CN107248456A - The preparation method of CNT yarn based flexible super capacitor combination electrode material - Google Patents
The preparation method of CNT yarn based flexible super capacitor combination electrode material Download PDFInfo
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- CN107248456A CN107248456A CN201710282655.6A CN201710282655A CN107248456A CN 107248456 A CN107248456 A CN 107248456A CN 201710282655 A CN201710282655 A CN 201710282655A CN 107248456 A CN107248456 A CN 107248456A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/46—Metal oxides
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Abstract
The invention discloses a kind of preparation method of CNT yarn based flexible super capacitor combination electrode material, it is related to electrode material for super capacitor technical field.Weaving preparation of its step of including CNT yarn, the galvanoplastic of electrode material crude product are combined the graphene ink impregnation process of heating purification processes, the preparation of graphene ink and the composite of preparation and electrode material, CNT (CNT)/transiting state metal oxide/graphene (GN) combination electrode material is finally given, attached transiting state metal oxide on the carbon nanotubes includes cobaltosic oxide (Co3O4) nano particle, nickel oxide (NiO) nano particle or manganese dioxide (MnO2) nano particle.The present invention have have a extensive future, electrochemical performance and the characteristics of technique environmental protection, it is simple and easy to apply, it is easy to promote the use of.
Description
Technical field
The present invention relates to electrode material for super capacitor technical field, and in particular to a kind of CNT yarn base is soft
The preparation method of property solid-state super capacitor combination electrode material.
Background technology
The energy, as the most basic power support of 21 century human survival and development, is the disaster of world today's urgent need to resolve ten
How one of topic, be asking jointly of facing of current whole world scientists and engineers in one sustainable new energy of future development
Topic.Battery and ultracapacitor be it is the most frequently used be also the energy storage device for most widely using value, compared with battery,
Ultracapacitor has the advantages that power density is high, cycle life up to more than ten thousand times, charge-discharge velocity is fast, operating temperature is wide, together
The characteristic that Shi Yongyou is simple in construction, property is stable, is allowed in consumption-orientations such as automobile, science and techniques of defence, Aero-Space and household electrical appliance
Electronic product industry is used widely, and has turned into the focus that countries in the world are studied.
At present, carbon material is due to good electric property, mechanical performance, corrosion resistance, chemistry and high-temperature stability
It is one of preferable electrode material of ultracapacitor Deng many advantages.CNT, as one kind of active carbon material, is individual layer
Or the hollow nanoscale tubular material of Multi-layer graphite curling, it has larger specific surface area and good electric conductivity,
These are characterized in that it turns into the advantage of electrode material for super capacitor.But CNT is used as ultracapacitor merely
Electrode material, its capacitance and energy density are limited, often need to be by CNT and other counterfeit electric materials, such as transiting state metal oxygen
Compound is compound to be prepared into combination electrode material, capacitance, energy density and stability to improve ultracapacitor etc.；And stone
Black alkene is a kind of carbon material of the hexagonal lattice of bi-dimensional cellular shape, because it has electrical conductivity height, specific surface area big and chemically stable
The advantages of property is good and be widely used, it is also one of ideal electrode material of ultracapacitor.
The need for adapt to portable high integration electronics miniaturization and be lightening, flexible super capacitor is opened
Hair and its correlation theory research, which turn into, is engaged in the focus of attention of capacitor Research Scientist in recent years, the flexibility of ultracapacitor
Research need to often start with from the structure of ultracapacitor, improve electrode material for super capacitor and ion transport mechanism, be allowed to soft
There is chemical property stable as common ultracapacitor under conditions of tough and relatively thin.It is general to use carbon paper or carbon cloth
Flexible super capacitor is prepared as flexible electrode material, but these flexible super capacitors are often two dimension or three-dimensional, not
Can effectively it weave in common wearable daily necessities, and the CNT yarn of one-dimensional linear is not only flexible with textile
Property and stitchability, and be to prepare the advantages of inherit CNT good mechanical property, electric conductivity high and stable chemical performance
Linearly, the preferable electrode material of flexible, wearable ultracapacitor.However, using CNT yarn as electrode merely
Material, due to the limitation of its Storage mechanism, its capacitance stored and energy density be not high.Based on this, design a kind of carbon and receive
The preparation method of mitron yarn base flexible solid-state supercapacitor combination electrode material or necessary.
