CN101525760A - Electrodeposition technology for preparing electrode material of RuO2 of super capacitor - Google Patents
Electrodeposition technology for preparing electrode material of RuO2 of super capacitor Download PDFInfo
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- CN101525760A CN101525760A CN 200910043146 CN200910043146A CN101525760A CN 101525760 A CN101525760 A CN 101525760A CN 200910043146 CN200910043146 CN 200910043146 CN 200910043146 A CN200910043146 A CN 200910043146A CN 101525760 A CN101525760 A CN 101525760A
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- Y02E60/13—Energy storage using capacitors
Abstract
The invention relates to a DC-differential pulse combined electrodeposition technology for preparing an electrode material of RuO2 of a super capacitor. The technology comprises the following steps: adopting a metal foil with the purity larger than 99.95 percent as a basal piece, preparing a mixed solution of RuCl3.3H2O, SnCl2 and NaNO3 with the concentrations of 1 to 5mmol/L, 0.2 to 1mmol/L and 10 to 200mmol/L, and fully stirring and standing; using graphite as an anode and the metal foil as a cathode, firstly sedimentating with 1 to 3mA/cm<2> of DC for 0.5 hour to 1 hour, and then adopting a differential pulse current to sedimentate for 2 hours to 3 hours with the voltage pulse width of 1 to 10sec, the pulse period of 2 to 20sec, the amplitude of 0.01 to 0.02mA/cm<2>, the point voltage gain of 0.005 to 0.01mA/cm<2> and the final current concentration of 5 to 8mA/cm<2>; and preparing a film precursor of RuCl3.3H2O, naturally airing and processing a film at 200 DEG C to 500 DEG C with the heating speed of 10 DEG C/s and the heat-preservation time of 2 hours to 3 hours. The firstly proposed DC-differential pulse combined electrodeposition technology for preparing the film of RuO2 has simple process and simple and convenient operation, has a certain industrial value. An electrochemical tester CHI660C is used for testing the electrochemical performance of the film material, and adhesive force is tested by a drawing method of GB5210-82 to obtain the test results: the specific capacitance reaches 720F/g, and the adhesive force reaches 11.3MPa.
Description
Technical field
The present invention relates to the electrochemical capacitor field, is a kind of method of prepared by electrodeposition ultracapacitor coating electrode material.
Background technology
Along with high-end electronic devices develops towards miniaturization, lightweight, highly reliable, long-life direction, the electrical condenser in the electron device must be big to capacity, volume is little, power density is high and the direction of impulsive discharge excellent performance develops.Traditional electrical condenser can not satisfy the requirement of high-end electronic devices, ultracapacitor decuples the specific power of store battery with its number, hundreds of times to the specific energy of physical capacitor, and efficiency for charge-discharge height, can continue to emit big electric current, do not need maintaining, characteristics such as the life-span is long, be widely used in fields such as Aeronautics and Astronautics, science and techniques of defence, mobile communication, electronic information technology, environmental protection energy industry, electromobile, extremely wide application prospect and important strategic meaning are being arranged.
According to the storage mechanism of electric charge, ultracapacitor can be divided into double layer capacitor and faraday's standard (counterfeit) electrical condenser, and double layer capacitor uses carbon materials as electrode, than electric capacity about 200F/g.The pseudo capacitance device uses RuO
2, MnO
2, NiO, SnO
2As electrode, finish to discharge and recharge Deng metal oxide by faraday's redox reaction.RuO wherein
2H
2O electrode materials specific capacitance can be up to more than the 700F/g, and specific capacitance is bigger 3 times than carbon dioxide process carbon electrode, and specific power is than big 1 order of magnitude of carbon dioxide process carbon electrode, and stable performance in sulfuric acid electrolyte has extended cycle life and the charge-discharge performance excellence, so RuO
2H
2O is applied to the different electrode materials of high specific energy ultracapacitor best performance at present, has demonstrated important status and wide application prospect, is containing huge business opportunity.
