CN110581264B - High-performance nickel-zinc battery negative electrode active material and preparation method thereof - Google Patents
High-performance nickel-zinc battery negative electrode active material and preparation method thereof Download PDFInfo
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
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Abstract
The invention belongs to the technical field of energy and materials, and particularly relates to a high-performance nickel-zinc battery negative electrode active material and a preparation method thereof. The negative active material is a carbon dot/zinc oxide nano composite material with a cluster structure. The preparation method comprises the following steps: dropwise adding a mixed aqueous solution of carbon dots and zinc salt into an alkaline aqueous solution, heating for reaction until a large amount of products are separated out, cooling and centrifuging the reaction solution to obtain a precipitate, washing and drying the precipitate; and (3) heating the precipitate in a nitrogen atmosphere to prepare the carbon dot/zinc oxide nano composite material. The carbon dot/zinc oxide nano composite material has the advantages of multiple aspects: large specific surface area, more lattice defects, good conductivity, high specific capacity and strong corrosion resistance; in the nickel-zinc battery, the nickel-zinc battery has excellent rate performance and cycle stability, excellent safety and long-term stability, and can be applied to many fields of electrochemical energy storage.
Description
Technical Field
The invention belongs to the technical field of energy and materials, and particularly relates to a nickel-zinc battery cathode material and a preparation method thereof.
Background
In recent years, the adjustment of energy structure has highlighted the advantages of clean, convenient, efficient, wide and practical electric energy, and it is very important to utilize a secondary battery with high capacity and excellent cycle performance to realize effective storage, transportation and use of electric energy. The existing secondary battery systems have some problems which are difficult to solve, such as serious pollution of lead-acid batteries and low power and energy density; the nickel-metal hydride battery has low working voltage and expensive hydrogen storage cathode; the organic electrolyte of the lithium battery is inflammable and explosive, and the reserves of lithium and cobalt ore resources are insufficient. In contrast, aqueous zinc ion batteries, such as nickel zinc batteries, have the advantages of high safety factor, high power density, low price, etc., and thus become powerful competitors in the next generation of battery systems. At present, the short plates of the batteries are mainly concentrated on zinc cathode materials, so that the improvement of the performance of the electrodes has important significance for promoting the development and application of the related batteries.
Taking a nickel-zinc battery as an example, the key problems to be solved are mainly focused on the problems of easy dissolution, easy corrosion, poor conductivity and the like of a negative electrode zinc oxide material. As a result, the cycle stability and rate performance of the battery material are directly worried. Taking the commercial zinc oxide material as an example, when the current density is increased from 1A/g to 10A/g, the capacity retention rate is only about 40 percent. Under the current density of 1A/g, the capacity retention rate is only about 30 percent after 100 cycles. The method effectively solves the problems of the cathode and has important significance and value for preparing the high-performance nickel-zinc battery. Related studies have shown that carbon compounding processes are relatively reliable, for example, by introducing carbon materials such as carbon nanotubes or carbon black when preparing negative electrodes. However, although the conductivity and corrosion resistance of such composite materials are improved to some extent, the rate capability and the cycle performance under large current still need to be improved.
The carbon dots, as a novel zero-dimensional carbon nano material, have the characteristics of low price, simple and convenient preparation, good dispersibility, good conductivity, stable chemical property and the like. Relevant researches and the invention show that the carbon dots can play a role in regulating and controlling the microstructure of the zinc oxide electrode material, improving the electronic conductivity, inhibiting self-corrosion and the like. Thereby improving the rate capability and the cycle performance by nearly 30 percent and 50 percent respectively. Compared with the related research results, the invention basically solves the main defects of the traditional zinc oxide electrode material and provides a very powerful support for the development of the nickel-zinc battery.
Disclosure of Invention
The invention aims to solve the problem of insufficient performance of the conventional cathode active material of a nickel-zinc battery and provides a cathode active material of a nickel-zinc battery with excellent rate performance and cycle performance and a preparation method thereof.