The content of the invention
In view of the shortcomings of the prior art, the present invention seeks to be that providing a kind of CNT yarn base flexibility surpasses
The preparation method of level capacitor composite electrode material, simple and easy to apply, the ultracapacitor chemical property being assembled into is excellent, and work
Skill environmental protection, it is easy to promote the use of.
To achieve these goals, the present invention is to realize by the following technical solutions：CNT yarn base is flexible
The preparation method of composite electrode material for super capacitor, its preparation process is：
(1) prepared by the weaving of CNT (CNT) yarn：The carbon nano pipe array of chemical vapor deposition preparation is crossed, is adopted
Control rotating speed under the conditions of 1000~5000rpm, to pull out carbon nanometer from array carbon nano tube by motor with Weaving device
Manage and rotate weaving after twisting and obtain a diameter of 20~50 μm of CNT yarns；
(2) electrodeposition process of electrode material crude product is compound prepares：Using three electrode electro-deposition, with obtained by step (1)
CNT yarn is as working electrode, and Ag/AgCl is reference electrode, and metal platinum is comparison electrode, is containing transiting state metal
The crude product that electro-deposition obtains electrode material is carried out in the electroplate liquid of salt；
(3) the heating purification processes of electrode material：It is combined and has prepared in the electrodeposition process of step (2) electrode material crude product
Afterwards, the electrode material crude product obtained by step (2) is heated into 60~150min under the conditions of 80~300 DEG C, you can obtain carbon and receive
Mitron yarn load transitions state metal oxide composite；
(4) preparation of graphene (GN) ink：A certain amount of graphene is added to the mixed solution (water of water and absolute ethyl alcohol
Volume ratio with ethanol is 3：2) in, stone is obtained after then adding 0.1~2ml perfluorinated sulfonic acid solution, 10~50min of ultrasonic disperse
Black alkene ink；
(5) the graphene ink impregnation process of electrode material：CNT complex yarn obtained by step (3) is immersed in
In the graphene ink that step (4) is obtained, each dip time is 10~30min, then by electrode material at 60~80 DEG C
It can obtain after drying and CNT/transition gold finally obtained after the product after impregnating for the first time, so repeatedly 3~5 times dippings
Belong to oxide/graphene complex yarn electrode.
Preferably, the carbon nano-pipe array in the step (1) is classified as the multi-walled carbon nanotube of chemical vapor deposition, institute
State a diameter of 10~30nm of Single Carbon Nanotubes in carbon nano pipe array.
Preferably, three electrode electro-deposition in the step (2) are constant potential electro-deposition, the voltage of electro-deposition is 0.5
~2.0V；Sedimentation time is 5~600s；The electroplate liquid is the aqueous solution of sodium salt containing metal and transiting state metal salt, described
The molar concentration of metal sodium salt is 0.05~0.5mol/L, and the concentration of transiting state metal salt is 0.02~1.0mol/L.
Preferably, the metal sodium salt contained by described electroplate liquid is NaNO3、Na2SO4, one or more in NaCl；
Contained transiting state metal salt is Co (NO in described electroplate liquid3)2、CoSO4、Co(CH3COO)2And one kind in their hydrates
Or it is a variety of；Transiting state metal salt is alternatively Ni (NO3)2、NiSO4、Ni(CH3COO)2And one kind or many in their hydrate
Kind；Transiting state metal salt can also be Mn (NO3)2、MnSO4、Mn(CH3COO)2And the one or more in their hydrate.
Preferably, the perfluorinated sulfonic acid solution in described step (4) is the Nafion 117 that du pont company is produced
Solution, obtained graphene drop mass concentration is 3~10mg/ml.
Beneficial effects of the present invention：(1) small-sized electronic equipment and wearable electronic textile be can be applied to.The present invention
Prepared combination electrode material preparation method is simple, and the ultracapacitor chemical property being assembled into is excellent, and can be with
Other ultracapacitors are knitted into electric conductivity textile together, are had broad application prospects.
(2) technical process is environmentally safe.The present invention uses constant potential to be electrodeposited in carbon nano-tube yarn linear load mistake
State metal oxide is crossed, graphene formation composite three layer structure electrode, electroplating bath components used are then covered with by infusion process again
Simply, it is environmentally safe, and electrodeposition technology is simply controllable, carries out at normal temperatures, the process is without discharge of steam.
