CN108832114B - Preparation method of graphene-coated CuFeO2 composite negative electrode material - Google Patents
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Abstract
The invention discloses a graphene-coated CuFeO2The preparation method of the composite negative electrode material comprises the following steps: (1) adding a certain amount of copper salt and iron salt into deionized water, stirring to form a solution A, preparing a sodium hydroxide solution with a certain concentration, slowly adding the sodium hydroxide solution into the solution A, and simultaneously adding a reducing agent and graphene serving as a conductive agent to form a solution B; (2) transferring the solution B into a reaction kettle for hydrothermal reaction, centrifuging the product, washing the product for several times by using ethanol and deionized water, and drying to obtain the graphene coated CuFeO2Composite cathode material CuFeO2@ G. The invention adopts a hydrothermal method to prepare the nano CuFeO2The material has a large surface area, the contact area with an electrolyte is increased, and the conductivity of the material is improved by utilizing the graphene, so that the composite material has high specific capacity, high charge-discharge rate and long cycle life when being used for a lithium ion battery.
Description
Technical Field
The invention relates to a preparation method of a battery cathode material, in particular to graphene-coated CuFeO2A preparation method of the composite negative electrode material.
Background
With the global energy crisis and the aggravation of environmental pollution, the development and application of new energy are imperative. Lithium ion batteries have been rapidly developed since commercialization was achieved in the 90 s of the 20 th century. Compared with the traditional chemical battery, the battery has the advantages of light weight, small volume, high voltage, high specific energy, wide working temperature range, high specific power, stable discharge, long storage time, no memory effect, no pollution and the like. At present, lithium ion batteries are widely applied to portable electronic products such as mobile phones, digital cameras, notebook computers and the like, and show wide application prospects in Electric Vehicles (EV), Hybrid Electric Vehicles (HEV) and power grid energy storage systems.
At present, various commercialized lithium ion battery negative electrode materials are mainly carbon materials, and the carbon materials are widely applied lithium ion battery negative electrode materials and carbon negative electrodesThe material has low lithium-inserting potential, good conductivity, abundant natural reserve, no pollution and simple preparation process, the volume expansion in the lithium inserting and extracting process is basically below 9 percent, and the material shows higher coulombic efficiency and excellent circulation stability. However, as the performance requirements for lithium batteries have increased, the deficiencies of graphite as a negative electrode material have also developed, such as low gram capacity (372 mAh g)-1) And when the cycle times are more, the layered structure is easy to peel off and fall off, and the like, so that the specific energy and the performance of the lithium battery are limited to be further improved.
CuFeO2The copper-iron ore material has the characteristics of good stability, rich earth crust reserves and the like, has the property of a p-type semiconductor, and has good application prospect in the fields of lithium ion batteries and photoelectrocatalysis. CuFeO2The cathode material of the lithium ion battery has a synthesized voltage platform (1.0V (Vs. L i)+/L i)), higher theoretical specific capacity (708 mAh g)-1) The material is very suitable for the cathode material of the lithium ion battery which requires high safety and high capacity at present. However, CuFeO2The material has low conductivity, so that the capacity of the material is quickly attenuated under high multiplying power, and the performance of the material is poor. At the same time CuFeO2The particle size and the contact area of the electrolyte are also important factors influencing the high rate performance of the electrolyte.
Graphene is a planar two-dimensional structure composed of a single layer of carbon atoms, similar to graphite, 3 of the 4 valence electrons of which are sp2The hybridized form and the nearest three carbon atoms form a honeycomb structure connected by a plane regular hexagon, and the other sigma-z orbital electron perpendicular to the plane of the carbon atoms forms a large pi bond with high tourism on two sides of the lattice plane like a benzene ring. The binary electronic valence bond structure determines the unique and abundant performances of graphene: sp2The bond has high strength and stability, and the large pi-bond electrons highly circulating on two sides of the lattice plane enable the crystal to have zero-band-gap semiconductor and Dirac carrier characteristics, and show good conductivity and extremely high electron mobility (2.5 × 105 cm)2•V-1·s-1). The excellent performances enable the graphene to be applied to various fields of solar batteries, high-performance batteries, super capacitors and composite materialsHas potential application.
