CN102354612A - 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 PDFInfo
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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 oxide 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
Technical field
The present invention relates to a kind of array carbon nano tube/carbon fiber base flexible compound electrode material and preparation method thereof, belong to the energy storage material technology.
Background technology
Along with the development of science and technology with society, many occasions such as electric automobile, instant power supply, mobile communication, defence and military etc. improve the requirement of power greatly, head and shoulders above the ability to bear of battery.Though 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-storing device between storage battery and traditional sucrose capacitor; Characteristics such as its charging interval weak point, long service life, good temp characteristic, energy savings and environmental protection; Make its characteristic 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 a 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 extensive studies and application (Wu Feng, Xu Bin. the Research development 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 through 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, at electrode and electrolyte interface store charge; Electronics migrates to positive pole through 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 big 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 industrialization at present mainly is an absorbent charcoal material, and activated carbon electrodes has a large amount of microcellular structures and big 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 bigger obstruction when the electrolyte particle embeds and deviates from electrode; The transmission resistance that particularly under high current density, discharges and recharges this electrode increases; Thereby influenced 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 bigger 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 electric transmission network efficiently; 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 carbon nano-tube to improve the related patent U.S. Patent No. and bibliographical information (the Niu CM of electrode performance with excellent electrochemical 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 introduced in Chinese patent (application number is 00136008.6) " carbon-doped nanometer tube capacity with very high capacitance " like: Fu Xutao etc. in the combination electrode of ultracapacitor and improve the electrode electricity conductance; 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.However, during the preparation of the electrodes is often necessary, the conductive agent, bonding agent is coated on the composite of the collector, since the conductive agent and a binder agent is present results in a larger contact resistance, while the active material and the collector of the physical binding is not very satisfactory, they have reduced the charge transfer efficiency, thus further affecting the performance of supercapacitors (Zhang? H,? 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, the carbon nanotubes arranged in a disordered heap or state with no directivity, which is formed between the carbon nanotube clutter stacked irregularly shaped pores, can lead to electrolyte particles during embedding and extraction increased steric large, reducing the magnification of the capacitor performance and frequency response performance, limiting the specific power of the capacitor to improve the performance (Zhang? H,? 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 so need just can directly not use as electrode with the compound of conductive electrode and adhesive; Greatly reduced the contact resistance between carbon nano-tube and collector; And simplified preparation section (the Talapatra S of electrode greatly; 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 no adhesive greatly reduces contact resistance.But the general density of metal as collector in this electrode is bigger, and easy 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 for lightweight, conduction, increasing 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 base material material; And gained array carbon nano tube/carbon fiber complex is used for the electrode material of 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 store energy 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 big, can reach tens times of EDLC generally speaking.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, in the cycle charge discharge electric process, can cause active material volume contraction or quality to reduce because the mouldability and the conductivity of transition metal oxide are all relatively poor, this can further limit its cyclical stability.Therefore; If the array carbon nano tube/carbon fiber complex and the transition metal oxide of growth in situ can be combined; Utilize the cooperative effect between these two kinds of materials; Have complementary advantages; Be expected to novel electrode material (the Zhang H that realizes that capacitive property is fabulous; 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 combination electrode "; With metal oxide attached to growth in situ on the carbon nano-tube on the metallic matrix; Utilize the flourishing conductive network of this electrode; It is little to have obtained contact resistance; The electrode good rate capability, the electrode material that specific power is high.But do not see as yet at present and relate to the array carbon nano tube/preparation of carbon fiber base flexible compound electrode material and the 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 base flexible compound electrode material and preparation method thereof; This procedure 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 realizes through following technical scheme: a kind of array carbon nano tube/carbon fiber base flexible compound electrode material; It is characterized in that; This composite material is a matrix with three-dimensional carbon fiber knit body; 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 base flexible compound electrode material is characterized in that comprising following process:
(1) preliminary treatment of three-dimensional carbon fiber knit body
At first the three-dimensional carbon fiber knit body with 2cm * 2cm places the tubular type high temperature reaction stove, under argon shield, is warming up to 700-900 ℃, 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; Be positioned over then and be hydrolyzed 5-10 minute in the water vapour; Take out the back as in the high temperature process furnances, is warming up to 1000-1200 ℃ under the argon shield, it is subsequent use be incubated after 10-30 minute taking-up;
(2) preparation carbon source and catalyst mix solution
With ethanol, xylenes and ethylenediamine are that the mixed liquor of 1:1:0.1 ~ 0.5 is a 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 xylenes 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) in three-dimensional carbon fiber knit surface carbon nano tube array grows
The three-dimensional carbon fiber knit body that step (1) is handled 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 array carbon nano tube/carbon fiber complex;
(4) preparation of array carbon nano tube/carbon fiber base flexible compound electrode material
Prepared array carbon nano tube/the carbon fiber complex of step (3) is placed in the Muffle furnace, at temperature 100-300 ℃ of following heat treatment 1-4 hour.Mixed solution with the sodium sulphate of manganese acetate, manganese sulfate or the manganese nitrate of concentration 0.01-0.5M and concentration 0.01-0.5M is an electrolyte; With array carbon nano tube/carbon fiber is work electrode; With calomel electrode is to electrode, is reference electrode with the platinized platinum, is 0.1-5mA/cm in current density
2Under carry out electrochemical deposition, sedimentation time is set at 1-30 min, obtains array carbon nano tube/carbon fiber base flexible compound electrode material.
