CN104201006A - Preparation method of carbon nanotube/manganese dioxide hybridization supercapacitor electrode material - Google Patents
Preparation method of carbon nanotube/manganese dioxide hybridization supercapacitor electrode material Download PDFInfo
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- CN104201006A CN104201006A CN201410404029.6A CN201410404029A CN104201006A CN 104201006 A CN104201006 A CN 104201006A CN 201410404029 A CN201410404029 A CN 201410404029A CN 104201006 A CN104201006 A CN 104201006A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 128
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 47
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000007772 electrode material Substances 0.000 title claims abstract description 23
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 238000009396 hybridization Methods 0.000 title abstract description 5
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 82
- 239000004744 fabric Substances 0.000 claims abstract description 68
- 238000000034 method Methods 0.000 claims abstract description 23
- 239000012535 impurity Substances 0.000 claims description 30
- 239000003990 capacitor Substances 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 16
- 238000000137 annealing Methods 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- 229910021529 ammonia Inorganic materials 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 230000008020 evaporation Effects 0.000 claims description 8
- 238000001704 evaporation Methods 0.000 claims description 8
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 8
- 238000010792 warming Methods 0.000 claims description 8
- 239000002131 composite material Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 4
- CNGFUKTUURDVOU-UHFFFAOYSA-N [C].CC(C)=O Chemical compound [C].CC(C)=O CNGFUKTUURDVOU-UHFFFAOYSA-N 0.000 claims description 2
- 238000000151 deposition Methods 0.000 claims description 2
- 230000008021 deposition Effects 0.000 claims description 2
- 238000005229 chemical vapour deposition Methods 0.000 abstract description 5
- 229910003144 α-MnO2 Inorganic materials 0.000 abstract description 2
- 239000013543 active substance Substances 0.000 abstract 1
- 239000011248 coating agent Substances 0.000 abstract 1
- 238000000576 coating method Methods 0.000 abstract 1
- 238000009792 diffusion process Methods 0.000 abstract 1
- 239000000463 material Substances 0.000 description 11
- 230000008569 process Effects 0.000 description 11
- 238000004146 energy storage Methods 0.000 description 8
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 229910003481 amorphous carbon Inorganic materials 0.000 description 4
- 239000012286 potassium permanganate Substances 0.000 description 4
- 238000006479 redox reaction Methods 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- 238000010306 acid treatment Methods 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000012423 maintenance Methods 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 239000011232 storage material Substances 0.000 description 3
- 229910000314 transition metal oxide Inorganic materials 0.000 description 3
- 239000003643 water by type Substances 0.000 description 3
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000004070 electrodeposition Methods 0.000 description 2
- 238000005566 electron beam evaporation Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 238000001755 magnetron sputter deposition Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 239000002135 nanosheet Substances 0.000 description 2
- GOPYZMJAIPBUGX-UHFFFAOYSA-N [O-2].[O-2].[Mn+4] Chemical group [O-2].[O-2].[Mn+4] GOPYZMJAIPBUGX-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005234 chemical deposition Methods 0.000 description 1
- 230000004087 circulation Effects 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000002322 conducting polymer Substances 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000006193 liquid solution Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
Classifications
-
- 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
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- Battery Electrode And Active Subsutance (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
Provided is a preparation method of a carbon cloth/carbon nanotube/manganese dioxide hybridization supercapacitor electrode material. According to the preparation method, a plasma chemical vapor deposition method is used for directional growth of orderly carbon nanotubes of great binding force on a carbon cloth, and a hydrothermal mode is used for completely coating the periphery of the carbon nanotubes with a layer of nano sheet-like alpha-MnO2 active substances. The hybridization electrode material prepared through the method is simple in structure and has a directional porous channel for facilitating the embedding, removing and diffusion of the plasma, thereby having the characteristics such as high capacity and high cycle performance.
Description
Technical field
The invention belongs to energy storage material and devices field, relate to particularly the Preparation method and use of the polynary compound high-performance super capacitor electrode material of a kind of flexible carbon cloth, aligned carbon nanotube and manganese dioxide hydridization.
