CN102969171A - Preparation method of non-stoichiometry ruthenium dioxide electrode material - Google Patents
Preparation method of non-stoichiometry ruthenium dioxide electrode material Download PDFInfo
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- CN102969171A CN102969171A CN2012104380053A CN201210438005A CN102969171A CN 102969171 A CN102969171 A CN 102969171A CN 2012104380053 A CN2012104380053 A CN 2012104380053A CN 201210438005 A CN201210438005 A CN 201210438005A CN 102969171 A CN102969171 A CN 102969171A
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Abstract
The invention provides a preparation method of a non-stoichiometry ruthenium dioxide electrode material. The preparation method is characterized by including the following steps of strictly controlling a potential of hydrogen (PH) value before synthesis system reaction during preparation of a non-stoichiometry ruthenium dioxide synthesis system; adding reactants; adding oxidizing agents to oxidize simple substance ruthenium remained in the synthesis system into ruthenium dioxide; removing the oxidizing agents and other reaction by-products; and performing pressure-reduction washing and filtering, drying, sintering and ball-milling. Compared with preparation methods in prior art, the preparation method has the advantages that obtained non-stoichiometry ruthenium dioxide electrodes have higher specific capacitance, multiplying power characteristics and cycling stability, and the method can be widely applied to fields of national defense and civil energy storage.
Description
Technical field
The present invention relates to field of chemical power source, relate to especially a kind of non-stoichiometry ruthenic oxide electrode material preparation method.
Background technology
Ultracapacitor (Super capacitor, Ultra capacitor) claims that again " electrochemical capacitor (Electrochemical Capacitor, EC) " is a kind of new chemical energy storage device between traditional capacitor and battery.Compare traditional capacitor, it has higher energy density, and static capacity can reach hundreds of even thousands of farads; Compare battery, it has higher power density and the cycle life of overlength, so it combines the advantage of traditional capacitor and battery, is a kind of chemical power source that has a extensive future.It has the specific capacity height, power is large, the life-span is long, the warm limit for width of working, the characteristics such as non-maintaining.
Difference according to energy storage principle, ultracapacitor generally is divided into two large classes: a class is based on the formed electric double layer of electrode/electrolyte interface separation of charge (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; Sometimes 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-ruthenic oxide (TaRuO).Wherein, (people are usually with " hydration ruthenic oxide (RuO for non-stoichiometric ruthenic oxide
2.xH
2O) " expression) has high ratio electric capacity (specific activity carbon is large more than 1 times) and the general conductivity of metal; therefore; have 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 ruthenic oxide consists of, because its frequency response characteristic and high low-temperature stability with excellence is monopolized the world in the national defence field.
In existing technology, as the core component of tantalum ruthenium ultracapacitor, during non-stoichiometry hydration ruthenic oxide material preparation is improving and optimizes always.At present, improved colloid method (being the collosol and gel method) is owing to the preparation method is relatively simple, equipment needed thereby and controlled condition is less is widely adopted.But being prepared material, the greatest problem of the method comprises the inactive metal Ru simple substance of part.Owing to do not possess electro-chemical activity, the existence of ruthenium simple substance has not only limited the performance of ruthenic oxide height ratio capacity greatly, and has a strong impact on the quality of tantalum ruthenium capacitor product.Through retrieval, not yet there is relevant technology to come out at present.
Summary of the invention
The object of the invention is to overcome deficiency of the prior art, propose a kind of preparation method of non-stoichiometry ruthenic oxide electrode material, remove metal Ru simple substance wherein, improve the quality of tantalum ruthenium capacitor product.
The present invention proposes a kind of non-stoichiometry ruthenic oxide electrode material preparation method, it is characterized in that comprising the steps: 1) in the reaction synthetic system of preparation non-stoichiometry ruthenic oxide, strictly control the front pH value of synthetic system reaction; 2) add reactant; 3) add oxidant, simple substance ruthenium remaining in the synthetic system is oxidized to ruthenic oxide; 4) remove oxidant and other byproducts of reaction; 5) decompression washing filtering, drying, sintering, ball milling.