RuO
2H
2O electrode materials performance is the key factor that directly influences the ultracapacitor overall performance, accounts for more than 50% of ultracapacitor manufacturing cost.The RuO of different shape structure
2H
2Ratio electric capacity and the energy density of O differ greatly, to microvoid structure RuO
2H
2The highly quick redox reaction of reversible because electrolytic solution enters active substance inside easily, can take place in that electrode active material surface and body are equal in mutually in the O electrode materials; RuO with crystalline structure
2H
2O compares, and proton is easier of unformed RuO
2H
2Freely spread RuO among the O
2H
2The O electrode materials has bigger ratio electric capacity.Therefore, the preparation of development high performance electrode material and the important topic that to disclose its Effect on Performance rule be material supplier author.The RuO of present report
2The preparation method of electrode materials mainly contains as Sol-gel method, coating thermolysis.But be equipped with RuO with the Sol-gel legal system
2Adhesive force is relatively poor; Prepared RuO with high temperature methods such as coating thermolysiss
2Electrode materials, the combination water content of film is lower, has influenced capacitance characteristic.We propose to adopt direct current-differential pulse combined prepared by electrodeposition technology to prepare ultracapacitor tantalum base RuO
2NH
2The O thin-film electrode material can effectively solve the problem of thin film deposition poor adhesive force, can control depositing of thin film speed and thickness, improves RuO
2NH
2The ratio electric capacity of O thin-film electrode material.Present contriver yet there are no employing direct current-differential pulse combined prepared by electrodeposition technology and prepares RuO
2NH
2The O thin-film electrode material
Summary of the invention
The purpose of this invention is to provide and a kind ofly can prepare, porous unbodied RuO strong with basal body binding force
2NH
2The technology of O film.This process using direct current-differential pulse combined electrodeposition technology is controlled electrodeposition process, can effectively prevent to deposit the formation that the initial stage liberation of hydrogen causes film defects, improves the speed of later stage film growth, thereby obtains high performance RuO
2NH
2The O thin-film electrode material.
Technology of the present invention comprises following processing step:
(1) with purity greater than 99.95% metal tantalum foil as substrate, and clean through pre-treatment;
(2) configuration RuCl
33H
2O, SnCl
2And NaNO
3Mixing solutions, their concentration in mixing solutions is respectively 1～5mmol/L, 0.2～1mmol/L and 10～200mmol/L, through fully stirring, leaving standstill;
(3) do anode with graphite, the metal tantalum piece is a negative electrode, (2) step join electrodeposit liquid in, earlier with substrate with 1～3mA/cm
2Galvanic current density deposition 0.5～1h adopts differential pulsed current deposition 2～3h again, and voltage pulse width is 1～10sec, and the recurrence interval is 2～20sec, and amplitude is 0.01～0.02mA/cm
2, every point voltage gain is 0.005～0.01mA/cm
2, the termination current density is 6mA/cm
2
(4) with (3) step behind the film airing of prepared by electrodeposition on the substrate through 200～500 ℃ of thermal treatments, soaking time is 2～3h.
The thickness of substrate is 0.1mm in described (1) step, is of a size of Φ 12～34mm.
Pre-treatment is cleaned and is adopted the abrasive paper for metallograph sanding and polishing in described (1) step, the acetone oil removing, and alkali lye adds heat soaking, and mixing acid cleans, and uses the deionized water ultrasonic cleaning.
The dipping by lye temperature is 70～80 ℃, and the time is 5～10min, and the alkali lye composition is NaHCO
3Or Na
3PO
4Or NaH
2PO
4Or Na
2CO
3, mass percent concentration is 2～10%.Mixing acid cleans 40sec; Each composition volume ratio of described mixing acid is: with the volume percent of the aqueous solution be 40% hydrofluoric acid: 1.40gcm
-3Nitric acid: 1.84gcm
-3Sulfuric acid=10～25: 2～15: 5～20.
Mixing solutions needs churning time at 0.5-1h in described (2) step, and stirring velocity is 2-10r/min, and time of repose is 5-30min.
The timed interval in described (3) step between direct current and the differential pulse electrodeposition is no more than 1sec.Direct current-differential pulse combined electrodeposition technology forms gradient deposition speed.
The heat treated temperature rise rate of film of prepared by electrodeposition is 2～10 ℃/s in described (4) step.
