CN108257796B - A kind of reduction fluorinated graphene-cobalt manganese alloy oxide nano-slice compound preparation method and applications - Google Patents
A kind of reduction fluorinated graphene-cobalt manganese alloy oxide nano-slice compound preparation method and applications Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
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- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
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- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
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- H—ELECTRICITY
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
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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
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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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
- Y02E60/13—Energy storage using capacitors
Abstract
The present invention provides a kind of reduction fluorinated graphene-cobalt manganese alloy oxide nano-slice compound preparation method, substantially reduction fluorinated graphene is made with solvothermal and high-temperature heat treatment secondary reduction in preparation method, the cobalt manganese alloy oxide nano-slice for going out meso-hole structure to restore fluorinated graphene as substrate growth again, the compound of reduction fluorinated graphene and cobalt manganese alloy oxide nano-slice is made finally by high-temperature calcination.Reduction fluorinated graphene produced by the present invention/cobalt manganese alloy oxide nano-slice compound can be used for anode composite material of lithium sulfur battery or supercapacitor, and the lithium-sulfur cell and supercapacitor assembled significantly improves chemical property relative to simple reduction fluorinated graphene or cobalt manganese alloy.
Description
Technical field
The invention belongs to energy application, specifically a kind of reduction fluorinated graphene-cobalt manganese alloy oxide nano-slice
The preparation method and applications of compound.
Background technique
Increasingly serious energy problem and environmental problem is the two big basic problems for perplexing mankind nowadays.It is main as the mankind
The fossil fuel of one of the energy, on the one hand because it in the reserves finiteness of the earth and is difficult to reproducibility, on the other hand to the big of it
Amount consumption can bring very severe existence bad border to the mankind.Since reform and opening-up with the fast development of Chinese economy, to change
The consumption of stone fuel is also to increase year by year, and air pollution is extremely serious.Therefore, to the pursuit of clean energy resource and renewable energy at
For the theme that various countries competitively develop, solar energy, wind energy, water energy, supercapacitor, secondary cell, fuel electricity are such as greatly developed
The new cleaning fuels such as pond become the most important thing, and China is also a large amount of manpower of investment and money in these areas in recent years
Gold.It is secondary lithium battery industrialization already in charge-discharge battery and big portion to be successfully applied in these new energies
Divide in portable electronic device.But due to the limited capacity of traditional lithium battery itself, it can not meet it in large-scale energy-storage system
With the utilization in the electric car of long range traveling (500KM or so)；Therefore people have to be sought for energy density bigger
Energy-storage battery to meet growing energy demand.Lithium-sulfur cell was considered as most one of potential and secondary filled in recent years
Discharge energy-storage battery, the theoretical energy density possessed are up to 2600Whkg-1, about (cobalt is sour for traditional commerce lithium ion battery
Lithium-graphite cell is about 384Whkg-1) more than 5 times, therefore it is enough have the electric car in long-distance running and large-scale energy storage system
Potential application in system.Secondly, itself having up to 1675mAhg using S as positive electrode-1It is had both while theoretical specific capacity
The advantages such as cheap, pollution-free, rich reserves, constantly cause the extensive concern of world related science researcher.
Supercapacitor has power density height, charge and discharge as a kind of power supply between traditional capacitor and battery
The many advantages such as the electric time is short, have extended cycle life, operating temperature range is wide, in the energy, traffic, communication, power electronics, national defence etc.
There is very wide application prospect in field.But compared with traditional secondary cell, energy density is lower to be largely determined by electricity
The lower specific capacitance of pole material.Fake capacitance material has higher theoretical specific capacitance relative to electric double layer capacitance material, is most to have
Wish the material of raising super capacitor energy density.However there is also at high cost, material uses for current fake capacitance material
The problems such as rate is low, high rate performance and cyclical stability are insufficient.
Summary of the invention
In view of the above shortcomings of the prior art, the present invention provides a kind of reduction fluorinated graphene-cobalt manganese alloy oxide and receives
The preparation method of rice piece compound, compound obtained have high fold honeycomb layered structure, and chemical property is superior.Using
The shuttle effect that can effectively contain more sulphions in lithium-sulfur cell to lithium-sulfur cell, being applied on fake capacitance electrode can have
Effect improves the problems such as its high rate performance and insufficient cyclical stability.
