CN102354612B - Array carbon nano-tube/carbon fiber-based flexible composite electrode material and preparation method thereof - Google Patents

Array carbon nano-tube/carbon fiber-based flexible composite electrode material and preparation method thereof Download PDF

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CN102354612B
CN102354612B CN 201110261817 CN201110261817A CN102354612B CN 102354612 B CN102354612 B CN 102354612B CN 201110261817 CN201110261817 CN 201110261817 CN 201110261817 A CN201110261817 A CN 201110261817A CN 102354612 B CN102354612 B CN 102354612B
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封伟
张鹏
冯奕钰
吕鹏
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Tianjin University
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Abstract

The invention discloses an array carbon nano-tube/carbon fiber-based flexible composite electrode material and a preparation method thereof. The composite material takes a three-dimensional carbon fiber woven body as a substrate, a carbon nano-tube array is grown on the substrate, and nano-scale manganese dioxide particles are deposited on the surface. The preparation process comprises the following steps: performing high-temperature treatment on the three-dimensional carbon fiber woven body under the protection of inert gas; wrapping a layer of nano-scale silicon dioxide on the surface of the carbon fiber; using a chemical vapor deposition method to grow the carbon nano-tube array on the surface of the three-dimensional carbon fiber woven body; and utilizing a constant current electrochemical deposition method to uniformly deposit nano-scale manganese dioxide on an array carbon nano-tube/carbon fiber composite body. The process is simple, and the prepared flexible composite electrode has the advantages of developed conductive network, porous structure, large specific surface area, higher utilization rate of active substances, excellent mechanical strength and excellent chemical stability, thus the composite material provided by the invention is an ideal material for the high-performance large-capacity supercapacitor flexible electrode.

Description

Array carbon nano-tube/carbon fiber-based flexible composite electrode material and preparation method thereof
Technical field
The present invention relates to a kind of array carbon nano-tube/carbon fiber-based flexible composite electrode material and preparation method thereof, belong to the energy storage material technology.
Background technology
Along with the development of science and technology and society, many occasions such as electric automobile, instant power supply, mobile communication, defence and military etc. improve greatly to the requirement of power, head and shoulders above the ability to bear of battery.Although traditional capacitor can provide very large power, its energy density is extremely limited, can not satisfy actual needs.Ultracapacitor is as a kind of Novel energy storage apparatus between storage battery and traditional sucrose capacitor, the characteristics such as its charging interval weak point, long service life, good temp characteristic, energy savings and environmental protection, make its feature that has battery high-energy-density and traditional capacitor high-specific-power concurrently (Frackowiak E, Beguin F. Carbon materials for the electrochemical storage of energy in capacitors. Carbon. 2001; 39 (6): 937-50.).The specific capacity of ultracapacitor is 20-200 times of traditional capacitor, and specific power is far longer than secondary cell generally greater than 1000W/kg, cycle life (〉 10 5Inferior) also be better than battery, thereby its as a kind of novel energy-storing device obtained studying widely and used (Wu Feng, Xu Bin. the application study progress of carbon nano-tube in ultracapacitor. new carbon, 2006, the 21 volumes, the 2nd phase, 176.).Electrode material is as one of critical material of ultracapacitor, affects the discharging and recharging of device, energy density, power density, frequency response, cycle performance and high rate performance.Difference according to energy storage mechanism in the electrode material, ultracapacitor can be divided into electrochemical double layer capacitor (EDLC) and two kinds of (Futaba DN of redox pseudo-capacitance device (pseuocapacitor), Hata K, Yamada T, et al. Shape-engineerable and highly densely packed single-walled carbon nanotubes and their application as super-capacitor electrodes. Nat Mater. 2006; 5 (12): 987-94; Simon P, Gogotsi Y. Materials for electrochemical capacitors. Nat Mater. 2008; 7 (11): 845-54.).Wherein the energy storage of EDLC is based on the storage of electric charge on material with carbon element electrode/electrolyte interface and separates, during charging, electronics passes to negative pole by external power from positive pole, because the electrostatic interaction of electric field, negative ions in the electrolyte is respectively to negative electrode and positive electrode migration, thereby align the formation electric double layer thereon, store electric charge at electrode and electrolyte interface; Electronics migrates to positive pole by applied load from negative pole during discharge, negative ions then comes back to the electrolyte from electrode surface, return to original disordered state (Elzbieta Frackowiak. Carbon materials for supercapacitor application. Phys. Chem. Chem. Phys., 2007,9,1774 – 1785; Inagaki M, Konno H, Tanaike O. Carbon materials for electrochemical capacitors. J Power Sources. 2010; 195 (24): 7880-903.).This shows that the course of work of EDLC is a simple electrostatic process, do not have electrochemical reaction to participate in, thereby can carry out the fast charging and discharging of large electric current moment have excellent power characteristic, and its cycle charge-discharge number of times does not have theoretic restriction yet.
