CN109103439B - Flexible self-supporting lithium-sulfur battery positive electrode material, preparation method and battery thereof - Google Patents
Flexible self-supporting lithium-sulfur battery positive electrode material, preparation method and battery thereof Download PDFInfo
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Abstract
The invention relates to the technical field of nano materials, in particular to a flexible self-supporting lithium-sulfur battery positive electrode material, a preparation method and a battery thereof. The invention discloses a preparation method of a flexible self-supporting lithium-sulfur battery positive electrode material, which comprises the following steps: step 1: carrying out a first hydrothermal reaction on nitrogen-doped graphene and a tin salt solution to prepare a graphene-tin oxide nano composite material; step 2: mixing the graphene-tin oxide nano composite material with elemental sulfur, and carrying out vacuum melting diffusion reaction to obtain a sulfur/tin oxide/graphene nano composite material; and step 3: and carrying out a second hydrothermal reaction on the sulfur/tin oxide/graphene nano composite material and the graphene oxide solution to obtain the flexible self-supporting lithium-sulfur battery positive electrode material. The invention also discloses the flexible self-supporting lithium-sulfur battery positive electrode material prepared by the method and a battery thereof. The invention solves the technical problems of short service life, poor conductivity, poor cycle stability and poor safety performance of the lithium-sulfur battery in the prior art.
Description
Technical Field
The invention relates to the technical field of nano materials, in particular to a flexible self-supporting lithium-sulfur battery positive electrode material, a preparation method and a battery thereof.
Background
Along with more and more attention paid to the environment, the occupation ratio of fossil fuel in the energy field will continuously go low, and the development of a new energy storage system follows with the occupation ratio, and moreover, products such as portable electronic equipment, unmanned aerial vehicles, intelligent household appliances and automobiles which are continuously updated also put forward higher requirements on the energy storage technology. On the contrary, the lithium ion batteries used in large scale nowadays encounter the bottleneck of technical re-development, and the lithium ion batteries are increasingly unable to meet the requirements of people, so the development of a new electrochemical energy storage system is of great importance. In a new energy storage system, the lithium-sulfur battery becomes a hotspot of research of people due to the advantages of higher theoretical specific capacity, abundant and cheap raw materials and basically no pollution to the environment, is considered to be the most valuable energy storage system of the next generation, and is expected to solve the increasing demands of people and achieve the desire of protecting the environment.
However, the lithium-sulfur battery is still under research stage, and there are some problems in large-scale use, such as the polysulfide is easily dissolved, the ion conduction capability is reduced, the active material is lost, the negative electrode material is damaged, and the battery capacity is reduced, and the service life is shortened; the conductivity of elemental sulfur is poor; during the charging and discharging process, the conversion of elemental sulfur and sulfide can change the volume of the positive electrode, so that the capacity of the battery is attenuated, and even the structure of the battery is damaged. These problems lead to deterioration of battery capacity and cycle performance, and may also cause safety problems.
Therefore, the short service life, poor conductivity, poor cycle stability and poor safety performance of the lithium-sulfur battery in the prior art become technical problems to be solved urgently by the technical personnel in the field.
Disclosure of Invention
In view of the above, the invention provides a flexible self-supporting lithium-sulfur battery positive electrode material, a preparation method and a battery thereof, and solves the technical problems of short service life, poor conductivity, poor cycle stability and poor safety performance of a lithium-sulfur battery in the prior art.
The invention provides a preparation method of a flexible self-supporting lithium-sulfur battery positive electrode material, which comprises the following steps:
step 1: carrying out a first hydrothermal reaction on nitrogen-doped graphene and a tin salt solution to prepare a graphene-tin oxide nano composite material;
step 2: mixing the graphene-tin oxide nano composite material with elemental sulfur to obtain a mixture, and carrying out vacuum melting diffusion reaction on the mixture to obtain a sulfur/tin oxide/graphene nano composite material;
and step 3: and carrying out a second hydrothermal reaction on the sulfur/tin oxide/graphene nano composite material and a graphene oxide solution to obtain a product, namely the flexible self-supporting lithium-sulfur battery positive electrode material.