Preparation method of the present invention is simple, and technical maturity is controlled, and in the array carbon nano tube of gained/carbon fiber base flexible compound electrode material, on the tube wall of nano level manganese dioxide uniform particles deposition attached to carbon nano pipe array, the physics contact is good.The electro-chemical test that in the sodium sulphate electrolyte of 0.5M, carries out shows; This flexible compound electrode material has very excellent chemical property; Comprise that higher ratio electric capacity, frequency response are fast, excellent high rate performance during high current charge-discharge, cyclical stability and mechanical performance etc. preferably, be the ideal electrode material of the big 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 behind the constant current electrochemical deposition manganese dioxide among the embodiment 2/carbon fiber base flexible compound electrode material.
The I-V response curve that the array carbon nano tube that Fig. 3 makes for embodiment 2/carbon fiber base flexible compound electrode material obtains under the sweep speed of 50 mV/s.
The array carbon nano tube that Fig. 4 makes for embodiment 2/carbon fiber base flexible compound electrode material is the constant current charge-discharge curve under the 5A/g in current density.
Embodiment
Providing 4 embodiment of the present invention below, is to further specify of the present invention, rather than limits scope of the present invention.
Embodiment 1:
With the plane is 2cm * 2cm, and thickness is that the three-dimensional carbon fiber knit 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 after the protection of argon gas drops to room temperature, takes out afterwards.Three-dimensional carbon fiber knit body after handling is put in the mixed solution of 0.46g tetraethoxysilane, 0.74g silicon tetrachloride and 16.34g xylenes and soaked 10 minutes.In steam, expose 10 minutes then, afterwards under vacuum in 60 ℃ of dryings of temperature.Again three-dimensional carbon fiber knit 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 protection at argon gas afterwards drops to room temperature.Preparation 17.2g xylenes, 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, reduce to room temperature and can make 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 sodium sulphate of manganese acetate and the 0.1M of 0.1M, as the electrolyte of electrochemical deposition manganese dioxide.In three-electrode system, be work electrode with the array carbon nano tube/carbon fiber complex after the heat treatment, the platinized platinum of 2cm * 4cm is an auxiliary electrode, is reference electrode with the calomel electrode, applies the constant current of 1mA.After waiting to deposit 5 minutes, take out, put into 80 ℃ vacuum drying chamber vacuumize 48 hours, promptly get the array carbon nano tube/carbon fiber base flexible compound electrode material that deposits manganese dioxide at last with deionized water rinsing 5 times.
Array carbon nano tube/carbon fiber base flexible compound the electrode material that makes with said process is a work electrode, is to electrode with 2cm * 4cm platinized platinum, and 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:
With the plane is 2cm * 2cm, and thickness is that the three-dimensional carbon fiber knit 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 after the protection of argon gas drops to room temperature, takes out afterwards.Three-dimensional carbon fiber knit body after handling is put in the mixed solution of 0.46g tetraethoxysilane, 0.74g silicon tetrachloride and 16.34g xylenes and soaked 10 minutes.In steam, expose 10 minutes then, afterwards under vacuum in 60 ℃ of dryings of temperature.Again three-dimensional carbon fiber knit 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 protection at argon gas afterwards drops to room temperature.Preparation 17.2g xylenes, 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, reduce to room temperature and can make 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 sodium sulphate of manganese acetate and the 0.1M of 0.1M, as the electrolyte of electrochemical deposition manganese dioxide.In three-electrode system, be work electrode with the array carbon nano tube/carbon fiber complex after the heat treatment, the platinized platinum of 2cm * 4cm is an auxiliary electrode, is reference electrode with the calomel electrode, applies the constant current of 1mA.After waiting to deposit 10 minutes, take out, put into 80 ℃ vacuum drying chamber vacuumize 48 hours, promptly get the array carbon nano tube/carbon fiber base flexible compound electrode material that deposits manganese dioxide at last with deionized water rinsing 5 times.
