CN105632790A - MnO2 nano array supercapacitor electrode material and preparation method thereof - Google Patents
MnO2 nano array supercapacitor electrode material and preparation method thereof Download PDFInfo
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- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 239000007772 electrode material Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 229920000049 Carbon (fiber) Polymers 0.000 claims abstract description 57
- 239000004917 carbon fiber Substances 0.000 claims abstract description 57
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 57
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 32
- 239000012286 potassium permanganate Substances 0.000 claims abstract description 27
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- 238000005406 washing Methods 0.000 claims abstract description 14
- 238000001816 cooling Methods 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 4
- 239000003990 capacitor Substances 0.000 claims description 40
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 28
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 12
- 230000008021 deposition Effects 0.000 claims description 9
- 238000012545 processing Methods 0.000 claims description 7
- 238000001338 self-assembly Methods 0.000 claims description 6
- 230000008901 benefit Effects 0.000 abstract description 3
- 238000005516 engineering process Methods 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 32
- 239000000463 material Substances 0.000 description 18
- 238000000151 deposition Methods 0.000 description 13
- 238000000034 method Methods 0.000 description 10
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 10
- 239000002243 precursor Substances 0.000 description 9
- 239000000047 product Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 6
- 239000002086 nanomaterial Substances 0.000 description 6
- 235000001674 Agaricus brunnescens Nutrition 0.000 description 5
- 238000005234 chemical deposition Methods 0.000 description 5
- 238000004140 cleaning Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 239000008151 electrolyte solution Substances 0.000 description 3
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 230000012010 growth Effects 0.000 description 2
- 239000012456 homogeneous solution Substances 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 229960004756 ethanol Drugs 0.000 description 1
- 230000007773 growth pattern Effects 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- -1 manganese oxide compound Chemical class 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000011800 void material Substances 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
- H01G11/84—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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- 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
- H01G11/46—Metal oxides
-
- 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)
- Nanotechnology (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Materials Engineering (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Physics & Mathematics (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
The invention relates to an MnO2 nano array supercapacitor electrode material and a preparation method thereof. The electrode material is formed by self-assembling MnO2 fin clusters at intervals, wherein the electrode material is in the shape of a nano array of a mushroom-shaped structure, and the space between the MnO2 fin clusters is 8-12 microns. The electrode material is prepared and formed through the following steps: (1) taking clean and dry carbon fiber paper to be soaked in a potassium permanganate solution, and putting in a closed reaction kettle together for a hydrothermal reaction; and (2) after the reaction is finished, taking out the carbon fiber paper after cooling, washing and drying to obtain the target product deposited on the surface of the carbon fiber paper. Compared with the prior art, the MnO2 nano array supercapacitor electrode material has the advantages of excellent electrochemical performance, simple preparation technology, low cost and the like.
Description
Technical field
The present invention relates to MnO2The preparation field of super capacitor material, especially relates to a kind of MnO2Nano-array electrode material for super capacitor and its preparation method.
Background technology
Ultracapacitor is the feature such as fast and service life cycle length with the high capacitance of its uniqueness, big current, discharge and recharge speed, more and more causes the concern of people. Many investigators are striving to find the electrode materials of a kind of novel excellent property always. Transition metal oxide is as the important aspect that electrode materials is research, and achieves some gratifying achievements. The people such as T.R.jow, by preparing the precursor of ruthenium dioxide 150 DEG C of thermal treatments, record hydration ruthenium dioxide RuO2��H2The ratio capacitance of O can reach 768F/g, is the capacitor material that the ratio capacitance of report at present is the highest. Due to RuO2��H2The cost of O this kind of material is too high, and contaminate environment, therefore is difficult to widespread use. So the material as an alternative such as many investigator's trial manganese oxide, nickel oxide, cobalt oxide. MnO2There is the properties similar with ruthenium dioxide, and resource is enriched, cheap. So sight is turned to MnO by many investigators2, it is desirable to it can become optimal capacitor material.