Brief description of the drawings
Describe the present invention in detail with reference to the accompanying drawings and detailed description；
Fig. 1 is CNT yarn/cobaltosic oxide nickel oxide/graphene (CNT/Co in embodiments of the invention 13O4@
NiO/GN) the SEM structural representations of combination electrode material.
Embodiment
To be easy to understand the technical means, the inventive features, the objects and the advantages of the present invention, with reference to
Embodiment, is expanded on further the present invention.
Reference picture 1, present embodiment uses following technical scheme：CNT yarn based flexible super capacitor is answered
The preparation method of composite electrode material, its preparation process is：
(1) prepared by the weaving of CNT (CNT) yarn：The carbon nano pipe array of chemical vapor deposition preparation is crossed, is adopted
Control rotating speed under the conditions of 1000~5000rpm, to pull out carbon nanometer from array carbon nano tube by motor with Weaving device
Manage and rotate weaving after twisting and obtain a diameter of 20~50 μm of CNT yarns；
(2) electrodeposition process of electrode material crude product is compound prepares：Using three electrode electro-deposition, with obtained by step (1)
CNT yarn is as working electrode, and Ag/AgCl is reference electrode, and metal platinum is comparison electrode, is containing transiting state metal
The crude product that electro-deposition obtains electrode material is carried out in the electroplate liquid of salt；
(3) the heating purification processes of electrode material：It is combined and has prepared in the electrodeposition process of step (2) electrode material crude product
Afterwards, the electrode material crude product obtained by step (2) is heated into 60~150min under the conditions of 80~300 DEG C, you can obtain carbon and receive
Mitron yarn load transitions state metal oxide composite；
(4) preparation of graphene (GN) ink：A certain amount of graphene is added to the mixed solution (water of water and absolute ethyl alcohol
Volume ratio with ethanol is 3：2) in, stone is obtained after then adding 0.1~2ml perfluorinated sulfonic acid solution, 10~50min of ultrasonic disperse
Black alkene ink；
(5) the graphene ink impregnation process of electrode material：CNT complex yarn obtained by step (3) is immersed in
In the graphene ink that step (4) is obtained, each dip time is 10~30min, then by electrode material at 60~80 DEG C
It can obtain after drying and CNT/transition gold finally obtained after the product after impregnating for the first time, so repeatedly 3~5 times dippings
Belong to oxide/graphene complex yarn electrode.
It is worth noting that, the carbon nano-pipe array in the step (1) is classified as the multi-wall carbon nano-tube of chemical vapor deposition
A diameter of 10~the 30nm of Single Carbon Nanotubes in pipe, the carbon nano pipe array.
It is worth noting that, three electrode electro-deposition in the step (2) are constant potential electro-deposition, the voltage of electro-deposition is
0.5~2.0V；Sedimentation time is 5~600s；The electroplate liquid is the aqueous solution of sodium salt containing metal and transiting state metal salt, described
The molar concentration of metal sodium salt be 0.05~0.5mol/L, the concentration of transiting state metal salt is 0.02~1.0mol/L；It is described
Electroplate liquid contained by metal sodium salt be NaNO3、Na2SO4, one or more in NaCl, transiting state metal salt is Co (NO3)2、
CoSO4、Co(CH3COO)2And the one or more in their hydrates；Transiting state metal salt is alternatively Ni (NO3)2、NiSO4、Ni
(CH3COO)2And the one or more in their hydrate；Transiting state metal salt can also be Mn (NO3)2、MnSO4、Mn
(CH3COO)2And the one or more in their hydrate.
In addition, the perfluorinated sulfonic acid solution in described step (4) is the solution of Nafion 117 that du pont company is produced,
Obtained graphene drop mass concentration is 3~10mg/ml.
Present embodiment preparation method is simple, and the ultracapacitor chemical property being assembled into is excellent, and can be with
It is knitted into together in electric conductivity textile with other ultracapacitors, overcomes conventional linear flexible solid-state supercapacitor capacitance
The features such as low and undesirable energy density, and technical process is environmentally safe, with wide market application foreground.