Specific embodiment of the present invention is:
1. high pure metal tantalum paper tinsel purity is of a size of Φ 12～34mm greater than 99.95%, and thickness is 0.1mm, uses the abrasive paper for metallograph sanding and polishing, the acetone oil removing, and dipping by lye, mixing acid cleans 40sec, uses the deionized water ultrasonic cleaning.The dipping by lye temperature is 70～80 ℃, and the time is 5～10min, and the alkali lye composition is NaHCO
3Or Na
3PO
4Or NaH
2PO
4Or Na
2CO
3, mass percent concentration is 2～10%.The proportioning components of mixing acid is hydrofluoric acid (volume percent is 40%): nitric acid (1.40gcm
-3): sulfuric acid (1.84gcm
-3)=10～25: 2～15: 5～20 (volume ratios).
2. the prescription of electrodeposit liquid: configuration RuCl
33H
2O, SnCl
2And NaNO
3Mixing solutions, make its concentration be respectively 1～5mmol/L, 0.2～1mmol/L and 10～200mmol/L, through fully stirring, leaving standstill.The mixing solutions churning time is 0.5～1h, and stirring velocity is 2-10r/min, and time of repose is 5-30min.
3. electrodeposition technology: adopt direct current-differential pulse combined electrodeposition technology, do anode with graphite, the metal tantalum piece is a negative electrode, earlier with 1～3mA/cm
2Less galvanic current density deposition 0.5～1h adopts differential pulsed current deposition 2～3h again, and voltage pulse width is 1～10sec, and the recurrence interval is 2～20sec, and amplitude is 0.01～0.02mA/cm
2, every point voltage gain is 0.005～0.01mA/cm
2, it stops current density is 5～8mA/cm
2As shown in Figure 1.Direct current and differential pulse electrodeposition carry out successively, and can not there be the timed interval above 1 minute the centre, and direct current-differential pulse combined electrodeposition technology forms gradient deposition speed.
4. coating thermal treatment: through 200～500 ℃ of processing, temperature rise rate is 2～10 ℃/s behind the film nature airing of prepared by electrodeposition, and soaking time is 2-3h.
With the CHI660C electrochemical test chemical property of thin-film material is tested, three-electrode system adopts the platinized platinum electrode as supporting electrode, and the mercurous sulfate electrode is as reference electrode, tantalum base RuO
2NH
2The O film is as working electrode, and electrolytic solution is the H of 0.5mol/L
2SO
4Solution, mensuration reaches 720F/g than electric capacity.The test of sticking power adopts GB5210-82 to draw back method, and test sticking power reaches 11.3MPa.
In the electrodeposition process of the present invention, before the solution pH value continues to increase near the negative electrode in the deposition process process that descends is fast arranged, this is because when galvanic deposit begins, negative electrode forms negative electrode cationic chemical potential gradient on every side to cationic strong adsorption, near the pH value of negative electrode is reduced fast, when the migration under the electric field action, this three of the convection current that diffusion and stirring produced under the chemical potential gradient reached balance to solute transfer influence, the tendency of changes balance of the PH of solution as shown in Figure 2.Dynamically the pH value of control solution at the uniform velocity increases the PH of solution, and the pH value of solution is controlled at 3.0 after deposit, can effectively prevent colloidal precipitation, prepares that form is even, sticking power thin-film material preferably.
In heat treatment process, there is not the crystalline diffraction peak, exists with non-crystalline state at the film of handling below 150 ℃.During greater than 200 ℃, the X-ray diffractogram of film exists Ru and RuO
2Two kinds of crystalline characteristic diffraction peaks, as shown in Figure 3.In the time of 200 ℃, Ru crystalline characteristic diffraction peak is narrow and strong, and RuO
2Characteristic diffraction peak compare broad.Along with temperature raises, Ru crystalline characteristic diffraction peak dies down RuO
2Characteristic diffraction peak become narrow and sharp.The X-ray diffraction analysis presentation of results is in the temperature elevation process, and the Ru crystal increases afterwards earlier and subtracts, and RuO
2In continuous generation, and change to crystalline state from non-crystalline state.
Description of drawings
Fig. 1 direct current-differential pulse combined electrodeposition technology map of current.The solution pH value concerns over time in Fig. 2 deposition process.The X-ray diffractogram of Fig. 3 treatment of different temperature film.
