CN102176385A - Electrochemical preparation method of ruthenium oxide electrode material - Google Patents
Electrochemical preparation method of ruthenium oxide electrode material Download PDFInfo
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- CN102176385A CN102176385A CN 201010593495 CN201010593495A CN102176385A CN 102176385 A CN102176385 A CN 102176385A CN 201010593495 CN201010593495 CN 201010593495 CN 201010593495 A CN201010593495 A CN 201010593495A CN 102176385 A CN102176385 A CN 102176385A
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Abstract
The invention discloses an electrochemical preparation method of a ruthenium oxide electrode material, belonging to a preparation method of the ruthenium oxide electrode material for a capacitor, and aims to provide a method for preparing ruthenium oxide electrode material, which is of simple process and has high specific capacity and low internal resistance. The method comprises the following steps: adding hydrochloric acid into 0.005-0.1 mol/L RuCl3 aqueous solution and adjusting the pH value to 1-5; inserting a collector, a reference electrode and an auxiliary electrode; and performing electrochemical cyclic voltammetry deposition with alternating current, wherein the initial level is (-1.4)-1.9 V, the final level is (-1.4)-1.9 V, the upper limit of level is 1.2-1.9 V, the lower limit of level is (-1.4)-(-0.6) V, the scanning rate speed is 1 mV/s-10 V/s, and the cycle index is 100-1,000. According to the invention, the prepared capacitor has large specific capacity, small internal resistance and fast charge/discharge; and the electrochemical preparation method is an ideal method for preparing the ruthenium oxide electrode material of the capacitor.
Description
Technical field: the present invention relates to a kind of method for preparing the capacitor ruthenium oxide electrode material, relate in particular to the preparation method of a kind of ultracapacitor with ruthenium oxide electrode material.
Background technology: ultracapacitor is meant that employing has material with carbon element or the metal oxide that quick faraday's reaction can take place in employing or a kind of electrochemical capacitor that conducting polymer is made as electrode material of high-specific surface area, its Capacity Ratio traditional capacitor Senior Three to four order of magnitude; The core of ultracapacitor is an electrode active material.In various active materials, the electric double layer energy storage that material with carbon element can only utilize its surface and electrolyte interface to form, specific capacity is lower, is difficult to surpass 200F/g.Conducting polymer can utilize body that faraday is taken place mutually to react energy storage, though theoretical specific capacity is higher, it is insulator when discharging fully, so actual specific capacity is still lower; In addition, because the volumetric expansion or the contraction that produce in the charge and discharge process make that the cycle life of conducting polymer is shorter.Metal oxide can utilize the energy storage of body phase equally, and therefore the high theoretical specific capacity is also arranged; But the conductivity of conventional metal oxide electrode material lower (as the conductivity of amorphous manganese dioxide less than 1S/cm), the electrode material internal resistance of preparation is big, power density is low.Ruthenium oxide electrode material not only have high theoretical specific capacity (＞1000F/g), and conductivity higher (＞100S/cm); In addition, ruthenium-oxide also has wide electrochemical window and good advantages such as cyclical stability, is a kind of different electrode material for super capacitor of best performance that is acknowledged as therefore.Usually, the method for preparing ruthenium oxide electrode material has chemical method and electrochemical process.
It is to prepare the ruthenium-oxide powder by chemical reaction earlier that chemical method prepares ruthenium oxide electrode material, adds binding agent and conductive agent then and makes slurry and be coated in the collector electrode surface.Therefore though this method is accomplished scale production easily, there are the following problems: (1) has added non-conductive in electrode material and usually has been hydrophobic binding agent, can increase the internal resistance of electrode material and reduces peak power output density (maximum power density P
Max=V
2/ (4R), V is a voltage, R is internal resistance); (2) can reduce internal resistance though add conductive agent, binding agent and conductive agent can obviously reduce the specific capacity of electrode material, thereby reduce the energy density and the power density of capacitor; (3) binding agent easily lost efficacy under hot environment, and adhesive failure rear oxidation ruthenium powder breaks away from collector electrode easily and causes electrode and whole ultracapacitor to lose efficacy; (4) the ruthenium-oxide thickness on collector electrode surface is difficult to accurate control.Electrochemical process prepares ruthenium oxide electrode material can directly become oxidative ruthenium membrane on the collector electrode surface, have technology and simply, do not need binding agent and conductive additive, internal resistance is low, capacity is high, thickness of electrode is even, plurality of advantages such as thickness can be by the deposition electric energy control, and production technology and equipment are full-fledged; But there is following defective in the electrochemical preparation ruthenium-oxide: the ruthenium-oxide sedimentation potential is higher, is difficult to directly at common metal collector electrode surface depositions such as titanium, tantalum and nickel.At present, adopt usually earlier and decompose one deck ruthenium-oxide as precoated shet, at precoated shet surface electrochemistry method deposition ruthenium-oxide, not only increased process complexity, and the ruthenium-oxide specific capacity of preparation is lower then at common metal collector electrode surface heats such as titanium, tantalum and nickel.Therefore, present electrode material for super capacitor based on ruthenium-oxide still adopts the chemical method preparation.
