CN110033955B - Preparation method for constructing nickel-cobalt-ore binary composite material based on graphene - Google Patents
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- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
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Abstract
The invention relates to a preparation method for constructing a nickel-cobalt-ore binary composite material based on graphene, which comprises the steps of adopting graphene with a single-layer carbon atom structure as a framework carrier, growing a nickel-cobalt-metal organic framework (Ni-Co-MOF) on a graphene framework in situ by a solvothermal method, and then carbonizing in an air atmosphere to obtain the graphene-based nickel-cobalt-ore composite material with a three-dimensional structure. Compared with the prior art, the nickel-cobalt oxide particles obtained by the method are uniformly loaded on the graphene framework, the method has the advantages of simple process, mild conditions, low cost and the like, and the graphene-based nickel-cobalt ore composite material with the three-dimensional structure prepared by the method has good electrochemical performance as a supercapacitor electrode material.
Description
Technical Field
The invention belongs to the technical field of material science and electrochemistry, and particularly relates to a preparation method for constructing a nickel-cobalt-ore binary composite material based on graphene.
Background
With the increasing consumption of non-renewable resources such as coal, petroleum, natural gas and the like and the increasing environmental pollution caused by energy consumption, research and development of novel efficient environment-friendly electrochemical energy storage devices for replacing internal combustion engines become one of the important strategic choices for the sustainable development of the current society. At present, people have achieved remarkable results in the research and development of energy storage devices such as super capacitors, fuel cells and chemical batteries. The Super Capacitor (SC) is a novel energy storage device between a conventional capacitor and a rechargeable battery, has a power density significantly higher than that of the rechargeable battery, has a great number of advantages of high charging and discharging efficiency, long service life, environmental friendliness and the like, and is widely applied to numerous fields such as electronic communication, energy chemical industry, aerospace and the like.
One of the most critical factors affecting the performance of the supercapacitor is the electrode material, and therefore, the development of the electrode material with high specific capacitance is the focus of research on the supercapacitor. The electrode materials widely applied to the super capacitor at present comprise carbon materials, transition metal oxides, conductive polymers and the like. The transition metal oxide is used as a cheap metal compound, has the characteristics of simple preparation process, low cost, high theoretical specific capacity and the like, and is a research focus of the current electrode material.
The transition metal element has a plurality of oxidation states, and can generate pseudo capacitance by using redox reaction between the oxidation states for energy storage. However, most metal oxides have poor conductivity, and the electrode structure may collapse due to stress of pure metal oxides during charge and discharge, resulting in poor cycle stability; the high resistance increases the charge transfer resistance and the interface resistance of the electrode, and particularly generates a large voltage drop (iR) under a large current density, so that the power density and the rate capability are reduced; the specific surface area, pore size distribution and porosity of the metal oxide are difficult to control, so that the transition metal oxide alone serving as the electrode material of the supercapacitor is limited due to the defects.
Chinese patent CN102891016B discloses a nickel cobaltate-graphene composite material and a preparation method thereof, wherein the composite material is composed of graphene and nickel cobaltate, nickel cobaltate nanowires uniformly grow on graphene sheets, the length of the nickel cobaltate nanowires is 50-300nm, and the line width is 5-30 nm. The preparation method comprises the steps of mixing the ultrasonically dispersed graphene oxide aqueous solution with the cobalt salt aqueous solution and the nickel salt aqueous solution, adding a precipitator, stirring and mixing uniformly, transferring the mixture into a high-temperature reaction kettle, carrying out hydrothermal reaction for a certain time, filtering, washing, drying and carrying out heat treatment on the obtained product to obtain the nickel cobaltate nanowire-graphene composite material. However, the patent synthesizes a two-dimensional nano composite material, which has insufficient porous structure, insufficient surface activity and insufficient conductivity and loading capacity.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a preparation method for constructing a nickel-cobalt-ore binary composite material based on graphene.
The purpose of the invention can be realized by the following technical scheme:
a preparation method for constructing a nickel-cobalt-ore binary composite material based on graphene adopts graphene with a single-layer carbon atom structure as a framework carrier, grows a nickel-cobalt-metal organic framework (Ni-Co-MOF) on a graphene framework in situ by a solvothermal method, and then obtains the graphene-based nickel-cobalt-ore composite material with a three-dimensional structure by carbonization in an air atmosphere, and the specific method is as follows:
replacing the graphene oxide aqueous solution with N, N-dimethylformamide;
stirring and dissolving nickel nitrate hexahydrate and cobalt nitrate hexahydrate in an N, N-dimethylformamide solution containing graphene oxide;
stirring and adding polyvinylpyrrolidone and 1,3, 5-benzene tricarboxylic acid;
carrying out solvent heat treatment on the solution;
standing and washing the obtained product with deionized water, and performing freeze-drying treatment;
and (3) carrying out heating carbonization treatment on the obtained product in an air atmosphere, and cooling to room temperature to obtain the nickel-cobalt ore binary composite material constructed based on the graphene.
