CN107240511A - Graphene hybrid electrode of flexible self-supporting and preparation method and application - Google Patents
Graphene hybrid electrode of flexible self-supporting and preparation method and application Download PDFInfo
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- CN107240511A CN107240511A CN201710532466.XA CN201710532466A CN107240511A CN 107240511 A CN107240511 A CN 107240511A CN 201710532466 A CN201710532466 A CN 201710532466A CN 107240511 A CN107240511 A CN 107240511A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 239000007788 liquid Substances 0.000 claims abstract description 30
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000006185 dispersion Substances 0.000 claims abstract description 21
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 17
- 239000012266 salt solution Substances 0.000 claims abstract description 14
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims abstract description 11
- 150000003624 transition metals Chemical class 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 239000002041 carbon nanotube Substances 0.000 claims description 48
- 239000011259 mixed solution Substances 0.000 claims description 11
- 239000003990 capacitor Substances 0.000 claims description 9
- 239000002002 slurry Substances 0.000 claims description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 238000001704 evaporation Methods 0.000 claims description 2
- 230000008020 evaporation Effects 0.000 claims description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 239000010408 film Substances 0.000 claims 1
- 150000003839 salts Chemical class 0.000 claims 1
- 239000010409 thin film Substances 0.000 claims 1
- 239000000243 solution Substances 0.000 abstract description 19
- 238000000034 method Methods 0.000 abstract description 16
- 239000007772 electrode material Substances 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 6
- 239000000126 substance Substances 0.000 abstract description 3
- 239000006229 carbon black Substances 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 238000002207 thermal evaporation Methods 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 19
- -1 transition metal Salt Chemical class 0.000 description 18
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 16
- 239000004810 polytetrafluoroethylene Substances 0.000 description 16
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 14
- 238000004132 cross linking Methods 0.000 description 9
- 238000009938 salting Methods 0.000 description 9
- 238000001035 drying Methods 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 238000002604 ultrasonography Methods 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 7
- 238000005452 bending Methods 0.000 description 7
- 229940075397 calomel Drugs 0.000 description 7
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical compound Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 7
- 230000005611 electricity Effects 0.000 description 7
- 239000008151 electrolyte solution Substances 0.000 description 7
- 238000005259 measurement Methods 0.000 description 7
- 229910052697 platinum Inorganic materials 0.000 description 7
- 229910052938 sodium sulfate Inorganic materials 0.000 description 7
- 238000010025 steaming Methods 0.000 description 7
- 239000007832 Na2SO4 Substances 0.000 description 6
- 239000000853 adhesive Substances 0.000 description 5
- 230000001070 adhesive effect Effects 0.000 description 5
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 5
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 description 4
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 4
- 239000011565 manganese chloride Substances 0.000 description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 3
- 238000004079 fireproofing Methods 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 2
- 238000000137 annealing Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- BXRRQHBNBXJZBQ-UHFFFAOYSA-L dichloromanganese;hydrate Chemical compound O.Cl[Mn]Cl BXRRQHBNBXJZBQ-UHFFFAOYSA-L 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229940099607 manganese chloride Drugs 0.000 description 1
- 235000002867 manganese chloride Nutrition 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910021392 nanocarbon Inorganic materials 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
-
- 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
-
- 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
- H01G11/22—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 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
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
-
- 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 invention discloses a kind of flexible self-supporting electrode based on graphene and preparation method and application, belong to electrode material technical field.Its preparation method is：(1) graphene oxide dispersion and CNT (or carbon black) dispersion liquid are prepared；(2) hexachlorocyclotriph,sphazene is dispersed in N methylpyrrolidone solutions, is configured to solution；(3) solution in step (1) and (2) is formed into film with certain proportion mixing thermal evaporation；(4) film for obtaining step (3) soaks transition metal salt solution, is placed in Alcohol Flame and burns, obtains the graphene hybrid electrode of flexible self-supporting.Material required for this technical scheme is cheap and easy to get, technique is simple, flow is short, is adapted to industrialized production, and the electrode of preparation has excellent chemical property.