Summary of the invention: at the above-mentioned defective that exists in the prior art, the present invention aims to provide that a kind of technology is simple, specific capacity is high, internal resistance is low, can realize the electrochemical preparation method of the ruthenium oxide electrode material of large-scale production.
To achieve these goals, the present invention is by the following technical solutions:
1) to concentration is the RuCl of 0.005mol/L～0.1mol/L
3Add hydrochloric acid in the aqueous solution, regulate RuCl
3PH value of aqueous solution is 1～5;
2) to above-mentioned RuCl
3Insert collector electrode, reference electrode and auxiliary electrode in the aqueous solution, pass to alternating current then and carry out electrochemistry cyclic voltammetric deposition; Wherein, initial potential for-1.4V～1.9V, stop current potential for-1.4V～1.9V, upper limit current potential be 1.2V～1.9V, lower limit current potential for-1.4V～-0.6V, sweep speed are that 1mV/s～10V/s, cycle-index are 100～1000 times; Described current collection is tantalum electrode, titanium electrode or nickel electrode very, and described reference electrode is saturated calomel electrode, Ag electrode or AgCl electrode, and described auxiliary electrode is platinum electrode or graphite electrode;
3) take out collector electrode, washing, oven dry.
In technique scheme, RuCl
3The preferred concentration of the aqueous solution is 0.02mol/L～0.07mol/L, and preferred pH value is 2～4, and sweep speed is preferably 50mV/s～500mV/s; In technique scheme, RuCl
3The optium concentration of the aqueous solution is 0.045mol/L～0.055mol/L, and optimal pH is 3, and optimum scanning speed is 100mV/s～150mV/s.
Compared with the prior art, therefore the present invention has the following advantages owing to adopted technique scheme:
(1) metal Ru is deposited on the collector electrode when the negative scanning of circulation, and metal Ru is oxidized to the active oxidation ruthenium when circulation is just scanning; Therefore can directly on collector electrodes such as tantalum, titanium or nickel, deposit ruthenium-oxide, not need thermal decomposed deposition ruthenium-oxide precoated shet in advance; Technology is simple, is beneficial to large-scale production.
(2) because the metal Ru that is deposited on the collector electrode when negative scanning is a nanoscale, the ruthenium-oxide that is depositing when just scanning when circulation is a Nanoparticulate also, is different from the existing galvanostatic method block structure ruthenium-oxide that is similar to dry and cracked earth that electrochemical deposition goes out on the ruthenium-oxide precoated shet; Therefore the ruthenium-oxide that adopts the present invention to deposit has higher specific area, and electronics during capacitor charging/discharging, ion transfer path are shorter, and capacitor has higher specific capacity and charge-discharge performance faster.
(3) the present invention be owing to can directly prepare ruthenium-oxide on collector electrode, so electrode material need not to add additives such as binding agent and conductive agent; Adopt the present invention ruthenium-oxide collector electrode that obtains and advantages such as comparing of employing chemical method preparation has the specific capacity height, internal resistance is little.
Description of drawings:
Fig. 1 is a cyclic voltammetric Parameter Map of the present invention.
Embodiment: the invention will be further described below in conjunction with specific embodiment:
Embodiment 1
1) to concentration is the RuCl of 0.005mol/L
3Add hydrochloric acid in the aqueous solution, regulate RuCl
3PH value of aqueous solution is 1;
2) to above-mentioned RuCl
3Insert collector electrode, reference electrode and auxiliary electrode in the aqueous solution, pass to alternating current then and carry out electrochemistry cyclic voltammetric deposition; Wherein, initial potential for-1.2V, stop current potential for-1.2V, upper limit current potential be 1.6V, lower limit current potential for-1.2V, sweep speed be that 1mV/s, cycle-index are 100 times; Described collector electrode can be tantalum electrode, also can be titanium electrode or nickel electrode, and described reference electrode can be saturated calomel electrode, also can be Ag electrode or AgCl electrode that described auxiliary electrode can be platinum electrode or graphite electrode;
3) collector electrode is taken out, washing, oven dry get final product.