Wherein, the reaction synthetic system of described preparation non-stoichiometry ruthenic oxide is the reaction synthetic system of ruthenium trichloride and carbonic hydroammonium or ammonium carbonate or sodium acid carbonate or sodium carbonate.
Wherein, described oxidant is one of ozone, oxygen difluoride, perchloric acid, hyperbromic acid, hypochlorous acid, hypoiodous acid, hypobromous acid, dichromic acid, persulfuric acid or hydrogen peroxide.
Wherein, described pH value is between 3.5-8.5.
With respect to prior art, the non-stoichiometry ruthenic oxide electrode that uses preparation method of the present invention to obtain has higher ratio electric capacity, multiplying power property and cyclical stability, can be widely used in national defence and civilian energy storage field.
Embodiment
Describe technical scheme of the present invention in detail below in conjunction with specific embodiment.
Embodiment 1:
The commercially available technical pure ruthenium trichloride of 10g is dissolved in the 150ml deionized water, add respectively the anhydrous low mass molecule alcohol of 5ml (methyl alcohol) and fuming hydrochloric acid in the course of dissolution, strong stirring 30 minutes, continuing in the situation about stirring until completely dissolved, continue to add deionized water, and continue to stir until the pH value of solution reaches 4.5.Adopting spray pattern is the carbonic hydroammonium adding reaction system of 0.5M with concentration.In the situation that continues stirring reaction liquid, adopt spray pattern, in system, add 5ml perchloric acid, continue stirring reaction liquid and leave standstill after 30 minutes, the ageing washing filtering that reduces pressure after 10 hours obtains filter cake 3 times.60 ℃ of forced air dryings of filter cake were ground into fine particle after 6 hours, then place Muffle furnace to carry out sintering 8 hours, sintering temperature is 175 ℃, ball milling after 80 ℃ of dryings, obtain at last non-stoichiometry ruthenic oxide product of the present invention, electrochemistry cyclic voltammetry experiment test result shows, under the sweep speed of 1mV/s, material has the ratio electric capacity of 910F/g, only be 8% than capacitance fade under the 50mV/s sweep speed, 2000 times the cyclical stability test result shows, this material ratio capacitance fade under the same conditions only is 4%, and material does not find to contain zeroth order simple substance ruthenium through detecting.
Embodiment 2:
The commercially available technical pure ruthenium trichloride of 20g is dissolved in the 150ml deionized water, add respectively the anhydrous low mass molecule alcohol of 8ml (ethylene glycol) and fuming hydrochloric acid in the course of dissolution, strong stirring 30 minutes, continuing in the situation about stirring until completely dissolved, continue to add deionized water, and continue to stir until the pH value of solution reaches 5.3.Adopting spray pattern is the sodium acid carbonate adding reaction system of 0.5M with concentration.In the situation that continues stirring reaction liquid, pass into ozone to reaction system and leave standstill after 60 minutes, the ageing washing filtering that reduces pressure after 8 hours obtains filter cake 3 times.60 ℃ of forced air dryings of filter cake were ground into fine particle after 6 hours, then place Muffle furnace to carry out sintering 8 hours, sintering temperature is 145 ℃, ball milling after 80 ℃ of dryings, obtain at last non-stoichiometry ruthenic oxide product of the present invention, electrochemistry cyclic voltammetry experiment test result shows, under the sweep speed of 1mV/s, material has the ratio electric capacity of 880F/g, only be 7% than capacitance fade under the 50mV/s sweep speed, 2000 times the cyclical stability test result shows, this material ratio capacitance fade under the same conditions only is 3%, and material detects through XPS and do not find to contain zeroth order simple substance ruthenium.
