CN102225334B - Active material containing Hf (hydrogen fluoride) oxide and preparation method thereof - Google Patents
Active material containing Hf (hydrogen fluoride) oxide and preparation method thereof Download PDFInfo
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- CN102225334B CN102225334B CN 201110110826 CN201110110826A CN102225334B CN 102225334 B CN102225334 B CN 102225334B CN 201110110826 CN201110110826 CN 201110110826 CN 201110110826 A CN201110110826 A CN 201110110826A CN 102225334 B CN102225334 B CN 102225334B
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Abstract
The invention relates to an active material containing Hf(hydrogen fluoride) oxide and a preparation method thereof. Ru (ruthenium) salt and Hf salt are taken as the raw materials of the active material. Mole ratio of Hf to Hf puls Ru is (1-9):10. The preparation method comprises the following steps: taking the Ru salt and Hf salt as the raw materials; dissolving the raw materials in an alcoholic solution, thereby preparing active slurry; after evaporating and solidifying the active slurry by heating, performing oxidization sintering on a solidified product, thereby acquiring a hafnium-containing Ru oxide containing active material powder. Compared with a pure Ru active material, the prepared active material has an active area which is obviously increased, so that the active material has a superior electro-catalytic activity. The preparation method for preparing the active material is simple and has the advantages of strong operability, easily acquired raw materials and low cost.
Description
Technical field
The invention belongs to the electrode material field of Applied Electrochemistry and energy industry, be specifically related to a kind of active material that contains the Hf oxide with high electrocatalysis characteristic and preparation method thereof.
Background technology
After containing the oxide appearance of precious metal element in 1967, it is found that this type oxide has very high electro catalytic activity, therefore be called as activating oxide material, or simply be called active material.This active material has replaced Delanium gradually at electrochemical industry.Up to the present, the most superior active material remains the ruthenium containing oxides material.Great many of experiments shows, having adopted the oxide that has a same crystal structure (being Rutile Type) with ruthenic oxide is carrier, electrocatalysis characteristic is improved, and can obviously reduce the consumption of noble metal, thereby reduce cost.In these materials, the most common activating oxide is binary or the multivariant oxide materials such as Ti-Ru, Sn-Ru, Ti-Ru-Ir, Sn-Ru-Ir, the Sn-Ru-Ti take titanium and tin as carrier.
At present, employing is that carrier is that people explore the important topic that how further reduces cost with the oxide that ruthenic oxide has the different crystal structure, and other carrier of research also has Co, Ce, Si etc.In the research of the project of national nature science fund project " nano active oxide carrier material " that this scientific research team is presided over, other oxide has been carried out systematic research, if find to control the crystal formation of oxide, might obtain novel mixed oxide active material.Hafnium oxide belongs to high-k material, adds this element and often is unfavorable for activity, and belong to monocline at normal temperature, differs greatly with rutile structure, with the interpolation element of hafnium as active material, the research report is not arranged.If can hafnium and ruthenium be formed active material by effective method, improve the electro catalytic activity of material, can effectively reduce the production cost of this material, impel it to obtain the application of wider scope.
Summary of the invention
In order to address the above problem, the invention provides active material of a kind of Hf of containing oxide and preparation method thereof, this manufacture of materials cost is low, and the preparation method is simple, has high electrocatalysis characteristic.
The present invention implements by following technical solution:
A kind of active material of the Hf of containing oxide is that Hf: the Hf+Ru molar ratio is 1～9: 10 take Ru salt and Hf salt as the source material.
Hf in the described active material: the Hf+Ru molar ratio is 3 ~ 7: 10.
The ratio of the molar content of Hf in total Hf+Ru molar content≤90% in the described active material.
Described Ru salt comprises RuCl
3, described Hf salt comprises HfCl
4, HfOCl
2Or HfO (NO
3)
2In any one.