Chinese patent 201410667067.0 discloses the preparation method of a kind of element-doping manganese bioxide electrode material for super capacitor, specifically borate solution and manganous salt solution joining mol ratio successively that carry out hydro-thermal reaction, manganous salt and potassium permanganate in potassium permanganate solution is 1:0.5-5; Boron ionic concn is 0.001-5M, and temperature of reaction is 60-160 DEG C, and the reaction times is 1-24h, finally by reaction product respectively with ethanol and deionized water wash, and vacuum-drying 4-24h at 60-120 DEG C.
Summary of the invention
The object of the present invention is exactly the defect in order to overcome the existence of above-mentioned prior art and provides a kind of MnO2Nano-array electrode material for super capacitor and its preparation method.
The object of the present invention can be achieved through the following technical solutions:
A kind of MnO2Nano-array electrode material for super capacitor, this electrode materials is by MnO2The self-assembly of sheet bunch gap and become, its shape is the nano-array in mushroom-shaped structure, each MnO2The spacing of sheet bunch is 8��12 ��m.
A kind of MnO2The preparation method of nano-array electrode material for super capacitor, comprises the following steps:
(1) get the carbon fiber paper after clean dry to immerse in potassium permanganate solution, it is placed in together in closed reactor, hydro-thermal reaction;
(2) reaction terminates, and takes out carbon fiber paper after cooling again, and washing is dry, namely obtains object product in carbon fiber paper surface deposition.
In step (1), the processing step cleaned of carbon fiber paper is: successively with hydrochloric acid, dehydrated alcohol and deionized water wash, so just can take out in carbon cloth the impurity that may exist, thus ensures the pure property of experiment.
The concentration of described hydrochloric acid is 4��6mol/L.
The concentration of the potassium permanganate solution described in step (1) is 10��50mol/L, and the amount of the potassium permanganate solution of interpolation and the volumetric ratio of closed reactor are (24��30): (40��50).
In step (1), the processing condition of hydro-thermal reaction are: hydro-thermal reaction 10��120min at 80��120 DEG C of temperature.
Processing condition dry in step (2) are: at 30��80 DEG C of drying 2��5h.
In step (2) before hydro-thermal reaction, in closed reactor, keep normal temperature and pressure.
The present invention adopts soft chemical deposition technique, by allocating specific reaction soln, is immersed in reaction soln by the carbon fiber paper of cleaning, obtains the MnO of the mushroom-shaped structure of electrochemical performance through hydro-thermal reaction deposition2Nano-array super capacitor material. The super capacitor material of this kind of shape both make use of the feature of nano-array composite bigger serface, make use of again the advantage on its geometry (such as one-dimensional single crystal nanometer rod is conducive to the directional transmissions of electronics simultaneously, gap between ordered nano line is conducive to infiltration and the diffusion of ion), thus improve energy-storage property.
Whole reaction, on the basis without follow-up use low-surface energy substance modified product surface, taking common mineral solution as raw material, by regulating and controlling the parameters such as the concentration softening the reactant learned in deposition process in homogeneous solution and time, prepares the MnO of structure uniqueness2Nano-array, obtains that big area is evenly distributed, the MnO of electrochemical performance2Nano-electrode material, it is even higher that its capacitance can reach 318F/g. May cause according to other processing parameter that sedimentation velocity is too fast causes material form multiple accumulation instead of be uniformly distributed, thus void distribution is less, is unfavorable for that electrolytic solution transmits, and causes performance on the low side.
