CN104465123A - Electrode material of C@MnO2 nanotube super capacitor and preparation method and application of electrode material - Google Patents
Electrode material of C@MnO2 nanotube super capacitor and preparation method and application of electrode material Download PDFInfo
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- CN104465123A CN104465123A CN201410720452.7A CN201410720452A CN104465123A CN 104465123 A CN104465123 A CN 104465123A CN 201410720452 A CN201410720452 A CN 201410720452A CN 104465123 A CN104465123 A CN 104465123A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/46—Metal oxides
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Abstract
The invention provides an electrode material of a three-dimensional C@MnO2 composite nanotube array super capacitor and a preparation method and application of the electrode material. A nanotube-shaped carbon layer is arranged inside the material, and a MnO2 material is arranged outside the material. The preparation method includes the steps that (1) a flexible carbon fiber cloth is subjected to pretreatment and magnetron sputtering to deposit a zinc oxide thin film; (2) zinc oxide nanorod array growth is conducted; (3) a zinc oxide nanorod array carbon cloth with the surface being coated with thin-layer carbon is prepared; (4) the carbon cloth obtained in the step (3) is used as a working electrode, and a three-electrode electrodeposition system is used for conducting manganese dioxide electrochemical deposition, flushing and drying to obtain the super capacitor electrode material which is of a three-dimensional C@MnO2 nanotube-shaped array structure. According to the material, the carbon material with good electrical conductivity and the MnO2 material with high specific capacitance and poor electrical conductivity are compounded, the advantages of the carbon material and the advantages of the MnO2 material are fully performed, due to hollow nanotubes, electrolyte solution ions can better enter and exit, and thus the rate capability of the capacitor can be greatly improved.
Description
Technical field
The invention belongs to energy storage and devices field, particularly relate to a kind of three Vc MnO
2composite nano tube array super capacitance electrode material and its production and use.
Background technology
Flexible wearable electronic product more and more attracts people more to pay close attention to and interest, but it is also proposed higher requirement to its electric power energy supply parts, such as lightweight, flexibility, high power, long-life, high-energy-density etc. simultaneously.Conventional device mainly lithium battery and the ultracapacitor that energy storage is provided, compared with lithium ion battery, although the energy density of ultracapacitor is lower, but ultracapacitor can provide higher power density and cycle life, special effect and performance can be played, especially for the electronic device needing fast charging and discharging, its advantage is that lithium ion battery is incomparable.
Ultracapacitor can be divided into two classes, the double electric layer capacitor of a class to be main with material with carbon element be electrode material, another kind of be with oxide be electrode material be Faradic electricity container, or pseudocapacitors.Double electric layer capacitor is mainly made up of various material with carbon element, such as carbon nano-tube, Graphene, carbon fiber and carbon black etc.The electrode active material of Faradic electricity container is mainly oxidized (RuO by various low transition metal
2, NiO, CO
3o
4, MnO
2deng) and conducting polymer formation.Faradic electricity container is relative to double electric layer capacitor, its energy storage mechnism is the chemical reaction that Rapid reversible occurs electrode material in the process of discharge and recharge, therefore higher specific capacity can be had, also be study hotspot in recent years, its shortcoming is that conductivity is poor, and people attempt to improve its conductivity by various method.
For the ultracapacitor that flexible wearable electronic product is used, not only require that device unit are ratio capacitance capacity is high, and require lighting as far as possible.Carbon cloth is the conductive carbon fibre material of being worked out by conductive carbon fibre, it is a kind of excellent lightweight electric double layer super capacitor material, can be applied to flexible wearable electronic product, its shortcoming is that unit are ratio capacitance is low, is difficult to the demand adapting to high-energy-density device.In order to improve unit are ratio capacitance, people are complex carbon material or faraday's electric capacity oxide material on the basis of carbon cloth, to improve area ratio electric capacity.Such as Zhou cheng etc. are by CVD mode random growth carbon nano-tube on carbon cloth, make flexible super capacitor (Zhou cheng, et al.Carbon nanotubenetwork film directly grown on carbon cloth for high-performance solid-state flexiblesupercapacitors.Nanotechnology.2014, DOI:10.1088/0957-4484/25/3/035402).Feng Wei etc. adopt liquid solution as carbon source and catalyst source in patent CN102354612A, grown surface density and all very high carbon pipe of draw ratio by CVD mode on carbon cloth fiber, the MnO that utilized the mode of electro-deposition coated on the carbon nanotubes
2particle, this carbon pipe due to draw ratio too high and easily lodge, be unfavorable for that electrolyte enters the embedding of the inner and ion of array carbon nanotube and deviates from, cause high-rate charge-discharge capability and cycle performance poor.
The method that above-mentioned CVD grows carbon pipe is all at high temperature carry out, and equipment requirement is high, complex process, and cost is high, is also unfavorable for the integrated of energy device and other devices.
