CN101967654A - Ruthenium oxide electrode material by adopting carburization and modification of titanium base material and preparation method thereof - Google Patents

Ruthenium oxide electrode material by adopting carburization and modification of titanium base material and preparation method thereof Download PDF

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CN101967654A
CN101967654A CN 201010502407 CN201010502407A CN101967654A CN 101967654 A CN101967654 A CN 101967654A CN 201010502407 CN201010502407 CN 201010502407 CN 201010502407 A CN201010502407 A CN 201010502407A CN 101967654 A CN101967654 A CN 101967654A
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base material
titanium base
carburizing
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modification
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CN101967654B (en
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唐电
何云南
王欣
邵艳群
张腾
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Fuzhou University
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Abstract

The invention provides a ruthenium oxide electrode material by adopting carburization and modification of a titanium base material and a preparation method thereof. A Ru oxide active coating is deposited after the titanium base material is carburized and modified. The preparation method of the electrode material comprises the following steps of: carburizing the titanium base material, namely carbonizing at 700-900 DEG C; then coating Ru-contained active slurry on a carburized titanium material; and oxidizing and sintering to form the ruthenium oxide electrode material by adopting carburization and modification of the titanium base material. The obtained electrode material has the electric catalytic activity which is obviously higher than that the conventional electrode material without carburization processing, combines the advantages of a titanium base electrode material and a carbon base electrode material, maintains the mechanical stability of the titanium base electrode material and retains high activity of the carbon base electrode material. The invention only improves the titanium base material, can be suitable for the improvement of the Ru oxide electrode material and has the advantages of simple preparation method, high operability, easy acquisition of raw materials and low cost.

