CN100514516C - Composite nano carbon-base film electrode and use therefor - Google Patents
Composite nano carbon-base film electrode and use therefor Download PDFInfo
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- CN100514516C CN100514516C CNB2005100287040A CN200510028704A CN100514516C CN 100514516 C CN100514516 C CN 100514516C CN B2005100287040 A CNB2005100287040 A CN B2005100287040A CN 200510028704 A CN200510028704 A CN 200510028704A CN 100514516 C CN100514516 C CN 100514516C
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Abstract
Comparing with prior art, the invention prepares electrode of capacitor from composite Nano carbon base film. Structure of device and preparing technique are simplified. Resistance of electrode material is small, and operating voltage is small so as to lower energy consumption and cost greatly. The said composite Nano carbon base film is composite material composed of Nano carbon tubes and Nano carbon fibers. The composite material is key material for the electrode. Capacitor made from the disclosed electrode is new generation of energy storage device. Advantages are: high efficiency of ionic adsorption, thin and light, low power consumption, quick response speed, and reusable.
Description
[technical field]
The present invention relates to energy storage, ionic adsorption device and water treatment field, specifically a kind of composite nano carbon-base membrane electrode and application thereof.
[background technology]
Water, for the importance of living organism beyond any doubt, the scarcity day by day of world's water resources makes people adopt desalinization to want water to the ocean.At industrial water also as cleaning agent, solvent, dilution, cold-producing medium and reactant; What are extremely important to commercial Application for ion meltage in the water, and for example, the ionic weight in the ultra-pure water that uses in nuclear power plant and semiconductor chip are produced is wanted strict control, to guarantee steady production and high-quality product.
People have adopted a lot of deionization technologies to be used to desalinate bitter and have produced high purity water.The deionization technology of classical water comprises distillation (evaporation) method, active carbon adsorption, ion-exchange, embrane method (reverse osmosis, film distillation, nanofiltration), electroosmose process.Although these process quilt extensive uses, the power consumption of distillation (evaporation) method is very big, only is applicable to the Gulf states of energy abundance; The regeneration technology of activated carbon adsorbent, ion exchange resin and reverse osmosis membrane is all very expensive, and needs to use chemicals, brings secondary pollution.Recently, and electrodialysis (electrodialysis, EDI) system obtains commercialization, only needs to use electric energy, and does not need to use hazardous chemicals; Only need electricity consumption during continuous purification water, very convenient.But take very much electricity, because the voltage very high (tens to 150 volts are not waited) that uses, also produce a lot of gas simultaneously, increased the danger of processing because of the electrolysis of water.
In energy today in short supply day by day, the meaning of deionization treatment technology of developing a kind of energy-conservation water is self-evident.For this reason, people have developed a kind of novel energy-conservation water technology, promptly use the electrode of the bigger porous material of specific area as capacitor, utilize electric capacity absorption carrying out ion remaval.When the former water that contains ion flow through capacitor, to capacitor charging and make electrode polarization, ion was adsorbed on the electric double layer of electrode surface under electrostatic field.When electrode for capacitors adsorbs when saturated, with electrode two terminal shortcircuits or add reverse voltage, the ion of absorption just leaves electrode by discharge, and the concentrate that will contain the desorption ion collects, and electrode just obtains regeneration, can reuse.When reality was used, applied voltage was controlled at that the state of electrolysis (theoretical decomposition voltage is 1.23V) does not take place water on the electrode surface, so operating voltage is very low, and compare this method with electrodialysis very energy-conservation.Main at present carbon aerogels and the active carbon material of adopting of this porous electrode material.Adopt carbon aerogels and active carbon material to carry out capacitive deionization water in various degree shortcoming is arranged in the commercialization process: carbon aerogels is because its high preparation cost, makes that it is difficult in the desalination field promote to come.Though activated carbon has very big specific area, but specific area is mainly provided by micropore (aperture is less than 2nm), account for 60%～70%, and form electric double layer is the mesopore of aperture greater than 2nm basically, mesopore such in activated carbon only accounts for 20%～30%, make a lot of hydrated ions freely not enter in the hole, the specific area utilance is lower, and capacitive deionization efficient can not further improve; Simultaneously, the conductivity of activated carbon is not very good, if make its conduction good, need carry out special activation processing, has so improved cost yet.