More preferably, before the step 1, the method further comprises the step of reacting the graphene oxide with a nitrogen source at 80-100 ℃ for 20-26 hours by a Hummers method to obtain the nitrogen-doped graphene.
More preferably, the reaction temperature of the Hummers method is 80 ℃, 90 ℃ or 100 DEG C
Further preferably, the Hummers method has a reaction time of 20h, 24h or 26 h.
More preferably, the nitrogen source comprises one or any two of cyanamide, aryl cyanamide, melamine, nitroaniline and azobisisobutyronitrile.
Preferably, the solute mass fraction of the graphene oxide solution in the mixed solution in the step 3 is 8-12%.
More preferably, the solute mass fraction of the graphene oxide solution in the mixed solution in the step 3 is 8%, 10%, 11% or 12%.
Preferably, after the second hydrothermal reaction, before obtaining the flexible self-supporting lithium-sulfur battery cathode material, the method further comprises suction filtering the product into a film.
Preferably, after the second hydrothermal reaction, adding deionized water into the product before filtering the product to form a membrane.
Preferably, the volume ratio of the deionized water to the mixed solution is (0.5-2): 1.
More preferably, the volume ratio of the deionized water to the mixed solution is 0.5:1, 2:1 or 1: 1.
Preferably, the temperature of the first hydrothermal reaction is 110-130 ℃, and the time of the first hydrothermal reaction is 1-4 h.
More preferably, the temperature of the first hydrothermal reaction is 110 ℃, 120 ℃ or 130 ℃, and the time of the first hydrothermal reaction is 1h, 2h or 4 h.
More preferably, the solute of the tin salt solution includes one or two of stannous oxalate, stannous chloride, stannic chloride and stannic nitrate.
Further preferably, the solute of the tin salt solution is stannous chloride, stannous oxalate or stannic chloride.
The solvent of the tin salt solution is one or more of methanol, carbon disulfide and absolute ethyl alcohol
Preferably, the content of sulfur in the mixture is 60-70%.
More preferably, the sulphur element content of the mixture is 60%, 65% or 70%.
Preferably, the temperature of the vacuum melting diffusion reaction is 140-160 ℃, and the time of the vacuum melting diffusion reaction is 0.5-24 h.
More preferably, the temperature of the vacuum melt diffusion reaction is 140 ℃, 150 ℃ or 160 ℃, so that
The time of the vacuum melting diffusion reaction is 8h, 9h, 10h or 12 h.
More preferably, the time of the second hydrothermal reaction is 90 ℃ or 100 ℃.
The invention also provides a flexible self-supporting lithium-sulfur battery positive electrode material, which is prepared by the preparation method of the flexible self-supporting lithium-sulfur battery positive electrode material.
The invention also provides a battery, wherein the cathode of the battery is a cathode material of a lithium-sulfur battery, and the anode of the battery comprises the flexible self-supporting cathode material of the lithium-sulfur battery.
According to the flexible self-supporting lithium-sulfur battery positive electrode material prepared by the invention, high-viscosity graphene oxide is used for bonding, deionized water is added during suction filtration and film formation to provide the combined action of hydrogen bonds and intermolecular forces to strengthen the connection between graphene layers, so that the flexible self-supporting lithium-sulfur battery positive electrode material has good toughness, active substances in a solution after hydrothermal reaction are uniformly dispersed during suction filtration and film formation of the solution, compared with a common powder material, slurry preparation, coating and the like are required, the flexible self-supporting lithium-sulfur battery positive electrode material has the advantages that the distribution of the active substances on the surface of the flexible self-supporting material is more uniform, the preparation process and the application of a film material are simpler and more convenient, and the application range is wider.