The present invention is in preparation process, and the Mn oxide of deposition is the hydrated manganese oxide compound that the various mn ions of indefinite form exist simultaneously, grows at carbon fiber surface with the form of nano wire, and has and be agglomerated into mushroom nanometer ball on a small quantity. The tridimensional network of this kind of growth pattern and carbon cloth is all conducive to the immersion of electrolytic solution and soaks. The present invention adopts hydrothermal method, with KMnO4For raw material, finally prepare mushroom MnO with 10mol/L with different concentration respectively2Nano-array. Design and adopt hydrothermal method to achieve the concentration by MnO4-in the hierarchy of control, reach MnO2Controllable growth. Analyze this process MnO2The growth mechanism of crystal: be first MnO4 -At high temperature carry out decomposition reaction, obtain non-crystalline state MnO2, along with the carrying out decomposed, the O of generation2Increasing gradually, thus add the pressure of system, therefore impact grows into the MnO of different shape2. The multiplying power of the loading capacity that the mushroom nano material of manganese dioxide that the experiment through us obtains when finding the potassium permanganate solution reaction adopting 24ml30mol/L in the reactor of 40ml is very high and excellence, it is possible to meet high-power battery to the requirement of electrode materials.
Compared with prior art, the present invention has the following advantages:
(1) the main reaction process of the present invention carries out in homogeneous solution, obtained MnO2Nano-array is evenly distributed, and just can big area preparation without the need to template.
(2) obtained MnO2In nano-array, between sheet and sheet, there are enough gaps (being about 8��12 ��m), it are beneficial to electrolyte ion transmission.
(3) preparation technology of the present invention is very simple, by hydro-thermal reaction and wash drying and settle at one go, it is not necessary to complicated equipment, in addition, each raw material sources are wide, it does not have relate to and use expensive precious metal, with low cost.
(4) MnO obtained by the present invention2Nano-array has excellent chemical property, and its capacitance up to 318F/g, can expand preparation method and the Application Areas of electrochemical capacitor material.
Accompanying drawing explanation
Fig. 1 is the mushroom MnO of the present invention2The scanning electron microscope diagram sheet of nano-array super capacitor material.
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is described in detail.
Embodiment 1
Prepare the MnO of mushroom-shaped structure2The method of nano-array super capacitor material, adopt soft chemical deposition technique, by allocating specific reaction soln, the carbon fiber paper of cleaning is immersed in reaction soln, obtains the MnO being self-assembled into mushroom-shaped structure by sheet bunch of electrochemical performance through hydro-thermal reaction deposition2Nano-array super capacitor material, specifically comprises the following steps:
(1) successively with dry after the clean carbon fiber paper of the hydrochloric acid of 5mol/L, dehydrated alcohol and deionized water;
(2) configure the potassium permanganate solution of 10mol/L, obtain precursor solution;
(3) carbon fiber paper in step (1) is immersed in 30ml precursor solution, under normal temperature and pressure, it is placed in the closed reactor of 50ml together, carries out hydro-thermal reaction 120min when temperature is 80 DEG C.
(4) after having reacted, after hydrothermal reaction kettle takes out at room temperature so cooling, carbon fiber paper being taken out washing, then dry 5h at the temperature of 30 DEG C, deposits MnO at carbon fiber paper surface2Nano material.
To above-mentioned obtained MnO2Nano material detects, and Fig. 1 is its scanning electron microscope diagram sheet, it is seen that, its structure is mushroom, assembles by sheet bunch gap, and the spacing between each bunch is about 8��12 ��m.
Embodiment 2
Preparation MnO2The method of nano-array super capacitor material, adopt soft chemical deposition technique, by allocating specific reaction soln, the carbon fiber paper of cleaning is immersed in reaction soln, obtains the MnO being self-assembled into mushroom-shaped structure by sheet bunch of electrochemical performance through hydro-thermal reaction deposition2Nano-array super capacitor material.
