CN111769284A - Carbon quantum dot/CNTs composite positive electrode conductive agent and preparation method thereof - Google Patents
Carbon quantum dot/CNTs composite positive electrode conductive agent and preparation method thereof Download PDFInfo
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- CN111769284A CN111769284A CN202010580011.7A CN202010580011A CN111769284A CN 111769284 A CN111769284 A CN 111769284A CN 202010580011 A CN202010580011 A CN 202010580011A CN 111769284 A CN111769284 A CN 111769284A
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- H01M10/05—Accumulators with non-aqueous electrolyte
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Abstract
The invention discloses a carbon quantum dot/CNTs composite anode conductive agent and a preparation method thereof, relating to the technical field of lithium ion batteries, and the preparation steps are as follows: dispersing the CNTs slurry, citric acid and ethylenediamine in water, then transferring the mixture into a hydrothermal reaction kettle for hydrothermal reaction, and dialyzing after the reaction is finished to obtain the carbon quantum dot/CNTs composite conductive agent. The invention takes CNTs as a carrier and utilizes an in-situ growth method to grow carbon quantum dots on the surface of the CNTs. On one hand, the carbon quantum dots have excellent conductivity, and the conductivity of the CNTs can be further improved; on the other hand, the surface of the carbon quantum dot contains a large number of oxygen-containing functional groups such as carboxyl, hydroxyl and the like, so that the CNTs have good dispersibility; in addition, the conductive agent is prepared by an in-situ growth method, and the structure is stable. The prepared positive electrode conductive agent is applied to the lithium ion battery, and the integral multiplying power and the cycle performance of the lithium ion battery can be effectively improved.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a carbon quantum dot/CNTs composite anode conductive agent and a preparation method thereof.
Background
Among chemical power sources, lithium ion batteries have attracted much attention because of their advantages of high energy density, long service life, low self-discharge, no memory effect, and environmental protection. The main constituent materials of the lithium ion battery comprise electrolyte, isolating materials, positive and negative electrode materials and the like, wherein the positive electrode material occupies a large proportion, and the performance of the lithium ion battery is directly influenced by the performance of the positive electrode material, so that the actual performance of the positive electrode material is exerted as much as possible in the actual production.
In order to reduce the internal resistance between the positive electrode materials and the current collector, a conductive agent is added in the manufacturing process of the positive electrode plate, and the conductive agent is dispersed in the positive electrode materials to form a conductive network. However, conventional positive electrode conductive agents such as carbon black, conductive graphite, carbon fiber, etc. have problems in that the conductivity has a limitation and it is difficult to uniformly disperse them in the electrode. Although the graphene conductive paste commonly used in the industry at present can make up for the defects of the traditional conductive agent, the cost is high.
Disclosure of Invention
Based on the technical problems in the background art, the invention provides a carbon quantum dot/CNTs composite positive electrode conductive agent and a preparation method thereof, and the prepared conductive agent has high conductivity and dispersibility, is cheap and is easy to obtain.
The invention provides a preparation method of a carbon quantum dot/CNTs composite anode conductive agent, which comprises the following steps: dispersing the CNTs slurry, citric acid and ethylenediamine in water, then transferring the mixture into a hydrothermal reaction kettle for hydrothermal reaction, and dialyzing after the reaction is finished to obtain the carbon quantum dot/CNTs composite conductive agent.
Preferably, the weight ratio of the CNTs to the citric acid in the CNTs slurry is 0.01-0.03: 1, the weight volume ratio g/mL of the citric acid to the ethylenediamine is 3.0-3.5: 1.
preferably, the CNTs slurry, the citric acid and the ethylene diamine are dispersed in water by ultrasonic, the ultrasonic power is 400-600W, and the ultrasonic time is 10-20 min.
Preferably, the reaction temperature of the hydrothermal reaction is 150-.
Preferably, dialysis is performed using dialysis bags having a molecular weight cut-off of 1-3 KD.
Preferably, the dialysis time is 24-48 h.
Preferably, the dialysis is dialysis in water.
The invention also provides the carbon quantum dot/CNTs composite positive electrode conductive agent prepared by the method.
Has the advantages that: the invention provides a preparation method of a carbon quantum dot/CNTs composite anode conductive agent, which takes CNTs as a carrier and utilizes an in-situ growth method to grow carbon quantum dots on the surface of the CNTs. On one hand, the carbon quantum dots have excellent conductivity, and the conductivity of the CNTs can be further improved; on the other hand, the surface of the carbon quantum dot contains a large number of oxygen-containing functional groups such as carboxyl, hydroxyl and the like, so that the CNTs have good dispersibility; in addition, the conductive agent is prepared by an in-situ growth method, and the structure is stable. The prepared positive electrode conductive agent is applied to the lithium ion battery, and the integral multiplying power and the cycle performance of the lithium ion battery can be effectively improved. The raw materials are cheap and easy to obtain, the preparation method is simple, and industrial application is expected to be realized.