Recently, people begin to adopt the electrode material of carbon nano-tube as the deionized water capacitor.Its technology is mainly mixes carbon nano-tube processing back with organic resin (for example phenolic resins), make carbon nano-tube combination electrode after handling through high temperature carbonization.Owing to contain a large amount of resins in this combination electrode, make carbon nano-tube material only account for the part of electrode; Resin and carbon nano-tube are mixed, and are coated on carbon nano tube surface, make the surface area of carbon nano-tube that very big loss be arranged.This makes that all the actual specific surface area of this carbon nano-tube combination electrode is less, can not reach very high capacitance, thereby obtains higher capacitive deionization efficient.Resin and carbon nano-tube are mixed, and the resistance of electrode is higher, and energy consumption increases.Simultaneously, the technology that carbon nano-tube is handled is numerous and diverse, and cost is very high, and repeatability is difficult to guarantee, is not suitable for requirement of mass production.
[summary of the invention]
What the objective of the invention is to design in order to overcome the deficiencies in the prior art is a kind of with the electrode material of composite nano carbon-base thin-film material as high-effect ionic adsorption capacitance device, make stacked logical liquid type capacitor with the kind electrode material, utilize stacked logical liquid type double electric layer capacitor to carry out capacitive adsorption deionizing water.
For achieving the above object, design a kind of composite nano carbon-base membrane electrode, it is characterized in that coating on the matrix laminated film of one deck carbon nano-tube and carbon nano-fiber; The material of matrix adopting is nickeliferous or the simple metal of iron or cobalt or alloy sheet or alloy network or nickel sheet or nickel screen or iron plate or iron net or stainless steel substrates or stainless (steel) wire or be coated with metallic matrix or titanium or titanium chrome alloy or titanium chrome alloy net or the graphite flake or the carbon cloth of above-mentioned metal; The thickness of nickel sheet, iron plate, stainless steel substrates, titanium sheet, graphite flake or carbon cloth is 0.1～2mm, and the hole density of nickel screen, iron net, stainless (steel) wire and titanium net is the 20-100 order; The production method of composite nano carbon-base membrane electrode, it is characterized in that a. adopts the laminated film of low-pressure chemical vapor deposition (CVD) method direct growth carbon nano-tube and carbon nano-fiber on the metallic conduction matrix, reaction gas is an acetylene, methane, methyl alcohol, ethanol, acetone, benzene, toluene, a kind of and hydrogen in the cyclohexane, growth conditions is 5-500sccm for the carbon source flow, hydrogen flowing quantity is 50-1000sccm, air pressure is 1-80kPa, reaction temperature is 400-1200 ℃, the laminated film form of carbon nano-tube and carbon nano-fiber is that carbon nano-tube is wrapped on the skeleton with carbon nano-fiber, the carbon nano-tube diameter is 1-100nm, and the carbon nano-fiber diameter is 50-500nm; B. when the former water that contains ion flows through capacitor, to the capacitor charging and make electrode polarization, ion is adsorbed on the electric double layer of electrode surface under electrostatic field, reaches the effect of removing the water intermediate ion; C. adsorb when saturated when electrode for capacitors, with electrode two terminal shortcircuits or add reverse voltage, the ion of absorption just leaves electrode by discharge, and the concentrate that will contain the desorption ion collects, and electrode just obtains regeneration, can reuse; The purposes of composite nano carbon-base membrane electrode is characterized in that can be used for energy storage, ionic adsorption device and water treatment field and comprises adsorption deionizing water, desalinization, removes microbe and germ in anhydrating.
