CN105513829A - Carbon nanotube/carbon fiber composite material and carbon-base/manganese oxide composite electrode material - Google Patents
Carbon nanotube/carbon fiber composite material and carbon-base/manganese oxide composite electrode material Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 236
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 title claims abstract description 142
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 114
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 113
- 239000002131 composite material Substances 0.000 title claims abstract description 104
- 229920000049 Carbon (fiber) Polymers 0.000 title abstract description 13
- 239000004917 carbon fiber Substances 0.000 title abstract description 13
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title abstract description 13
- 239000007772 electrode material Substances 0.000 title abstract description 12
- 239000000463 material Substances 0.000 claims abstract description 70
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 60
- 239000011149 active material Substances 0.000 claims abstract description 17
- 239000012528 membrane Substances 0.000 claims abstract description 11
- 238000003828 vacuum filtration Methods 0.000 claims abstract description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 55
- 239000006185 dispersion Substances 0.000 claims description 47
- 239000000835 fiber Substances 0.000 claims description 45
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims description 22
- 238000002360 preparation method Methods 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 17
- 238000004108 freeze drying Methods 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 8
- 238000000967 suction filtration Methods 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 239000003990 capacitor Substances 0.000 abstract description 34
- 239000000126 substance Substances 0.000 abstract description 8
- 230000007547 defect Effects 0.000 abstract 1
- 239000008204 material by function Substances 0.000 abstract 1
- 230000000717 retained effect Effects 0.000 abstract 1
- 239000007864 aqueous solution Substances 0.000 description 25
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 20
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 18
- 150000001875 compounds Chemical class 0.000 description 14
- 238000007254 oxidation reaction Methods 0.000 description 11
- 238000012360 testing method Methods 0.000 description 11
- 229910002804 graphite Inorganic materials 0.000 description 10
- 239000010439 graphite Substances 0.000 description 10
- 239000006227 byproduct Substances 0.000 description 9
- 238000000840 electrochemical analysis Methods 0.000 description 9
- 239000011259 mixed solution Substances 0.000 description 9
- 238000005406 washing Methods 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- -1 after ultrasonic 1h Substances 0.000 description 3
- 238000002484 cyclic voltammetry Methods 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000004087 circulation Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/66—Current collectors
- H01G11/68—Current collectors characterised by their material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
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- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Nanotechnology (AREA)
- Manufacturing & Machinery (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
The invention relates to a carbon nanotube/carbon fiber composite material and a carbon-base/manganese oxide composite electrode material and belongs to the technical field of electronic functional materials. The carbon nanotube/carbon fiber composite material is a membrane material prepared from carbon nanotubes and conductive carbon fiber by vacuum filtration and has the advantages of good flexibility, good tensile strength, good conductivity, good chemical stability and the like. The above carbon nanotube/carbon fiber composite material is used as a current collector and a reduced graphene oxide/manganese oxide material, a carbon nanotube/manganese oxide composite and a graphene oxide/carbon nanotube/manganese oxide composite material are used as active materials, preparing the carbon-base/manganese oxide composite electrode material. The active materials of the carbon-base/manganese oxide composite electrode material adsorb to the surface of the current collector, giving good strength of flexibility; the advantages such as high specific capacitance and high conductivity are retained, and the defect that a traditional capacitor is poor in flexibility is improved.
Description
Technical field
The present invention relates to carbon nano-tube/carbon fibre composite and a kind of carbon back/manganese oxide composite electrodes material, belong to electronic functional material technical field.