Drawings
FIG. 1 is a graph of the power-multiplying performance of assembled lithium ion batteries in example 1 of the present invention and a control;
fig. 2 is a graph of the high temperature cycle performance of assembled lithium ion batteries in example 1 of the present invention and a control.
Detailed Description
The technical solution of the present invention will be described in detail below with reference to specific examples.
Example 1
A preparation method of a carbon quantum dot/CNTs composite positive electrode conductive agent comprises the following steps: adding 0.21014g of CNTs slurry (the solid content of CNTs in the slurry is 10%), 1.0507g of citric acid and 335 mu L of ethylenediamine into 15mL of water, adjusting the power to 500W, performing ultrasonic treatment for 15min to disperse uniformly, transferring the mixture into a 30mL tetrafluoroethylene reaction kettle, heating to 200 ℃, keeping the temperature for 5h, cooling to room temperature, placing the mixture into 1L of water, stirring at a low speed, and dialyzing for 24h, wherein the cut-off molecular weight of a dialysis bag is 1 KD; and finally, centrifuging to obtain the precipitate, and drying to obtain the CNTs conductive agent containing the carbon quantum dots.
Example 2
A preparation method of a carbon quantum dot/CNTs composite positive electrode conductive agent comprises the following steps: adding 0.10507g of CNTs slurry (the solid content of CNTs in the slurry is 10%), 1.0507g of citric acid and 335 mu L of ethylenediamine into 15mL of water, adjusting the power to 400W, performing ultrasonic treatment for 10min to disperse uniformly, transferring the mixture into a 30mL tetrafluoroethylene reaction kettle, heating to 200 ℃, keeping the temperature for 5h, cooling to room temperature, placing the mixture into 1L of water, stirring at a low speed, and dialyzing for 24h, wherein the cut-off molecular weight of a dialysis bag is 2 KD; and finally, centrifuging to obtain the precipitate, and drying to obtain the CNTs conductive agent containing the carbon quantum dots.
Example 3
A preparation method of a carbon quantum dot/CNTs composite positive electrode conductive agent comprises the following steps: adding 0.31521g of CNTs slurry (the solid content of CNTs in the slurry is 10%), 1.0507g of citric acid and 350 mu L of ethylenediamine into 15mL of water, adjusting the power to 600W, performing ultrasonic treatment for 20min to disperse uniformly, transferring the mixture into a 30mL tetrafluoroethylene reaction kettle, heating to 200 ℃, keeping the temperature for 5h, cooling to room temperature, placing the mixture into 1L of water, stirring at a low speed, and dialyzing for 24h, wherein the cut-off molecular weight of a dialysis bag is 3 KD; and finally, centrifuging to obtain the precipitate, and drying to obtain the CNTs conductive agent containing the carbon quantum dots.
Example 4
A preparation method of a carbon quantum dot/CNTs composite positive electrode conductive agent comprises the following steps: adding 0.21014g of CNTs slurry (the solid content of CNTs in the slurry is 10%), 1.0507g of citric acid and 300 mu L of ethylenediamine into 15mL of water, adjusting the power to 500W, performing ultrasonic treatment for 15min to disperse uniformly, transferring the mixture into a 30mL tetrafluoroethylene reaction kettle, heating to 150 ℃, preserving the temperature for 4h, cooling to room temperature, placing the mixture into 1L of water, stirring at a low speed, and dialyzing for 36h, wherein the cut-off molecular weight of a dialysis bag is 1 KD; and finally, centrifuging to obtain the precipitate, and drying to obtain the CNTs conductive agent containing the carbon quantum dots.
Example 5
A preparation method of a carbon quantum dot/CNTs composite positive electrode conductive agent comprises the following steps: adding 0.21014g of CNTs slurry (the solid content of CNTs in the slurry is 10%), 1.0507g of citric acid and 335 mu L of ethylenediamine into 15mL of water, adjusting the power to 500W, performing ultrasonic treatment for 15min to disperse uniformly, transferring the mixture into a 30mL tetrafluoroethylene reaction kettle, heating to 250 ℃, preserving the temperature for 6h, cooling to room temperature, placing the mixture into 1L of water, stirring at a low speed, and dialyzing for 48h, wherein the cut-off molecular weight of a dialysis bag is 1 KD; and finally, centrifuging to obtain the precipitate, and drying to obtain the CNTs conductive agent containing the carbon quantum dots.