Embodiment 3:
The commercially available technical pure ruthenium trichloride of 10g is dissolved in the 150ml deionized water, add respectively the anhydrous low mass molecule alcohol of 5ml (isopropyl alcohol) and fuming hydrochloric acid in the course of dissolution, strong stirring 30 minutes, continuing in the situation about stirring until completely dissolved, continue to add deionized water, until the pH value of solution reaches 6.7.Adopting spray pattern is the carbonic hydroammonium adding reaction system of 0.5M with concentration, in the situation that continues stirring reaction liquid, adopt spray pattern, in system, add the 4ml hydrogen peroxide, continue stirring reaction liquid and leave standstill after 30 minutes, the ageing washing filtering that reduces pressure after 10 hours obtains filter cake 3 times.60 ℃ of forced air dryings of filter cake were ground into fine particle after 6 hours, then place Muffle furnace to carry out sintering 8 hours, sintering temperature is 160 ℃, ball milling after 80 ℃ of dryings, obtain at last non-stoichiometry ruthenic oxide product of the present invention, electrochemistry cyclic voltammetry experiment test result shows, under the sweep speed of 1mV/s, material has the ratio electric capacity of 900F/g, only be 10% than capacitance fade under the 50mV/s sweep speed, 2000 times the cyclical stability test result shows, this material ratio capacitance fade under the same conditions only is 6%, and material detects through XPS and do not find to contain zeroth order simple substance ruthenium.
Embodiment 4:
The commercially available technical pure ruthenium trichloride of 15g is dissolved in the 150ml deionized water, add respectively the anhydrous low mass molecule alcohol of 6ml (ethanol) and fuming hydrochloric acid in the course of dissolution, strong stirring 30 minutes, continuing in the situation about stirring until completely dissolved, continue to add deionized water, until the pH value of solution reaches 6.4.Adopting spray pattern is the sodium acid carbonate adding reaction system of 0.5M with concentration, in the situation that continues stirring reaction liquid, adopt spray pattern, in system, add the 5ml hypoiodous acid, continue stirring reaction liquid and leave standstill after 30 minutes, the ageing washing filtering that reduces pressure after 10 hours obtains filter cake 3 times.60 ℃ of forced air dryings of filter cake were ground into fine particle after 6 hours, then place Muffle furnace to carry out sintering 8 hours, sintering temperature is 155 ℃, ball milling after 80 ℃ of dryings, obtain at last non-stoichiometry ruthenic oxide product of the present invention, electrochemistry cyclic voltammetry experiment test result shows, under the sweep speed of 1mV/s, material has the ratio electric capacity of 905F/g, only be 11% than capacitance fade under the 50mV/s sweep speed, 2000 times the cyclical stability test result shows, this material ratio capacitance fade under the same conditions only is 7%, and material detects through XPS and do not find to contain zeroth order simple substance ruthenium.
Embodiment 5:
The commercially available technical pure ruthenium trichloride of 15g is dissolved in the 150ml deionized water, and strong stirring 40 minutes is continuing in the situation about stirring until completely dissolved, continues to add deionized water, until the pH value of solution reaches 6.8.Adopting spray pattern is the carbonic hydroammonium adding reaction system of 0.5M with concentration, in the situation that continues stirring reaction liquid, adopt spray pattern, in system, add 4ml hypochlorous acid, continue stirring reaction liquid and leave standstill after 30 minutes, the ageing washing filtering that reduces pressure after 10 hours obtains filter cake 3 times.60 ℃ of forced air dryings of filter cake were ground into fine particle after 6 hours, then place Muffle furnace to carry out sintering 8 hours, sintering temperature is 155 ℃, ball milling after 80 ℃ of dryings, obtain at last non-stoichiometry ruthenic oxide product of the present invention, electrochemistry cyclic voltammetry experiment test result shows, under the sweep speed of 1mV/s, material has the ratio electric capacity of 860F/g, only be 10% than capacitance fade under the 50mV/s sweep speed, 2000 times the cyclical stability test result shows, this material ratio capacitance fade under the same conditions only is 9%, and material detects through XPS and do not find to contain zeroth order simple substance ruthenium.