Background technology
Ultracapacitor is a kind of novel green energy-storage travelling wave tube, the advantage such as have high-specific-power, bulky capacitor value, high charge-discharge efficiencies, have extended cycle life, and is a kind of energy storing device of highly effective environmental protection, has a wide range of applications in stored energy application aspect.In recent years, along with the develop rapidly of wearable Portable, personal multimedia equipment, more and more higher to the demand of rollable flexible energy memory device.Energy storage device is towards high power, high-energy-density, flexible future development.And the raising of these performances depends on the optimization of equipment and materials to a great extent.Material with carbon element with the diversity of its existence form and various premium properties, often as energy storage device especially electrode material for super capacitor, wherein especially with Graphene and carbon nano-tube material the most promising.The material such as Graphene, carbon nano-tube has nanostructure and the mechanical performance of extraordinary conductivity, high specific area, good chemical stability and uniqueness.Transition metal oxide especially manganese dioxide has very high theoretical ratio capacitance, good cyclical stability, and has multiple oxidation state, and electrochemical window is wider, and manganese oxide resource is extensive, cheap, and environment is friendly.Often be used as electrode material for super capacitor.But simple manganese dioxide electric conductivity is poor, therefore frequent and material with carbon element compound uses.But there is the problem that flexibility is poor, tensile strength is low in current carbon back manganese oxide hybrid supercapacitor material.
Summary of the invention
The object of the present invention is to provide a kind of flexible, carbon back/manganese oxide recombiner condenser electrode material that tensile strength is good.
The present invention also with carbon nano-tube and carbon fiber for material provides a kind of flexible, current collector material---carbon nano-tube/carbon fibre composite that tensile strength is good.
Technical scheme
A kind of carbon nano-tube/carbon fibre composite, be with carbon nano-tube and conductive carbon fibre for raw material, adopt the film material that vacuum filtration method is prepared into; Wherein, the mass ratio of carbon nano-tube and conductive carbon fibre is 15-35:1.
Above-mentioned carbon nano-tube/carbon fibre composite is a kind of porous film material; Its thickness is 100-400 μm.
Above-mentioned carbon nano-tube/carbon fibre composite, preferably, the mass ratio of carbon nano-tube and conductive carbon fibre is 25:1(embodiment 1).
Above-mentioned carbon nano-tube/carbon fibre composite, its preparation method is:
After the aqueous dispersions of carbon nano-tube and the aqueous dispersions of conductive carbon fibre mix, vacuum filtration is on composite fibre filter membrane, then freeze drying.
After freeze drying terminates, by composite fibre, carbon carbon nano-tube/carbon fibre composite is taken and obtained to the film material of considering on film off.
Described composite fibre filter membrane, be a kind of water-based filter membrane, aperture is below 0.45 μm; Its effect filters out the water in various material, and carbon nano-tube etc. can not be made through filter membrane.
Cryodesiccated object is in the Free water keeping removing in the indeclinable situation of hybrid films structure in hybrid films.Freeze drying temperature is-60 DEG C, and cooling time selects 72h; Time too short being difficult to removes the moisture in composite material, causes membrane structure to be out of shape.
In the present invention, the concentration of the aqueous dispersions of carbon nano-tube and the aqueous dispersions of conductive carbon fibre is less, and carbon nanotube dispersed is better, and the film thickness that suction filtration obtains is more even; But fibre weight is too small affects film strength and flexility.Concentration is excessive, and fibre weight is excessive, and fiber can appear suddenly out on membrane material surface, affects membrane structure and the combination with active material.So preferably, the concentration of the aqueous dispersions of carbon nano-tube is 2mg/mL, and the concentration of the aqueous dispersions of conductive carbon fibre is 0.1mg/mL.
In the present invention, carbon fibre material, plays support and electric action, requires to have good electric conductivity, and length is unsuitable long, and length is 2-4mm, diameter 300-400 μm.
Carbon nano-tube/carbon fibre composite of the present invention, can use as collector.Relative to the collector before the present invention, carbon nano-tube of the present invention/carbon fibre composite collector its have the advantage that pliability is good, hot strength is good; In addition good conductivity (sheet resistance is 4.97/), good chemical stability is also had.
A kind of carbon back/manganese oxide composite electrodes material is using carbon nano-tube/carbon fibre composite of the present invention as collector.
Above-mentioned carbon back/manganese oxide composite electrodes material, adopts redox graphene/manganese oxide composite material, carbon nanotube/manganese oxide composite material, graphene oxide/carbon nanotube/manganese oxide composite material as active material.