According to the invention, the positive electrode material is prepared from the nitrogen-doped graphene, wherein the nitrogen-doped graphene has an ultrahigh specific surface area and a large number of active sites, so that the sulfur loading capacity can be improved, and the sulfur content in the positive electrode material and the conductivity of the positive electrode material are further improved. According to the invention, nitrogen-doped graphene and a tin salt solution are subjected to a first hydrothermal reaction, so that nano metal oxide, namely tin oxide, can be uniformly loaded on the surface of the nitrogen-doped graphene. The nano-scale tin oxide has small particle size and large surface energy, can effectively fix elemental sulfur, and effectively reduces the particle size of the tin oxide through the action of hydrothermal reaction and nitrogen-doped graphene. The reason is that tin ions can be coordinated with nitrogen in nitrogen-doped graphene to be loaded on the surface of the graphene, the added deionized water can hydrolyze the tin ions, and tin hydroxide generated by hydrolysis is decomposed to generate tin oxide particles through hydrothermal reaction. The smaller the tin oxide particle is, the larger the surface energy is, the higher the tin oxide particle can adsorb sulfur and polysulfide through stronger chemical action, the content of high sulfide in the electrolyte is reduced, the conversion efficiency is improved, the volume change of the anode material is buffered through adsorbing polysulfide, the electrode structure of a conductive framework and an active substance is kept, the capacity stability is improved, the service life is prolonged, and the electrochemical performance of the lithium-sulfur battery is greatly improved.
In the embodiment of the invention, graphene with a large number of active sites is obtained through the reaction of graphene oxide and nitrogen-containing substances, so that the sulfur carrying amount of the nitrogen-doped graphene is increased.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without inventive exercise.
Fig. 1 is an XPS chart of a graphene-tin oxide nanocomposite in example 1 of the present invention;
fig. 2 is an XRD pattern of graphene-tin oxide nanocomposite in example 1 of the present invention;
FIG. 3 is an XRD pattern of a sulfur/tin oxide/graphene nanocomposite material in example 1 of the present invention;
FIG. 4 is a TEM image of the positive electrode material of the flexible self-supporting lithium-sulfur battery in example 1 of the present invention;
FIG. 5 is an SEM image of the positive electrode material of the flexible self-supporting lithium-sulfur battery in example 1 of the present invention;
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a flexible self-supporting lithium-sulfur battery positive electrode material, a preparation method and a battery thereof, and solves the technical problems of short service life, poor conductivity, poor cycle stability and poor safety performance of a lithium-sulfur battery in the prior art.
In order to illustrate the invention in more detail, the following describes a flexible self-supporting lithium-sulfur battery positive electrode material, a preparation method and a battery thereof provided by the invention in detail with reference to examples.
Example 1
Preparing a graphene-tin oxide nano composite material: stirring graphene oxide and aryl cyanamide at 80 ℃ for 26h for reaction, naturally cooling a product to room temperature after the reaction is finished, then performing suction filtration, freezing, freeze drying and grinding to obtain a nitrogen-doped graphene powder material, ultrasonically dispersing the powder material in a stannous chloride/methanol solution with the concentration of 0.1mol/L, then dropwise adding deionized water to ensure that the using amount ratio of tin salt to the deionized water is 1mol/L:1mol/L, transferring the dispersion liquid into a reaction kettle, controlling the temperature at 130 ℃, keeping the temperature for 1h, performing a first hydrothermal reaction, naturally cooling after the reaction is finished, performing suction filtration, washing and drying on the obtained product to obtain a graphene-tin oxide nano composite material;
preparing a sulfur/tin oxide/graphene nanocomposite material: mixing and grinding the graphene-tin oxide nano composite material and elemental sulfur according to a certain proportion to enable the sulfur content in the mixture to reach 60%, filling the mixture into a sealed tube, controlling the temperature at 140 ℃, controlling the heat preservation time at 12h, and removing air in the tube to enable the elemental sulfur to be fully combined with the graphene-tin oxide nano composite material, thereby finally obtaining the sulfur/tin oxide/graphene nano composite material.
