CN1994635A - Electrochemical preparation method of superfine tantalum powder - Google Patents

Electrochemical preparation method of superfine tantalum powder Download PDF

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CN1994635A
CN1994635A CN 200610125442 CN200610125442A CN1994635A CN 1994635 A CN1994635 A CN 1994635A CN 200610125442 CN200610125442 CN 200610125442 CN 200610125442 A CN200610125442 A CN 200610125442A CN 1994635 A CN1994635 A CN 1994635A
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electrolysis
reference electrode
metal
tantalum
cacl
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CN100551589C (en
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金先波
陈政
吴田
汪的华
胡晓宏
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Wuhan University WHU
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Abstract

The invention relates to an electrochemical method for preparing ultra-fine tantalum powder, wherein it uses the mixture slat flux with CaCl2 or CaCl2 as electrolyte; composites Ta2O5 powder/block with metal collector as solid cathode; uses graphite or inertia anode as anode; uses reference polar to control the electrolysis level, under inertia gas to electrolyze at 500-1000Deg. C; and the electrolysis time should make electrolysis electricity reach needed amount; reduces Ta2O5 into ultra-fine metal tantalum powder. The invention has simple process, low energy consumption, and less pollution, while the tantalum powder is stable in air.

Description

The electrochemical preparation method of superfine tantalum powder
Technical field:
The present invention relates to a kind of preparation method of superfine tantalum powder, promptly adopt the oxide of melten salt electriochemistry reduction tantalum to prepare superfine metal tantalum powder.
Background technology:
Along with the arriving in 3G epoch, personal electronic equipments is changing our life more and more significantly.And the related of tantalum and electronic market is tangible, because tantalum electric capacity has stable oxide film and high dielectric constant, thereby the unit volume energy storage capacity is big, tantalum electric capacity also has good leakage current characteristic in addition, therefore have 80% tantalum to be used for electronics industry approximately, and Ta powder used in capacitor account for that whole tantalums use 60%.According to estimates, in the several years from now on, the demand of Ta powder used in capacitor still can keep 7%～10% annual growth.
When tantalum metal during as the electrolytic condenser anode material, powder is thin more, and then specific area is big more, and is bigger more than electric capacity.The miniaturization development of electronic product and the sustainable development of environmental resource have proposed subjective and objective requirement to research preparation superfine tantalum powder.
The main city K of preparation method of present Ta powder used in capacitor 2TaF 7Metal Na reduction, chemical process is K 2TaF 7+ 5Na  Ta+2KF+5NaF.Such as the method for U.S. Pat 3012877 disclosed sodium metal fused salt thermal reduction potassium floutaramites, to add a large amount of halide diluents in preparation during superfine tantalum powder, except the excessive impurity of easy introducing, also cause productivity ratio seriously to reduce.Its shortcoming comprises the cost height, pollutes greatly, can not produce continuously etc.
Chinese patent CN 1169643C discloses and has a kind ofly prepared the method for superfine tantalum powder by reduce the oxide of tantalum in the halide fused salt of alkali metal, alkaline-earth metal with alkali metal.Similarly, (J.Phys.Chem.Solids 2005,66, and 466-470) report prepares superfine tantalum powder with solid-state tantalum pentoxide in the calcium metal reduction calcium chloride fused salt for document.Its chemical process is Ta 2O 5+ 5x L  2Ta+5L xO (L is alkali metal or alkaline-earth metal).(4000ppm～37000ppm), this mainly is owing to L in the halide fused salt but the tantalum powder oxygen content that adopts this method preparation is all very high xO or oxonium ion constantly accumulate, and are unfavorable for removing of dissolved oxygen in the metal tantalum on the thermodynamics.
If in the reduction process of above-mentioned tantalum pentoxide, L in the halide fused salt xO or oxonium ion can be removed at the scene, then will help reducing the oxygen content in the prepared metal.As patent CN 1309724A disclose a kind of in calcium chloride and fused salt mixt thereof electrolysis solid metal oxide negative electrode prepare the method for metal dust, the wherein L of Sheng Chenging xO or oxonium ion discharge on anode and remove, and have obtained the Titanium of oxygen content less than 2000ppm.Adopt the mode of two electrodes to carry out electrolysis by the mode of control flume pressure in this patent, current efficiency is on the low side, and the while energy consumption is higher.As document (Angew.Chem.Int.Ed.2006,45, current efficiency is lower than 30% when 428-432) being reported in electrolytic titanium.And for example document (Acta Metallurgica Sinica, 2006,42 (3), 285-289) adopt two electrode systems (graphite anode) control flume to press 3.1V at CaCl 2In-NaCl the fused salt during the solid-state tantalum pentoxide of electrolysis, during still up to 16000ppm (1.6%), current efficiency is lower than 40% in oxygen content, and power consumption is serious.
