CN110136989A - A kind of positive, preparation method and supercapacitor obtained - Google Patents
A kind of positive, preparation method and supercapacitor obtained Download PDFInfo
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- CN110136989A CN110136989A CN201910498609.9A CN201910498609A CN110136989A CN 110136989 A CN110136989 A CN 110136989A CN 201910498609 A CN201910498609 A CN 201910498609A CN 110136989 A CN110136989 A CN 110136989A
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- 238000002360 preparation method Methods 0.000 title claims description 35
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 91
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 81
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims abstract description 42
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 33
- 238000000034 method Methods 0.000 claims description 22
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 21
- 239000004202 carbamide Substances 0.000 claims description 21
- 239000000243 solution Substances 0.000 claims description 19
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical group S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 16
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 16
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 16
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 238000004140 cleaning Methods 0.000 claims description 13
- 239000002184 metal Substances 0.000 claims description 13
- 229910052751 metal Inorganic materials 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 12
- 239000011259 mixed solution Substances 0.000 claims description 11
- 229910001868 water Inorganic materials 0.000 claims description 11
- 229910052799 carbon Inorganic materials 0.000 claims description 10
- 239000003792 electrolyte Substances 0.000 claims description 10
- 239000002002 slurry Substances 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 229910017052 cobalt Inorganic materials 0.000 claims description 9
- 239000010941 cobalt Substances 0.000 claims description 9
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 9
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 8
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 8
- 229910052742 iron Inorganic materials 0.000 claims description 8
- 229910052708 sodium Inorganic materials 0.000 claims description 8
- 239000011734 sodium Substances 0.000 claims description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 7
- 239000004744 fabric Substances 0.000 claims description 7
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 7
- 241000446313 Lamella Species 0.000 claims description 5
- 239000000853 adhesive Substances 0.000 claims description 5
- 230000001070 adhesive effect Effects 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 5
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 229910052717 sulfur Inorganic materials 0.000 claims description 5
- 239000011593 sulfur Substances 0.000 claims description 5
- -1 polyethylene Polymers 0.000 claims description 4
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 3
- 239000011245 gel electrolyte Substances 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims 1
- 238000002156 mixing Methods 0.000 claims 1
- 229920000573 polyethylene Polymers 0.000 claims 1
- 239000007772 electrode material Substances 0.000 abstract description 32
- 238000006479 redox reaction Methods 0.000 abstract description 3
- 239000000463 material Substances 0.000 description 15
- 239000000835 fiber Substances 0.000 description 12
- 239000003990 capacitor Substances 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 239000002122 magnetic nanoparticle Substances 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000002131 composite material Substances 0.000 description 5
- 230000007812 deficiency Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 238000011065 in-situ storage Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000005518 electrochemistry Effects 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- 239000005864 Sulphur Substances 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- INPLXZPZQSLHBR-UHFFFAOYSA-N cobalt(2+);sulfide Chemical compound [S-2].[Co+2] INPLXZPZQSLHBR-UHFFFAOYSA-N 0.000 description 2
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000003487 electrochemical reaction Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 230000036632 reaction speed Effects 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000004073 vulcanization Methods 0.000 description 2
- 229910002546 FeCo Inorganic materials 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 150000001868 cobalt Chemical group 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 150000002815 nickel Chemical group 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
- H01G11/30—Electrodes characterised by their material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- Nanotechnology (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
The present invention relates to a kind of anode, described just extremely flexible electrode, the anode include graphene film and the bimetallic sulfide being attached on the graphene film.Bimetallic sulfide is compared to monometallic sulfide in the prior art in the present invention, the conductivity of bimetallic sulfide electrode material is several times even tens times of monometallic sulfide, compensate for the poor circulation of monometallic sulfide electrode material, the disadvantage of multiplying power property difference.Furthermore, redox reaction can occur for two components, it is possible thereby to provide bigger specific capacitance, the bimetallic sulfide that the present invention spreads macroion and the Flexible graphene piece collaborative combination with high conductivity, it prepares with high specific surface area and high conductivity, shows that it has larger application potential in high power, high security and power field.
Description
Technical field
The invention belongs to field of energy source materials, and in particular to a kind of positive, preparation method and supercapacitor obtained.
Background technique
With the development that portable electronic products such as mobile phone, notebook, tablet computer can make rapid progress, people in addition to it most
Except the demand of basic application function, the challenge that lighter, thinner, foldable, wearable etc. are higher level is also proposed to it.
In order to meet the energy requirement of these novel flexible electronic products, novel flexible energy storage device such as flexible lithium ion battery, flexibility
The research and development of supercapacitor etc. become one of research emphasis of energy storage field.The function of all-solid-state flexible supercapacitor Yin Qigao
Rate density, fast charge-discharge velocity, wide operating temperature, good stability, the service life of length and cheap later maintenance
Expense, especially graphene-based all-solid-state flexible supercapacitor develop rapidly in recent years, have good development space and answer
Use prospect.However, the energy-storage property for the most all-solid-state flexible supercapacitors developed at present is still difficult to meet people
Daily demand, for example specific capacitance is still smaller, energy density is not still high, and high rate performance is also relatively poor etc..