Description
Technical field
The invention provides a kind of flexible self-supporting hybrid electrode based on graphene and preparation method and application, belong to
Electrode material for super capacitor technical field.
Background technology
With the fast development of novel energy material and flexible electronic product, people to energy storage equipment it is flexible,
Portability demand also more and more higher.Ultracapacitor has high-energy-density, overlength cycle life, environment-friendly and high security
The advantages of, however, its electrode is generally rigidity, in order to which supercapacitor applications in flexible device, to be reduced to its total quality,
Need the electrode of exploitation flexible self-supporting structure.
When making electrode of super capacitor, typically active material, conductive agent, adhesive are mixed as electrode material, so
It is attached to afterwards in rigid metal collector.Due to unique two-dimensional structure, excellent physicochemical characteristic and high mechanical properties,
Graphene is considered as a kind of preferable flexible electrode material, traditional rigid electrode for replacing.But, between graphene film
π-π interact and Van der Waals force would generally make the serious reunion of electrode generation and stacking, reduce its overall chemical property,
Thus, graphene and other materials hydridization can be weakened this reuniting effect.Patent [CN102412065A] has been reported a kind of and incited somebody to action
Graphene and CNTs (CNT) hydridization, form combination electrode material, for the method for electrode of super capacitor, however, multiple
Composite electrode material still employs conductive substrates.In addition, flame method has had been reported for preparing carbon-based electrode, paper [Journal
Of Power Sources 229 (2013) 102~111] propose to use transition metal salt solution with surfactant for forerunner
Thing, based on the method for flame synthesis nano carbon electrode, but electrode also using conductive substrates, and the electrode be not used for it is super
Capacitor.HCCP (hexachlorocyclotriph,sphazene) is a kind of fire proofing, the security of potential raising ultracapacitor, however, existing
The present yet there are no the report for being applied to electrode material for super capacitor.
The content of the invention
It is an object of the invention to provide graphene hybrid electrode of a kind of flexible self-supporting and preparation method and application.
The preparation method of the graphene hybrid electrode of flexible self-supporting of the present invention, it is to use GO (graphite oxides
Alkene) and CNTs (CNT) or using GO (graphene oxide) and BC (conductive black) deposited in HCCP (hexachlorocyclotriph,sphazene)
In lower formation film, transition metal salt solution is then infiltrated, then is placed in burning in Alcohol Flame, the graphite of flexible self-supporting is formed
Alkene hybrid electrode, electrode has the aerogel-like structure of crosslinking.
In the preparation method of the graphene hybrid electrode of flexible self-supporting described above, it is preferred that the GO is configured to
2mg ml-1~10mg ml-1Dispersion liquid, the CNTs or BC are configured to 2mg ml-1~10mg ml-1Dispersion liquid.
In the preparation method of the graphene hybrid electrode of flexible self-supporting described above, it is preferred that the HCCP dissolvings
20~30mg ml are prepared in 1-METHYLPYRROLIDONE-1Slurry.
In the preparation method of the graphene hybrid electrode of flexible self-supporting described above, it is preferred that described GO, CNTs or
The mass ratio of BC, HCCP three are 1:(0.05~5):(0.5~10), more preferably 1:(0.05~2):(0.5~5).
In the preparation method of the graphene hybrid electrode of flexible self-supporting described above, it is preferred that the transition metal
Salt includes one or more of mixing in water miscible nickel, manganese, cobalt, the sulfate of copper, nitrate and villaumite, such as can be sulphur
One or more of mixing in sour nickel, six hydration nickel sulfate, manganese chloride, four chloride hydrate manganese, cobalt chloride, copper sulphate.