It is considered herein that causing above-mentioned current efficiency is low, energy consumption is a high major reason is that employing two electrode systems that above-mentioned patent or document are reported are controlled the experimental technique that permanent groove piezoelectricity separates and the actual needs of incompatibility tantalum pentoxide solid state cathode electrochemical reduction.The present invention has proposed a kind of electrochemical preparation method of superfine tantalum powder of new efficient, energy-saving and environmental protection on the basis in conjunction with experimental data and theory analysis.
Summary of the invention:
It is low to the purpose of this invention is to provide a kind of energy consumption, the electrolytic efficiency height, and production procedure is short, pollutes and lacks, and technology is simple, is easy to the electrochemical preparation method of the low-cost superfine tantalum powder of quantity-produced.
Technical scheme provided by the invention is: the electrochemical preparation method of superfine tantalum powder, and with CaCl 2Perhaps contain CaCl 2The mixed salt melt be electrolyte, with Ta 2O 5Powder or piece and metal collector are compound as solid state cathode; with graphite or inert anode as anode; under inert atmosphere protection, carry out electrolysis with reference electrode control electrolytic potential; electrolysis temperature is controlled at 500-1000 ℃; control electrolysis time make electrolysis electricity reach theoretical required electric weight and more than, be superfine metal tantalum powder with the tantalum pentoxide electrochemical reduction.
Above-mentioned electrolysis time generally was controlled at 1-40 hour greater than 0.5h.
The serviceability temperature of above-mentioned reference electrode in principle, can adopt and anyly can or contain CaCl at calcium chloride between 500 ℃ to 1000 ℃ 2The mixed salt melt in the reference electrode of steady operation certain hour (0.5h or more than).Preferential, can adopt as the all-sealed Ag/AgCl reference electrode of patent CN 200420017446.7 disclosed high temperature, this reference electrode can be in various molten chlorides and mixed salt thereof steady operation, can be by long-time, repeated multiple times ground uses.Also can select the metal reference electrode that in the solution that contains corresponding alkali metal or alkaline-earth metal ions, is constituted by alkali metal and alloy thereof or alkaline-earth metal and alloy thereof for use.
Above-mentioned electrolytic potential is controlled at is defeated by tantalum pentoxide at CaCl 2Or contain CaCl 2The mixed salt melt in can be reduced to the thermodynamics current potential of metal tantalum, if with electricity that calcium metal/calcium ion was constituted at CaCl 2Or contain CaCl 2The mixed salt melt in formed current potential be reference, then electrolytic potential is controlled at and is defeated by 1.1V.When using above-mentioned all-sealed Ag/AgCl reference electrode, electrolytic potential should be lower than-0.5V, and is preferred, with respect to above-mentioned all-sealed Ag/AgCl reference electrode-0.7V～-1.7V.
Above-mentioned inert gas is stable in the high temperature fused salt electrolysis process, and is preferred as high-purity argon gas.
After above-mentioned electrolytic process was finished, product can take out from fused salt with working electrode, if necessary, can put into new Ta in the fused salt 2O 5Solid state cathode begins new round electrolysis, thereby realizes the continuous production of ta powder.
Above-mentioned product is cooled to normal temperature after taking out under inert atmosphere, washing in water, rare inorganic acid (as nitric acid, hydrochloric acid, sulfuric acid, hydrofluoric acid, hydrogen peroxide or their any combination) then, drying in atmosphere or vacuum.
The tantalum powder of above-mentioned preparation is about 100～300 nanometers, is evenly distributed, and specific surface is big, the purity height, and oxygen content is low, is superfine tantalum powder, has good stable in air.Adopt the present invention to prepare superfine metal tantalum powder electrolytic efficiency and can be higher than 75%, energy consumption can be lower than 2.4KWh/Kg-Ta.
