CN109103439A - A kind of flexible self-supporting lithium sulfur battery anode material, preparation method and its battery - Google Patents
A kind of flexible self-supporting lithium sulfur battery anode material, preparation method and its battery Download PDFInfo
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- CN109103439A CN109103439A CN201811004909.9A CN201811004909A CN109103439A CN 109103439 A CN109103439 A CN 109103439A CN 201811004909 A CN201811004909 A CN 201811004909A CN 109103439 A CN109103439 A CN 109103439A
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Abstract
The present invention relates to technical field of nano material more particularly to a kind of flexible self-supporting lithium sulfur battery anode materials, preparation method and its battery.The invention discloses a kind of preparation methods of flexible self-supporting lithium sulfur battery anode material, comprising the following steps: step 1: graphene-tin oxide nano composite material is made by the first hydro-thermal reaction in nitrogen-doped graphene and tin-salt solution；Step 2: graphene-tin oxide nano composite material being mixed with elemental sulfur, sulphur/tin oxide/graphene nanocomposite material is made by vacuum fusion diffusion reaction；Step 3: sulphur/tin oxide/graphene nanocomposite material and graphene oxide solution are obtained into flexible self-supporting lithium sulfur battery anode material by the second hydro-thermal reaction.The invention also discloses the flexible self-supporting lithium sulfur battery anode materials and its battery that are prepared by the above method.The present invention solves short lithium-sulfur cell service life in the prior art, electric conductivity, cyclical stability and the poor technical problem of security performance.
Description
Technical field
The present invention relates to technical field of nano material more particularly to a kind of flexible self-supporting lithium sulfur battery anode materials, system
Preparation Method and its battery.
Background technique
As people increasingly pay attention to environment, fossil fuel will persistently drop in the accounting of energy field, thereupon
Be new energy storage system development, moreover, the continuous renewals such as portable electronic device, unmanned plane, intelligent appliance, automobile
Also to energy storage technology, more stringent requirements are proposed for product.By contrast, nowadays the lithium ion battery of large-scale use but encounters
The bottleneck technically developed again, lithium ion battery is not able to satisfy the demand of people more and more yet, so new electrochemical energy storage
The development of system is most important.In new energy storage system, lithium-sulfur cell because of higher theoretical specific capacity, enrich cheap original
Material becomes the focus of people's research the substantially free of contamination advantage of environment, is more considered as next-generation most valuable energy storage
System is expected to solve the increasing demand of people and reaches the wish of protection environment.
But lithium-sulfur cell there is also some problems, such as more at present also in conceptual phase in large-scale use above
Sulfide is soluble, reduce ionic conductivity, loss active material, destroy negative electrode material etc., cause battery capacity to decline, the longevity
Life shortens；The electric conductivity of elemental sulfur is poor；In charge and discharge process, the conversion of elemental sulfur and sulfide can be such that anode volume becomes
Change, battery capacity is made to decay, or even destroys battery structure.These problems cause battery capacity decaying, cycle performance to be deteriorated together
When, it is also possible to there is safety problem.
Therefore, lithium-sulfur cell service life is short in the prior art, electric conductivity, cyclical stability and security performance is poor becomes
Those skilled in the art technical problems urgently to be resolved.
Summary of the invention
In view of this, the present invention provides a kind of flexible self-supporting lithium sulfur battery anode material, preparation method and its battery,
Solve short lithium-sulfur cell service life in the prior art, electric conductivity, cyclical stability and the poor technical problem of security performance.
The present invention provides a kind of preparation methods of flexible self-supporting lithium sulfur battery anode material, comprising the following steps:
Step 1: nitrogen-doped graphene is multiple by the obtained graphene-tin oxide nano of the first hydro-thermal reaction with tin-salt solution
Condensation material；
Step 2: the graphene-tin oxide nano composite material and elemental sulfur are mixed to get mixture, it will be described mixed
It closes object and sulphur/tin oxide/graphene nanocomposite material is made by vacuum fusion diffusion reaction；
Step 3: the sulphur/tin oxide/graphene nanocomposite material and graphene oxide solution are passed through into the second hydro-thermal
Reaction obtains product i.e. flexible self-supporting lithium sulfur battery anode material.
