatly met.
The graphene oxide adopted by the invention is conventional in the field, and can be obtained through a commercial channel or prepared by self. The self-preparation process includes: can be prepared by adopting natural crystalline flake graphite (325 meshes) according to a modified Hummer's method, and comprises the following specific processes: a) 1.0g of graphite and 2.0g of sodium nitrate are weighed and added into 30mL of concentrated sulfuric acid, and the mixture is stirred uniformly in an ice water bath; b) Slowly adding 3.0g of potassium permanganate solids to obtain a greenish black mixture; note that at the time of adding highEnsuring that the temperature of the reaction mixture does not exceed 5 ℃ in the process of potassium manganate; c) After the addition of potassium permanganate was completed, the solution was stirred in a 35℃water bath for 2H, followed by dropwise addition of 100mL of H 2 O; d) Wait for H 2 After O is added dropwise, the mixture is placed in a water bath at 90 ℃ for reaction for 1h; e) After the reaction, 12mL of H was poured in 2 O 2 At this time, the color of the mixture turns golden yellow; f) Finally, washing with 1.7mol/L hydrochloric acid, dialyzing, and calibrating the concentration of the graphene oxide solution by a differential method when the graphene oxide solution is slightly acidic.
Preferably, in the step 1), the concentration of graphene oxide in the graphene oxide dispersion liquid is 1.0-5.0 mg/mL. In order to facilitate the addition and promote the uniform dispersion of the graphene oxide, in practical operation, a graphene oxide solution can be directly obtained, and then the graphene oxide solution is added into deionized water for ultrasonic dispersion. Preferably, the solvent used for the graphene oxide solution is distilled water.
Preferably, in the nickel salt solution, the concentration of nickel salt is 2-10 mg/mL.
The invention does not limit the types of the nickel salt excessively, and only ensures that the nickel salt is soluble nickel salt. Preferably, in step 1), the nickel salt is one of nickel acetate tetrahydrate, nickel chloride hexahydrate and nickel nitrate hexahydrate.
The amino trimethylene phosphonic acid is used as a phosphorus source and a nitrogen source, the dosage and the adding mode of the amino trimethylene phosphonic acid have great influence on the morphology and the structure of a product, and meanwhile, the dosage of the amino trimethylene phosphonic acid needs to be matched with the dosage of nickel salt. Preferably, the volume of the corresponding aminotrimethylene phosphonic acid in the mixed solution A is 0.1-1.0mL for each 20-100 mg of nickel salt. More preferably, 50mg of nickel salt corresponds to a volume of 0.5mL of aminotrimethylene phosphonic acid in the mixture A.
In order to further optimize the structure of the composite material and improve the multiplying power performance of the material, preferably, in the step 3), the mass ratio of the nickel salt to the graphene oxide is 1:1, wherein the mass of the graphene oxide in the corresponding mixed solution A is 0.2-5 mg.
In step 3), the reaction under the condition of 70 to 80 ℃ can be performed under the condition of water bath, and in order to ensure the preparation effect of the precursor, the reaction time is preferably 60 to 120min, based on the consideration of promoting the structural stability of the precursor powder.
The drying is performed to remove the moisture in the product after the reaction sufficiently, preferably, in the step 3), the drying is performed at a temperature of 70 to 90 ℃ for 10 to 14 hours. More preferably, the drying temperature is 80 ℃ and the drying time is 12 hours.
By heat treatment at a specific temperature, graphene oxide in the precursor can be partially reduced, and the structure of the resulting composite material can be optimized. In order to ensure the cycle performance of the composite material and simultaneously consider the heat treatment efficiency and the cost, the time of the heat treatment is preferably 60-180 min in the step 4).
The invention relates to a nitrogen-doped reduced graphene oxide loaded nickel phosphide composite material, which adopts the following technical scheme:
the nitrogen-doped reduced graphene oxide loaded nickel phosphide composite material prepared by the preparation method is provided.
The nitrogen-doped reduced graphene oxide loaded nickel phosphide composite material prepared by the preparation process has good conductivity and sodium ion energy storage capacity. Based on the characteristics, the polymer can be used for the sodium ion battery electrode material, can exert good electrochemical stability and rate capability, and greatly meets the use requirement of the sodium ion battery electrode material.