Above-mentioned carbon back/manganese oxide composite electrodes material, described active material passes through the direct suction filtration of method of vacuum filtration to the surface of collector, then carries out freeze drying.
Above-mentioned carbon back/manganese oxide composite electrodes material, the component content change wherein in active material can have an impact to the ratio capacitance of capacitor; But, no matter how the component content in active material changes, the good capacitor electrode material of ratio capacitance all can be prepared.
Preferably, in redox graphene/manganese oxide composite material: the mass ratio of redox graphene and manganese oxide is 27-65:73-35; Preferred, the mass ratio of redox graphene and manganese oxide is 65:35,48:52,38:62,31:69 or 27:73.
Preferably, in carbon nanotube/manganese oxide composite material: the mass ratio of carbon nano-tube and manganese oxide is 82-65:18-35; Preferred, the mass ratio of carbon nano-tube and manganese oxide is 82:18,75:25,69:31 or 65:35.
Preferably, in graphene oxide/carbon nanotube/manganese oxide composite material: the mass ratio 12:60:28 of redox graphene, carbon nano-tube and manganese oxide.
Redox graphene plays the effect providing transferring charge plane, and redox graphene causes grapheme material blocked up too much, and then causes charge transport properties to be deteriorated; Carbon nanotube/manganese oxide composite material too much also can affect the ratio capacitance of electrode material.So the mass content of redox graphene is preferably 20-40% in active material.
The present invention gives wherein a kind of preparation method of above-mentioned carbon back/manganese oxide composite electrodes material active material used:
The preparation method of redox graphene/manganese oxide:
The aqueous dispersions of redox graphene and MnSO
4solution mixing, tune pH are 2, then add KMnO
4solution, after ultrasonic 1h, products therefrom is redox graphene/manganese oxide;
Wherein, the reaction principle of this preparation method is 2MnO
4 -+ 3Mn
2++ 2H
2o → 5MnO
2+ 4H
+; Adjustment redox graphene (RGO) and (KMnO
4+ MnSO
4) ratio, thus control compound RGO/MnO
2middle MnO
2ratio.
The preparation method of carbon nanotube/manganese oxide composite material:
Carbon nano tube dispersion liquid and MnSO
4solution mixing, tune pH are 2, then add KMnO
4solution, after ultrasonic 1h, products therefrom is carbon nanotube/manganese oxide composite material.
The same, adjustment carbon nano-tube (CNT) and (KMnO
4+ MnSO
4) ratio, thus control compound CNT/MnO
2middle MnO
2ratio.
The preparation method of redox graphene/carbon nanotube/manganese oxide composite material:
Aqueous dispersions and the carbon nanotube/manganese oxide composite material of redox graphene mix.
Carbon back of the present invention/manganese oxide composite electrodes material is a kind of capacitor, and redox graphene manganese oxide composite material is adsorbed on carbon nano-tube/carbon fibre composite collector top layer uniformly, and flexibility strength is better; Both remained Graphene/manganese oxide material or carbon nano-tube the advantage such as manganese oxide high specific capacitance and high conduction performance, which in turn improve the shortcoming of traditional capacitor pliability difference.Compared with traditional carbon back manganese oxide composite electrodes material, the combination electrode material that the present invention obtains is improved significantly in flexility and tensile strength is obviously improved compared with Graphene manganese oxide film material.In addition the good advantage of chemical property (chemical property specifically: good conductivity, specific volume are large) is also had.Active material is combined with collector by the method adopting direct suction filtration and freeze drying to combine, and avoids adding of binding agent and conductive agent, and the combination of active material and collector is tight, difficult drop-off; Thus the chemical properties such as specific volume, cyclical stability and impedance can be improved.
Accompanying drawing explanation
Fig. 1 redox graphene dispersion liquid;
As seen from Figure 1, this redox graphene has good dispersiveness, is applicable to carrying out following RGO/MnO
2synthesis.
Fig. 2 is redox graphene stereoscan photograph;
This redox graphene has the distinctive accordion pattern of Graphene.Tulle shape proves that this redox graphene is thinner, is conducive to the performance playing Graphene.
