Efficient attenuation-resistant graphene power lithium battery material and preparation method thereof
Technical Field
The invention belongs to the field of materials, and particularly relates to a high-efficiency anti-attenuation graphene power lithium battery material and a preparation method thereof.
Background
The negative electrode material of the battery is one of important factors for improving the energy and cycle life of the lithium ion battery. The traditional carbon-based material has the problems of low specific capacity, such as: the theoretical specific capacity of the graphite cathode material is 372 mAh/g, and the increasing demand on the high-energy density lithium ion battery is difficult to meet. Whereas tin-based materials have a higher theoretical specific capacity, such as: the theoretical specific capacity of SnS is 782 mAh/g, so that the energy density of the lithium ion battery can be improved to a great extent by using the tin-based material as the cathode material of the battery. However, the tin-based material has great volume change in the charging and discharging processes, so that the capacity of the tin-based material is rapidly attenuated, and the cycle life of the tin-based material is poor.
Disclosure of Invention
The invention aims to provide a high-efficiency anti-attenuation graphene power lithium battery material and a preparation method thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
a high-efficiency anti-attenuation graphene power lithium battery material is composed of the following raw materials in parts by weight:
10-13 parts of modified graphene, 100-140 parts of stannous sulfide, 0.4-1 part of butyltin mercaptide, 18-20 parts of methyl cellulose and 30-40 parts of nickel sulfate.
The modified graphene is prepared from the following raw materials in parts by weight:
10-14 parts of pyromellitic dianhydride, 4-6 parts of triethanolamine, 2-4 parts of sodium borohydride, 30-40 parts of graphene oxide, 2-5 parts of nickel powder, 3-5 parts of oleic acid, 30-40 parts of methyl methacrylate and 1-2 parts of ammonium persulfate.
The preparation method of the modified graphene comprises the following steps:
(1) adding ammonium persulfate into deionized water with the weight 30-40 times of that of the ammonium persulfate, and uniformly stirring;
(2) mixing methyl methacrylate, pyromellitic dianhydride, oleic acid and graphene oxide, adding thionyl chloride which is 2-4 times of the weight of the mixture, performing ultrasonic treatment for 15-20 minutes, distilling to remove the thionyl chloride, adding the mixture into deionized water which is 10-17 times of the weight of the mixture, uniformly stirring, feeding the mixture into a reaction kettle, introducing nitrogen, adjusting the temperature of the reaction kettle to be 60-70 ℃, adding the ammonium persulfate aqueous solution, performing heat preservation stirring for 3-5 hours, discharging and cooling to obtain a graphene polymer emulsion;
(3) mixing triethanolamine with sodium borohydride and nickel powder, adding the mixture into deionized water with the weight being 20-30 times of that of the mixture, uniformly stirring, mixing with the graphene polymer emulsion, sending the mixture into a constant-temperature water bath with the temperature being 30-40 ℃, keeping the temperature and stirring for 6-8 hours, discharging, cooling, performing suction filtration, washing a filter cake, and drying the filter cake for 1-2 hours at the temperature being 70-80 ℃ in vacuum to obtain the modified graphene.
A preparation method of an efficient attenuation-resistant graphene power lithium battery material comprises the following steps:
(1) adding methyl cellulose into deionized water 30-40 times of the weight of the methyl cellulose, raising the temperature to 80-85 ℃, adding nickel sulfate, and stirring for 10-20 minutes under heat preservation to obtain a fiber dispersion liquid;
(2) adding modified graphene into the fiber dispersion liquid, placing the fiber dispersion liquid in a ball mill, and uniformly ball-milling to obtain a mixed liquid;
(3) and (3) mixing stannous sulfide and butyltin mercaptide, adding the mixture into the mixed solution, uniformly stirring, washing, filtering, drying, roasting, and cooling to obtain the efficient attenuation-resistant graphene power lithium battery material.
The roasting temperature in the step (3) is 650-700 ℃, and the time is 2-4 hours.