The invention provides a nickel-zinc battery cathode active material, which is a nanocluster (marked as carbon dot/zinc oxide nanomaterial) formed by compounding carbon dots and zinc oxide, and has the following structure:
(1) the diameter of the carbon dot is 1-10 nanometers, graphitized carbon with good conductivity is arranged inside the carbon dot, and various organic functional groups and defect structures are arranged outside the carbon dot and can be tightly combined with a zinc oxide material;
(2) the carbon layer on the surface of the carbon dot/zinc oxide nano composite material is 10-90 nanometers thick, a unique spherical cluster structure is formed after calcination, the particle size of the spherical cluster structure is 500-5000 nanometers, the surface layer of the spherical cluster structure is of an outward rodlike structure vertical to a spherical surface, the whole nano material is in a acanthosphere shape, and oxygen vacancies or zinc vacancies are formed on the surface of the nano material.
The preparation method of the cathode active material of the nickel-zinc battery combines a sol-gel method and a high-temperature calcination treatment technology, and comprises the following specific steps:
(1) adding the carbon dots into a zinc salt solution, mixing and stirring to prepare a carbon dot/zinc salt mixed solution; dropwise adding the mixed solution into an alkali solution, refluxing for 1-12 hours at the temperature of 50-85 ℃, naturally cooling to room temperature, centrifuging the reaction solution to obtain a solid precipitate, washing to remove unreacted impurities, and drying the cleaned precipitate;
(2) and (3) carrying out heat treatment on the precipitate at 300-600 ℃ for 1-3 hours in a nitrogen atmosphere to obtain the carbon dot/zinc oxide composite material. Specifically, the dried precipitate is put into a crucible, the crucible is placed into a tube furnace, and heating treatment is carried out for 1-3 hours in a nitrogen atmosphere.
In step (1), the carbon dots include but are not limited to graphene quantum dots, carbon nanodots and polymer quantum dots; the raw materials for synthesizing the carbon dots include but are not limited to graphene, aromatic compounds, citric acid, ethylenediamine, carbon nanotubes, polyvinylpyrrolidone or urea and the like; the carbon dots are prepared by a top-down or bottom-up method; the particle size of the carbon dots is 1-10 nm.
In step (1) of the present invention, the zinc salt includes, but is not limited to, zinc nitrate hexahydrate, zinc acetate dihydrate, zinc sulfate heptahydrate, zinc chloride, zinc phosphate, basic zinc carbonate, zinc methacrylate, or the like.
In step (1) of the present invention, the solution is water, ethanol or a mixed solution of water and ethanol.
In step (1) of the present invention, the base includes, but is not limited to, sodium hydroxide, potassium hydroxide, lithium hydroxide, ammonia, urotropin, urea, or the like.
In the step (1), the concentration of the carbon dots in the mixed solution is 0.01-2 mg/ml.
In the step (1), the mass concentration of the zinc salt is 0.005-3M; the mass concentration of the alkali is 0.01-4M; the mass concentration ratio of the zinc salt to the alkali is 4: 1-1: 4.
In the step (2), the temperature rise rate of the heat treatment is 0.5-5 ℃/min.
The carbon dot/zinc oxide composite material provided by the invention can be used as a negative active material for a nickel-zinc battery.