Most of the synthesized CuFeO2The method is characterized in that high-temperature solid phase method and sol-gel method are followed by high-temperature calcination, and the method has high required temperature, high energy consumption, high calcination temperature and long calcination time to prepare the CuFeO2The particles are large, so that the side length of a migration path of lithium ions in the particles is long, and the lithium ions are difficult to be inserted and extracted, and the electrochemical performance of the particles is influenced. How to synthesize nano CuFeO2The material solves the conductivity of the material and is CuFeO2The development of the material industry is an important problem.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides a graphene coated CuFeO2The preparation method of the composite cathode material solves the problem of CuFeO2The material has low conductivity and particle size.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows: graphene-coated CuFeO2The preparation method of the composite negative electrode material comprises the following steps:
(1) adding a certain amount of copper salt and iron salt into deionized water, stirring to form a solution A, preparing a sodium hydroxide solution with a certain concentration, slowly adding the sodium hydroxide solution into the solution A, and simultaneously adding a reducing agent and graphene serving as a conductive agent to form a solution B;
(2) transferring the solution B into a reaction kettle for hydrothermal reaction, centrifuging the product, washing the product for several times by using ethanol and deionized water, and drying to obtain the graphene coated CuFeO2Composite cathode material CuFeO2@G。
Further, in the step (1), the copper salt is one or more of copper nitrate, copper sulfate and copper chloride; the ferric salt is one or more of ferric nitrate, ferric sulfate and ferric chloride; and the copper and iron salts correspond in root.
Further, in the step (1), the mass ratio of the copper salt, the iron salt and the graphene is 1: 1: 0.01 to 0.05.
Further, in the step (1), the reducing agent is one or more of propionaldehyde, ascorbic acid and glucose.
Further, in the step (2), the hydrothermal reaction temperature is 160-240 ℃, and the hydrothermal time is 16-36 h.
The beneficial technical effects of the invention are as follows: preparing nano CuFeO by hydrothermal method2The material has a large surface area, the contact area with an electrolyte is increased, and the conductivity of the material is improved by utilizing the graphene, so that the composite material has high specific capacity, high charge-discharge rate and long cycle life when being used for a lithium ion battery.
Drawings
The invention is further elucidated with reference to the drawings and the embodiments.
FIG. 1 shows CuFeO in example 1 of the present invention2The discharge curve of the material under the multiplying power of 0.2C;
FIG. 2 shows CuFeO in example 1 of the present invention2Material and CuFeO2The @ G composite material is assembled into a cycle performance comparison graph of a half cell which circulates 500 circles at room temperature under 1C multiplying power;
FIG. 3 shows CuFeO in example 1 of the present invention2The @ G composite material is assembled into a cycle performance graph of the half cell which is cycled for 500 circles at room temperature under 1C multiplying power.
Detailed Description
Example 1
0.00625mol copper nitrate and 0.00625mol iron nitrate were dissolved in 30ml deionized water with magnetic stirring. Next, 0.125mol of sodium hydroxide was dissolved in 20ml of deionized water with stirring until completely dissolved, and then slowly added to the prepared mixed nitrate solution with stirring and stirred for 90 minutes. 0.01g of graphene subjected to ultrasonic dispersion and 0.625ml of reducing agent propionaldehyde are added into the mixed solution.
Transferring the mixed solution into an autoclave (70 ml), heating at 180 ℃ for 16h, naturally cooling to room temperature, centrifuging the product, washing with alcohol and deionized water for several times, and drying at 80 ℃ to obtain CuFeO2A composite material.
The conductivity of the composite material can be improved by adding a proper amount of graphene, so that the electrochemical performance of the composite material is improved, and the content of grapheneLess, not enough to improve the conductivity of the composite material, and too much content, which may affect the specific capacity of the composite material, therefore, the amount to mass ratio of the copper salt, iron salt and graphene is 1: 1: 0.01 to 0.05. The hydrothermal temperature and time are proper to ensure that the synthesized CuFeO2The material has the advantages of uniform particle size distribution, good crystal form and no agglomeration.