In the preparation method of the graphene hybrid electrode of flexible self-supporting described above, it is preferred that the transition metal
The concentration of salting liquid is 0.1mol ml-1~4mol ml-1。
In the preparation method of the graphene hybrid electrode of flexible self-supporting described above, it is preferred that the film be by
GO, CNTs or BC, the mixed solution of HCCP three are dried evaporation 36-60h in 40~65 DEG C and formed.
In the preparation method of the graphene hybrid electrode of flexible self-supporting described above, it is preferred that fired in the flame
Burn 20s~600s, more preferably 60s~300s.
Described GO, CNTs or BC, HCCP three refer to GO, CNTs and HCCP three or GO, BC and HCCP three.
The preparation method of the graphene hybrid electrode of the flexible self-supporting of the present invention, it may include following step：
1) GO dispersion liquids, CNTs or BC dispersion liquid are prepared；
2) the 1-METHYLPYRROLIDONE solution for preparing HCCP is used as adhesive；
3) by step 1) and 2) in solution mix, ultrasound after and stir；
4) by step 3) in mixed solution be transferred in the mould of polytetrafluoroethylene (PTFE), in drying box evaporate, formed film.
5) prepare transition metal salt solution, by step 4) in film infiltrate the salting liquid, be placed in Alcohol Flame burn, shape
Into the electrode of the CNTs/ graphenes with three dimensions conducting net of crosslinking.
The graphene hybrid electrode of flexible self-supporting of the present invention or by preparation method described above obtain it is soft
The graphene hybrid electrode of property self-supporting can be used as electrode of super capacitor application.
The present invention is combined GO and CNTs or BC by simply mixing, and CNTs or BC addition improve overall electrode
Electric conductivity, then short annealing Jing Guo Alcohol Flame cause GO fully to be reduced.HCCP both can as a kind of adhesive,
, so as to ensure the integrally-built integrality of electrode in combustion, the mechanical stability of electrode can be improved as fireproof agent.
Transition metal salt is used as catalyst so that CNTs is generated in combustion process, so as to form a kind of being led with three dimensions for crosslinking
CNTs (or BC)/rGO (redox graphene)/CNTs of logical net structure, effectively prevents the heap between graphene nanometer sheet
Folded, promotion electrolyte diffusion, improves the overall chemical property of electrode.Obtained application of electrode is in super electricity in this way
During container, its area specific capacitance is up to 1.60F cm-2。
By such scheme, the electrode prepared by the present invention has the three-dimensional structure of self-supporting, high-flexibility, applied to super
During capacitor, with high area specific capacitance, long-life and high stability.
Electrode of the present invention prepares growing principle (by taking CNTs as an example, BC is similarly)：After GO, CNTs and HCCP are mixed, dry
During dry, pi-pi bond is formed between the carboxyl group and CNTs on GO surfaces, stable film is integrally formed as adhesive in HCCP
Structure.Infiltrated on film after transition metal salt solution, during film burns in Alcohol Flame, on the one hand, high temperature
GO is quickly reduced to rGO by flame, so as to form stable two-dimensional film with CNTs；On the other hand, in Alcohol Flame, alcohol
As CNTs carbon source, CNTs can be based on film surface transition metal salt, perpendicular to film surface growth, so as to further be formed
Overall three-dimensional structure；In addition, HCCP is as a kind of fire proofing material, the rupture of film can be effectively prevented in combustion, and
The electronics of integral material will not be hindered to transport, charge storage, so as to form highly conductive, high activity, the three of high-mechanical property
The rGO/CNTs of dimension hybrid electrode.The present invention is a kind of effectively to be combined graphene, CNT based on flame combustion process
Method, obtained electrode is without metal collector, and the structure of its self-supporting also makes the conductive substrates that the electrode is depended on without routine, i.e.,
Electrode is integrally applied not only to electric power storage, and for conduction.