With array carbon nano tube/carbon fiber base flexible compound electrode material is work electrode, is to electrode with platinized platinum, and 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:
With the plane is 2cm * 2cm, and thickness is that the three-dimensional carbon fiber knit 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 after the protection of argon gas drops to room temperature, takes out afterwards.Three-dimensional carbon fiber knit body after handling is put in the mixed solution of 0.46g tetraethoxysilane, 0.74g silicon tetrachloride and 16.34g xylenes and soaked 10 minutes.In steam, expose 10 minutes then, afterwards under vacuum in 60 ℃ of dryings of temperature.Again three-dimensional carbon fiber knit 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 protection at argon gas afterwards drops to room temperature.Preparation 17.2g xylenes, 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, reduce to room temperature and can make 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 sodium sulphate of manganese acetate and the 0.1M of 0.1M, as the electrolyte of electrochemical deposition manganese dioxide.In three-electrode system, be work electrode with the array carbon nano tube/carbon fiber complex after the heat treatment, the platinized platinum of 2cm * 4cm is an auxiliary electrode, is reference electrode with the calomel electrode, applies the constant current of 1mA.After waiting to deposit 20 minutes, take out, put into 80 ℃ vacuum drying chamber vacuumize 48 hours, promptly get the array carbon nano tube/carbon fiber base flexible compound electrode material that deposits manganese dioxide at last with deionized water rinsing 5 times.
With array carbon nano tube/carbon fiber base flexible compound electrode material is work electrode, is to electrode with platinized platinum simultaneously, and 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:
With the plane is 2cm * 2cm, and thickness is that the three-dimensional carbon fiber knit 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 after the protection of argon gas drops to room temperature, takes out afterwards.Three-dimensional carbon fiber knit body after handling is put in the mixed solution of 0.46g tetraethoxysilane, 0.74g silicon tetrachloride and 16.34g xylenes and soaked 10 minutes.In steam, expose 10 minutes then, afterwards under vacuum in 60 ℃ of dryings of temperature.Again three-dimensional carbon fiber knit 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 protection at argon gas afterwards drops to room temperature.Preparation 17.2g xylenes, 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, reduce to room temperature and can make 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 sodium sulphate of manganese acetate and the 0.1M of 0.1M, as the electrolyte of electrochemical deposition manganese dioxide.In three-electrode system, be work electrode with the array carbon nano tube/carbon fiber complex after the heat treatment, the platinized platinum of 2cm * 4cm is an auxiliary electrode, is reference electrode with the calomel electrode, applies the constant current of 1mA.After waiting to deposit 30 minutes, take out, put into 80 ℃ vacuum drying chamber vacuumize 48 hours, promptly get the array carbon nano tube/carbon fiber base flexible compound electrode material that deposits manganese dioxide at last with deionized water rinsing 5 times.
With array carbon nano tube/carbon fiber base flexible compound electrode material is work electrode, is to electrode with platinized platinum simultaneously, and 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 (2)
1. array carbon nano tube/carbon fiber base flexible compound electrode material; It is characterized in that; This composite material is a matrix with three-dimensional carbon fiber knit body; 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.
2. method for preparing the described array carbon nano tube of claim 1/carbon fiber base flexible compound electrode material is characterized in that comprising following process:
(1) preliminary treatment of three-dimensional carbon fiber knit body
At first the three-dimensional carbon fiber knit body with 2cm * 2cm places the tubular type high temperature reaction stove, under argon shield, is warming up to 700-900 ℃, 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; Be positioned over then and be hydrolyzed 5-10 minute in the water vapour; Take out the back as in the high temperature process furnances, is warming up to 1000-1200 ℃ under the argon shield, it is subsequent use be incubated after 10-30 minute taking-up;
(2) preparation carbon source and catalyst mix solution
With ethanol, xylenes and ethylenediamine are that the mixed liquor of 1:1:0.1 ~ 0.5 is a 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 xylenes 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) in three-dimensional carbon fiber knit surface carbon nano tube array grows
The three-dimensional carbon fiber knit body that step (1) is handled 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 array carbon nano tube/carbon fiber complex;
(4) preparation of array carbon nano tube/carbon fiber base flexible compound electrode material
Prepared array carbon nano tube/the carbon fiber complex of step (3) is placed in the Muffle furnace, at temperature 100-300 ℃ of following heat treatment 1-4 hour.Mixed solution with the sodium sulphate of manganese acetate, manganese sulfate or the manganese nitrate of concentration 0.01-0.5M and concentration 0.01-0.5M is an electrolyte; With array carbon nano tube/carbon fiber is work electrode; With calomel electrode is to electrode, is reference electrode with the platinized platinum, is 0.1-5mA/cm in current density
2Under carry out electrochemical deposition, sedimentation time is set at 1-30 min, obtains array carbon nano tube/carbon fiber base flexible compound electrode material.
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