Fig. 3 RGO/MnO
2stereoscan photograph;
Graphenic surface has the manganese oxide of flower ball-shaped to generate, and the combination of manganese oxide and redox graphene is better, is conducive to playing manganese oxide Graphene performance separately.
Fig. 4 carbon nano-tube carbon fiber collector pictorial diagram and scanning electron microscope (SEM) photograph;
Can find out that this carbon nano-tube carbon fiber collector is uniform film-like material by the photo in kind of collector, can find out that this collector is the three-dimensional network loose structure that carbon nano-tube carbon fiber forms by scanning electron microscope (SEM) photograph, this structure is conducive to the transmission of ion, and with the combination of active material.
Fig. 5 CCRM cycles samples volt-ampere curve;
The shape of the CV curve of this sample is symmetrical rectangle, illustrates that this electrode has good invertibity and capacitance characteristic.And along with the increase of sweep speed, the shape of curve is not obviously out of shape, and proves that the stability of this material is good.
Fig. 6 CNT/MnO
2scanning electron microscope (SEM) photograph;
As can be seen from scanning electron microscope (SEM) photograph, prepare uniform carbon nano-tube manganese oxide composite material under the program, the load of manganese oxide homogenize material is in carbon nano tube surface.Be suitable as electroactive substance.
Fig. 7 CCCM cycles samples volt-ampere curve;
The shape of the CV curve of this sample is symmetrical rectangle, illustrates that this electrode has good invertibity and capacitance characteristic.And along with the increase of sweep speed, the shape of curve is not obviously out of shape, and proves that the stability of this material is good.
Fig. 8 CCCMR cycles samples volt-ampere curve;
The shape of the CV curve of this sample is symmetrical rectangle, illustrates that this electrode has good invertibity and capacitance characteristic.And along with the increase of sweep speed, the shape of curve is not obviously out of shape, and proves that the stability of this material is good.
Embodiment
Embodiment 1
(1) redox graphene powder ultrasonic is distributed in the deionized water of certain volume and prepares the redox graphene aqueous dispersions that concentration is 0.2mg/mL.The photo in kind of gained redox graphene aqueous dispersions and the stereoscan photograph of redox graphene, respectively as shown in Figure 1 and Figure 2.
(2) redox graphene/manganese dioxide composite material (RGO/MnO is prepared
2)
Compound concentration is 0.01mol/LKMnO
4the aqueous solution and 0.015mol/LMnSO
4the aqueous solution is for subsequent use.Measure reduction-oxidation graphite aqueous dispersions 20mL prepared by step (1), add 1mLMnSO
4the aqueous solution, adds appropriate watery hydrochloric acid and regulates the pH of mixed solution to be 2, makes RGO aqueous dispersions (that is, step (1) prepare reduction-oxidation graphite aqueous dispersions) and MnSO ultrasonic half an hour
4the aqueous solution fully mixes, and then adds 1mLKMnO
4the aqueous solution, continues ultrasonic 1h(and namely reacts complete; Except the reaction time, also has the mark that other judgement reactions are not complete).By product centrifuge washing, repeatedly final vacuum is dry.Namely RGO/MnO is obtained
2.In this composite material, RGO and MnO
2mass ratio be 65:35.The scanning electron microscopic picture of gained redox graphene/manganese dioxide composite material is shown in Fig. 3.
(3) carbon nano-tube/carbon fibre composite flexible current-collecting body material (CNT/CF collector) is prepared
First getting 25mL concentration is that the carbon nano-tube aqueous dispersions of 2mg/mL is stand-by.Then take the conductive carbon fibre that 2mg length is 2-4mm, diameter is 400-500 μm, be distributed in 20mL deionized water, long-time stirring makes it dispersed, obtains carbon fiber water dispersion liquid.Finally by CNT dispersion liquid (that is, carbon nano-tube aqueous dispersions) and CF dispersion liquid (that is, carbon fiber water dispersion liquid) fully mix and blend.Vacuum filtration is that the composite fibre of 0.45 μm is considered on film to aperture, and then freeze drying 72h, after drying completes, the film material of composite fibre being considered on film is taken off, namely obtains CNT/CF collector.The composition weight proportion of this carbon nano-tube/carbon fibre composite flexible current-collecting body material is 25:1.Fig. 4 is pictorial diagram and the scanning electron microscope (SEM) photograph of this collector.
