CN113130862A - Three-dimensional graphene composite material and preparation method and application thereof - Google Patents

Three-dimensional graphene composite material and preparation method and application thereof Download PDF

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CN113130862A
CN113130862A CN202110258558.XA CN202110258558A CN113130862A CN 113130862 A CN113130862 A CN 113130862A CN 202110258558 A CN202110258558 A CN 202110258558A CN 113130862 A CN113130862 A CN 113130862A
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doped carbon
dimensional graphene
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CN113130862B (en
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刘安然
陆小军
刘松琴
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Southeast University
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Abstract

The invention discloses a three-dimensional graphene composite material and a preparation method and application thereof, wherein the three-dimensional graphene composite material is NiCo2O4‑NiO‑Ni2O3The nitrogen-doped carbon/three-dimensional graphene composite material is prepared by wrapping ppy @ NiCo with three-dimensional graphene through a hydrothermal self-assembly strategy2-Pre nanotube composite to form ppy @ NiCo2-Pre @ GO hydrogel as a precursor, and calcining the hydrogel at two steps of high-temperature carbonization reduction and low-temperature oxidation to form NiCo2O4‑NiO‑Ni2O3a/N-doped carbon/three-dimensional graphene composite material and NiCo2O4‑NiO‑Ni2O3The/nitrogen-doped carbon/three-dimensional graphene composite material is used as a negative electrode material of the lithium ion battery. The composite material prepared by the invention has the advantages of high capacity, good rate capability, strong cycling stability, simple preparation process and the like.

Description

Three-dimensional graphene composite material and preparation method and application thereof
Technical Field
The invention belongs to the technical field of new energy materials, and particularly relates to a three-dimensional graphene composite material and a preparation method and application thereof.
Background
In order to achieve the development planning goal of power batteries, domestic enterprises and research institutions are all researching how to improve the energy density of power batteries. Although the performance of the power battery is influenced by not only an index of specific energy density, but also various factors such as specific power density, safety, consistency, cycle life and the like of the power battery, the energy density is really a key factor, and a key parameter for improving the energy density is the specific capacity of a material. For the traditional carbon negative electrode material, the theoretical specific capacity is low, the technical route planning target of 500Wh/kg is expected to be achieved in the future, and the difficulty is high, so that the development of a new generation of lithium ion battery negative electrode material is an important factor for achieving the ambitious target.
Redox oxide electrode materials, as lithium ion battery negative electrode materials, are favored by researchers due to their abundant redox properties and high capacity, but metal oxide materials have poor conductivity and low rate capacity; meanwhile, in the process of repeated charge and discharge, the volume can generate serious expansion and contraction effects, so that the material is pulverized, and the cycling stability of the material is poor.
Disclosure of Invention
The purpose of the invention is as follows: the first purpose of the invention is to provide NiCo2O4-NiO-Ni2O3The second purpose of the invention is to provide the NiCo2O4-NiO-Ni2O3The third purpose of the invention is to provide the NiCo composite material2O4-NiO-Ni2O3The application of the/nitrogen-doped carbon/three-dimensional graphene composite material in chemical energy sources.
The technical scheme is as follows: in order to solve the technical problem, the invention provides NiCo2O4-NiO-Ni2O3the/N-doped carbon/three-dimensional graphene composite material is of a three-dimensional macroporous network structure, wherein NiCo2O4-NiO-Ni2O3the/N-doped carbon nanotube is wrapped by a three-dimensional graphene network, and the NiCo2O4-NiO-Ni2O3the/N-doped carbon nanotubes are inserted between the three-dimensional graphene sheets.
The invention relates to NiCo2O4-NiO-Ni2O3The preparation method of the/nitrogen-doped carbon/three-dimensional graphene composite material comprises the following steps:
1) preparing a polypyrrole nanotube with a modified surface;
2) taking the polypyrrole nanotube prepared in the step 1) as a substrate material, and growing a nickel-cobalt-based precursor composite material on the surface of the polypyrrole nanotube to obtain ppy @ NiCo2-Pre composite material;
3) in ppy @ NiCo2Carrying out hydrothermal self-assembly on the-Pre composite material and a graphene oxide solution to form ppy @ NiCo2-Pre @ GO hydrogel;
4) in ppy @ NiCo2Forming NiCo by taking-Pre @ GO hydrogel as a precursor through high-temperature carbonization reduction and low-temperature oxidation2O4-NiO-Ni2O3The nitrogen-doped carbon/three-dimensional graphene composite material.