Embodiment 6:
As different from Example 5, bringing Selection In property oxidant is for passing into ozone, the hydration ruthenic oxide product that obtains at last, electrochemistry cyclic voltammetry experiment test result shows that under the sweep speed of 1mV/s, material has the ratio electric capacity of 890F/g, only be 6.5% than capacitance fade under the 50mV/s sweep speed, 2000 times the cyclical stability test result shows, this material ratio capacitance fade under the same conditions only is 7.5%, and material detects through XPS and do not find to contain zeroth order simple substance ruthenium.
Embodiment 7:
As different from Example 5, bringing Selection In property oxidant is hydrogen peroxide, the hydration ruthenic oxide product that obtains at last, electrochemistry cyclic voltammetry experiment test result shows that under the sweep speed of 1mV/s, material has the ratio electric capacity of 877F/g, only be 6.9% than capacitance fade under the 50mV/s sweep speed, 2000 times the cyclical stability test result shows, this material ratio capacitance fade under the same conditions only is 8.2%, and material detects through XPS and do not find to contain zeroth order simple substance ruthenium.
Embodiment 8:
As different from Example 5, bringing Selection In property oxidant is persulfuric acid, the hydration ruthenic oxide product that obtains at last, electrochemistry cyclic voltammetry experiment test result shows that under the sweep speed of 1mV/s, material has the ratio electric capacity of 847F/g, only be 8.8% than capacitance fade under the 50mV/s sweep speed, 2000 times the cyclical stability test result shows, this material ratio capacitance fade under the same conditions only is 7.4%, and material detects through XPS and do not find to contain zeroth order simple substance ruthenium.
With respect to prior art, the non-stoichiometry ruthenic oxide electrode that uses preparation method of the present invention to obtain has higher ratio electric capacity, multiplying power property and cyclical stability, can be widely used in national defence and civilian energy storage field.
Described in this specification 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 (4)
1. a non-stoichiometry ruthenic oxide electrode material preparation method is characterized in that comprising the steps:
1) in the synthetic system of preparation non-stoichiometry ruthenic oxide, strictly controls the front pH value of synthetic system reaction;
2) add reactant;
3) add oxidant, simple substance ruthenium remaining in the synthetic system is oxidized to ruthenic oxide;
4) remove oxidant and other byproducts of reaction;
5) decompression washing filtering, drying, sintering, ball milling.
2. preparation method as claimed in claim 1, the synthetic system that it is characterized in that described preparation non-stoichiometry ruthenic oxide is the synthetic system of ruthenium trichloride and carbonic hydroammonium or ammonium carbonate or sodium acid carbonate or sodium carbonate.
3. preparation method as claimed in claim 1 is characterized in that described oxidant is one of ozone, oxygen difluoride, perchloric acid, hyperbromic acid, hypochlorous acid, hypoiodous acid, hypobromous acid, dichromic acid, persulfuric acid or hydrogen peroxide.
4. preparation method as claimed in claim 1 is characterized in that described pH value is between 3.5-8.5.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1806914A (en) * | 2006-02-23 | 2006-07-26 | 华南理工大学 | Method for preparing carbon nanotube supported nanometer hydrated ruthenium oxide |
| CN101797649A (en) * | 2010-01-19 | 2010-08-11 | 兰州大学 | Method and device for preparing high-purity ruthenium |
| CN102005307A (en) * | 2010-09-28 | 2011-04-06 | 中国科学院电工研究所 | Preparation method of graphene supported ruthenium oxide electrode materials |
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- 2012-11-06 CN CN2012104380053A patent/CN102969171A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1806914A (en) * | 2006-02-23 | 2006-07-26 | 华南理工大学 | Method for preparing carbon nanotube supported nanometer hydrated ruthenium oxide |
| CN101797649A (en) * | 2010-01-19 | 2010-08-11 | 兰州大学 | Method and device for preparing high-purity ruthenium |
| CN102005307A (en) * | 2010-09-28 | 2011-04-06 | 中国科学院电工研究所 | Preparation method of graphene supported ruthenium oxide electrode materials |
Non-Patent Citations (1)
| Title |
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| 徐艳: "电化学电容器钽基氧化钌电极的制备和性能研究", 《工程科技Ⅱ辑》 * |
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Application publication date: 20130313 |