(4) CNT/CF/RGO/MnO
2(CCRM) flexible compound capacitor material preparation
By redox graphene/manganese dioxide composite material, by the direct suction filtration of the method for vacuum filtration, to the surface of CNT/CF collector, (concrete operations are: first, by the carbon nano-tube carbon fiber dispersion liquid suction filtration that is uniformly mixed on filter membrane, after forming membrane structure, add fresh preparation and the RGO/MnO stirred
2dispersion liquid continues suction filtration), then adopted by the sample that suction filtration obtains the dry 72h of cryodesiccated method shaping.
Flexible composite obtained by the present invention, redox graphene/manganese oxide composite material is adsorbed on carbon nano-tube/carbon fiber collector top layer uniformly.This material has excellent super electrical property, and pliability is better, and intensity is larger.
(5) capacitor material prepared by step (4) is cut into 1 × 1cm
2the electrode slice of size, and using this electrode slice as positive electrode, be to electrode with platinized platinum, saturated calomel electrode is reference electrode, adopts 1mol/LNa
2sO
4for electrolyte carries out electrochemical property test on electrochemical workstation (CHI604D).Result has 326Fg under being presented at the sweep speed of 2mV/s
-1specific capacity.
Embodiment 2
(1) measure reduction-oxidation graphite aqueous dispersions 20mL prepared by embodiment 1 step (1), add the KMnO that 2mL concentration is 0.015mol/L
4the aqueous solution, adds appropriate watery hydrochloric acid and regulates the pH of mixed solution to be 2, makes RGO aqueous dispersions (that is, step (1) prepare reduction-oxidation graphite aqueous dispersions) and MnSO ultrasonic half an hour
4the aqueous solution fully mixes, and then adds the KMnO that 2mL concentration is 0.01mol/L
4the aqueous solution, continues ultrasonic 1h.By product centrifuge washing, repeatedly final vacuum is dry; Namely RGO/MnO is obtained
2.In this composite material, RGO and MnO
2mass ratio be 48:52.The scanning electron microscopic picture of gained redox graphene/manganese dioxide composite material is shown in Fig. 3.
(2) CNT/CF/RGO/MnO
2(CCRM) preparation of flexible compound capacitor material is with embodiment 1.
(3) capacitor material prepared by step 2 is cut into 1 × 1cm
2size electrode slice, tests according to embodiment 1 electrochemical test method.Result has 390Fg under being presented at the sweep speed of 2mV/s
-1specific capacity.The cyclic voltammetry curve of this sample is as Fig. 5.
Embodiment 3
(1) measure reduction-oxidation graphite aqueous dispersions 20mL prepared by embodiment 1 step (1), add the KMnO that 3mL concentration is 0.015mol/L
4the aqueous solution, adds appropriate watery hydrochloric acid and regulates the pH of mixed solution to be 2, makes RGO aqueous dispersions (that is, step (1) prepare reduction-oxidation graphite aqueous dispersions) and MnSO ultrasonic half an hour
4the aqueous solution fully mixes, and then adds the KMnO that 3mL concentration is 0.01mol/L
4the aqueous solution, continues ultrasonic 1h.By product centrifuge washing, repeatedly final vacuum is dry; Namely RGO/MnO is obtained
2.In this composite material, RGO and MnO
2mass ratio be 38:62.The scanning electron microscopic picture of gained redox graphene/manganese dioxide composite material is shown in Fig. 3.
(2) CNT/CF/RGO/MnO
2(CCRM) preparation of flexible compound capacitor material is with embodiment 1.
(3) capacitor material prepared by step 2 is cut into 1 × 1cm
2size electrode slice, tests according to embodiment 1 electrochemical test method.Result has 308Fg under being presented at the sweep speed of 2mV/s
-1specific capacity.