Description

That adopts titanium base material carburizing modification contains ru oxide electrode materials and preparation method thereof
Technical field
The invention belongs to the preparing technical field of the electrode materials of Applied Electrochemistry and energy industry, be specifically related to a kind of adopt titanium base material carburizing modification contain ru oxide electrode materials and preparation method thereof.
Background technology
The electrode materials of electrochemical industry use the earliest is a synthetic graphite.After containing the oxide compound appearance of precious metal element in 1967, Graphite Electrodes is replaced by it gradually.It is found that this type oxide has very high electro catalytic activity, therefore be called as the activating oxide material, or simply be called active material.Up to the present, the most superior active material remains and contains the ru oxide material.A large amount of experiments show, adopt the titanium material as carrier, utilize the stability of titanium base material, and what the Ti base of acquisition contained the Ru oxide compound becomes the electrochemical industry high performance electrode material.
Recently, it is base material that people adopt with the carbon material, and deposition contains Ru oxide compound making electrode materials thereon, and very common aspect energy electrode materials, its main purpose is exactly to utilize the electroconductibility of carbon material to improve electrode performance.
Summary of the invention
The object of the present invention is to provide a kind of adopt titanium base material carburizing modification contain ru oxide electrode materials and preparation method thereof, thereby can obtain more superior electrocatalysis characteristic.
Employing titanium base material carburizing modification of the present invention contain the ru oxide electrode materials, adopting after the titanium base material carburizing modification again, deposition contains Ru oxide compound activated coating.
Wherein the carburizing modification of titanium base material is the carbonizing treatment through 700~900 ℃, and it is carbon-containing bed to obtain one deck at the titanium substrate surface.Preferably, the carburizing modification of titanium base material is through 800 ℃ carbonizing treatment.
The described Ru of containing oxide compound activated coating is the single Ru of containing oxide compound activated coating or the polynary Ru oxide compound activated coating that contains.The wherein said single Ru of containing oxide compound activated coating is RuO 2Activated coating; The described polynary molar ratio 〉=10mol% that contains active component Ru in the Ru oxide compound activated coating.
The preparation method of titanium base material carburizing modified electrode material of the present invention comprises titanium base material carburizing pre-treatment, carburizing treatment and follow-up active material deposition, and concrete steps are as follows:
1) titanium base material pre-treatment:
The titanium base material is through decontamination, and the heating pickling is washed, dried;
2) titanium base material carburizing treatment:
Pretreated titanium base material is through 700~900 ℃ carburizing treatment, and it is carbon-containing bed to obtain one deck at the titanium substrate surface;
3) contain the preparation of Ru active slurry:
The source material of taking by weighing is dissolved in ethanolic soln, mixes the formation active slurry, and the solute concentration of control active slurry is 0.5 ~ 5 mol/L, mixes, and leaves standstill 9 ~ 15h;
4) contain the deposition of Ru activating oxide:
To contain the Ru active slurry and be coated on the titanium base material of carburizing treatment, be heating and curing, oxidation and sinter, the cooling of coming out of the stove; Annealing thermal treatments under 250 ~ 450 ℃ in box-type furnace at last promptly become titanium base material carburizing modification and contain the Ru oxide electrode material.
Wherein said titanium base material adopts industrially pure titanium.
For the single oxide activated coating that contains Ru, active component adopts RuCl in the step 3) 3Be the source material, the source material of taking by weighing is dissolved in ethanolic soln, mixes the formation active slurry, and the solute concentration of control active slurry is 0.5 ~ 5 mol/L, mixes, and leaves standstill 9 ~ 15h; For multicomponent reactive oxide compound activated coating, active component adopts with RuCl 3Be the source material, nonactive constituent element is the source material with other metal-salt, method preparation according to conventional multicomponent reactive coating, method is as follows: the molar ratio 〉=10mol% by active component Ru takes by weighing each source material, be dissolved in ethanolic soln, mix the formation active slurry, the solute concentration of control active slurry is 0.5 ~ 5 mol/L, mix, leave standstill 9 ~ 15h.
Described carburizing treatment adopts solid carburizing, gas cementation or liquid carburizing.Preferred solid carburizing will soon be imbedded in the solid carburizer through pretreated titanium base material, handle through 700~900 ℃ of high temperature cabonizations, and it is carbon-containing bed to obtain one deck at the titanium substrate surface.Preferred 800~850 ℃ of carbonization temperature is more preferably through 800 ℃ carbonizing treatment.
Employing titanium base material carburizing modified electrode material of the present invention and preparation method thereof, its key is to adopt the titanium base material before the deposition activating oxide, carrying out the carburizing modification earlier handles, promptly utilize the technology of carburizing, it is carbon-containing bed to increase one deck in titanium base material and activating oxide, increasing carbon-containing bed purpose is that the electroconductibility in active coating and the titanium base material is increased, thereby improves the performance of electrode.
Titanium base material carburizing modification provided by the invention contains the Ru oxide electrode material, had the advantage of titanium-matrix electrode material and carbon-based electrode material concurrently, the mechanical stability that had both kept the titanium-matrix electrode material has also kept the high reactivity of carbon-based electrode material, for electrode materials provides a kind of design.