The common electrode that is used for EDLC of at present industrialization mainly is absorbent charcoal material, and activated carbon electrodes has a large amount of microcellular structures and large specific area, and can be mass-produced, thereby is widely used in the preparation of ultracapacitor.But this activated carbon electrodes is applied to ultracapacitor and is difficult to break away from some inherent shortcomings: because active carbon electrode is a kind of poromerics, its aperture is less than 2 nm(Huang CW, Chuang CM, Ting JM, et al. Significantly enhanced charge conduction in electric double layer capacitors using carbon nanotube-grafted activated carbon electrodes. J Power Sources. 2008; 183 (1): 406-10.), this narrow and small space can produce larger obstruction when the electrolyte particle embeds and deviates from electrode, the transmission resistance that particularly discharges and recharges this electrode under high current density increases, thereby affected the high rate performance of ultracapacitor, and its power characteristic and frequency response characteristic are not good enough; On the other hand, active carbon material itself is a kind of material of non-graphite-structure, and conductance is lower, and the active material that is applied as electrode of super capacitor has larger internal resistance, has reduced the performance of capacitor.
Carbon nano-tube (CNTs) is as quasi-one-dimensional nano material, owing to its unique hollow structure, excellent electric conductivity, huge specific area, be fit to hole (〉 2 nm of electrolyte ion migration) and nanoscale on efficient electric transmission network, be considered to the especially ideal electrode material of high-capacity super capacitor (Zhang LL, Zhao XS. Carbon-based materials as supercapacitor electrodes. Chem Soc Rev. 2009 of ultracapacitor; 38 (9): 2520-31; Pan H, Li JY, Feng YP. Carbon Nanotubes for Supercapacitor. Nanoscale Res Lett. 2010; 5 (3): 654-68.).Therefore, occurred very early utilizing the carbon nano-tube with excellent electrochemical performance to improve Patents and bibliographical information (the Niu CM of electrode performance, Sichel EK, Hoch R, et al. High power electrochemical capacitors based on carbon nanotube electrodes. Appl Phys Lett 1997; 70 (11): 1480-2.).Carbon nano-tube is introduced in Chinese patent (application number is 00136008.6) " carbon-doped nanometer tube capacity with very high capacitance " such as: Fu Xutao etc. in the combination electrode of ultracapacitor and improved electrode conductivity; Liang Kui etc. disclose in Chinese patent (ZL02133455.2) " superhigh-capacitance capacitor with composite carbon nanotube and preparation method thereof " and have utilized the carbon nano-tube of introducing to improve capacitor performance.But above-mentioned electrode is in preparation process, usually need and conductive agent, be coated on the collector after adhesive etc. are compound, because the existence of conductive agent and adhesive causes larger contact resistance, the physical bond of active material and collector neither be very desirable simultaneously, these have all reduced the conduction efficiency of electric charge, thereby further have influence on performance (the Zhang H of ultracapacitor, Cao GP, Yang YS. Carbon nanotube arrays and their composites for electrochemical capacitors and lithium-ion batteries. Energ Environ Sci. 2009; 2 (9): 932-43.).On the other hand, carbon nano-tube is in unordered accumulation or the state of arranging, there is not directionality, form hole in irregular shape between the carbon nano-tube of this mixed and disorderly accumulation, can cause the electrolyte particle in embedding and deviate from steric hindrance increase in the process, reduce high rate performance and the frequency response performance of capacitor, limited raising (the Zhang H of the specific power performance of capacitor, Cao GP, Yang YS, Gu ZN. Comparison between electrochemical properties of aligned carbon nanotube array and entangled carbon nanotube electrodes. J Electrochem Soc. 2008; 155 (2): K19-K22.).