Compared with prior art, advantages of the present invention：(1) flame method short annealing is used, technique is simply efficient；(2)
HCCP addition, both made graphene film and CNTs effectively combine as adhesive, and was used as fire proofing material reduction flame injury；
(3) application of electrode made from is when ultracapacitor, and area specific capacitance is 1.60Fcm to the maximum-2, compared to existing report, property
Can be higher；(4) electrode size, thickness made from can be adjusted by the amount of mixed solution, can be by large-scale production and application；
(5) electrode made from has high bending stability, can be applied to flexible super capacitor.
Brief description of the drawings
Fig. 1 is the electrode scanning electron microscope diagram of electrode 2 in example 1.It is layer structure to illustrate the electrode interior.
Fig. 2 is the electrode scanning electron microscope diagram of electrode 1 in example 1.Illustrate that the electrode has more micro-nano structures.
Fig. 3 is the constant current charge-discharge curve of 2 electrodes in example 1.Illustrate that the charge storage of electrode 1 is higher than electrode 2.
When Fig. 4 is that electrode 1 carries out constant current cycle discharge and recharge 2000 times in example 1, the change curve of area specific capacitance.Explanation
Electrode 1 has good cyclical stability.
Fig. 5 is the bending photo of electrode 1 in example 1.
Fig. 6 is the bending stability test of electrode 1 in example 1.When illustrating to bend different angles to electrode 1, electric capacity is stable.
Embodiment
Following embodiments are further illustrating using as the explaination to the technology of the present invention content for present invention, but
The present invention substantive content be not limited in described in following embodiments, one of ordinary skill in the art can with and should know appoint
What simple change or replacement based on true spirit all should belong to protection domain of the presently claimed invention.
Embodiment 1
1) 90mg GO are taken to configure 5mg ml‐1Dispersion liquid, take 20mg CNTs to configure 5mg ml‐1Dispersion liquid.
2) 100mg HCCP are dissolved in 1-METHYLPYRROLIDONE solution and configure 25mg ml-1Slurry.
3) then, solution in step 1 and 2 is mixed, ultrasound after and stir 30 minutes.
4) then, mixed solution in step 3 is transferred in the mould of polytetrafluoroethylene (PTFE), steaming is dried for 45 DEG C in drying box
48h is sent out, film is formed.
5) configuration 1mol L-1NiSO4Film in metal salt solution, the step 4 of clip 1.00 × 1.50cm sizes, infiltration
NiSO4Salting liquid, is placed in Alcohol Flame and burns 1 minute, so as to form the CNTs/ that there is three dimensions to turn on net of crosslinking
RGO/CNTs electrode 1.Film in the step 4 of clip 1.00 × 1.50cm sizes, is placed directly within Alcohol Flame and burns 1 point
Clock, so as to form the CNTs/rGO of hydridization electrode 2.
6) scanning electron microscopic picture of electrode 2 is as shown in figure 1, the scanning electron microscopic picture of electrode 1 is as shown in Fig. 2 contrast can be sent out
Existing, electrode 1 has more micro-nano structures.Using the electrode being made, platinized platinum and calomel electrode as working electrode, to electrode
With reference electrode, with 0.50M sodium sulphate (Na2SO4) aqueous solution be electrolyte solution, using constant current charge-discharge system carry out electricity
Hold measurement.In test, charging current and discharge current are all 1mA cm-2, voltage window is set to 0~1.20V, and test curve is as schemed
Shown in 3.Obtained through repeatedly test, the area specific capacitance of electrode 1 is 1.60F cm-2, and the area specific capacitance of electrode 2 is only
0.41F cm-2, the former adds 290.24% than the area specific capacitance of the latter.Thus illustrate, in the present invention, transition metal salt
Addition improves area specific capacitance.Then, cycle charge discharge electrical testing is carried out to electrode 1, charging and discharging currents are 4mA cm-2, test
As a result curve as shown in figure 4, show, after 2000 times circulate, electric capacity is the 86% of initial value, and further, electrode 1 is carried out
Bending test, bending photo is as shown in figure 5, and in identical sweep speed 10mV s-1Under, carry out cyclic voltammetric analysis, test
As a result curve as shown in fig. 6, show, when electrode 45-degree-buckling and 90 °, electric capacity is 95% and 92% of capacitance when not bending,
Illustrate that electrode 1 has high bending stability.
