CN102923797A - Method for preparing high-dispersion high-activity hydration ruthenium dioxide electrode material - Google Patents
Method for preparing high-dispersion high-activity hydration ruthenium dioxide electrode material Download PDFInfo
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- CN102923797A CN102923797A CN2012104379380A CN201210437938A CN102923797A CN 102923797 A CN102923797 A CN 102923797A CN 2012104379380 A CN2012104379380 A CN 2012104379380A CN 201210437938 A CN201210437938 A CN 201210437938A CN 102923797 A CN102923797 A CN 102923797A
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Abstract
The invention discloses a method for preparing a high-dispersion high-activity hydration ruthenium dioxide electrode material. The method is characterized by comprising steps of adding a certain amount of anionic surfactant in a reaction system for preparing hydration ruthenium dioxide, strictly controlling a potential of hydrogen (PH) value and temperature before reaction of the system, adding reactants, depressurizing, cleaning by water, filtering, drying, sintering and conducting mall milling. Compared with the prior art, the prepared hydration ruthenium dioxide electrode has high dispersion and specific capacitance and can be used in chemical energy storage fields of national defense and civilian use widely.
Description
Technical field
The present invention relates to field of chemical power source, relate to especially a kind of high dispersive, high reactivity hydration ruthenium dioxide electrochemical electrode material preparation method.
Background technology
Along with the attention of national governments to new forms of energy and correlation function material, increasing investigator and mechanism begin to pay attention to ultracapacitor (Supercapacitor, Ultracapacitor) development, its major cause is that as a kind of model electrochemical energy storage device, ultracapacitor combines the advantage of traditional physical capacitor and chemical cell, on the one hand, with respect to physical capacitor, it has higher energy density, and electrostatic capacity can reach hundreds of even thousands of farads; On the other hand, compare battery, it has higher power density and the cycle life of overlength.Therefore, at new energy field, the future prospect of ultracapacitor is extensively had an optimistic view of.
Difference according to energy storage principle, ultracapacitor generally is divided into two large classes: a class is based on the formed electrical double layer of electrode/electrolyte interface charge separation (Electrical Double Layer) principle energy storage, another kind ofly is based on fast faraday's " pseudo-capacitance " principle energy storage of producing of redox reaction of electrode surface.Different according to the electrode structure classification, ultracapacitor can be divided into again symmetric form (Symmetric) and asymmetric (Asymmetric; Also claim mixed type, Hybrid) two classes, the former is the most common with activated carbon-activated carbon (CC), most typical example is the product of U.S. Maxwell company, the latter is the most common with activated carbon-metal oxide (CMO), and typical example is activated carbon-nickel oxide (CNiO) and tantalum oxide-ruthenium dioxide (TaRuO).Wherein, hydration ruthenium dioxide (RuO
2.xH
2O) has high ratio electric capacity (specific activity carbon is large more than 1 times) and the general electroconductibility of metal, therefore, has important application in the national defence such as military aerospace and specific area, particularly anode is that tantalum pentoxide, negative electrode are the hybrid super capacitor that the hydration ruthenium dioxide consists of, and monopolizes the world in the national defence field because it has excellent frequency response characteristic and high low-temperature stability.
In existing technology, as the core component of tantalum ruthenium ultracapacitor, hydration ruthenium dioxide material preparation mainly contain 3 kinds [Yin Binchuan, Guo Li etc. the progress of ruthenium oxide electrode of super capacitor material
. power technology, 2006,130 (6): 436-438], a kind of is that direct heat is decomposed, its advantage is that preparation technology is simple, but shortcoming is than electric capacity lower (being generally less than 380F/g); Another kind is colloid method, namely reacts in the colloid environment and carries out, and the ratio electric capacity of gained is higher; Also having a kind of method is exactly electrochemical process, but electrochemical production technique is comparatively complicated, and is difficult for extensive preparation.At present, improved colloid method (being the collosol and gel method) is because the preparation method is relatively simple, required equipment and control condition are less, and easily extensive preparation and being widely adopted.But the technical problem underlying that the method exists is product particle large (generally greater than 5 μ m), dispersed bad, this means that the part material can not bring into play its active function, cause the consumption of ruthenium dioxide to increase, because ruthenium is precious metal element, consider from the cost aspect, need further to solve technically.And not yet have relevant technology to occur at present.
Summary of the invention
The object of the invention is to overcome deficiency of the prior art, propose a kind of high dispersive, high reactivity hydration ruthenium dioxide electrochemical electrode material preparation method.
The present invention proposes a kind of high dispersive, high reactivity hydration ruthenium dioxide electrode materials preparation method, it is characterized in that comprising the steps:
1) in the reaction synthetic system of preparation hydration ruthenium dioxide, adds the doses anion surfactant;
2) strictly control front pH value and the temperature of synthetic system reaction;
3) add reactant;
4) decompression washing filtering, drying, sintering, ball milling.
Wherein, the reaction synthetic system of described preparation hydration ruthenium dioxide is the reaction synthetic system of ruthenium trichloride and bicarbonate of ammonia or volatile salt or sodium bicarbonate or yellow soda ash.