The water contained in the graphene oxide was removed by high-speed centrifugation, and the graphene oxide was dissolved in an N, N-dimethylformamide solvent.
The nickel nitrate hexahydrate and the cobalt nitrate hexahydrate are mixed according to the mass ratio of 1: 2-1: 0.5.
The mass ratio of the nickel nitrate hexahydrate to the graphene oxide is 3: 1-15: 1.
The mass ratio of the polyvinylpyrrolidone to the 1,3, 5-benzenetricarboxylic acid is 20: 3.
The mass ratio of the polyvinylpyrrolidone to the graphene oxide is 20: 1-100: 1.
The temperature of the solvent heat treatment is 150-200 ℃, and the time is 6-20 h.
The temperature range of the freeze-drying treatment is-10 ℃ to-50 ℃, the pressure is 1.3Pa to 13Pa, and the time is 48h to 60 h.
The nickel cobalt ore binary oxide is prepared by constructing Ni-Co-MOF at the early stage and then carbonizing the Ni-Co-MOF in an air atmosphere, wherein the temperature of carbonization treatment is 200-500 ℃, and the heating rate is 1-5 ℃ per minute-1The time is 2-4 h.
In the solvothermal process, hydroxyl and carboxyl on the surface of graphene and nickel-cobalt nano particles are subjected to coordination reaction at a certain high temperature and under a certain high pressure, the graphene is reduced to form a three-dimensional gel, then the three-dimensional structure of the graphene can be protected by adopting freeze drying, and finally carbonization treatment is carried out at a certain temperature, so that the graphene is completely reduced, the conductivity of the surface of the material is improved, and when the material is applied to a super capacitor electrode material, the material shows good circulation stability and rate capability.
In order to solve the problems in the prior art, the invention provides the method for compounding two or more transition metal oxides to improve the conductivity of the material on one hand, and constructs a three-dimensional mixed material with high conductivity, flexibility and chemical stability on the other hand, and the material can be used as an anchoring electrochemical active material and a containing metal oxide which circulates on the basis of a carbon materialVolumetric changes in course have been proposed as one of the most promising strategies. The graphene is an ideal atom-thickness two-dimensional material, has extremely large surface area, excellent conductivity and high mechanical strength, and can be used as an ideal substrate nano material for functional growth. Spinel nickel cobalt ore (NiCo)2O4) Is a low-cost and environmentally friendly transition metal oxide, has better electron conductivity, and is at least two orders of magnitude higher than nickel oxide or cobalt oxide. Furthermore, its enormous ability to provide rich redox reactions (nickel and cobalt ion contributions) can lead to higher electrochemical activity. Finally, the technical scheme is provided, and the graphene is used as a substrate material, and the compound of two or more transition metal oxides is polymerized on the graphene in situ to prepare the three-dimensional nano composite material. Compared with the prior art, the invention has the following advantages:
1. the graphene-based nickel-cobalt composite material is prepared by a solvothermal method, and in the solvothermal process, the assembly of a graphene three-dimensional structure and spinel nickel-cobalt (NiCo) are performed2O4) The in-situ uniform growth on the surface of the graphene skeleton can be completed in one step, and the method is simple and convenient;
2. the composite material is prepared by taking the graphene as a base material and Ni-Co-MOF precursor, and the composite material has designability of raw materials, low cost and environmental friendliness;
3. the graphene-based nickel-cobalt composite material prepared by the method has good specific capacitance, good cycle stability and rate capability, is prepared by compounding two metal oxides with graphene in the preparation aspect of the electrode material of the super capacitor, solves the problems of metal volume change and graphene aggregation, and has innovativeness and wide application prospect.
Drawings
FIG. 1 is a morphology diagram of a three-dimensional graphene-based spinel nickel-cobalt ore composite material obtained in example 1;
FIG. 2 is a graph of the cycle performance of the three-dimensional graphene-based spinel nickel-cobalt composite material obtained in example 1 as a supercapacitor electrode material;
FIG. 3 is a graph of rate capability of the three-dimensional graphene-based spinel nickel-cobalt composite material obtained in example 1 as a supercapacitor electrode material;
fig. 4 is a long cycle performance graph of the three-dimensional graphene-based spinel nickel-cobalt ore composite material obtained in example 1 as a supercapacitor electrode material.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the spirit of the invention. All falling within the scope of the present invention.