Further, in step 1), the preparation of the surface-modified polypyrrole nanotube includes the following steps: dissolving ferric chloride hexahydrate in methyl orange solution, stirring by magnetic force, slowly dripping pyrrole monomer into the solution, continuously stirring, centrifuging, washing, drying, finally dispersing the obtained polypyrrole nanotube into sodium dodecyl sulfate solution, performing ultrasonic dispersion, centrifuging, separating and drying.
Further, the concentration of methyl orange in the methyl orange solution is 5mmol/L, and the molar ratio of ferric chloride hexahydrate, methyl orange and pyrrole monomer is 1.5: 0.15: (1.5-2.25).
Further, in the step 2), the ppy @ NiCo2-Pre composite material preparation comprising the following steps: adding the polypyrrole nanotubes obtained in the step 1) into a methanol solution of nickel salt and cobalt salt, performing ultrasonic stirring to obtain a mixed solution, adding hexamethylenetetramine into the mixed solution, performing ultrasonic stirring, and performing hydrothermal reaction to obtain the polypyrrole nanotube material.
Further, the cobalt salt is one of cobalt nitrate, cobalt acetate, cobalt sulfate, cobalt chloride and water-containing salts thereof; the nickel salt is one of nickel nitrate, nickel acetate, nickel sulfate, nickel chloride and water-containing salt thereof; the concentration of the polypyrrole nano-tubes is 0.5-4g/L, the concentration of the nickel salt is 0.01-0.02mol/L, the molar ratio of the nickel salt to the cobalt salt is 1:2, the concentration of the hexamethylenetetramine is 11.2-80g/L, the hydrothermal reaction temperature is 140-220 ℃, and the hydrothermal reaction time is 6-18 h.
Further, in the step 3), the ppy @ NiCo2-Pre @ GO hydrogel was prepared comprising the following steps: the ppy @ NiCo obtained in the step 2) is added2Dispersing the Pre composite material in water, performing ultrasonic treatment to obtain a solution, then pouring the graphene oxide aqueous solution into the solution, performing ultrasonic dispersion, and performing hydrothermal reaction to obtain the graphene oxide/graphene oxide composite material.
Further, the graphene oxide is mixed with ppy @ NiCo2-Pre is in a mass ratio of 1: (1-6), wherein the concentration of the graphene oxide aqueous solution is more than or equal to 0.5mg/mL, the hydrothermal reaction temperature is 90-180 ℃, and the hydrothermal reaction time is 1-12 h.
Further, in the step 4), the high-temperature carbonization-reduction is carried out in a tube furnace, under the protection of inert gas, the heating rate is 1-10 ℃/min, the calcination temperature is more than 500 ℃, the heat preservation time is 2-10h, the low-temperature oxidation is carried out in the air atmosphere, the heating rate is 1-10 ℃/min, the calcination temperature is 150-.
The invention relates to NiCo2O4-NiO-Ni2O3The application of the/nitrogen-doped carbon/three-dimensional graphene composite material in a chemical power supply.
Specifically, the chemical source of electrical energy comprises:
(1) the anode material is a metal lithium sheet or a commercial anode material (such as lithium iron phosphate, lithium manganate, lithium cobaltate, ternary material and the like);
(2) LiPF with electrolyte of 1mol/L6Dispersing in ethylene carbonate/dimethyl carbonate/ethyl methyl carbonate solution (wherein the volume ratio of ethylene carbonate, dimethyl carbonate and ethyl methyl carbonate is 1:1: 1);
(3) the cathode material is NiCo prepared by the method2O4-NiO-Ni2O3The/nitrogen-doped carbon/three-dimensional graphene composite material is prepared;
(4) the septum was Celgard 2400.
Has the advantages that: compared with the prior art, the invention has the following remarkable advantages:
(1) NiCo prepared by the invention2O4-NiO-Ni2O3The/nitrogen-doped carbon/three-dimensional graphene composite material has excellent rate capacity and cycle stability;
(2) the invention adopts a method of combining hydrothermal self-assembly with high-temperature calcination to synthesize NiCo2O4-NiO-Ni2O3the/N-doped carbon/three-dimensional graphene composite material takes polypyrrole and nitrogen-doped carbon nanotubes derived from the polypyrrole as a conductive substrate, and is beneficial to an active material NiCo2O4-NiO-Ni2O3Nanocrystallization is carried out, active material agglomeration is avoided, and the conductivity of the material is improved; the nano-scale active material is beneficial to relieving the volume expansion effect of the active material, shortening the diffusion distance of lithium ions and increasing reaction active sites; the three-dimensional graphene on the outermost layer can further improve the conductivity of the material and maintain the structural integrity. In addition, the combination of the one-dimensional nanotube composite material and the three-dimensional network conductive structure is beneficial to the rapid diffusion of electrolysis and improves the conductivity of the whole material.