ZnO nano-rod array has three-dimensional structure, electrode as 3D ultracapacitor prepares template, give play to potential advantage (Yong Zhao, Peng Jiang.MnO2nanosheets grown on theZnO-nanorod-modifiedcarbon fiber paper for supercapacitor electrode materials, Colloids and SurfacesA:Physicochem.Eng.Aspects, 2014,444,232-239; YongZhao, Peng Jiang, Sishen Xie.Template-mediated synthesis of three-dimensionalcoral-like MnO2nanostructure for supercapacitors, Journal of Power Sources, 2013,239,393-398.), but ZnO nanorod is almost nil for the capacitance contribution of ultracapacitor, and adds the quality of electrode for capacitors, is unfavorable for the lighting demand for development of ultracapacitor.
Existing carbon nano-tube (CNT)@MnO
2hybrid supercapacitor electrode material growth technique is complicated, equipment requirement is high, cost is high, is difficult to large-scale promotion and application.ZnO@Au@MnO
2although hybrid supercapacitor electrode material excellent performance, do not have contributive ZnO nano array to add electrode quality to condenser capacity, and adopt noble metal to improve conductivity, ultracapacitor lighting, development trend that cost is low cannot be met.
Carbon cloth unit are ratio capacitance is there is in sum low in prior art; ZnO nanorod is not contributed for the capacitance of ultracapacitor and adds the quality of electrode for capacitors; Coated MnO
2the carbon nano-tube draw ratio of particle is too high and easily lodge, and is unfavorable for that electrolyte enters the embedding of the inner and ion of array carbon nanotube and deviates from, cause high-rate charge-discharge capability and cycle performance poor; Existing carbon nano-tube hybrid supercapacitor electrode material growth technique is complicated, equipment requirement is high, cost is high, is difficult to the problem such as large-scale promotion and application.
Summary of the invention
The invention provides a kind of novelty three Vc MnO grown based on flexible carbon cloth
2the preparation method of composite nano tube array electrode material for super capacitor and device thereof, the MnO that this material is by the material with carbon element of good conductivity and ratio capacitance is high, conductivity is poor
2combine, give full play to the advantage of the two, and utilize the H produced in electrodeposition process dexterously
+remove the ZnO template of capacity without contribution, prepare novel lightweight high power capacity electrode material for super capacitor.
For reaching this object, the present invention by the following technical solutions:
A kind of three Vc MnO
2composite nano tube array super capacitance electrode material, described material internal is nanotube-shaped carbon-coating, and outside is MnO
2material.
The preparation method of the above super capacitance electrode material, said method comprising the steps of:
(1) preliminary treatment is carried out to flexible carbon fibre cloth, then magnetron sputtering deposition ZnO film is carried out to pretreated carbon cloth, as the growth Seed Layer of ZnO nanorod;
(2) array growth of ZnO nanorod: the carbon cloth after process in step (1) is placed in container, add deionized water, the salting liquid of zinc, complexing agent one, complexing agent two and ammoniacal liquor respectively and fully stir sealing, then carry out heating water bath and obtain ZnO nano-rod array, be evenly distributed in carbon cloth fiber peripheral;
(3) growth obtained the 3rd step has the carbon cloth of ZnO nano-rod array to rinse, immerse in saccharide solution after making its surperficial complete wetting, drying is carried out after being blown off by the saccharide solution of excess surface by carbon cloth taking-up inert gas again, then the carbon cloth of bone dry is carried out annealing in process under the protection of inert gas, make the carbohydrate carbonization around clading ZnO nano rod, obtain the ZnO@C nano rod array that ZnO nanorod Surface coating has thin layer carbon;
(4) obtaining load using step (3) has the carbon cloth of ZnO@C nano rod array to obtain having C@MnO as the electrochemical deposition that work electrode adopts three electrode electro-deposition systems to carry out manganese dioxide
2the carbon cloth of nano tubular structure, utilizes the H produced in deposition process
+znO nanorod is removed, just can obtain C@MnO
2nano tubular structure, wherein electrodeposition time needs accurately to control, and the time, too short ZnO nanorod was removed not exclusively, can not get the nano tube structure of hollow; And then rinse, wash unnecessary electrolyte off, and drying obtains having three Vc MnO
2the super capacitance electrode material of nano-tube structure structure.
In step (1), preprocessing process carries out Ultrasonic Cleaning with acetone and alcohol to flexible carbon fibre cloth respectively, then dries.
The time of described Ultrasonic Cleaning is 1 ~ 5min, such as 1min, 1.5min, 2min, 2.5min, 3min, 3.5min, 4min, 4.5min or 5min etc., preferred 2min.
