CN111244424B - Preparation method of sericin carbon film coated Ni/NiO microsphere composite material - Google Patents
Preparation method of sericin carbon film coated Ni/NiO microsphere composite material Download PDFInfo
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- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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Abstract
The invention discloses a preparation method of a composite material, which comprises the following steps: s11, dissolving urea in deionized water, stirring until the urea is dissolved to obtain a first solution, adding nickel nitrate hexahydrate, and continuously stirring to form a blue solution; s12, transferring the blue solution to a high-pressure reaction kettle for reaction to obtain a second solution; centrifuging and washing the second solution until the second solution is clear to obtain a first precipitate; filtering and drying the first precipitate to obtain a first precursor; s13, placing the first precursor in a muffle furnace to calcine to obtain NiO flower-shaped microspheres; s14, soaking the NiO flower-shaped microsphere powder in a sericin aqueous solution, performing centrifugal separation to obtain a second precipitate, and drying to obtain dried NiO flower-shaped microsphere powder; s15, placing the dried NiO flower-shaped microsphere powder in a tubular furnace to calcine under the protection of nitrogen or argon to obtain a sericin carbon film coated microsphere composite material; s16, putting the obtained composite material of the sericin carbon film coated microspheres into a muffle furnace to be calcined to obtain the composite material of the sericin carbon film coated Ni/NiO microspheres.
Description
Technical Field
The invention relates to the technical field of electrochemical energy storage and conversion, in particular to a preparation method of a sericin carbon film coated Ni/NiO microsphere composite material.
Background
Nickel oxide (NiO) is a typical transition metal oxide, with a cubic crystal structure similar to that of sodium chloride, i.e., a halite structure in which six nearest-spaced O atoms surround each Ni, the oxygen atoms form octahedra, and the nickel atoms are in the center; vice versa, the oxygen atoms are also in the octahedra formed by the nickel atoms. The whole crystal can be regarded as formed by interlacing Ni which is arranged in a face-centered cubic manner and O which is also arranged in the face-centered cubic manner, and has wide application prospect in the fields of new energy such as super capacitors, lithium ion batteries, lithium sulfur batteries and the like due to good thermal stability and electrochemical performance. Currently, NiO has become one of the transition metal oxides that are studied and developed faster as a battery electrode material because NiO has the following attractive and unique advantages: a) the raw materials are easy to obtain, and the synthesis is simple; b) the lithium ion battery cathode material has higher theoretical capacity; c) good thermal stability and electrochemical performance.
As a positive electrode material of a lithium sulfur battery, the electrochemical performance of single NiO is not ideal. The main reason is that the active material can not be activated completely to participate in the charge-discharge reaction, and the NiO has poor conductivity and serious sulfur volume expansion in the charge-discharge process, so that the development of the active material in the field of energy storage is limited. In order to solve the problems, a great deal of improvement work is carried out, wherein one of the more effective methods is to mix carbon materials into NiO, the carbon materials not only have good cycling stability, but also mostly have good conductivity, so that the mixing of a small amount of carbon materials into NiO is one of effective ways for improving the conductivity of NiO so as to improve the electrochemical performance of the battery. Therefore, the invention provides a preparation method of the sericin carbon film coated Ni/NiO microsphere composite material.
Disclosure of Invention
The invention aims to provide a preparation method of a sericin carbon film coated Ni/NiO microsphere composite material aiming at the defects of the prior art, adopts waste water-soluble sericin in the silk extraction process, and has the advantages of simplicity, convenience, environmental friendliness, waste utilization and the like in the whole preparation process.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a sericin carbon film coated Ni/NiO microsphere composite material comprises the following steps:
s1, taking a certain amount of urea CO (NH)2)2Dissolving in deionized water with a certain volume, and magnetically stirring at room temperature until the solution is dissolved to obtain a first solution; adding a certain amount of nickel nitrate hexahydrate Ni (NO) into the first solution3)2·6H2Continuously stirring the mixture for 0.5 to 1 hour to form a uniformly mixed blue solution;
s2, transferring the obtained blue solution into a polytetrafluoroethylene lining of a high-pressure reaction kettle, and reacting at the temperature of 120-200 ℃ for 2-12h to obtain a second solution; centrifuging the obtained second solution, and washing with absolute ethyl alcohol and deionized water until the second solution is clear to obtain a first precipitate; filtering the obtained first precipitate, and drying at 60-100 ℃ for 12h to obtain a first precursor;
s3, placing the obtained first precursor in a muffle furnace to calcine for 2-4h to obtain NiO flower-shaped microspheres;
s4, soaking the obtained NiO flower-like microsphere powder in 0.5-2mmol/L sericin aqueous solution for 1-3h, and carrying out centrifugal separation to obtain a second precipitate; drying the obtained second precipitate at 60-100 ℃ for 12h to obtain dried NiO flower-like microsphere powder;
s5, placing the dried NiO flower-shaped microsphere powder in a tubular furnace to calcine for 2-4 hours under the protection atmosphere of nitrogen or argon to obtain a sericin carbon film coated microsphere composite material;
s6, putting the obtained composite material of the sericin carbon film coated microspheres into a muffle furnace to be calcined for 0.5-3h to obtain the composite material of the sericin carbon film coated Ni/NiO microspheres.