A kind of technical solution provided by the invention: reduction fluorinated graphene-cobalt manganese alloy oxide nano-slice compound
Preparation method includes the following steps:
(1) it weighs a certain amount of fluorographite to be dissolved in solvent, specific reduction auxiliary agent is added, ultrasonic disperse dissolves, then
It is transferred to solvent thermal reaction in reaction kettle, finally filters and is dried to obtain reduction fluorinated graphene head product；
(2) by the resulting reduction fluorinated graphene head product of step (1) and nitrogenous compound, anionic surfactant is mixed
It closes, is subsequently placed in the tube furnace for be connected with nitrogen and calcines, product is washed through ethanol solution, washed, and is filtered, is dried to obtain and goes back protofluorine
Graphite alkene；
(3) the reduction fluorinated graphene in step (2) is weighed, deionized water ultrasonic disperse is added to form reduction fluorinated graphene
Suspension, then weigh again potassium citrate, cobalt-manganese salt mixture, urea difference it is molten in deionized water, obtain concentration be (0.1-
10) potassium citrate solution of g/ml, mass fraction are the cobalt-manganese salt solution of (5-30) %, and concentration is that (0.1-10) g/ml urea is molten
Liquid；
(4) the resulting reduction fluorinated graphene suspension of step (3) is first mixed with potassium citrate solution, cobalt is then added dropwise
Manganese salt solution, then urea liquid is added dropwise, finally to the appropriate ammonium hydroxide of mixed solution and dripping, it is ultrasonic again to alkalinity to adjust pH value of solution；
(5) solution of step (4) is transferred to heat in ptfe autoclave and is reacted, solution is filtered later
Then it dries；
(6) step (5) resulting product is placed in quartz ampoule and is calcined in air atmosphere, the black powder finally obtained
As restore the compound of fluorinated graphene and cobalt manganese alloy oxide nano-slice.
Further, specific reduction auxiliary agent is one of sodium ethoxide, sodium oxalate or both mixing in the step (1)
The addition mass ratio of object, fluorographite and specific reduction auxiliary agent is 1:0.5-5.
Further, the solvent in the step (1) is by dehydrated alcohol, methanol, isopropanol, n-butanol, N, N- dimethyl
1:1 is mixed to get by volume for one of formamide, N-Methyl pyrrolidone or a variety of mixtures and deionized water.
Further, in the step (1), 0.5~3h of ultrasonic time, solvent thermal reaction temperature is 80~250 DEG C, the time
5~20h, drying temperature are 60~80 DEG C, 0.5~5h of drying time.
Further, step (2) nitrogenous compound be one of hexamethylenetetramine, urea, melamine or
More than one mixture, anionic surfactant are neopelex, dodecyl sodium sulfate, dodecyl sulphur
One of sour sodium is a variety of, the reduction fluorinated graphene head product and nitrogenous compound, and anionic surfactant presses matter
Measure than 1:(0.1~10): the ratio mixing of (0.5~5).
Further, calcination temperature is 300~1200 DEG C, 1~10h of calcination time in the step (2), dry temperature
It is 60~80 DEG C, 0.5~5h of drying time.
Further, cobalt-manganese salt mixture is that cobalt salt and manganese salt 1:1 in mass ratio are mixed in the step (3),
Middle cobalt salt is one of cobalt nitrate, cobaltous sulfate, cobalt chloride, cobalt oxalate, and manganese salt is manganese nitrate, manganese sulfate, manganese chloride, manganese oxalate
One of.
Further, the pH value of solution is adjusted to 8-10 in the step (4), restores fluorinated graphene suspension, citric acid
Potassium solution, cobalt-manganese salt solution, urea liquid 1:(0.1-10 by volume): (0.1-10): (0.1-10) is added dropwise.
Further, 150~200 DEG C of heating temperature, 100~300min of heating time in the step (5), drying temperature
It is 60~80 DEG C, in step (6), 20~60min of calcination time, 400-1000 DEG C of calcination temperature.
A kind of reduction fluorinated graphene-cobalt manganese alloy oxide nano-slice compound application, the reduction fluorinated graphene-
Cobalt manganese alloy oxide nano-slice compound is compound rear for lithium-sulfur cell for electrode of super capacitor or with sulphur melting.