Wherein, described anion surfactant is one or more in sodium lauryl sulfate, sodium dodecyl benzenylsulfonate, Lamepon A, acetoxyl sodium laurylsulfonate, lauroyl methylamine sodium acetate, the alkyl polyoxyethylene ether sodium sulfate.
Wherein, the add-on of described anion surfactant is the 0.05%-5.0% mass percent.
Wherein, described pH value is between 5.5-8.5.
Wherein, described temperature of reaction is between-20-60 ℃.，
With respect to prior art, the hydration ruthenium dioxide electrode of the present invention preparation has higher dispersed and than electric capacity, can be widely used in national defence and the chemical energy storage field such as civilian.
Embodiment
Describe technical scheme of the present invention in detail below in conjunction with specific embodiment.
Embodiment 1:
Under 25 ℃ of envrionment conditionss, the commercially available ruthenium trichloride of 15g is dissolved in the 150ml deionized water, add respectively 2ml methyl alcohol/anhydrous hydrochloric acid mixed solution in the dissolution process, strong stirring 15 minutes, continuing in the situation about stirring, add the 10mg sodium dodecyl benzenylsulfonate to system, continue to stir, continue simultaneously to add deionized water until the pH value of solution reaches 5.9.Adopting spray pattern is the bicarbonate of ammonia adding reaction system of 1.0M with concentration, continues stirring reaction liquid, until the end that reacts completely.The reaction system ageing washing filtering that reduces pressure after 10 hours is obtained filter cake 3 times.60 ℃ of forced air dryings of filter cake were ground into fine particle after 6 hours, then place retort furnace to carry out sintering 8 hours, sintering temperature is 175 ℃, ball milling after 80 ℃ of dryings, obtain at last hydration ruthenium dioxide product of the present invention, the laser particle size measurement result shows that the median size of this material is 1.1 μ m, and electrochemistry cyclic voltammetry experiment test result shows, under the sweep velocity of 1mV/s, material has the ratio electric capacity of 832F/g.
Embodiment 2:
Under 25 ℃ of envrionment conditionss, 10g analytical pure ruthenium trichloride is dissolved in the 150ml deionized water, add respectively 1ml methyl alcohol in the dissolution process, strong stirring 15 minutes, continuing in the situation about stirring, add the 15mg sodium lauryl sulfate to system, continue to stir, continue simultaneously to add deionized water until the pH value of solution reaches 6.2.Adopting spray pattern is the sodium bicarbonate adding reaction system of 1.0M with concentration, continues stirring reaction liquid, until the end that reacts completely.The reaction system ageing washing filtering that reduces pressure after 10 hours is obtained filter cake 3 times.60 ℃ of forced air dryings of filter cake were ground into fine particle after 6 hours, then place retort furnace to carry out sintering 8 hours, sintering temperature is 175 ℃, ball milling after 80 ℃ of dryings, obtain at last hydration ruthenium dioxide product of the present invention, the laser particle size measurement result shows that the median size of this material is 1.4 μ m, and electrochemistry cyclic voltammetry experiment test result shows, under the sweep velocity of 1mV/s, material has the ratio electric capacity of 810F/g.
Embodiment 3:
Under 15 ℃ of envrionment conditionss, 20g analytical pure ruthenium trichloride is dissolved in the 150ml deionized water, add respectively 1ml methyl alcohol in the dissolution process, strong stirring 15 minutes, continuing in the situation about stirring, add 13mg acetoxyl sodium laurylsulfonate to system, continue to stir, continue simultaneously to add deionized water until the pH value of solution reaches 6.4.Adopting spray pattern is the sodium bicarbonate adding reaction system of 1.0M with concentration, continues stirring reaction liquid, until the end that reacts completely.The reaction system ageing washing filtering that reduces pressure after 10 hours is obtained filter cake 3 times.60 ℃ of forced air dryings of filter cake were ground into fine particle after 6 hours, then place retort furnace to carry out sintering 8 hours, sintering temperature is 175 ℃, ball milling after 80 ℃ of dryings, obtain at last hydration ruthenium dioxide product of the present invention, the laser particle size measurement result shows that the median size of this material is 1.6 μ m, and electrochemistry cyclic voltammetry experiment test result shows, under the sweep velocity of 1mV/s, material has the ratio electric capacity of 814F/g.
Embodiment 4:
Under 10 ℃ of envrionment conditionss, 20g analytical pure ruthenium trichloride is dissolved in the 150ml deionized water, add respectively 1ml methyl alcohol in the dissolution process, strong stirring 15 minutes, continuing in the situation about stirring, add the 15mg Lamepon A to system, continue to stir, continue simultaneously to add deionized water until the pH value of solution reaches 6.6.Adopting spray pattern is the sodium bicarbonate adding reaction system of 1.0M with concentration, continues stirring reaction liquid, until the end that reacts completely.The reaction system ageing washing filtering that reduces pressure after 10 hours is obtained filter cake 3 times.60 ℃ of forced air dryings of filter cake were ground into fine particle after 6 hours, then place retort furnace to carry out sintering 8 hours, sintering temperature is 175 ℃, ball milling after 80 ℃ of dryings, obtain at last hydration ruthenium dioxide product of the present invention, the laser particle size measurement result shows that the median size of this material is 1.3 μ m, and electrochemistry cyclic voltammetry experiment test result shows, under the sweep velocity of 1mV/s, material has the ratio electric capacity of 821F/g.