A preparation method for constructing a nickel-cobalt-ore binary composite material based on graphene comprises the following steps:
removing moisture contained in graphene oxide in a high-speed centrifugation state, and dissolving the graphene oxide in an N, N-dimethylformamide solvent, thereby replacing the graphene oxide aqueous solution with N, N-dimethylformamide;
under magnetic stirring, mixing nickel nitrate hexahydrate and cobalt nitrate hexahydrate according to the proportion of 1: 2-1: 0.5, and dissolving the mixture in an N, N-dimethylformamide solution containing graphene oxide;
adding polyvinylpyrrolidone and 1,3, 5-benzene tricarboxylic acid under vigorous stirring, and stirring for 30-60 min;
transferring the solution into a stainless steel autoclave with a Teflon lining, and then keeping the solution in an oven at the temperature of 150-200 ℃ for 6-20 hours;
standing and replacing the obtained product with deionized water for several times, and freeze-drying the product in a freeze dryer;
carrying out temperature rise carbonization treatment on the obtained product in an air atmosphere, and controlling the temperature rise rate to be 1-5 ℃ per minute-1And cooling to room temperature at the temperature of 200-500 ℃ for 2-4 h to obtain the nickel-cobalt ore binary composite material constructed based on graphene.
The following are more detailed embodiments, and the technical solutions and the technical effects obtained by the present invention will be further described by the following embodiments.
The amount of chemical used in the various embodiments of the present invention is determined in predetermined ranges, in grams, milliliters, etc. units of measure.
The information on the model and manufacturer of the instrument or equipment used in various embodiments of the invention is as follows:
air-blast drying oven, model DHG-9920A, manufacturer: Shanghai-Hengchang scientific instruments, Inc.;
vacuum drying oven, DZF-6030A, Shanghai-Heng scientific instruments Ltd;
tube furnace, model SL 1700/model, manufacturer Shanghai Lily test instruments, Inc.;
scanning Electron Microscope (SEM), S-3400N Hitachi, Japan;
the electrochemical performance test of the electrode material used by the super capacitor adopts cyclic voltammetry, constant current charge-discharge and impedance test. The instrument was the CHI760e electrochemical workstation of Shanghai Chenghua instruments, Inc., using the three-electrode method with a platinum electrode as the counter electrode, a calomel electrode as the reference electrode, and 3M KOH aqueous solution as the electrolyte.
Example 1
A preparation method for constructing a nickel-cobalt-ore binary composite material based on graphene specifically comprises the following steps:
(1) adding 2mg/mL of graphene oxide DMF solution (5mL) into 15mL of DMF solution, and performing ultrasonic treatment to form uniformly mixed dispersion liquid;
(2) 0.07745g of nickel nitrate hexahydrate and 0.1549g of cobalt nitrate hexahydrate were added to the above solution dissolved in DMF containing graphene oxide with magnetic stirring;
(3) adding 0.5g of polyvinylpyrrolidone (PVP, K30) and 0.075g of 1,3, 5-benzenetricarboxylic acid under vigorous stirring, and stirring for 30-60 min;
(4) transferring the solution into a Teflon-lined stainless steel autoclave, and then keeping the solution in an oven at 150 ℃, 180 ℃ and 200 ℃ for 12 hours;
(5) the resulting product was replaced several times with deionized water on standing and the product was lyophilized in a lyophilizer.
(6) And putting the obtained product into a tube furnace, annealing for 2 hours at the temperature of 400 ℃ in the air at the heating rate of 2 ℃/min, and cooling to room temperature to obtain the final black product.
The product obtained above was observed by scanning electron microscopy, as shown in FIG. 1, NiCo2O4The graphene grows on the surface of the graphene uniformly, and the three-dimensional structure of the graphene is maintained through a freeze drying technology.
The nickel-cobalt ore graphene composite material obtained by the method is prepared into an electrode material for a super capacitor, and the preparation method comprises the following steps: the obtained active material, the polytetrafluoroethylene emulsion and the conductive graphite are calculated according to the mass ratio, namely the active material is as follows: polytetrafluoroethylene emulsion: the conductive graphite is 8: 1:1, fully grinding the mixture in a mass ratio, dropwise adding a few drops of 1-methyl-2-pyrrolidone to obtain a mud mixture, uniformly coating the mud mixture on a nickel net (1cm x 1cm), treating the mixture under the pressure of 10MPa, and performing vacuum drying at 120 ℃ for 10 hours to obtain the material for the super capacitor.