CN107342173B discloses a kind of flexible super capacitor electrode, including graphene paper and is compound in the stone
The three-dimensional porous graphene of black alkene paper.The preparation method of the flexible super capacitor electrode includes the following steps: that (1) will be passed through
The discontinuous organic phase of the magnetic nano-particle of surface modification and the water dispersion of graphene oxide mix stirring, after being reacted from
Heart washing obtains the graphene oxide of magnetic nano-particle modification, the graphene oxide that the magnetic nano-particle is modified point
It dissipates in ethanol solution, obtains the graphene oxide alcohol dispersion liquid of magnetic nano-particle modification；(2) oxygen is coated in substrate surface
Graphite alkene gel is placed in ethanol solution, applies magnetic field, Xiang Suoshu ethanol solution below the graphene oxide gel
The middle graphene oxide alcohol dispersion liquid that magnetic nano-particle modification is added, the graphene oxide of the magnetic nano-particle modification
It is enriched with, arranged and assembled on the graphene oxide gel surface by magnetic fields, obtain flexible super capacitor electrode
Presoma；(3) the flexible super capacitor electrode precursor restore and cleaned with deionized water, obtain flexible super
Electrode for capacitors.The method preparation process is complicated, and obtained electrode conductivuty is poor, and electrochemistry performance is unable to satisfy excellent
The requirement of different electrode of super capacitor.
CN108597905A discloses a kind of preparation method of fiber/graphene/cobalt sulfide nickel flexible electrode material, described
Method repeats this step the following steps are included: A, pretreated fabric is impregnated in graphene oxide suspension and is dried
Suddenly fiber/graphene oxide composite material is obtained several times, and the graphene oxide suspension is by graphene oxide powder ultrasound point
It dissipates and is made in deionized water；B, in-situ reducing is carried out to fiber/graphene oxide composite material and obtains fiber/grapheme material；C,
Fiber/grapheme material that step B is obtained is immersed in the hydrothermal reaction kettle containing nickel salt, cobalt salt and sulfur-bearing precursor solution
In, heating reaction synthesis obtains fiber/graphene/cobalt sulfide nickel flexible electrode material.Electrode conductivuty made from the method
Poor, chemical property is poor.
CN108597906A discloses a kind of preparation method of fiber/graphene/copper sulfide flexible electrode material, the side
Method repeats this step the following steps are included: A, pretreated fabric is impregnated in graphene oxide suspension and is dried
Fiber/graphene oxide composite material is obtained several times, and the graphene oxide suspension is by graphene oxide powder ultrasonic disperse
It is made in deionized water；B, in-situ reducing is carried out to fiber/graphene oxide composite material and obtains fiber/grapheme material；C, will
Fiber/grapheme material that step B is obtained is immersed in the hydrothermal reaction kettle containing mantoquita and sulfur-bearing precursor solution, and heating is anti-
It should synthesize to obtain fiber/graphene/copper sulfide flexible electrode material.Electrode conductivuty made from the method is poor, electrochemistry
Performance is poor.
Therefore, how there is the self-supporting fexible film of satisfactory electrical conductivity, and then structure by simple effective method preparation
It builds and provides the all-solid-state flexible supercapacitor of excellent electrochemical behavior and become the emphasis in current supercapacitor field.
Summary of the invention
It is described just great the purpose of the present invention is to provide a kind of anode, preparation method and supercapacitor obtained
There are high specific surface area and high conductivity, there is high power density and area specific capacity compared to other electrode materials.
To achieve this purpose, the present invention adopts the following technical scheme:
One of the objects of the present invention is to provide a kind of anode, described just extremely flexible electrode, the anode include graphite
Alkene piece and the bimetallic sulfide being attached on the graphene film.
The conductivity of bimetallic sulfide electrode material of the present invention is several times even tens times of monometallic sulfide,
Compensate for the poor circulation of monometallic sulfide electrode material, the disadvantage of multiplying power property difference.
The present invention is self-assembled into flexible electrode using bimetallic sulfide and graphene, forms 3D flower-like structure, has more
Big specific surface area and higher conductivity, the collector with high conductivity, improves the energy of supercapacitor
Density and power density.Show that it has larger application potential in high power, high security and power field.
Preferably, the bimetallic sulfide is FeCo2S4。
Preferably, the diameter of the bimetallic sulfide is 3~4 μm, such as 3.1 μm, 3.2 μm, 3.3 μm, 3.4 μm, 3.5
μm, 3.6 μm, 3.7 μm, 3.8 μm or 3.9 μm etc..
FeCo in the present invention2S4Other bimetallic sulfide in compared with the prior art, with other bimetallic testing sulphides
Than ferro element imparts bimetallic sulfide more high conductivity, and cobalt element provides outstanding specific capacity and element sulphur and provides
Enough conductivity and richer redox state, and redox reaction can occur for two components, it is possible thereby to mention
For bigger specific capacitance, therefore, bimetallic sulfide fake capacitance electrode material shows excellent chemical property.
Anode of the present invention be it is green, environmental-friendly, by macroion diffusion bimetallic sulfide with have height
The Flexible graphene piece collaborative combination of electric conductivity is prepared with high specific surface area and high conductivity, compared to life in situ
Other long electrode materials have high power density and area specific capacity, show that it is used in high power, high security and power
There is larger application potential in field.