Drawings
FIG. 1 is an XRD pattern of a nitrogen-doped reduced graphene oxide-supported nickel phosphide composite material prepared in example 1 of the present invention;
fig. 2 is an SEM image of a nitrogen-doped reduced graphene oxide supported nickel phosphide composite material prepared in example 1 of the present invention;
FIG. 3 is an SEM image of a nitrogen-doped reduced graphene oxide supported nickel phosphide composite material prepared in example 2 of the present invention;
fig. 4 is an SEM image of a nitrogen-doped reduced graphene oxide supported nickel phosphide composite material prepared in example 3 of the present invention;
FIG. 5 shows the electrochemical rate performance of the nitrogen-doped reduced graphene oxide-supported nickel phosphide composite material prepared in example 1 of the present invention as a negative electrode material of a sodium ion battery;
FIG. 6 shows the electrochemical rate performance of the nitrogen-doped reduced graphene oxide-supported nickel phosphide composite material prepared in example 2 of the present invention as a negative electrode material of a sodium ion battery;
FIG. 7 shows the electrochemical rate performance of the nitrogen-doped reduced graphene oxide-supported nickel phosphide composite material prepared in example 3 of the present invention as a negative electrode material of a sodium ion battery;
FIG. 8 is an electrochemical rate capability of the nitrogen-phosphorus co-doped reduced graphene oxide material prepared in comparative example 1 as a negative electrode material for sodium ion batteries;
fig. 9 is an electrochemical rate performance of the nickel phosphide material prepared in comparative example 2 of the present invention as a negative electrode material for sodium ion batteries.
Detailed Description
The invention is further described below in connection with the drawings and the detailed description, but does not constitute any limitation of the invention. The materials and operation techniques involved in the following examples are conventional in the art unless otherwise specified.
The preparation method of the graphene oxide raw material comprises the following steps: a) 1.0g of graphite and 2.0g of sodium nitrate are weighed and added into 30mL of concentrated sulfuric acid, and the mixture is stirred uniformly in an ice water bath; b) Slowly adding 3.0g of potassium permanganate solids to obtain a greenish black mixture; care was taken to ensure that the temperature of the reaction mixture did not exceed 5 ℃ during the addition of potassium permanganate; c) After the addition of potassium permanganate was completed, the solution was stirred in a 35℃water bath for 2H, followed by dropwise addition of 100mL of H 2 O; d) Wait for H 2 After O is added dropwise, the mixture is placed in a water bath at 90 ℃ for reaction for 1h; e) After the reaction, 12mL of H was poured in 2 O 2 At this time, the color of the mixture turns golden yellow; f) Finally, washing with 1.7mol/L hydrochloric acid, dialyzing, and calibrating the concentration of the graphene oxide solution by a differential method when the graphene oxide solution is slightly acidic.
1. Examples
Example 1
The preparation method of the nitrogen-doped reduced graphene oxide loaded nickel phosphide composite material comprises the following steps:
1) Mixing 5mL of Graphene Oxide (GO) solution with 15mL of deionized water, and performing ultrasonic dispersion for 30min to obtain graphene oxide dispersion; in the graphene oxide dispersion liquid, the concentration of graphene oxide is 5mg/mL;
dissolving 20mg of nickel acetate tetrahydrate in 10mL of deionized water, and magnetically stirring until the nickel acetate tetrahydrate is completely dissolved to obtain a nickel salt solution;
2) Dropwise adding 0.1mL of aminotrimethylene phosphonic acid into the graphene oxide dispersion liquid obtained in the step 1), and magnetically stirring for 120min to obtain a mixed liquid A;
3) Dropwise adding the nickel salt solution obtained in the step 1) into the mixed solution A, placing the mixed solution A in a water bath at 70 ℃ for reaction for 120min, and drying the mixed solution in an oven overnight (the temperature is 80 ℃ and the time is 12 h) to obtain a precursor;
4) And (3) carrying out heat treatment on the precursor in an argon atmosphere at 800 ℃ for 60min, and cooling to obtain the catalyst.
The nitrogen-doped reduced graphene oxide loaded nickel phosphide composite material of the embodiment is prepared by adopting the preparation method.
