CN101407925B - Carbon nano-tube enhanced composite type metallic oxide electrode material and preparation thereof - Google Patents
Carbon nano-tube enhanced composite type metallic oxide electrode material and preparation thereof Download PDFInfo
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- CN101407925B CN101407925B CN2008101726373A CN200810172637A CN101407925B CN 101407925 B CN101407925 B CN 101407925B CN 2008101726373 A CN2008101726373 A CN 2008101726373A CN 200810172637 A CN200810172637 A CN 200810172637A CN 101407925 B CN101407925 B CN 101407925B
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Abstract
The invention relates to a novel composite electrode material and a preparation method thereof, pertaining to the technical field of electrochemical electrode materials. Aiming at the problems of poor compactness of coating, low generating capacity and complex technology of the existing mixed metal oxides, the invention utilizes the high strength, good conductibitily, and the regulating effect to the traditional mixed metal oxide coating solution viscosity and leveling property of a carbon nano tube to prepare a composite mixed metal oxide electrode material with even and smooth appearance, compact microstructure, good mechanical property, good inoxidability, high generating capacity and reinforced carbon nano tube. The preparation process comprises the following steps: a mixed metal oxide precursor solution containing 0.1g/L to 5g/L of single-walled or multi-walled carbon nano tube that is processed with purification, short cutting and dispersion is coated on a conductive substrate surface which is roughened; the substrate is dried after being roasted at the temperature of 100 to 200 DEG C for 5 to 15min, sintered for 5 to 10min at the temperature of 400 to 600 DEG C; the coating and sintering steps are repeated till the required electrode coating thickness is reached; and finally the substrate is sintered for 50 to 150min at the temperature of 400 to 600 DEG C. As the coating solution velocity of the carbon nano tube is increased, the smoothness of the solution is improved, and the thickness and leveling property of the single-walled electrode coating are improved, the invention shortens the preparation time of electrode coatings with the same thickness, and leads the yield and production stability to be improved.
Description
Technical field:
The present invention relates to a kind of carbon nanotube enhanced mixed metal oxide novel composite electrode material and preparation method thereof, belong to electrochemical electrode material technology field.
Background technology:
The mixed metal oxide (Mixed Metal Oxide is called for short MMO) that obtains in recent years developing rapidly is a kind of novel electrode materials, is called dimensionally stable electrode material (Dimensionally Stable Anode is called for short DSA) again.Development along with chlorine industry produces this material in nineteen sixties.Employed anode material requires to have stronger corrosion resistance nature in the chlorine industry, long life-span and higher mechanical properties.And by electroactive oxide compound IrO
2, RuO
2, RhO
2, PtO
xDeng and enhancement type indifferent oxide Ta
2O
5, TiO
2, MnO
2Just in time can satisfy this requirement Deng the Mixed Metal Oxide Coated Titanium Anodes of forming; therefore replaced traditional Graphite Electrodes rapidly after this anode material occurs and obtain rapidly promoting, and in industries such as some other association area such as impressed current cathodic protection, plating, hydrometallurgy, electrolytic synthesis, also be used widely.
Compare with traditional electrode materials, mixed metal oxide electrode material tool in stability and cost has great advantage: the kind electrode coating adopts thermal oxidation method to prepare under hot conditions, and therefore this material thickness is evenly distributed, and is good with the matrix bond performance.Compare with other anode materials; Mixed Metal Oxide Coated Titanium Anodes has extremely low rate of consumption; for example being about 2mg/ (Aa) in cathodic protection system at the bottom of the jar (sees: Song Jiwu; appoint yulan. the application [J] of netted Mixed Metal Oxide Coated Titanium Anodes in the large-scale storage tank galvanic protection. corrosion science and guard technology; 2001,13:505-507.).When using as the anode material of impressed current cathodic protection system, mixed metallic oxide material also has following advantage:
1) distribution of current is very even, can guarantee that metal construction is adequately protected;
2) do not produce stray current substantially, can not cause obvious corrosion to disturb other steel building;
3) do not need backfill, install simply, quality easily guarantees, long service life.