(3) The invention provides a new hydrothermal self-assembly strategy, constructs a novel three-dimensional macroporous network structure formed by inserting one-dimensional nanotubes into a three-dimensional graphene network, is expected to improve the electrochemical properties of active materials such as oxides, sulfides, phosphides and silicon-based materials with high volume expansion rate and poor conductivity, has certain universality, and provides a new thought for the design and preparation of lithium ion battery electrode materials.
(4) The invention adopts a simple hydrothermal self-assembly combined calcination method to synthesize NiCo2O4-NiO-Ni2O3The preparation process of the/nitrogen-doped carbon/three-dimensional graphene composite material is simple and feasible.
Drawings
FIG. 1 is NiCo2O4-NiO-Ni2O3Reaction scheme of/nitrogen doped carbon/three-dimensional graphene composite material;
FIG. 2 is NiCo2O4-NiO-Ni2O3，NiCo2O4-NiO-Ni2O3Nitrogen doped carbon and NiCo2O4-NiO-Ni2O3XRD pattern of/nitrogen doped carbon/three-dimensional graphene composite material;
FIG. 3 is NiCo2O4-NiO-Ni2O3，NiCo2O4-NiO-Ni2O3Nitrogen doped carbon and NiCo2O4-NiO-Ni2O3Scanning electron microscope images of the/nitrogen-doped carbon/three-dimensional graphene composite material;
FIG. 4 is NiCo2O4-NiO-Ni2O3、NiCo2O4-NiO-Ni2O3Nitrogen doped carbon and NiCo2O4-NiO-Ni2O3A multiplying power capacity diagram of the/nitrogen-doped carbon/three-dimensional graphene composite material under different current densities;
FIG. 5 is NiCo2O4-NiO-Ni2O3、NiCo2O4-NiO-Ni2O3Nitrogen doped carbon and NiCo2O4-NiO-Ni2O3And (3) a cyclic charge-discharge diagram of the/nitrogen-doped carbon/three-dimensional graphene composite material at a current density of 2.0A/g.
Detailed Description
The technical scheme of the invention is further explained by combining the attached drawings.
Example 1
1) Preparation of surface modified polypyrrole nanotubes
Dissolving 2.4g ferric trichloride hexahydrate in 180mL of 5mmol/L methyl orange aqueous solution in a 250mL flask, magnetically stirring for 0.5h, slowly dropping 0.9mL pyrrole monomer into the mixed solution, stirring for 24h, centrifuging, washing, drying, dispersing the obtained powder in saturated sodium dodecyl sulfate aqueous solution, and performing ultrasonic treatment for 3h to obtain the polypyrrole nanotube (ppy) with the surface modified negative charge.
2)NiCo2O4-NiO-Ni2O3Preparation of/nitrogen-doped carbon/three-dimensional graphene composite material
Weighing 0.15g of polypyrrole nanotube powder prepared in the step 1), 0.2967g of nickel nitrate hexahydrate and 0.5821g of cobalt nitrate hexahydrate, dispersing in 70mL of methanol solution, and performing ultrasonic treatment for 1 h; and weighing 1.16g of hexamethylenetetramine, adding the hexamethylenetetramine into the mixed solution, stirring and ultrasonically treating for 10min, transferring the hexamethylenetetramine into a 100mL hydrothermal reaction kettle, and carrying out hydrothermal reaction at the hydrothermal temperature of 180 ℃ for 12 h. After the reaction is finished and the temperature is reduced to room temperature, centrifuging, washing and drying are carried out to obtain the polypyrrole nanotube @ nickel cobalt-based precursor composite material (ppy @ NiCo)2-Pre), as shown in fig. 1 (a), (a) represents the preparation of a composite material ppy @ NiCo from polypyrrole nanotubes ppy2-Pre scheme.