A kind of preparation method of active material of the Hf of containing oxide comprises the steps:
1) preparation of active slurry: the active component of active slurry is with RuCl
3Be the source material, nonactive constituent element is with HfCl
4, HfOCl
2Or HfO (NO
3)
2In any one be the source material, according to described Hf: the Hf+Ru molar ratio takes by weighing each source material, and is dissolved in respectively in the alcoholic solution, after each source material of solid fully dissolves the two is mixed, and obtains active slurry;
2) sintering: with above-mentioned active slurry, through 80 ~ 100 ℃ of heating evaporations, again through 120 ~ 180 ℃ be heating and curing after, oxidation and sinter in 250 ~ 400 ℃ batch-type furnace, the cooling of coming out of the stove becomes the RuHf active material of the described Hf of containing oxide.
The molar concentration that mixes rear solute in the described step 1) is 2-3mol/L.
Alcoholic solution in the described step 1) comprises ethanol, isopropyl alcohol, n-butanol etc.
The Hf of containing oxide electrode provided by the invention is the Hf active material that adds high-load, for electrode material provides a kind of new Composition Design scheme.The active component of main body is RuO in the active material of employing the present invention preparation
2, HfO
2As carrier material.Combination property is preferably Hf: the Hf+Ru mol ratio is 1 ~ 3: 10 ratio.
The Hf oxide material that contains of the present invention's preparation has than existing RuO
2The electro catalytic activity that material is much higher.Can be applied to electrochemistry parts and the devices such as aqueous solution electrolysis, electrochemical capacitance, organic solution electrolysis, fuel cell.
Remarkable advantage of the present invention:
1) the present invention can obtain the cubic oxide hafnium, thereby a high proportion of Hf can be dissolved in the ruthenic oxide by adopting suitable preparation technology, obtains the Ru-Hf oxide.Can obtain to contain Hf by technique of the present invention and contain the Ru active material up to 90 mol%.
2) adopt preparation technology of the present invention to solve to adopt the defective of the high electrocatalysis material that routine techniques can't obtain.The microscopic structure that adopts preparation technology of the present invention to obtain has embodied amorphous structural form, thereby effectively make two kinds of ion mixing under high-load, the final activated centre that obtains the institutional framework of high degree of dispersion and highly distribute, thus the electro catalytic activity that contains the Ru oxide material significantly improved.
3) raw materials of the present invention's selection is simple, is easy to get process stabilizing.The chlorate of selecting is the source material, make them in slurries mixing, sintering and subsequent heat treatment, remain a high proportion of mixing and distribution state, obtained the activating oxide material take hafnium oxide and ruthenic oxide as main body, cost is very low, technique is simple, feasible, has reached practical and industrialized condition.
Description of drawings
The RuO that Fig. 1 is traditional
2The cyclic voltammetry curve of oxide coating anode;
Fig. 2 Hf
0.18Ru
0.82O
2The cyclic voltammetry curve of mixed oxide.
The specific embodiment
A kind of active material of the Hf of containing oxide is that Hf: the Hf+Ru molar ratio is 1～9: 10 take Ru salt and Hf salt as the source material.
Hf in the described active material: the Hf+Ru molar ratio is 3 ~ 7: 10.
The ratio of the molar content of Hf in total Hf+Ru molar content≤90% in the described active material.
Described Ru salt comprises RuCl
3, described Hf salt comprises HfCl
4, HfOCl
2Or HfO (NO
3)
2In any one.
A kind of preparation method of active material of the Hf of containing oxide comprises the steps:
1) preparation of active slurry: the active component of active slurry is with RuCl
3Be the source material, nonactive constituent element is with HfCl
4, HfOCl
2Or HfO (NO
3)
2In any one be the source material, according to described Hf: the Hf+Ru molar ratio takes by weighing each source material, and be dissolved in respectively in the alcoholic solution, after each source material of solid fully dissolves, the two is mixed, mix with magnetic stirrer, leave standstill 12h, obtain active slurry, the molar concentration that mixes rear solute in the described step 1) is 2-3mol/L.
Alcoholic solution in the described step 1) comprises ethanol, isopropyl alcohol, n-butanol.
2) sintering: with above-mentioned active slurry, through 80 ~ 100 ℃ of heating evaporations, again through 120 ~ 180 ℃ be heating and curing after, oxidation and sinter in 250 ~ 400 ℃ batch-type furnace, the cooling of coming out of the stove becomes the RuHf active material of the described Hf of containing oxide.