Further, the ratio of the urea to the nickel nitrate hexahydrate in step S1 is (3-15): 1.
further, the temperature of the calcination in the step S3 is 400-600 ℃.
Further, the diameter of the NiO flower-like microspheres in the step S3 is 1-2 μm.
Further, the temperature of the calcination in the step S5 is 400-600 ℃.
Further, the temperature rise rate of the calcination in the steps S3, S5 and S6 is 3-5 ℃/min.
Further, the molecular weight of the sericin in the step S4 is 5000-10000.
Further, the temperature of the calcination in the step S6 is 250-350 ℃.
Further, in the step S1, both the urea and the nickel nitrate hexahydrate are chemically pure.
Further, the sericin carbon film-coated Ni/NiO microsphere composite material obtained in the step S6 is applied to a lithium-sulfur battery cathode material.
Compared with the prior art, the invention has the beneficial effects that:
1. the organic sericin is adopted as a carbon source, so that the carbon source is low-carbon and environment-friendly, wastes are utilized, and the manufacturing cost can be further reduced.
2. If the sericin carbon film-coated Ni/NiO microsphere composite material prepared by the method is used as a lithium-sulfur battery anode material, the volume expansion of sulfur in the charging and discharging processes of a lithium-sulfur battery can be relieved, and NiO has a certain inhibiting effect on polysulfide dissolution. The coating of the sericin carbon film and Ni can effectively improve the conductivity of the sulfur anode material and improve the cycle stability of the lithium-sulfur battery.
Drawings
FIG. 1 is a flow chart of a method for preparing a sericin carbon film-coated Ni/NiO microsphere composite material according to a first embodiment;
FIG. 2 is a SEM diagram of a sericin carbon film coated Ni/NiO microsphere prepared in the first example;
fig. 3 is a schematic diagram of charge-discharge specific capacity and coulombic efficiency curves of the lithium-sulfur battery using S @ Ni/NiO/C as the cathode material, provided in the first example, for 100 times of charge-discharge at 1C.
Detailed Description
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention. It is to be noted that the features in the following embodiments and examples may be combined with each other without conflict.
The invention aims to provide a preparation method of a sericin carbon film coated Ni/NiO microsphere composite material aiming at the defects of the prior art. The sericin carbon film-coated Ni/NiO microsphere composite material is applied to a lithium-sulfur battery, and the specific test process is as follows: in an argon-protected glove box, the prepared S @ C/NiO is used as a positive electrode, Celgard 2500 is used as a separator, a metal lithium sheet is used as a negative electrode, and 1.0mol/L LiTFSI (DOL/DME ═ 1:1) is added with 0.1mol/L LiNO3 to be used as an electrolyte to assemble the battery. In the charge and discharge test system, the charge and discharge test voltage is 1.5-3.0V.
Example one
The embodiment provides a preparation method of a sericin carbon film-coated Ni/NiO microsphere composite material, as shown in FIG. 1, which comprises the following steps:
s11, taking a certain amount of urea CO (NH)2)2Dissolving in deionized water with a certain volume, and magnetically stirring at room temperature until the solution is dissolved to obtain a first solution; adding a certain amount of nickel nitrate hexahydrate Ni (NO) into the first solution3)2·6H2Continuously stirring the mixture for 0.5 to 1 hour to form a uniformly mixed blue solution;
s12, transferring the obtained blue solution into a polytetrafluoroethylene lining of a high-pressure reaction kettle, and reacting at the temperature of 120-200 ℃ for 2-12h to obtain a second solution; centrifuging the obtained second solution, and washing with absolute ethyl alcohol and deionized water until the second solution is clear to obtain a first precipitate; filtering the obtained first precipitate, and drying at 60-100 ℃ for 12h to obtain a first precursor;
s13, placing the obtained first precursor in a muffle furnace to calcine for 2-4h to obtain NiO flower-shaped microspheres;
s14, soaking the obtained NiO flower-like microsphere powder in 0.5-2mmol/L sericin aqueous solution for 1-3h, and performing centrifugal separation to obtain a second precipitate; drying the obtained second precipitate at 60-100 ℃ for 12h to obtain dried NiO flower-like microsphere powder;
s15, placing the dried NiO flower-shaped microsphere powder in a tubular furnace to calcine for 2-4 hours under the protection atmosphere of nitrogen or argon to obtain a sericin carbon film coated microsphere composite material;
s16, putting the obtained composite material of the sericin carbon film coated microspheres into a muffle furnace to be calcined for 0.5-3h to obtain the composite material of the sericin carbon film coated Ni/NiO microspheres.