The invention has the following advantages:
(1) the traditional expensive carbon materials, such as graphene, carbon nanotubes and the like, have poor dispersibility in water, and the carbon dots used in the invention have the advantages of good water solubility and low price. The zinc oxide anode material has good dispersibility in water, and the surface carbon layer can be used for uniformly and effectively wrapping the zinc oxide anode material. Meanwhile, unreacted carbon points can be removed through simple washing, so that the content of zinc oxide in the composite material is increased, and the full battery is further ensured to have considerable specific capacity. In addition, the carbon dots are low in price, and are more beneficial to practical production and application;
(2) the carbon dot/zinc oxide composite material is prepared by utilizing a sol-gel method and a high-temperature calcination treatment technology, and has the advantages of simple and convenient preparation method, high repeatability, wide application range and the like. The carbon dot/zinc oxide composite material has large specific surface area and abundant lattice holes, and is beneficial to the migration of electrons or ions;
(3) the prepared carbon dot/zinc oxide composite material has the advantages of less side reaction, more reaction sites, strong corrosion resistance, small resistance and the like;
(4) the full cell prepared from the carbon dot/zinc oxide composite material has excellent rate capability and cycle performance. Taking carbon dots prepared by using citric acid as an example, the carbon dot/zinc oxide cathode material synthesized by using the carbon dots is used for preparing a nickel-zinc battery and is tested, and the result shows that: when the current density is increased from 1A/g to 10A/g, the capacity retention rate is 75.1%. At a current density of 5A/g, the capacity retention rate was 92% after 5000 charge-discharge cycles.
Drawings
FIG. 1 is a transmission electron micrograph of the carbon dot/zinc oxide composite in example 1.
FIG. 2 is an X-ray diffraction pattern of the carbon dot/zinc oxide composite of example 1.
FIG. 3 is a cyclic voltammogram of the carbon dot/zinc oxide composite of example 1 at different sweep rates.
Fig. 4 is a charge and discharge curve of a nickel zinc battery composed of the carbon dot/zinc oxide composite in example 1.
Fig. 5 is a graph showing the cycling stability at a current density of 5A/g for a nickel zinc cell composed of the carbon dot/zinc oxide composite in example 1.
FIG. 6 is a schematic view of the preparation process of the carbon dot/zinc oxide composite material of the present invention.
Detailed Description
In order to better explain the present disclosure, the present invention is further illustrated below with reference to specific examples, example results and corresponding figures, but the examples should not be construed as limiting the scope of the present invention.
Example 1
(1) Carbon dots prepared by using citric acid as raw material
6 g of anhydrous citric acid, 1.6 g of ethylenediamine and 3 ml of water were added to a polytetrafluoroethylene reaction vessel, and then reacted at 160 ℃ for 6 hours. After the system was cooled to room temperature, the liquid in the tank was transferred to a dialysis bag (3500 Da) and dialyzed in deionized water for 24 hours. Transferring the carbon dot aqueous solution obtained by dialysis into a centrifuge tube, precipitating carbon dots by using anhydrous ethanol, centrifuging to obtain a precipitate, and washing the precipitate with ethanol for three times. And drying the cleaned precipitate in an oven at 85 ℃ to obtain carbon dots.
(2) Preparation of carbon dot/zinc oxide composite material
150 ml of 0.014M aqueous zinc nitrate hexahydrate solution was added to the mixture, 150 mg of carbon dots were added and dissolved by sonication to form a uniform mixed aqueous solution. The mixed aqueous solution of carbon point and zinc nitrate was added dropwise to 150 ml of 0.017M urotropine aqueous solution and reacted at 85 ℃ for 10 hours. After cooling to room temperature, the solution was centrifuged to give a solid precipitate, which was washed three times with water and dried under vacuum at 85 ℃. The dried solid was precipitated and placed in a crucible in a tube furnace. In the nitrogen atmosphere, the temperature is raised to 600 ℃ at the temperature raising speed of 1 ℃/min, then the temperature is kept at 600 ℃ for 2 hours, and then the temperature is returned to the room temperature at the temperature lowering speed of 1 ℃/min. Thus obtaining the carbon dot/zinc oxide composite material.
(3) Preparation of the negative electrode
8 mg of the carbon dot/zinc oxide composite material and 1 mg of acetylene black were put in a mortar and ground for 15 minutes. Subsequently, the mixed powder was transferred to a beaker, and 4 mg of 25% PTFE emulsion and an appropriate amount of ethanol were added thereto, sufficiently stirred, and dried in a drying oven at 85 ℃. A small amount of ethanol was added, and the dried electrode material was rolled sufficiently and applied on a 316L stainless steel net (1.5 cm. times.9 cm). And compacting the electrode plates, and drying in an oven at 85 ℃ for 10 hours to obtain the battery cathode.