125mg of the above-obtained ppy @ NiCo was weighed2-Pre composite material, dispersing in 20.188mL of ultrapure water, performing ultrasonic treatment for 10min, then pouring 11.062mL of 5.65mg/mL graphene oxide aqueous solution into the upper solution, if precipitation occurs, adding 3 drops of ammonia water, performing ultrasonic dispersion for 10min, transferring to a 50mL hydrothermal reaction kettle, and performing hydrothermal reaction at 180 ℃ for 12 h. After the reaction is finished and the temperature is reduced to room temperature, centrifuging, washing and drying are carried out to obtain ppy @ NiCo2-Pre @ graphene oxide hydrogel (ppy @ NiCo)2-Pre @ GO hydrogel), as shown in fig. 1 (b), (b) represents a composite material ppy @ NiCo2Preparation of ppy @ NiCo by Pre2-Pre @ GO hydrogel schematic.
Freeze-drying ppy @ NiCo2-Pre @ GO hydrogel is placed in a tubular furnace for high-temperature calcination, and is sintered for 2 hours at 650 ℃ at the heating rate of 10 ℃/min under the protection of nitrogen; cooling the furnace, transferring the furnace into a muffle furnace, and sintering the furnace for 12 hours at 200 ℃ at the heating rate of 2 ℃/min in the air atmosphere to obtain NiCo2O4-NiO-Ni2O3a/N-doped carbon/three-dimensional graphene composite material (NCO @ NC @3DG) as shown in (c) in FIG. 1, wherein (c) represents a carbon/three-dimensional graphene composite material formed by ppy @ NiCo2Preparation of NiCo from-Pre @ GO hydrogel2O4-NiO-Ni2O3Schematic diagram of/nitrogen-doped carbon/three-dimensional graphene composite material (NCO @ NC @3 DG).
Comparative example 1NiCo2O4-NiO-Ni2O3Preparation of the material:
weighing 0.2967g of nickel nitrate hexahydrate and 0.5821g of cobalt nitrate hexahydrate, dispersing in 70mL of methanol solution, and carrying out ultrasonic treatment for 1 h; and weighing 1.16g of hexamethylenetetramine, adding the hexamethylenetetramine into the mixed solution, stirring and ultrasonically treating for 10min, transferring the hexamethylenetetramine into a 100mL hydrothermal reaction kettle, and carrying out hydrothermal reaction at the hydrothermal temperature of 180 ℃ for 12 h. After the reaction is finished and the temperature is reduced to room temperature, centrifuging, washing and drying are carried out to obtain the nickel-cobalt-based precursor composite material (NiCo)2-Pre)。
Drying the ppy @ NiCo2-Pre composite material is placed in a tube furnace for high temperature calcination, and is sintered for 2h at 650 ℃ at the heating rate of 10 ℃/min under the protection of nitrogen; cooling the furnace, transferring the furnace into a muffle furnace, and sintering the furnace for 12 hours at 200 ℃ at the heating rate of 2 ℃/min in the air atmosphere to obtain NiCo2O4-NiO-Ni2O3Material (NCO).
Comparative example 2NiCo2O4-NiO-Ni2O3Preparation of nitrogen-doped carbon material
Weighing 0.15g of polypyrrole nanotube powder prepared in example 1, 0.2967g of nickel nitrate hexahydrate and 0.5821g of cobalt nitrate hexahydrate, dispersing in 70mL of methanol solution, and performing ultrasonic treatment for 1 h; and weighing 1.16g of hexamethylenetetramine, adding the hexamethylenetetramine into the mixed solution, stirring and ultrasonically treating for 10min, transferring the hexamethylenetetramine into a 100mL hydrothermal reaction kettle, and carrying out hydrothermal reaction at the hydrothermal temperature of 180 ℃ for 12 h. After the reaction is finished and the temperature is reduced to room temperature, centrifuging, washing and drying are carried out to obtain the polypyrrole nanotube @ nickel cobalt-based precursor composite material (ppy @ NiCo)2-Pre)；
Drying the ppy @ NiCo2-Pre composite material is placed in a tube furnace for high temperature calcination, and is sintered for 2h at 650 ℃ at the heating rate of 10 ℃/min under the protection of nitrogen; cooling the furnace, transferring the furnace into a muffle furnace, and sintering the furnace for 12 hours at 200 ℃ at the heating rate of 2 ℃/min in the air atmosphere to obtain NiCo2O4-NiO-Ni2O3A/nitrogen doped carbon composite (NCO @ NC).