The invention has the advantages that:
according to the invention, methyl methacrylate and pyromellitic dianhydride are used as monomers, oleic acid is used as a doping agent, the monomers and graphene oxide are blended, polymerization is carried out under the action of an initiator, graphene polymer emulsion is obtained, then triethanolamine is used for treating nickel powder, sodium borohydride is used as a reducing agent, and the graphene polymer emulsion is reduced to obtain modified graphene, through the modification treatment of the invention, not only is the surface activity of the graphene improved, but also the dispersion phase compatibility between the graphene and a methyl cellulose matrix is enhanced, the mechanical property of a finished material is improved, and the electrical property of the material is improved by compounding with the nickel powder, so that the stability of the finished material is improved, the specific capacity retention rate of the material is more than 90% after 100 cycles, and the cycle life of a stannous sulfide-based material is prolonged.
Detailed Description
Example 1
A high-efficiency anti-attenuation graphene power lithium battery material is composed of the following raw materials in parts by weight:
modified graphene 13, stannous sulfide 140, butyltin mercaptide 1, methyl cellulose 20 and nickel sulfate 40.
The modified graphene is prepared from the following raw materials in parts by weight:
10-14 parts of pyromellitic dianhydride, 4-6 parts of triethanolamine, 4 parts of sodium borohydride, 40 parts of graphene oxide, 2-5 parts of nickel powder, 3-5 parts of oleic acid, 40 parts of methyl methacrylate and 1-2 parts of ammonium persulfate.
The preparation method of the modified graphene comprises the following steps:
(1) adding ammonium persulfate into deionized water with the weight 40 times that of the ammonium persulfate, and uniformly stirring;
(2) mixing methyl methacrylate, pyromellitic dianhydride, oleic acid and graphene oxide, adding thionyl chloride which is 4 times of the weight of the mixture, performing ultrasonic treatment for 20 minutes, distilling to remove the thionyl chloride, adding the mixture into deionized water which is 17 times of the weight of the mixture, uniformly stirring, feeding the mixture into a reaction kettle, introducing nitrogen, adjusting the temperature of the reaction kettle to 70 ℃, adding the ammonium persulfate aqueous solution, performing heat preservation and stirring for 5 hours, discharging and cooling to obtain graphene polymer emulsion;
(3) mixing triethanolamine, sodium borohydride and nickel powder, adding the mixture into deionized water with the weight being 20-30 times that of the mixture, uniformly stirring, mixing the mixture with the graphene polymer emulsion, sending the mixture into a constant-temperature water bath with the temperature of 40 ℃, keeping the temperature and stirring for 8 hours, discharging, cooling, performing suction filtration, washing a filter cake with water, and drying the filter cake for 2 hours at the temperature of 80 ℃ in vacuum to obtain the modified graphene.
A preparation method of an efficient attenuation-resistant graphene power lithium battery material comprises the following steps:
(1) adding methyl cellulose into deionized water 40 times of the weight of the methyl cellulose, raising the temperature to 85 ℃, adding nickel sulfate, and stirring for 20 minutes under the condition of heat preservation to obtain a fiber dispersion liquid;
(2) adding modified graphene into the fiber dispersion liquid, placing the fiber dispersion liquid in a ball mill, and uniformly ball-milling to obtain a mixed liquid;
(3) and (3) mixing stannous sulfide and butyltin mercaptide, adding the mixture into the mixed solution, uniformly stirring, washing, filtering, drying, roasting, and cooling to obtain the efficient attenuation-resistant graphene power lithium battery material.
In the step (3), the roasting temperature is 700 ℃ and the roasting time is 4 hours.
Example 2
A high-efficiency anti-attenuation graphene power lithium battery material is composed of the following raw materials in parts by weight:
modified graphene 10, stannous sulfide 100, butyltin mercaptide 0.4, methyl cellulose 18 and nickel sulfate 30.
The modified graphene is prepared from the following raw materials in parts by weight:
pyromellitic dianhydride 10, triethanolamine 4, sodium borohydride 2, graphene oxide 30, nickel powder 2, oleic acid 3, methyl methacrylate 30 and ammonium persulfate 1.