(4) Preparation of the Positive electrode
40 mg of commercial nickel hydroxide and 5 mg of acetylene black were put in a mortar and ground for 15 minutes. The mixed powder was transferred to a small beaker, added with 20 mg of 25% PTFE emulsion and an appropriate amount of ethanol, stirred well and dried in a drying oven at 85 ℃. A small amount of ethanol was added, and the dried electrode material was rolled down sufficiently and applied to a nickel foam (1.5 cm. times.9 cm). And compacting the electrode plates, and drying in an oven at 85 ℃ for 10 hours to obtain the battery anode.
(5) Assembly of battery
A mixed aqueous solution of 4M potassium hydroxide, 0.1M lithium hydroxide, 0.9M potassium fluoride and saturated zinc oxide was used as an electrolytic solution. The positive electrode and the negative electrode are separated by a polypropylene microporous membrane, and are compacted on a manual tablet press after a proper amount of electrolyte is dripped. And then fixing the system by using an organic glass plate, injecting liquid and sealing to obtain the nickel-zinc battery. Electrochemical performance of the cell was characterized using an electrochemical workstation and a cell testing system.
Example 2
The preparation was carried out in the same manner as in example 1, except that in step (2), the addition of 150 mg of carbon sites was changed to the addition of 100 mg of carbon sites, and the remaining conditions were not changed. Nickel zinc cells were also prepared and the electrochemical performance of the cells was characterized using an electrochemical workstation and a cell testing system.
Example 3
The preparation method is the same as that of example 1, but 150 ml of 0.017M urotropine aqueous solution is changed into 150 ml of 0.01M urotropine aqueous solution in the step (2), and the rest conditions are not changed. Nickel zinc cells were also prepared and the electrochemical performance of the cells was characterized using an electrochemical workstation and a cell testing system.
Example 4
The preparation method is the same as that of example 1, but 150 ml of 0.017M urotropine aqueous solution is changed into 150 ml of 0.017M potassium hydroxide aqueous solution in the step (2), and the rest conditions are not changed. Nickel zinc cells were also prepared and the electrochemical performance of the cells was characterized using an electrochemical workstation and a cell testing system.
Example 5
The procedure was as in example 1, except that in step (2), 150 ml of 0.014M zinc nitrate hexahydrate was changed to 150 ml of 0.01M zinc nitrate hexahydrate solution, and the remaining conditions were not changed. Nickel zinc cells were also prepared and the electrochemical performance of the cells was characterized using an electrochemical workstation and a cell testing system.
Example 6
The procedure was as in example 1, except that in step (2), 0.014M zinc nitrate hexahydrate was changed to 0.014M zinc acetate dihydrate, and the remaining conditions were changed. Nickel zinc cells were also prepared and the electrochemical performance of the cells was characterized using an electrochemical workstation and a cell testing system.
Example 7
The preparation method is the same as that of example 1, but in the step (2), the reaction is carried out at 85 ℃ for 10 hours and at 60 ℃ for 12 hours, and the rest conditions are not changed. Nickel zinc cells were also prepared and the electrochemical performance of the cells was characterized using an electrochemical workstation and a cell testing system.
Example 8
The preparation method is the same as that of the example 1, but in the step (2), the temperature is raised to 600 ℃ at the temperature raising speed of 1 ℃/min, then the temperature is kept at 600 ℃ for 2 hours, then the temperature is returned to the room temperature at the temperature lowering speed of 1 ℃/min, the temperature is raised to 400 ℃ at the temperature raising speed of 0.5 ℃/min, then the temperature is kept at 400 ℃ for 2 hours, then the temperature is returned to the room temperature at the temperature lowering speed of 0.5 ℃/min, and the other conditions are not changed. Nickel zinc cells were also prepared and the electrochemical performance of the cells was characterized using an electrochemical workstation and a cell testing system.