As shown in FIG. 1, CuFeO obtained in this example was used2The material is assembled into a half cell, and the discharge curve is under 0.2C multiplying power at room temperature;
FIG. 2 shows CuFeO2Material and CuFeO2The @ G composite material is assembled into a half cell and is cycled for 200 circles at room temperature under the multiplying power of 1C, wherein a refers to CuFeO2Material, b means CuFeO2@ G composite;
FIG. 3 shows CuFeO2The @ G composite material is assembled into a half-cell, and is subjected to a cycle performance diagram of 500 cycles of 1C rate cycle at room temperature, wherein a refers to charge-discharge efficiency, and b refers to discharge specific capacity.
CuFeO in this example2Material and CuFeO2Electrochemical performance of the @ G composite Material, CuFeO, is shown in FIG. 12The material has a suitable voltage platform and a first discharge specific capacity; as can be seen from FIG. 2, CuFeO2The material is coated by graphene, so that the electrochemical performance is obviously improved, and the material has longer cycle performance; as can be seen from FIG. 3, CuFeO2The circulation performance graph of the @ G composite material after 500 cycles of long circulation shows that the composite material has good circulation performance and charge-discharge efficiency.
Example 2
0.00625mol of copper sulfate and 0.00625mol of iron sulfate were dissolved in 30ml of deionized water with magnetic stirring. Next, 0.125mol of sodium hydroxide was dissolved in 20ml of deionized water with stirring until completely dissolved, and then slowly added to the prepared mixed sulfate solution with stirring and stirred for 90 minutes. 0.02g of graphene subjected to ultrasonic dispersion and 0.625ml of reducing agent ascorbic acid are added into the mixed solution.
The above mixed solution was transferred to an autoclave (70 ml) and heated at 200 ℃ for 18 hours, after naturally cooled to room temperature, the product was centrifugedWashing with alcohol and deionized water for several times, and drying at 80 deg.C to obtain CuFeO2A composite material.
Example 3
0.00625mol of copper chloride and 0.00625mol of iron chloride were dissolved in 30ml of deionized water with magnetic stirring. Next, 0.125mol of sodium hydroxide was dissolved in 20ml of deionized water with stirring until completely dissolved, and then slowly added to the prepared mixed chloride solution with stirring and stirred for 90 minutes. 0.03g of graphene subjected to ultrasonic dispersion and 0.625ml of reducing agent glucose are added into the mixed solution.
Transferring the mixed solution into an autoclave (70 ml), heating at 220 ℃ for 24h, naturally cooling to room temperature, centrifuging the product, washing with alcohol and deionized water for several times, and drying at 80 ℃ to obtain CuFeO2A composite material.
Example 4
0.00625mol of copper nitrate and 0.00625mol of iron nitrate were dissolved in 30ml of deionized water with magnetic stirring. Next, 0.125mol of sodium hydroxide was dissolved in 20ml of deionized water with stirring until completely dissolved, and then slowly added to the prepared mixed nitrate solution with stirring and stirred for 90 minutes. 0.01g of graphene subjected to ultrasonic dispersion and 0.625ml of reducing agent propionaldehyde are added into the mixed solution.
Transferring the mixed solution into an autoclave (70 ml), heating at 230 ℃ for 24h, naturally cooling to room temperature, centrifuging the product, washing with alcohol and deionized water for several times, and drying at 80 ℃ to obtain CuFeO2A composite material.
Comparative example
0.00625mol of copper nitrate and 0.00625mol of iron nitrate were dissolved in 30ml of deionized water with magnetic stirring. Next, 0.125mol of sodium hydroxide was dissolved in 20ml of deionized water with stirring until completely dissolved, and then slowly added to the prepared mixed nitrate solution with stirring and stirred for 90 minutes. 0.625ml of a reducing agent ascorbic acid was added to the above mixed solution.