Background technology
The requirement that portable and wearable electronic product energy storage device and device have proposed gentlier, thinner, less, capacity is larger, in numerous energy storage modes, ultracapacitor has very high power density and higher energy density has obtained paying close attention to widely.Ultracapacitor is divided into double electric layer capacitor and Faraday pseudo-capacitance device two classes.The electrode material of double electric layer capacitor is mainly material with carbon element, and the electrode material of fake capacitance device is transition metal oxide, hydroxide and conducting polymer.In order to obtain higher capacity, by compound to material with carbon element and transition metal oxide, bring into play both advantages at present, preparation hydridization capacitor electrode material becomes study hotspot.
Flexible energy storage material need to be taken into account conductive flexible and mechanical flexibility, and carbon cloth is one of extraordinary selection as collector electrode or electrode material.Traditional ultracapacitor is often solidificated in electrode material on collector electrode by binding agent, cause its mechanical energy and high rate performance to be greatly affected, so preparation, does not add the self-supporting super capacitor material of any binding agent and conductive agent and is paid close attention to more and more widely and study.
Carbon nano-tube is the one dimension tubular nanostructures being curled into by Graphene, between carbon atom wherein with Sp
2hybrid form bonding, makes carbon nano-tube both have very high mechanical strength, also has very high conductivity and chemical property, is a kind of advanced person's flexible energy storage material.In numerous transition metal oxide materials, manganese dioxide has higher ratio electric capacity, environmental friendliness, the advantage such as cheap, obtain paying close attention to widely, especially α-MnO2 has larger channel diameter, be conducive to some at a low price the embedding of cations (Li+, K+, Na+ etc.) deviate from and spread in mutually at body, there is very high electric capacity high rate performance.But MnO
2material has the shortcoming of poorly conductive, has limited its further use as super capacitor material.So, utilize high conductivity and the MnO of carbon nano-tube
2high specific capacitance, carbon nano-tube and MnO2 Material cladding are made to the direction that hydridization capacitor is competitively studied.
Hu liangbing etc. is coated in CNT on polyester fiber cloth, forms 3D structure, is then coated on around carbon pipe as substrate electro-deposition MnO2, makes flexible hydridization capacitor (Hu liangbing, et al.Symmetrical mnO
2-carbon nanotube-textile nanostructures for wearable pseudocapacitors with high mass loading.Acs Nano.2011, Vol.5:8904-8913).Zhou cheng etc. are by CVD mode unordered carbon nano-tube of having grown on carbon cloth, make flexible super capacitor (Zhou cheng, et al.Carbon nanotube network film directly grown on carbon cloth for high-performance solid-state flexible supercapacitors.Nanotechnology.2014, DOI:10.1088/0957-4484/25/3/035402).CN 102354612A adopts liquid solution as carbon source and catalyst source, and the carbon pipe that surface density is very high, draw ratio is very high of having grown on carbon cloth fiber by CVD mode, utilizes the mode of electro-deposition in carbon nano-tube, to be coated MnO
2particle, this carbon pipe is due to the too high and easily lodging of draw ratio, and surface density is too high is unfavorable for that electrolyte enters the embedding of array carbon nanotube inside and ion and deviates from, and causes high-rate charge-discharge capability and cycle performance poor.
Prepared by above-mentioned technology is carbon nano tube structure or the hybrid structure of disordering, and this disordered structure and non-hydridization capacitor are deposited and be unfavorable for the embedding of ion and deviate from, and have affected capacity and the high rate performance of capacitor.
Summary of the invention
For overcoming the defect of prior art, one of object of the present invention is to provide a kind of Preparation method and use of carbon nano-tube/manganese dioxide hydridization electrode material for super capacitor.Using plasma chemical deposition mode of the present invention, the strong ordered carbon nanotube of oriented growth adhesion on carbon cloth, and adopt hydro-thermal mode, to the carbon nano-tube α-MnO of completely coated one deck nano-sheet around
2active material.The hybridization electrode that the present invention makes is simple in structure, has directed porous channel, be conducive to ion embedding, deviate from and spread, make electrode material there is the characteristic such as high power capacity, high cycle performance.