Preparing a flexible self-supporting lithium-sulfur battery cathode material: uniformly dispersing the sulfur/tin oxide/graphene nano composite material in absolute ethyl alcohol water, adding a graphene oxide water solution with the mass fraction of 12% while stirring, uniformly mixing, transferring to a hydrothermal kettle, carrying out a second hydrothermal reaction at the temperature of 90 ℃, naturally cooling after the reaction is finished, uniformly mixing a product obtained after the reaction and deionized water according to the volume ratio of 1:1, and carrying out suction filtration to form a film, thus obtaining the flexible self-supporting lithium-sulfur battery positive electrode material.
And (3) carrying out performance test on the prepared flexible self-supporting lithium-sulfur battery cathode material.
Fig. 1 is an XPS diagram of the graphene-tin oxide nanocomposite, and it can be seen from fig. 1 and table 1 that the mass percentage content of tin element in the graphene-tin oxide is 60.0%.
Table 1 mass percentage of each element in graphene-tin oxide
Fig. 2 is an XRD pattern of the graphene-tin oxide nanocomposite material of example 1, and it can be seen from fig. 2 that the metal oxide particles in the finally obtained sample are tin oxide particles;
FIG. 3 is an XRD pattern of the sulfur/tin oxide/graphene nanocomposite material of example 1, and it can be seen from FIG. 3 that the sulfur content in the sample material is high;
fig. 4 is a TEM image of the flexible self-supporting lithium-sulfur battery cathode material prepared in example 1, and it can be seen from fig. 4 that tin oxide particles are uniformly distributed on the surface of graphene, and the average particle size of the tin oxide particles is about 5 nm.
Fig. 5 is an SEM image of the positive electrode material of the flexible self-supporting lithium-sulfur battery prepared in example 1, and it can be seen from fig. 5 that the active material is uniformly distributed on the surface of the graphene.
Example 2
Preparing a graphene-tin oxide nano composite material: stirring graphene oxide and a proper amount of azodiisobutyronitrile at 100 ℃ for 20 hours for reaction, naturally cooling a product to room temperature after the reaction is finished, and then performing suction filtration, freezing, freeze drying and grinding to obtain a nitrogen-doped graphene powder material; ultrasonically dispersing the obtained powder material in a stannous oxalate/carbon disulfide solution with the concentration of 0.001mol/L, and then dropwise adding deionized water to ensure that the dosage ratio of tin salt to the deionized water is 1.0 multiplied by 10-2And (3) 1mol/L, transferring the dispersion liquid into a reaction kettle, controlling the temperature at 110 ℃ and the heat preservation time at 4h, carrying out a first hydrothermal reaction, naturally cooling after the reaction is finished, and carrying out suction filtration, washing and drying on the obtained product to obtain the graphene-tin oxide nano composite material.
Preparing a sulfur/tin oxide/graphene nanocomposite material: mixing and grinding the obtained graphene-tin oxide nano composite material and elemental sulfur according to a certain proportion to enable the sulfur content in the mixture to reach 70%, filling the mixture into a sealing tube, controlling the temperature at 160 ℃, controlling the heat preservation time at 8h, and pumping out air in the tube to enable the elemental sulfur to be fully combined with the graphene-tin oxide nano composite material, thereby finally obtaining the sulfur/tin oxide/graphene nano composite material.
Preparing a flexible self-supporting lithium-sulfur battery cathode material: uniformly dispersing a sulfur/tin oxide/graphene nano composite material in absolute ethyl alcohol water, adding a graphene oxide water solution accounting for 10% of the total solute mass while stirring, uniformly mixing, transferring to a hydrothermal kettle, carrying out a second hydrothermal reaction at the temperature of 95 ℃, naturally cooling after the reaction is finished, uniformly mixing the reacted solution and deionized water according to the volume ratio of 2:1, and carrying out suction filtration to form a membrane, thus obtaining the flexible self-supporting lithium-sulfur battery anode material.