Titanium base of the present invention carburizing contains the Ru oxide material, has than existing titanium base to contain the much higher electro catalytic activity of Ru oxide material.Can be applied to electrochemistry parts and devices such as aqueous electrolysis, electrochemical capacitance, organic solution electrolysis, fuel cell.The present invention only improves the titanium base material, goes for containing the improvement of Ru oxide electrode material, and the preparation method is simple, and is workable, and raw material is easy to get, and cost is low.
Remarkable advantage of the present invention:
A) the invention solves employing is the mechanical stability of substrate preparation high reactivity electrode materials with the carbon material, suitable especially preparation film-type and small-sized electrode materials.Not only can obtain to have the high reactivity that carbon back contains Ru activating oxide material by technology of the present invention, can also solve carbon back and contain the easy fracture of ruthenium activating oxide material and a difficult problem that is difficult to make miniature device.
B) adopt material of the present invention and preparation technology can further improve the electro catalytic activity that conventional titanium base contains the Ru oxide material.The activity that contains the Ru activating oxide for different sorts promotes and can play a significant role.
C) carburizing treatment that adopts of the present invention is easy to get at the raw material raw material, technology is simple, can realize scale operation.The high activity oxide material that obtains, cost is very low, and technology is simple, feasible, has reached practicability and industrialized condition.
Description of drawings
Fig. 1 is the cyclic voltammetry curve of two kinds of electrodes; Wherein 1 is traditional titanium coated Ru 0.3Ti 0.7O 2Anode, 2 for titanium through adopting 800 ℃ of carburizings be the Ru that base material is covered again 0.3Ti 0.7O 2Anode.
Embodiment
Employing titanium base material carburizing modified electrode material of the present invention and preparation method thereof relates generally to carburization process and thermal decomposed deposition method.Concrete implementation step is as follows:
1) titanium base material treatment:
The titanium base material mainly adopts the industrially pure titanium material.Base material is through heating degrease in containing the washing powder of 100g/L, the heating pickling is 1 hour in the oxalic acid solution of 50g/L, washing and oven dry.
2) solid carburizing of titanium base material is handled:
Conventional solid carburizing method is adopted in the carburizing of titanium base material.Be about to titanium and case through pretreated titanium base material, imbed and contain barium carbonate and the graphite mass ratio is in the solid carburizer of 90:10, carbonizing treatment is 1 hour under through 700~900 ℃ temperature, and is carbon-containing bed at titanium substrate surface acquisition one deck.The carburizing of titanium base material can be adopted methods such as solid carburizing, gas cementation and liquid carburizing.
3) contain the preparation of Ru active slurry: for the single oxide activated coating that contains Ru, active component adopts with RuCl 3Be the source material, the source material of taking by weighing is dissolved in ethanolic soln, mixes the formation active slurry, and the solute concentration of control active slurry mixes being 0.5 ~ 5 mol/L, leaves standstill 9 ~ 15h;
For multicomponent reactive oxide compound activated coating, active component adopts with RuCl 3Be the source material, nonactive constituent element can other metal-salt be the source material according to routine, comprise that in titanium chloride, tin chloride, cobalt chloride, the Cerium II Chloride etc. one or more are (referring to Zhang Teng " the high cerium of nano level contains phase structure, thermodynamics, kinetics and the chemical property of ruthenium activating oxide ", University of Fuzhou's Ph D dissertation, 2009).According to the method preparation of conventional multicomponent reactive coating, method is as follows: take by weighing each source material, wherein molar ratio 〉=10mol% of active component Ru, be dissolved in ethanolic soln, mix the formation active slurry, the solute concentration of control active slurry is 0.5 ~ 5 mol/L, mix, leave standstill 9 ~ 15h.
4) contain the deposition of Ru activating oxide:
To contain the layering of Ru active slurry is coated on the carburizing titanium material, through 80 ~ 100 ℃ of heating evaporations, again through 120 ~ 180 ℃ be heating and curing after, oxidation and sinter 10min in 250 ~ 450 ℃ box-type furnace, the cooling of coming out of the stove, at last in box-type furnace 250 ~ 450 ℃ of annealing thermal treatments down.Promptly become titanium base material carburizing modification and contain the Ru oxide electrode material.
The constructional feature of the titanium base material carburizing modified electrode material that obtains by above-mentioned enforcement of the present invention is that to increase one deck in titanium base material and activating oxide carbon-containing bed, the carbon-containing bed purpose that increases is that the electroconductibility in active coating and the titanium base material is increased, thereby improves the performance of electrode.
The performance characteristics of the titanium base material carburizing modified electrode material that obtains by above-mentioned enforcement of the present invention is to have very high electro catalytic activity.For example we are with the experiment that compares of acquisition titanium base material carburizing modified electrode material and unmodified titanium-matrix electrode material, and the result shows that the activity of the electrode materials that is obtained is significantly increased.Because the size of the integral charge area of cyclic voltammetry curve has determined the activity of electrode materials.Its raising embodies a concentrated reflection of in the increase of integral charge Q* of cyclic voltammetry curve, and as shown in Figure 1, test condition is :-0.1-1.1V potential range, carry out the cyclic voltammetric test with the scanning speed of 25mv/s, and electrolytic solution is 0.5mol/L H 2SO 4Solution.That mark 1 is traditional