The present invention proposes to adopt three-electrode system (negative electrode, anode and reference electrode) at high-temp chlorination calcium fused salt or contain CaCl 2The mixed salt melt in prepare ta powder by the solid-state tantalum pentoxide of electrochemical electrolysis, find based on following experiment:
Electrolytic curve as shown in Figure 1 is at potentiostatic deposition Ta 2O 5During solid state cathode, kinetic current is reduced to about 200～300mA rapidly about by about 3A, and Ta is described 2O 5Reduction process mainly occur in the initial reaction stage 1 hour, simultaneously, the oxygen content in the product is promptly dropping to below about 8000ppm about 1 hour.But this numerical value further is reduced to 2000ppm with the other electrolysis in 4 hours of next need, and in these 4 hours, kinetic current remains between 100～200mA.
It is considered herein that the reason that this phenomenon occurs mainly is to form tantalum oxygen solid solution Ta (O owing to be easy to dissolved oxygen in the metal tantalum x) cause, wherein Ta and O mainly exist with the form of atom.Therefore, the entire electrode reduction process of tantalum pentoxide comprises:
Ta 2O 5+(10-4x)e＝2Ta(O x)+(5-2x)O 2- (x＜1) (1a)
Ta(O x)+2xe＝Ta+xO 2- (1b)
Electrode reaction formula 1a mainly is the process of the compound of the tantalum oxygen metal (tantalum oxygen solid solution) that is reduced to tantalum, and reaction mainly is subjected to activation polarization and the liquid phase diffusion polarization of oxonium ion in calcium chloride that generated controlled.Because the diffusion coefficient of salt ion in calcium chloride reaches 10 -5Cm 2/ s, this is a relative very big diffusion coefficient, and is therefore theoretical substantially according to electrochemistry, as long as enough activation polarizations are provided, is lower than-0.7V Ta as the control electrolytic potential with respect to above-mentioned all-sealed Ag/AgCl reference electrode 2O 5Can fast restore be Ta (O x).But reaction 1b then relates to the diffusion of oxygen atom in tantalum oxygen solid solution metal, because its diffusion coefficient is generally less than 10 -8Cm 2/ s, reaction 1b is controlled by the diffusion of oxygen atom in tantalum oxygen solid solution metal mainly, is a very slow process.
Consider from the angle of actual production, for saving electrolysis time, Ta 2O 5Main body reduction part can under big kinetic current, carry out fast.Further oxygen removal process subsequently then can only be under very little electric current by the electrolysis time that prolongs to reach the oxygen content requirement of product.As seen, Ta 2O 5It must be an electrolytic process first quick and back slow that solid state cathode is reduced to metal tantalum.
Consider from the angle of electrolysis energy consumption again, the electrolysis energy consumption of electrolytic process be Faradaic current, electrolysis time and the electrolytic cell groove integration of pressing and, therefore except above-mentioned understanding, also must compress into row analysis to the electrolytic cell groove to Faradaic current and electrolysis time.The electrolytic cell groove is pressed by Ta 2O 5Ohmmic drop in the cathodic polarization of solid state cathode, the electrolysis loop and the anode polarization on the anode constitute, and then both are controlled by Faradaic current all, and promptly the greatly then corresponding groove of electric current is pressed height, and electric current is little, and then corresponding groove forces down.Be understood that Ta 2O 5In the solid state cathode electroreduction process, the groove of an optimization is pressed and supplied with also must be a low process in high earlier back.
Based on above experimental fact and basic theories understanding, patent of the present invention proposes to adopt the method electrolysis Ta of three-electrode system (negative electrode, anode and reference electrode) by the control electrolytic potential 2O 5, can realize that superfine tantalum powder is quick, efficient, the production of low energy consumption.Compare with conventional art, technical scheme provided by the invention prepares superfine tantalum powder, can be according to Ta 2O 5Actual needs regulation and control Faradaic current in the solid state cathode electrolytic process is realized distributing rationally of electrolytic bath pressure simultaneously.In potentiostatic deposition process as shown in Figure 2, the about 3.3V when electrolytic cell groove pressure is reduced by the big electric current of beginning is reduced to about 2.8V afterwards immediately.In conjunction with Fig. 1, Fig. 2, can find that except the electrolysis initial stage most of the time of electrolytic process only needs lower electrolysis power.Compare with the electrolysis mode that existing two electrode systems, control flume are pressed, by adopting three-electrode system, control potential electrolysis Ta 2O 5Solid state cathode prepares superfine metal tantalum powder, can reach the Automatic Optimal electrolytic cell and press supply, reduces the purpose of electrolysis energy consumption.Such as, adopting the present invention to prepare superfine metal tantalum powder electrolytic efficiency and can be higher than 75%, energy consumption can be lower than 2.4KWh/Kg-Ta.