Embodiment 1：The preparation method of CNT yarn based flexible super capacitor combination electrode material, its preparation process
For：The CNT yarn that diameter is about 30 μm is prepared by making spinning equipment weaving under the conditions of rotating speed is 5000rpm by oneself；Adopt
Constant potential electrodeposition process is used, using the CNT yarn as working electrode, Ag/AgCl is reference electrode, and metal platinum is contrast
Electrode, plating solution is to contain 0.5mol/L Co (NO3)2、0.5mol/L Ni(NO3)2、0.1mol/L NaNO3The aqueous solution,
10min is deposited under the conditions of 1.3V constant voltages, adds the CNT complex yarn in 250 DEG C of Muffle furnace after the completion of electro-deposition
Hot 150min, produces the carbon nano-tube yarn linear load cobaltosic oxide and nickel oxide (CNT/Co3O4@NiO) composite；Will
To composite to be immersed in the concentration for preparing be 10min in 10mg/ml graphene ink, then in 80 DEG C of baking oven
30min is dried, is so repeated four times and obtains final CNT/cobaltosic oxide@nickel oxide/graphene (CNT/Co3O4@
NiO/GN) complex yarn electrode.
Embodiment 2：The preparation method of CNT yarn based flexible super capacitor combination electrode material, its preparation process
For：By spinning equipment, weaving prepares the CNT yarn that diameter is about 35 μm under the conditions of rotating speed is 5000rpm；Using perseverance
Current potential electrodeposition process, using the CNT yarn as working electrode, Ag/AgCl is reference electrode, and metal platinum is comparison electrode,
Plating solution is to contain 0.5mol/L Co (NO3)2、0.1mol/L NaNO3The aqueous solution, under the conditions of 1.3V constant voltages deposit
10min, 120min is heated after the completion of electro-deposition by the CNT complex yarn in 250 DEG C of Muffle furnace, is produced the carbon and is received
Mitron yarn supported cobaltosic oxide (CNT/Co3O4) composite；Obtained composite is immersed in the concentration prepared is
10min in 10mg/ml graphene ink, then dries 30min in 80 DEG C of baking oven, so obtains final carbon nanometer
Pipe/cobalt oxide/graphene (CNT/Co3O4/ GN) complex yarn electrode.
Embodiment 3：The preparation method of CNT yarn based flexible super capacitor combination electrode material, its preparation process
For：By spinning equipment, weaving prepares the CNT yarn that diameter is about 25 μm under the conditions of rotating speed is 2000rpm；Using perseverance
Current potential electrodeposition process, using the CNT yarn as working electrode, Ag/AgCl is reference electrode, and metal platinum is comparison electrode,
Plating solution is to contain 0.5mol/L Ni (NO3)2、0.1mol/L NaNO3The aqueous solution, under the conditions of 1.0V constant voltages deposit
10min, 120min is heated after the completion of electro-deposition by the CNT complex yarn in 200 DEG C of Muffle furnace, is produced the carbon and is received
Mitron yarn loads nickel oxide (CNT/NiO) composite；It is 8mg/ that obtained composite is immersed in the concentration prepared
10min in ml graphene ink, then dries 30min in 80 DEG C of baking oven, so repeats to obtain final carbon five times to receive
Mitron/nickel oxide/graphene (CNT/NiO/GN) complex yarn electrode complex yarn electrode.
Embodiment 4：The preparation method of CNT yarn based flexible super capacitor combination electrode material, its preparation process
For：By spinning equipment, weaving prepares the CNT yarn that diameter is about 28 μm under the conditions of rotating speed is 2000rpm；Using perseverance
Current potential electrodeposition process, using the CNT yarn as working electrode, Ag/AgCl is reference electrode, and metal platinum is comparison electrode,
Plating solution is to contain 0.2mol/L Co (CH3COO)2、0.2mol/L Ni(CH3COO)2, 0.2mol/L NaCl the aqueous solution,
10min is deposited under the conditions of 1.0V constant voltages, adds the CNT complex yarn in 250 DEG C of Muffle furnace after the completion of electro-deposition
Hot 150min, produces the carbon nano-tube yarn linear load cobaltosic oxide and nickel oxide (CNT/Co3O4@NiO) composite；Will
To composite to be immersed in the concentration for preparing be 10min in 6mg/ml graphene ink, then in 80 DEG C of baking oven
30min is dried, so repeats to obtain final CNT/cobaltosic oxide@nickel oxide/graphene (CNT/Co five times3O4@
NiO/GN) complex yarn electrode.