Example 3
Preparing a graphene-tin oxide nano composite material: stirring graphene oxide and a proper amount of cyanamide at 90 ℃ for 24 hours to react, naturally cooling a product to room temperature after the reaction is finished, then carrying out suction filtration, freezing, freeze drying and grinding to obtain a nitrogen-doped graphene powder material, ultrasonically dispersing the powder material in 0.05mol/L tin tetrachloride/anhydrous ethanol, then dropwise adding deionized water to ensure that the using amount ratio of the tin tetrachloride to the deionized water is 1.0mol/L:4.0mol/L, transferring the dispersion liquid to a reaction kettle, controlling the temperature at 120 ℃, controlling the heat preservation time at 2 hours, carrying out a first hydrothermal reaction, naturally cooling after the reaction is finished, and carrying out suction filtration, washing and drying on the obtained product to obtain a graphene-tin oxide nano composite material;
preparing a sulfur/tin oxide/graphene nanocomposite material: mixing and grinding the graphene-tin oxide nano composite material and elemental sulfur according to a certain proportion to enable the sulfur content in the mixture to reach 70%, filling the mixture into a sealed tube, controlling the temperature at 150 ℃ and the heat preservation time at 10h, and pumping out air in the tube to enable the elemental sulfur to be fully combined with the graphene-tin oxide nano composite material, thereby finally obtaining the sulfur/tin oxide/graphene nano composite material.
Preparing a flexible self-supporting lithium-sulfur battery cathode material: uniformly dispersing a sulfur/tin oxide/graphene nano composite material in absolute ethyl alcohol water, adding a graphene oxide water solution accounting for 8% of the total solute mass while stirring, uniformly mixing, transferring to a hydrothermal kettle, carrying out a second hydrothermal reaction at 100 ℃, naturally cooling after the reaction is finished, uniformly mixing the reacted solution and deionized water according to a volume ratio of 1:1, and carrying out suction filtration to form a membrane, thus obtaining the flexible self-supporting lithium-sulfur battery anode material.
Example 4
Preparing a graphene-tin oxide nano composite material: stirring graphene oxide and a proper amount of melamine at 90 ℃ for 20 hours, naturally cooling a product to room temperature after the reaction is finished, then carrying out suction filtration, freezing, freeze drying and grinding to obtain a nitrogen-doped graphene powder material, ultrasonically dispersing the powder material in a stannous chloride/methanol solution with the concentration of 0.09mol/L, then dropwise adding deionized water to ensure that the using ratio of stannic chloride to deionized water is 1.8mol/L:4.0mol/L, transferring the dispersion liquid into a reaction kettle, controlling the temperature at 110 ℃, controlling the heat preservation time at 2 hours, carrying out a first hydrothermal reaction, naturally cooling after the reaction is finished, carrying out suction filtration, washing and drying on the obtained product to obtain a graphene-stannic oxide nano composite material;
preparing a sulfur/tin oxide/graphene nanocomposite material: mixing and grinding the graphene-tin oxide nano composite material and elemental sulfur according to a certain proportion to enable the sulfur content in the mixture to reach 65%, filling the mixture into a sealing tube, controlling the temperature at 160 ℃, controlling the heat preservation time at 9h, and removing air in the tube to enable the elemental sulfur to be fully combined with the graphene-tin oxide nano composite material, thereby finally obtaining the sulfur/tin oxide/graphene nano composite material.
Preparing a flexible self-supporting lithium-sulfur battery cathode material: uniformly dispersing a sulfur/tin oxide/graphene nano composite material in absolute ethyl alcohol, adding a graphene oxide aqueous solution accounting for 11% of the total solute mass while stirring, uniformly mixing, transferring to a hydrothermal kettle, carrying out a second hydrothermal reaction at 90 ℃, naturally cooling after the reaction is finished, uniformly mixing the reacted solution and deionized water according to a volume ratio of 1:1, and carrying out suction filtration to form a membrane, thus obtaining the flexible self-supporting lithium-sulfur battery anode material.