Embodiment
The invention will be further described by the following examples, but do not limit the present invention, and those skilled in the art can make replacement, distortion according to the present invention, only otherwise break away from basic thought of the present invention, and all within the scope of the present invention.
Embodiment 1:
1. at first with abrasive paper for metallograph to purity greater than 99.95% metal tantalum foil sanding and polishing, be of a size of 12mm, the acetone oil removing, dipping by lye, mixing acid cleans 40sec, uses the deionized water ultrasonic cleaning.The dipping by lye temperature is 75 ℃, and the time is 6min, and the alkali lye composition is NaHCO
3, mass percent concentration is 3%.The proportioning components of mixing acid is hydrofluoric acid (volume percent is 40%): nitric acid (1.40gcm
-3): sulfuric acid (1.84gcm
-3)=10: 2: 5 (volume ratio).
2. dispose RuCl
33H
2O, SnCl
2And NaNO
3Mixing solutions, concentration is respectively 1mmol/L, 0.2mmol/L and 10mmol/L, through fully stirring, leaving standstill.The mixing solutions churning time is 0.5h, and stirring velocity is 2r/min, and time of repose is 10min.
3. electrodeposition technology: adopt direct current-differential pulse combined electrodeposition technology, do anode with graphite, the metal tantalum piece is a negative electrode, uses 1mA/cm earlier
2Less galvanic current density deposition 0.5h adopts differential pulsed current deposition deposition 3h again, and voltage pulse width is 7sec, and the recurrence interval is 14sec, and amplitude is 0.02mA/cm
2, every point voltage gain is 0.01mA/cm
2, it stops current density is 5mA/cm
2
4. coating thermal treatment: through 200 ℃ of processing, temperature rise rate is 2 ℃/s behind the film nature airing of prepared by electrodeposition, and soaking time is 3h.
With the CHI660C electrochemical test chemical property of thin-film material is tested, three-electrode system adopts the platinized platinum electrode as supporting electrode, and the mercurous sulfate electrode is as reference electrode, tantalum base RuO
2NH
2The O film is as working electrode, and electrolytic solution is the H of 0.5mol/L
2SO
4Solution, mensuration reaches 680F/g than electric capacity.The test of sticking power adopts GB5210-82 to draw back method, and test sticking power reaches 14.2MPa.
Embodiment 2:
1. at first with abrasive paper for metallograph to purity greater than 99.95% metal tantalum foil sanding and polishing, be of a size of 18mm, the acetone oil removing, dipping by lye, mixing acid cleans 40sec, uses the deionized water ultrasonic cleaning.The dipping by lye temperature is 72 ℃, and the time is 8min, and the alkali lye composition is Na
3PO
4, mass percent concentration is 5%.The proportioning components of mixing acid is hydrofluoric acid (volume percent is 40%): nitric acid (1.40gcm
-3): sulfuric acid (1.84cm
-3)=15: 8: 10 (volume ratio).
2. dispose RuCl
23H
2O, SnCl
2And NaNO
3Mixing solutions, concentration is respectively 3mmol/L, 1mmol/L and 200mmol/L, through fully stirring, leaving standstill.The mixing solutions churning time is 0.8h, and stirring velocity is 6r/min, and time of repose is 18min.
3. electrodeposition technology: adopt direct current-differential pulse combined electrodeposition technology, do anode with graphite, the metal tantalum piece is a negative electrode, uses 2.5mA/cm earlier
2Less galvanic current density deposition 0.75h adopts differential pulsed current deposition deposition 2.25h again, and voltage pulse width is 5sec, and the recurrence interval is 10sec, and amplitude is 0.01mA/cm
2, every point voltage gain is 0.005mA/cm
2, it stops current density is 8mA/cm
2
4. coating thermal treatment: through 300 ℃ of processing, temperature rise rate is 4 ℃/s behind the film nature airing of prepared by electrodeposition, and soaking time is 2.5h.
With the CHI660C electrochemical test chemical property of thin-film material is tested, three-electrode system adopts the platinized platinum electrode as supporting electrode, and the mercurous sulfate electrode is as reference electrode, tantalum base RuO
2NH
2The O film is as working electrode, and electrolytic solution is the H of 0.5mol/L
2SO
4Solution, mensuration reaches 710F/g than electric capacity.The test of sticking power adopts GB5210-82 to draw back method, and test sticking power reaches 12.3MPa.