Taking the carbon quantum dot/CNTs composite positive electrode conductive agent prepared in the embodiment 1 for preparing a corresponding lithium ion battery; as a control, the corresponding lithium ion batteries were prepared using unmodified CNTs conductive agents. The two groups of batteries are identical in other materials, dosage and battery preparation methods except that the positive conductive agents of the two groups of batteries are different (wherein the battery assembly materials are specifically a Haichuan Ni85 ternary positive electrode material, a fir EV7 negative electrode material and a new aeubang E32 electrolyte).
The following are the results of testing the performance of the assembled batteries in example 1 and the control group.
(1) Battery rate capability test
The specific test method comprises the following steps: the batteries of the test group and the comparison group are charged to 4.2V from 2.8V constant current at 1C, the 4.2V constant voltage charging is kept, and the current is cut off at 0.05C; then, the discharge capacity retention rates at different multiplying factors are recorded in sequence after discharging to 2.8V at 1C/2C/3C respectively, and the test results are shown in table 1 and fig. 1.
Table 1 capacity retention at different rates for batteries in example 1 and control
As can be seen from table 1 and fig. 1, the capacity retention rate of the battery in example 1 is significantly better than that of the control battery under high-rate discharge, and when the battery is discharged at 3C rate, the capacity retention rate of example 1 still reaches 93% or more; therefore, the CNTs conductive agent containing the carbon quantum dots, which is prepared by the invention, is applied to the lithium ion battery, and the multiplying power performance of the battery is greatly improved.
(2) High temperature cycle performance test of battery
The specific test method comprises the following steps: the batteries of the test group and the comparison group are charged to 4.2V from 2.8V constant current at 1C, the 4.2V constant voltage charging is kept, and the current is cut off at 0.05C; then, the constant current of 1C is discharged to 2.8V, and the charging and discharging are cycled for 800 weeks according to the working procedure, and the test results are shown in Table 2 and FIG. 2.
Table 2 capacity retention of batteries in example 1 and control
As can be seen from table 2 and fig. 2, the capacity retention rate of the control battery is about 87.8% after about 400 weeks of current cycle; in the embodiment 1, the battery is circulated for more than 400 weeks, and the capacity retention rate is still as high as 91.7 percent; therefore, the CNTs conductive agent containing the carbon quantum dots, which is prepared by the method, is applied to the lithium ion battery, and the high-temperature cycle performance of the battery is further improved.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (8)
1. A preparation method of a carbon quantum dot/CNTs composite positive electrode conductive agent is characterized by comprising the following steps: dispersing the CNTs slurry, citric acid and ethylenediamine in water, then transferring the mixture into a hydrothermal reaction kettle for hydrothermal reaction, and dialyzing after the reaction is finished to obtain the carbon quantum dot/CNTs composite conductive agent.
2. The method for preparing the carbon quantum dot/CNTs composite positive electrode conductive agent according to claim 1, wherein the weight ratio of CNTs to citric acid in the CNTs slurry is 0.01-0.03: 1, the weight volume ratio g/mL of the citric acid to the ethylenediamine is 3.0-3.5: 1.
3. the preparation method of the carbon quantum dot/CNTs composite positive electrode conductive agent according to claim 1 or 2, characterized in that CNTs slurry, citric acid and ethylenediamine are dispersed in water by ultrasound, the ultrasound power is 400-600W, and the ultrasound time is 10-20 min.
4. The method for preparing the carbon quantum dot/CNTs composite positive electrode conductive agent according to any one of claims 1-3, wherein the reaction temperature of the hydrothermal reaction is 150-.
5. The method for preparing the carbon quantum dot/CNTs composite positive electrode conductive agent according to any one of claims 1-4, characterized in that dialysis is carried out by using a dialysis bag, and the cut-off molecular weight of the dialysis bag is 1-3 KD.
6. The method for preparing the carbon quantum dot/CNTs composite positive electrode conductive agent according to any one of claims 1-5, characterized in that the dialysis time is 24-48 h.
7. The method for preparing the carbon quantum dot/CNTs composite positive electrode conductive agent according to any one of claims 1-6, characterized in that dialysis is dialysis in water.
8. A carbon quantum dot/CNTs composite positive electrode conductive agent, characterized in that it is prepared by the method of any one of claims 1-7.
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| CN113683082A (en) * | 2021-08-13 | 2021-11-23 | 肇庆中特能科技投资有限公司 | Graphene quantum dot composite material and application thereof |
| CN113980295A (en) * | 2021-11-12 | 2022-01-28 | 中国石油大学(华东) | Chitosan/sodium alginate hydrogel and preparation method and use method thereof |
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Cited By (4)
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| CN113683082A (en) * | 2021-08-13 | 2021-11-23 | 肇庆中特能科技投资有限公司 | Graphene quantum dot composite material and application thereof |
| CN113980295A (en) * | 2021-11-12 | 2022-01-28 | 中国石油大学(华东) | Chitosan/sodium alginate hydrogel and preparation method and use method thereof |
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