The above mixed solution was transferred to an autoclave (70 ml) and heated at 200 ℃ for 24 hours, followed by natural coolingAfter cooling to room temperature, the product was centrifuged and washed several times with alcohol and deionized water, and then dried at 80 ℃ to give CuFeO2A composite material.
TABLE 1500 cycle half-cell Room temperature cycling data
| Specific discharge capacity (mAh/g) at 1C rate | Capacity retention after 500 cycles | |
| Example 1 | 455 | 93% |
| Example 2 | 440 | 91% |
| Example 3 | 450 | 92% |
| Example 4 | 465 | 94% |
| Comparative example | 160 | 90% |
Verification of effects
Table 1 shows the specific capacity at room temperature at 1C rate and the capacity retention rate after 500 cycles of the half cell assembled by the examples and the comparative examples.
By contrast, in examples 1 to 4, CuFeO was formed by adding graphene and a reducing agent2The specific discharge capacity of the composite material is far greater than that of a comparative example, and the capacity retention rate is higher than that of the comparative example.
Therefore, the invention adopts a hydrothermal method to prepare the nano CuFeO2The material has a large surface area, the contact area with an electrolyte is increased, and the conductivity of the material is improved by utilizing the graphene, so that the composite material has high specific capacity, high charge-discharge rate and long cycle life when being used for a lithium ion battery.
The foregoing description of specific embodiments of the present invention has been presented. It is to be understood that the present invention is not limited to the specific embodiments described above, and that various changes and modifications may be made by one skilled in the art within the scope of the appended claims without departing from the spirit of the invention.
Claims (3)
1. Graphene-coated CuFeO2The preparation method of the composite negative electrode material is characterized by comprising the following steps:
(1) adding a certain amount of copper salt and iron salt into deionized water, stirring to form a solution A, preparing a sodium hydroxide solution with a certain concentration, slowly adding the sodium hydroxide solution into the solution A, and simultaneously adding a reducing agent and graphene serving as a conductive agent to form a solution B;
(2) transferring the solution B into a reaction kettle for hydrothermal reaction, centrifuging the product, washing the product for several times by using ethanol and deionized water, and drying to obtain the graphene coated CuFeO2Composite cathode material CuFeO2@G；
In the step (1), the copper salt is one or more of copper nitrate, copper sulfate and copper chloride; the ferric salt is one or more of ferric nitrate, ferric sulfate and ferric chloride; the copper salt and the iron salt correspond to each other;
in the step (1), the mass ratio of the copper salt to the iron salt is 1: 1, graphene quality and synthesized CuFeO2Mass ratio of0.01-0.05: 1.
2. the graphene-coated CuFeO according to claim 12The preparation method of the composite negative electrode material is characterized by comprising the following steps: in the step (1), the reducing agent is one or more of propionaldehyde, ascorbic acid and glucose.
3. The graphene-coated CuFeO according to claim 12The preparation method of the composite negative electrode material is characterized by comprising the following steps: in the step (2), the hydrothermal reaction temperature is 160-240 ℃, and the hydrothermal time is 16-36 h.
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| CN111229161A (en) * | 2020-01-22 | 2020-06-05 | 青岛农业大学 | Using CuFeO2Method for adsorbing oxytetracycline by/BC composite magnetic material |
| CN111389351B (en) * | 2020-01-22 | 2022-05-17 | 青岛农业大学 | CuFeO 2/biochar composite magnetic material and preparation method thereof |
| CN111185137A (en) * | 2020-01-22 | 2020-05-22 | 青岛农业大学 | Method for preparing biological carbon with magnetism and photocatalysis simultaneously by using pepper straws |
| CN113809318A (en) * | 2021-09-24 | 2021-12-17 | 长春工业大学 | Preparation method and application of CuO/graphene composite material |
| CN115569660B (en) * | 2022-10-25 | 2024-02-06 | 安徽大学 | High-dispersion carbon dioxide hydrogenation catalyst taking CuFeO2@GO as precursor and preparation method and application thereof |
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