The present invention compares with prior art, adopts the capacitor of composite nano carbon-base film as electrode.The structure and the preparation technology of device greatly simplify, and the resistance of electrode material is very little, and institute's making alive is very little during work, thereby greatly reduce the energy consumption and the manufacturing cost and use cost of device.The composite material that composite nano carbon-base thin-film material among the present invention is made up of carbon nano-tube and carbon nano-fiber, it is the critical material of electrode in the high efficiency capacitor, it has excellent ionic adsorption performance, and the capacitor element made from this composite nano carbon-base thin-film material is efficient, energy-saving energy storage device of new generation.Its advantage is ionic adsorption efficient height, thin and light, good stability, the life-span is long, low in energy consumption, response speed is fast and reusable etc.
[description of drawings]
Fig. 1 is the structural representation of composite nano carbon-base membrane electrode of the present invention.
Fig. 2 contains ion liquid schematic diagram for the present invention handles, and wherein (a) is the deionising process schematic diagram, (b) is electrode regeneration Principle of Process figure.
Fig. 3 is the graph of a relation over time of electrical conductivity of solution under the present invention's work period.
Fig. 4 is the graph of a relation over time of conductivity and electric current under the present invention's two work periods.
Fig. 5 is the present invention's conductivity graph of a relation over time under different voltages.
Fig. 6 carries out constant voltage, reversal connection, constant voltage, short circuit conductivity graph of a relation over time for the present invention under same voltage.
Referring to Fig. 1, the electrode section is sandwich structure, and 1 is metal electrode, and 2 is composite Nano carbon Base film.
Shown in Fig. 2 (a), when the former water that contains ion flows through capacitor, to capacitor charging And make electrode polarization, ion is adsorbed on the electric double layer of electrode surface under electrostatic field, reaches To the effect of removing the water intermediate ion. Such as Fig. 2 (b) when electrode for capacitors adsorbs when saturated, with electrode two Terminal shortcircuit or add backward voltage, the ion of absorption just leaves electrode by discharge, will contain desorption from The concentrate of son collects, and electrode just obtains regeneration, can reuse.
Be U=1.2V referring to Fig. 3 voltage, process the NaCl aqueous solution, constant voltage and short circuit alternately apply.
Be U=1.2V referring to Fig. 4 voltage, process the NaCl aqueous solution, constant voltage and short circuit alternately apply Circulation twice has provided simultaneously and has flowed out the electrical conductivity of solution and filling of capacitor when flowing through capacitor Discharge current concerns over time.
Referring to Fig. 5 voltage is U=0.4V, 0.6V, and 0.8V, 1.0V, 1.2V, 2.0V handles the NaCl aqueous solution, and be t=20 minute conduction time.
Referring to Fig. 6 voltage is under the U=1.2V, handles the NaCl aqueous solution, and wherein constant voltage, reversal connection, constant voltage, short circuit alternately apply circulation twice, has provided the conductivity of outflow solution when flowing through capacitor and the charging and discharging currents of capacitor simultaneously and has concerned over time.
[embodiment]
The making way of carbon nano-tube and carbon nano-fiber is as follows:
Adopt low-pressure chemical vapor deposition (CVD) method direct growth carbon nano-tube and carbon nano-fiber film on the metallic conduction matrix, reaction gas is hydrocarbon gas/liquid and hydrogen, and hydrocarbon gas/liquid comprises acetylene, methane, methyl alcohol, ethanol, acetone, benzene, toluene, cyclohexane etc.With acetylene is example, cleaned metallic catalyst matrix (as the nickel sheet) is put into reative cell and vacuumize that (back of base vacuum ~ 0.1Pa) feeds hydrogen, and flow is 50-1000sccm, and pressure is 1-80kPa.By controlling different acetylene flows (5-500sccm) and reaction temperature (400-1200oC), obtain the carbon nano-tube and the fiber composite thin-film material of different shape.