Example 9
(1) Preparation of carbon dots by using p-phenylenediamine as raw material
0.2 g of p-phenylenediamine, 3 ml of phosphoric acid and 50 ml of water are added into a polytetrafluoroethylene reaction kettle and reacted for 10 hours at 160 ℃. After cooling the system to room temperature, a clear solution was obtained by filtration. The solution was adjusted to neutral using potassium hydroxide, centrifuged to give a bottom precipitate, and the precipitate was washed three times with ethanol and water. And drying the cleaned precipitate in an oven at 85 ℃ to obtain carbon dots.
(2) Preparation of carbon dot/zinc oxide composite material
150 ml of 0.02M zinc nitrate hexahydrate aqueous solution was added to 100 mg of carbon dots, and the mixture was dispersed by ultrasonic dispersion to form a mixed solution. The mixed solution of carbon point and zinc nitrate was added dropwise to 150 ml of a 0.03M aqueous solution of urotropin and reacted at 85 ℃ for 8 hours. After cooling to room temperature, the solution was centrifuged to give a solid precipitate, which was washed three times with water and dried under vacuum at 85 ℃. The dried solid was precipitated and placed in a crucible in a tube furnace. Heating to 600 deg.C at a heating rate of 1 deg.C/min in nitrogen atmosphere, maintaining at 600 deg.C for 2 hr, and cooling to room temperature at a cooling rate of 1 deg.C/min. Thus obtaining the carbon dot/zinc oxide composite material.
Steps (3), (4) and (5) were the same as in example 1, and a nickel zinc cell was also prepared, and the electrochemical performance of the cell was characterized using an electrochemical workstation and a cell test system.
Example 10
The procedure was as in example 9, except that in step (2), the addition of 100 mg of carbon sites was changed to 50 mg of carbon sites, and the remaining conditions were not changed. Nickel zinc cells were also prepared and the electrochemical performance of the cells was characterized using an electrochemical workstation and a cell testing system.
Example 11
The preparation was carried out in the same manner as in example 9 except that 150 ml of a 0.03M aqueous solution of urotropin was changed to 150 ml of a 0.01M aqueous solution of urotropin in the step (2), and the remaining conditions were not changed. Nickel zinc cells were also prepared and the electrochemical performance of the cells was characterized using an electrochemical workstation and a cell testing system.
Example 12
The procedure was as in example 9, except that in step (2), 150 ml of a 0.03M aqueous solution of urotropin was changed to 150 ml of a 0.03M aqueous solution of sodium hydroxide, and the remaining conditions were not changed. Nickel zinc cells were also prepared and the electrochemical performance of the cells was characterized using an electrochemical workstation and a cell testing system.
Example 13
The procedure was as in example 9, except that in step (2), 150 ml of 0.02M zinc nitrate hexahydrate was replaced by 150 ml of 0.01M zinc nitrate hexahydrate solution, and the remaining conditions were not changed. Nickel zinc cells were also prepared and the electrochemical performance of the cells was characterized using an electrochemical workstation and a cell testing system.
Example 14
The procedure was as in example 9, except that in step (2), 150 ml of 0.02M zinc nitrate hexahydrate was changed to 150 ml of 0.02M zinc acetate dihydrate, and the remaining conditions were not changed. Nickel zinc cells were also prepared and the electrochemical performance of the cells was characterized using an electrochemical workstation and a cell testing system.
Example 15
The preparation method is the same as that of example 9, but in the step (2), the reaction is carried out at 85 ℃ for 8 hours and at 60 ℃ for 12 hours, and the rest conditions are not changed. Nickel zinc cells were also prepared and the electrochemical performance of the cells was characterized using an electrochemical workstation and a cell testing system.