Experimental results Performance characterization:
NiCo prepared in comparative example 12O4-NiO-Ni2O3NiCo prepared in comparative example 22O4-NiO-Ni2O3Nitrogen doped carbon and NiCo prepared in example 12O4-NiO-Ni2O3The XRD pattern is obtained by X-ray diffraction scanning of the/nitrogen-doped carbon/three-dimensional graphene composite material, and the result is shown in figure 2. FIG. 2 is NiCo2O4-NiO-Ni2O3，NiCo2O4-NiO-Ni2O3Nitrogen doped carbon and NiCo2O4-NiO-Ni2O3XRD pattern of/nitrogen doped carbon/three-dimensional graphene composite material; wherein NCO represents NiCo2O4-NiO-Ni2O3A material; NCO @ NCO stands for NiCo2O4-NiO-Ni2O3Nitrogen-doped carbon; NC @ NCO @3DG for NiCo2O4-NiO-Ni2O3The nitrogen-doped carbon/three-dimensional graphene composite material. As can be seen from FIG. 2, the peaks on the XRD spectra of the three materials correspond to NiCo2O4NiO and Ni2O3Shows that after calcination, NiCo was successfully synthesized2O4-NiO-Ni2O3，NiCo2O4-NiO-Ni2O3Nitrogen doped carbon and NiCo2O4-NiO-Ni2O3The nitrogen-doped carbon/three-dimensional graphene composite material.
NiCo prepared in comparative example 12O4-NiO-Ni2O3NiCo prepared in comparative example 22O4-NiO-Ni2O3Nitrogen doped carbon and NiCo prepared in example 12O4-NiO-Ni2O3The result of scanning the/nitrogen-doped carbon/three-dimensional graphene composite material by an electron microscope is shown in fig. 3. FIG. 3 is NiCo2O4-NiO-Ni2O3，NiCo2O4-NiO-Ni2O3Nitrogen doped carbon and NiCo2O4-NiO-Ni2O3Scanning electron microscope images of the/nitrogen-doped carbon/three-dimensional graphene composite material; wherein (a) is NiCo2O4-NiO-Ni2O3Scanning electron microscope images of; (b) is NiCo2O4-NiO-Ni2O3Scanning electron microscope image of/nitrogen doped carbon; (c) and (d) is NiCo2O4-NiO-Ni2O3Scanning electron microscope images of the/nitrogen-doped carbon/three-dimensional graphene composite material. NiCo, shown in FIG. 3 (a)2O4-NiO-Ni2O3The particles are large, about 10 μm. As shown in FIG. 3 (b), after the conductive substrate polypyrrole and its derivatives nitrogen-doped carbon nanotubes are introduced as the conductive substrate, NiCo2O4-NiO-Ni2O3Greatly reduced in particle size, NiCo2O4-NiO-Ni2O3The particles are uniformly dispersed along the nitrogen-doped carbon nanotubes to form NiCo2O4-NiO-Ni2O3Nitrogen doped carbon. As shown in fig. 3 (c) and (d), NiCo is formed after self-assembly with graphene oxide, high-temperature carbonization, and low-temperature oxidation2O4-NiO-Ni2O3the/N-doped carbon nano tube is wrapped by a three-dimensional graphene network to form NiCo2O4-NiO-Ni2O3the/N-doped carbon/three-dimensional graphene three-dimensional macroporous network structure is characterized in that nanotubes are embedded between sheet layers of three-dimensional graphene.