Described bake out temperature is 105 ~ 115 DEG C, such as 105 DEG C, 106 DEG C, 107 DEG C, 108 DEG C, 109 DEG C, 110 DEG C, 111 DEG C, 112 DEG C, 113 DEG C, 114 DEG C or 115 DEG C etc., preferably 110 DEG C.
Described drying time is 1 ~ 3h, such as 1h, 1.5h, 2h, 2.5h or 3h etc., preferred 1h.
The zinc-oxide film of magnetron sputtering deposition 50 ~ 60nm on carbon cloth after treatment in described step (1), such as 50nm, 51nm, 52nm, 53nm, 54nm, 55nm, 56nm, 57nm, 58nm, 59nm or 60nm etc., preferred 50nm.
In described step (2), the carbon cloth after process in step (1) is placed in resealable container.
The salting liquid of zinc is the combination of any one or at least two kinds in zinc nitrate, zinc sulfate, zinc chloride, zinc acetate or trbasic zinc phosphate in described step (2), described combination typical case but limiting examples have: the combination of zinc nitrate and zinc sulfate, the combination of zinc chloride and zinc acetate, the combination of zinc acetate and trbasic zinc phosphate, the combination of zinc nitrate, zinc sulfate and zinc chloride, the combination etc. of zinc sulfate, zinc chloride, zinc acetate and trbasic zinc phosphate, preferred zinc nitrate.
Described step (2) complexing agent one is the combination of any one or at least two kinds in polyethylenimine solution, phenol solution, malonic acid dimethyl ester solution or cyclohexanoneimine solution, described combination typical case but limiting examples have: the combination of polyethylenimine solution and phenol solution, the combination of phenol solution and malonic acid dimethyl ester solution, the combination of malonic acid dimethyl ester solution and cyclohexanoneimine solution, the combination etc. of polyethylenimine solution, phenol solution, malonic acid dimethyl ester solution and cyclohexanoneimine solution, preferably polyethylene base imide liquor.
Described step (2) complexing agent two is hexamethylenetetramine solution, ethylenediamine tetrapropionic acid solution, the combination of any one or at least two kinds in triethylenetetramine solution or diethanolamine solution, described combination typical case but limiting examples have: the combination of hexamethylenetetramine solution and ethylenediamine tetrapropionic acid solution, the combination of ethylenediamine tetrapropionic acid solution and triethylenetetramine solution, the combination of triethylenetetramine solution and diethanolamine solution, hexamethylenetetramine solution, the combination of ethylenediamine tetrapropionic acid solution and triethylenetetramine solution, hexamethylenetetramine solution, ethylenediamine tetrapropionic acid solution, the combination etc. of triethylenetetramine solution and diethanolamine solution, preferred hexamethylenetetramine solution.
The volume ratio of the salting liquid of deionized water, zinc, complexing agent one, complexing agent two and ammoniacal liquor is 30 ~ 35:2 ~ 5:3 ~ 5:2 ~ 5:1 ~ 2 in described step (2), such as 30:2:3:2:1,31:3:4:3:2,32:4:5:4:1,33:5:3:5:2,34:3:3:4:2 or 35:4:5:3:1 etc., preferred 32:2:4:2:1.
In described step (2), the concentration of the salting liquid of zinc is 0.3 ~ 0.7mol/L, such as 0.3mol/L, 0.35mol/L, 0.4mol/L, 0.45mol/L, 0.5mol/L, 0.55mol/L, 0.6mol/L, 0.65mol/L or 0.7mol/L etc., preferred 0.5mol/L.
The concentration of described step (2) complexing agent one is 0.05 ~ 0.15mol/L, such as 0.05mol/L, 0.06mol/L, 0.07mol/L, 0.08mol/L, 0.09mol/L, 0.1mol/L, 0.11mol/L, 0.12mol/L, 0.13mol/L, 0.14mol/L or 0.15mol/L etc., preferred 0.1mol/L.
The concentration of described step (2) complexing agent two is 0.2 ~ 0.3mol/L, such as 0.2mol/L, 0.21mol/L, 0.22mol/L, 0.23mol/L, 0.24mol/L, 0.25mol/L, 0.26mol/L, 0.27mol/L, 0.28mol/L, 0.29mol/L or 0.3mol/L etc., preferred 0.25mol/L.
The concentration of ammoniacal liquor is 70 ~ 80% in described step (2), such as 70%, 71%, 72%, 73%, 74%, 75%, 76%, 77%, 78%, 79% or 80% etc., preferably 75%.
The temperature of heating water bath is 60 ~ 70 DEG C in described step (2), such as 60 DEG C, 61 DEG C, 62 DEG C, 63 DEG C, 64 DEG C, 65 DEG C, 66 DEG C, 67 DEG C, 68 DEG C, 69 DEG C or 70 DEG C etc., preferably 65 DEG C.
In described step (2), the time of heating water bath is 8 ~ 12h, such as 8h, 8.5h, 9h, 9.5h, 10h, 10.5h, 11h, 11.5h or 12h etc., preferred 10h.