It is furthermore preferred that before step 1 further including that graphene oxide and nitrogen source are passed through Hummers at 80~100 DEG C
Method reacts 20~26h, and nitrogen-doped graphene is made.
Further preferably, the reaction temperature of the Hummers method is 80 DEG C, 90 DEG C or 100 DEG C
Further preferably, the reaction time of the Hummers method is 20h, for 24 hours or 26h.
It is furthermore preferred that the nitrogen source includes cyanamide, aryl cyanamide, melamine, nitroaniline and azodiisobutyronitrile
One of or it is two kinds any.
Preferably, Solute mass fraction of the graphene oxide solution described in step 3 in the mixed solution be 8%~
12%.
It is furthermore preferred that Solute mass fraction of the graphene oxide solution described in step 3 in the mixed solution is
8%, 10%, 11% or 12%.
Preferably, after second hydro-thermal reaction, obtain the flexible self-supporting lithium sulfur battery anode material it
Before further include, by the product filter form a film.
Preferably, after second hydro-thermal reaction, before the product is filtered film forming, further include, described
Deionized water is added in product.
Preferably, the deionized water and the volume ratio of the mixed solution are (0.5~2): 1.
It is furthermore preferred that the deionized water and the volume ratio of the mixed solution are 0.5:1,2:1 or 1:1.
Preferably, the temperature of first hydro-thermal reaction is 110~130 DEG C, time of first hydro-thermal reaction is 1~
4h。
It is furthermore preferred that the temperature of first hydro-thermal reaction is 110 DEG C, 120 DEG C or 130 DEG C, first hydro-thermal reaction
Time be 1h, 2h or 4h.
It is furthermore preferred that the solute of the tin-salt solution includes in stannous oxalate, stannous chloride, tin tetrachloride and nitric acid tin
It is one or two kinds of.
Further preferably, the solute of the tin-salt solution is stannous chloride, stannous oxalate or tin tetrachloride.
The solvent of the tin-salt solution is the one or more of methanol, carbon disulfide and dehydrated alcohol
Preferably, the content of element sulphur is 60%~70% in the mixture.
It is furthermore preferred that the content of element sulphur is 60%, 65% or 70% in the mixture.
Preferably, the temperature of the vacuum fusion diffusion reaction is 140~160 DEG C, the vacuum fusion diffusion reaction
Time be 0.5~for 24 hours.
It is furthermore preferred that the temperature of the vacuum fusion diffusion reaction is 140 DEG C, 150 DEG C or 160 DEG C, institute
The time for stating vacuum fusion diffusion reaction is 8h, 9h, 10h or 12h.
It is furthermore preferred that the time of second hydro-thermal reaction is 90 DEG C or 100 DEG C.
The present invention also provides a kind of flexible self-supporting lithium sulfur battery anode materials, by above-mentioned flexible self-supporting lithium sulphur electricity
The preparation method of pond positive electrode is made.
The present invention also provides a kind of battery, cathode is lithium-sulfur cell negative electrode material, and anode includes above-mentioned flexibility
Self-supporting lithium sulfur battery anode material.
The flexible self-supporting lithium sulfur battery anode material that the present invention is prepared, by using highly viscous graphene oxide
It is bonded, deionized water is added when filtering film forming and provides between hydrogen bond and the collective effect reinforcement graphene layer of intermolecular force
Connection, make the flexible self-supporting lithium sulfur battery anode material that there is good toughness, the solution after hydro-thermal reaction filters film forming
When solution in active material it is evenly dispersed, also need to prepare slurry and coating etc. compared to ordinary powder material, have flexible from propping up
The active material distribution on its surface of timbering material is more uniform, and thin-film material preparation section and application are more easy, and use scope is more
It is extensive.