The reduction fluorinated graphene-cobalt manganese alloy oxide nano-slice compound further goes back protofluorine with sulphur melt-synthesizing
Graphite alkene-cobalt manganese alloy oxide nano-slice/sulphur composite material, specific steps are as follows: weigh the reduction fluorination stone of certain mass
Black alkene-cobalt manganese alloy oxide nano-slice composite powder and distillation sulfur powder, wherein sublimed sulfur proportion be 40%~
70%, the two is mixed and is ground to mix powder of the granularity less than 50 mesh；It will mixing under 120~180 DEG C of molten conditions
Object magnetic agitation 0.5-2h；It is crushed after mixture after stirring is taken out and regrinds the mixture powder for granularity less than 50 mesh
End, as reduction fluorinated graphene-cobalt manganese alloy oxide nano-slice/sulphur composite material, the reduction fluorinated graphene-cobalt manganese
Alloyed oxide nanometer sheet/sulphur composite material is used for lithium-sulfur cell.
Reduction fluorinated graphene is made with solvothermal and high-temperature heat treatment secondary reduction in the present invention, then to restore fluorination
Graphene is the cobalt manganese alloy oxide nano-slice that substrate growth goes out meso-hole structure, then reduction fluorination stone is made by high-temperature calcination
The compound of black alkene and cobalt manganese alloy oxide nano-slice, preparation method are simple and efficient, and compound obtained has high fold
Honeycomb layered structure, chemical property are superior.
Detailed description of the invention
Fig. 1 is high fold stratiform reduction fluorinated graphene-cobalt manganese alloy oxide nano-slice compound transmission electron microscope TEM figure
Picture.
1 is more sulphion solution in Fig. 2, and 2 be absorption of the conductive black to more sulphions, and 3 be cobalt-manganese salt solution to more sulphur
The absorption of ion.
Fig. 3 is reduction fluorinated graphene-cobalt manganese alloy oxide nano-slice/sulfur compound electrode and reduction fluorographite
Multiplying power figure of the alkene/sulfur electrode under different current densities.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to the accompanying drawings and embodiments, right
The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and
It is not used in the restriction present invention.As long as in addition, technical characteristic involved in the various embodiments of the present invention described below
Not constituting a conflict with each other can be combined with each other.
Embodiment 1
The fluorographite powder 1g that fluorine/atom ratio is 0.02 is weighed, sodium ethoxide 0.25g, sodium oxalate 0.25g are placed in
In 250ml vial, be added 150ml mixed solvent (dehydrated alcohol, isopropanol, DMF by volume 1:1:1 mixing after with go
1:1 is mixed ionized water by volume), ultrasonic disperse 0.5h.Then 80 DEG C of reaction 5h in 100ml reaction kettle are moved to.Reaction solution warp
It filters, reduction fluorinated graphene head product is obtained after 60 DEG C of dry 1h.Take product 1g, hexamethylenetetramine 0.1g, 12
Sodium alkyl benzene sulfonate 0.5g is put into 300 DEG C of calcining 10h in the tube furnace for be connected with nitrogen after mixing.Product passes through ethyl alcohol respectively later
Solution washing, washing, then filtered, dry (60 DEG C, 1h) obtain reduction fluorinated graphene.Weigh reduction fluorinated graphene 0.5g
In 250ml beaker, 70ml deionized water, 1ml potassium citrate solution (0.1g/ml), after mixing in magnetic stirring is added
The lower cobalt-manganese salt mixture solution (CoSO that 1ml mass fraction 5% is successively added dropwise4With Mn (NO3)2The mixing of 1:1 in mass ratio), 1ml
Urea liquid (0.1g/ml) is finally added dropwise ammonium hydroxide and adjusts solution PH to 8-10, ultrasonic 2h.Mixed solution after reaction is transferred to
100min is reacted at 150 DEG C in 100ml reaction kettle, filters drying later.Desciccate is calcined at 400 DEG C in tube furnace
30min.Products therefrom is to restore fluorinated graphene/cobalt manganese alloy oxide nano-slice compound.