In described step (3), absolute ethyl alcohol and deionized water rinsing are used successively to the carbon cloth being distributed with nanometic zinc oxide rod array.
Saccharide solution in described step (3) is glucose solution, sucrose solution, maltose solution, the combination of any one or at least two kinds in fructose soln or lactose solution, described combination typical case but limiting examples have: the combination of glucose solution and sucrose solution, the combination of sucrose solution and maltose solution, the combination of maltose solution and fructose soln, the combination of fructose soln and lactose solution, glucose solution, the combination of sucrose solution and maltose solution, sucrose solution, maltose solution, the combination of fructose soln and lactose solution, glucose solution, sucrose solution, maltose solution, the Assembled lamp of fructose soln and lactose solution, preferred glucose solution.
In described step (3), the concentration of saccharide solution is 0.5 ~ 1.5mol/L, such as 0.5mol/L, 0.6mol/L, 0.7mol/L, 0.8mol/L, 0.9mol/L, 1mol/L, 1.1mol/L, 1.2mol/L, 1.3mol/L, 1.4mol/L or 1.5mol/L etc., preferred 1mol/L.
In described step (3), carbon cloth soaks 4 ~ 7h, such as 4h, 4.5h, 5h, 5.5h, 6h, 6.5h or 7h etc., preferred 5h in saccharide solution.
Inert gas is the combination of any one or at least two kinds in nitrogen, argon gas, helium or neon in described step (3), described combination typical case but limiting examples have: the combination of nitrogen and argon gas, the combination of argon gas and helium, the combination of helium and neon, the combination of nitrogen, argon gas and helium, the combination etc. of nitrogen, argon gas, helium and neon.
Temperature dry after purging in described step (3) is 75 ~ 85 DEG C, such as 75 DEG C, 76 DEG C, 77 DEG C, 78 DEG C, 79 DEG C, 80 DEG C, 81 DEG C, 82 DEG C, 83 DEG C, 84 DEG C or 85 DEG C etc., preferably 80 DEG C.
Time dry in described step (3) is 4 ~ 6h, such as 4h, 4.5h, 5h, 5.5h or 6h etc., preferred 5h.
In described step (3), the flow of the inert gas of protective effect is 45 ~ 55sccm; such as 45sccm, 46sccm, 47sccm, 48sccm, 49sccm, 50sccm, 51sccm, 52sccm, 53sccm, 54sccm or 55sccm etc., preferred 50sccm.
In described step (3), annealing in process is carried out in quartz tube furnace.
The temperature of annealing in process is 500 ~ 700 DEG C in described step (3), such as 500 DEG C, 530 DEG C, 550 DEG C, 570 DEG C, 600 DEG C, 630 DEG C, 650 DEG C, 670 DEG C or 700 DEG C etc., preferably 600 DEG C.
In described step (3), the time of annealing in process is 4 ~ 6h, such as 4h, 4.5h, 5h, 5.5h or 6h etc., preferred 5h.
Using saturated calomel electrode as reference electrode in described step (4) three electrode electro-deposition system, be to electrode with platinized platinum.
Using the mixed solution of manganese salt and metal salt solution as electrolyte in described step (4) three electrode electro-deposition system.
In described step (4) three electrode electro-deposition system, manganese salt is the combination of any one or at least two kinds in manganese nitrate, manganese sulfate, manganese acetate, manganese phosphate or manganese chloride, described combination typical case but limiting examples have: the combination of manganese nitrate and manganese sulfate, the combination of manganese sulfate and manganese acetate, the combination of manganese phosphate and manganese chloride, the combination of manganese nitrate, manganese sulfate and manganese acetate, the combination of manganese sulfate, manganese acetate, manganese phosphate and manganese chloride, the combination of manganese nitrate, manganese sulfate, manganese acetate, manganese phosphate and manganese chloride, preferred manganese nitrate.
In described step (4) three electrode electro-deposition system, metal salt solution is sodium nitrate, sodium sulphate, sodium chloride, sodium acetate, nickel nitrate, nickel acetate, nickel chloride, potassium nitrate, potassium acetate, the combination of any one or at least two kinds in potassium chloride or potassium sulfate, described combination typical case but limiting examples have: the combination of sodium nitrate and sodium sulphate, the combination of sodium sulphate and sodium chloride, the combination of sodium acetate and nickel nitrate, nickel nitrate, the combination of nickel acetate and nickel chloride, nickel chloride, the combination of potassium nitrate and potassium acetate, potassium nitrate, potassium acetate, the combination of potassium chloride and potassium sulfate, sodium nitrate, sodium sulphate, sodium chloride, sodium acetate, nickel nitrate, the combination of nickel acetate and nickel chloride, nickel acetate, nickel chloride, potassium nitrate, potassium acetate, the combination etc. of potassium chloride and potassium sulfate, preferred sodium nitrate.