3) contain the preparation of the active electrode material of hafnium:
Contain the preparation of the active electrode material of hafnium, can adopt the active slurry after will being heating and curing, batch-type furnace is directly inserted in repressed moulding, and oxidation and sinter is 1 ~ 2 hour under 250 ~ 400 ℃ temperature, and the cooling of coming out of the stove namely becomes the oxide active electrode material that contains hafnium; Also the active powder (or slurry) that contains hafnium can be sneaked into other and support material (such as inorganic material, material with carbon element etc.), mix compressing rear sintering, the active material powder is distributed in supports between the material, become the electrode material that support type contains the hafnium activating oxide; Also the active slurry gradation that contains hafnium can be coated on the metal material such as titanium material, be heating and curing, oxidation and sinter is 10 minutes in 250 ~ 400 ℃ the batch-type furnace, the cooling of coming out of the stove, at last in batch-type furnace 250 ~ 400 ℃ of lower annealing heat treatments.Namely become the oxide active coated Ti that contains hafnium.
Embodiment 1
Contain the preparation of the Ru-Hf mixed oxide material of hafnium, with ruthenium trichloride and HfCl
4Be the source material, in Hf: the Hf+Ru mol ratio is that 5: 10 ratio takes by weighing each source material, and be dissolved in respectively ethanolic solution, adopt sonic oscillation to make it Uniform Dispersion, after solid medicine fully dissolves, the two is mixed, the concentration of solute is controlled at about 2 mol/L, and leaves standstill 12h, be mixed with slurry.Prepare pure titanium base material, namely first to corrosion 1 h under the fluidized state of pure titanium base material in 10% oxalic acid solution, take out and use distilled water flushing, drying.With above-mentioned 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 320 ℃ batch-type furnace, the air cooling of coming out of the stove, continue to apply, repeat aforesaid operations until titanium-based surface ruthenium content reach 8 g/L, after applying for the last time and drying in 300 ℃ of lower annealing 1h, the cooling of coming out of the stove.The employing electrochemical workstation is measured, and all Q* that contain the active electrode material of hafnium are 1420 mC/cm
2About.
Embodiment 2
The Ru-Hf mixed oxide material of Ru base with ruthenium trichloride and HfCl
4Be the source material, in Hf: the Hf+Ru mol ratio is that 3: 10 ratio takes by weighing each source material, and be dissolved in respectively ethanolic solution, adopt sonic oscillation to make it Uniform Dispersion, after solid medicine fully dissolves, the two is mixed, the concentration of solute is controlled at about 2.5 mol/L, and leaves standstill 12h, be mixed with masking liquid.With above-mentioned active slurry, be coated on pretreated titanium plate with brush pen and (see example 1), through 80 ~ 100 ℃ of heating evaporations, again through 120 ~ 180 ℃ after being heating and curing under the infrared light, oxidation 10min in 300 ℃ batch-type furnace, the air cooling of coming out of the stove, continue to apply, repeat aforesaid operations until until titanium-based surface ruthenium content reach 10 g/L, after applying for the last time and drying in 300 ℃ of lower annealing 1h, the cooling of coming out of the stove.The employing electrochemical workstation is measured, and the Q* of the active electrode material of the Hf-Ru oxide that obtains is 1140 mC/cm
2
Embodiment 3
The Ru-Hf mixed oxide material of Ru base with ruthenium trichloride and HfCl
4Be the source material, in Hf: the Hf+Ru mol ratio is that 1: 10 ratio takes by weighing each source material, and to be dissolved in respectively volume fraction be 50% ethanolic solution, adopt sonic oscillation to make it Uniform Dispersion, after solid medicine fully dissolves, the two is mixed, the concentration of solute is controlled at about 3.1 mol/L, and leaves standstill 10h, be mixed with masking liquid.With above-mentioned active slurry, be coated on pretreated titanium plate with brush pen and (see example 1), through 80 ~ 100 ℃ of heating evaporations, again through 120 ~ 180 ℃ after being heating and curing under the infrared light, oxidation 10min in 300 ℃ batch-type furnace, the air cooling of coming out of the stove, continue to apply, repeat aforesaid operations until until titanium-based surface ruthenium content reach 6 g/L, after applying for the last time and drying in 280 ℃ of lower annealing 1h, the cooling of coming out of the stove.The employing electrochemical workstation is measured, and the Q* of the Hf-Ru oxide active electrode material that obtains is 540 mC/cm