Embodiment 2
The fluorographite powder 1g that fluorine/atom ratio is 0.02 is weighed, sodium ethoxide 2g is placed in 250ml vial, adds
Enter the mixed solvent (mixing after methanol, n-butanol, NMP 1:1:1 mixing by volume with deionized water 1:1) of 150ml, ultrasound point
Dissipate 1.5h.Then 150 DEG C of reaction 10h in 100ml reaction kettle are moved to.Reaction solution obtains going back protofluorine through filtering dry (60 DEG C, 3h)
Graphite alkene head product.Take product 1g, urea admixture (urea, melamine 1:1 in mass ratio mixing) 5g, dodecyl
Benzene sulfonic acid sodium salt mixture (neopelex is mixed with lauryl sodium sulfate mass ratio 1:1) 2g is put into after mixing and is connected with
700 DEG C of calcining 5h in the tube furnace of nitrogen.Product passes through ethanol solution washing, washing respectively later, then is filtered, dries (60
DEG C, 3h) obtain reduction fluorinated graphene.Above-mentioned desciccate 0.5g is weighed in 250ml beaker, 70ml deionized water is added,
5ml potassium citrate solution (0.3g/ml), the cobalt-manganese salt that 3ml mass fraction 15% is successively added dropwise after mixing under magnetic stirring are mixed
Polymer solution (CoSO4With Mn (NO3)2The mixing of 1:1 in mass ratio), ammonium hydroxide adjustment is finally added dropwise in 5ml urea liquid (0.5g/ml)
Solution PH is to 8-10, ultrasonic 2h.Mixed solution after reaction is transferred in 100ml reaction kettle at 200 DEG C and reacts 300min, later
Filter drying.Desciccate calcines 1h at 400 DEG C in tube furnace.Products therefrom is to restore fluorinated graphene/cobalt manganese alloy
Oxide nano-slice compound.
Embodiment 3
The fluorographite powder 1g that fluorine/atom ratio is 0.02 is weighed, sodium oxalate 5g is placed in 250ml vial, adds
Enter the mixed solvent (mixing after DMF, NMP 1:1 mixing by volume with deionized water 1:1) of 150ml, ultrasonic disperse 3h.Then
Move to 250 DEG C of reaction 20h in 100ml reaction kettle.Reaction solution is filtered dry (80 DEG C, 3h), at the beginning of obtaining reduction fluorinated graphene
Product.Product 1g is taken, (hexamethylenetetramine, urea, melamine 1:1:1 in mass ratio are mixed for hexamethylenetetramine mixture
Close) 10g, dodecyl sodium sulfate mixture (dodecyl sodium sulfate is mixed with lauryl sodium sulfate mass ratio 1:1) 5g mix
1000 DEG C of calcining 1h in the tube furnace for be connected with nitrogen are put into after even.Product passes through ethanol solution washing, washing respectively later, then passes through
It filters, dry (80 DEG C, 3h) obtain reduction fluorinated graphene.Above-mentioned desciccate 0.5g is weighed in 250ml beaker, is added
70ml deionized water, 3ml potassium citrate solution (0.6g/ml), is successively added dropwise 5ml mass fraction after mixing under magnetic stirring
25% cobalt-manganese salt mixture solution (CoSO4With Mn (NO3)2The mixing of 1:1 in mass ratio), 2ml urea liquid (0.7g/ml), most
Ammonium hydroxide is added dropwise afterwards and adjusts solution PH to 8-10, ultrasonic 2h.Mixed solution after reaction is transferred in 100ml reaction kettle at 200 DEG C
200min is reacted, filters drying later.Desciccate calcines 30min at 500 DEG C in tube furnace.Products therefrom is to go back protofluorine
Graphite alkene/cobalt manganese alloy oxide nano-slice compound.