Embodiment 4
(1) measure reduction-oxidation graphite aqueous dispersions 20mL prepared by embodiment 1 step (1), add the KMnO that 4mL concentration is 0.015mol/L
4the aqueous solution, adds appropriate watery hydrochloric acid and regulates the pH of mixed solution to be 2, makes RGO aqueous dispersions (that is, step (1) prepare reduction-oxidation graphite aqueous dispersions) and MnSO ultrasonic half an hour
4the aqueous solution fully mixes, and then adds the KMnO that 4mL concentration is 0.01mol/L
4the aqueous solution, continues ultrasonic 1h.By product centrifuge washing, repeatedly final vacuum is dry; Namely RGO/MnO is obtained
2.In this composite material, RGO and MnO
2mass ratio be 31:69.The scanning electron microscopic picture of gained redox graphene/manganese dioxide composite material is shown in Fig. 3.
(2) CNT/CF/RGO/MnO
2(CCRM) preparation of flexible compound capacitor material is with embodiment 1.
(3) capacitor material prepared by step 2 is cut into 1 × 1cm
2size electrode slice, tests according to embodiment 1 electrochemical test method.Result has 258Fg under being presented at the sweep speed of 2mV/s
-1specific capacity.
Embodiment 5
(1) measure reduction-oxidation graphite aqueous dispersions 20mL prepared by embodiment 1 step (1), add the KMnO that 5mL concentration is 0.015mol/L
4the aqueous solution, adds appropriate watery hydrochloric acid and regulates the pH of mixed solution to be 2, makes RGO aqueous dispersions (that is, step (1) prepare reduction-oxidation graphite aqueous dispersions) and MnSO ultrasonic half an hour
4the aqueous solution fully mixes, and then adds the KMnO that 5mL concentration is 0.01mol/L
4the aqueous solution, continues ultrasonic 1h.By product centrifuge washing, repeatedly final vacuum is dry; Namely RGO/MnO is obtained
2.In this composite material, RGO and MnO
2mass ratio be 27:73.The scanning electron microscopic picture of gained redox graphene/manganese dioxide composite material is shown in Fig. 3.
(2) CNT/CF/RGO/MnO
2(CCRM) preparation of flexible compound capacitor material is with embodiment 1.
(3) capacitor material prepared by step 2 is cut into 1 × 1cm
2size electrode slice, tests according to embodiment 1 electrochemical test method.Result has 214Fg under being presented at the sweep speed of 2mV/s
-1specific capacity.
Embodiment 6
(1) get the carbon nano-tube aqueous dispersions 20mL that concentration is 0.5mg/mL, add the MnSO that concentration is 0.015mol/L
4aqueous solution 1mL, add appropriate watery hydrochloric acid and regulate the pH of mixed solution to be 2, ultrasonic half an hour makes CNT and MnSO
4abundant mixing, then adds the KMnO that concentration is 0.01mol/L
4aqueous solution 1mL, continues ultrasonic 1h.By product centrifuge washing, repeatedly final vacuum is dry, namely obtains CNT/MnO
2.In this composite material, CNT and MnO
2mass ratio is 82:18.The scanning electron microscopic picture of this composite material is shown in Fig. 6.
(2) preparation of CCCM flexible compound capacitor material is with embodiment 1.
(3) capacitor material prepared by step 2 is cut into 1 × 1cm
2size electrode slice, tests according to embodiment 1 electrochemical test method.Result has 304Fg under being presented at the sweep speed of 2mV/s
-1specific capacity.
Embodiment 7
(1) get the carbon nano-tube aqueous dispersions 20mL that concentration is 0.5mg/mL, add the MnSO that concentration is 0.015mol/L
4aqueous solution 1.5mL, add appropriate watery hydrochloric acid and regulate the pH of mixed solution to be 2, ultrasonic half an hour makes CNT and MnSO
4abundant mixing, then adds the KMnO that concentration is 0.01mol/L
4aqueous solution 1.5mL, continues ultrasonic 1h.By product centrifuge washing, repeatedly final vacuum is dry, namely obtains CNT/MnO
2.In this composite material, CNT and MnO
2mass ratio is 75:25.The scanning electron microscopic picture of this composite material is shown in Fig. 6.