NiCo prepared in example 12O4-NiO-Ni2O3N-doped carbon/three-dimensional graphene composite material and NiCo prepared in comparative example 12O4-NiO-Ni2O3Materials and NiCo prepared in comparative example 22O4-NiO-Ni2O3Uniformly mixing nitrogen-doped carbon with acetylene black and polyvinylidene fluoride according to the mass ratio of 8:1:1 to prepare a negative electrode, using a high-purity lithium sheet as a counter electrode, assembling the counter electrode into a button half cell in a glove box (under argon atmosphere), and carrying out the following electrochemical performance tests:
respectively carrying out electricity at current densities of 0.1A/g, 0.2A/g, 0.5A/g, 1.0A/g and 2.0A/gChemical properties were measured as shown in FIG. 4. FIG. 4 is NiCo2O4-NiO-Ni2O3、NiCo2O4-NiO-Ni2O3Nitrogen doped carbon and NiCo2O4-NiO-Ni2O3A multiplying power capacity diagram of the/nitrogen-doped carbon/three-dimensional graphene composite material under different current densities; wherein NCO represents NiCo2O4-NiO-Ni2O3A material; NCO @ NCO stands for tetra NiCo2O4-NiO-Ni2O3Nitrogen-doped carbon; NC @ NCO @3DG for NiCo2O4-NiO-Ni2O3The nitrogen-doped carbon/three-dimensional graphene composite material. As can be seen from FIG. 4, NiCo2O4-NiO-Ni2O3The nitrogen-doped carbon/three-dimensional graphene composite material has more excellent rate capacity, and average discharge capacity is 871mAh/g, 827mAh/g, 757mAh/g, 693mAh/g and 625mAh/g respectively; and NiCo prepared in comparative example 12O4-NiO-Ni2O3Material, and NiCo prepared according to comparative example 22O4-NiO-Ni2O3the/N-doped carbon material has relatively low rate capability. As shown in FIG. 4, for NiCo2O4-NiO-Ni2O3 material, the average discharge capacity is only 252mAh/g, 241mAh/g, 204mAh/g, 174mAh/g, 137mAh/g at current densities of 0.1A/g, 0.2A/g, 0.5A/g, 1.0A/g, 2.0A/g, and for NiCo2O4-NiO-Ni2O 3/nitrogen-doped carbon material, the average discharge capacity is only 668mAh/g, 545mAh/g, 447mAh/g, 388 h/g, 330 h/g at current densities of 0.1A/g, 0.5A/g, 1.0A/g, 2.0A/g. At a current density of 2A/g, NiCo2O4-NiO-Ni2O3The/nitrogen-doped carbon/three-dimensional graphene composite material exhibits higher capacity and better cycle stability, as shown in fig. 5. FIG. 5 is NiCo2O4-NiO-Ni2O3、NiCo2O4-NiO-Ni2O3Nitrogen doped carbon and NiCo2O4-NiO-Ni2O3A cyclic charge-discharge diagram of the/nitrogen-doped carbon/three-dimensional graphene composite material at a current density of 2.0A/g; wherein NCO represents NiCo2O4-NiO-Ni2O3A material; NCO @ NCO stands for tetra NiCo2O4-NiO-Ni2O3Nitrogen-doped carbon; NC @ NCO @3DG for NiCo2O4-NiO-Ni2O3The nitrogen-doped carbon/three-dimensional graphene composite material. As can be seen in FIG. 5, after 500 cycles of NiCo2O4-NiO-Ni2O3The capacity of the/N-doped carbon/three-dimensional graphene composite material can still reach 739.6mAh/g, while NiCo prepared by comparative example 12O4-NiO-Ni2O3Material and NiCo prepared according to comparative example 22O4-NiO-Ni2O3the/N-doped carbon material has the capacity of only 109.4mAh/g and 278.9mAh/g respectively, and the capacity is lower.
The invention adopts a method of combining hydrothermal self-assembly with high-temperature calcination to prepare NiCo2O4-NiO-Ni2O3N-doped carbon/three-dimensional graphene composite material, compared with NiCo2O4-NiO-Ni2O3And NiCo2O4-NiO-Ni2O3The nitrogen-doped carbon material shows more excellent electrochemical performance.

Claims (10)

1. NiCo2O4-NiO-Ni2O3the/N-doped carbon/three-dimensional graphene composite material is characterized in that the NiCo2O4-NiO-Ni2O3the/N-doped carbon/three-dimensional graphene is of a three-dimensional macroporous network structure, wherein NiCo2O4-NiO-Ni2O3the/N-doped carbon nanotube is wrapped by a three-dimensional graphene network, and the NiCo2O4-NiO-Ni2O3the/N-doped carbon nanotubes are inserted between the three-dimensional graphene sheets.
2. A NiCo product of claim 12O4-NiO-Ni2O3The preparation method of the/nitrogen-doped carbon/three-dimensional graphene composite material is characterized by comprising the following steps of:
1) preparing a polypyrrole nanotube with a modified surface;
2) taking the polypyrrole nanotube prepared in the step 1) as a substrate material, and growing a nickel-cobalt-based precursor composite material on the surface of the polypyrrole nanotube to obtain ppy @ NiCo2-Pre composite material;
3) in ppy @ NiCo2Carrying out hydrothermal self-assembly on the-Pre composite material and a graphene oxide solution to form ppy @ NiCo2-Pre @ GO hydrogel;
4) in ppy @ NiCo2Forming NiCo by taking-Pre @ GO hydrogel as a precursor through high-temperature carbonization reduction and low-temperature oxidation2O4-NiO-Ni2O3The nitrogen-doped carbon/three-dimensional graphene composite material.