Application example 1
Reduction fluorinated graphene-cobalt manganese alloy oxide nano-slice compound obtained in embodiment 1 is configured to 15mg/
The solution of mL is applied in electrode of super capacitor.Wherein electrolyte is 0.8molL-1H2SO4, diaphragm is
Celgard3501, binder nafion ratio are 8%, deionized water and isopropanol ratios 1:6.By solution drop coating in graphitic carbon
Button capacitor is assembled into using two electrode slices identical in quality as cathode and anode as electrode slice on paper.Measurement is different
The specific capacity of capacitor under current density, the results are shown in Table 1, and when current density is in 2A/g, specific capacity reaches 1550Fg-1.When current density increases to 30Ag-1, still remain in 980Fg-1。
Table 1 restores fluorinated graphene-cobalt manganese alloy oxide nano-slice compound capacitor capacitance
Application example 2
Reduction fluorinated graphene-cobalt manganese alloy oxide nano-slice compound obtained in embodiment 2 is pressed with sublimed sulfur
Mass ratio 1:1 mixing, be ground to granularity less than after the mix powder of 50 mesh under the conditions of 150 DEG C magnetic agitation 1h, after cooling
Mix powder of the granularity less than 50 mesh is regrind, it is multiple that reduction fluorinated graphene/cobalt manganese alloy oxide nano-slice/sulphur is made
Condensation material.The composite material is applied to lithium-sulfur rechargeable battery, binder is sodium carboxymethylcellulose (CMC-Na) and butylbenzene rubber
Glue (SBR), CMC-Na:SBR: reduction fluorinated graphene/cobalt manganese alloy oxide nano-slice/sulphur composite material: elemental sulfur:
The mass ratio of Super-P is 6:6:20:48:20, and grinding slurry carries out smear, carries out tabletting conduct after 80 DEG C of vacuum drying 12h
Positive electrode, for lithium metal as cathode, electrolyte selects addition 2wt%LiNO31M1,3- dioxolanes (DOL)/ethylene glycol
The mixed solution (DEM, DOL volume ratio are 1:1) of two (trifluoromethane sulfonic acid) imine lithium (LiTFSI) of dimethyl ether (DME) base, every
Film selects Celgard2400, the assembled battery under argon gas protection in glove box.As a control group using reduction fluorinated graphene,
It carries out assembled battery under the same conditions and test, test result is shown in Fig. 3, using reduction fluorographite produced by the present invention
Alkene-cobalt manganese alloy oxide nano-slice compound assembling battery, when charging and discharging currents density is 0.1C, discharge specific volume for the first time
Amount is about 1100mAh/g, and after 50 circulations, specific discharge capacity is still maintained at about 850mAh/g.
Application example 3
Reduction fluorinated graphene/cobalt manganese alloy oxide nano-slice compound obtained in embodiment 1 is configured to 5mg/
The solution of mL, in 2molL-1Li2SO4As electro-chemical test is carried out in the three-electrode system of electrolyte, Ag/AgCl is reference
Electrode, platinum electrode are auxiliary electrode.Binder nafion mass accounts for the 6% of active material, deionized water and isopropanol ratios
1:7 is used as working electrode after dry by solution drop coating on vitreous carbon.CV cyclic voltammetric is carried out under voltage 0-1.6V range
Test, test result are shown in Table 2, show that material has good capacitance behavior and good high rate performance.
Fluorinated graphene-cobalt manganese alloy oxide nano-slice compound capacitor is restored under 2 different scanning rates of table
The foregoing is merely the detailed descriptions of specific embodiments of the present invention, do not limit the present invention with this, all at this
Made any modifications, equivalent replacements, and improvements etc. in the mentality of designing of invention, should be included in protection scope of the present invention it
It is interior.
Claims (10)
1. a kind of reduction fluorinated graphene-cobalt manganese alloy oxide nano-slice compound preparation method, it is characterised in that including
Following steps:
(1) it weighs a certain amount of fluorographite to be dissolved in solvent, reduction auxiliary agent is added, ultrasonic disperse dissolution is then transferred to anti-
Solvent thermal reaction in kettle is answered, finally filters and is dried to obtain reduction fluorinated graphene head product；
(2) by the resulting reduction fluorinated graphene head product of step (1) and nitrogenous compound, anionic surfactant is mixed,
It is subsequently placed in the tube furnace for be connected with nitrogen and calcines, product is washed through ethanol solution, washed, and is filtered, is dried to obtain reduction fluorination
Graphene；
(3) the reduction fluorinated graphene in step (2) is weighed, adds deionized water ultrasonic disperse to form reduction fluorinated graphene suspended
Liquid, then weigh again potassium citrate, cobalt-manganese salt mixture, urea difference it is molten in deionized water, obtain concentration be (0.1-10)
The potassium citrate solution of g/ml, mass fraction are the cobalt-manganese salt solution of (5-30) %, and concentration is (0.1-10) g/ml urea liquid；
(4) the resulting reduction fluorinated graphene suspension of step (3) is first mixed with potassium citrate solution, cobalt-manganese salt is then added dropwise
Solution, then urea liquid is added dropwise, finally to the appropriate ammonium hydroxide of mixed solution and dripping, it is ultrasonic again to alkalinity to adjust pH value of solution；
(5) solution of step (4) is transferred to heat in ptfe autoclave and is reacted, later then solution is filtered
Drying；
(6) step (5) resulting product is placed in quartz ampoule and is calcined in air atmosphere, the black powder finally obtained is
Restore the compound of fluorinated graphene and cobalt manganese alloy oxide nano-slice.