Preferably, the mass percentage of the bimetallic sulfur element is 10wt%~50wt%, such as
10wt%, 15wt%, 20wt%, 25wt%, 30wt%, 35wt%, 40wt%, 45wt% or 50wt% etc..
When the mass percentage of bimetallic sulfur element of the present invention is less than 10wt%, because of electro-chemical activity
Substance cannot be fully used in electrochemical reaction process, reduce the specific capacity and cyclical stability of material；It is described double
When the mass percentage of element sulphur is greater than 50wt% in metal sulfide, sulfide excessively reduces the specific surface area drop of material
The active site of low electrochemical reaction reduces the specific capacity and cyclical stability of material.
Preferably, the pattern of the bimetallic sulfide is the flower-like structure that lamella is piled into.
Flower-like structure of the present invention refers to that the bimetallic sulfide lamella is mutually built and accumulated, and between lamella not
It is overlapped, formation is similar to flower-shaped structure, and the flower-like structure is typical but attached restrictive example is as shown in Figure 1.
Preferably, the flower-like structure of the bimetallic sulfide is having a size of 4~5 μm, for example, 4.1 μm, 4.2 μm, 4.3 μm,
4.4 μm, 4.5 μm, 4.6 μm, 4.7 μm, 4.8 μm or 4.9 μm etc..
Preferably, the graphene film with a thickness of 10nm~100nm, such as 20nm, 30nm, 40nm, 50nm, 60nm,
70nm, 80nm or 90nm etc..
Preferably, it is described anode in graphene film content be 30wt%~50wt%, such as 32wt%, 35wt%,
38wt%, 40wt%, 42wt%, 45wt% or 48wt% etc..
The second object of the present invention is to provide a kind of positive preparation method as described in the first purpose, the preparation method
Include the following steps:
(1) mixed solution containing source metal, fluoride and basic matterial is mixed with graphene film, then carries out hydro-thermal
Reaction, obtains presoma；
(2) presoma is mixed with sulfide solution, hydro-thermal obtains positive electrode.
The present invention obtains the vulcanization of sheet bimetallic by way of the growth in situ bimetallic sulfide on graphene film
Object mutually accumulates the flower-like structure of formation, and the structure can effectively increase the specific surface area of electrode, positive system in the present invention
Preparation Method is relatively simple to be easy, highly beneficial for its large scale preparation, development and application.
Preferably, step (1) described source metal includes source of iron and cobalt source.
Preferably, the molar ratio of source of iron, cobalt source and basic matterial is 1:1~4:2~8 in step (1) described mixed solution,
Such as 1:2:6,1:3:4,1:2:5,1:2:6,1:3:5,1:4:3,1:3:7,1:2:8,1:3:6,1:1:5 or 1:4:8 etc..
Preferably, the molar ratio of step (1) fluoride and basic matterial is 1:1~3, such as 1:1.2,1:1.4,1:
1.5,1:1.6,1:1.8,1:2,1:2.1,1:2.3,1:2.5,1:2.6,1:2.7,1:2.8 or 1:2.9 etc..
When the molar ratio of fluoride and basic matterial of the present invention is greater than 1:1, because the amount deficiency of precipitating reagent cannot be formed
Complete flower-shaped electrode material, influences the cycle performance of capacitor；The molar ratio of the fluoride and basic matterial is less than 1:3
When, because the flower-like structure of precipitating reagent excess generation is blocked up, it is unfavorable for electrode material and sufficiently reacts the specific capacity for reducing electrode material.
Preferably, step (1) graphene film and the mass ratio of source metal are 1:1~3, such as 1:1.2,1:1.4,1:
1.5,1:1.6,1:1.8,1:2,1:2.1,1:2.3,1:2.5,1:2.6,1:2.7,1:2.8 or 1:2.9 etc..
When graphene film of the present invention and the mass ratio of source metal are less than 1:3, the graphene film of formation is relatively thin to be reduced
The flexibility of electrode material；When the graphene film and the mass ratio of source metal are greater than 1:1, the graphene film quality of formation relative to
The quality of electrode active material is larger, reduces the specific capacity of entire electrode.
Preferably, step (1) source of iron is Fe (NO3)2。
Preferably, step (1) cobalt source is Co (NO3)2。
Preferably, step (1) fluoride is ammonium fluoride.
Preferably, step (1) basic matterial is urea.
Preferably, the temperature of step (1) described hydro-thermal be 100~140 DEG C, such as 105 DEG C, 110 DEG C, 115 DEG C, 120 DEG C,
125 DEG C, 130 DEG C or 135 DEG C etc..
When the temperature of hydro-thermal of the present invention is less than 100 DEG C, electrode material size becomes smaller, and surface can excessive or sealing end point
The amount deficiency of son reduces the electric conductivity of material；When the temperature of the hydro-thermal is greater than 140 DEG C, because reaction speed is too fast, temperature
It increases initial nucleus and increases the specific surface area to form reduction electrode material of reuniting, specific capacity and the circulation for reducing electrode material are steady
It is qualitative.
Preferably, the time of step (1) described hydro-thermal is 6~10h, such as 7h, 8h or 9h etc..
When the time of hydro-thermal of the present invention is less than 6h, cannot form complete flower-like structure pattern influences electrode material
Cycle performance；When the time of the hydro-thermal is greater than 10h, flower-like structure pattern, which can collapse, is unfavorable for the abundant reaction of electrode material,
Reduce the specific capacity of material.