The ratio of the amounts of urea to nickel nitrate hexahydrate in step S11 was (3-15): 1. the urea and the nickel nitrate hexahydrate are both chemically pure.
The temperature of calcination in step S13 is 400-600 ℃; the diameter of the NiO flower-shaped microspheres is 1-2 mu m.
The temperature of calcination in step S15 was 400-600 ℃.
The temperature increase rate of the calcination in step S13, step S15, step S16 is 3-5 deg.C/min.
The molecular weight of the sericin is 5000-10000 in step S14.
The temperature of calcination in step S16 is 250-350 ℃; the composite material of the sericin carbon film coated Ni/NiO microspheres obtained in the step S16 is applied to a lithium-sulfur battery anode material.
In this embodiment, the following are specifically mentioned:
dissolving 0.01638mol of urea in 180ml of deionized water, magnetically stirring at room temperature to form a uniform solution to obtain a first solution, adding 0.00182mol of nickel nitrate hexahydrate into the first solution, and continuously stirring for 1h to form a uniformly mixed blue solution; transferring the obtained blue solution into a polytetrafluoroethylene lining of a high-pressure reaction kettle, and reacting for 4 hours at 180 ℃ to obtain a second solution; centrifugally separating the obtained second solution, and washing the second solution with absolute ethyl alcohol and deionized water for three times respectively until the second solution is clarified to obtain a first precipitate; separating the obtained first precipitate, and drying at 70 ℃ for 12h to obtain a first precursor;
and transferring the dried first precursor into a muffle furnace, heating at a rate of 5 ℃/min and a sintering temperature of 400 ℃, and calcining for 2h to obtain the NiO microspheres. Soaking the NiO microsphere powder in 2mmol/L sericin (molecular weight is 10000) aqueous solution, magnetically stirring for 1h, and then carrying out centrifugal separation to obtain a second precipitate; the second precipitate which separated out was dried at 80 ℃ for 12 h. And placing the dried powder in a tubular furnace, calcining for 2 hours in a nitrogen protective atmosphere at the calcining temperature of 500 ℃, and sintering for 300 ℃ in a muffle furnace for 3 hours to obtain the sericin carbon film coated Ni/NiO microsphere composite material.
30mg of sublimed sulphur was dissolved in CS2And adding 20mg of sericin carbon film coated Ni/NiO microsphere powder into the solution, and stirring at room temperature until the mixture is dried. And then the mixture is moved into a polytetrafluoroethylene stainless steel reaction kettle under the protection of argon atmosphere, and the temperature is kept at 155 ℃ for 12 hours to obtain the S @ Ni/NiO/C compound.
The S @ Ni/NiO/C composite material, the Ketjen black and the PVDF are uniformly mixed according to the mass ratio of 7:2:1, the concentration of the N-methyl pyrrolidone is adjusted, and the mixture is stirred for 3 hours to prepare the slurry. Coating the prepared slurry on a current collector by a blade coating method, and drying for 12h at 60 ℃ in a vacuum environment. Circular pole pieces 16mm in diameter were cut and assembled for battery testing.
FIG. 1 is an SEM image of Ni/NiO microspheres coated with sericin carbon film prepared in the example, and it can be seen that the diameter of the microspheres is about 1-2 μm. FIG. 2 is a graph showing the specific charge-discharge capacity and the coulombic efficiency of the lithium-sulfur battery with S @ Ni/NiO/C as the cathode material prepared in this example, in 100 times of charge-discharge at 1C.
Electrochemical performance test results show that the first discharge specific capacity of the S @ Ni/NiO/C composite material prepared in the example reaches 861.93mAh/g under the multiplying power of 1C, and 392.59mAh/g is kept after 100 times of circulation.