Therefore, the Mixed Metal Oxide Coated Titanium Anodes material is at present ideal and one of the most promising anode material.
Though have above numerous advantage, also there are some limitation in mixed metal oxide electrode.At first, because this material is by the high-temperature thermal oxidation prepared, so inevitably there are some crackles in the coating finished product.So not only reduced the sticking power and the wear resistance of this material and matrix, and these cracks also can become the center of destructive electrochemical reaction, make mixed metal oxide electrode begin to take place damage inactivation by this place.In addition, to compare the Mixed Metal Oxide Coated Titanium Anodes generated energy lower with traditional anode material, in use just needs to consume more electrode materials for reaching the magnitude of current that needs.For example iron and steel anodic generated energy can reach 1000A/m
2, and the rated current of Mixed Metal Oxide Coated Titanium Anodes in seawater is 600A/m
2, only be 100A/m in fresh water and soil
2(see: Hu Shixin. cathodic protection engineering handbook [M]. Chemical Industry Press, Beijing, 1999.).Therefore generated energy is low is another important restrictions condition of restriction mixed metallic oxide material widespread use.If the generated energy that can improve mixed metal oxide will be widened the range of application of this material, save material cost, reduce the pollution that causes in producing, produce huge economic benefit and social benefit.
Summary of the invention:
Purpose of the present invention is to utilize the high strength and the good electrical conductivity of carbon nanotube, and to the regulating effect of conventional hybrid coating of metal oxides solution viscosity, leveling property, prepare have apparent evenly smooth, dense micro-structure, mechanical property is good, good corrosion resistance, the compound mixed metal oxide electrode material of the carbon nanotube enhanced that generated energy is high.Technology of the present invention increases the thickness that single is coated with brush layer because the adding of carbon nanotube can increase the sliminess of precursor solution, shortens the preparation time of same thickness electrode coating, enhances productivity.The adding of carbon nanotube can also be regulated the homogeneity of brushing, avoids owing to defectives such as the too low sagging that causes of presoma dissolving viscosity, tricklings yield rate and production stability being improved.
Compound mixed metal oxide electrode material of the present invention is characterized in that applying the compound electrode materials that a kind of carbon nanotube enhanced mixed metal oxide coating constitutes by the method for thermooxidizing on solid-state conducting base.This electrode materials comprises as the lower section:
1) solid-state conducting base can be that metallic substance such as titanium, platinum, tantalum, tungsten, copper, steel, aluminium also can be non-metallic material such as graphite.
2) carbon nanotube enhanced mixed metal oxide coating.
This compound mixed metal oxide electrode material preparation process is characterized in that being made up of following steps:
1) oil removing and surface cleaning processing are carried out in the conducting base surface, and adopt machinery or chemical method that body material is carried out suitable roughened.
2) the mixed metal oxide precursor solution is by one or more metal oxides (IrO
2, RuO
2, RhO
2, PtOx, Ta
2O
5, TiO
2, MnO
2, Al
2O
3Deng) solution of presoma constitutes.
3) with the carbon nanotube purifying, cut out short and dispersion treatment, and be that 0.1g/L takes by weighing required carbon nanotube to 5g/L and joins in the metal oxide precursor solution according to the content of carbon nanotube in solution.
4) the mixed metal oxide precursor solution that will be mixed with processed carbon nanotubes is coated in the conducting base surface through roughened, carry out drying at 100-200 ℃ of baking 5-15min earlier, sintering 5-10min under 400-600 ℃ condition again, repeat the coating sintering process to the electrode coating thickness that needs, last at sintering 50-150min under 400-600 ℃ condition.