Example 2
The preparation method of the nitrogen-doped reduced graphene oxide loaded nickel phosphide composite material comprises the following steps:
1) Mixing 5mL of Graphene Oxide (GO) solution with 15mL of deionized water, and performing ultrasonic dispersion for 30min to obtain graphene oxide dispersion; in the graphene oxide dispersion liquid, the concentration of graphene oxide is 2.5mg/mL;
dissolving 50mg of nickel acetate tetrahydrate in 10mL of deionized water, and magnetically stirring until the nickel acetate tetrahydrate is completely dissolved to obtain a nickel salt solution;
2) Dropwise adding 0.5mL of aminotrimethylene phosphonic acid into the graphene oxide dispersion liquid obtained in the step 1), and magnetically stirring for 120min to obtain a mixed liquid A;
3) Dropwise adding the nickel salt solution obtained in the step 1) into the mixed solution A, placing the mixed solution A in a water bath at 80 ℃ for reaction for 60min, and drying the mixed solution in an oven overnight (the temperature is 90 ℃ and the time is 10 h) to obtain a precursor;
4) And (3) carrying out heat treatment on the precursor in an argon atmosphere at 600 ℃ for 120min, and cooling to obtain the catalyst.
The nitrogen-doped reduced graphene oxide loaded nickel phosphide composite material of the embodiment is prepared by adopting the preparation method.
Example 3
The preparation method of the nitrogen-doped reduced graphene oxide loaded nickel phosphide composite material comprises the following steps:
1) Mixing 5mL of Graphene Oxide (GO) solution with 15mL of deionized water, and performing ultrasonic dispersion for 30min to obtain graphene oxide dispersion; in the graphene oxide dispersion liquid, the concentration of graphene oxide is 1mg/mL;
dissolving 100mg of nickel acetate tetrahydrate in 10mL of deionized water, and magnetically stirring until the nickel acetate tetrahydrate is completely dissolved to obtain a nickel salt solution;
2) Dropwise adding 1mL of amino trimethylene phosphonic acid into the graphene oxide dispersion liquid obtained in the step 1), and magnetically stirring for 120min to obtain a mixed liquid A;
3) Dropwise adding the nickel salt solution obtained in the step 1) into the mixed solution A, placing the mixed solution A in a water bath at 70 ℃ for reaction for 120min, and drying the mixed solution in an oven overnight (the temperature is 70 ℃ and the time is 14 h) to obtain a precursor;
4) And (3) carrying out heat treatment on the precursor in an argon atmosphere at 500 ℃ for 180min, and cooling to obtain the catalyst.
The nitrogen-doped reduced graphene oxide loaded nickel phosphide composite material of the embodiment is prepared by adopting the preparation method.
2. Comparative example
Comparative example 1
The preparation method of the nitrogen-doped reduced graphene oxide supported nickel phosphide composite material of the comparative example is different from that of example 2 in that: the reaction raw material of step 3) was replaced with deionized water in the same amount without adding a nickel source, and the other steps were the same as in example 2.
Comparative example 2
The preparation method of the nitrogen-doped reduced graphene oxide supported nickel phosphide composite material of the comparative example is different from that of example 2 in that: step 3) was carried out using equal amounts of deionized water instead of GO, without GO, and the other steps were the same as in example 2.
3. Experimental example
Experimental example 1XRD analysis
This experimental example XRD analysis was performed on the composite material of example 2. The scan angle is 10-90 deg., and a waveform image is obtained by scanning, as shown in fig. 1.
The XRD pattern of fig. 1 shows that the prepared samples show characteristic peaks of nickel phosphide NiP (74-1385) at 2θ of 40.4 °, 44.5 °, 47.5 ° and 54.1 °, corresponding to (111), (201), (210) and (300) crystal planes of NiP, respectively, and no other peaks appear, demonstrating that the synthesized samples are NiP pure phases.
Experimental example 2 scanning electron microscope SEM analysis
The surface morphology of the composite materials prepared in examples 1 to 3 was analyzed by a scanning electron microscope in this experiment. SEM images are shown in fig. 2 to 4.
As can be seen from fig. 2 to 4, as the ratio of the phosphorus source to GO is changed, the number of nickel phosphide particles in the reduced graphene oxide interlayer is also changed, and the particle size is not significantly changed.
Experimental example 3 electrochemical circulation Rate stability test
The electrochemical performance measurement method and parameters are as follows: to test the sodium ion storage properties of the prepared samples, sodium ion coin half cells were assembled, and the assembly of coin cells was completed in a glove box filled with argon. Before the button cell is assembled, the battery case and the separator should be placed in an oven to remove moisture adsorbed on the surface, and the pole pieces should be weighed. The oxide layer on the surface of the sodium block and the potassium block should be cut off before rolling into slices. Assembly sequence of half cells: positive electrode shell, pole piece, electrolyte, diaphragm, electrolyte, sodium sheet, gasket, elastic sheet, negative electrode shell, and sealing and pressing. Wherein the electrolyte is 1.0M NaClO 4 EC/DMC (volume ratio 1:1,5% fec).