For reaching above-mentioned purpose, the present invention adopts following technical scheme:
A preparation method for carbon cloth/carbon nano-tube/manganese dioxide hydridization electrode material for super capacitor, comprises the steps:
(1) will after flexible carbon cloth (CC) removal inorganic impurity, remove organic impurities;
(2) on carbon cloth, deposit layer of Ni film by physical evaporation mode (comprising magnetron sputtering, electron beam evaporation, hot evaporation etc.), as the catalyst of carbon nano-tube;
(3) carbon cloth of step (1) being removed after impurity is inserted in carbon nano-tube plasma chemistry deposition (PECVD) growth furnace, to the nodularization of annealing of Ni film;
(4) cooling passes into C
2h
4, start plasma power supply, in chamber, produce plasma, carry out the ordering growth of carbon nano-tube (CNT);
(5) there is the carbon cloth of pipe to insert in reactor step (4) gained growth, seal after adding liquor potassic permanganate, be then heated lower reaction, make potassium permanganate and the outermost amorphous carbon layer generation of carbon pipe redox reaction, generation MnO
2lamellar structure;
(6) reaction finishes to open reactor after rear quick cooling reactor, takes out carbon cloth, rinses with deionized water, then, by carbon cloth baking, obtains carbon cloth/carbon nano-tube/MnO
2composite material.
Using plasma of the present invention strengthens chemical vapour deposition (CVD) mode (PECVD) mode, the very strong orderly CNT array of oriented growth and carbon cloth fibrous binding force on flexible carbon cloth, carbon pipe diameter is at 130-150nm, length is in 5-6 micron left and right, there is good self-supporting strength, between carbon pipe, keep certain gap, so that the entering of electrolyte; And adopt simple hydro-thermal reaction, to the coated one deck nano-sheet α-MnO of carbon pipe growth around
2material, can form 3 D stereo duct, is conducive to the embedding of ion and deviates from, and has prepared high power capacity and the hydridization capacitor electrode material with excellent cycling performance.
The loose structure of this orderly hydridization can improve the contact area of electrode active material and electrolyte greatly, and is conducive to the exchange of ion, can carry the capacity and the high rate performance that significantly improve flexible capacitor, can be applicable to the power material of flexible device.
As optimal technical scheme, preparation method of the present invention, the method for removing inorganic impurity in step (1) is: flexible carbon cloth salpeter solution is soaked, then use deionized water rinsing.
Preferably, the method of described removal inorganic impurity is: for example, by 2-8mol/L for flexible carbon cloth (5cm × 5cm), be for example more than the salpeter solution immersion 0.5h of 2.3mol/L, 2.9mol/L, 3.5mol/L, 5.0mol/L, 6.5mol/L, 7.8mol/L etc., be for example 0.8h, 1.2h, 2.0h, 3.5h etc., preferably 1h, then uses a large amount of deionized water rinsings.
Preferably, the method for described removal organic impurities is: will be through removing inorganic impurity acetone, successively ultrasonic cleaning of ethanol for carbon cloth after treatment.
Preferably, the method for described removal organic impurities is: will be through removing inorganic impurity acetone carbon cloth for after treatment, ethanol priority is carried out 3-5 ultrasonic cleaning.
As optimal technical scheme, preparation method of the present invention, in step (2), the thickness of Ni film is 5-20nm, for example, be 7nm, 10nm, 14nm, 18nm etc., is preferably 8-15nm.
As optimal technical scheme preparation method of the present invention, the condition of nodularization of annealing described in step (3) is: passing into ammonia, be warming up to 700-800 DEG C, for example, is 720 DEG C, 760 DEG C, 790 DEG C etc., keeping 5-20min, for example, is 8min, 12min, 17min etc.
Preferably, the condition of described annealing nodularization is: pass into 150-250ccm, and the preferably ammonia of 200ccm, in growth furnace chamber, pressure is 15-25mbar, is preferably 20mbar, is warming up to 730-770 DEG C, preferably 750 DEG C, keeps 10-12min.