As required this electrode materials being processed into the size that needs then gets final product.Electrode materials of the present invention has apparent evenly smooth, dense micro-structure, and the bonding force height, good corrosion resistance, generated energy is big, the characteristics that workability is good.Electrode materials preparation technology efficient height of the present invention, process stabilizing.
Description of drawings:
Accompanying drawing 1. is the comparison of not adding the carbon nanotube mixed metal oxide electrode and adding the mixed metal oxide electrode surface macro morphology of carbon nanotube.Wherein (a) be not for adding the macro morphology on carbon nanotube electrode surface, (b) for adding the macro morphology on carbon nanotube electrode surface.
Accompanying drawing 2. is the comparison of not adding the carbon nanotube mixed metal oxide electrode and adding the mixed metal oxide electrode surface microscopic topographic of carbon nanotube.Wherein (a) be not for adding the electrode surface of carbon nanotube, (b) for adding the planar section on carbon nanotube electrode surface, (c) for adding the trench portions on carbon nanotube electrode surface.
Accompanying drawing 3. for metal titanium, do not add the carbon nanotube mixed metal oxide electrode and add the comparison of carbon nanotube mixed metal oxide electrode polarization curve in neutral 3.5%NaCl solution.Wherein (a) is pure titanium electrode, (b) for not adding the mixed metal oxide electrode of carbon nanotube, (c) for adding the mixed metal oxide electrode of carbon nanotube.
Accompanying drawing 4. for metal titanium, do not add the carbon nanotube mixed metal oxide electrode and add the comparison of carbon nanotube mixed metal oxide electrode cyclic voltammetry curve in neutral 3.5%NaCl solution.Wherein (a) is pure titanium electrode, (b) for not adding the mixed metal oxide electrode of carbon nanotube, (c) for adding the mixed metal oxide electrode of carbon nanotube.
Embodiment:
[Comparative Examples] titanium base iridium, tantalum mixed metal oxide electrode preparation methods
1. titanium sheet (TA1) is soaked under 95 ℃ of conditions with 10% oxalic acid solution and carried out roughened in 1 hour, use washed with de-ionized water, clean with alcohol or acetone then or blower dries up.
2. coating oxidation thing precursor solution is H
2IrCl
6XH
2O (being dissolved in the hydrochloric acid) solution+TaCl
5(being dissolved in the propyl carbinol) solution is the solution of 0.2mol/L with concentrated hydrochloric acid to metal ion with this solution dilution.
3. be brushed to through pretreated matrix surface with the just above-mentioned mixed solution of soft plastics hairbrush, then sample put into sintering oven, carry out drying at 100 baking 5min earlier, again at 600 ℃ of sintering 10min.Repeat above-mentioned brushing, drying and sintering process to obtain certain oxide coating carrying capacity.Last sintering time extends to 150min makes coating obtain oxidation more fully.
4. deposit behind the carbon nano tube-doped mixed metal oxide electrode material air cooling that will prepare.
[embodiment one] titanium base carbon nanotube strengthens iridium, tantalum mixed metal oxide electrode preparation methods
1. titanium sheet (TA1) is soaked under 95 ℃ of conditions with 10% oxalic acid solution and carried out roughened in 1 hour, use washed with de-ionized water, clean with alcohol or acetone then or blower dries up.
2. at first carbon nanotube was cut out weak point in 2 hours with ball milling, reflux in the concentrated nitric acid and the vitriol oil then activated and purification process in 10 hours, standby with the washed with de-ionized water after drying.
3. coating oxidation thing precursor solution is H
2IrCl
6XH
2O (being dissolved in the hydrochloric acid) solution+TaCl
5(being dissolved in the propyl carbinol) solution is the solution of 0.2mol/L with concentrated hydrochloric acid to metal ion with this solution dilution.
4. calculate, take by weighing needed carbon nanotube by the amount of 0.1g/L, add in the coating solution, in ultrasonic, fully disperse.