Embodiment 5：The preparation method of CNT yarn based flexible super capacitor combination electrode material, its preparation process
For：By spinning equipment, weaving prepares the CNT yarn that diameter is about 32 μm under the conditions of rotating speed is 5000rpm；Using perseverance
Current potential electrodeposition process, using the CNT yarn as working electrode, Ag/AgCl is reference electrode, and metal platinum is comparison electrode,
Plating solution is to contain 0.05mol/L MnSO4, 0.2mol/L Na2SO4The aqueous solution, deposit 30s under the conditions of 1.3V constant voltages,
The CNT complex yarn is dried into 60min under conditions of 80 DEG C after the completion of electro-deposition, the CNT yarn is produced and bears
Carry manganese dioxide (CNT/MnO2) composite；Obtained composite is immersed in the graphite that the concentration prepared is 8mg/ml
15min in alkene ink, 30min is then dried in 80 DEG C of baking oven, final CNT/dioxy is so obtained in triplicate
Change manganese/graphene (CNT/MnO2/ GN) complex yarn electrode.
To sum up, in order to verify that the present invention prepares the performance of gained combination electrode material, respectively to answering obtained by embodiment 1-5
Composite electrode material carries out electrochemical property test, and concrete outcome is as follows：
Electrical performance test method is：CNT yarn composite well prepared in advance is assembled into super capacitor
Device, with PVA-H2SO4(5g PVA are dissolved in 50mL molar concentrations for 1mol/L H to gel2SO4In) as electrolyte and barrier film,
Using CHI660E electrochemical workstations, according to the cyclic voltammetry curve of gained under 0.01V/s sweep speeds, specific capacitance is calculated
And energy density, specific data are as shown in table 1.
The ratio that the ultracapacitor that electrode material described in the embodiment 1-5 of table 1 is assembled is calculated under 0.01V/s sweep speeds
Electric capacity and energy density
The general principle and principal character and advantages of the present invention of the present invention has been shown and described above.The technology of the industry
Personnel are it should be appreciated that the present invention is not limited to the above embodiments, and the simply explanation described in above-described embodiment and specification is originally
The principle of invention, without departing from the spirit and scope of the present invention, various changes and modifications of the present invention are possible, these changes
Change and improvement all fall within the protetion scope of the claimed invention.The claimed scope of the invention by appended claims and its
Equivalent thereof.
Claims (10)
1. the preparation method of CNT yarn based flexible super capacitor combination electrode material, it is characterised in that it prepares step
Suddenly it is：
(1) prepared by the weaving of CNT (CNT) yarn：The carbon nano pipe array of chemical vapor deposition preparation is crossed, using spinning
Equipment is knitted to control rotating speed under the conditions of 1000~5000rpm, CNT is pulled out simultaneously from array carbon nano tube by motor
Weaving obtains a diameter of 20~50 μm of CNT yarns after rotation twisting；
(2) electrodeposition process of electrode material crude product is compound prepares：Using three electrode electro-deposition, received with the carbon obtained by step (1)
Mitron yarn is as working electrode, and Ag/AgCl is reference electrode, and metal platinum is comparison electrode, is containing transiting state metal salt
The crude product that electro-deposition obtains electrode material is carried out in electroplate liquid；
(3) the heating purification processes of electrode material：Step (2) electrode material crude product electrodeposition process it is compound prepared after,
Electrode material crude product obtained by step (2) is heated into 60~150min under the conditions of 80~300 DEG C, you can obtain CNT
Yarn load transitions state metal oxide composite；
(4) preparation of graphene (GN) ink：A certain amount of graphene is added to mixed solution (water and the second of water and absolute ethyl alcohol
The volume ratio of alcohol is 3：2) in, graphene is obtained after then adding 0.1~2ml perfluorinated sulfonic acid solution, 10~50min of ultrasonic disperse
Ink；
(5) the graphene ink impregnation process of electrode material：CNT complex yarn obtained by step (3) is immersed in step
(4) in the graphene ink obtained, each dip time is 10~30min, then dries electrode material at 60~80 DEG C
CNT/oxo transition metal is finally obtained after can obtain the product after impregnating for the first time, so repeatedly 3~5 times dippings afterwards
Compound/graphene complex yarn electrode.