(2) preparation of CCCM flexible compound capacitor material is with embodiment 1.
(3) capacitor material prepared by step 2 is cut into 1 × 1cm
2size electrode slice, tests according to embodiment 1 electrochemical test method.Result has 353Fg under being presented at the sweep speed of 2mV/s
-1specific capacity.The cyclic voltammetry curve of this sample is as Fig. 7.
Embodiment 8
(1) get the carbon nano-tube aqueous dispersions 20mL that concentration is 0.5mg/mL, add the MnSO that concentration is 0.015mol/L
4aqueous solution 2mL, add appropriate watery hydrochloric acid and regulate the pH of mixed solution to be 2, ultrasonic half an hour makes CNT and MnSO
4abundant mixing, then adds the KMnO that concentration is 0.01mol/L
4aqueous solution 2mL, continues ultrasonic 1h.By product centrifuge washing, repeatedly final vacuum is dry, namely obtains CNT/MnO
2.In this composite material, CNT and MnO
2mass ratio is 69:31.The scanning electron microscopic picture of this composite material is shown in Fig. 6.
(2) preparation of CCCM flexible compound capacitor material is with embodiment 1.
(3) capacitor material prepared by step 2 is cut into 1 × 1cm
2size electrode slice, tests according to embodiment 1 electrochemical test method.Result has 366Fg under being presented at the sweep speed of 2mV/s
-1specific capacity.
Embodiment 9
(1) get the carbon nano-tube aqueous dispersions 20mL that concentration is 0.5mg/mL, add the MnSO that concentration is 0.015mol/L
4aqueous solution 2.5mL, add appropriate watery hydrochloric acid and regulate the pH of mixed solution to be 2, ultrasonic half an hour makes CNT and MnSO
4abundant mixing, then adds the KMnO that concentration is 0.01mol/L
4aqueous solution 2.5mL, continues ultrasonic 1h.By product centrifuge washing, repeatedly final vacuum is dry, namely obtains CNT/MnO
2.In this composite material, CNT and MnO
2mass ratio is 65:35.The scanning electron microscopic picture of this composite material is shown in Fig. 6.
(2) preparation of CCCM flexible compound capacitor material is with embodiment 1.
(3) capacitor material prepared by step 2 is cut into 1 × 1cm
2size electrode slice, tests according to embodiment 1 electrochemical test method.Result has 321Fg under being presented at the sweep speed of 2mV/s
-1specific capacity.
Embodiment 10
(1) the redox graphene aqueous dispersions 10mL that concentration is 0.2mg/mL is got, the CNT/MnO prepared with embodiment 9
2be uniformly mixed and obtain RGO/CNT/MnO
2composite material.In this composite material, RGO, CNT and MnO
2mass ratio be 12:60:28.
(2) preparation of flexible compound capacitor material is with embodiment 1.
(3) capacitor material prepared by step 2 is cut into 1 × 1cm
2size electrode slice, tests according to embodiment 1 electrochemical test method.Result has 391Fg under being presented at the sweep speed of 2mV/s
-1specific capacity.The cyclic voltammetry curve of this capacitor material is as Fig. 8.
Flexible capacitor material obtained by this example, redox graphene/carbon nanotube/manganese oxide composite material is adsorbed on carbon fiber carbon nanotube collector top layer uniformly.This material has excellent super electrical property, and pliability is better, and intensity is comparatively large, is a kind of desirable flexible super capacitance material.
Comparative example 1
With redox graphene/manganese dioxide composite material (RGO/MnO prepared by embodiment 1
2) be active material, adopt nickel foam collector to prepare capacitor.Prepared capacitor, different except collector and embodiment 1, the condition that the condition of other influences capacitor electrode chemical property is identical with embodiment 1 is identical.
Coprecipitation method is adopted to prepare RGO/MnO
2composite material is that to prepare electrode material be 158Fg to collector under 2mV/s speed with nickel foam
-1, lower than electrode material prepared by this programme.