5. be brushed to through pretreated matrix surface with the just above-mentioned mixed solution of soft plastics hairbrush, then sample put into sintering oven, carry out drying at 100 ℃ of baking 5min earlier, again at 600 ℃ of sintering 10min.Repeat above-mentioned brushing, drying and sintering process to obtain certain oxide coating carrying capacity.Last sintering time extends to 150min makes coating obtain oxidation more fully.
6. deposit behind the carbon nano tube-doped mixed metal oxide electrode material air cooling that will prepare.
[embodiment two] titanium base carbon nanotube strengthens iridium, tantalum mixed metal oxide electrode preparation methods
1. the fine copper sheet is carried out roughened with 300# sand paper, use washed with de-ionized water, clean with alcohol or acetone then or blower dries up.
2. at first carbon nanotube was cut out weak point in 2 hours with ball milling, reflux in the concentrated nitric acid and the vitriol oil then activated and purification process in 10 hours, standby with the washed with de-ionized water after drying.
3. coating oxidation thing precursor solution is H
2IrCl
6XH
2O (being dissolved in the hydrochloric acid) solution+C
16H
36O
4Ti (tetrabutyl titanate) solution is the solution of 0.2mol/L with concentrated hydrochloric acid to metal ion with this solution dilution.
4. calculate, take by weighing needed carbon nanotube by the amount of 5g/L, add in the coating solution, in ultrasonic, fully disperse.
5. be brushed to through pretreated matrix surface with the just above-mentioned mixed solution of soft plastics hairbrush, then sample put into sintering oven, carry out drying at 200 ℃ of baking 15min earlier, again at 500 ℃ of sintering 5min.Repeat above-mentioned brushing, drying and sintering process to obtain certain oxide coating carrying capacity.Last sintering time extends to 50min makes coating obtain oxidation more fully.
6. deposit behind the carbon nano tube-doped mixed metal oxide electrode material air cooling that will prepare.
[means of testing]
Be the difference of electrode materials more of the present invention and traditional mixed metal oxide electrode material, Comparative Examples and embodiment one resulting electrode materials have been carried out test relatively.
Morphology observation adopts LEO-450 type scanning electronic microscope (SEM) to observe the microstructure of MMO coating.
Electro-chemical test utilization PE electro-chemical test system of company (comprising Potentiostat/Galvanostat Model 273A and 5210 lock-in amplifiers), adopt three-electrode system, with saturated calomel electrode (SCE) is reference electrode, platinum electrode (Pt) is a supporting electrode, measures polarization curve and the cyclic voltammetry curve of electrode materials in 3.5%NaCl solution.Sample is coated with envelope with the HY914 fast binder, the about 0.5cm of exposed area
2Polarization curve electrokinetic potential scanning speed is 1.0mV/s.
Can be found out that by accompanying drawing 1 the mixed metal oxide electrode surface of not adding carbon nanotube is made up of a lot of rugged particulate state projections, be that the channel form structure of even even curface and net distribution constitutes and add electrode surface after the carbon nanotube.
Each particulate state projection of being found out the mixed metal oxide electrode surface portion that does not add carbon nanotube by accompanying drawing 2 is all chapped, skin effect phenomenon, and this line of chapping spreads all over electrode surface.Add after the carbon nanotube because carbon nanotube plays enhancing and smooth effect to mixed metal oxide, eliminated the skin effect phenomenon of chapping, the electrode surface main part is carbon nano tube-doped mixed metal oxide uniform coating, be evenly distributed with groove structure at coatingsurface, the side and the bottom of these grooves also are that fine and close carbon nanotube strengthens mixed metal oxide as can be seen from figure (C).Be distributed with numerous carbon nanotubes owing to add the electrode surface of carbon nanotube, therefore the effective surface area that directly contacts with the kind electrode material in electrolytic solution is compared with traditional electrode and is improved a lot.