Therefore, solution be directly with the carbon nano pipe array growth in situ on the conducting base that can serve as collector, the carbon nano pipe array that obtains does not so need just can directly use as electrode with the compound of conductive electrode and adhesive, greatly reduced the contact resistance between carbon nano-tube and collector, and greatly simplified preparation section (the Talapatra S of electrode, Kar S, Pal SK, et al. Direct growth of aligned carbon nanotubes on bulk metals. Nat Nanotechnol. 2006; 1 (2): 112-6.).Zhang Hao etc. utilize directly on metallic substrates the carbon nano pipe array of growth in situ as the electrode material of EDLC in Chinese patent (200820136763.9) " a kind of array electrode ", only there is a small amount of contact point in kind electrode between array and metallic matrix, inner bindless greatly reduces contact resistance.But the general density of metal as collector in this electrode is larger, and easily oxidized in water electrolyte, has limited its large-scale practical application, especially requires harsh field in Aero-Space and national defense and military etc.In recent years, people increase day by day for lightweight, conduction, demand efficient, cheap, pliable and tough collapsible collector.And carbon fiber is as the material with carbon element of a kind of electric conductivity excellence, steady chemical structure, corrosion-resistant, lightweight flexible, become choosing (the Hsieh CT of the ideal of collector, Chen WY, Lin JH. Synthesis of carbon nanotubes on carbon fabric for use as electrochemical capacitor. Micropor Mesopor Mat. 2009; 122 (1-3): 155-9.).At present, there has been bibliographical information to go out the array of carbon nano-tube in the superficial growth of three-dimensional carbon fiber-based material, and with the electrode material of gained array carbon nano-tube/carbon fiber complex for ultracapacitor, has very excellent chemical property (Qu LT, Zhao Y, Dai LM. Carbon microfibers sheathed with aligned carbon nanotubes:Towards multidimensional, multicomponent, and multifunctional nanomaterials. Small. 2006; 2 (8-9): 1052-9; Kim HS, Kim B, Lee B, et al. Synthesis of Aligned Few-Walled Carbon Nanotubes on Conductive Substrates. J Phys Chem C. 2009; 113 (42): 17983-8; Kim B, Chung H, Kim W. Supergrowth of Aligned Carbon Nanotubes Directly on Carbon Papers and Their Properties as Supercapacitors. J Phys Chem C. 2010; 114 (35): 15223-7.).
On the other hand, because the maximum power density of ultracapacitor depends critically upon the size than electric capacity, and material with carbon element is extremely limited by the ratio capacitance size that electric double layer produces.By contrast, react the fake capacitance of generation based on transition metal oxide or quick, the reversible faraday in conducting polymer surface and realize that the redox pseudo-capacitance device of energy storage has attracted numerous scientific research personnel's sight (Zhang WD, Xu B, Jiang LC. Functional hybrid materials based on carbon nanotubes and metal oxides. J. Mater. Chem., 2010,20,6383 – 6391; Wei WF, Cui XW, Chen WX, et al. Manganese oxide-based materials as electrochemical supercapacitor electrodes. Chem. Soc. Rev., 2011, 40, 1697 – 1721).Under identical electrode area, the ratio electric capacity of pseudo-capacitance device is very large, can reach generally speaking tens times of EDLC.For example the theory of manganese dioxide up to 1370F/g, is the choosing of the ideal of capacitor than electric capacity.But not as good as EDLC, specific area is less to cause the utilization of active material incomplete to the power characteristic that its instantaneous large-current discharges and recharges far away.And because mouldability and the conductivity of transition metal oxide are all relatively poor, in the cycle charge discharge electric process, can cause active material volume contraction or quality to reduce, this can further limit its cyclical stability.Therefore, if array carbon nano-tube/carbon fiber complex and the transition metal oxide of growth in situ can be combined, utilize the cooperative effect between this bi-material, have complementary advantages, be expected to realize the fabulous new electrode materials of capacitive property (Zhang H, Cao GP, Wang ZY, et al. Growth of manganese oxide nanoflowers on vertically-aligned carbon nanotube arrays for high-rate electrochemical capacitive energy storage. Nano Lett. 2008; 8 (9): 2664-8.).Zhang Hao etc. are in Chinese patent (200820136765.8) " a kind of array-based combined electrode ", metal oxide is attached to growth in situ on the carbon nano-tube on the metallic matrix, utilize the conductive network of this electrode prosperity, it is little to have obtained contact resistance, the electrode good rate capability, the electrode material that specific power is high.But have not yet to see the preparation that relates to array carbon nano-tube/carbon fiber-based flexible composite electrode material and report and the patent of capacitive property aspect thereof.