It preferably, further include cleaning and dry process after step (1) described hydro-thermal.
Preferably, the temperature of the drying is 40~80 DEG C, such as 45 DEG C, 50 DEG C, 55 DEG C, 60 DEG C, 65 DEG C, 70 DEG C or 75
DEG C etc..
Preferably, the time of the drying is 2~4h, such as 2.2h, 2.5h, 2.8h, 3h, 3.2h, 3.5h or 3.8h etc..
Preferably, the preparation process of step (1) described graphene film includes: to prepare graphene oxide using Hummers method,
Then it is heat-treated, obtains graphene film.
Preferably, the temperature of the heat treatment is 200~400 DEG C, such as 220 DEG C, 250 DEG C, 280 DEG C, 300 DEG C, 320
DEG C, 350 DEG C or 380 DEG C etc..
Dry graphene oxide sheet piece is placed under 200~400 DEG C of environment quickly heating and brought it about quickly by the present invention
Reduction reaction, generate graphene film, during reduction reaction, the functional group of graphene oxide, which decomposes, generates CO2, CO and H2O
Gas, graphene oxide is stripped in the generating process of above-mentioned gas, obtains flexible substrates graphene film.
Preferably, the time of the heat treatment be 2~6h, such as 2h, 2.5h, 3h, 3.5h, 4h, 4.5h, 5h, 5.5h or
6h etc..
Preferably, the ratio between integral molar quantity of source of iron described in step (2) sulfide and step (1) and cobalt source for 1~
2:1, such as 1.1:1,1.2:1,1.3:1,1.4:1,1.5:1,1.6:1,5:3,1.7:1,1.8:1 or 1.9:1 etc..
Preferably, step (2) sulfide is vulcanized sodium and/or thiocarbamide.
Preferably, the temperature of step (2) described hydro-thermal be 140~180 DEG C, such as 145 DEG C, 150 DEG C, 155 DEG C, 160 DEG C,
165 DEG C, 170 DEG C or 175 DEG C etc..
When the temperature of hydro-thermal of the present invention is less than 140 DEG C, electrode material size becomes smaller surface can excessive or sealing end point
The amount deficiency of son reduces the electric conductivity of material；When the temperature of the hydro-thermal is greater than 180 DEG C, because reaction speed is too fast, temperature
Increase initial nucleus increase to be formed reunite reduce electrode material specific surface area reduce electrode material specific capacity and circulation it is steady
It is qualitative.
Preferably, the temperature of temperature > step (1) described hydro-thermal of step (2) described hydro-thermal.
Preferably, the time of step (2) described hydro-thermal be 6~10h, such as 6.5h, 7h, 7.5h, 8h, 8.5h, 9h or
9.5h waiting.
When the time of hydro-thermal of the present invention is less than 6h, because reaction time deficiency cannot adequately form bimetallic sulfide
Reduce the specific capacity and service efficiency of material；When the time of the hydro-thermal is greater than 10h, flower-shaped lamella thickens and reduces material
Specific surface area reduces the cyclical stability of material.
It preferably, further include cleaning and dry process after step (2) described hydro-thermal.
Preferably, the temperature of the drying is 40~80 DEG C, such as 45 DEG C, 50 DEG C, 55 DEG C, 60 DEG C, 65 DEG C, 70 DEG C or 75
DEG C etc..
Preferably, the time of the drying is 4~8h, such as 4.5h, 5h, 5.5h, 6h, 6.5h, 7h or 7.5h etc..
As optimal technical scheme, a kind of preparation method of anode of the present invention includes the following steps:
(1) graphene oxide is prepared using Hummers method, then carries out 200~400 DEG C of 2~6h of heat treatment, obtains graphite
Alkene piece；
(2) Fe (NO will be contained3)2、Co(NO3)2, ammonium fluoride and urea mixed solution mixed with graphene film, it is described mixed
Close Fe (NO in solution3)2、Co(NO3)2Molar ratio with urea is 1:1~4:2~8, the molar ratio of the ammonium fluoride and urea
For 1:1~3, the graphene film with a thickness of 10nm~100nm, the mass ratio of the graphene film and source metal be 1:1~
3,100~140 DEG C of 6~10h of hydro-thermal reaction, cleaning are then carried out, 40~80 DEG C of dry 2~4h obtain presoma；
(3) presoma is mixed with sodium sulfide solution, Fe (NO described in the vulcanized sodium and step (1)3)2And Co
(NO3)2The ratio between integral molar quantity be 1~2:1,140~180 DEG C of 6~10h of hydro-thermal, cleaning, 40~80 DEG C of dry 4~8h are obtained
Anode.
The third object of the present invention is to provide a kind of supercapacitor, and the supercapacitor includes described in the first purpose
Anode.
Preferably, the supercapacitor further includes cathode and gel electrolyte.
The supercapacitor that the present invention obtains corresponding ratio under 1A/g, 2A/g, 5A/g, 8A/g and 10A/g current density
Capacitor can reach 247.93F/g, 228.32F/g, 197.11F/g, 175.85F/g and 149.72F/g, and energy density is reachable
88.2Wh/kg, power density is up to 8001Wh/kg, and the cycle performance of 5000 circle of circulation is up to 85.1%., and bending and
Its electrochemical behavior is had substantially no effect in the state of distortion, have biggish energy density and power density and it is light, can roll over
The advantages that folded, it can be applied to some special dimensions, such as wearable, foldable electronic etc..