3. A NiCo according to claim 22O4-NiO-Ni2O3The preparation method of the/nitrogen-doped carbon/three-dimensional graphene composite material is characterized in that in the step 1), the preparation step of the surface-modified polypyrrole nanotube comprises the following steps: dissolving ferric chloride hexahydrate in methyl orange solution, stirring by magnetic force, slowly dripping pyrrole monomer into the solution, continuously stirring, centrifuging, washing, drying, finally dispersing the obtained polypyrrole nanotube into sodium dodecyl sulfate solution, performing ultrasonic dispersion, centrifuging, separating and drying.
4. A NiCo according to claim 32O4-NiO-Ni2O3The preparation method of the/nitrogen-doped carbon/three-dimensional graphene composite material is characterized in that the concentration of methyl orange in the methyl orange solution is 5mmol/L, and the molar ratio of ferric chloride hexahydrate, methyl orange and pyrrole monomers is 1.5: 0.15: 1.5-2.25.
5. A NiCo according to claim 22O4-NiO-Ni2O3The preparation method of the/nitrogen-doped carbon/three-dimensional graphene composite material is characterized in that in the step 2), the ppy @ NiCo2-Pre composite material preparation comprising the following steps: adding the polypyrrole nano-tubes obtained in the step 1) into a methanol solution of nickel salt and cobalt saltAnd ultrasonically stirring to obtain a mixed solution, adding hexamethylenetetramine into the mixed solution, ultrasonically stirring, and carrying out hydrothermal reaction to obtain the catalyst.
6. A NiCo according to claim 52O4-NiO-Ni2O3The preparation method of the/nitrogen-doped carbon/three-dimensional graphene composite material is characterized in that the cobalt salt is one of cobalt nitrate, cobalt acetate, cobalt sulfate, cobalt chloride and water-containing salt thereof; the nickel salt is one of nickel nitrate, nickel acetate, nickel sulfate, nickel chloride and water-containing salt thereof; the concentration of the polypyrrole nano-tubes is 0.5-4g/L, the concentration of the nickel salt is 0.01-0.02mol/L, the concentration of the hexamethylenetetramine is 11.2-80g/L, the hydrothermal reaction temperature is 140-220 ℃, and the hydrothermal reaction time is 6-18 h.
7. A NiCo according to claim 22O4-NiO-Ni2O3The preparation method of the/nitrogen-doped carbon/three-dimensional graphene composite material is characterized in that in the step 3), the ppy @ NiCo2-Pre @ GO hydrogel was prepared comprising the following steps: the ppy @ NiCo obtained in the step 2) is added2Dispersing the Pre composite material in water, performing ultrasonic treatment to obtain a solution, then pouring the graphene oxide aqueous solution into the solution, performing ultrasonic dispersion, and performing hydrothermal reaction to obtain the graphene oxide/graphene oxide composite material.
8. A NiCo according to claim 72O4-NiO-Ni2O3The preparation method of the/nitrogen-doped carbon/three-dimensional graphene composite material is characterized in that the graphene oxide and ppy @ NiCo2-Pre is in a mass ratio of 1: 1-6, wherein the concentration of the graphene oxide aqueous solution is more than or equal to 0.5mg/mL, the hydrothermal reaction temperature is 90-180 ℃, and the hydrothermal reaction time is 1-12 h.
9. A NiCo according to claim 22O4-NiO-Ni2O3The preparation method of the/nitrogen-doped carbon/three-dimensional graphene composite material is characterized by comprising the following stepsIn the step 4), the high-temperature carbonization and reduction is carried out in a tubular furnace, under the protection of inert gas, the heating rate is 1-10 ℃/min, the calcination temperature is more than 500 ℃, the heat preservation time is 2-10h, the low-temperature oxidation is carried out in the air atmosphere, the heating rate is 1-10 ℃/min, the calcination temperature is 150-.
10. A NiCo alloy as claimed in claim 12O4-NiO-Ni2O3The application of the/nitrogen-doped carbon/three-dimensional graphene composite material in a chemical power supply.
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CN106158418A (en) * 2016-07-14 2016-11-23 江苏大学 A kind of preparation method of NiO/ nitrogen-doped graphene composite nano-electrode material
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