As optimal technical scheme, preparation method of the present invention, described in step (4), cooling is for being cooled to 680-750 DEG C.
Preferably, described C
2h
4the speed passing into is 40-80Sccm, is preferably 60Sccm.
Preferably, the power of described plasma power supply is 50-90W, is preferably 70W.
Preferably, pressure when pressure is with annealing nodularization in described growth furnace chamber is identical.
Preferably, the time of described growth is 15min-60min, is preferably 30min.
As optimal technical scheme, preparation method of the present invention, described in step (5), the concentration of liquor potassic permanganate is 0.05-0.15mol/L, is preferably 0.1mol/L.
Preferably, the addition of described liquor potassic permanganate is 10-50ml/cm with the ratio of carbon cloth surface area
2, for example, be 13ml/cm
2, 19ml/cm
2, 26ml/cm
2, 35ml/cm
2, 46ml/cm
2deng, be preferably 25ml/cm
2.
Preferably, described heating is carried out in baking oven.
Preferably, the temperature of described heating is 150-200 DEG C, is preferably 180 DEG C; The time of described reaction is 15min-40min, is preferably 25min.
As optimal technical scheme, preparation method of the present invention, cooling use flowing cool water described in step (6) carries out cooling fast, after cooling 2-10min, opens reactor.
Preferably, described baking is carried out on hot platform.
Preferably, the temperature of described baking is 100-200 DEG C, is preferably 150 DEG C; The time of described baking is 0.5-3h, is preferably 1h.Baking is in order to remove moisture.
One of object of the present invention is also to provide the purposes of the electrode material that the present invention makes, and can be applied to portable type electronic product or wearable electronic product.
The super capacitor material of flexibility provided by the invention, there is the features such as high power capacity, high cyclicity, can be as the energy storage device of the wearable electronic product of flexibility or device, can meet the demand of people for modern science and technology product and high-quality green living, the light flexible energy storage device for development with high-energy-density, high power density and high cyclical stability provides technical support.Can be applicable to portable type electronic product and wearable electronic product, for future, the development of flexible device provides energy storage mode.
Brief description of the drawings
Fig. 1 is process chart of the present invention;
Fig. 2 is the scanning electron microscope diagram of the carbon fiber after cleaning;
Fig. 3 is the scanning electron microscope diagram of the carbon pipe that grows out;
Fig. 4 is for being CNT/ α-MnO
2eSEM (left side) and transmission electron microscope photo (right side);
Fig. 5 is the solid-state flexible super capacitor of assembling;
Fig. 6 be the ultracapacitor assembled of Fig. 5 under different discharge current densities charging and discharging curve;
Fig. 7 is ultracapacitor cycle performance figure under the current density of 7A/g that Fig. 5 assembles.
Embodiment
For ease of understanding the present invention, it is as follows that the present invention enumerates embodiment.Those skilled in the art should understand, described embodiment only, for helping to understand the present invention, should not be considered as concrete restriction of the present invention.
Fig. 1 is process chart of the present invention.
Embodiment of the present invention are as follows:
A preparation method for carbon nano-tube/manganese dioxide hydridization electrode material for super capacitor, comprises the steps:
(1) will after flexible carbon cloth removal inorganic impurity, remove organic impurities;
(2) on carbon cloth, deposit by physical evaporation mode the Ni film that a layer thickness is 5-20nm;
(3) carbon cloth of step (1) being removed after impurity is inserted in carbon nano-tube PECVD growth furnace, to the nodularization of annealing of Ni film;
(4) be cooled to 680-750 DEG C and pass into C taking speed as 40-80Sccm
2h
4, starting plasma power supply maintenance power is 50-90W, carries out the ordering growth of carbon nano-tube; Pressure when pressure is with annealing nodularization in described growth furnace chamber is identical; The time of described growth is 15min-60min;
(5) there is the carbon cloth of pipe to insert in reactor step (4) gained growth, seal after adding the liquor potassic permanganate of 0.05-0.15mol/L, be then heated to 150-200 DEG C of reaction 15min-40min;
(6) reaction finishes rear with opening reactor after the quick cooling reactor 2-10min of flowing cool water, take out carbon cloth, rinse with deionized water, be then 100-200 DEG C to toast 0.5-3h in temperature by carbon cloth on hot platform, obtains carbon cloth/carbon nano-tube/MnO
2composite material;
The method of removing inorganic impurity in step (1) is: flexible carbon cloth salpeter solution is soaked, then use deionized water rinsing;
The method of removing organic impurities described in step (1) is: will be through removing inorganic impurity acetone, successively ultrasonic cleaning of ethanol for carbon cloth after treatment;
The condition of nodularization of annealing described in step (3) is: pass into ammonia, be warming up to 700-800 DEG C, keep 5-20min.