Summary of the invention
The object of the present invention is to provide a kind of array carbon nano-tube/carbon fiber-based flexible composite electrode material and preparation method thereof, the method process is simple, prepared combination electrode material has large aperture, high-specific surface area, low internal resistance, the characteristics of lightweight flexible, and its chemical property is good.
The present invention is realized by following technical solution: a kind of array carbon nano-tube/carbon fiber-based flexible composite electrode material, it is characterized in that, this composite material is take the three-dimensional carbon fibrage body as matrix, diameter is arranged is 20-50nm to the original position controllable growth on matrix, length is the carbon nano pipe array of 10-60 μ m, and at the carbon nano pipe array surface deposition diameter range being arranged is the nanoscale manganese oxide particle of 0.1-1 μ m.
The preparation method of above-mentioned array carbon nano-tube/carbon fiber-based flexible composite electrode material is characterized in that comprising following process:
(1) preliminary treatment of three-dimensional carbon fibrage body
At first the three-dimensional carbon fibrage body with 2cm * 2cm places the tubular type high temperature reaction stove, is warming up to 700-900 ℃ under argon shield, heats and carries out surface treatment in 1-3 hour.Be immersed in afterwards in the xylene solution of silester that mass concentration is 1-3% or silicon tetrachloride 5-10 minute, then be positioned over and be hydrolyzed 5-10 minute in the water vapour, as in the high temperature process furnances, is warming up to 1000-1200 ℃ under the argon shield after taking out, it is for subsequent use be incubated after 10-30 minute taking-up;
(2) preparation carbon source and catalyst mix solution
With ethanol, dimethylbenzene and ethylenediamine are that the mixed liquor of 1:1:0.1 ~ 0.5 is carbon source by its volume ratio, to contain Co 3+, Ni 2+, Fe 3+A kind of in the dis-cyclopentadiene compounds or their mixture are catalyst, are that the proportioning of 100:1 ~ 5 is dissolved in ethanol or the dimethylbenzene according to the mass ratio of carbon source and catalyst, and ultrasonic dispersion 10-60 min makes the mixed solution of carbon source and catalyst;
(3) with chemical vapour deposition (CVD) at three-dimensional carbon fibrage body superficial growth carbon nano pipe array
The three-dimensional carbon fibrage body that step (1) is processed places high temperature process furnances, heating rate with 5-20 ℃/min is warming up to 700 ~ 900 ℃, with 10-25 mL/h the mixed solution that step (2) makes is expelled in the tube furnace, growth 30-120 min, after the protection of argon gas drops to room temperature, obtain the array carbon nano-tube/carbon fiber complex;
(4) preparation of array carbon nano-tube/carbon fiber-based flexible composite electrode material
The array carbon nano-tube/carbon fiber complex that step (3) is prepared was placed in the Muffle furnace, at temperature 100-300 ℃ of lower heat treatment 1-4 hour.Take manganese acetate in mixed solution concentration as 0.01-0.5M and sodium sulphate in mixed solution concentration as the mixed solution of 0.01-0.5M as electrolyte, take array carbon nano-tube/carbon fiber as work electrode, take calomel electrode as to electrode, take platinized platinum as reference electrode, be 0.1-5mA/cm in current density 2Under carry out electrochemical deposition, sedimentation time is set as 1-30 min, obtains array carbon nano-tube/carbon fiber-based flexible composite electrode material.