Embodiment 5:
As different from Example 1, the system temperature of reaction is under 0 ℃ of envrionment conditions, and the pH value of reacting precursor system is controlled at 6.1.Obtain at last hydration ruthenium dioxide product of the present invention, the laser particle size measurement result shows that the median size of this material is 1.0 μ m, and electrochemistry cyclic voltammetry experiment test result shows that under the sweep velocity of 1mV/s, material has the ratio electric capacity of 850F/g.
Embodiment 6:
As different from Example 3, system has added 8mg acetoxyl sodium laurylsulfonate and 9mg Lamepon A, and the pH value of reacting precursor system is controlled at 6.5.Obtain at last hydration ruthenium dioxide product of the present invention, the laser particle size measurement result shows that the median size of this material is 1.3 μ m, and electrochemistry cyclic voltammetry experiment test result shows that under the sweep velocity of 1mV/s, material has the ratio electric capacity of 825F/g.
With respect to prior art, the hydration ruthenium dioxide electrode of the present invention preparation has higher dispersed and than electric capacity, can be widely used in national defence and the chemical energy storage field such as civilian.
Described in this specification sheets is preferred embodiment of the present invention, and above embodiment is only in order to illustrate technical scheme of the present invention but not limitation of the present invention.All those skilled in the art all should be within the scope of the present invention under this invention's idea by the available technical scheme of logical analysis, reasoning, or a limited experiment.
Claims (6)
1. a high dispersive, high reactivity hydration ruthenium dioxide electrode materials preparation method is characterized in that comprising the steps:
1) in the reaction system of preparation hydration ruthenium dioxide, adds the doses anion surfactant;
2) pH value and the temperature before the strict hierarchy of control reaction;
3) add reactant;
4) decompression washing filtering, drying, sintering, ball milling.
2. preparation method as claimed in claim 1, the reaction system that it is characterized in that described preparation hydration ruthenium dioxide is the reaction system of ruthenium trichloride and bicarbonate of ammonia or volatile salt or sodium bicarbonate or yellow soda ash.
3. preparation method as claimed in claim 1 is characterized in that described anion surfactant is one or more in sodium lauryl sulfate, sodium dodecyl benzenylsulfonate, Lamepon A, acetoxyl sodium laurylsulfonate, lauroyl methylamine sodium acetate, the alkyl polyoxyethylene ether sodium sulfate.
4. preparation method as claimed in claim 1, the add-on that it is characterized in that described anion surfactant is the 0.05%-5.0% mass percent.
5. preparation method as claimed in claim 1 is characterized in that described pH value is between 5.5-8.5.
6. preparation method as claimed in claim 1 is characterized in that described temperature of reaction is between-20-60 ℃.
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Cited By (5)
| 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 |
| CN104961165A (en) * | 2015-06-19 | 2015-10-07 | 东华大学 | Surface-modified ruthenium oxide hydrate, preparation thereof and application of surface-modified ruthenium oxide hydrate |
| CN105271446A (en) * | 2015-09-28 | 2016-01-27 | 中国船舶重工集团公司第七一二研究所 | Preparation method of hydrous ruthenium dioxide for resistance slurry |
| CN106952745A (en) * | 2017-03-14 | 2017-07-14 | 苏州海凌达电子科技有限公司 | A kind of preparation method of ultracapacitor ruthenium-oxide based combined electrode material |
| CN116550321A (en) * | 2023-05-22 | 2023-08-08 | 康纳新型材料(杭州)有限公司 | High-dispersity ruthenium catalyst for preparing chlorine by hydrogen chloride oxidation and preparation method thereof |
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| CN101269851A (en) * | 2008-04-23 | 2008-09-24 | 江苏集晟电子科技有限公司 | Method for preparing ruthenium oxide electrode material |
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Cited By (6)
| 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 |
| CN104961165A (en) * | 2015-06-19 | 2015-10-07 | 东华大学 | Surface-modified ruthenium oxide hydrate, preparation thereof and application of surface-modified ruthenium oxide hydrate |
| CN105271446A (en) * | 2015-09-28 | 2016-01-27 | 中国船舶重工集团公司第七一二研究所 | Preparation method of hydrous ruthenium dioxide for resistance slurry |
| CN106952745A (en) * | 2017-03-14 | 2017-07-14 | 苏州海凌达电子科技有限公司 | A kind of preparation method of ultracapacitor ruthenium-oxide based combined electrode material |
| CN116550321A (en) * | 2023-05-22 | 2023-08-08 | 康纳新型材料(杭州)有限公司 | High-dispersity ruthenium catalyst for preparing chlorine by hydrogen chloride oxidation and preparation method thereof |
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Application publication date: 20130213 |