Can find out with metal titanium, traditional mixed metal oxide electrode by accompanying drawing 3 and to compare, carbon nanotube enhanced Mixed Metal Oxide Coated Titanium Anodes material has higher open circuit potential in 3.5% NaCl solution, and this electrode materials can send bigger electric current under the driving of identical impressed voltage.
Electrode surface has produced tangible activation after applying the mixed metal oxide electrode coating as can be seen by the cyclic voltammetry curve of accompanying drawing 4 on the titanium matrix, along with the effective active area on the introducing mixed metal oxide electrode surface of carbon nanotube has had very big amplitude to increase.
Therefore carbon of the present invention have apparent evenly smooth, dense micro-structure, mechanical property is good, good corrosion resistance, the characteristics that generated energy is high. Nanotube of the present invention strengthen mixed metal oxide electrode material preparation technology since CNT increased coating solution viscosity, improved the trickling of solution, thickness and the planarization of single-layer electrodes coating have been increased, so shortened the preparation time of same thickness electrode coating, yield rate and production stability be improved.
Claims (1)
1. technology for preparing compound mixed metal oxide electrode material is characterized in that being made up of following steps:
1) oil removing and surface cleaning processing are carried out in the conducting base surface, and adopt machinery or chemical method that body material is carried out suitable roughened, described conducting base is titanium, platinum, tantalum, tungsten, copper, steel, aluminium, graphite;
2) mixed metal oxide precursor solution is made of the solution of one or more metal oxide precursors, and described metal oxide is IrO
2, RuO
2, RhO
2, PtO
x, Ta
2O
5, TiO
2, MnO
2, Al
2O
3
3) with the carbon nanotube purifying, cut out short and dispersion treatment, and be that 0.1g/L takes by weighing required carbon nanotube to 5g/L and joins in the metal oxide precursor solution according to the content of carbon nanotube in solution;
4) the mixed metal oxide precursor solution that will be mixed with processed carbon nanotubes is coated in the conducting base surface through roughened, carry out drying at 100-200 ℃ of baking 5-15min earlier, sintering 5-10min under 400-600 ℃ condition again, repeat the coating sintering process to the electrode coating thickness that needs, at last sintering 50-150min under 400-600 ℃ condition.
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|---|---|---|---|---|
| US20130048078A1 (en) * | 2010-05-20 | 2013-02-28 | Korea Institute Of Machinery And Materials | Carbon nanotube-invaded metal oxide composite film, manufacturing method thereof, and organic solar cell with improved photoelectric conversion efficiency and improved duration using same |
| CN102592844B (en) * | 2012-03-06 | 2014-02-12 | 昆明贵容电子材料有限公司 | Cathode piece of high-capacity tantalum capacitor and preparation method |
| CN102659222B (en) * | 2012-05-17 | 2013-08-21 | 江苏沃奇环保工程有限公司 | Manufacturing method for corrosion resisting composite electrolysis electrode |
| CN107937920B (en) * | 2017-11-29 | 2019-07-12 | 青岛双瑞海洋环境工程股份有限公司 | For ocean platform cathodic protection reparation oxide anode material and preparation process |
| CN108483583B (en) * | 2018-04-03 | 2020-10-27 | 西安交通大学 | IrO (IrO)2·Ta2O5Preparation method of coated titanium electrode |
| CN109763146B (en) * | 2019-03-27 | 2021-03-26 | 贵州省过程工业技术研究中心 | Preparation method of titanium-based composite material anode for aluminum electrolysis |
| CN109935473A (en) * | 2019-03-29 | 2019-06-25 | 福州大学 | A kind of carbon nano tube-doped combination electrode material and preparation method thereof |
| CN111188052B (en) * | 2020-02-27 | 2021-01-12 | 上海广锋生物科技有限公司 | Preparation method of high-performance hypochlorous acid |
| CN113562812B (en) * | 2021-07-01 | 2022-11-22 | 河北科技大学 | Preparation method and application of composite electrode for treating high-chlorine organic wastewater |
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