Example 16
The preparation method is the same as example 9, but in the step (2), the temperature is raised to 600 ℃ at the temperature raising speed of 1 ℃/min, then the temperature is kept at 600 ℃ for 2 hours, then the temperature is returned to the room temperature at the temperature lowering speed of 1 ℃/min, the temperature is raised to 500 ℃ at the temperature raising speed of 0.5 ℃/min, then the temperature is kept at 500 ℃ for 2 hours, then the temperature is returned to the room temperature at the temperature lowering speed of 0.5 ℃/min, and the rest conditions are not changed. Nickel zinc cells were also prepared and the electrochemical performance of the cells was characterized using an electrochemical workstation and a cell testing system.
Example 17
(1) Method for preparing carbon dots by taking polyvinylpyrrolidone as raw material
2.5g of polyvinylpyrrolidone is placed in a crucible in a tube furnace, heated to 450 ℃ at a heating rate of 3 ℃/min, then kept at 450 ℃ for 2 hours, and then returned to room temperature at a cooling rate of 1 ℃/min. And grinding the obtained sample, washing the sample with ethanol for three times, and drying the sample in an oven at 85 ℃ for 10 hours to obtain the carbon dots.
(2) Preparation of carbon dot/zinc oxide composite material
120 ml of 0.014M aqueous solution of zinc nitrate hexahydrate was added to 120 mg of carbon dots and dissolved by ultrasonic waves to form a uniform mixed aqueous solution. The mixed aqueous solution of carbon point and zinc nitrate was added dropwise to 120 ml of 0.017M urotropine aqueous solution and reacted at 85 ℃ for 5 hours. After cooling to room temperature, the solution was centrifuged to give a solid precipitate, which was washed three times with water and dried under vacuum at 85 ℃. The dried solid was precipitated and placed in a crucible in a tube furnace. In a nitrogen atmosphere, the temperature was raised to 300 ℃ at a temperature raising rate of 1.5 ℃/min, then maintained at 300 ℃ for 3 hours, and then returned to room temperature at a temperature lowering rate of 1.5 ℃/min. Thus obtaining the carbon dot/zinc oxide composite material.
Steps (3), (4) and (5) were the same as in example 1, and a nickel zinc cell was also prepared, and the electrochemical performance of the cell was characterized using an electrochemical workstation and a cell test system.
Example 18
The procedure was as in example 17, except that in step (2), the carbon number was changed to 60 mg instead of 120 mg, and the remaining conditions were not changed. Nickel zinc cells were also prepared and the electrochemical performance of the cells was characterized using an electrochemical workstation and a cell testing system.
Example 19
The preparation method was the same as example 17, except that 120 ml of 0.017M urotropine aqueous solution was changed to 120 ml of 0.01M urotropine aqueous solution in the step (2), and the remaining conditions were not changed. Nickel zinc cells were also prepared and the electrochemical performance of the cells was characterized using an electrochemical workstation and a cell testing system.
Example 20
The preparation method is the same as example 17, but in the step (2), 120 ml of 0.017M urotropine aqueous solution is changed into 120 ml of 0.017M potassium hydroxide aqueous solution, and the rest conditions are not changed. Nickel zinc cells were also prepared and the electrochemical performance of the cells was characterized using an electrochemical workstation and a cell testing system.
Example 21
The procedure was as in example 17, except that in step (2), the 0.014M aqueous solution of zinc nitrate hexahydrate was changed to 0.01M aqueous solution of zinc nitrate hexahydrate, and the remaining conditions were changed. Nickel zinc cells were also prepared and the electrochemical performance of the cells was characterized using an electrochemical workstation and a cell testing system.
Example 22
The procedure was as in example 17, except that in step (2), the 0.014M aqueous solution of zinc nitrate hexahydrate was changed to 0.014M aqueous solution of zinc acetate dihydrate, and the conditions were otherwise unchanged. Nickel zinc cells were also prepared and the electrochemical performance of the cells was characterized using an electrochemical workstation and a cell testing system.