Ru among the figure 0.3Ti 0.7O 2The cyclic voltammetry curve of the anode material of mixed oxide.The encirclement area of its cyclic voltammetry curve is less, and the integral charge Q* of cyclic voltammetry curve is less, so its electro catalytic activity is not outstanding.And the curve of the mark 2 shown in Fig. 1 is for through the titanium of 800 ℃ of carburizings being the base material Ru that is covered again 0.3Ti 0.7O 2The cyclic voltammetry curve of the anode material of mixed oxide.As can be seen, the area that its cyclic voltammetry curve surrounded is very big, has increased about 1.5 times than the corresponding integral charge that does not carry out the electrode materials of carbonizing treatment.Illustrate that the present invention has tangible effect to the electrocatalysis characteristic that improves electrode materials.Also clearly illustrated that this improvement effect with the experiment on year-on-year basis of traditional anode material.
Below be several specific embodiment of the present invention, but the present invention not only is limited to this.
Embodiment 1
Prepare pure titanium base material, promptly, take out and use distilled water flushing, drying earlier to corrosion 1 h under the boiling state of pure titanium base material in 10% oxalic acid solution.Imbed and contain barium carbonate and the graphite mass ratio is in the solid carburizer of 90:10,, obtain the titanium plate of handling through carbonizing and modifying through carbonizing treatment under 900 ℃ the temperature 1 hour.
Reactive coating is the source material with the ruthenium trichloride, is dissolved in ethanolic soln, mixes.The concentration of solute is controlled at 1.5 mol/L, mixes with magnetic stirrer, leaves standstill 12h.Be mixed with slurry.With this active slurry, be coated on pretreated titanium plate with the brush pen, through 80 ~ 100 ℃ of heating evaporations, again through 120 ~ 180 ℃ after being heating and curing under the infrared light, oxidation 10min in 450 ℃ box-type furnace, the air cooling of coming out of the stove, continue to apply, repeat aforesaid operations and reach 8 g/L, apply and dry back annealing 1h under 450 ℃ for the last time until ruthenium content at titanium-based surface, the cooling of coming out of the stove is the electrode materials of titanium base material carburizing modification.Prepare the electrode materials without carbonizing treatment simultaneously, their other experiment condition is identical.Adopt electrochemical workstation to compare and measure and show that through the electrode materials after the carbonizing treatment, the integral charge Q* of its cyclic voltammetry curve has increased about 1.3 times.
Embodiment 2
Prepare pure titanium base material, promptly, take out and use distilled water flushing, drying earlier to corrosion 1 h under the boiling state of pure titanium base material in 10% oxalic acid solution.Imbed and contain barium carbonate and the graphite mass ratio is in the solid carburizer of 90:10,, obtain the titanium plate of handling through carbonizing and modifying through carbonizing treatment under 850 ℃ the temperature 1 hour.
Reactive coating is with ruthenium trichloride and TiCl 3Being the source material, is that the ratio of 3:7 is dissolved in ethanolic soln in the mole number of Ru:Ti, mixes.The concentration of solute is controlled at 0.5 mol/L, mixes with magnetic stirrer, leaves standstill 12h.Be mixed with slurry.With this active slurry, be coated on pretreated titanium plate with the brush pen, through 80 ~ 100 ℃ of heating evaporations, again through 120 ~ 180 ℃ after being heating and curing under the infrared light, oxidation 10min in 450 ℃ box-type furnace, the air cooling of coming out of the stove, continue to apply, repeat aforesaid operations and reach 8 g/L, apply and dry back annealing 1h under 450 ℃ for the last time until ruthenium content at titanium-based surface, the cooling of coming out of the stove is the Ru that is covered after the titanium base material carburizing modification 0.3Ti 0.7O 2The electrode materials of mixed oxide.Prepare electrode materials simultaneously, promptly traditional Ru without carbonizing treatment 0.3Ti 0.7O 2The anode material of mixed oxide.Adopt electrochemical workstation to compare mensuration to the two and show, through the lining Ru after the carbonizing treatment 0.3Ti 0.7O 2Electrode materials, the integral charge Q* of its cyclic voltammetry curve is than traditional lining Ru 0.3Ti 0.7O 2Electrode materials increased about 1.5 times.
Embodiment 3
Prepare pure titanium base material, promptly, take out and use distilled water flushing, drying earlier to corrosion 1 h under the boiling state of pure titanium base material in 10% oxalic acid solution.Imbed and contain barium carbonate and the graphite mass ratio is in the solid carburizer of 90:10,, obtain the titanium plate of handling through carbonizing and modifying through carbonizing treatment under 750 ℃ the temperature 1 hour.
Reactive coating is with ruthenium trichloride, SnCl 4And TiCl 3Being the source material, is that the ratio of 3:0.5:6.5 is dissolved in ethanolic soln in the mole number of Ru:Sn:Ti, mixes.The concentration of solute is controlled at 5mol/L, mixes with magnetic stirrer, leaves standstill 12h.Be mixed with slurry.With this active slurry, be coated on pretreated titanium plate with the brush pen, through 80 ~ 100 ℃ of heating evaporations, again through 120 ~ 180 ℃ after being heating and curing under the infrared light, oxidation 10min in 450 ℃ box-type furnace, the air cooling of coming out of the stove, continue to apply, repeat aforesaid operations and reach 8 g/L, apply and dry back annealing 1h under 450 ℃ for the last time until ruthenium content at titanium-based surface, the cooling of coming out of the stove is the Ru that is covered after the titanium base material carburizing modification 0.30Sn 0.05Ti 0.0.65O 2The electrode materials of mixed oxide.Prepare electrode materials simultaneously, promptly traditional Ru without carbonizing treatment 0.30Sn 0.05Ti 0.0.65O 2The anode material of mixed oxide.Adopt electrochemical workstation to compare mensuration to the two and show, through the lining Ru after the carbonizing treatment 0.30Sn 0.05Ti 0.0.65O 2Electrode materials, the integral charge Q* of its cyclic voltammetry curve is than traditional lining Ru 0.30Sn 0.05Ti 0.0.65O 2Electrode materials increased about 1.2 times.