2. reduction fluorinated graphene-cobalt manganese alloy oxide nano-slice compound preparation method according to claim 1,
It is characterized by: reduction auxiliary agent is one of sodium ethoxide, sodium oxalate or both mixture, fluorographite in the step (1)
Addition mass ratio with reduction auxiliary agent is 1:0.5-5；Solvent in the step (1) is by dehydrated alcohol, methanol, isopropanol, just
One of butanol, n,N-Dimethylformamide, N-Methyl pyrrolidone or a variety of mixtures and deionized water 1:1 by volume
It is mixed to get.
3. reduction fluorinated graphene-cobalt manganese alloy oxide nano-slice compound preparation method according to claim 1,
It is characterized by: 0.5~3h of ultrasonic time, solvent thermal reaction temperature is 80~250 DEG C in the step (1), the time 5~
20h, drying temperature are 60~80 DEG C, 0.5~5h of drying time.
4. reduction fluorinated graphene-cobalt manganese alloy oxide nano-slice compound preparation method according to claim 1,
It is characterized by: step (2) nitrogenous compound be one of hexamethylenetetramine, urea, melamine or two kinds with
On mixture, anionic surfactant is neopelex, dodecyl sodium sulfate, in lauryl sodium sulfate
One or more, the reduction fluorinated graphene head product and nitrogenous compound, anionic surfactant in mass ratio 1:
(0.1~10): the ratio mixing of (0.5~5).
5. reduction fluorinated graphene-cobalt manganese alloy oxide nano-slice compound preparation method according to claim 1,
It is characterized by: in the step (2) calcination temperature be 300~1200 DEG C, 1~10h of calcination time, dry temperature be 60~
80 DEG C, 0.5~5h of drying time.
6. reduction fluorinated graphene-cobalt manganese alloy oxide nano-slice compound preparation method according to claim 1,
It is characterized by: cobalt-manganese salt mixture is that cobalt salt and manganese salt 1:1 in mass ratio are mixed in the step (3), wherein cobalt salt
For one of cobalt nitrate, cobaltous sulfate, cobalt chloride, cobalt oxalate, manganese salt is manganese nitrate, manganese sulfate, manganese chloride, one in manganese oxalate
Kind.
7. reduction fluorinated graphene-cobalt manganese alloy oxide nano-slice compound preparation method according to claim 1,
It is characterized by: the pH value of solution is adjusted to 8-10 in the step (4), reduction fluorinated graphene suspension, potassium citrate solution,
Cobalt-manganese salt solution, urea liquid 1:(0.1-10 by volume): (0.1-10): (0.1-10) is added dropwise.
8. reduction fluorinated graphene-cobalt manganese alloy oxide nano-slice compound preparation method according to claim 1,
It is characterized by: 150~200 DEG C of heating temperature, 100~300min of heating time in the step (5), drying temperature is 60~
80 DEG C, in step (6), 20~60min of calcination time, 400-1000 DEG C of calcination temperature.
9. reduction fluorinated graphene-cobalt manganese alloy oxide nano-slice of any one of -8 method preparations is compound according to claim 1
The application of object, it is characterised in that: the reduction fluorinated graphene-cobalt manganese alloy oxide nano-slice compound is used for supercapacitor
Electrode is compound rear for lithium-sulfur cell with sulphur melting.
10. reduction fluorinated graphene-cobalt manganese alloy oxide nano-slice compound application according to claim 9,
Be characterized in that: the reduction fluorinated graphene-cobalt manganese alloy oxide nano-slice compound is further melt-synthesized with sulphur and is restored
Fluorinated graphene-cobalt manganese alloy oxide nano-slice/sulphur composite material, specific steps are as follows: weigh the reduction fluorination of certain mass
Graphene-cobalt manganese alloy oxide nano-slice composite powder and distillation sulfur powder, wherein sublimed sulfur proportion be 40%~
70%, the two is mixed and is ground to mix powder of the granularity less than 50 mesh；It will mixing under 120~180 DEG C of molten conditions
Object magnetic agitation 0.5-2h；It is crushed after mixture after stirring is taken out and regrinds the mixture powder for granularity less than 50 mesh
End, as reduction fluorinated graphene-cobalt manganese alloy oxide nano-slice/sulphur composite material, the reduction fluorinated graphene-cobalt manganese
Alloyed oxide nanometer sheet/sulphur composite material is used for lithium-sulfur cell.
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