Embodiment 2
Each step is with embodiment 1, wherein: RuCl
3The concentration of the aqueous solution is 0.1mol/L, and the pH value is 5; Initial potential be 1.9V, termination current potential be 1.9V, upper limit current potential be 1.9V, lower limit current potential for-1.4V, sweep speed be that 10V/s, cycle-index are 1000 times.
Embodiment 3
Each step is with embodiment 1, wherein: RuCl
3Concentration of aqueous solution is 0.07mol/L, and the pH value is 2; Initial potential for-1.4V, stop current potential for-1.4V, upper limit current potential be 1.8V, lower limit current potential for-1.4V, sweep speed be that 50mV/s, cycle-index are 200 times.
Embodiment 4
Each step is with embodiment 1, wherein: RuCl
3Concentration of aqueous solution is 0.02mol/L, and the pH value is 4; Initial potential for-1.4V, stop current potential for-1.4V, upper limit current potential be 1.8V, lower limit current potential for-1.4V, sweep speed be that 500mV/s, cycle-index are 800 times.
Embodiment 5
Each step is with embodiment 1, wherein: RuCl
3Concentration of aqueous solution is 0.055mol/L, and the pH value is 3; Initial potential for-1.2V, stop current potential for-1.2V, upper limit current potential be 1.2V, lower limit current potential for-1.2V, sweep speed be that 100mV/s, cycle-index are 400 times.
Embodiment 6
Each step is with embodiment 1, wherein: RuCl
3Concentration of aqueous solution is 0.045mol/L, and the pH value is 3; Initial potential for-1.2V, stop current potential for-1.2V, upper limit current potential be 1.7V, lower limit current potential for-1.2V, sweep speed be that 150mV/s, cycle-index are 500 times.
Embodiment 7
Each step is with embodiment 1, wherein: RuCl
3Concentration of aqueous solution is 0.02mol/L, and the pH value is 2; Initial potential be 0V, termination current potential be 1.8V, upper limit current potential be 1.8V, lower limit current potential for-0.6V, sweep speed be that 100mV/s, cycle-index are 200 times.
Embodiment 8
Each step is with embodiment 1, wherein: RuCl
3Concentration of aqueous solution is 0.03mol/L, and the pH value is 2; Initial potential be 0V, termination current potential be 1.8V, upper limit current potential be 1.8V, lower limit current potential for-1.2V, sweep speed be that 500mV/s, cycle-index are 400 times.
As shown in Figure 1: when electrochemical deposition, the current potential in the various embodiments described above increases to upper limit current potential from initial potential gradually by the sweep speed of setting, and drops to the lower limit current potential gradually by sweep speed again, constantly moves in circles, until stopping current potential.
Claims (3)
1. the electrochemical preparation method of a ruthenium oxide electrode material is characterized in that concrete steps are as follows:
1) to concentration is the RuCl of 0.005mol/L～0.1mol/L
3Add hydrochloric acid in the aqueous solution, regulate RuCl
3PH value of aqueous solution is 1～5;
2) to above-mentioned RuCl
3Insert collector electrode, reference electrode and auxiliary electrode in the aqueous solution, pass to alternating current then and carry out electrochemistry cyclic voltammetric deposition; Wherein, initial potential for-1.4V～1.9V, stop current potential for-1.4V～1.9V, upper limit current potential be 1.2V～1.9V, lower limit current potential for-1.4V～-0.6V, sweep speed are that 1mV/s～10V/s, cycle-index are 100～1000 times; Described current collection is tantalum electrode, titanium electrode or nickel electrode very, and described reference electrode is saturated calomel electrode, Ag electrode or AgCl electrode, and described auxiliary electrode is platinum electrode or graphite electrode;
3) take out collector electrode, washing, oven dry.
2. the electrochemical preparation method of ruthenium oxide electrode material according to claim 1 is characterized in that: RuCl
3The concentration of the aqueous solution is 0.02mol/L～0.07mol/L, and the pH value is 2～4, and sweep speed is 50mV/s～500mV/s.