(1) successively with dry after the clean carbon fiber paper of the hydrochloric acid of 5mol/L, dehydrated alcohol and deionized water;
(2) configure the potassium permanganate solution of 30mol/L, obtain precursor solution;
(3) carbon fiber paper in step (1) is immersed in 24ml precursor solution, under normal temperature and pressure, it is placed in the closed reactor of 40ml together, carries out hydro-thermal reaction 60min when temperature is 90 DEG C;
(4) after having reacted, after hydrothermal reaction kettle takes out at room temperature so cooling, carbon fiber paper being taken out washing, then dry 4h at the temperature of 50 DEG C, deposits MnO at carbon fiber paper surface2Nano material.
Embodiment 3
Prepare the MnO of mushroom-shaped structure2The method of nano-array super capacitor material, adopt soft chemical deposition technique, by allocating specific reaction soln, the carbon fiber paper of cleaning is immersed in reaction soln, obtains the MnO being self-assembled into mushroom-shaped structure by sheet bunch of electrochemical performance through hydro-thermal reaction deposition2Nano-array super capacitor material.
(1) successively with dry after the clean carbon fiber paper of the hydrochloric acid of 5mol/L, dehydrated alcohol and deionized water;
(2) configure the potassium permanganate solution of 40mol/L, obtain precursor solution;
(3) carbon fiber paper in step (1) is immersed in 24ml precursor solution, under normal temperature and pressure, it is placed in the closed reactor of 50ml together, carries out hydro-thermal reaction 30min when temperature is 100 DEG C.
(4) after having reacted, after hydrothermal reaction kettle takes out at room temperature so cooling, carbon fiber paper being taken out washing, then dry 3h at the temperature of 60 DEG C, deposits MnO at carbon fiber paper surface2Nano material.
Embodiment 4
Preparation MnO2The method of nano-array super capacitor material, adopt soft chemical deposition technique, by allocating specific reaction soln, the carbon fiber paper of cleaning is immersed in reaction soln, obtains the MnO being self-assembled into mushroom-shaped structure by sheet bunch of electrochemical performance through hydro-thermal reaction deposition2Nano-array super capacitor material
(1) successively with dry after the clean carbon fiber paper of the hydrochloric acid of 5mol/L, dehydrated alcohol and deionized water;
(2) configure the potassium permanganate solution of 50mol/L, obtain precursor solution;
(3) carbon fiber paper in step (1) is immersed in 30ml precursor solution, under normal temperature and pressure, it is placed in the closed reactor of 40ml together, carries out hydro-thermal reaction 10min when temperature is 120 DEG C.
(4) after having reacted, after hydrothermal reaction kettle takes out at room temperature so cooling, carbon fiber paper being taken out washing, then dry 2h at the temperature of 80 DEG C, deposits MnO at carbon fiber paper surface2Nano material.
Embodiment 5
A kind of MnO2The preparation method of nano-array electrode material for super capacitor, comprises the following steps:
(1) by carbon fiber paper successively with dry after the hydrochloric acid of 4mol/L, dehydrated alcohol and deionized water wash, immerse in the potassium permanganate solution of 27ml10mol/L again, then the closed reactor that under normal temperature and pressure, carbon fiber paper is placed in together with potassium permanganate solution 45ml, hydro-thermal reaction 120min at 80 DEG C of temperature;
(2) after reaction terminates, under room temperature, after naturally cooling, take out carbon fiber paper, washing, at 30 DEG C of dry 5h, namely obtain object product in carbon fiber paper surface deposition. It will be seen that the electrode material for super capacitor prepared is the MnO of the mushroom-shaped structure become by the self-assembly of sheet bunch gap after after testing2Nano-array, each MnO2The spacing of sheet bunch is about 8��12 ��m.
Embodiment 6
A kind of MnO2The preparation method of nano-array electrode material for super capacitor, comprises the following steps:
(1) by carbon fiber paper successively with dry after the hydrochloric acid of 6mol/L, dehydrated alcohol and deionized water wash, immerse in the potassium permanganate solution of 27ml50mol/L again, then the closed reactor that under normal temperature and pressure, carbon fiber paper is placed in together with potassium permanganate solution 50ml, hydro-thermal reaction 10min at 120 DEG C of temperature;
(2) after reaction terminates, under room temperature, after naturally cooling, take out carbon fiber paper, washing, at 80 DEG C of dry 2h, namely obtain object product in carbon fiber paper surface deposition. It will be seen that the electrode material for super capacitor prepared is the MnO of the mushroom-shaped structure become by the self-assembly of sheet bunch gap after after testing2Nano-array, each MnO2The spacing of sheet bunch is about 8��12 ��m.