Constructed supercapacitor can be together in series or parallel use, such as several devices connected in the present invention
Miniaturized electronics such as LED lamp bead etc. can be driven to work normally after fully charged.
The fourth object of the present invention is to provide a kind of preparation method of supercapacitor as described in the third purpose, the system
Preparation Method includes the following steps: to separate anode and cathode using diaphragm, is then injected into electrolyte, obtains supercapacitor.
Preferably, the preparation process of the cathode includes: that active carbon and adhesive are mixed and made into slurry, by the slurry
Coated on carbon cloth, cathode is obtained after dry.
Preferably, the preparation process of the electrolyte includes: to mix polyvinyl alcohol with hot water, is stirred clear to occurring
Gel, it is cooling, the gel is mixed with KOH then, obtains electrolyte.
Preferably, the temperature of the hot water is 80~100 DEG C, such as 85 DEG C, 90 DEG C or 95 DEG C etc..
Preferably, in the mixed solution of the polyvinyl alcohol and hot water, the concentration of polyvinyl alcohol is 0.05~0.2g/mL,
Such as 0.06g/mL, 0.08g/mL, 0.1g/mL, 0.12g/mL, 0.15g/mL or 0.18g/mL etc..
Preferably, the KOH and polyvinyl alcohol mass ratio are 0.5~1.5:1, such as 0.6:1,0.7:1,0.8:1,0.9:
1,1:1,1.1:1,1.2:1,1.3:1 or 1.4:1 etc..
Compared with prior art, the invention has the following beneficial effects:
(1) conductivity of bimetallic sulfide electrode material is several times of monometallic sulfide even tens in the present invention
Times, compensate for the poor circulation of monometallic sulfide electrode material, the disadvantage of multiplying power property difference.In addition, two components can be with
Redox reaction occurs, it is possible thereby to bigger specific capacitance is provided, therefore, the performance of bimetallic sulfide fake capacitance electrode material
Excellent chemical property out.
(2) anode of the present invention is green, environmental-friendly, by macroion diffusion bimetallic sulfide with have
The Flexible graphene piece collaborative combination of high conductivity, is prepared with high specific surface area and high conductivity, compared to original position
Other electrode materials of growth have high power density and area specific capacity, show it in high power, high security and power
With in field have larger application potential.
(3) supercapacitor specific surface area >=50m constructed in the present invention2/ g, in 1A/g, 2A/g, 5A/g, 8A/g and
Corresponding specific capacitance can reach 247.93F/g under 10A/g current density, 228.32F/g, 197.11F/g, 175.85F/g and
149.72F/g, energy density is up to 88.2Wh/kg, and for power density up to 8001Wh/kg, the cycle performance of 5000 circle of circulation can
Up to 85.1%, and its electrochemical behavior is had substantially no effect in the state of bending and distortion, have biggish energy density and
Power density and it is light, foldable the advantages that, can be applied to some special dimensions, such as wearable, foldable electronics device
Part etc., meanwhile, constructed supercapacitor can be together in series or parallel use, such as several devices connected in the present invention
Part can drive miniaturized electronics such as LED lamp bead etc. to work normally after fully charged.
Detailed description of the invention
Fig. 1 is the SEM figure for the anode that the specific embodiment of the invention 1 obtains；
Fig. 2 is the XRD spectra for the anode that the specific embodiment of the invention 1 obtains；
Fig. 3 is the XPS spectrum figure for the anode that the specific embodiment of the invention 1 obtains；
Fig. 4 is the supercapacitor constant current charge-discharge curve that the specific embodiment of the invention 1 obtains；
Fig. 5 is the supercapacitor structures that the specific embodiment of the invention 1 obtains and performance test figure.
Specific embodiment
Of the invention for ease of understanding, it is as follows that the present invention enumerates embodiment.Those skilled in the art are it will be clearly understood that the implementation
Example is only to aid in the understanding present invention, should not be regarded as a specific limitation of the invention.