The rate performance test is carried out on a blue battery tester, namely the discharge-charge test is carried out on the battery with different current densities, and finally, when the current density returns to the low current density from the high current density, if the capacity can be recovered, the material has good rate performance. The voltage window of the rate performance test is 0.01-3V. The experimental results are shown in FIGS. 5 to 9.
As can be seen from FIGS. 5 to 7, when the concentration of the phosphorus source is too high, the doubling and capacity are low, because the source of Ni may be too much, resulting in Ni 2 P particles accumulate and the conductivity decreases. With the decrease of the phosphorus source, a peak occurs in capacity and magnification, but when the concentration of the phosphorus source is too small, ni is generated 2 Less P reduces capacity.
As can be seen from fig. 8, when no nickel source is added, the sample exhibits lower capacity and rate performance at each current density, probably due to the reduced graphene oxide sheets being stacked by pi-pi action, resulting in a reduced ion-contactable area and reduced ion transport efficiency.
As can be seen from FIG. 9, the synthesized sample decays rapidly during the first few turns of the sodium ion performance test without adding GO during the material preparation process, which may be Ni 2 Pulverization of P causes irreversible attenuation of the capacity.
The above embodiments are only preferred embodiments of the present invention, and the scope of the present invention is not limited thereto, but any insubstantial changes and substitutions made by those skilled in the art on the basis of the present invention are intended to be within the scope of the present invention as claimed.

Claims (9)

1. The preparation method of the nitrogen-doped reduced graphene oxide loaded nickel phosphide composite material is characterized by comprising the following steps of:
1) Mixing graphene oxide with water, and performing ultrasonic dispersion to obtain graphene oxide dispersion liquid; dissolving nickel salt in water to obtain nickel salt solution;
2) Dropwise adding the amino trimethylene phosphonic acid into the graphene oxide dispersion liquid obtained in the step 1), and stirring to obtain a mixed liquid A;
3) Dropwise adding the nickel salt solution obtained in the step 1) into the mixed solution A, reacting at 70-80 ℃, and drying to obtain a precursor;
4) And (3) carrying out heat treatment on the precursor in an inert atmosphere at 500-800 ℃ and cooling to obtain the catalyst.
2. The method for preparing the nitrogen-doped reduced graphene oxide supported nickel phosphide composite material according to claim 1, wherein in step 1), the concentration of graphene oxide in the graphene oxide dispersion liquid is 1.0-5.0 mg/mL; in the nickel salt solution, the concentration of nickel salt is 2-10 mg/mL.
3. The method for preparing a nitrogen-doped reduced graphene oxide supported nickel phosphide composite material as described in claim 1, wherein in step 1), the nickel salt is one of nickel acetate tetrahydrate, nickel chloride hexahydrate and nickel nitrate hexahydrate.
4. The method for preparing the nitrogen-doped reduced graphene oxide supported nickel phosphide composite material according to any one of claims 1-3, wherein in the step 3), the volume of the corresponding aminotrimethylene phosphonic acid in the mixed solution A is 0.1-1.0mL per 20-100 mg of nickel salt.
5. The method for preparing a nitrogen-doped reduced graphene oxide supported nickel phosphide composite material according to any one of claims 1-3, wherein in step 3), the mass of graphene oxide in the corresponding mixed solution a is 0.2-5.0 mg per milligram of nickel salt.
6. The method for preparing a nitrogen-doped reduced graphene oxide supported nickel phosphide composite material according to any one of claims 1 to 3, wherein in step 3), the reaction time is 60 to 120min.
7. The method for preparing a nitrogen-doped reduced graphene oxide supported nickel phosphide composite material according to any one of claims 1-3, wherein in step 3), the drying temperature is 70-90 ℃ and the time is 10-14 h.
8. The method for preparing a nitrogen-doped reduced graphene oxide supported nickel phosphide composite material according to any one of claims 1 to 3, wherein in step 4), the heat treatment time is 60 to 180 minutes.
9. A nitrogen-doped reduced graphene oxide-supported nickel phosphide composite material prepared by the preparation method as claimed in any one of claims 1 to 8.
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