Embodiment 7
A kind of MnO2The preparation method of nano-array electrode material for super capacitor, comprises the following steps:
(1) by carbon fiber paper successively with dry after the hydrochloric acid of 5mol/L, dehydrated alcohol and deionized water wash, immerse in the potassium permanganate solution of 25ml30mol/L again, then the closed reactor that under normal temperature and pressure, carbon fiber paper is placed in together with potassium permanganate solution 45ml, hydro-thermal reaction 60min at 100 DEG C of temperature;
(2) after reaction terminates, under room temperature, after naturally cooling, take out carbon fiber paper, washing, at 50 DEG C of dry 3h, namely obtain object product in carbon fiber paper surface deposition. It will be seen that the electrode material for super capacitor prepared is the MnO of the mushroom-shaped structure become by the self-assembly of sheet bunch gap after after testing2Nano-array, each MnO2The spacing of sheet bunch is about 8��12 ��m.
Embodiment 8
A kind of MnO2The preparation method of nano-array electrode material for super capacitor, comprises the following steps:
(1) by carbon fiber paper successively with dry after the hydrochloric acid of 5mol/L, dehydrated alcohol and deionized water wash, immerse in the potassium permanganate solution of 26ml20mol/L again, then the closed reactor that under normal temperature and pressure, carbon fiber paper is placed in together with potassium permanganate solution 40ml, hydro-thermal reaction 50min at 95 DEG C of temperature;
(2) after reaction terminates, under room temperature, after naturally cooling, take out carbon fiber paper, washing, at 50 DEG C of dry 4h, namely obtain object product in carbon fiber paper surface deposition. It will be seen that the electrode material for super capacitor prepared is the MnO of the mushroom-shaped structure become by the self-assembly of sheet bunch gap after after testing2Nano-array, each MnO2The spacing of sheet bunch is about 8��12 ��m.
Comparative example 1
A kind of MnO2The preparation method of nano capacitor electrode materials, comprises the following steps:
(1) by carbon fiber paper successively with dry after the hydrochloric acid of 5mol/L, dehydrated alcohol and deionized water wash, immerse in the potassium permanganate solution of 24ml5mol/L again, then the closed reactor that under normal temperature and pressure, carbon fiber paper is placed in together with potassium permanganate solution 40ml, hydro-thermal reaction 60min at 90 DEG C of temperature;
(2) after reaction terminates, under room temperature, after naturally cooling, take out carbon fiber paper, washing, at 50 DEG C of dry 4h, namely obtain object product in carbon fiber paper surface deposition.
Comparative example 2
A kind of MnO2The preparation method of nano capacitor electrode materials, comprises the following steps:
(1) by carbon fiber paper successively with dry after the hydrochloric acid of 5mol/L, dehydrated alcohol and deionized water wash, immerse in the potassium permanganate solution of 24ml70mol/L again, then the closed reactor that under normal temperature and pressure, carbon fiber paper is placed in together with potassium permanganate solution 40ml, hydro-thermal reaction 60min at 90 DEG C of temperature;
(2) after reaction terminates, under room temperature, after naturally cooling, take out carbon fiber paper, washing, at 50 DEG C of dry 4h, namely obtain object product in carbon fiber paper surface deposition.
Example 2, comparative example 1 and the obtained nano-manganese dioxide sample of comparative example 2, be placed in 0.5mol/LNa respectively after making electrode2SO4In electrolytic solution, at voltage range 0��0.8V, test in current density 300mA/g. Result is as shown in the table.