The present invention prepares positive electrode using nitrogen-doped graphene, wherein nitrogen-doped graphene have superhigh specific surface area and
The load capacity of sulphur can be improved in a large amount of active site, further increases leading for the content of sulphur and positive electrode in positive electrode
Electrical property.Nitrogen-doped graphene and tin-salt solution by the first hydro-thermal reaction, are made the surface of nitrogen-doped graphene can by the present invention
With uniform load nano-metal-oxide, that is, tin oxide.Nanoscale granules of stannic oxide size is small, and surface can be big, can effectively consolidate
Determine elemental sulfur, in addition, the present invention passes through the effect of hydro-thermal reaction and nitrogen-doped graphene, significantly reduces the particle of tin oxide
Size.The reason is that tin ion be coordinated with the nitrogen in nitrogen-doped graphene to load on the surface of graphene, addition
Deionized water can be such that tin ion hydrolyzes, then decomposed by the stannic hydroxide that hydro-thermal reaction generates hydrolysis and generate tin oxide
Particle, during this, tin ion is first combined with nitrogen coordination, then in-situ hydrolysis, decomposition and inversion are tin oxide, so the group of being not easy
Poly-, the particle of formation is smaller.Granules of stannic oxide is smaller, and surface can be bigger, allows to adsorb sulphur by stronger chemical action
With polysulfide, the content of high-sulfur compound in electrolyte is reduced, transformation efficiency is not only increased, it is also slow by absorption polysulfide
The volume change of positive electrode has been rushed, the electrode structure of conducting matrix grain and active material is kept, has improved capacity stability and use
Service life, to be greatly improved the chemical property of lithium-sulfur cell.
The embodiment of the present invention obtains the stone for having a large amount of active sites by reacting in graphene oxide with nitrogenous substance
Black alkene improves the load sulfur content of nitrogen-doped graphene, in addition, the embodiment of the present invention, which successfully prepares load, granules of stannic oxide
Nitrogen-doped graphene, and the stronger flexible self-supporting lithium-sulphur cell positive electrode material of toughness is prepared by using the second hydro-thermal reaction,
The flexible membrane prepared bent hundred times and sulfur content is high, is widely used.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
Some embodiments of invention without any creative labor, may be used also for those of ordinary skill in the art
To obtain other attached drawings according to these attached drawings.
Fig. 1 is graphene-tin oxide nano composite material XPS figure in the embodiment of the present invention 1；
Fig. 2 is graphene-tin oxide nano composite material XRD diagram in the embodiment of the present invention 1；
Fig. 3 is sulphur/tin oxide/graphene nanocomposite material XRD diagram in the embodiment of the present invention 1；
Fig. 4 is the TEM figure of flexible self-supporting lithium sulfur battery anode material in the embodiment of the present invention 1；
Fig. 5 is the SEM figure of flexible self-supporting lithium sulfur battery anode material in the embodiment of the present invention 1；
Specific embodiment
The technical scheme in the embodiments of the invention will be clearly and completely described below, it is clear that described implementation
Example is only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, this field is common
Technical staff's every other embodiment obtained without making creative work belongs to the model that the present invention protects
It encloses.
The present invention provides a kind of flexible self-supporting lithium sulfur battery anode material, preparation method and its battery, solve existing
There are short lithium-sulfur cell service life in technology, electric conductivity, cyclical stability and the poor technical problem of security performance.
In order to which the present invention is described in more detail, below with reference to embodiment to a kind of flexible self-supporting lithium sulphur electricity provided by the invention
Pond positive electrode, preparation method and its battery, are specifically described.