Embodiment 2
1) 160mg GO are taken to configure 10mg ml‐1Dispersion liquid, take 8mg CNTs to configure 2mg ml‐1Dispersion liquid.
2) 100mg HCCP are dissolved in 1-METHYLPYRROLIDONE solution and configure 25mg ml-1Slurry.
3) then, solution in step 1 and 2 is mixed, ultrasound after and stir 30 minutes.
4) then, mixed solution in step 3 is transferred in the mould of polytetrafluoroethylene (PTFE), steaming is dried for 55 DEG C in drying box
48h is sent out, film is formed.
5) configuration 0.2mol L-1NiSO4With 2mol L-1MnCl2Mixed salt solution, clip 1.00 × 1.50cm chis
Film in tiny step rapid 4, infiltrates the salting liquid, be placed in Alcohol Flame burn 2 minutes so that formed crosslinking have three dimensions
Turn on the CNTs/rGO/CNTs of net electrode 3.Film in 1.00 × 1.50cm of clip size procedures 4, is placed directly within Alcohol Flame
Middle burning 2 minutes, so as to form the CNTs/rGO of hydridization electrode 4.
6) using the electrode being made, platinized platinum and calomel electrode as working electrode, to electrode and reference electrode, with
0.50M Na2SO4The aqueous solution is electrolyte solution, and capacitance measurement is carried out using constant current charge-discharge system.In test, charging current
It is all 1mA cm with discharge current density-2, voltage window is set to 0~1.20V.Obtained through repeatedly test, the area of electrode 3 is than electricity
Hold for 0.49F cm-2, and the area specific capacitance of electrode 4 is 0.21F cm-2, the former adds than the area specific capacitance of the latter
133.33%.Thus illustrate, in the present invention, the addition of transition metal salt improves the area specific capacitance of electrode.
Embodiment 3
1) 32mg GO are taken to configure 2mg ml‐1Dispersion liquid, take 40mg CNTs to configure 10mg ml‐1Dispersion liquid.
2) 100mg HCCP are dissolved in 1-METHYLPYRROLIDONE solution and configure 25mg ml-1Slurry.
3) then, solution in step 1 and 2 is mixed, ultrasound after and stir 30 minutes.
4) then, mixed solution in step 3 is transferred in the mould of polytetrafluoroethylene (PTFE), steaming is dried for 45 DEG C in drying box
48h is sent out, film is formed.
5) configuration 1.2mol L-1NiSO4With 0.05mol L-1CoCl2Mixed salt solution, clip 1.00 ×
Film in 1.50cm size procedures 4, infiltrates the salting liquid, is placed in Alcohol Flame and burns 1 minute, so as to form having for crosslinking
The CNTs/rGO/CNTs of three dimensions conducting net electrode 5.Film in 1.00 × 1.50cm of clip size procedures 4, is placed directly within
Burnt 1 minute in Alcohol Flame, so as to form the CNTs/rGO of hydridization electrode 6.
6) using the electrode being made, platinized platinum and calomel electrode as working electrode, to electrode and reference electrode, with
0.50M Na2SO4The aqueous solution is electrolyte solution, and capacitance measurement is carried out using constant current charge-discharge system.In test, charging current
It is all 1mA cm with discharge current density-2, voltage window is set to 0~1.20V.Obtained through repeatedly test, the area of electrode 5 is than electricity
Hold for 0.63F cm-2, and the area specific capacitance of electrode 6 is 0.12F cm-2, the former adds than the area specific capacitance of the latter
425.00%.Thus illustrate, in the present invention, the addition of transition metal salt improves the area specific capacitance of electrode.