Compared with the prior art, the beneficial effect of this embodiment:
1. the organic sericin is adopted as a carbon source, so that the carbon source is low-carbon and environment-friendly, wastes are utilized, and the manufacturing cost can be further reduced.
2. If the sericin carbon film-coated Ni/NiO microsphere composite material prepared by the method is used as a lithium-sulfur battery anode material, the volume expansion of sulfur in the charging and discharging processes of a lithium-sulfur battery can be relieved, and NiO has a certain inhibiting effect on polysulfide dissolution. The coating of the sericin carbon film and Ni can effectively improve the conductivity of the sulfur anode material and improve the cycle stability of the lithium-sulfur battery.
Example two
The embodiment provides a preparation method of a sericin carbon film-coated Ni/NiO microsphere composite material, which is different from the first embodiment in that:
0.01638mol of urea is dissolved in 180ml of deionized water, uniform solution is formed by magnetic stirring at room temperature, 0.00182mol of nickel nitrate hexahydrate is added, the mixture is continuously stirred for 0.5h, the mixture is placed into a polytetrafluoroethylene lining of a high-pressure reaction kettle, the reaction is carried out for 4h at 180 ℃, centrifugal separation is carried out, the obtained solution is respectively washed for three times by absolute ethyl alcohol and deionized water, and the separated precipitate is dried for 12h at 70 ℃. And transferring the dried precursor into a muffle furnace, heating at a rate of 5 ℃/min, sintering at a temperature of 400 ℃, and calcining for 2h to obtain the NiO microspheres.
30mg of sublimed sulphur was dissolved in CS2To the solution, 20mg of NiO microsphere powder was added, and the mixture was stirred at room temperature until dried. And then the mixture is moved into a polytetrafluoroethylene stainless steel reaction kettle under the protection of argon atmosphere, and the temperature is kept at 155 ℃ for 12 hours to obtain the S @ NiO compound.
The S @ NiO composite material, the Ketjen black and the PVDF are uniformly mixed according to the mass ratio of 7:2:1, the concentration of the N-methyl pyrrolidone is adjusted, and the mixture is stirred for 3 hours to prepare the slurry. Coating the prepared slurry on a current collector by a blade coating method, and drying for 12h at 60 ℃ in a vacuum environment. Circular pole pieces 16mm in diameter were cut and assembled for battery testing.
The S @ NiO composite material prepared in the embodiment is directly used as an electrode material without being coated by sericin, and an electrochemical performance test result shows that the first discharge specific capacity reaches only 715.65mAh/g under the multiplying power of 1C, only 165.1mAh/g is left after 100 times of circulation, and the electrochemical performance of the battery in the embodiment is lower than that in the embodiment I.
EXAMPLE III
The embodiment provides a preparation method of a sericin carbon film-coated Ni/NiO microsphere composite material, which is different from the first embodiment in that:
0.00546mol of urea is dissolved in 180ml of deionized water, magnetic stirring is carried out at room temperature to form uniform solution, 0.00182mol of nickel nitrate hexahydrate is added, stirring is continued for 1h, the mixture is placed into a polytetrafluoroethylene lining of a high-pressure reaction kettle, reaction is carried out for 12h at 120 ℃, centrifugal separation is carried out, the obtained solution is washed for three times by absolute ethyl alcohol and deionized water respectively, and the separated precipitate is dried for 12h at 70 ℃.
And transferring the dried precursor into a muffle furnace, heating at the rate of 5 ℃/min, sintering at the temperature of 600 ℃, and calcining for 2h to obtain the NiO microspheres. Soaking the NiO microsphere powder in 0.5mmol/L sericin (molecular weight is 10000) aqueous solution, magnetically stirring for 0.5h, then performing centrifugal separation, and drying the separated precipitate at 80 ℃ for 12 h. And placing the dried powder in a tubular furnace, calcining for 2 hours in a nitrogen protective atmosphere at the calcining temperature of 500 ℃, and sintering for 300 ℃ in a muffle furnace for 2 hours to obtain the sericin carbon film coated Ni/NiO microsphere composite material.
30mg of sublimed sulphur was dissolved in CS2And adding 20mg of sericin carbon film coated Ni/NiO microsphere powder into the solution, and stirring at room temperature until the mixture is dried. And then the mixture is moved into a polytetrafluoroethylene stainless steel reaction kettle under the protection of argon atmosphere, and the temperature is kept at 155 ℃ for 12 hours to obtain the S @ Ni/NiO/C compound.