The electrode material for the super capacitor obtained above was subjected to electrochemical performance test by the electrochemical workstation of Chenghua CHI760e, and its cycle performance diagram, rate performance diagram and impedance diagram were respectively shown in FIGS. 2, 3 and 4 at 1A g-1The specific capacitance of the capacitor can reach 250 F.g under the charge-discharge current-1At 15A · g-1The lower specific capacitance is 153F g-1And has good rate capability (the capacity retention rate is 61.2%). At high scan rates, redox peaks are still present with good chemical stability. When comparing pure NiCo2O4And NiCo2O4The EIS curves for/RGO are very similar in the high frequency region with a semicircular line profile, but the difference in the diagonal lines is easily observed: NiCo2O4Slash ratio NiCo of/RGO2O4Is more straight, indicating NiCo2O4The diffusion resistance of the/RGO electrode is lower than that of a pure NiO electrode. This may be due to the use of graphene sheets and NiCo2O43D network structure of particle formationThis provides a large surface area and a rich pore structure for diffusion of electrolyte ions.
Example 2
A preparation method for constructing a nickel-cobalt-ore binary composite material based on graphene adopts graphene with a single-layer carbon atom structure as a framework carrier, grows a nickel-cobalt-metal organic framework (Ni-Co-MOF) on a graphene framework in situ by a solvothermal method, and then obtains the graphene-based nickel-cobalt-ore composite material with a three-dimensional structure by carbonization in an air atmosphere, and the specific method is as follows:
(1) removing moisture contained in graphene oxide in a high-speed centrifugation state, dissolving the graphene oxide in an N, N-dimethylformamide solvent, and replacing a graphene oxide aqueous solution with N, N-dimethylformamide;
(2) stirring and dissolving nickel nitrate hexahydrate and cobalt nitrate hexahydrate in an N, N-dimethylformamide solution containing graphene oxide according to the mass ratio of 1:2, wherein the mass ratio of the nickel nitrate hexahydrate to the graphene oxide is 3: 1;
(3) stirring and adding polyvinylpyrrolidone and 1,3, 5-benzene tricarboxylic acid, wherein the mass ratio of the polyvinylpyrrolidone to the 1,3, 5-benzene tricarboxylic acid is 20:3, and the mass ratio of the added polyvinylpyrrolidone to the added graphene oxide is 20: 1;
(4) controlling the temperature to be 150 ℃, and carrying out solvent heat treatment on the solution for 20 h;
(5) standing and washing the obtained product with deionized water, and freeze-drying at-10 deg.C under 1.3Pa for 48 hr;
(6) heating and carbonizing the obtained product in air atmosphere at 200 deg.C at a heating rate of 1 deg.C/min-1And the time is 4 hours, and then the nickel-cobalt ore binary composite material is cooled to room temperature to obtain the nickel-cobalt ore binary composite material constructed based on the graphene.
Example 3
A preparation method for constructing a nickel-cobalt-ore binary composite material based on graphene adopts graphene with a single-layer carbon atom structure as a framework carrier, grows a nickel-cobalt-metal organic framework (Ni-Co-MOF) on a graphene framework in situ by a solvothermal method, and then obtains the graphene-based nickel-cobalt-ore composite material with a three-dimensional structure by carbonization in an air atmosphere, and the specific method is as follows:
(1) removing moisture contained in graphene oxide in a high-speed centrifugation state, dissolving the graphene oxide in an N, N-dimethylformamide solvent, and replacing a graphene oxide aqueous solution with N, N-dimethylformamide;
(2) stirring and dissolving nickel nitrate hexahydrate and cobalt nitrate hexahydrate in an N, N-dimethylformamide solution containing graphene oxide according to the mass ratio of 1:1, wherein the mass ratio of the nickel nitrate hexahydrate to the graphene oxide is 6: 1;
(3) stirring and adding polyvinylpyrrolidone and 1,3, 5-benzene tricarboxylic acid, wherein the mass ratio of the polyvinylpyrrolidone to the 1,3, 5-benzene tricarboxylic acid is 20:3, and the mass ratio of the added polyvinylpyrrolidone to the added graphene oxide is 50: 1;
(4) controlling the temperature to be 180 ℃, and carrying out solvent heat treatment on the solution for 12 h;
(5) standing and washing the obtained product with deionized water, and freeze-drying at-30 deg.C under 10Pa for 50 h;
(6) heating and carbonizing the obtained product in air atmosphere at 300 deg.C at a heating rate of 2 deg.C/min-1And the time is 3 hours, and then the nickel-cobalt ore binary composite material is cooled to room temperature to obtain the nickel-cobalt ore binary composite material constructed based on the graphene.