In described step (4) three electrode electro-deposition system, the concentration of manganese salt is 0.01 ~ 0.03mol/L, such as 0.01mol/L, 0.013mol/L, 0.015mol/L, 0.017mol/L, 0.02mol/L, 0.023mol/L, 0.025mol/L, 0.027mol/L or 0.03mol/L etc., preferred 0.02mol/L.
In described step (4) three electrode electro-deposition system, the concentration of metal salt solution is 0.05 ~ 0.15mol/L, such as 0.05mol/L, 0.06mol/L, 0.07mol/L, 0.08mol/L, 0.09mol/L, 0.1mol/L, 0.11mol/L, 0.12mol/L, 0.13mol/L, 0.14mol/L or 0.15mol/L etc., preferred 0.1mol/L.
The current density of described step (4) electrochemical deposition is 1 ~ 2mA/cm
2, such as 1mA/cm
2, 1.1mA/cm
2, 1.2mA/cm
2, 1.3mA/cm
2, 1.4mA/cm
2, 1.5mA/cm
2, 1.6mA/cm
2, 1.7mA/cm
2, 1.8mA/cm
2, 1.9mA/cm
2or 2mA/cm
2deng, preferred 1.5mA/cm
2.
The time of described step (4) electrochemical deposition is 35 ~ 45min, such as 35min, 36min, 37min, 38min, 39min, 40min, 41min, 42min, 43min, 44min or 45min etc., preferred 40min.
In described step (4), electrochemical deposition obtains having C@MnO
2the carbon cloth deionized water of nano tubular structure rinses.
Baking temperature is 140 ~ 160 DEG C in described step (4), such as 140 DEG C, 143 DEG C, 145 DEG C, 147 DEG C, 150 DEG C, 153 DEG C, 155 DEG C, 157 DEG C, 159 DEG C or 160 DEG C etc., preferably 150 DEG C.
In described step (4), drying time is 5 ~ 15min, such as 5min, 6min, 7min, 8min, 9min, 10min, 11min, 12min, 13min, 14min or 15min etc., preferred 10min.
The three Vc MnO that method described in more than one prepares
2the purposes of composite nano tube array super capacitance electrode material, it is applied in wearable electronic product scope.
Compared with prior art, the present invention at least has following beneficial effect:
The present invention utilizes ZnO template, prepares a kind of novel three-dimensional C@MnO grown based on flexible carbon cloth
2composite nano tube array electrode material for super capacitor, the MnO that this material is by the material with carbon element of good conductivity and ratio capacitance is high, conductivity is poor
2combine, give full play to the advantage of the two, and utilize the H produced in electrodeposition process dexterously
+remove the ZnO template of capacity without contribution.
Material prepared by the present invention can as the electrode material of ultracapacitor, and inner nanotube-shaped carbon-coating can be the MnO of outside high power capacity
2material provides good electron conduction, and the nanotube of hollow is beneficial to the turnover of electrolyte ion, can increase substantially the high rate performance of capacitor.
This electrode material lightweight, there is higher area ratio electric capacity and power characteristic, cycle performance is superior, utilize this electrode material to assemble the flexible solid-state supercapacitor obtained and there is good chemical property, capacity when sweeping speed and being 2mV/s is 405F/g, and when sweeping speed and being 100mV/s, capacity still can reach 200F/g.This device has good flexibility simultaneously, and before the CV curve fundamental sum of the rear device of bending 1800 does not bend, the CV curve of (00) is substantially identical, illustrates that this device has excellent electrochemical structure stability.This electrode material cost is low simultaneously, makes simple, can be wearable electronic product and provide energy storage, and can meet the powerful electric discharge demand of electronic device.
Accompanying drawing explanation
Fig. 1 is the ZnO nano-rod array figure that flexible carbon fibre cloth of the present invention grows;
Fig. 2 is the C@MnO that electro-deposition 40min obtains
2the SEM photo of nano tube structure different amplification;
Fig. 3 is C@MnO
2nano tube structure TEM photo;
Fig. 4 adopts two panels carbon cloth@C@MnO
2the symmetrical solid-state super capacitor free bend figure of electrode material assembling;
Fig. 5 is that LED figure is lighted in the symmetrical solid-state super capacitor series connection of employing two;
Fig. 6 adopts two panels carbon cloth@C@MnO
2the cyclic voltammogram of the symmetrical solid-state super capacitor of electrode material assembling;
Fig. 7 is the cyclic voltammetry curve contrast figure that the symmetrical solid-state super capacitor of preparation bends before and after 180 degree.
Embodiment
Technical scheme of the present invention is further illustrated by embodiment below in conjunction with accompanying drawing.