Embodiment 1
(1) the flexible carbon cloth of 5cm × 5cm is soaked 1 hour with the salpeter solution of 100 milliliters of 4mol/L, then use a large amount of deionized water rinsings, remove inorganic impurity; Acetone, alcohol for carbon cloth after nitric acid treatment are successively carried out to 4 ultrasonic cleaning, and to remove organic impurities, the carbon fiber after cleaning as shown in Figure 2;
(2) on carbon cloth, deposit the Ni film of one deck 10 nanometers by physical evaporation mode electron beam evaporation, as the catalyst of carbon nano-tube;
(3) carbon cloth is inserted in carbon nano-tube PECVD growth furnace, pass into the ammonia of 200ccm, pressure 20mbar, is warming up to 750 DEG C, keeps 10min, to the nodularization of annealing of Ni film;
(4) be cooled to 720 DEG C, pass into the C of 60Sccm
2h
4, start plasma electric source power, keep power at 70W, in chamber, produce plasma, keeping chamber pressure is still 20mbar, carries out the ordering growth of carbon nano-tube, and growth time is 30min, and the carbon pipe growing out is as shown in Figure 3.
(5) growth there is is the carbon cloth of pipe insert in the reactor of 250ml, after adding the liquor potassic permanganate of 200 milliliters of 0.1mol/L, seal, rapidly the reactor assembling is placed in to the baking oven that is heated to 180 DEG C, keep 180 DEG C of temperature, reaction time is 25min, make potassium permanganate and the outermost amorphous carbon layer generation of carbon pipe redox reaction, generate MnO
2lamellar structure;
(6) from baking oven, remove reactor, carry out immediately coolingly fast with flowing cool water, after 5min, open reactor, take out carbon cloth, repeatedly rinse with a large amount of deionized waters, finally carbon cloth is put on the hot platform of 150 DEG C and toasts 1h, remove moisture, can obtain CC/CNT/MnO
2composite material.
Fig. 4 is α-MnO
2stereoscan photograph (left side) and transmission electron microscope photo (right side), can find out laminated structure MnO
2evenly be coated on around carbon nano-tube, do not have lodging phenomenon, manganese dioxide atom is shortrange order and arranges.
Utilize hybridization compounding electrode material prepared by this embodiment positive pole and the negative pole as capacitor, taking PVA/LiCl as solid electrolyte, ultra-thin filter membrane is barrier film, assembles solid-state flexible super capacitor, as shown in Figure 5.Under its different discharge current densities charging and discharging curve as shown in Figure 6, all curves are the shape of linear change and near symmetrical, show that this electrode material has good electrochemical reversibility and volumetric properties; This device under the current density of 7A/g cycle performance as shown in Figure 7, through 5000 circulations, device still keeps approximate 100% volumetric properties, shows that this material structure has very excellent cycle performance.