Embodiment 4
1) 90mg GO are taken to configure 5mg ml‐1Dispersion liquid, take 20mg BC to configure 5mg ml‐1Dispersion liquid.
2) 100mg HCCP are dissolved in 1-METHYLPYRROLIDONE solution and configure 25mg ml-1Slurry.
3) then, solution in step 1 and 2 is mixed, ultrasound after and stir 30 minutes.
4) then, mixed solution in step 3 is transferred in the mould of polytetrafluoroethylene (PTFE), steaming is dried for 45 DEG C in drying box
48h is sent out, film is formed.
5) configuration 1mol L-1CoCl2With 0.1mol L-1CuSO4Mixed salt solution, clip 1.00 × 1.50cm chis
Film in tiny step rapid 4, infiltrates the salting liquid, be placed in Alcohol Flame burn 10 minutes so that formed crosslinking have three-dimensional space
Between turn on net BC/rGO/CNTs electrode 7.Film in 1.00 × 1.50cm of clip size procedures 4, is placed directly within Alcohol Flame
Middle burning 10 minutes, so as to form the BC/rGO of hydridization electrode 8.
6) using the electrode being made, platinized platinum and calomel electrode as working electrode, to electrode and reference electrode, with
0.50M Na2SO4The aqueous solution is electrolyte solution, and capacitance measurement is carried out using constant current charge-discharge system.In test, charging current
It is all 1mA cm with discharge current density-2, voltage window is set to 0~1.20V.Obtained through repeatedly test, the area of electrode 7 is than electricity
Hold for 0.39F cm-2, and the area specific capacitance of electrode 8 is 0.12F cm-2, the former adds than the area specific capacitance of the latter
225.00%.Thus illustrate, in the present invention, the addition of transition metal salt improves the area specific capacitance of electrode.
Embodiment 5
1) 32mg GO are taken to configure 2mg ml‐1Dispersion liquid, take 40mg BC to configure 10mg ml‐1Dispersion liquid.
2) 100mg HCCP are dissolved in 1-METHYLPYRROLIDONE solution and configure 25mg ml-1Slurry.
3) then, solution in step 1 and 2 is mixed, ultrasound after and stir 30 minutes.
4) then, mixed solution in step 3 is transferred in the mould of polytetrafluoroethylene (PTFE), steaming is dried for 45 DEG C in drying box
48h is sent out, film is formed.
5) configuration 2mol L-1NiSO4、0.5mol L-1MnCl2With 0.5mol L-1CuSO4Mixed salt solution, cut
Film in 1.00 × 1.50cm size procedures 4 is taken, the salting liquid is infiltrated, is placed in Alcohol Flame and burns 2 minutes, so as to form friendship
The BC/rGO/CNTs with three dimensions conducting net of connection electrode 9.Film in 1.00 × 1.50cm of clip size procedures 4, directly
Connect to be placed in Alcohol Flame and burn 2 minutes, so as to form the BC/rGO of hydridization electrode 10.
6) using the electrode being made, platinized platinum and calomel electrode as working electrode, to electrode and reference electrode, with
0.50M Na2SO4The aqueous solution is electrolyte solution, and capacitance measurement is carried out using constant current charge-discharge system.In test, charging current
It is all 1mA cm with discharge current density-2, voltage window is set to 0~1.20V.Obtained through repeatedly test, the area of electrode 9 is than electricity
Hold for 1.04F cm-2, and the area specific capacitance of electrode 10 is 0.36F cm-2, the former adds than the area specific capacitance of the latter
188.89%.Thus illustrate, in the present invention, the addition of transition metal salt improves the area specific capacitance of electrode.
Embodiment 6
1) 90mg GO are taken to configure 5mg ml‐1Dispersion liquid, take 8mg BC to configure 2mg ml‐1Dispersion liquid.