Embodiment 1:
C@MnO
2the preparation of electrode material:
(1) flexible carbon fibre cloth is used respectively acetone, alcohol Ultrasonic Cleaning 2 minutes, then toast 1 hour at 110 DEG C; Utilize magnetron sputtering mode, the ZnO film of sputtering sedimentation 50nm on pretreated carbon cloth, as the growth Seed Layer of zinc oxide nano rod;
(2) nanometic zinc oxide rod array growth: carbon cloth sample prepared by above-mentioned steps (1) is inserted in sealable container, according to the volume ratio of 32:2:4:2:1, add respectively deionized water, the zinc nitrate solution of 0.5mol/L, the polyethylenimine solution of 0.1mol/L, the hexamethylenetetramine solution of 0.25mol/L and 75% ammoniacal liquor.Seal after abundant stirring, then heating water bath 10 hours at 65 DEG C, obtains the nanometic zinc oxide rod array of 6 microns, is evenly distributed in carbon cloth fiber peripheral, as shown in Figure 1.
(3) carbon cloth of ZnO nanowire array there is is to use absolute ethyl alcohol, deionized water rinsing successively the growth that (2) step obtains, make its surperficial complete wetting, then carbon cloth is immersed in the glucose solution of 1mol/L and keep 5h, take out carbon cloth afterwards and blow off with the glucose solution of nitrogen by excess surface, at the baking oven inner drying 5h of 80 DEG C.Then by the carbon cloth of bone dry; under the argon shield of 50sccm, in quartz tube furnace, anneal at 600 DEG C 5h; make the glucose carbonization around clading ZnO nano rod, finally can obtain the ZnO@C nano rod array that ZnO nanorod Surface coating has thin layer carbon.
(4) load obtained using (3) step has the carbon cloth of ZnO@C nano rod array directly as work electrode, adopt three electrode electro-deposition systems, take saturated calomel electrode as reference electrode, platinized platinum is Mn (NO to electrode, 0.02mol/L
3)
2with the NaNO of 0.1mol/L
3mixed solution be electrolyte, at 1.5mA/cm
2current density under carry out MnO
2electrochemical deposition, sedimentation time is 40min; Fall unnecessary electrolyte with a large amount of deionized water rinsing afterwards, and at 150 DEG C dry 10min, obtain three Vc MnO of carbon cloth fiber surface growth in situ
2nano-tube structure structure, its electrode structure as shown in Figures 2 and 3.
The preparation of all-solid-state flexible ultracapacitor:
Lithium chloride and PVA are dissolved in appropriate deionized water according to mass ratio 2:1, at 85 DEG C of stirring in water bath 1h, obtain solid electrolyte.Adopt two panels carbon cloth/C@MnO
2electrode material (3cm × 2cm), on each plate electrode material, the PVA/LiCl solid electrolyte that uniform application configures, utilize ultra-thin filter membrane as barrier film, two panels electrode material is assembled, just obtains flexible solid-state supercapacitor, as shown in Figure 4.The chemical property of this device as shown in Figure 6 and Figure 7.
Embodiment 2:
C@MnO
2the preparation of electrode material:
(1) except the Ultrasonic Cleaning time is 1min, dry 2h at 105 DEG C, outside the ZnO film of sputtering sedimentation 55nm, other processes are identical with step (1) in embodiment 1.
(2) except add respectively by 30:5:5:2:1 volume ratio deionized water, the zinc nitrate solution of 0.3mol/L, the phenol solution of 0.05mol/L, the ethylenediamine tetrapropionic acid solution of 0.2mol/L and 70% ammoniacal liquor, outside 60 DEG C of washing 12h, other processes are identical with step (2) in embodiment 1.
(3) keep 4h except in sucrose solution carbon cloth being immersed 1.5mol/L, at the baking oven inner drying 4h of 85 DEG C, under the nitrogen protection of 55sccm, anneal outside 6h at 500 DEG C, other processes are identical with step (3) in embodiment 1.
(4) mixed solution divided by the manganese acetate of 0.03mol/L and the sodium acetate of 0.15mol/L is electrolyte, at 2mA/cm
2current density under carry out MnO
2electrochemical deposition, sedimentation time is 35min, and at 160 DEG C outside dry 5min, other processes are identical with step (4) in embodiment 1.
The preparation of all-solid-state flexible ultracapacitor: in the same manner as in Example 1.
Embodiment 3:
C@MnO
2the preparation of electrode material:
(1) except the Ultrasonic Cleaning time is 5min, dry 3h at 115 DEG C, outside the ZnO film of sputtering sedimentation 60nm, other processes are identical with step (1) in embodiment 1.
(2) except add respectively by 35:2:3:5:2 volume ratio deionized water, the liquor zinci chloridi of 0.7mol/L, the malonic acid dimethyl ester solution of 0.15mol/L, the triethylenetetramine solution of 0.3mol/L and 80% ammoniacal liquor, outside 70 DEG C of washing 8h, other processes are identical with step (2) in embodiment 1.