The S @ Ni/NiO/C composite material, the Ketjen black and the PVDF are uniformly mixed according to the mass ratio of 7:2:1, the concentration of the N-methyl pyrrolidone is adjusted, and the mixture is stirred for 3 hours to prepare the slurry. Coating the prepared slurry on a current collector by a blade coating method, and drying for 12h at 60 ℃ in a vacuum environment. Circular pole pieces 16mm in diameter were cut and assembled for battery testing.
Electrochemical performance test results show that the first discharge specific capacity of the S @ Ni/NiO/C composite material prepared in the example reaches 752.49mAh/g under the multiplying power of 1C, and 307.65mAh/g is kept after 100 times of circulation. The electrochemical performance of the battery of this example was lower than that of the first example.
Example four
The embodiment provides a preparation method of a sericin carbon film-coated Ni/NiO microsphere composite material, which is different from the first embodiment in that:
dissolving 0.0273mol of urea in 180ml of deionized water, magnetically stirring at room temperature to form a uniform solution, adding 0.00182mol of nickel nitrate hexahydrate, continuously stirring for 1h, placing into a polytetrafluoroethylene lining of a high-pressure reaction kettle, reacting for 4h at 180 ℃, performing centrifugal separation, washing the obtained solution with anhydrous ethanol and deionized water for three times respectively, and drying the separated precipitate at 70 ℃ for 12 h.
And transferring the dried precursor into a muffle furnace, heating at the rate of 3 ℃/min, sintering at the temperature of 600 ℃, and calcining for 4h to obtain the NiO microspheres. Soaking the NiO microsphere powder in 2mmol/L sericin (molecular weight is 10000) aqueous solution, magnetically stirring for 1h, then performing centrifugal separation, and drying the separated precipitate at 80 ℃ for 12 h. And placing the dried powder in a tubular furnace, calcining for 2h under the nitrogen protection atmosphere, heating at the rate of 3 ℃/min and the calcining temperature of 600 ℃, and sintering in a muffle furnace for 300 ℃ for 3h to obtain the sericin carbon film coated Ni/NiO microsphere composite material.
30mg of sublimed sulphur was dissolved in CS2And adding 20mg of sericin carbon film coated Ni/NiO microsphere powder into the solution, and stirring at room temperature until the mixture is dried. And then the mixture is moved into a polytetrafluoroethylene stainless steel reaction kettle under the protection of argon atmosphere, and the temperature is kept at 155 ℃ for 12 hours to obtain the S @ Ni/NiO/C compound.
The S @ Ni/NiO/C composite material, the Ketjen black and the PVDF are uniformly mixed according to the mass ratio of 7:2:1, the concentration of the N-methyl pyrrolidone is adjusted, and the mixture is stirred for 3 hours to prepare the slurry. Coating the prepared slurry on a current collector by a blade coating method, and drying for 12h at 60 ℃ in a vacuum environment. Circular pole pieces 16mm in diameter were cut and assembled for battery testing.
Electrochemical performance test results show that the first discharge specific capacity of the S @ Ni/NiO/C composite material prepared in the example reaches 824.48mAh/g under the multiplying power of 1C, and 268.63mAh/g is kept after 100 times of circulation. The electrochemical performance of the battery of this example was lower than that of the first example.
EXAMPLE five
The embodiment provides a preparation method of a sericin carbon film-coated Ni/NiO microsphere composite material, which is different from the first embodiment in that:
0.01638mol of urea is dissolved in 180ml of deionized water, uniform solution is formed by magnetic stirring at room temperature, 0.00182mol of nickel nitrate hexahydrate is added, the mixture is continuously stirred for 0.5h, the mixture is placed into a polytetrafluoroethylene lining of a high-pressure reaction kettle, the reaction is carried out for 2h at 200 ℃, centrifugal separation is carried out, the obtained solution is respectively washed for three times by absolute ethyl alcohol and deionized water, and the separated precipitate is dried for 12h at 70 ℃. And transferring the dried precursor into a muffle furnace, heating at a rate of 5 ℃/min, sintering at a temperature of 400 ℃, and calcining for 2h to obtain the NiO microspheres. Soaking the NiO microsphere powder in 2mmol/L sericin (molecular weight is 10000) aqueous solution, magnetically stirring for 1h, then performing centrifugal separation, and drying the separated precipitate at 80 ℃ for 12 h. And placing the dried powder in a tubular furnace, calcining for 4 hours in a nitrogen protective atmosphere at the temperature of 600 ℃, and sintering for 350 ℃ in a muffle furnace for 0.5 hour to obtain the sericin carbon film coated Ni/NiO microsphere composite material.