Description of drawings:
Fig. 1 has enumerated a certain potentiostatic deposition Ta 2O 5Oxygen content in current-time curvel during solid state cathode and the electrolysis different time afterproduct.
Fig. 2 has enumerated a certain potentiostatic deposition Ta 2O 5Groove during solid state cathode is pressed time graph.
Fig. 3 is the XRD figure of the superfine tantalum powder of embodiment of the invention generation.
Fig. 4 is the TEM figure of the superfine tantalum powder of embodiment of the invention generation.
The specific embodiment:
Below will present invention is described further combined with drawings and Examples.These are described is for further the present invention will be described, rather than limits the invention.
Among the present invention, Ta 2O 5Powder purity is 99.99%, can be prepared into the tantalum oxide porous piece of specific dimensions by mechanical pressure or casting method, in 100-1500 ℃ of air, dewater or sintering after, gained Ta 2O 5The porosity of piece is about 20-80%.
The molten salt electrolyte that adopts among the present invention is CaCl 2Perhaps contain CaCl 2The mixed salt solution, handle through dehydrating in advance with removal of impurities.The material of electrolytic cell is an exotic material, as specialty metal, metal alloy crucibles such as high-temperature special steel or graphite or aluminium oxide or tantalum, molybdenum, tungsten.
Patent of the present invention adopts three electrodes (negative electrode, anode and reference electrode) work system.With Ta 2O 5The cathode collector bluk recombination of powder or piece and conduction is as solid state cathode, and current collector material is the metallic conduction material, can select the silk of iron, molybdenum, tungsten or tantalum, sheet, net, basket etc.Anode is selected graphite or inert anode for use, carries out the control cathode potential electrolysis under inert atmosphere protection, and electrolysis time was generally 0.5-40 hour.
After taking out electrolysate, it is washed routine or vacuum drying then in water, inorganic acid (as nitric acid, hydrochloric acid, sulfuric acid, hydrofluoric acid, hydrogen peroxide or their any combination).Product X RD is ta powder as shown in Figure 3, and its particle size is 100～300nm, shown in Fig. 4 A.The ta powder of this method preparation has the thick protect oxide layer film of one deck 2～5nm on its surface, as Fig. 4 B, thereby have good stable in air.
Below embodiments of the present invention is described in detail.
Embodiment 1:
With purity 99.99% commercially available Ta 2O 5The about 1.5g of powder is compressed to the about 20mm of diameter by mechanical pressure at 5-10MPa, and thickness heated 0.5～8 hour in 100-1600 ℃ of air at 1.3-1.5mm, and the porosity of gained sample is 20～80%.Ta with sinter molding 2O 5The cathode collector bluk recombination of test piece and conduction is as working electrode, with graphite rod as to electrode, with fusion CaCl 2Perhaps CaCl 2+ NaCl is an electrolyte, and in the environment of argon gas, temperature is 650,750,850 and 950 ℃, carries out potentiostatic deposition with the all-sealed Ag/AgCl reference electrode of the above-mentioned No. 200420017446.7 disclosed high temperature of patent control current potential, current potential is-0.7～-1.7V.Through 30,60, with after product process water successively, 0.1M HCl, water flushing, the drying, product is the superfine metal tantalum powder of 100～300 nanometers after the electrolysis in 120,180,300 minutes respectively, and electrolytic efficiency is 70～95%, and energy consumption is 1.8～2.6KWh/Kg-Ta.