(3) keep 7h except in fructose soln carbon cloth being immersed 0.5mol/L, at the baking oven inner drying 6h of 75 DEG C, under the nitrogen protection of 45sccm, anneal outside 4h at 700 DEG C, other processes are identical with step (3) in embodiment 1.
(4) mixed solution divided by the manganese chloride of 0.01mol/L and the sodium chloride of 0.05mol/L is electrolyte, at 1mA/cm
2current density under carry out MnO
2electrochemical deposition, sedimentation time is 45min, and at 140 DEG C outside dry 15min, other processes are identical with step (4) in embodiment 1.
The preparation of all-solid-state flexible ultracapacitor: in the same manner as in Example 1.
The result of integrated embodiment 1-3 can find out that the present invention utilizes ZnO template, prepares a kind of novel three-dimensional C@MnO grown based on flexible carbon cloth
2composite nano tube array electrode material for super capacitor, the MnO that this material is by the material with carbon element of good conductivity and ratio capacitance is high, conductivity is poor
2combine, give full play to the advantage of the two, and utilize the H produced in electrodeposition process dexterously
+remove the ZnO template of capacity without contribution.
This electrode material lightweight, have higher area ratio electric capacity and power characteristic, cycle performance is superior, after being assembled into symmetric capacitor, adopt bipolar electrode to test the cycle performance of its constant current charge-discharge, after 5000 circulations, its capacity still can keep 82% of initial capacity.Utilize this electrode material to assemble the flexible solid-state supercapacitor obtained and there is good chemical property, as shown in Figure 6 and Figure 7.This electrode material cost is low simultaneously, makes simple, can be wearable electronic product and provide energy storage, and can meet the powerful electric discharge demand of electronic device.
Applicant states, the present invention illustrates method detailed of the present invention by above-described embodiment, but the present invention is not limited to above-mentioned method detailed, does not namely mean that the present invention must rely on above-mentioned method detailed and could implement.Person of ordinary skill in the field should understand, any improvement in the present invention, to equivalence replacement and the interpolation of auxiliary element, the concrete way choice etc. of each raw material of product of the present invention, all drops within protection scope of the present invention and open scope.
Claims (10)
1. a Vc MnO
2composite nano tube array electrode material for super capacitor, is characterized in that, described material internal is nanotube-shaped carbon-coating, and outside is MnO
2material.
2. a preparation method for super capacitance electrode material as claimed in claim 1, is characterized in that, said method comprising the steps of:
(1) preliminary treatment is carried out to flexible carbon fibre cloth, then magnetron sputtering deposition zinc-oxide film is carried out to pretreated carbon cloth;
(2) array growth of zinc oxide nano rod: the carbon cloth after process in step (1) is placed in container, add deionized water, the salting liquid of zinc, complexing agent one, complexing agent two and ammoniacal liquor respectively and stir sealing, then carrying out the carbon cloth that heating water bath obtains being distributed with nanometic zinc oxide rod array;
(3) rinse in rear immersion saccharide solution to the carbon cloth being distributed with nanometic zinc oxide rod array, drying is carried out again by after carbon cloth taking-up inert gas purge, then under the protection of inert gas, carry out annealing in process, obtain the nanometic zinc oxide rod array carbon cloth that Surface coating has thin layer carbon;
(4) carbon cloth obtained using step (3) obtains having C@MnO as the electrochemical deposition that work electrode adopts three electrode electro-deposition systems to carry out manganese dioxide
2the carbon cloth of nano tubular structure, then carry out rinsing, drying and obtain that there are three Vc MnO
2the super capacitance electrode material of nano-tube structure structure.
3. preparation method according to claim 2, is characterized in that, in step (1), preprocessing process carries out Ultrasonic Cleaning with acetone and alcohol to flexible carbon fibre cloth respectively, then dries;
Preferably, the time of described Ultrasonic Cleaning is 1 ~ 5min, preferred 2min;
Preferably, described bake out temperature is 105 ~ 115 DEG C, preferably 110 DEG C;
Preferably, described drying time is 1 ~ 3h, preferred 1h;
Preferably, the zinc-oxide film of magnetron sputtering deposition 50 ~ 60nm on carbon cloth after treatment in described step (1), preferred 50nm.