30mg of sublimed sulphur was dissolved in CS2And adding 20mg of sericin carbon film coated Ni/NiO microsphere powder into the solution, and stirring at room temperature until the mixture is dried. And then the mixture is moved into a polytetrafluoroethylene stainless steel reaction kettle under the protection of argon atmosphere, and the temperature is kept at 155 ℃ for 12 hours to obtain the S @ Ni/NiO/C compound.
The S @ Ni/NiO/C composite material, the Ketjen black and the PVDF are uniformly mixed according to the mass ratio of 7:2:1, the concentration of the N-methyl pyrrolidone is adjusted, and the mixture is stirred for 3 hours to prepare the slurry. Coating the prepared slurry on a current collector by a blade coating method, and drying for 12h at 60 ℃ in a vacuum environment. Circular pole pieces 16mm in diameter were cut and assembled for battery testing.
Electrochemical performance test results show that the first discharge specific capacity of the S @ Ni/NiO/C composite material prepared in the example reaches 643.2mAh/g under the multiplying power of 1C, and the specific capacity of the S @ Ni/NiO/C composite material can be kept at 210.6mAh/g after 100 times of circulation. The electrochemical performance of the battery of this example was lower than that of the first example.
The specific embodiments described herein are merely illustrative of the spirit of the invention. Various modifications or additions may be made to the described embodiments or alternatives may be employed by those skilled in the art without departing from the spirit or ambit of the invention as defined in the appended claims.
Claims (7)
1. A preparation method of a sericin carbon film coated Ni/NiO microsphere composite material is characterized by comprising the following steps:
s1, taking a certain amount of urea CO (NH)2)2Dissolving in deionized water with a certain volume, and magnetically stirring at room temperature until the solution is dissolved to obtain a first solution; adding a certain amount of nickel nitrate hexahydrate Ni (NO) into the first solution3)2·6H2Continuously stirring the mixture for 0.5 to 1 hour to form a uniformly mixed blue solution;
the mass ratio of the urea to the nickel nitrate hexahydrate in the step S1 is (3-15): 1;
s2, transferring the obtained blue solution into a polytetrafluoroethylene lining of a high-pressure reaction kettle, and reacting at the temperature of 120-200 ℃ for 2-12h to obtain a second solution; centrifuging the obtained second solution and washing with absolute ethyl alcohol and deionized water to obtain a first precipitate; drying at 60-100 ℃ for 12h to obtain a first precursor;
s3, placing the obtained first precursor in a muffle furnace to calcine for 2-4h to obtain NiO flower-shaped microspheres;
s4, soaking the obtained NiO flower-like microsphere powder in 0.5-2mmol/L sericin aqueous solution for 1-3h, and performing centrifugal separation to obtain a second precipitate; drying the obtained second precipitate at 60-100 ℃ for 12h to obtain dried NiO flower-like microsphere powder;
s5, placing the dried NiO flower-shaped microsphere powder in a tubular furnace to calcine for 2-4 hours under the protection atmosphere of nitrogen or argon to obtain a sericin carbon film coated microsphere composite material;
the calcination temperature in the step S5 is 400-600 ℃;
s6, putting the obtained composite material of the sericin carbon film coated microspheres into a muffle furnace to be calcined for 0.5-3h to obtain the composite material of the sericin carbon film coated Ni/NiO microspheres;
the temperature of the calcination in the step S6 is 250-350 ℃.
2. The method as claimed in claim 1, wherein the calcination temperature in step S3 is 400-600 ℃.
3. The method for preparing the sericin carbon film coated Ni/NiO microsphere composite material as claimed in claim 1, wherein the diameter of the NiO flower-like microspheres in the step S3 is 1-2 μm.
4. The method for preparing the sericin carbon film coated Ni/NiO microsphere composite material as claimed in claim 1, wherein the temperature rise rate of the calcination in the steps S3, S5 and S6 is 3-5 ℃/min.
5. The method as claimed in claim 1, wherein the molecular weight of the sericin in the step S4 is 5000-10000.
6. The method of claim 1, wherein the urea and the nickel nitrate hexahydrate in step S1 are both chemically pure.
7. The method of claim 1, wherein the sericin carbon film-coated Ni/NiO microsphere composite obtained in the step S6 is applied to a positive electrode material of a lithium-sulfur battery.
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