Embodiment 1
A kind of preparation method of supercapacitor includes the following steps:
(1) graphene oxide solution that 5mg/mL is prepared using Hummers method, is then carried out 300 DEG C of heat treatment 2h, obtained
Graphene film；
(2) Fe (NO will be contained3)2、Co(NO3)2, ammonium fluoride and urea mixed solution mixed with graphene film, it is described mixed
Close Fe (NO in solution3)2、Co(NO3)2It is 1:2:6 with the molar ratio of urea, the molar ratio of the ammonium fluoride and urea is 1:2,
The graphene film with a thickness of 20nm, the mass ratio of the graphene film and source metal is 1:2, then carries out 120 DEG C of hydro-thermals
8h, cleaning are reacted, 60 DEG C of dry 3h obtain presoma；
(3) presoma is mixed with sodium sulfide solution, Fe (NO described in the vulcanized sodium and step (1)3)2And Co
(NO3)2The ratio between integral molar quantity be 5:3,160 DEG C of hydro-thermal 8h, cleaning, 60 DEG C of dry 6h obtain anode；
The pattern of the anode is as shown in Figure 1, as can be seen from Figure, FeCo2S4It is successfully supported on graphene film surface,
And composite material keeps flower-shaped array pattern, diameter is about 3~4 μm；The XRD spectra of the anode is as shown in Fig. 2, by can in figure
To find out, 30.8 °, 36.1 °, 43.2 °, 58.1 ° and 63.9 ° corresponding crystal faces are (220), (311), (400), (511)
(440) Co in corresponding PDF card3O4(PDF 42-1467), after vulcanization 21.9 °, 31.2 °, 37.9 °, 49.9 ° and
55.3 ° of corresponding crystal faces are the Co in (220), (311), (400), (511) and (440) corresponding PDF card3S4(PDF 47-
1738), it can thus be appreciated that FeCo2S4Successfully it is supported on graphene film surface；The XPS spectrum figure of the anode is as shown in figure 3, by figure
The ratio of Fe:Co:S be can be seen that close to 1:2:4, it can thus be appreciated that FeCo2S4Successfully it is supported on graphene film surface；
(4) active carbon and adhesive are mixed and made into slurry, the slurry is coated on carbon cloth, born after dry
Pole；
(5) it is 0.1g/mL by the concentration of polyvinyl alcohol, polyvinyl alcohol is mixed with 90 DEG C of hot water, stirs to clarifying
Gel, it is cooling, then the gel mix with KOH, the KOH is 1:1 with polyvinyl alcohol mass ratio, obtains electrolyte；
(6) anode and cathode are separated using diaphragm, is then injected into the electrolyte, obtains supercapacitor；Institute
State supercapacitor structure and performance test figure as shown in figure 5, the supercapacitor constant current charge-discharge map such as Fig. 4
It is shown, as can be seen from Figure, corresponding numerical value difference under the conditions of current density 1A/g, 2A/g, 5A/g, 8A/g and 10A/g
For 247.93F/g, 228.32F/g, 197.11F/g, 175.85F/g and 149.72F/g.
Embodiment 2
The difference from embodiment 1 is that step (2) the hydro-thermal time is 6h.
Embodiment 3
The difference from embodiment 1 is that step (2) the hydro-thermal time is 10h.
Embodiment 4
The difference from embodiment 1 is that step (2) the hydro-thermal time is 5h.
Embodiment 5
The difference from embodiment 1 is that step (2) the hydro-thermal time is 12h.
Embodiment 6
The difference from embodiment 1 is that Fe (NO described in step (3) vulcanized sodium and step (1)3)2With Co (NO3)2
The ratio between integral molar quantity be 1.2:1.
Embodiment 7
The difference from embodiment 1 is that the molar ratio of step (2) ammonium fluoride and urea is 2:1.
Embodiment 8
The difference from embodiment 1 is that the molar ratio of step (2) ammonium fluoride and urea is 1:4.
Embodiment 9
A kind of preparation method of supercapacitor includes the following steps:
(1) graphene oxide solution that 5mg/mL is prepared using Hummers method, is then carried out 200 DEG C of heat treatment 2h, obtained
Graphene film；
(2) Fe (NO will be contained3)2、Co(NO3)2, ammonium fluoride and urea mixed solution mixed with graphene film, it is described mixed
Close Fe (NO in solution3)2、Co(NO3)2It is 1:4:8 with the molar ratio of urea, the molar ratio of the ammonium fluoride and urea is 1:2,
The graphene film and the mass ratio of source metal are 1:1.5, then carry out 100 DEG C of hydro-thermal reaction 8h, are cleaned, 40 DEG C of dry 4h,
Obtain presoma；
(3) presoma is mixed with sodium sulfide solution, Fe (NO described in the vulcanized sodium and step (1)3)2And Co
(NO3)2The ratio between integral molar quantity be 2:1,140 DEG C of hydro-thermal 10h, cleaning, 40 DEG C of dry 8h obtain anode；
(4) active carbon and adhesive are mixed and made into slurry, the slurry is coated on carbon cloth, born after dry
Pole；
(5) it is 0.05g/mL by the concentration of polyvinyl alcohol, polyvinyl alcohol is mixed with 80 DEG C of hot water, stirs to clarifying
Gel, it is cooling, then the gel mix with KOH, the KOH is 1.5:1 with polyvinyl alcohol mass ratio, is electrolysed
Matter；
(6) anode and cathode are separated using diaphragm, is then injected into the electrolyte, obtains supercapacitor.
Embodiment 10
A kind of preparation method of supercapacitor includes the following steps:
(1) graphene oxide solution that 5mg/mL is prepared using Hummers method, is then carried out 400 DEG C of heat treatment 2h, obtained
Graphene film；
(2) Fe (NO will be contained3)2、Co(NO3)2, ammonium fluoride and urea mixed solution mixed with graphene film, it is described mixed
Close Fe (NO in solution3)2、Co(NO3)2It is 1:1:2 with the molar ratio of urea, the molar ratio of the ammonium fluoride and urea is 1:2,
The graphene film and the mass ratio of source metal are 1:3, then carry out 130 DEG C of hydro-thermal reaction 8h, cleaning, and 80 DEG C of dry 2h are obtained
To presoma；
(3) presoma is mixed with sodium sulfide solution, Fe (NO described in the vulcanized sodium and step (1)3)2And Co
(NO3)2The ratio between integral molar quantity be 5:3,180 DEG C of hydro-thermal 6h, cleaning, 80 DEG C of dry 4h obtain anode；
(4) active carbon and adhesive are mixed and made into slurry, the slurry is coated on carbon cloth, born after dry
Pole；
(5) it is 0.2g/mL by the concentration of polyvinyl alcohol, polyvinyl alcohol is mixed with 100 DEG C of hot water, stirs to clarifying
Gel, it is cooling, then the gel mix with KOH, the KOH is 0.5:1 with polyvinyl alcohol mass ratio, is electrolysed
Matter；
(6) anode and cathode are separated using diaphragm, is then injected into the electrolyte, obtains supercapacitor.