3. the electrochemical preparation method of ruthenium oxide electrode material according to claim 1 is characterized in that: RuCl
3The concentration of the aqueous solution is 0.045mol/L～0.055mol/L, and the pH value is 3, and sweep speed is 100mV/s～150mV/s.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102496473A (en) * | 2011-12-12 | 2012-06-13 | 中国振华（集团）新云电子元器件有限责任公司 | Method for preparing ruthenium oxide coating on inner wall of tantalum shell of electrolytic capacitor |
| CN103215628A (en) * | 2013-04-17 | 2013-07-24 | 中国石油大学(华东) | Method for electro-chemical compounding of graphene and metallic oxide |
| CN103422116A (en) * | 2013-08-15 | 2013-12-04 | 重庆大学 | Method for producing porous nickel-based ruthenium oxide composite hydrogen evolution electrode |
| CN108411349A (en) * | 2018-04-03 | 2018-08-17 | 西安交通大学 | A kind of porous RuO of graphene doping2The preparation method of anode |
| CN112225295A (en) * | 2020-10-19 | 2021-01-15 | 南京理工大学 | Tubular microporous titanium-based ruthenium oxide film anode applied to wastewater treatment and preparation method thereof |
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| US5369547A (en) * | 1993-03-22 | 1994-11-29 | The Evans Findings Co., Ltd. | Capacitor |
| US20070271751A1 (en) * | 2005-01-27 | 2007-11-29 | Weidman Timothy W | Method of forming a reliable electrochemical capacitor |
| CN101728084A (en) * | 2010-01-19 | 2010-06-09 | 西安华泰有色金属实业有限责任公司 | Method for preparing cathode of fully-sealed liquid mixed tantalum capacitor |
| CN101752089A (en) * | 2008-12-10 | 2010-06-23 | 阿维科斯公司 | Electrochemical capacitor containing ruthenium-oxide electrode |
| CN101819883A (en) * | 2009-03-14 | 2010-09-01 | 兰州理工大学 | Method for preparing mesoporous carbon composite material used for supercapacitor electrode |
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2010
- 2010-12-17 CN CN 201010593495 patent/CN102176385A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5369547A (en) * | 1993-03-22 | 1994-11-29 | The Evans Findings Co., Ltd. | Capacitor |
| US20070271751A1 (en) * | 2005-01-27 | 2007-11-29 | Weidman Timothy W | Method of forming a reliable electrochemical capacitor |
| CN101752089A (en) * | 2008-12-10 | 2010-06-23 | 阿维科斯公司 | Electrochemical capacitor containing ruthenium-oxide electrode |
| CN101819883A (en) * | 2009-03-14 | 2010-09-01 | 兰州理工大学 | Method for preparing mesoporous carbon composite material used for supercapacitor electrode |
| CN101728084A (en) * | 2010-01-19 | 2010-06-09 | 西安华泰有色金属实业有限责任公司 | Method for preparing cathode of fully-sealed liquid mixed tantalum capacitor |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102496473A (en) * | 2011-12-12 | 2012-06-13 | 中国振华（集团）新云电子元器件有限责任公司 | Method for preparing ruthenium oxide coating on inner wall of tantalum shell of electrolytic capacitor |
| CN103215628A (en) * | 2013-04-17 | 2013-07-24 | 中国石油大学(华东) | Method for electro-chemical compounding of graphene and metallic oxide |
| CN103215628B (en) * | 2013-04-17 | 2015-11-18 | 中国石油大学(华东) | A kind of method of electrochemical copolymerization Graphene and metal oxide |
| CN103422116A (en) * | 2013-08-15 | 2013-12-04 | 重庆大学 | Method for producing porous nickel-based ruthenium oxide composite hydrogen evolution electrode |
| CN103422116B (en) * | 2013-08-15 | 2016-08-17 | 重庆大学 | A kind of porous Ni-base ru oxide is combined the preparation method of hydrogen-precipitating electrode |
| CN108411349A (en) * | 2018-04-03 | 2018-08-17 | 西安交通大学 | A kind of porous RuO of graphene doping2The preparation method of anode |
| CN112225295A (en) * | 2020-10-19 | 2021-01-15 | 南京理工大学 | Tubular microporous titanium-based ruthenium oxide film anode applied to wastewater treatment and preparation method thereof |
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Application publication date: 20110907 |