Example 23
The preparation method was the same as example 17, except that in the step (2), the reaction was carried out at 85 ℃ for 5 hours and at 60 ℃ for 10 hours, and the remaining conditions were not changed. Nickel zinc cells were also prepared and the electrochemical performance of the cells was characterized using an electrochemical workstation and a cell testing system.
Example 24
The preparation method is the same as example 17, but in the step (2), the temperature is raised to 300 ℃ at the temperature raising speed of 1.5 ℃/min, then the temperature is kept at 300 ℃ for 3 hours, then the temperature is returned to the room temperature at the temperature lowering speed of 1.5 ℃/min, the temperature is raised to 250 ℃ at the temperature raising speed of 0.5 ℃/min, then the temperature is kept at 250 ℃ for 2 hours, then the temperature is returned to the room temperature at the temperature lowering speed of 0.5 ℃/min, and the rest conditions are not changed. Nickel zinc cells were also prepared and the electrochemical performance of the cells was characterized using an electrochemical workstation and a cell testing system.
The results of the examples are tabulated below:
Claims (6)
1. a high-performance nickel-zinc battery negative electrode active material is a nanocluster formed by compounding carbon dots and zinc oxide, and the structure of the nanocluster has the following characteristics:
(1) the diameter of the carbon dot is 1-10 nanometers, graphitized carbon with good conductivity is arranged inside the carbon dot, and various organic functional groups and defect structures are arranged outside the carbon dot and can be tightly combined with a zinc oxide material;
(2) the thickness of a surface carbon layer of the nanocluster is 10-90 nanometers, a unique spherical cluster structure is formed after calcination, the particle size of the spherical cluster structure is 500-5000 nanometers, the surface layer of the spherical cluster structure is of an outward rod-shaped structure perpendicular to the spherical surface, the whole nano material is in a thorn-ball shape, and oxygen vacancies or zinc vacancies exist on the surface of the nano material.
2. The preparation method of the negative active material of the nickel-zinc battery as claimed in claim 1, which is characterized by comprising the following steps:
(1) adding the carbon dots into a zinc salt solution, mixing and stirring to prepare a carbon dot/zinc salt mixed solution; dropwise adding the mixed solution into an alkaline aqueous solution, refluxing for 1-12 hours at the temperature of 50-85 ℃, centrifuging the solution after the solution is cooled to obtain a solid precipitate, and washing and drying the precipitate;
(2) heating in a nitrogen atmosphere at the temperature rising speed of 0.5-5 ℃/min, and carrying out heat treatment on the dried precipitate at the temperature of 300-600 ℃ for 1-3 hours to obtain the carbon dot/zinc oxide nanocomposite.
3. The preparation method of the negative active material of the nickel-zinc battery as claimed in claim 2, wherein the carbon dots in step (1) are graphene quantum dots, carbon nanodots or polymer quantum dots; the particle size of the carbon dots is 1-10 nm.
4. The method for preparing the negative active material of the nickel-zinc battery according to claim 2, wherein the zinc salt in the step (1) is zinc nitrate hexahydrate, zinc acetate dihydrate, zinc sulfate heptahydrate, zinc chloride, zinc phosphate, basic zinc carbonate, or zinc methacrylate.
5. The method for preparing the negative active material of the nickel-zinc battery as claimed in claim 2, wherein the alkali used in the step (1) is sodium hydroxide, potassium hydroxide, ammonia water or urotropin.
6. The method for preparing the negative electrode active material of the nickel-zinc battery according to claim 2, wherein the mass volume concentration of the carbon dots in the mixed solution in the step (1) is 0.01 to 2 mg/ml, the mass concentration of the zinc salt is 0.005 to 3M, the mass concentration of the alkali is 0.01 to 4M, and the mass concentration ratio of the zinc salt to the alkali is 4:1 to 1: 4.
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