Preparation method of the present invention is simple, and technical maturity is controlled, and in the array carbon nano-tube/carbon fiber-based flexible composite electrode material of gained, nano level manganese dioxide uniform particles deposition is attached on the tube wall of carbon nano pipe array, and physical contact is good.The electro-chemical test that carries out in the sodium sulphate electrolyte of 0.5M shows, this flexible composite electrode material has very excellent chemical property, comprise that higher ratio electric capacity, frequency response are fast, high rate performance, preferably cyclical stability and the mechanical performance etc. of excellence during high current charge-discharge, be the ideal electrode material of the large capacity lightweight flexible of preparation high-performance ultracapacitor.
Description of drawings
Fig. 1 is the SEM photo that adopts the array carbon nano-tube/carbon fiber complex of chemical vapour deposition technique preparation among the embodiment 1.
Fig. 2 is the SEM photo of the array carbon nano-tube/carbon fiber-based flexible composite electrode material behind the constant current electrochemical deposition manganese dioxide among the embodiment 2.
Fig. 3 is the I-V response curve that array carbon nano-tube/carbon fiber-based flexible composite electrode material that embodiment 2 makes obtains under the sweep speed of 50 mV/s.
Fig. 4 is the array carbon nano-tube/carbon fiber-based flexible composite electrode material that makes of embodiment 2 in current density is constant current charge-discharge curve under the 5A/g.
Embodiment
The below provides 4 embodiment of the present invention, is to further specify of the present invention, rather than limits the scope of the invention.
Embodiment 1:
Be 2cm * 2cm with the plane, thickness is that the three-dimensional carbon fibrage body of 0.2cm is put in the tube type high-temperature furnace, with 300 cm 3Behind the air in the argon gas drain of/min flow, the temperature of boiler tube rises to 800 ℃, is incubated 1 hour and takes out after the protection of argon gas drops to room temperature afterwards.Three-dimensional carbon fibrage body after processing is put in the mixed solution of 0.46g tetraethoxysilane, 0.74g silicon tetrachloride and 16.34g dimethylbenzene and soaked 10 minutes.Then in steam, expose 10 minutes, dry in temperature 60 C under vacuum afterwards.Again the three-dimensional carbon fibrage body being put into high temperature process furnances after the drying, is 300 cm at gas flow 3Be warming up to 1000 ℃ under the argon shield of/min, be incubated 10 minutes, the afterwards protection at argon gas drops to room temperature.Preparation 17.2g dimethylbenzene, 15.8g ethanol, 7.2g ethylenediamine and 1.2g ferrocene homogeneous mixture solotion, under argon shield, be warming up to 850 ℃ after, beginning is with the solution of 10 mL/h injection carbon source and catalyst.Grow after 1 hour, be down to room temperature and can make the array carbon nano-tube/carbon fiber complex.The complex of preparation is placed in the Muffle furnace in 300 ℃ of heat treatments of temperature 3 hours.
0.98g manganese acetate and 0.568g sodium sulphate are dissolved in the 40 mL deionized waters, and ultrasonic 10 min mix it, are mixed with the mixed solution of the sodium sulphate of the manganese acetate of 0.1M and 0.1M, as the electrolyte of electrochemical deposition manganese dioxide.In three-electrode system, the array carbon nano-tube/carbon fiber complex after the heat treatment is as work electrode, and the platinized platinum of 2cm * 4cm is auxiliary electrode, take calomel electrode as reference electrode, applies the constant current of 1mA.After depositing 5 minutes, take out with deionized water rinsing 5 times, put into 80 ℃ vacuum drying chamber vacuumize 48 hours, namely get at last the array carbon nano-tube/carbon fiber-based flexible composite electrode material that deposits manganese dioxide.