Because carbon nano-tube and fiber are grown on the bulk metal catalyst matrix, and the catalyst metals matrix is wrapped up, like this, the combination of pipe and metallic conduction matrix is very firm.Logical liquid mode:
Adopt constant flow pump to make boiler water circulation pass through capacitor, the deionization of switching on simultaneously after electrical conductivity of water drops to certain limit, can be drawn water by a valve.
Step mode:
(A) during deionising process, in capacitor, apply direct current constant voltage or direct current constant current in flow of liquid; Added voltage swing is at 0.2～1.5V, and deionization efficient was very low when voltage was too small, and voltage is crossed the decomposition that conference causes water, and energy consumption increases simultaneously.
Adopt short circuit, constant-current discharge or collector electrode reversal connection when (B) regenerating.Generally speaking, electrode regeneration can adopt short circuit and constant-current discharge, when having only electrode performance to descend, can be with the method for reversal connection so that electrode performance recover, and reversal connection institute making alive is in the 0.8-1.5V scope.
Application example:
Example 1:
Adopt a capacitor cell, electrode is that diameter is carbon nanotubes grown and a fiber composite film on the Ni sheet of 85mm, and the electrode used therein number is 2.The solution of handling is 30ml NaCl solution, and initial conductivity is 50 μ S/cm, makes the NaCl solution circulated with constant flow pump.Institute's making alive is U=1.2V.Fig. 3 has provided the increase along with conduction time, and the conductivity of solution descends, and shows that this capacitive means has the deionization effect to NaCl solution.The 45 minutes rear electrode short circuit dischanges of switching on, electrical conductivity of solution increases, and conductivity is recovered initial value before the energising in the time of 100 minutes, and the complete desorption of ion of absorption be described, and electrode obtains regenerating.
Example 2:
Adopt a capacitor cell, electrode is that diameter is carbon nanotubes grown and a fiber composite film on the Ni sheet of 85mm, and the electrode used therein number is 2.The solution of handling is 30ml NaCl solution, and initial conductivity is 50 μ S/cm, makes the NaCl solution circulated with constant flow pump.Energising is a period of time t1=15 minute under U=1.2V, and short circuit was then switched on a period of time t2=20 minute during initial value before conductivity is near energising once more, short circuit then, and conductivity still returns to initial value before the energising.Fig. 4 has provided the increase along with conduction time, the variation of the conductivity of solution.Find out obviously that from Fig. 4 the nano carbon-base membrane electrode that the present invention uses can be reused.
Example 3:
Adopt a capacitor cell, electrode is that diameter is carbon nanotubes grown and a fiber composite film on the Ni sheet of 85mm, and the electrode used therein number is 2.The solution of handling is 30ml NaCl solution, and initial conductivity is 50 μ S/cm, makes the NaCl solution circulated with constant flow pump.At different voltage U=0.4V, 0.6V, 0.8V, 1.0V, 1.2V, 2.0V switched on identical time t=20 minute down.Fig. 5 has provided the increase along with conduction time, the downward trend of the conductivity of solution.Therefrom as can be seen in institute's making alive scope, along with voltage raises, capacitive deionization efficient increases.When U=2.0V, capacitive deionization efficient reaches 50%, and during U=1.2V, capacitive deionization efficient also reaches 40%.During U=2.0V, do not see water decomposition.The theoretical decomposition voltage of water is 1.23V, considers the voltage drop that impedance caused of electrode interior and contact conductor coupling part, and electrode institute making alive can reach U=2V.Reuse for electrode is stable, voltage uses U=1.2V to be advisable, and capacitive deionization efficient is also bigger.
Example 4:
Adopt a capacitor cell, electrode is that diameter is carbon nanotubes grown and a fiber composite film on the Ni sheet of 85mm, and the electrode used therein number is 2.The solution of handling is 30ml NaCl solution, and initial conductivity is 50 μ S/cm, makes the NaCl solution circulated with constant flow pump.Energising is identical time t1=20 minute under voltage U=1.2V; Depressed reversal connection t2=20 minute in same electrical then,, promptly get back to initial polarity, continue energising t3=45 minute, then then short circuit then with electrode reversal connection once more.Fig. 6 has provided the increase along with conduction time, the variation tendency of the conductivity of solution.Therefrom as can be seen, compare short circuit, reversal connection can be so that electrode be regenerated rapidly, and this is the result of electric desorption.