Embodiment 2
(1) the flexible carbon cloth of 5cm × 5cm is soaked 2 hours with the salpeter solution of 100 milliliters of 2M, then use a large amount of deionized water rinsings, remove inorganic impurity; Carbon cloth after nitric acid treatment is entered and successively carries out 5 ultrasonic cleaning with acetone, alcohol, to remove organic impurities;
(2) on carbon cloth, deposit the Ni film of one deck 8 nanometers by physical evaporation mode magnetron sputtering, as the catalyst of carbon nano-tube;
(3) carbon cloth is inserted in the PECVD growth furnace such as carbon nano-tube, pass into the ammonia of 250ccm, pressure 25mbar, is warming up to 730 DEG C, keeps 12min, to the nodularization of annealing of Ni film;
(4) be cooled to 680 DEG C, pass into the C of 45Sccm
2h
4, start plasma electric source power, keep power at 50W, in chamber, produce plasma, keeping chamber pressure is still 25mbar, carries out the ordering growth of carbon nano-tube, growth time is 60min;
(5) growth there is is the carbon cloth of pipe insert in the reactor of 250ml, after adding the liquor potassic permanganate of 200 milliliters of 0.15mol/L, seal, rapidly the reactor assembling is placed in to the baking oven that is heated to 150 DEG C, maintenance thermotonus is 35min, make potassium permanganate and the outermost amorphous carbon layer generation of carbon pipe redox reaction, generate MnO
2lamellar structure;
(6) from baking oven, remove reactor, carry out immediately coolingly fast with flowing cool water, after 10min, open reactor, take out carbon cloth, repeatedly rinse with a large amount of deionized waters, finally carbon cloth is put on the hot platform of 100 DEG C and toasts 3h, remove moisture, can obtain CC/CNT/MnO
2composite material.
Embodiment 3
(1) the flexible carbon cloth of 5cm × 5cm is soaked 0.5 hour with the salpeter solution of 100 milliliters of 8mol/L, then use a large amount of deionized water rinsings, remove inorganic impurity; Carbon cloth after nitric acid treatment is entered and successively carries out 3 ultrasonic cleaning with acetone, alcohol, to remove organic impurities;
(2) on carbon cloth, deposit the Ni film of one deck 15 nanometers by the hot evaporation of physical evaporation mode, as the catalyst of carbon nano-tube;
(3) carbon cloth is inserted in the PECVD growth furnace such as carbon nano-tube, pass into the ammonia of 150ccm, pressure 15mbar, is warming up to 770 DEG C, keeps 10min, to the nodularization of annealing of Ni film;
(4) be cooled to 740 DEG C, pass into the C of 75Sccm
2h
4, start plasma electric source power, keep power at 90W, in chamber, produce plasma, keeping chamber pressure is still 15mbar, carries out the ordering growth of carbon nano-tube, growth time is 15min;
(5) growth there is is the carbon cloth of pipe insert in the reactor of 250ml, after adding the liquor potassic permanganate of 200 milliliters of 0.05M, seal, rapidly the reactor assembling is placed in to the baking oven that is heated to 200 DEG C, maintenance thermotonus is 15min, make potassium permanganate and the outermost amorphous carbon layer generation of carbon pipe redox reaction, generate MnO
2lamellar structure;
(6) from baking oven, remove reactor, carry out immediately cooling fast with flowing cool water, after 2min, open reactor, take out carbon cloth, repeatedly rinse with a large amount of deionized waters, finally carbon cloth is put on the hot platform of 200 DEG C and toasts 0.5h, remove moisture, can obtain carbon cloth/carbon nano-tube/MnO
2composite material.
The electrode material that embodiment 2 and 3 is made carries out charging and discharging and cycle performance test has obtained the suitable result of electrode material making with embodiment 1.
Applicant's statement, the present invention illustrates detailed process equipment and process flow process of the present invention by above-described embodiment, but the present invention is not limited to above-mentioned detailed process equipment and process flow process, do not mean that the present invention must rely on above-mentioned detailed process equipment and process flow process and could implement.Person of ordinary skill in the field should understand, any improvement in the present invention, and the selections of the equivalence replacement to the each raw material of product of the present invention and the interpolation of auxiliary element, concrete mode etc., within all dropping on protection scope of the present invention and open scope.