Embodiment 2:
With purity 99.99% commercially available Ta 2O 5The about 5g of powder, heated 2 hours in 900 ℃ of air at the disk that 6MPa is compressed to the about 20mm of diameter by mechanical pressure.With Ta 2O 5The cathode collector bluk recombination of test piece and conduction is as working electrode, with graphite rod as to electrode, with fusion CaCl 2Be electrolyte, in the environment of argon gas, temperature is 850 ℃, with above-mentioned all-sealed Ag/AgCl reference electrode, the control cathode current potential is-1.0V, and electrolysis is after 5 hours, and it passes through water successively with electrolysate, 0.1M HCl, after the water flushing, drying obtains the superfine metal tantalum powder of 100～300 nanometers, its electrolytic efficiency is up to 78%, and energy consumption is lower than 2.4KWh/Kg-Ta.
Embodiment 3:
With purity 99.99% commercially available Ta 2O 5The about 2g of powder, heating is 3.5 hours in air more than 100 ℃, in the basket that the molybdenum filament of packing into is weaved into, and draw as working electrode with the molybdenum filament of diameter 2mm, i.e. negative electrode, with graphite rod as to electrode, with fusion CaCl 2Be electrolyte, in the environment of argon gas, temperature is 850 ℃, with above-mentioned all-sealed Ag/AgCl reference electrode, the control cathode current potential is-1.3V, and electrolysis is after 5 hours, and it passes through water successively with electrolysate, 0.1M HCl, after the water flushing, drying obtains the superfine metal tantalum powder of 100～300 nanometers, its electrolytic efficiency is higher than 80%, and energy consumption is lower than 2.6KWh/Kg-Ta.
Embodiment 4:
With purity 99.99% commercially available Ta 2O 5The about 2g of powder, heated 3.5 hours in 800 ℃ of air at the disk that 6MPa is compressed to the about 20mm of diameter by mechanical pressure.With Ta 2O 5The cathode collector bluk recombination of test piece and conduction is as working electrode, with graphite rod as to electrode, with fusion CaCl 2Be electrolyte, in the environment of argon gas, temperature is 850 ℃, with above-mentioned all-sealed Ag/AgCl reference electrode, the control cathode current potential is-1.7V, and electrolysis is after 2 hours, and it passes through water successively with electrolysate, 0.1M HCl, after the water flushing, drying obtains the superfine metal tantalum powder of 100～300 nanometers, its electrolytic efficiency is higher than 80%, and energy consumption is lower than 2.6KWh/Kg-Ta.
Embodiment 5:
With purity 99.99% commercially available Ta 2O 5The about 2g of powder, heated 3 hours in 1000 ℃ of air at the disk that 9MPa is compressed to the about 20mm of diameter by mechanical pressure.With Ta 2O 5The cathode collector bluk recombination of test piece and conduction is as working electrode, with graphite rod as to electrode, with fusion CaCl 2-KCl salt-mixture is an electrolyte, and in the environment of argon gas, temperature is 750 ℃, with above-mentioned all-sealed Ag/AgCl reference electrode, the control cathode current potential is-1.0V, and electrolysis is after 5 hours, and it passes through water successively with electrolysate, 0.1M HCl, after the water flushing, drying obtains the superfine metal tantalum powder of 100～300 nanometers, its electrolytic efficiency is higher than 75%, and energy consumption is lower than 2.5KWh/Kg-Ta.
Embodiment 6:
With purity 99.99% commercially available Ta 2O 5The about 2g of powder, heated 3 hours in 300 ℃ of air at the disk that 9MPa is compressed to the about 20mm of diameter by mechanical pressure.With Ta 2O 5The cathode collector bluk recombination of test piece and conduction is as working electrode, with graphite rod as to electrode, with fusion CaCl 2-LiCl salt-mixture is an electrolyte, and in the environment of argon gas, temperature is 600 ℃, with above-mentioned all-sealed Ag/AgCl reference electrode, the control cathode current potential is-1.0V, and electrolysis is after 5 hours, and it passes through water successively with electrolysate, 0.1M HCl, after the water flushing, drying obtains the superfine metal tantalum powder of 100～300 nanometers, its electrolytic efficiency is higher than 75%, and energy consumption is lower than 2.5KWh/Kg-Ta.