Comparative example 1
The difference from embodiment 1 is that Fe (NO in step (2)3)2Replace with the Co (NO of equimolar amounts3)2。
Comparative example 2
The difference from embodiment 1 is that Co (NO in step (2)3)2Replace with the Fe (NO of equimolar amounts3)2。
Performance test:
The anode and supercapacitor that are prepared are tested as follows:
(1) pattern test: the positive electrode surface pattern obtained using scanning electron microscopic observation.
(2) specific surface area is tested: carrying out specific surface area test using Bei Shide specific-surface area detection instrument.
(3) electrochemistry electrochemical property test: is carried out using supercapacitor described in occasion China 660C electrochemical workstation
It can test, the specific capacity of battery be tested respectively under 1A/g, 2A/g, 5A/g, 8A/g and 10A/g current density, in 5A g-1Electric current
The cycle performance of 5000 circle of energy density, power density and circulation of battery is tested under density.
Table 1
It can be seen from Table 1 that the positive chemical property that the present invention obtains is good, specific surface area >=50m2/ g, in 1A/
G, corresponding specific capacitance can reach 247.93F/g under 2A/g, 5A/g, 8A/g and 10A/g current density, 228.32F/g,
197.11F/g, 175.85F/g and 149.72F/g, energy density are followed up to 88.2Wh/kg, power density up to 8001Wh/kg
The cycle performance that ring 5000 encloses is up to 85.1%.
It can be seen from Table 1 that the embodiment of the present invention 4 obtained relative to embodiment 1 positive specific capacitance, energy density,
Power density and cycle performance are lower, because the time of hydro-thermal is less in embodiment 4, and then cannot form complete flower-like structure
Pattern influences the chemical property of electrode material, and especially cycle performance is poor, so embodiment 4 is obtained relative to embodiment 1
Positive specific capacitance, energy density, power density and cycle performance it is lower.
It can be seen from Table 1 that the embodiment of the present invention 5 relative to embodiment 1 obtain anode specific surface area, specific capacitance,
Energy density and power density are lower, because the time of hydro-thermal is more in embodiment 5, and then flower-like structure can collapse, and be unfavorable for
The abundant reaction of electrode material reduces the specific capacity, energy density and power density of material, so 5 phase of the embodiment of the present invention
Specific surface area, specific capacitance, energy density and the power density for obtaining anode for embodiment 1 are lower.
It can be seen from Table 1 that the embodiment of the present invention 7 relative to embodiment 1 obtain anode specific surface area, specific capacitance,
Energy density, power density and cycle performance are lower, because the molar ratio of ammonium fluoride and urea is 2:1 in embodiment 7, and then urinate
The amount deficiency of element cannot form complete flower-shaped electrode material, influence the chemical property of capacitor, especially cycle performance, institute
With embodiment 7 relative to embodiment 1 obtain anode specific surface area, specific capacitance, energy density, power density and cycle performance compared with
It is low.
It can be seen from Table 1 that the embodiment of the present invention 8 relative to embodiment 1 obtain anode specific surface area, specific capacitance,
Energy density, power density and cycle performance are lower, because the molar ratio of ammonium fluoride and urea is 1:4 in embodiment 8, and then urinate
The flower-like structure of plain excess generation is blocked up, is unfavorable for electrode material and sufficiently reacts, and reduces the chemical property of anode, especially compares
Capacity, so embodiment 8 obtains positive specific surface area, specific capacitance, energy density, power density relative to embodiment 1 and follows
Ring performance is lower.
It can be seen from Table 1 that comparative example 1 of the present invention and comparative example 2 obtain the specific surface of anode relative to embodiment 1
Product, specific capacitance, energy density, power density and cycle performance are lower, because obtained in comparative example 1 and comparative example 2 just extremely
Monometallic sulfide electrode, monometallic sulfide electrode cycle performance is poor, and multiplying power property is poor, so 2 phase of comparative example 1 and comparative example
For embodiment 1, specific surface area, specific capacitance, energy density, power density and the cycle performance for obtaining anode are lower.
The Applicant declares that the present invention is explained by the above embodiments detailed process equipment and process flow of the invention,
But the present invention is not limited to the above detailed process equipment and process flow, that is, it is above-mentioned detailed not mean that the present invention must rely on
Process equipment and process flow could be implemented.It should be clear to those skilled in the art, any improvement in the present invention,
Addition, selection of concrete mode of equivalence replacement and auxiliary element to each raw material of product of the present invention etc., all fall within of the invention
Within protection scope and the open scope.
Claims (10)
1. a kind of anode, which is characterized in that the just extremely flexible electrode, the anode include graphene film and be attached to institute
State the bimetallic sulfide on graphene film.