Claims (9)
1. a preparation method for carbon cloth/carbon nano-tube/manganese dioxide hydridization electrode material for super capacitor, comprises the steps:
(1) will after flexible carbon cloth removal inorganic impurity, remove organic impurities;
(2) on carbon cloth, deposit layer of Ni film by physical evaporation mode;
(3) carbon cloth of step (1) being removed after impurity is inserted in carbon nano-tube plasma chemistry deposition growing stove, to the nodularization of annealing of Ni film;
(4) cooling passes into C
2h
4, start plasma power supply, carry out the ordering growth of carbon nano-tube;
(5) there is the carbon cloth of pipe to insert in reactor step (4) gained growth, seal after adding liquor potassic permanganate, be then heated lower reaction;
(6) reaction finishes to open reactor after rear quick cooling reactor, takes out carbon cloth, rinses with deionized water, then, by carbon cloth baking, obtains carbon cloth/carbon nano-tube/MnO
2composite material.
2. preparation method according to claim 1, is characterized in that, the method for removing inorganic impurity in step (1) is: flexible carbon cloth salpeter solution is soaked, then use deionized water rinsing;
Preferably, the method for described removal inorganic impurity is: more than flexible carbon cloth is soaked to 0.5h with the salpeter solution of 2-8mol/L, preferably 1h, then uses a large amount of deionized water rinsings.
3. preparation method according to claim 1 and 2, is characterized in that, the method for removing organic impurities described in step (1) is: will be through removing inorganic impurity acetone, successively ultrasonic cleaning of ethanol for carbon cloth after treatment;
Preferably, the method for described removal organic impurities is: will be through removing inorganic impurity acetone carbon cloth for after treatment, ethanol priority is carried out 3-5 ultrasonic cleaning.
4. according to the preparation method described in claim 1-3 any one, it is characterized in that, in step (2), the thickness of Ni film is 5-20nm, is preferably 8-15nm.
5. according to the preparation method described in claim 1-4 any one, it is characterized in that, the condition of the nodularization of annealing described in step (3) is: pass into ammonia, be warming up to 700-800 DEG C, keep 5-20min;
Preferably, the condition of described annealing nodularization is: pass into 150-250ccm, and the preferably ammonia of 200ccm, in growth furnace chamber, pressure is 15-25mbar, is preferably 20mbar, is warming up to 730-770 DEG C, preferably 750 DEG C, keeps 10-12min.
6. according to the preparation method described in claim 1-5 any one, it is characterized in that, described in step (4), cooling is for being cooled to 680-750 DEG C;
Preferably, described C
2h
4the speed passing into is 40-80Sccm, is preferably 60Sccm;
Preferably, the power of described plasma power supply is 50-90W, is preferably 70W;
Preferably, pressure when pressure is with annealing nodularization in described growth furnace chamber is identical;
Preferably, the time of described growth is 15min-60min, is preferably 30min.
7. according to the preparation method described in claim 1-6 any one, it is characterized in that, described in step (5), the concentration of liquor potassic permanganate is 0.05-0.15mol/L, is preferably 0.1mol/L;
Preferably, the addition of described liquor potassic permanganate is 10-50ml/cm with the ratio of carbon cloth surface area
2, be preferably 25ml/cm
2;
Preferably, described heating is carried out in baking oven;
Preferably, the temperature of described heating is 150-200 DEG C, is preferably 180 DEG C; The time of described reaction is 15min-40min, is preferably 25min.
8. according to the preparation method described in claim 1-7 any one, it is characterized in that, cooling use flowing cool water described in step (6) carries out cooling fast, after cooling 2-10min, opens reactor;
Preferably, described baking is carried out on hot platform;
Preferably, the temperature of described baking is 100-200 DEG C, is preferably 150 DEG C; The time of described baking is 0.5-3h, is preferably 1h.
9. the purposes of the electrode material that described in claim 1-8 any one, preparation method makes, is characterized in that, is applied to portable type electronic product or wearable electronic product.
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| CN106783203B (en) * | 2016-12-21 | 2019-07-09 | 浙江大学 | A kind of preparation method, product and the application of manganese dioxide/ultramicropore flexibility carbon cloth |
| CN107275113A (en) * | 2017-06-08 | 2017-10-20 | 中国科学院电工研究所 | The method that double medium agent jet plasmas prepare flexible super capacitor combination electrode |
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