4. the preparation method according to Claims 2 or 3, is characterized in that, is placed in resealable container in described step (2) by the carbon cloth after process in step (1);
Preferably, the salting liquid of zinc is the combination of any one or at least two kinds in zinc nitrate, zinc sulfate, zinc chloride, zinc acetate, trbasic zinc phosphate in described step (2), preferred zinc nitrate;
Preferably, described step (2) complexing agent one is the combination of any one or at least two kinds in polyethylenimine solution, phenol solution, malonic acid dimethyl ester solution or cyclohexanoneimine solution, preferably polyethylene base imide liquor;
Preferably, described step (2) complexing agent two is the combination of any one or at least two kinds in hexamethylenetetramine solution, ethylenediamine tetrapropionic acid solution, triethylenetetramine solution or diethanolamine solution, preferred hexamethylenetetramine solution;
Preferably, the volume ratio of the salting liquid of deionized water, zinc, complexing agent one, complexing agent two and ammoniacal liquor is 30 ~ 35:2 ~ 5:3 ~ 5:2 ~ 5:1 ~ 2 in described step (2), preferred 32:2:4:2:1;
Preferably, in described step (2), the concentration of the salting liquid of zinc is 0.3 ~ 0.7mol/L, preferred 0.5mol/L;
Preferably, the concentration of described step (2) complexing agent one is 0.05 ~ 0.15mol/L, preferred 0.1mol/L;
Preferably, the concentration of described step (2) complexing agent two is 0.2 ~ 0.3mol/L, preferred 0.25mol/L;
Preferably, the concentration of ammoniacal liquor is 70 ~ 80% in described step (2), preferably 75%.
5. the preparation method according to any one of claim 2-4, is characterized in that, in described step (2), the temperature of heating water bath is 60 ~ 70 DEG C, preferably 65 DEG C;
Preferably, in described step (2), the time of heating water bath is 8 ~ 12h, preferred 10h.
6. the preparation method according to any one of claim 2-5, is characterized in that, uses absolute ethyl alcohol and deionized water rinsing successively in described step (3) to the carbon cloth being distributed with nanometic zinc oxide rod array;
Preferably, the saccharide solution in described step (3) is the combination of any one or at least two kinds in glucose solution, sucrose solution, maltose solution, fructose soln or lactose solution, preferred glucose solution;
Preferably, in described step (3), the concentration of saccharide solution is 0.5 ~ 1.5mol/L, preferred 1mol/L;
Preferably, in described step (3), carbon cloth soaks 4 ~ 7h, preferred 5h in saccharide solution.
7. the preparation method according to any one of claim 2-6, is characterized in that, inert gas is the combination of any one or at least two kinds in nitrogen, argon gas, helium or neon in described step (3);
Preferably, temperature dry after purging in described step (3) is 75 ~ 85 DEG C, preferably 80 DEG C;
Preferably, the time dry in described step (3) is 4 ~ 6h, preferred 5h;
Preferably, in described step (3), the flow of the inert gas of protective effect is 45 ~ 55sccm, preferred 50sccm;
Preferably, in described step (3), annealing in process is carried out in quartz tube furnace;
Preferably, in described step (3), the temperature of annealing in process is 500 ~ 700 DEG C, preferably 600 DEG C;
Preferably, in described step (3), the time of annealing in process is 4 ~ 6h, preferred 5h.
8. the preparation method according to any one of claim 2-7, is characterized in that, using saturated calomel electrode as reference electrode in described step (4) three electrode electro-deposition system, is to electrode with platinized platinum;
Preferably, in described step (4) three electrode electro-deposition system using the mixed solution of manganese salt and metal salt solution as electrolyte;
Preferably, in described step (4) three electrode electro-deposition system, manganese salt is the combination of any one or at least two kinds in manganese nitrate, manganese sulfate, manganese acetate, manganese phosphate or manganese chloride, preferred manganese nitrate;
Preferably, in described step (4) three electrode electro-deposition system, metal salt solution is the combination of any one or at least two kinds in sodium nitrate, sodium sulphate, sodium chloride, sodium acetate, nickel nitrate, nickel acetate, nickel chloride, potassium nitrate, potassium acetate, potassium chloride or potassium sulfate, preferred sodium nitrate;
Preferably, in described step (4) three electrode electro-deposition system, the concentration of manganese salt is 0.01 ~ 0.03mol/L, preferred 0.02mol/L;
Preferably, in described step (4) three electrode electro-deposition system, the concentration of metal salt solution is 0.05 ~ 0.15mol/L, preferred 0.1mol/L;
Preferably, the current density of described step (4) electrochemical deposition is 1 ~ 2mA/cm
2, preferred 1.5mA/cm
2;
Preferably, the time of described step (4) electrochemical deposition is 35 ~ 45min, preferred 40min.
9. the preparation method according to any one of claim 2-8, is characterized in that, in described step (4), electrochemical deposition obtains having C@MnO
2the carbon cloth deionized water of nano tubular structure rinses;
Preferably, in described step (4), baking temperature is 140 ~ 160 DEG C, preferably 150 DEG C;
Preferably, in described step (4), drying time is 5 ~ 15min, preferred 10min.
10. the three Vc MnO that method prepares as described in claim 2-9
2the purposes of composite nano tube array super capacitance electrode material, it is applied in wearable electronic product scope.
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