Example 5
Preparing a graphene-tin oxide nano composite material: stirring graphene oxide and a proper amount of nitroaniline for reaction for 24 hours at 90 ℃, naturally cooling a product to room temperature after the reaction is finished, and then performing suction filtration, freezing, freeze drying and grinding to obtain a nitrogen-doped graphene powder material; ultrasonically dispersing the obtained powder material in a stannous chloride/absolute ethyl alcohol solution with the concentration of 0.02mol/L, then dropwise adding deionized water, controlling the using amount ratio of stannic chloride to deionized water to be 0.3mol/L:4.0mol/L, transferring the dispersion liquid into a reaction kettle, controlling the temperature to be 120 ℃, controlling the heat preservation time to be 2 hours, carrying out a first hydrothermal reaction, naturally cooling after the reaction is finished, carrying out suction filtration, washing and drying on the obtained product, and obtaining the graphene-tin oxide nano composite material;
preparing a sulfur/tin oxide/graphene nanocomposite material: mixing and grinding the graphene-tin oxide nano composite material and elemental sulfur according to a certain proportion to enable the sulfur content in the mixture to reach 70%, filling the mixture into a sealing tube, controlling the temperature at 140 ℃, controlling the heat preservation time at 12h, and removing air in the tube to enable the elemental sulfur to be fully combined with the graphene-tin oxide nano composite material, thereby finally obtaining the sulfur/tin oxide/graphene nano composite material.
Preparing a flexible self-supporting lithium-sulfur battery cathode material: uniformly dispersing the sulfur/tin oxide/graphene nano composite material in absolute ethyl alcohol water, adding a graphene oxide water solution accounting for 10% of the total solute mass while stirring, uniformly mixing, transferring to a hydrothermal kettle, carrying out a second hydrothermal reaction at 90 ℃, naturally cooling after the reaction is finished, and carrying out suction filtration on the reacted solution to form a membrane to obtain the flexible self-supporting lithium-sulfur battery cathode material.
Comparative example 1
Preparing a graphene-tin oxide nano composite material: stirring graphene oxide and cyanamide at 90 ℃ for 24 hours for reaction, naturally cooling a product to room temperature after the reaction is finished, and then performing suction filtration, freezing, freeze drying and grinding to obtain a nitrogen-doped graphene powder material; ultrasonically dispersing the obtained powder material in a stannous chloride/absolute ethyl alcohol solution with the concentration of 0.02mol/L, then dropwise adding deionized water, controlling the using amount ratio of stannic chloride to deionized water to be 0.3mol/L:4.0mol/L, transferring the dispersion liquid into a reaction kettle, controlling the temperature to be 120 ℃, controlling the heat preservation time to be 2 hours, carrying out a first hydrothermal reaction, naturally cooling after the reaction is finished, carrying out suction filtration, washing and drying on the obtained product, and obtaining the graphene-tin oxide nano composite material;
preparing a sulfur/tin oxide/graphene nanocomposite material: mixing and grinding the graphene-tin oxide nano composite material and elemental sulfur according to a certain proportion to enable the sulfur content in the mixture to reach 60%, filling the mixture into a sealed tube, controlling the temperature at 155 ℃ and the heat preservation time at 10h, and pumping out air in the tube to enable the elemental sulfur to be fully combined with the graphene-tin oxide nano composite material, thereby finally obtaining the sulfur/tin oxide/graphene nano composite material.
Preparing a flexible self-supporting lithium-sulfur battery cathode material: uniformly dispersing the sulfur/tin oxide/graphene nano composite material in absolute ethyl alcohol water, adding a graphene oxide water solution accounting for 30% of the total solute mass while stirring, uniformly mixing, transferring to a hydrothermal kettle, carrying out a second hydrothermal reaction at 90 ℃, naturally cooling after the reaction is finished, and carrying out suction filtration on the reacted solution to form a membrane to obtain the flexible self-supporting lithium-sulfur battery cathode material.
Tests show that in the step of preparing the hydrothermal solution, a graphene oxide aqueous solution accounting for 30% of the total solute mass is added, and the film obtained by suction filtration has poor toughness after drying, cannot be bent and is fragile.
In conclusion, the flexible self-supporting membrane material is prepared by selecting and using the binder, and the graphene oxide has good toughness, is easy to bond with the sulfur/tin oxide/graphene nano composite material, and is suitable for being used as the binder of the flexible self-supporting electrode material. The requirement on the dosage is harsh, a part of active materials can be lost when the dosage is too low, the toughness of the flexible self-supporting material is reduced, and the performance of the material can be influenced when the dosage is too high.