The array carbon nano-tube/carbon fiber-based flexible composite electrode material that makes take said process is as work electrode, and take 2cm * 4cm platinized platinum as to electrode, calomel electrode is that reference electrode is constructed three-electrode system, at the Na of 0.5M 2SO 4Carrying out electro-chemical test in the aqueous solution, when sweep speed is 50mV/s, is 320.6F/g than electric capacity; When sweep speed is 200mV/s, be 203.8F/g than electric capacity, be 63.6% than electric capacity conservation rate; When the current density that discharges and recharges was 5A/g, it was 437.2 F/g than electric capacity; When current density was 20A/g, it was 260F/g than electric capacity, and the electric capacity conservation rate is 59.5%; Behind the cycle charge-discharge 1000 times, still can remain on 98% than electric capacity.
Embodiment 2:
Be 2cm * 2cm with the plane, thickness is that the three-dimensional carbon fibrage body of 0.2cm is put in the tube type high-temperature furnace, with 300 cm 3Behind the air in the argon gas drain of/min flow, the temperature of boiler tube rises to 850 ℃, is incubated 2 hours and takes out after the protection of argon gas drops to room temperature afterwards.Three-dimensional carbon fibrage body after processing is put in the mixed solution of 0.46g tetraethoxysilane, 0.74g silicon tetrachloride and 16.34g dimethylbenzene and soaked 10 minutes.Then in steam, expose 10 minutes, dry in temperature 60 C under vacuum afterwards.Again the three-dimensional carbon fibrage body being put into high temperature process furnances after the drying, is 300 cm at gas flow 3Be warming up to 1000 ℃ under the argon shield of/min, be incubated 10 minutes, the afterwards protection at argon gas drops to room temperature.Preparation 17.2g dimethylbenzene, 15.8g ethanol, 7.2g ethylenediamine and 1.2g ferrocene homogeneous mixture solotion, under argon shield, be warming up to 850 ℃ after, beginning is with the solution of 15 mL/h injection carbon source and catalyst.Grow after 1 hour, be down to room temperature and can make the array carbon nano-tube/carbon fiber complex.The complex of preparation is placed in the Muffle furnace in 300 ℃ of heat treatments of temperature 3 hours.
0.98g manganese acetate and 0.568g sodium sulphate are dissolved in the 40 mL deionized waters, and ultrasonic 10 min mix it, are mixed with the mixed solution of the sodium sulphate of the manganese acetate of 0.1M and 0.1M, as the electrolyte of electrochemical deposition manganese dioxide.In three-electrode system, the array carbon nano-tube/carbon fiber complex after the heat treatment is as work electrode, and the platinized platinum of 2cm * 4cm is auxiliary electrode, take calomel electrode as reference electrode, applies the constant current of 1mA.After depositing 10 minutes, take out with deionized water rinsing 5 times, put into 80 ℃ vacuum drying chamber vacuumize 48 hours, namely get at last the array carbon nano-tube/carbon fiber-based flexible composite electrode material that deposits manganese dioxide.
Take array carbon nano-tube/carbon fiber-based flexible composite electrode material as work electrode, take platinized platinum as to electrode, calomel electrode is that reference electrode is constructed three-electrode system, at the Na of 0.5M 2SO 4Carrying out electro-chemical test in the aqueous solution, when sweep speed is 50mV/s, is 549F/g than electric capacity; When sweep speed is 200mV/s, be 448.6F/g than electric capacity, be 81.7% than electric capacity conservation rate; When the current density that discharges and recharges was 5A/g, it was 486 F/g than electric capacity; When current density was 20A/g, it was 416F/g than electric capacity, and the electric capacity conservation rate is 85.6%; Behind the cycle charge-discharge 1000 times, still can remain on 83.5% than electric capacity.