Embodiment 3:
1. at first with abrasive paper for metallograph to purity greater than 99.95% metal tantalum foil sanding and polishing, be of a size of 34mm, the acetone oil removing, dipping by lye, mixing acid cleaned 40 seconds, used the deionized water ultrasonic cleaning.The dipping by lye temperature is 80 ℃, and the time is 10min, and the alkali lye composition is NaH
2PO
4Or Na
2CO
3, mass percent concentration is 10%.The proportioning components of mixing acid is hydrofluoric acid (volume percent is 40%): nitric acid (1.40gcm
-3): sulfuric acid (1.84cm
-3)=25: 8: 12 (volume ratio).
2. dispose RuCl
33H
2O, SnCl
2And NaNO
3Mixing solutions, concentration is respectively 5mmol/L, 1mmol/L and 200mmol/L, through fully stirring, leaving standstill.The mixing solutions churning time is 1h, and stirring velocity is 10r/min, and time of repose is 30min.
3. electrodeposition technology: adopt direct current-differential pulse combined electrodeposition technology, do anode with graphite, the metal tantalum piece is a negative electrode, uses 3mA/cm earlier
2Less galvanic current density deposition 1h adopts differential pulsed current deposition deposition 2h again, and voltage pulse width is 6sec, and the recurrence interval is 12sec, and amplitude is 0.012mA/cm
2, every point voltage gain is 0.006mA/cm
2, it stops current density is 6mA/cm
2
4. coating thermal treatment: through 500 ℃ of processing, temperature rise rate is 10 ℃/s behind the film nature airing of prepared by electrodeposition, and soaking time is 2h.
With the CHI660C electrochemical test chemical property of thin-film material is tested, three-electrode system adopts the platinized platinum electrode as supporting electrode, and the mercurous sulfate electrode is as reference electrode, tantalum base RuO
2NH
2The O film is as working electrode, and electrolytic solution is the H of 0.5mol/L
2SO
4Solution, mensuration reaches 730F/g than electric capacity.The test of sticking power adopts GB5210-82 to draw back method, and test sticking power reaches 11.3MPa.
Claims (7)
1, a kind ofly is used to prepare ultracapacitor RuO
2The direct current of electrode materials-differential pulse combined electrodeposition technology is characterized in that, comprises following processing step:
(1) with purity greater than 99.95% metal tantalum foil as substrate, and clean through pre-treatment;
(2) configuration RuCl
33H
2O, SnCl
2And NaNO
3Mixing solutions, RuCl
33H
2O, SnCl
2And NaNO
3Concentration in mixing solutions is respectively 1～5mmol/L, 0.2～1mmol/L and 10～200mmol/L, through fully stirring, leaving standstill;
(3) do anode with graphite, the metal tantalum piece is a negative electrode, (2) step join electrodeposit liquid in, earlier with substrate with 1～3mA/cm
2Galvanic current density deposition 0.5～1h adopts differential pulsed current deposition 2～3h again, and voltage pulse width is 1～10sec, and the recurrence interval is 2～20sec, and amplitude is 0.01～0.02mA/cm
2, every point voltage gain is 0.005～0.01mA/cm
2, the termination current density is 6mA/cm
2
(4) with (3) step behind the film airing of prepared by electrodeposition on the substrate through 200～500 ℃ of thermal treatments, soaking time is 2～3h.
2, according to right 1 described a kind of ultracapacitor RuO that is used to prepare
2The direct current of electrode materials-differential pulse combined electrodeposition technology is characterized in that: the thickness of substrate is 0.1mm in (1) step, is of a size of Φ 12～34mm.
3, a kind of ultracapacitor RuO that is used to prepare according to claim 1 and 2
2The direct current of electrode materials-differential pulse combined electrodeposition technology is characterized in that: pre-treatment is cleaned and is adopted the abrasive paper for metallograph sanding and polishing in (1) step, the acetone oil removing, and alkali lye adds heat soaking, and mixing acid cleans, and uses the deionized water ultrasonic cleaning.