Embodiment 1
It prepares graphene-tin oxide nano composite material: graphene oxide is stirred under the conditions of 80 DEG C with aryl cyanamide
26h is reacted, product cooled to room temperature, is then filtered, freezed, be freeze-dried, ground after reaction, and obtained nitrogen is mixed
Miscellaneous Graphene powder powder material, by above-mentioned dusty material concentration be 0.1mol/L stannous chloride/methanol solution in ultrasonic disperse,
Then deionized water is added dropwise, makes the amount ratio 1mol/L:1mol/L of pink salt and deionized water, dispersion liquid is transferred to reaction kettle
In, at 130 DEG C, soaking time control carries out the first hydro-thermal reaction, after reaction natural cooling, by institute in 1h for temperature control
The product obtained is filtered, is washed, is dried, and graphene-tin oxide nano composite material is obtained；
Prepare sulphur/tin oxide/graphene nanocomposite material: by graphene-tin oxide nano composite material and elemental sulfur
Mixed grinding according to a certain percentage makes sulfur content in mixture reach 60%, fills this blend into seal pipe, and temperature control exists
140 DEG C, soaking time is controlled in 12h, is pumped inner air tube, is kept elemental sulfur and graphene-tin oxide nano composite material abundant
In conjunction with finally obtaining sulphur/tin oxide/graphene nanocomposite material.
Prepare flexible self-supporting lithium sulfur battery anode material: by sulphur/tin oxide/graphene nanocomposite material in anhydrous second
It is evenly dispersed in alcohol water, the graphene oxide water solution that mass fraction is 12% is added while stirring, is transferred to after mixing
In water heating kettle, carry out the second hydro-thermal reaction at 90 DEG C of temperature, after reaction natural cooling, then by after reaction product with go
Ionized water filters film forming by the volume ratio of 1:1 after mixing, obtains flexible self-supporting lithium sulfur battery anode material.
Above-mentioned obtained flexible self-supporting lithium sulfur battery anode material is tested for the property.
Fig. 1 is graphene-tin oxide nano composite material XPS figure, and tin element is in graphene-oxygen known to Fig. 1 and table 1
Changing mass percentage content in tin is 60.0%.
The mass percentage of each element in 1 graphene of table-tin oxide
Fig. 2 is graphene-tin oxide nano composite material XRD diagram in embodiment 1, as shown in Figure 2, final gained sample
In metal oxide particle be granules of stannic oxide；
Fig. 3 is sulphur/tin oxide/graphene nanocomposite material XRD diagram in embodiment 1, as shown in Figure 3 in specimen material
Sulfur content is higher；
Fig. 4 is the TEM figure of flexible self-supporting lithium sulfur battery anode material prepared by embodiment 1, as shown in Figure 4, tin oxide
Particle is evenly distributed on the surface of graphene, and the average particle size particle size of granules of stannic oxide is about 5nm.
Fig. 5 is the SEM figure of flexible self-supporting lithium sulfur battery anode material prepared by embodiment 1, as shown in Figure 5, active material
Material is evenly distributed on the surface of graphene.
Embodiment 2
Prepare graphene-tin oxide nano composite material: by graphene oxide and appropriate azo-bis-isobutyl cyanide in 100 DEG C of items
It is stirred to react 20h under part, after reaction product cooled to room temperature, is then filtered, freezed, be freeze-dried, ground,
Nitrogen-doped graphene dusty material is made；By above-mentioned gained dusty material in stannous oxalate/bis- sulphur that concentration is 0.001mol/L
Change ultrasonic disperse in carbon solution, deionized water is then added dropwise, makes pink salt and the amount ratio of deionized water 1.0 × 10-2mol/L:
Dispersion liquid is transferred in reaction kettle by 1mol/L, and at 110 DEG C, it is anti-to carry out the first hydro-thermal in 4h for soaking time control for temperature control
It answers, after reaction natural cooling, resulting product is filtered, wash, is dried, it is multiple to obtain graphene-tin oxide nano
Condensation material.
Prepare sulphur/tin oxide/graphene nanocomposite material: by obtained graphene-tin oxide nano composite material with
Elemental sulfur mixed grinding according to a certain percentage, makes sulfur content in mixture reach 70%, fills this blend into seal pipe, temperature control
At 160 DEG C, soaking time is controlled in 8h system, is pumped inner air tube, is filled elemental sulfur with graphene-tin oxide nano composite material
Divide and combine, finally obtains sulphur/tin oxide/graphene nanocomposite material.