2) 100mg HCCP are dissolved in 1-METHYLPYRROLIDONE solution and configure 25mg ml-1Slurry.
3) then, solution in step 1 and 2 is mixed, ultrasound after and stir 30 minutes.
4) then, mixed solution in step 3 is transferred in the mould of polytetrafluoroethylene (PTFE), steaming is dried for 45 DEG C in drying box
48h is sent out, film is formed.
5) configuration 2mol L-1CoCl2With 1.2mol L-1CuSO4Mixed salt solution, clip 1.00 × 1.50cm chis
Film in tiny step rapid 4, infiltrates the salting liquid, be placed in Alcohol Flame burn 5 minutes so that formed crosslinking have three dimensions
Turn on the BC/rGO/CNTs of net electrode 11.Film in 1.00 × 1.50cm of clip size procedures 4, is placed directly within Alcohol Flame
Middle burning 5 minutes, so as to form the BC/rGO of hydridization electrode 12.
6) using the electrode being made, platinized platinum and calomel electrode as working electrode, to electrode and reference electrode, with
0.50M Na2The SO4 aqueous solution is electrolyte solution, and capacitance measurement is carried out using constant current charge-discharge system.In test, charging electricity
Stream and discharge current density are all 1mA cm-2, voltage window is set to 0~1.20V.Obtained through repeatedly test, the area of electrode 11
Specific capacitance is 0.48F cm-2, and the area specific capacitance of electrode 12 is 0.29F cm-2, the former increases than the area specific capacitance of the latter
65.5%.Thus illustrate, in the present invention, the addition of transition metal salt improves the area specific capacitance of electrode.
Embodiment 7
1) 90mg GO are taken to configure 5mg ml‐1Dispersion liquid, take 20mg CNTs to configure 5mg ml‐1Dispersion liquid.
2) 100mg HCCP are dissolved in 1-METHYLPYRROLIDONE solution and configure 25mg ml-1Slurry.
3) then, solution in step 1 and 2 is mixed, ultrasound after and stir 30 minutes.
4) then, mixed solution in step 3 is transferred in the mould of polytetrafluoroethylene (PTFE), steaming is dried for 45 DEG C in drying box
48h is sent out, film is formed.
5) configuration 0.2mol L-1CoCl2With 0.1mol L-1MnCl2Mixed salt solution, 1.00 × 1.50cm of clip
Film in size procedure 4, infiltrates the salting liquid, be placed in Alcohol Flame burn 20 seconds so that formed crosslinking have three-dimensional space
Between turn on net CNTs/rGO/CNTs electrode 13.Film in 1.00 × 1.50cm of clip size procedures 4, is placed directly within alcohol
Burnt 20 seconds in flame, so as to form the CNTs/rGO of hydridization electrode 14.
6) using the electrode being made, platinized platinum and calomel electrode as working electrode, to electrode and reference electrode, with
0.50M Na2SO4The aqueous solution is electrolyte solution, and capacitance measurement is carried out using constant current charge-discharge system.In test, charging current
It is all 1mA cm with discharge current density-2, voltage window is set to 0~1.20V.Obtained through repeatedly test, the area ratio of electrode 13
Electric capacity is 0.81F cm-2, and the area specific capacitance of electrode 14 is 0.53F cm-2, the former adds than the area specific capacitance of the latter
52.83%.Thus illustrate, in the present invention, the addition of transition metal salt improves the area specific capacitance of electrode.
Claims (10)
1. the preparation method of the graphene hybrid electrode of a kind of flexible self-supporting, it is characterised in that use GO and CNTs or adopt
Film is formed in the presence of HCCP with GO and BC, transition metal salt solution is then infiltrated, then is placed in burning in Alcohol Flame, is formed
The graphene hybrid electrode of flexible self-supporting.