Claims (10)

  1. One kind adopt titanium base material carburizing modification contain the ru oxide electrode materials, it is characterized in that: adopting after the titanium base material carburizing modification again, deposition contains Ru oxide compound activated coating.
  2. 2. employing titanium base material carburizing modification according to claim 1 contain the ru oxide electrode materials, it is characterized in that: the carburizing modification of titanium base material is the carbonizing treatment through 700~900 ℃, it is carbon-containing bed to obtain one deck at the titanium substrate surface.
  3. 3. employing titanium base material carburizing modification according to claim 2 contain the ru oxide electrode materials, it is characterized in that: the carburizing modification of described titanium base material is the carbonizing treatment through 800 ℃.
  4. 4. employing titanium base material carburizing modification according to claim 1 contain the ru oxide electrode materials, it is characterized in that: the described Ru of containing oxide compound activated coating is the single Ru of containing oxide compound activated coating or the polynary Ru of containing oxide compound activated coating.
  5. 5. the Ru activating oxide electrode materials that contains according to claim 4 is characterized in that: the described single Ru of containing oxide compound activated coating is RuO 2Activated coating.
  6. 6. employing titanium base material carburizing modification according to claim 4 contain the ru oxide electrode materials, it is characterized in that: molar ratio 〉=10mol% of active component Ru in the described polynary Ru of the containing oxide compound activated coating.
  7. 7. preparation method who contains the ru oxide electrode materials as claim 1,2,3,4,5 or 6 described employing titanium base material carburizing modifications, it is characterized in that: described preparation method's concrete steps are as follows:
    1) titanium base material pre-treatment:
    The titanium base material is through decontamination, and the heating pickling is washed, dried;
    2) titanium base material carburizing treatment:
    Pretreated titanium base material is through 700~900 ℃ carburizing treatment, and it is carbon-containing bed to obtain one deck at the titanium substrate surface;
    3) contain the preparation of Ru active slurry:
    The source material of taking by weighing is dissolved in ethanolic soln, mixes the formation active slurry, and the solute concentration of control active slurry is 0.5 ~ 5 mol/L, mixes, and leaves standstill 9 ~ 15h;
    4) contain the deposition of Ru activating oxide:
    To contain the Ru active slurry and be coated on the titanium base material of carburizing treatment, be heating and curing, oxidation and sinter, the cooling of coming out of the stove; Annealing thermal treatments under 250 ~ 450 ℃ in box-type furnace at last promptly become titanium base material carburizing modification and contain the Ru oxide electrode material.
  8. 8. employing titanium base material carburizing modification according to claim 7 contain ru oxide electrode materials preparation method, it is characterized in that: described titanium base material adopts industrially pure titanium.
  9. 9. employing titanium base material carburizing modification according to claim 7 contain ru oxide electrode materials preparation method, it is characterized in that: for the single oxide activated coating that contains Ru, active component adopts RuCl in the step 3) 3Be the source material, the source material of taking by weighing is dissolved in ethanolic soln, mixes the formation active slurry, and the solute concentration of control active slurry is 0.5 ~ 5 mol/L, mixes, and leaves standstill 9 ~ 15h; For multicomponent reactive oxide compound activated coating, active component adopts with RuCl 3Be the source material, nonactive constituent element is the source material with other metal-salt, method preparation according to conventional multicomponent reactive coating, method is as follows: the molar ratio 〉=10mol% by active component Ru takes by weighing each source material, be dissolved in ethanolic soln, mix the formation active slurry, the solute concentration of control active slurry is 0.5 ~ 5 mol/L, mix, leave standstill 9 ~ 15h.
  10. 10. employing titanium base material carburizing modification according to claim 7 contain ru oxide electrode materials preparation method, it is characterized in that: described carburizing treatment adopts solid carburizing, gas cementation or liquid carburizing.
CN2010105024076A 2010-10-11 2010-10-11 Ruthenium oxide electrode material by adopting carburization and modification of titanium base material and preparation method thereof Expired - Fee Related CN101967654B (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017113382A1 (en) * 2015-12-31 2017-07-06 深圳凯世光研股份有限公司 Carburising treatment process for thorium-tungsten electrode
CN110158087A (en) * 2019-05-16 2019-08-23 西安交通大学 A kind of preparation method of lamination shape electrolytic oxidation water electrode