Claims (1)
1. the production method of a composite nano carbon-base membrane electrode, it is characterized in that a. adopts the laminated film of low-pressure chemical vapor deposition CVD method direct growth carbon nano-tube and carbon nano-fiber on the metallic conduction matrix, reaction gas is an acetylene, methane, methyl alcohol, ethanol, acetone, benzene, toluene, a kind of and hydrogen in the cyclohexane, growth conditions is 5-500sccm for the carbon source flow, hydrogen flowing quantity is 50-1000sccm, air pressure is 1-80kPa, reaction temperature is 400-1200 ℃, the laminated film form of carbon nano-tube and carbon nano-fiber is that carbon nano-tube is wrapped on the skeleton of carbon nano-fiber formation, the carbon nano-tube diameter is 1-100nm, and the carbon nano-fiber diameter is 50-500nm; B. when the former water that contains ion flows through capacitor, to the capacitor charging and make electrode polarization, ion is adsorbed on the electric double layer of electrode surface under electrostatic field, reaches the effect of removing the water intermediate ion; C. adsorb when saturated when electrode for capacitors, with electrode two terminal shortcircuits or add reverse voltage, the ion of absorption just leaves electrode by discharge, and the concentrate that will contain the desorption ion collects, and electrode just obtains regeneration, can reuse.
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| CN101947417A (en) * | 2010-08-25 | 2011-01-19 | 上海理工大学 | Carbon nano tube-based nanofiltration membrane device and preparation method thereof |
| BR112013005529A2 (en) * | 2010-09-22 | 2016-05-03 | Applied Nanostructured Sols | carbon fiber substrates having carbon nanotubes developed therein, and processes for producing them |
| CN102354612B (en) * | 2011-09-06 | 2013-03-20 | 天津大学 | Array carbon nano-tube/carbon fiber-based flexible composite electrode material and preparation method thereof |
| CN106517423B (en) * | 2016-08-30 | 2023-06-16 | 浙江大维高新技术股份有限公司 | Special carbon aerogel electrode for capacitive deionization equipment and preparation method thereof |
| CN106935709B (en) * | 2017-05-05 | 2018-04-13 | 中北大学 | Carbon cloth base back electrode and solar cell and preparation method thereof |
| CN107119262A (en) * | 2017-05-27 | 2017-09-01 | 华南理工大学 | A kind of method of nickel metal base surface catalytic growth carbon nano-tube film |
| CN107604168A (en) * | 2017-09-28 | 2018-01-19 | 上海至铂环保科技服务有限公司 | The method of recovering copper, nickel, cobalt from the sludge containing non-ferrous metal |
| CN109781792B (en) * | 2019-03-12 | 2022-05-31 | 安徽工业大学 | Method for representing electrochemical activity of aluminum anode material through conductivity |
| CN111320160A (en) * | 2020-02-27 | 2020-06-23 | 广东工业大学 | Nitrogen-rich microporous carbon material and preparation method and application thereof |
| TWI751847B (en) * | 2020-12-19 | 2022-01-01 | 逢甲大學 | A porous electrode with composite structure and manufacturing method thereof |
| CN114843527A (en) * | 2022-05-23 | 2022-08-02 | 齐鲁工业大学 | Bioelectrochemical electrode, manufacturing method and application thereof in methane preparation |
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Effective date of registration: 20170726 Address after: 200062 science building, No. 3663, Putuo District, Shanghai, Zhongshan North Road A607 Patentee after: Najing Science & Technology Co., Ltd., Shanghai Address before: 201109 Shanghai city Minhang District Jianchuan Road No. 468 Co-patentee before: East China Normal University Patentee before: Najing Science & Technology Co., Ltd., Shanghai |