4, a kind of ultracapacitor RuO that is used to prepare according to claim 3
2The direct current of electrode materials-differential pulse combined electrodeposition technology is characterized in that: the dipping by lye temperature is 70～80 ℃, and the time is 5～10min, and the alkali lye composition is NaHCO
3Or Na
3PO
4Or NaH
2PO
4Or Na
2CO
3, mass percent concentration is 2～10%.Mixing acid cleans 40sec; Each composition volume ratio of described mixing acid is: with the volume percent of the aqueous solution be 40% hydrofluoric acid: 1.40gcm
-3Nitric acid: 1.84gcm
-3Sulfuric acid=10～25: 2～15: 5～20.
5, according to right 1 described a kind of ultracapacitor RuO that is used to prepare
2The direct current of electrode materials-differential pulse combined electrodeposition technology is characterized in that: mixing solutions needs churning time at 0.5-1h in (2) step, and stirring velocity is 2-10r/min, and time of repose is 5-30min.
6, according to right 1 described a kind of ultracapacitor RuO that is used to prepare
2The direct current of electrode materials-differential pulse combined electrodeposition technology is characterized in that: the timed interval in (3) step between direct current and the differential pulse electrodeposition is no more than 1sec.
7, a kind of ultracapacitor RuO that is used to prepare according to claim 1
2The direct current of electrode materials-differential pulse combined electrodeposition technology is characterized in that: the heat treated temperature rise rate of film of prepared by electrodeposition is 2～10 ℃/s in (4) step.
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| CN102575363A (en) * | 2009-09-23 | 2012-07-11 | 德诺拉工业有限公司 | Electrode for electrolytic processes with controlled crystalline structure |
| EP2581971A1 (en) | 2011-10-11 | 2013-04-17 | Bayer Intellectual Property GmbH | Catalyst coating and method for its production |
| 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 |
| WO2015003567A1 (en) * | 2013-07-12 | 2015-01-15 | City University Of Hong Kong | Porous framework and method for its manufacture |
| CN104422611A (en) * | 2013-09-02 | 2015-03-18 | 宁波江丰电子材料股份有限公司 | Metallurgical corrosive and metallurgical structure display method |
| CN107078291A (en) * | 2014-08-28 | 2017-08-18 | 英克罗恩有限公司 | Crystalline transitional oxide particle and the continuation method for preparing the crystalline transitional oxide particle |
| US9840789B2 (en) | 2014-01-20 | 2017-12-12 | City University Of Hong Kong | Etching in the presence of alternating voltage profile and resulting porous structure |
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|---|---|---|---|---|
| KR100578734B1 (en) * | 2003-11-19 | 2006-05-12 | 한국과학기술연구원 | Method for preparing thin film of ruthenium oxide using electrodeposition |
| CN100521014C (en) * | 2006-05-30 | 2009-07-29 | 中南大学 | Method for preparing RuO2 coating cathode film material of super capacitor |
| CN100588753C (en) * | 2007-05-21 | 2010-02-10 | 哈尔滨工程大学 | Method for preparing carbon nano-tube loading ruthenium oxide hydration composite material |
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Cited By (9)
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|---|---|---|---|---|
| CN102575363A (en) * | 2009-09-23 | 2012-07-11 | 德诺拉工业有限公司 | Electrode for electrolytic processes with controlled crystalline structure |
| CN102575363B (en) * | 2009-09-23 | 2015-07-01 | 德诺拉工业有限公司 | Electrode for electrolytic processes with controlled crystalline structure |
| EP2581971A1 (en) | 2011-10-11 | 2013-04-17 | Bayer Intellectual Property GmbH | Catalyst coating and method for its production |
| 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 |
| WO2015003567A1 (en) * | 2013-07-12 | 2015-01-15 | City University Of Hong Kong | Porous framework and method for its manufacture |
| CN104422611A (en) * | 2013-09-02 | 2015-03-18 | 宁波江丰电子材料股份有限公司 | Metallurgical corrosive and metallurgical structure display method |
| US9840789B2 (en) | 2014-01-20 | 2017-12-12 | City University Of Hong Kong | Etching in the presence of alternating voltage profile and resulting porous structure |
| CN107078291A (en) * | 2014-08-28 | 2017-08-18 | 英克罗恩有限公司 | Crystalline transitional oxide particle and the continuation method for preparing the crystalline transitional oxide particle |
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| CN101525760B (en) | 2011-03-23 |
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