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3788968A (en) * 1971-01-08 1974-01-29 Metallgesellschaft Ag Layered electrode
CN1612949A (en) * 2002-01-03 2005-05-04 拜尔材料科学股份公司 Electrode for electrolysis in acidic media
CN101289750A (en) * 2008-06-13 2008-10-22 福州大学 Titanium anodic of nano TiO2 seed coating and method for preparing same

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3788968A (en) * 1971-01-08 1974-01-29 Metallgesellschaft Ag Layered electrode
CN1612949A (en) * 2002-01-03 2005-05-04 拜尔材料科学股份公司 Electrode for electrolysis in acidic media
CN101289750A (en) * 2008-06-13 2008-10-22 福州大学 Titanium anodic of nano TiO2 seed coating and method for preparing same

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
《铸造技术》 20100331 刘景顺等 渗碳工艺下纯Ti板显微组织及晶粒长大动力学 第284-287页 1 第31卷, 第3期 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017113382A1 (en) * 2015-12-31 2017-07-06 深圳凯世光研股份有限公司 Carburising treatment process for thorium-tungsten electrode
CN110158087A (en) * 2019-05-16 2019-08-23 西安交通大学 A kind of preparation method of lamination shape electrolytic oxidation water electrode
CN110158087B (en) * 2019-05-16 2020-05-22 西安交通大学 Preparation method of laminated electrolytic oxidation water electrode

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