Example 4
A preparation method for constructing a nickel-cobalt-ore binary composite material based on graphene adopts graphene with a single-layer carbon atom structure as a framework carrier, grows a nickel-cobalt-metal organic framework (Ni-Co-MOF) on a graphene framework in situ by a solvothermal method, and then obtains the graphene-based nickel-cobalt-ore composite material with a three-dimensional structure by carbonization in an air atmosphere, and the specific method is as follows:
(1) removing moisture contained in graphene oxide in a high-speed centrifugation state, dissolving the graphene oxide in an N, N-dimethylformamide solvent, and replacing a graphene oxide aqueous solution with N, N-dimethylformamide;
(2) stirring and dissolving nickel nitrate hexahydrate and cobalt nitrate hexahydrate in an N, N-dimethylformamide solution containing graphene oxide according to the mass ratio of 1:0.5, wherein the mass ratio of the nickel nitrate hexahydrate to the graphene oxide is 15: 1;
(3) stirring and adding polyvinylpyrrolidone and 1,3, 5-benzene tricarboxylic acid, wherein the mass ratio of the polyvinylpyrrolidone to the 1,3, 5-benzene tricarboxylic acid is 20:3, and the mass ratio of the added polyvinylpyrrolidone to the added graphene oxide is 100: 1;
(4) controlling the temperature to be 200 ℃, and carrying out solvent heat treatment on the solution for 6 h;
(5) standing and washing the obtained product with deionized water, and freeze-drying at-50 deg.C under 13Pa for 60 hr;
(6) heating and carbonizing the obtained product in air atmosphere at 500 deg.C at a heating rate of 5 deg.C/min-1And the time is 2 hours, and then the nickel-cobalt ore binary composite material is cooled to room temperature to obtain the nickel-cobalt ore binary composite material constructed based on the graphene.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (8)
1. A preparation method for constructing a nickel-cobalt-ore binary composite material based on graphene is characterized by comprising the following steps of:
replacing the graphene oxide aqueous solution with N, N-dimethylformamide;
stirring and dissolving nickel nitrate hexahydrate and cobalt nitrate hexahydrate in an N, N-dimethylformamide solution containing graphene oxide;
stirring and adding polyvinylpyrrolidone and 1,3, 5-benzene tricarboxylic acid;
carrying out solvent heat treatment on the solution;
standing and washing the obtained product with deionized water, and performing freeze-drying treatment; the temperature of the freeze-drying treatment is controlled to be-10 ℃ to-50 ℃, the pressure is 1.3Pa to 13Pa, and the time is 48h to 60 h;
and (3) carrying out heating carbonization treatment on the obtained product in an air atmosphere, and cooling to room temperature to obtain the graphene-based nickel-cobalt-ore binary composite material with the three-dimensional structure.
2. The method for preparing the binary composite material for constructing the nickel-cobalt-ore based on the graphene as claimed in claim 1, wherein the graphene oxide is dissolved in the N, N-dimethylformamide solvent by removing moisture contained in the graphene oxide under a high-speed centrifugation state.
3. The preparation method of the nickel-cobalt-ore binary composite material based on graphene, according to claim 1, is characterized in that the nickel nitrate hexahydrate and the cobalt nitrate hexahydrate are mixed in a mass ratio of 1: 2-1: 0.5.
4. The preparation method of the nickel-cobalt-ore binary composite material based on graphene, according to claim 1, wherein the mass ratio of the nickel nitrate hexahydrate to the graphene oxide is 3: 1-15: 1.
5. The preparation method of the nickel-cobalt-ore binary composite material based on graphene as claimed in claim 1, wherein the mass ratio of polyvinylpyrrolidone to 1,3, 5-benzenetricarboxylic acid is 20: 3.
6. The preparation method of the nickel-cobalt-ore binary composite material based on graphene, according to claim 1 or 5, wherein the mass ratio of polyvinylpyrrolidone to graphene oxide is 20: 1-100: 1.
7. The preparation method of the nickel-cobalt-ore binary composite material based on graphene, according to claim 1, is characterized in that the temperature of the solvent heat treatment is 150-200 ℃ and the time is 6-20 h.
8. The preparation method of the nickel-cobalt-ore binary composite material based on graphene according to claim 1, wherein the temperature of the carbonization treatment is 200-500 ℃, and the temperature rise rate is 1-5 ℃ per minute-1The time is 2-4 h.
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