2. anode as described in claim 1, which is characterized in that the bimetallic sulfide is FeCo2S4；
Preferably, the diameter of the bimetallic sulfide is 3~4 μm；
Preferably, the mass percentage of the bimetallic sulfur element is 10wt%~50wt%；
Preferably, the pattern of the bimetallic sulfide is the flower-like structure that lamella is piled into；
Preferably, the flower-like structure of the bimetallic sulfide is having a size of 4~5 μm；
Preferably, the graphene film with a thickness of 10nm~100nm；
Preferably, the content of graphene film is 30wt%~50wt% in the anode.
3. a kind of preparation method of anode as claimed in claim 1 or 2, which is characterized in that the preparation method includes following step
It is rapid:
(1) mixed solution containing source metal, fluoride and basic matterial is mixed with graphene film, it is anti-then carries out hydro-thermal
It answers, obtains presoma；
(2) presoma is mixed with sulfide solution, hydro-thermal obtains positive electrode.
4. preparation method as claimed in claim 3, which is characterized in that step (1) described source metal includes source of iron and cobalt source；
Preferably, the molar ratio of source of iron, cobalt source and basic matterial is 1:1~4:2~8 in step (1) described mixed solution；
Preferably, the molar ratio of step (1) fluoride and basic matterial is 1:1~3；
Preferably, step (1) graphene film and the mass ratio of source metal are 1:1~3；
Preferably, step (1) source of iron is Fe (NO3)2；
Preferably, step (1) cobalt source is Co (NO3)2；
Preferably, step (1) fluoride is ammonium fluoride；
Preferably, step (1) basic matterial is urea；
Preferably, the temperature of step (1) described hydro-thermal is 100~140 DEG C；
Preferably, the time of step (1) described hydro-thermal is 6~10h；
It preferably, further include cleaning and dry process after step (1) described hydro-thermal；
Preferably, the temperature of the drying is 40~80 DEG C；
Preferably, the time of the drying is 2~4h；
Preferably, the preparation process of step (1) described graphene film includes: to prepare graphene oxide using Hummers method, then
It is heat-treated, obtains graphene film；
Preferably, the temperature of the heat treatment is 200~400 DEG C；
Preferably, the time of the heat treatment is 2~6h.
5. preparation method as described in claim 3 or 4, which is characterized in that institute in step (2) sulfide and step (1)
Stating the ratio between integral molar quantity of source of iron and cobalt source is 1~2:1；
Preferably, step (2) sulfide is vulcanized sodium and/or thiocarbamide；
Preferably, the temperature of step (2) described hydro-thermal is 140~180 DEG C；
Preferably, the temperature of temperature > step (1) described hydro-thermal of step (2) described hydro-thermal；
Preferably, the time of step (2) described hydro-thermal is 6~10h；
It preferably, further include cleaning and dry process after step (2) described hydro-thermal；
Preferably, the temperature of the drying is 40~80 DEG C；
Preferably, the time of the drying is 4~8h.
6. the preparation method as described in one of claim 3-5, which is characterized in that the preparation method includes the following steps:
(1) graphene oxide is prepared using Hummers method, then carries out 200~400 DEG C of 2~6h of heat treatment, obtains graphene
Piece；
(2) Fe (NO will be contained3)2、Co(NO3)2, ammonium fluoride and urea mixed solution mixed with graphene film, the mixing is molten
Fe (NO in liquid3)2、Co(NO3)2It is 1:1~4:2~8 with the molar ratio of urea, the molar ratio of the ammonium fluoride and urea is 1:1
~3, the graphene film with a thickness of 10nm~100nm, the mass ratio of the graphene film and source metal is 1:1~3, then
100~140 DEG C of 6~10h of hydro-thermal reaction, cleaning are carried out, 40~80 DEG C of dry 2~4h obtain presoma；
(3) presoma is mixed with sodium sulfide solution, Fe (NO described in the vulcanized sodium and step (1)3)2With Co (NO3)2
The ratio between integral molar quantity be 1~2:1,140~180 DEG C of 6~10h of hydro-thermal, cleaning, 40~80 DEG C of dry 4~8h obtain anode.
7. a kind of supercapacitor, which is characterized in that the supercapacitor includes anode of any of claims 1 or 2；
Preferably, the supercapacitor further includes cathode and gel electrolyte.
8. a kind of preparation method of supercapacitor as claimed in claim 7, which is characterized in that the preparation method includes as follows
Step: anode and cathode are separated using diaphragm, electrolyte is then injected into, obtains supercapacitor.
9. preparation method as claimed in claim 8, which is characterized in that the preparation process of the cathode include: by active carbon with
Adhesive is mixed and made into slurry, and the slurry is coated on carbon cloth, obtains cathode after dry.
10. preparation method as claimed in claim 8, which is characterized in that the preparation process of the electrolyte includes: by polyethylene
Alcohol is mixed with hot water, and to there is clear gel, then the gel is mixed with KOH, obtains electrolyte by cooling for stirring；
Preferably, the temperature of the hot water is 80~100 DEG C；
Preferably, in the mixed solution of the polyvinyl alcohol and hot water, the concentration of polyvinyl alcohol is 0.05~0.2g/mL；
Preferably, the KOH and polyvinyl alcohol mass ratio are 0.5~1.5:1.
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