Embodiment 3:
Be 2cm * 2cm with the plane, thickness is that the three-dimensional carbon fibrage body of 0.2cm is put in the tube type high-temperature furnace, with 300 cm 3Behind the air in the argon gas drain of/min flow, the temperature of boiler tube rises to 900 ℃, is incubated 1 hour and takes out after the protection of argon gas drops to room temperature afterwards.Three-dimensional carbon fibrage body after processing is put in the mixed solution of 0.46g tetraethoxysilane, 0.74g silicon tetrachloride and 16.34g dimethylbenzene and soaked 10 minutes.Then in steam, expose 10 minutes, dry in temperature 60 C under vacuum afterwards.Again the three-dimensional carbon fibrage body being put into high temperature process furnances after the drying, is 300 cm at gas flow 3Be warming up to 1000 ℃ under the argon shield of/min, be incubated 10 minutes, the afterwards protection at argon gas drops to room temperature.Preparation 17.2g dimethylbenzene, 15.8g ethanol, 7.2g ethylenediamine and 1.2g ferrocene homogeneous mixture solotion, under argon shield, be warming up to 850 ℃ after, beginning is with the solution of 20 mL/h injection carbon source and catalyst.Grow after 1 hour, be down to room temperature and can make the array carbon nano-tube/carbon fiber complex.The complex of preparation is placed in the Muffle furnace in 300 ℃ of heat treatments of temperature 2 hours.
0.98g manganese acetate and 0.568g sodium sulphate are dissolved in the 40 mL deionized waters, and ultrasonic 10 min mix it, are mixed with the mixed solution of the sodium sulphate of the manganese acetate of 0.1M and 0.1M, as the electrolyte of electrochemical deposition manganese dioxide.In three-electrode system, the array carbon nano-tube/carbon fiber complex after the heat treatment is as work electrode, and the platinized platinum of 2cm * 4cm is auxiliary electrode, take calomel electrode as reference electrode, applies the constant current of 1mA.After depositing 20 minutes, take out with deionized water rinsing 5 times, put into 80 ℃ vacuum drying chamber vacuumize 48 hours, namely get at last the array carbon nano-tube/carbon fiber-based flexible composite electrode material that deposits manganese dioxide.
Take array carbon nano-tube/carbon fiber-based flexible composite electrode material as work electrode, simultaneously take platinized platinum as to electrode, calomel electrode is that reference electrode is constructed three-electrode system, at the Na of 0.5M 2SO 4Carrying out electro-chemical test in the aqueous solution, when sweep speed is 50mV/s, is 572.1F/g than electric capacity; When sweep speed is 200mV/s, be 314.3F/g than electric capacity, be 54.9% than electric capacity conservation rate; When the current density that discharges and recharges was 5A/g, it was 667.1F/g than electric capacity; When current density was 20A/g, it was 430.5F/g than electric capacity, and the electric capacity conservation rate is 64.5%; Behind the cycle charge-discharge 1000 times, still can remain on 90.5% than electric capacity.
Embodiment 4:
Be 2cm * 2cm with the plane, thickness is that the three-dimensional carbon fibrage body of 0.2cm is put in the tube type high-temperature furnace, with 300 cm 3Behind the air in the argon gas drain of/min flow, the temperature of boiler tube rises to 800 ℃, is incubated 1 hour and takes out after the protection of argon gas drops to room temperature afterwards.Three-dimensional carbon fibrage body after processing is put in the mixed solution of 0.46g tetraethoxysilane, 0.74g silicon tetrachloride and 16.34g dimethylbenzene and soaked 10 minutes.Then in steam, expose 10 minutes, dry in temperature 60 C under vacuum afterwards.Again the three-dimensional carbon fibrage body being put into high temperature process furnances after the drying, is 300 cm at gas flow 3Be warming up to 1000 ℃ under the argon shield of/min, be incubated 10 minutes, the afterwards protection at argon gas drops to room temperature.Preparation 17.2g dimethylbenzene, 15.8g ethanol, 7.2g ethylenediamine and 1.2g ferrocene homogeneous mixture solotion, under argon shield, be warming up to 850 ℃ after, beginning is with the solution of 10 mL/h injection carbon source and catalyst.Grow after 1 hour, be down to room temperature and can make the array carbon nano-tube/carbon fiber complex.The complex of preparation is placed in the Muffle furnace in 300 ℃ of heat treatments of temperature 3 hours.