TABLE 2 Performance results for flexible self-supporting lithium-sulfur battery positive electrode materials prepared in examples 1-5 and comparative example 1
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (6)
1. A preparation method of a flexible self-supporting lithium-sulfur battery positive electrode material is characterized by comprising the following steps:
step 1: carrying out a first hydrothermal reaction on nitrogen-doped graphene and a tin salt solution to prepare a graphene-tin oxide nano composite material;
step 2: mixing the graphene-tin oxide nano composite material with elemental sulfur to obtain a mixture, and carrying out vacuum melting diffusion reaction on the mixture to obtain a sulfur/tin oxide/graphene nano composite material;
and step 3: mixing the sulfur/tin oxide/graphene nano composite material with a graphene oxide solution to obtain a mixed solution, and carrying out a second hydrothermal reaction on the mixed solution to obtain a product, namely the flexible self-supporting lithium-sulfur battery positive electrode material;
in the step 3, the mass fraction of the solute of the graphene oxide solution in the mixed solution is 8-12%;
after the second hydrothermal reaction, performing suction filtration on the product to form a film before obtaining the flexible self-supporting lithium-sulfur battery cathode material;
after the second hydrothermal reaction, adding deionized water into the product before filtering the product to form a membrane;
the volume ratio of the deionized water to the mixed solution is 2: 1.
2. The preparation method of the flexible self-supporting lithium-sulfur battery cathode material according to claim 1, wherein the temperature of the first hydrothermal reaction is 110-130 ℃, and the time of the first hydrothermal reaction is 1-4 h.
3. The method for preparing a flexible self-supporting lithium-sulfur battery positive electrode material according to claim 1, wherein the content of sulfur in the mixture is 60 to 70 percent.
4. The preparation method of the flexible self-supporting lithium-sulfur battery cathode material according to claim 1, wherein the temperature of the vacuum melting diffusion reaction is 140-160 ℃, and the time of the vacuum melting diffusion reaction is 0.5-24 h.
5. A flexible self-supporting lithium-sulfur battery cathode material is characterized by being prepared by the preparation method of the flexible self-supporting lithium-sulfur battery cathode material as claimed in any one of claims 1 to 4.
6. A battery having a negative electrode of a lithium sulfur battery negative electrode material and a positive electrode comprising the flexible self-supporting lithium sulfur battery positive electrode material of claim 5.
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| CN107394118A (en) * | 2017-09-05 | 2017-11-24 | 湘潭大学 | A kind of preparation method and applications of self-supporting flexible electrode |
| CN107732202A (en) * | 2017-10-16 | 2018-02-23 | 河源广工大协同创新研究院 | A kind of preparation method of lithium sulfur battery anode material |
| CN108011085A (en) * | 2017-11-29 | 2018-05-08 | 北京师范大学 | A kind of lithium sulfur battery anode material, its preparation method and its application |
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| CN102945947A (en) * | 2012-12-04 | 2013-02-27 | 中国科学院上海硅酸盐研究所 | Preparation method of flexible binding agent-free self-support combination electrode |
| CN105140490A (en) * | 2015-09-28 | 2015-12-09 | 中南大学 | Preparation method of lithium-sulfur battery flexible positive electrode |
| CN106876685A (en) * | 2017-04-12 | 2017-06-20 | 河北工业大学 | A kind of preparation method of lithium sulfur battery anode material |
| CN107394118A (en) * | 2017-09-05 | 2017-11-24 | 湘潭大学 | A kind of preparation method and applications of self-supporting flexible electrode |
| CN107732202A (en) * | 2017-10-16 | 2018-02-23 | 河源广工大协同创新研究院 | A kind of preparation method of lithium sulfur battery anode material |
| CN108011085A (en) * | 2017-11-29 | 2018-05-08 | 北京师范大学 | A kind of lithium sulfur battery anode material, its preparation method and its application |
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