2. the preparation method of the graphene hybrid electrode of flexible self-supporting as claimed in claim 1, it is characterised in that the GO
It is configured to 2mg ml-1~10mg ml-1Dispersion liquid, the CNTs or BC are configured to 2mg ml-1~10mg ml-1It is scattered
Liquid.
3. the preparation method of the graphene hybrid electrode of flexible self-supporting as claimed in claim 1, it is characterised in that described
HCCP, which is dissolved in 1-METHYLPYRROLIDONE, prepares 20~30mg ml-1Slurry.
4. the preparation method of the graphene hybrid electrode of flexible self-supporting as claimed in claim 1, it is characterised in that described
GO, CNTs or BC, the mass ratio of HCCP three are 1:(0.05~5):(0.5~10).
5. the preparation method of the graphene hybrid electrode of flexible self-supporting as claimed in claim 1, it is characterised in that the mistake
Crossing metal salt includes one or more of mixing in water miscible nickel, manganese, cobalt, the sulfate of copper, nitrate and villaumite.
6. the preparation method of the graphene hybrid electrode of flexible self-supporting as claimed in claim 5, it is characterised in that the mistake
The concentration for crossing metal salt solution is 0.1mol ml-1~4mol ml-1。
7. the preparation method of the graphene hybrid electrode of flexible self-supporting as claimed in claim 1, it is characterised in that described thin
Film is that GO, CNTs or BC, HCCP three mixed solution are dried into evaporation 36-60h in 40~65 DEG C to be formed.
8. the preparation method of the graphene hybrid electrode of flexible self-supporting as claimed in claim 1, it is characterised in that the fire
Burn 20s~600s in flame.
9. the graphene hybrid electrode of the flexible self-supporting obtained by any one of the claim 1-8 preparation methods.
10. the graphene hybrid electrode of flexible self-supporting described in claim 9 is used as the application of electrode of super capacitor.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107946086A (en) * | 2017-12-09 | 2018-04-20 | 北京化工大学 | It is a kind of using graphene as full carbon resistance rod of ultracapacitor flexible self-supporting of binding agent and preparation method thereof |
| CN108538645A (en) * | 2018-03-28 | 2018-09-14 | 国家纳米科学中心 | A kind of preparation method of carbon/transition metal based combined electrode and products thereof and purposes |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102509635A (en) * | 2011-10-31 | 2012-06-20 | 华中科技大学 | Preparation method of flexible super capacitor based on carbon cloth |
| CN102664106A (en) * | 2012-05-24 | 2012-09-12 | 山西迪诺科技有限公司 | Composite electrode material |
| CN105694915A (en) * | 2015-11-25 | 2016-06-22 | 北京旭碳新材料科技有限公司 | Composition for flame-retardant composite material and graphene flame-retardant foam and preparation method and application of foam |
-
2017
- 2017-07-03 CN CN201710532466.XA patent/CN107240511B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102509635A (en) * | 2011-10-31 | 2012-06-20 | 华中科技大学 | Preparation method of flexible super capacitor based on carbon cloth |
| CN102664106A (en) * | 2012-05-24 | 2012-09-12 | 山西迪诺科技有限公司 | Composite electrode material |
| CN105694915A (en) * | 2015-11-25 | 2016-06-22 | 北京旭碳新材料科技有限公司 | Composition for flame-retardant composite material and graphene flame-retardant foam and preparation method and application of foam |
Non-Patent Citations (1)
| Title |
|---|
| 龚成师: "基于氧化石墨烯纳米片柔性三维结构的制备及其在电化学电容器中的应用", 《中国博士学位论文全文数据库工程科技II辑》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107946086A (en) * | 2017-12-09 | 2018-04-20 | 北京化工大学 | It is a kind of using graphene as full carbon resistance rod of ultracapacitor flexible self-supporting of binding agent and preparation method thereof |
| CN108538645A (en) * | 2018-03-28 | 2018-09-14 | 国家纳米科学中心 | A kind of preparation method of carbon/transition metal based combined electrode and products thereof and purposes |
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