Testing result can be drawn compared with embodiment 1, collector of the present invention, except the good advantage of flexibility strength, can also significantly improve capacitor ratio capacitance and stable circulation performance (after 5000 circulations, ratio capacitance keeps 96%).
Claims (10)
1. carbon nano-tube/carbon fibre composite, is with carbon nano-tube and conductive carbon fibre for raw material, adopts the film material that vacuum filtration method is prepared into; Wherein, the mass ratio of carbon nano-tube and conductive carbon fibre is 15-35:1.
2. carbon nano-tube/carbon fibre composite according to claim 1, it is characterized in that, above-mentioned carbon nano-tube/carbon fibre composite, be a kind of porous film material, its thickness is 100-400 μm.
3. carbon nano-tube/carbon fibre composite according to claim 1, it is characterized in that, the mass ratio of carbon nano-tube and conductive carbon fibre is 25:1.
4. carbon nano-tube/carbon fibre composite according to claim 1, it is characterized in that, the preparation method of above-mentioned carbon nano-tube/carbon fibre composite is:
After the aqueous dispersions of carbon nano-tube and the aqueous dispersions of conductive carbon fibre mix, vacuum filtration is on composite fibre filter membrane, then freeze drying.
5. carbon nano-tube/carbon fibre composite according to claim 1, it is characterized in that, freeze drying temperature is-60 DEG C, and cooling time selects 72h; The concentration of the aqueous dispersions of carbon nano-tube is 2mg/mL, and the concentration of the aqueous dispersions of conductive carbon fibre is 0.1mg/mL; Carbon fibre material length is 2-4mm, diameter 300-400 μm.
6. carbon back/manganese oxide composite electrodes material, is characterized in that, is that carbon nano-tube/carbon fibre composite in claim 1-5 described in any one is as collector.
7. want carbon back described in 6/manganese oxide composite electrodes material according to right, it is characterized in that, adopt redox graphene/manganese oxide composite material, carbon nanotube/manganese oxide composite material, graphene oxide/carbon nanotube/manganese oxide composite material as active material.
8. want carbon back described in 7/manganese oxide composite electrodes material according to right, it is characterized in that, in active material, the mass content of redox graphene is 20-40%; Concrete:
In redox graphene/manganese oxide composite material: the mass ratio of redox graphene and manganese oxide is 27-65:73-35; Preferred, the mass ratio of redox graphene and manganese oxide is 65:35,48:52,38:62,31:69 or 27:73;
In carbon nanotube/manganese oxide composite material: the mass ratio of carbon nano-tube and manganese oxide is 82-65:18-35; Preferred, the mass ratio of carbon nano-tube and manganese oxide is 82:18,75:25,69:31 or 65:35;
In graphene oxide/carbon nanotube/manganese oxide composite material: the mass ratio 12:60:28 of redox graphene, carbon nano-tube and manganese oxide.
9. want carbon back described in 6,7,8/manganese oxide composite electrodes material according to right, it is characterized in that, above-mentioned carbon back/manganese oxide composite electrodes material, described active material passes through the direct suction filtration of method of vacuum filtration to the surface of collector, then carries out freeze drying.
10. a preparation method for carbon back described in claim 7,8,9/manganese oxide composite electrodes material active material used, is characterized in that:
The preparation method of redox graphene/manganese oxide:
The aqueous dispersions of redox graphene and MnSO
4solution mixing, tune pH are 2, then add KMnO
4solution, after ultrasonic 1h, products therefrom is redox graphene/manganese oxide;
The preparation method of carbon nanotube/manganese oxide composite material:
Carbon nano tube dispersion liquid and MnSO
4solution mixing, tune pH are 2, then add KMnO
4solution, after ultrasonic 1h, products therefrom is carbon nanotube/manganese oxide composite material;
The preparation method of redox graphene/carbon nanotube/manganese oxide composite material:
Aqueous dispersions and the carbon nanotube/manganese oxide composite material of redox graphene mix.
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