Prepare flexible self-supporting lithium sulfur battery anode material: by sulphur/tin oxide/graphene nanocomposite material in anhydrous second
It is evenly dispersed in alcohol water, the graphene oxide water solution for accounting for total soluble matters quality 10% is added while stirring, shifts after mixing
Into water heating kettle, carry out the second hydro-thermal reaction at 95 DEG C of temperature, after reaction natural cooling, then by after reaction solution with
Deionized water filters film forming by the volume ratio of 2:1 after mixing, obtains flexible self-supporting lithium sulfur battery anode material.
Embodiment 3
It prepares graphene-tin oxide nano composite material: graphene oxide and appropriate cyanamide is stirred instead at 90 DEG C
Should for 24 hours, product cooled to room temperature, is then filtered, is freezed, is freeze-dried, is ground after reaction, and N doping is made
Graphene powder powder material, by above-mentioned dusty material concentration be 0.05mol/L tin tetrachloride/dehydrated alcohol in ultrasonic disperse,
Then deionized water is added dropwise, makes the amount ratio 1.0mol/L:4.0mol/L of tin tetrachloride and deionized water, dispersion liquid is shifted
Into reaction kettle, at 120 DEG C, soaking time control carries out the first hydro-thermal reaction in 2h, naturally cold after reaction for temperature control
But, resulting product filtered, washed, dried, obtain graphene-tin oxide nano composite material；
Prepare sulphur/tin oxide/graphene nanocomposite material: by graphene-tin oxide nano composite material and elemental sulfur
Mixed grinding according to a certain percentage makes sulfur content in mixture reach 70%, fills this blend into seal pipe, and temperature control exists
150 DEG C, soaking time is controlled in 10h, is pumped inner air tube, is kept elemental sulfur and graphene-tin oxide nano composite material abundant
In conjunction with finally obtaining sulphur/tin oxide/graphene nanocomposite material.
Prepare flexible self-supporting lithium sulfur battery anode material: by sulphur/tin oxide/graphene nanocomposite material in anhydrous second
It is evenly dispersed in alcohol water, the graphene oxide water solution for accounting for total soluble matters quality 8% is added while stirring, is transferred to after mixing
In water heating kettle, carry out the second hydro-thermal reaction at 100 DEG C of temperature, after reaction natural cooling, then by after reaction solution with
Deionized water filters film forming by the volume ratio of 1:1 after mixing, obtains flexible self-supporting lithium sulfur battery anode material.
Embodiment 4
Prepare graphene-tin oxide nano composite material: by graphene oxide and appropriate melamine under the conditions of 90 DEG C
It is stirred to react 20h, after reaction product cooled to room temperature, is then filtered, freezed, be freeze-dried, ground, is made
Nitrogen-doped graphene dusty material, above-mentioned dusty material is ultrasonic in stannous chloride/methanol solution that concentration is 0.09mol/L
Dispersion, is then added dropwise deionized water, makes the amount ratio 1.8mol/L:4.0mol/L of tin tetrachloride and deionized water, will disperse
Liquid is transferred in reaction kettle, and at 110 DEG C, soaking time control carries out the first hydro-thermal reaction, after reaction in 2h for temperature control
Resulting product is filtered, is washed, is dried by natural cooling, obtains graphene-tin oxide nano composite material；
Prepare sulphur/tin oxide/graphene nanocomposite material: by graphene-tin oxide nano composite material and elemental sulfur
Mixed grinding according to a certain percentage makes sulfur content in mixture reach 65%, fills this blend into seal pipe, and temperature control exists
160 DEG C, soaking time is controlled in 9h, is pumped inner air tube, is tied elemental sulfur sufficiently with graphene-tin oxide nano composite material
It closes, finally obtains sulphur/tin oxide/graphene nanocomposite material.
Prepare flexible self-supporting lithium sulfur battery anode material: by sulphur/tin oxide/graphene nanocomposite material in anhydrous second
It is evenly dispersed in alcohol, the graphene oxide water solution for accounting for total soluble matters quality 11% is added while stirring, is transferred to after mixing
In water heating kettle, carry out the second hydro-thermal reaction at 90 DEG C of temperature, after reaction natural cooling, then by after reaction solution with go
Ionized water filters film forming by the volume ratio of 1:1 after mixing, obtains flexible self-supporting lithium sulfur battery anode material.
Embodiment 5
Prepare graphene-tin oxide nano composite material: by graphene oxide and appropriate nitroaniline under the conditions of 90 DEG C
It is stirred to react for 24 hours, after reaction product cooled to room temperature, is then filtered, freezed, be freeze-dried, ground, be made
Nitrogen-doped graphene dusty material；Above-mentioned gained dusty material is molten in stannous chloride/dehydrated alcohol that concentration is 0.02mol/L
Liquid ultrasonic disperse, is then added dropwise deionized water, makes the amount ratio 0.3mol/L:4.0mol/L of tin tetrachloride and deionized water,
Dispersion liquid is transferred in reaction kettle, at 120 DEG C, soaking time control carries out the first hydro-thermal reaction, reaction in 2h for temperature control
After natural cooling, resulting product is filtered, washed, is dried, graphene-tin oxide nano composite material is obtained；
Prepare sulphur/tin oxide/graphene nanocomposite material: by graphene-tin oxide nano composite material and elemental sulfur
Mixed grinding according to a certain percentage makes sulfur content in mixture reach 70%, fills this blend into seal pipe, and temperature control exists
140 DEG C, soaking time is controlled in 12h, is pumped inner air tube, is kept elemental sulfur and graphene-tin oxide nano composite material abundant
In conjunction with finally obtaining sulphur/tin oxide/graphene nanocomposite material.
Prepare flexible self-supporting lithium sulfur battery anode material: by sulphur/tin oxide/graphene nanocomposite material in anhydrous second
It is evenly dispersed in alcohol water, the graphene oxide water solution for accounting for total soluble matters quality 10% is added while stirring, shifts after mixing
Into water heating kettle, the second hydro-thermal reaction is carried out at 90 DEG C of temperature, after reaction natural cooling, then the solution after reaction is taken out
Filter film forming, obtains flexible self-supporting lithium sulfur battery anode material.
Comparative example 1
It prepares graphene-tin oxide nano composite material: graphene oxide and cyanamide being stirred under the conditions of 90 DEG C anti-
Should for 24 hours, product cooled to room temperature, is then filtered, is freezed, is freeze-dried, is ground after reaction, and N doping is made
Graphene powder powder material；By above-mentioned gained dusty material in the stannous chloride that concentration is 0.02mol/L/ethanol solution ultrasound
Dispersion, is then added dropwise deionized water, makes the amount ratio 0.3mol/L:4.0mol/L of tin tetrachloride and deionized water, will disperse
Liquid is transferred in reaction kettle, and at 120 DEG C, soaking time control carries out the first hydro-thermal reaction, after reaction in 2h for temperature control
Resulting product is filtered, is washed, is dried by natural cooling, obtains graphene-tin oxide nano composite material；
Prepare sulphur/tin oxide/graphene nanocomposite material: by graphene-tin oxide nano composite material and elemental sulfur
Mixed grinding according to a certain percentage makes sulfur content in mixture reach 60%, fills this blend into seal pipe, and temperature control exists
155 DEG C, soaking time is controlled in 10h, is pumped inner air tube, is kept elemental sulfur and graphene-tin oxide nano composite material abundant
In conjunction with finally obtaining sulphur/tin oxide/graphene nanocomposite material.
Prepare flexible self-supporting lithium sulfur battery anode material: by sulphur/tin oxide/graphene nanocomposite material in anhydrous second
It is evenly dispersed in alcohol water, the graphene oxide water solution for accounting for total soluble matters quality 30% is added while stirring, shifts after mixing
Into water heating kettle, the second hydro-thermal reaction is carried out at 90 DEG C of temperature, after reaction natural cooling, then the solution after reaction is taken out
Filter film forming, obtains flexible self-supporting lithium sulfur battery anode material.
After tested, in preparing the step for hydrothermal solution filters film forming, the oxidation stone for accounting for total soluble matters quality 30% is added
Black aqueous solution, toughness is very poor after the film filtered is dry, cannot bend, frangible.
In conclusion preparing selection and dosage that flexible self-supporting membrane material is binder, graphene oxide has good
Good toughness, while easily being bonded with sulphur/tin oxide/graphene nanocomposite material, it is suitable as this flexible self-supporting electrode material
The binder of material.Dosage requirement is harsher, and dosage is too low to lose a part of active material, reduces flexible self-supporting material
Toughness, it is excessively high, it will affect the performance of material.
The results of property of flexible self-supporting lithium sulfur battery anode material made from 2 Examples 1 to 5 of table and comparative example 1
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of preparation method of flexible self-supporting lithium sulfur battery anode material, which comprises the following steps:
Step 1: graphene-tin oxide nano composite wood is made by the first hydro-thermal reaction in nitrogen-doped graphene and tin-salt solution
Material；
Step 2: the graphene-tin oxide nano composite material and elemental sulfur being mixed to get mixture, by the mixture
Sulphur/tin oxide/graphene nanocomposite material is made by vacuum fusion diffusion reaction；
Step 3: the sulphur/tin oxide/graphene nanocomposite material and graphene oxide solution are mixed to get mixed solution,
Affiliated mixed solution is obtained into product i.e. flexible self-supporting lithium sulfur battery anode material by the second hydro-thermal reaction.
2. the preparation method of flexible self-supporting lithium sulfur battery anode material according to claim 1, which is characterized in that step
Solute mass fraction of the graphene oxide solution described in 3 in the mixed solution is 8%~12%.
3. the preparation method of flexible self-supporting lithium sulfur battery anode material according to claim 1, which is characterized in that in institute
After stating the second hydro-thermal reaction, further include before obtaining the flexible self-supporting lithium sulfur battery anode material, by the product
Filter film forming.
4. the preparation method of flexible self-supporting lithium sulfur battery anode material according to claim 3, which is characterized in that in institute
It further include that deionized water is added in the product before the product is filtered film forming after stating the second hydro-thermal reaction.
5. the preparation method of flexible self-supporting lithium sulfur battery anode material according to claim 4, which is characterized in that described
Deionized water and the volume ratio of the mixed solution are (0.5~2): 1.
6. the preparation method of flexible self-supporting lithium sulfur battery anode material according to claim 1, which is characterized in that described
The temperature of first hydro-thermal reaction is 110~130 DEG C, and the time of first hydro-thermal reaction is 1~4h.
7. the preparation method of flexible self-supporting lithium sulfur battery anode material according to claim 1, which is characterized in that described
The content of element sulphur is 60%~70% in mixture.
8. the preparation method of flexible self-supporting lithium sulfur battery anode material according to claim 1, which is characterized in that described
The temperature of vacuum fusion diffusion reaction is 140~160 DEG C, time of the vacuum fusion diffusion reaction is 0.5~for 24 hours.
9. a kind of flexible self-supporting lithium sulfur battery anode material, which is characterized in that as described in claim 1~8 any one
The preparation method of flexible self-supporting lithium sulfur battery anode material is made.
10. a kind of battery, which is characterized in that its cathode is lithium-sulfur cell negative electrode material, and anode includes as claimed in claim 9
Flexible self-supporting lithium sulfur battery anode material.
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| CN110165162A (en) * | 2019-04-28 | 2019-08-23 | 南京大学 | A kind of carbon-sulfur compound positive electrode of lithium-sulfur cell |
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