0.98g manganese acetate and 0.568g sodium sulphate are dissolved in the 40 mL deionized waters, and ultrasonic 10 min mix it, are mixed with the mixed solution of the sodium sulphate of the manganese acetate of 0.1M and 0.1M, as the electrolyte of electrochemical deposition manganese dioxide.In three-electrode system, the array carbon nano-tube/carbon fiber complex after the heat treatment is as work electrode, and the platinized platinum of 2cm * 4cm is auxiliary electrode, take calomel electrode as reference electrode, applies the constant current of 1mA.After depositing 30 minutes, take out with deionized water rinsing 5 times, put into 80 ℃ vacuum drying chamber vacuumize 48 hours, namely get at last the array carbon nano-tube/carbon fiber-based flexible composite electrode material that deposits manganese dioxide.
Take array carbon nano-tube/carbon fiber-based flexible composite electrode material as work electrode, simultaneously take platinized platinum as to electrode, calomel electrode is that reference electrode is constructed three-electrode system, at the Na of 0.5M 2SO 4Carrying out electro-chemical test in the aqueous solution, when sweep speed is 50mV/s, is 677F/g than electric capacity; When sweep speed is 200mV/s, be 368.4F/g than electric capacity, be 54.4% than electric capacity conservation rate; When the current density that discharges and recharges was 5A/g, it was 705F/g than electric capacity; When current density was 20A/g, it was 540F/g than electric capacity, and the electric capacity conservation rate is 76.6%; Behind the cycle charge-discharge 1000 times, still can remain on 80.1% than electric capacity.

Claims (1)

1. the preparation method of an array carbon nano-tube/carbon fiber-based flexible composite electrode material, this combination electrode material is take the three-dimensional carbon fibrage body as matrix, diameter is arranged is 20-50nm to the original position controllable growth on matrix, length is the carbon nano pipe array of 10-60 μ m, at the carbon nano pipe array surface deposition diameter range being arranged is the nanoscale manganese dioxide particle of 0.1-1 μ m, it is characterized in that comprising following process:
(1) preliminary treatment of three-dimensional carbon fibrage body
At first the three-dimensional carbon fibrage body with 2cm * 2cm places the tubular type high temperature reaction stove; under argon shield, be warming up to 700-900 ℃; heat and carried out surface treatment in 1-3 hour; be immersed in afterwards in the xylene solution of silester that mass concentration is 1-3% or silicon tetrachloride 5-10 minute; then be positioned over and be hydrolyzed 5-10 minute in the water vapour, after the taking-up PutIn high temperature process furnances, be warming up to 1000-1200 ℃ under the argon shield, be incubated after 10-30 minute take out for subsequent use;
(2) preparation carbon source and catalyst mix solution
With ethanol, dimethylbenzene and ethylenediamine are that the mixed liquor of 1:1:0.1 ~ 0.5 is carbon source by its volume ratio, to contain Fe 3+Dis-cyclopentadiene compounds be catalyst, be that the proportioning of 100:1 ~ 5 is dissolved in ethanol or the dimethylbenzene according to the mass ratio of carbon source and catalyst, ultrasonic dispersion 10-60 min makes the mixed solution of carbon source and catalyst;
(3) with chemical vapour deposition (CVD) at three-dimensional carbon fibrage body superficial growth carbon nano pipe array
The three-dimensional carbon fibrage body that step (1) is processed places high temperature process furnances, heating rate with 5-20 ℃/min is warming up to 700 ~ 900 ℃, with 10-25 mL/h the mixed solution that step (2) makes is expelled in the tube furnace, growth 30-120 min, after the protection of argon gas drops to room temperature, obtain the array carbon nano-tube/carbon fiber complex;
(4) preparation of array carbon nano-tube/carbon fiber-based flexible composite electrode material
The array carbon nano-tube/carbon fiber complex that step (3) is prepared is placed in the Muffle furnace, at temperature 100-300 ℃ of lower heat treatment 1-4 hour, take manganese acetate in mixed solution concentration as 0.01-0.5M and sodium sulphate in mixed solution concentration as the mixed solution of 0.01-0.5M as electrolyte, take array carbon nano-tube/carbon fiber as work electrode, take calomel electrode as to electrode, take platinized platinum as reference electrode, be 0.1-5mA/cm in current density 2Under carry out electrochemical deposition, sedimentation time is set as 1-30 min, obtains array carbon nano-tube/carbon fiber-based flexible composite electrode material.
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