The preparation method of the modified graphene comprises the following steps:
(1) adding ammonium persulfate into deionized water with the weight 30 times that of the ammonium persulfate, and uniformly stirring;
(2) mixing methyl methacrylate, pyromellitic dianhydride, oleic acid and graphene oxide, adding thionyl chloride which is 2 times of the weight of the mixture, performing ultrasonic treatment for 15 minutes, distilling to remove the thionyl chloride, adding the mixture into deionized water which is 10 times of the weight of the mixture, uniformly stirring, feeding the mixture into a reaction kettle, introducing nitrogen, adjusting the temperature of the reaction kettle to be 60 ℃, adding the ammonium persulfate aqueous solution, performing heat preservation stirring for 3 hours, discharging and cooling to obtain graphene polymer emulsion;
(3) mixing triethanolamine, sodium borohydride and nickel powder, adding the mixture into deionized water with the weight being 20 times that of the mixture, uniformly stirring, mixing the mixture with the graphene polymer emulsion, sending the mixture into a constant-temperature water bath with the temperature being 30 ℃, keeping the temperature and stirring for 6 hours, discharging, cooling, performing suction filtration, washing a filter cake with water, and drying the filter cake for 1 hour at the temperature of 70 ℃ in vacuum to obtain the modified graphene.
A preparation method of an efficient attenuation-resistant graphene power lithium battery material comprises the following steps:
(1) adding methyl cellulose into deionized water 30 times of the weight of the methyl cellulose, raising the temperature to 80 ℃, adding nickel sulfate, and stirring for 10 minutes under the condition of heat preservation to obtain a fiber dispersion liquid;
(2) adding modified graphene into the fiber dispersion liquid, placing the fiber dispersion liquid in a ball mill, and uniformly ball-milling to obtain a mixed liquid;
(3) and (3) mixing stannous sulfide and butyltin mercaptide, adding the mixture into the mixed solution, uniformly stirring, washing, filtering, drying, roasting, and cooling to obtain the efficient attenuation-resistant graphene power lithium battery material.
In the step (3), the roasting temperature is 650 ℃ and the roasting time is 2 hours.
Comparative example 1:
a high-efficiency anti-attenuation graphene power lithium battery material is composed of the following raw materials in parts by weight:
graphene 13, stannous sulfide 140, butyltin mercaptide 1, methyl cellulose 20 and nickel sulfate 40.
A preparation method of an efficient attenuation-resistant graphene power lithium battery material comprises the following steps:
(1) adding methyl cellulose into deionized water 40 times of the weight of the methyl cellulose, raising the temperature to 85 ℃, adding nickel sulfate, and stirring for 20 minutes under the condition of heat preservation to obtain a fiber dispersion liquid;
(2) adding graphene into the fiber dispersion liquid, placing the fiber dispersion liquid in a ball mill, and uniformly ball-milling to obtain a mixed liquid;
(3) and (3) mixing stannous sulfide and butyltin mercaptide, adding the mixture into the mixed solution, uniformly stirring, washing, filtering, drying, roasting, and cooling to obtain the efficient attenuation-resistant graphene power lithium battery material.
In the step (3), the roasting temperature is 700 ℃ and the roasting time is 4 hours.
Comparative example 2;
a high-efficiency anti-attenuation graphene power lithium battery material is composed of the following raw materials in parts by weight:
graphene 10, stannous sulfide 100, butyltin mercaptide 0.4, methyl cellulose 18 and nickel sulfate 30.
A preparation method of an efficient attenuation-resistant graphene power lithium battery material comprises the following steps:
(1) adding methyl cellulose into deionized water 30 times of the weight of the methyl cellulose, raising the temperature to 80 ℃, adding nickel sulfate, and stirring for 10 minutes under the condition of heat preservation to obtain a fiber dispersion liquid;
(2) adding graphene into the fiber dispersion liquid, placing the fiber dispersion liquid in a ball mill, and uniformly ball-milling to obtain a mixed liquid;
(3) and (3) mixing stannous sulfide and butyltin mercaptide, adding the mixture into the mixed solution, uniformly stirring, washing, filtering, drying, roasting, and cooling to obtain the efficient attenuation-resistant graphene power lithium battery material.
In the step (3), the roasting temperature is 650 ℃ and the roasting time is 2 hours.
And (3) performance testing: