CN106848232A - A kind of preparation method and applications of three-dimensional grapheme sulphur composite - Google Patents
A kind of preparation method and applications of three-dimensional grapheme sulphur composite Download PDFInfo
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- CN106848232A CN106848232A CN201710086529.3A CN201710086529A CN106848232A CN 106848232 A CN106848232 A CN 106848232A CN 201710086529 A CN201710086529 A CN 201710086529A CN 106848232 A CN106848232 A CN 106848232A
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a kind of preparation method and applications of three-dimensional grapheme sulphur composite, the method is that graphene oxide and elemental sulfur are carried out into hydro-thermal reaction under alkaline environment, hydro-thermal reaction product is by washing, freeze-drying, obtain final product three-dimensional grapheme sulphur composite, the method is simple to operate, low cost, safety and environmental protection, the three-dimensional grapheme sulphur composite sulfur doping amount of preparation is big and controllable, uniform doping, with preferable chemical property, shown compared with high charge-discharge specific capacity and high circulation stability for lithium-sulfur cell.
Description
Technical field
The present invention relates to a kind of preparation method of sulfur doping graphene composite material, and in particular to one kind is with elemental sulfur as sulphur
Source, the method that three-dimensional grapheme-sulphur composite (SG) is prepared in the basic conditions, and its application in lithium-sulfur cell, category
In lithium-sulfur cell technical field of material.
Background technology
In new energy field, people are devoted to finding always the energy storage side of low cost, long circulation life and high-energy-density
Method.In nature rich content, lithium-sulfur cell has theoretical energy density high and theoretical capacity high to sulphur, therefore suffers from pass extensively
Note.However, lithium-sulfur cell is applied to actually to still suffer from many problems, such as poorly conductive of sulphur, volumetric expansion, active matter
Matter loss and shuttle effect etc..In order to overcome drawbacks described above, can mainly be designed from novel electrolytes development, barrier film and anode structure
Etc. aspect set about, wherein, anode structure design is probed into the most extensive.Research finds, using carbon sulphur composite, metal sulphur
Oxide and conducting polymer etc. can significantly improve lithium-sulfur cell performance as positive electrode.Porous carbon materials such as microporous carbon, is situated between
Hole carbon, macropore carbon, graded porous carbon, CNT and graphene aerogel etc. have proved to be the ideal stent of lithium-sulfur cell,
These structures ensure that the close contact of active material and electrolyte, promotes charge migration and suppresses the molten of polysulfide
Solution.It can be mentioned that the carbon sulphur composite that different synthetic methods is obtained is larger to lithium-sulfur cell performance impact, example
Such as, (N.Jayaprakash, J.Shen, S.S.Moganty, A.Corona, the L.A.Archer.Porous such as Jayaprakash
hollow carbon@sulfur composites for high-power lithium–sulfur
Batteries.Angewandte Chemie, 2011,123 (26), 6026-6030) by the method evaporated prepare sulphur-
Hollow porous carbon composite, 91% is improve in 100 cycling condition stability inferiors.Additionally, current many synthetic methods are still
It is so relatively costly, it is impossible to realize producing in enormous quantities.Chinese patent (Publication No. CN105609773A) discloses a kind of three-dimensional knot
The lithium sulfur battery anode material of structure, and specifically disclose its preparation technology:(1) graphite oxide is added to the water ultrasound, is formed
Graphene oxide suspension;(2) benzene sulfonic acid sodium salt is added in graphene oxide suspension, is then transferred into being carried out in water heating kettle
Hydro-thermal reaction, ethanol is washed, washed after the completion of reaction, then freeze-drying, obtains three-dimensional sulfur doping Graphene;(3) step (2) is taken
Ultrasonic reaction forms suspension during the three-dimensional sulfur doping Graphene for obtaining is added to 1-METHYLPYRROLIDONE with Ketjen black;(4) will
Elemental sulfur is added in 1-METHYLPYRROLIDONE ultrasound at a certain temperature, and suspension is formed until elemental sulfur is completely dissolved;(5)
Two kinds of suspension mixing that (4) and (3) are obtained, stirs, then slow under agitation to add distilled water, centrifugation, water
Wash, dry after obtain the lithium sulfur battery anode material of three-dimensional structure.It uses benzene sulfonic acid sodium salt as sulfur doping reagent to oxidation stone
Black alkene is doped, but its sulfur doping amount is few, adulterates uneven, and benzene sulfonic acid sodium salt is organic reagent, high cost, stability
Difference, it is harmful.And the material is used for lithium-sulfur cell, it is 1~3V in charging/discharging voltage scope, and current density is
Under conditions of 0.01C, in 1100mAh/g or so, after 100 circulations, charging and discharging capacity is in 900mAh/g for charging and discharging capacity
Left and right.
The content of the invention
Poor for existing lithium sulfur battery anode material chemical property, production cost is higher, it is impossible to produce in enormous quantities
The problems such as, it is an object of the invention to provide a kind of simple to operate, low cost, safety and environmental protection to prepare three-dimensional grapheme-sulphur multiple
The method of condensation material (SG), three-dimensional grapheme-sulphur composite sulfur doping amount prepared by the method is big and controllable, uniform doping,
With preferable chemical property, overcome the poorly conductive of sulphur in existing electrode material, volumetric expansion, active material loss and
The defects such as shuttle effect.
Present invention also offers a kind of three-dimensional grapheme-sulphur composite as lithium-sulfur cell material application, preparation
Lithium-sulfur cell shows high charge-discharge specific capacity at higher current densities and height follows stabilizing ring performance.
In order to realize above-mentioned technical purpose, the invention provides a kind of preparation method of three-dimensional grapheme-sulphur composite,
The method is that graphene oxide and elemental sulfur carried out into hydro-thermal reaction under alkaline environment, and hydro-thermal reaction product is by washing, cold
It is lyophilized dry, obtain final product.
In the prior art, sulfur doping graphene composite material is prepared by hydro-thermal method, generally using inorganic sulphide
Salt or organic sulfur compound use these sulfiding reagents to there are some drawbacks as sulfiding reagent, and the sulphurizing salt as exists
Hydrogen sulfide pernicious gas is easily produced in hydrothermal reaction process, and organic sulfide reagent cost is high, particularly these sulfiding reagents
The common defects of presence are that the doping to graphene oxide is low, and it is uneven to adulterate, the sulfur doping grapheme material of preparation
Chemical property improves limited in one's ability.And technical scheme, it is right in the basic conditions using elemental sulfur as sulfiding reagent
Graphene be doped it is modified, elemental sulfur be disproportionated in the basic conditions generation S2O3 2-,HSn -And S2-Deng on Graphene skeleton
Oxygen-containing functional group reacts, while the low price sulphur for producing can effectively facilitate the reduction of graphene oxide and the formation of sulphur, obtains
Three-dimensional connected porous structure, successfully by sulfur doping to Graphene skeleton, it is ensured that the high dispersion of sulphur, and sulphur and graphite
The good electrical contact of alkene.
Preferred scheme, the elemental sulfur is 1~20 with the weight ratio of graphene oxide:1.By adjusting elemental sulfur and oxygen
The ratio of graphite alkene controls doping of the sulphur in graphene oxide, and elemental sulfur can be adjusted in the larger context
Section, it is 1~20 to add weight ratio in described elemental sulfur/graphene oxide:Under 1, be conducive to obtaining the three-dimensional stone of function admirable
Black alkene-sulphur composite.
More preferably scheme, the graphene oxide is obtained by Graphene through Hummer methods.Described graphene oxide by
Natural individual layer, bilayer, the improved Hummer methods of flake graphite alkene of few layer are obtained.For example, the preparation of described graphene oxide
Step is:Graphene powder and nitrate are placed in round-bottomed flask and are stirred, concentrated sulfuric acid stirring is slowly added under conditions of ice bath,
Oxidant (such as high temperature hydrochlorate) stirring is added afterwards, and heating makes system become pasty state;Then deionized water is added dropwise again, continues
Stirring;It is eventually adding aqueous hydrogen peroxide solution to continue to stir, until there is dark brown suspension;Suspension is collected by centrifugation,
Deionized water is washed to neutrality and obtains graphene oxide.
Preferred scheme, OH in the alkaline environment-It is 1 with the ratio between the amount of material of elemental sulfur:1~10.Maintain alkalescence
OH in environment-Content within the specific limits, can guarantee that disproportionated reaction is smoothed out, may advantageously facilitate sulfur doping reaction carry out,
Can prevent hydrogen sulfide gas from escaping simultaneously.More preferably scheme, includes alkali metal hydroxide, such as in the alkaline environment
At least one of LiOH, NaOH, KOH, RuOH, CsOH.Preferred scheme, in the alkaline environment comprising NaOH and/or
KOH。
Preferred scheme, the temperature of the hydro-thermal reaction is 120~220 DEG C, and the time is 5~72 hours.During hydro-thermal reaction
Between more preferably 6~14 hours.Hydrothermal temperature is too low, and reaction rate can be caused not react even slowly relatively, and hydro-thermal
Reaction temperature is too high, then can cause caving in for three-dimensional porous structure.The hydro-thermal reaction time is too short, still not sufficiently reactive, will cause
The doping of sulphur is relatively low, and reaction in 72 hours or so has been carried out completely.
The method for preparing three-dimensional grapheme-sulphur composite of the invention is specific as follows:To the dispersion liquid of graphene oxide
The aqueous solution (concentration is no more than 10mol/L) of sulphur and alkali compounds is added in (concentration is no more than 25mg/mL), is heated up after stirring
Hydro-thermal reaction, then again through separation of solid and liquid, washing, freeze-drying, obtains three-dimensional grapheme-sulphur composite.
Present invention also offers a kind of application of three-dimensional grapheme-sulphur composite, it is applied to as positive electrode
Lithium-sulfur cell.
Three-dimensional graphene framework not only contributes to electric transmission in three-dimensional grapheme-sulphur composite prepared by the present invention,
The release of long-chain polysulfide can effectively be suppressed simultaneously, solid loose structure is adapted to Volume Changes, and be ion and electronics
Fast transferring provides passage;Sulphur has high dispersion in porous graphene skeleton, the utilization rate of sulphur is improve, so as to improve
The performance of lithium-sulfur cell;Good electrical contact between sulphur and Graphene, it is suppressed that the diffusion of the polysulfide of lithium.Therefore, incite somebody to action this
Invention is applied in lithium-sulfur cell, can suppress the diffusion of the polysulfide of lithium, and electric conductivity and mechanical strength, battery are can guarantee that again
Performance is increased dramatically.Additionally, flow of the present invention is simple, cheap, the design of lithium sulfur battery anode material can be met
It is required that.
The method that three-dimensional grapheme of the invention-sulphur composite is assembled into lithium-sulfur cell is:Will be a certain proportion of described
Three-dimensional grapheme-sulphur composite (SG), acetylene black and adhesive (such as PTFE) are mixed and made into 0.2mm thick, 0.8cm2Circle
Piece, then, is pressed on a stainless (steel) wire of diameter 15mm under 10MPa.2025 type button cells are assembled in hand
Operated in casing, lithium piece is separated as negative pole, centre with Celgard 2300, electrolyte is the LiTFSi of 1mol/L.Discharge and recharge
Test is using blue electricity battery test system (LAND CT2001A).
Preferably, the ratio of described three-dimensional grapheme-sulphur composite (SG), acetylene black and adhesive (such as PTFE)
Respectively 70wt%, 10wt%, 20wt%.
Compared to prior art, technical scheme has advantages below:
1st, three-dimensional grapheme of the invention-sulphur composite sulfur doping amount is big and controllable, and sulphur has a high dispersion, and with
Graphene has good electrical contact, can suppress the diffusion of the polysulfide of lithium, and electric conductivity and mechanical strength, energy are can guarantee that again
Enough improve the defects such as poorly conductive, volumetric expansion, active material loss and the shuttle effect of sulphur present in current lithium-sulfur cell,
Battery performance is increased dramatically.
2nd, three-dimensional grapheme of the invention-sulphur composite shows high charge-discharge specific capacity and Gao Xun for lithium-sulfur cell
Ring stability, under 1C, battery initial specific capacities are up to 1349.3mAhg-1, capability retention is 64.84%,
Under 0.2C, first discharge specific capacity is up to 1636.1mAhg-1, corresponding sulphur utilization rate is up to 97.67%.
3rd, three-dimensional grapheme of the invention-sulphur composite preparation flow is simple, and cost of material is relatively low, safety and environmental protection, full
Sufficient requirements of mass production.
Brief description of the drawings
【Fig. 1】It is the preparation flow sketch of embodiment 1;
【Fig. 2】The structural analysis figure of three-dimensional grapheme-sulphur composite SG-44 obtained in embodiment 1;Wherein, figure a is
The TEM figures of SG-44;Figure b schemes for the SEM of SG-44;Figure c is characterized for the EDS of SG-44;Figure d-f schemes for the HAADF-STEM of SG-44
And corresponding C element and S distribution diagram of element;Above characterization result can clearly show that prepared three-dimensional grapheme-sulphur
Composite shows internal interconnected three-dimensional porous structure on microcosmic, and S elements are fairly evenly entrained in graphite
In alkene skeleton.
【Fig. 3】XRD, XPS and Raman light stave of three-dimensional grapheme-sulphur composite SG-44 obtained in embodiment 1
Levy;Wherein figure a is the XRD comparison diagrams of SG-44 and elemental sulfur;Figure b is the Raman spectrum comparison diagram of SG-44 and graphene oxide;
Figure c and figure d are respectively high-resolution C1s and the S2p spectrogram of SG-44;Above characterization result further demonstrates that element sulphur successfully
It is entrained in Graphene skeleton, exists rather than in the form of elemental sulfur.
【Fig. 4】Three-dimensional grapheme-sulphur composite SG-44 and three-dimensional graphite obtained in embodiment 2 obtained in embodiment 1
The thermogravimetric analysis figure of alkene-sulphur composite SG-22;The sulfur content for obtaining SG-44 and SG-22 by thermogravimetric analysis is respectively 44%
With 22%.
【Fig. 5】It is by three-dimensional stone obtained in three-dimensional grapheme obtained in embodiment 1-sulphur composite SG-44 and embodiment 2
Black alkene-sulphur composite SG-22 is applied to the charge-discharge performance comparison diagram of battery after lithium-sulfur cell;The figure shows, in 1C
Under, the initial capacity of SG-44 is up to 1349.3mAhg-1, capability retention is that the initial capacity of 64.84%, SG-22 is then
1210.9mA·h·g-1, performance is poor compared with SG-44, therefore the content of sulphur is higher, and battery performance is more excellent.
【Fig. 6】Three-dimensional grapheme obtained in embodiment 1-sulphur composite SG-44 is applied to the electrification after lithium-sulfur cell
Learn the performance test results;Wherein, figure a is charge-discharge performance curve of the battery under 0.2C;Figure b be battery in 0.2C, no
With voltage under cycle-index with specific capacity change;Figure c be battery under 4C, the long circulating performance of 150 times;Above electrochemistry
Display can be characterized, first discharge specific capacities of the SG-44 under 0.2C is up to 1636.1mAhg-1, corresponding sulphur utilization rate is high
Up to 97.67%, and still there is specific discharge capacity higher and good cyclical stability in the case of high magnification current charge-discharge electricity.
Specific embodiment
With reference to specific embodiment, the present invention is further elaborated.These embodiments are interpreted as being merely to illustrate
The present invention rather than limit the scope of the invention.After the content for having read record of the present invention, based on of the invention
The various changes or modification that principle is made to the present invention equally fall into claims of the present invention limited range.
Embodiment 1
Step (1):The preparation of graphene oxide
The sodium nitrate of the graphite powder of 2.0g and 1.5g is placed in round-bottomed flask and is stirred, be slowly added under conditions of ice bath
The concentrated sulfuric acid stirring 2h of 100ml, adds the potassium permanganate stirring 30min of 10.0g afterwards, is heated to 35 DEG C until becoming pasty state.
Then the deionized water of 100ml is added dropwise, continues to stir 2h, be eventually adding the aqueous hydrogen peroxide solution of 10ml 30%, be added dropwise
The deionized water of 200ml continues to stir 2h, dark brown suspension occurs.Suspension is collected by centrifugation, deionized water wash to
Neutrality obtains graphene oxide.
Step (2);The preparation of three-dimensional grapheme-sulphur composite SG-44
First, take 80mL it is ultrasonically treated after graphene oxide aqueous dispersions (0.5mg/mL) in 100mL hydrothermal reaction kettles
In, then it is separately added into 0.6g sulphur powders and 2mL NaOH solutions (3M), and in reacting 12h at 180 DEG C.After naturally cooling to room temperature
Product is repeatedly washed, then freeze-drying 48h, then product is dispersed in the dilution heat of sulfuric acid of 1mM remove it is any can
The impurity of energy, product is collected finally by vacuum filtration, and is washed with deionized to neutrality, and freeze-drying again is obtained finally
Product, labeled as SG-44.
Step (3):The assembling of battery and the test of battery performance
By three-dimensional grapheme obtained in the present embodiment of 70wt%-sulphur composite SG-44,10wt% acetylene black and
The PTFE (adhesive) of 20wt% is mixed and made into 0.2mm thickness, 0.8cm2Disk, then, one is pressed under 10MPa
On the stainless (steel) wire of diameter 15mm.Being assembled in glove box for 2025 type button cells is operated, and lithium piece is used as negative pole, centre
Celgard 2300 is separated, and electrolyte is the LiTFSi of 1mol/L.Charge-discharge test is using blue electricity battery test system (LAND
CT2001A)。
As shown in Figure 2, three-dimensional grapheme manufactured in the present embodiment-sulphur composite SG-44 shows inside on microcosmic
Interconnected three-dimensional porous structure, and S elements are fairly evenly entrained in Graphene skeleton.
From the figure 3, it may be seen that in three-dimensional grapheme manufactured in the present embodiment-sulphur composite SG-44, element sulphur is successfully mixed
It is miscellaneous in Graphene skeleton, rather than in the form of elemental sulfur exist.
As shown in Figure 4, in three-dimensional grapheme manufactured in the present embodiment-sulphur composite SG-44.The content of sulphur is
44%.
As shown in Figure 5, after three-dimensional grapheme manufactured in the present embodiment-sulphur composite SG-44 being applied into lithium-sulfur cell,
Under 1C, battery initial capacity is up to 1349.3mAhg-1, capability retention is 64.84%, excellent performance.
It will be appreciated from fig. 6 that after three-dimensional grapheme manufactured in the present embodiment-sulphur composite SG-44 is applied into lithium-sulfur cell,
First discharge specific capacity of the battery under 0.2C is up to 1636.1mAhg-1, corresponding sulphur utilization rate is up to 97.67%, and
Still there is specific discharge capacity higher and good cyclical stability in the case of high magnification current charge-discharge electricity.
Embodiment 2
The step of preparation of step (1) graphene oxide is with embodiment 1 (1)
The preparation of step (2) three-dimensional grapheme-sulphur composite SG-27
First, take 80mL it is ultrasonically treated after graphene oxide aqueous dispersions (1mg/mL) in 100mL hydrothermal reaction kettles,
Then it is separately added into 0.6g sulphur powders and 2mL NaOH solutions (3M), and in reacting 12h at 180 DEG C.It is right after room temperature to naturally cool to
Product is repeatedly washed, then freeze-drying 48h, then product is dispersed in the dilution heat of sulfuric acid of 1mM and is removed any possibility
Impurity, collect product finally by vacuum filtration, and be washed with deionized to neutrality, freeze-drying again is finally produced
Thing, labeled as SG-27.
The assembling of step (3) battery and the test of battery performance
By three-dimensional grapheme obtained in the present embodiment of 70wt%-sulphur composite SG-44,10wt% acetylene black and
The PTFE (adhesive) of 20wt% is mixed and made into 0.2mm thickness, and then the disk of 0.8cm2, is pressed into one under 10MPa
On the stainless (steel) wire of diameter 15mm.Being assembled in glove box for 2025 type button cells is operated, and lithium piece is used as negative pole, centre
Celgard 2300 is separated, and electrolyte is the LiTFSi of 1mol/L.Charge-discharge test is using blue electricity battery test system (LAND
CT2001A)。
As shown in Figure 4, in three-dimensional grapheme manufactured in the present embodiment-sulphur composite SG-27.The content of sulphur is
27%.
As shown in Figure 5, after three-dimensional grapheme manufactured in the present embodiment-sulphur composite SG-27 being applied into lithium-sulfur cell,
Under 1C, battery initial capacity is 1210.9mAhg-1, performance is poor compared with embodiment 1.By comparative example 1 and embodiment 2
As can be seen that for the three-dimensional grapheme prepared by the present invention-sulphur composite, the content of sulphur is higher, the lithium sulphur electricity for obtaining
Pond performance is more excellent.
Claims (8)
1. the preparation method of a kind of three-dimensional grapheme-sulphur composite, it is characterised in that:By graphene oxide and elemental sulfur in alkali
Property environment under carry out hydro-thermal reaction, hydro-thermal reaction product is obtained final product by washing, freeze-drying.
2. the preparation method of three-dimensional grapheme according to claim 1-sulphur composite, it is characterised in that:The simple substance
Sulphur is 1~20 with the weight ratio of graphene oxide:1.
3. the preparation method of three-dimensional grapheme according to claim 2-sulphur composite, it is characterised in that:The oxidation
Graphene is obtained by Graphene through Hummer methods.
4. the preparation method of three-dimensional grapheme according to claim 1-sulphur composite, it is characterised in that:The alkalescence
OH in environment-It is 1 with the ratio between the amount of material of elemental sulfur:1~10.
5. the preparation method of three-dimensional grapheme according to claim 4-sulphur composite, it is characterised in that:The alkalescence
Comprising at least one of LiOH, NaOH, KOH, RuOH, CsOH in environment.
6. the preparation method of three-dimensional grapheme according to claim 5-sulphur composite, it is characterised in that:The alkalescence
NaOH and/or KOH is included in environment.
7. the preparation method of the three-dimensional grapheme according to any one of claim 1~6-sulphur composite, it is characterised in that:
The temperature of the hydro-thermal reaction is 120~220 DEG C, and the time is 5~72 hours.
8. the application of three-dimensional grapheme-sulphur composite prepared by preparation method described in any one of claim 1~7, its feature
It is:Lithium-sulfur cell is applied to as positive electrode.
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