2. the preparation method of CNT yarn based flexible super capacitor combination electrode material according to claim 1,
Characterized in that, the carbon nano-pipe array in the step (1) is classified as the multi-walled carbon nanotube of chemical vapor deposition, the carbon is received
A diameter of 10~the 30nm of Single Carbon Nanotubes in mitron array.
3. the preparation method of CNT yarn based flexible super capacitor combination electrode material according to claim 1,
Characterized in that, three electrode electro-deposition in the step (2) are constant potential electro-deposition, the voltage of electro-deposition is 0.5~2.0V；
Sedimentation time is 5~600s；The electroplate liquid is the aqueous solution of sodium salt containing metal and transiting state metal salt.
4. the preparation method of CNT yarn based flexible super capacitor combination electrode material according to claim 3,
Characterized in that, the metal sodium salt contained by described electroplate liquid is NaNO3、Na2SO4, one or more in NaCl.
5. the preparation method of CNT yarn based flexible super capacitor combination electrode material according to claim 3,
Characterized in that, contained transiting state metal salt is Co (NO in described electroplate liquid3)2、CoSO4、Co(CH3COO)2And they are hydrated
One or more in thing.
6. the preparation method of CNT yarn based flexible super capacitor combination electrode material according to claim 3,
Characterized in that, transiting state metal salt contained in described electroplate liquid is Ni (NO3)2、NiSO4、Ni(CH3COO)2And they
One or more in hydrate.
7. the preparation method of CNT yarn based flexible super capacitor combination electrode material according to claim 3,
Characterized in that, contained transiting state metal salt is Mn (NO in described electroplate liquid3)2、MnSO4、Mn(CH3COO)2And their water
One or more in compound.
8. the preparation side of the CNT yarn based flexible super capacitor combination electrode material according to claim 4-7
Method, it is characterised in that the molar concentration of described metal sodium salt is 0.05~0.5mol/L, the concentration of transiting state metal salt is
0.02~1.0mol/L.
9. the preparation method of CNT yarn based flexible super capacitor combination electrode material according to claim 1,
Characterized in that, the perfluorinated sulfonic acid solution in described step (4) is the solution of Nafion 117 that du pont company is produced, obtain
The graphene drop mass concentration arrived is 3~10mg/ml.
10. the preparation method of CNT yarn based flexible super capacitor combination electrode material according to claim 1,
Characterized in that, its preparation process is：Prepare diameter by making spinning equipment weaving under the conditions of rotating speed is 5000rpm by oneself and be about
30 μm of CNT yarn；Using constant potential electrodeposition process, using the CNT yarn as working electrode, Ag/AgCl is
Reference electrode, metal platinum is comparison electrode, and plating solution is to contain 0.5mol/L Co (NO3)2、0.5mol/L Ni(NO3)2、
0.1mol/L NaNO3The aqueous solution, 10min is deposited under the conditions of 1.3V constant voltages, the CNT is answered after the completion of electro-deposition
Yarns heat 150min in 250 DEG C of Muffle furnace, produce the carbon nano-tube yarn linear load cobaltosic oxide and nickel oxide
(CNT/Co3O4@NiO) composite；Obtained composite is immersed in the concentration prepared black for 10mg/ml graphene
10min in water, then dries 30min in 80 DEG C of baking oven, is so repeated four times and obtains the oxidation three of final CNT/tetra-
Cobalt@nickel oxide/graphene (CNT/Co3O4@NiO/GN) complex yarn electrode.
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| 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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| CN110391768A (en) * | 2019-06-28 | 2019-10-29 | 江苏大学 | The mechanical energy harvester of carbon nanotube yarn based on vacuum high-temperature annealing |
| CN114496594A (en) * | 2022-01-24 | 2022-05-13 | 常熟理工学院 | Preparation method of yarn-based flexible supercapacitor composite electrode material |
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| CN114927354A (en) * | 2022-05-25 | 2022-08-19 | 南京航空航天大学 | Nitrogen-doped manganese dioxide/graphene carbon nanotube electrode material and preparation method thereof |
| CN114927354B (en) * | 2022-05-25 | 2023-08-22 | 南京航空航天大学 | Nitrogen-doped manganese dioxide/graphene carbon nanotube electrode material and preparation method thereof |
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