Embodiment 7:
With purity 99.99% commercially available Ta 2O 5The about 2g of powder, heated 1 hour in 1200 ℃ of air at the disk that 7MPa is compressed to the about 20mm of diameter by mechanical pressure.With Ta 2O 5The cathode collector bluk recombination of test piece and conduction is as working electrode, with graphite rod as to electrode, with fusion CaCl 2Be electrolyte, in the environment of argon gas, temperature is 850 ℃, with metal Ca/ fusion CaCl 2Be reference electrode, the control cathode current potential be the calcium deposition potential+0.2V, electrolysis is after 5 hours, it passes through water successively with electrolysate, 0.1M HCl, after the water flushing, drying, obtain the superfine metal tantalum powder of 100～300 nanometers, its electrolytic efficiency is higher than 70%, and energy consumption is lower than 2.6KWh/Kg-Ta.
Embodiment 8:
With purity 99.99% commercially available Ta 2O 5The about 10g of powder, is dewatering in the air more than 100 ℃ at the disk that 10MPa is compressed to the about 20mm of diameter by mechanical pressure.With anhydrous Ta 2O 5The cathode collector bluk recombination of test piece and conduction as to electrode, is an electrolyte with the fused calcium chloride with graphite rod as working electrode, and in the environment of argon gas, temperature is 920 ℃, with above-mentioned all-sealed Ag/AgCl reference electrode, current potential is-and 1.3V electrolysis 10 hours.It passes through water successively with electrolysate, and 0.1MHCl after the water flushing, through the vacuum drying chamber drying, obtains the superfine metal tantalum powder of 100～300 nanometers, and its electrolytic efficiency is higher than 70%, and energy consumption is lower than 2.6KWh/Kg-Ta.

Claims (9)

1. the electrochemical preparation method of superfine tantalum powder is characterized in that: with CaCl 2Perhaps contain CaCl 2The mixed salt melt be electrolyte, with Ta 2O 5Powder or piece and metal collector are compound as solid state cathode; with graphite or inert anode as anode; under inert atmosphere protection, carry out electrolysis with reference electrode control electrolytic potential; electrolysis temperature is controlled at 500-1000 ℃; control electrolysis time make electrolysis electricity reach theoretical required electric weight and more than, be superfine tantalum powder with the tantalum pentoxide electrochemical reduction.
2. according to the described preparation method of claim 1, it is characterized in that: described electrolytic potential is controlled at is defeated by tantalum pentoxide at CaC1 2Or contain CaCl 2The mixed salt melt in can be reduced to the thermodynamics current potential of metal tantalum.
3. according to claim 1 or 2 described preparation methods, it is characterized in that: described reference electrode is can be at CaCl 2Or contain CaCl 2The mixed salt melt in steady operation 0.5h or above reference electrode.
4. according to the described preparation method of claim 3, it is characterized in that: described reference electrode is the all-sealed reference electrodes of patent CN 200420017446.7 disclosed high temperature, electrolytic potential is controlled at-and below the 0.5V.
5. according to the described preparation method of claim 4, it is characterized in that: electrolytic potential is controlled at-0.7V～-1.7V.
6. according to the described preparation method of claim 3, it is characterized in that: the metal reference electrode of described reference electrode in the solution that contains corresponding alkali metal or alkaline-earth metal ions, being constituted by alkali metal, alkali metal alloy, alkaline-earth metal or alkaline earth metal alloy.
7. according to the described preparation method of claim 3, it is characterized in that: described reference electrode is calcium metal/calcium ion electricity at CaCl 2Or contain CaCl 2The mixed salt melt in the reference electrode that constituted, electrolytic potential is controlled at is defeated by 1.1V.
8. according to claim 1 or 2 described preparation methods, it is characterized in that: electrolysis time is controlled at greater than 0.5h.
9. according to the described preparation method of claim 8, it is characterized in that: electrolysis time was controlled between 1～40 hour.
CNB2006101254424A 2006-12-12 2006-12-12 The electrochemical preparation method of superfine tantalum powder Expired - Fee Related CN100551589C (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103310994A (en) * 2013-06-13 2013-09-18 株洲日望电子科技股份有限公司 Double-electrode-layer capacitor electrode material and manufacturing method thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103310994A (en) * 2013-06-13 2013-09-18 株洲日望电子科技股份有限公司 Double-electrode-layer capacitor electrode material and manufacturing method thereof
CN103310994B (en) * 2013-06-13 2016-04-20 株洲日望电子科技股份有限公司 A kind of electrode material for electric double layer capacitor and preparation method thereof

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