Table nanometer manganese dioxide electrode material performance table
| Numbering | Electric discharge is than capacitance (F/g) |
| Embodiment 2 | 310 |
| Comparative example 1 | 198 |
| Comparative example 2 | 225 |
The above-mentioned description to embodiment can understand and use invention for ease of those skilled in the art. These embodiments obviously easily can be made various amendment by person skilled in the art, and General Principle described herein are applied in other embodiments and need not pass through creative work. Therefore, the invention is not restricted to above-described embodiment, those skilled in the art, according to the announcement of the present invention, do not depart from improvement that category of the present invention makes and amendment all should within protection scope of the present invention.
Claims (9)
1. a MnO2Nano-array electrode material for super capacitor, it is characterised in that, this electrode materials is by MnO2The self-assembly of sheet bunch gap and become, its shape is the nano-array in mushroom-shaped structure, each MnO2The spacing of sheet bunch is 8��12 ��m.
2. a kind of MnO as claimed in claim 12The preparation method of nano-array electrode material for super capacitor, it is characterised in that, comprise the following steps:
(1) get the carbon fiber paper after clean dry to immerse in potassium permanganate solution, it is placed in together in closed reactor, hydro-thermal reaction;
(2) reaction terminates, and takes out carbon fiber paper after cooling again, and washing is dry, namely obtains object product in carbon fiber paper surface deposition.
3. a kind of MnO according to claim 22The preparation method of nano-array electrode material for super capacitor, it is characterised in that, in step (1), the processing step cleaned of carbon fiber paper is: successively with hydrochloric acid, dehydrated alcohol and deionized water wash.
4. a kind of MnO according to claim 32The preparation method of nano-array electrode material for super capacitor, it is characterised in that, the concentration of described hydrochloric acid is 4��6mol/L.
5. a kind of MnO according to claim 22The preparation method of nano-array electrode material for super capacitor, it is characterized in that, the concentration of the potassium permanganate solution described in step (1) is 10��50mol/L, and the amount of the potassium permanganate solution of interpolation and the volumetric ratio of closed reactor are (24��30): (40��50).
6. a kind of MnO according to claim 22The preparation method of nano-array electrode material for super capacitor, it is characterised in that, in step (1), the processing condition of hydro-thermal reaction are: hydro-thermal reaction 10��120min at 80��120 DEG C of temperature.
7. a kind of MnO according to claim 22The preparation method of nano-array electrode material for super capacitor, it is characterised in that, in step (2), washing is for using deionized water wash.
8. a kind of MnO according to claim 22The preparation method of nano-array electrode material for super capacitor, it is characterised in that, processing condition dry in step (2) are: at 30��80 DEG C of drying 2��5h.
9. a kind of MnO according to claim 22The preparation method of nano-array electrode material for super capacitor, it is characterised in that, in step (2) before hydro-thermal reaction, in closed reactor, keep normal temperature and pressure.
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| CN106683894A (en) * | 2016-12-30 | 2017-05-17 | 盐城工学院 | Co3O4 porous nanosheet array preparation method and application thereof |
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| CN111986931A (en) * | 2020-07-24 | 2020-11-24 | 华南理工大学 | Manganese oxide nano-structure electrode material and preparation method and application thereof |
| CN112435862A (en) * | 2020-11-16 | 2021-03-02 | 青岛科技大学 | Preparation method of novel asymmetric fibrous flexible supercapacitor |
| CN112435862B (en) * | 2020-11-16 | 2022-04-19 | 青岛科技大学 | Preparation method of novel asymmetric fibrous flexible supercapacitor |
| CN114613610A (en) * | 2022-02-25 | 2022-06-10 | 中国科学院宁波材料技术与工程研究所 | Adhesive-free supercapacitor electrode based on basic manganese oxide nano material modified carbon fiber and preparation and application thereof |
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