2
Embodiment 4
A kind of preparation method of active material of the Hf of containing oxide comprises the steps:
1) preparation of active slurry: the active component of active slurry is with RuCl
3Be the source material, nonactive constituent element is with HfOCl
2Be the source material, in Hf: the Hf+Ru mol ratio is that 9: 10 ratio takes by weighing each source material, and to be dissolved in respectively volume fraction be in 80% the aqueous isopropanol, after each source material of solid fully dissolves, the two is mixed, the molar concentration that mixes rear solute is 2mol/L, mix with magnetic stirrer after mixing, leave standstill 12h, obtain active slurry;
2) sintering: with above-mentioned active slurry, through 80 ~ 100 ℃ of heating evaporations, again through 180 ℃ be heating and curing after, oxidation and sinter is 2 hours in 250 ℃ batch-type furnace, the cooling of coming out of the stove becomes the RuHf active material of the described Hf of containing oxide.
Embodiment 5
A kind of preparation method of active material of the Hf of containing oxide comprises the steps:
1) preparation of active slurry: the active component of active slurry is with RuCl
3Be the source material, nonactive constituent element is with HfO (NO
3)
2Be the source material, in Hf: the Hf+Ru mol ratio is that 2: 10 ratio takes by weighing each source material, and to be dissolved in respectively volume fraction be in 20% the butanol solution, after each source material of solid fully dissolves, the two is mixed, the molar concentration that mixes rear solute is 3mol/L, mix with magnetic stirrer, leave standstill 12h, obtain active slurry;
2) sintering: with above-mentioned active slurry, through 80 ~ 100 ℃ of heating evaporations, again through 180 ℃ be heating and curing after, oxidation and sinter is 0.5 hour in 400 ℃ batch-type furnace, the cooling of coming out of the stove becomes the RuHf active material of the described Hf of containing oxide.
The active material that contains hafnium that the present invention obtains by above-mentioned enforcement composition characteristic be to contain the hafnium height.Because it is high to contain the hafnium proportioning, make the content of noble ruthenium can relative reduce, play direct effect to reducing material cost.The present invention is to have very high electro catalytic activity by the performance characteristics of the active material that contains hafnium that above-mentioned enforcement obtains.It embodies a concentrated reflection of on the size of integral charge area (Q*) of cyclic voltammetry curve.The size of the integral charge area of cyclic voltammetry curve has determined the activity of electrode material.For example we are with the active electrode material that contains hafnium and the pure RuO that obtain
2Electrode material compares experiment, and the result shows that all that obtain contain the active electrode material of hafnium all than RuO
2The Q* of electrode material is significantly increased.Pure RuO
2The Q* of electrode material is generally 100 mC/cm
2About, and adopt the present technique preparation all contain the Q* of the active electrode material of hafnium can 600 ~ 1500 mC/cm
2About, not only its electro catalytic activity is than conventional RuO
2Electrode has increased significantly, and owing to adopted the base metal raw material, cost is greatly descended.As shown in Figure 1, traditional RuO
2The cyclic voltammetry curve of oxide coating anode, its electro catalytic activity seem outstanding not.And the Hf shown in the accompanying drawing 2
0.18Ru
0.82O
2The cyclic voltammetry curve of mixed oxide material can find out that the area of its encirclement is very large, particularly at the redox peak of the projection of 0.1～0.8V and 0.0～0.7V, embodies obvious high electro-catalysis feature.
The above only is preferred embodiment of the present invention, and all equalizations of doing according to the present patent application claim change and modify, and all should belong to covering scope of the present invention.
Claims (1)
1. active material that contains the Hf oxide is characterized in that: described active material is take Ru salt and Hf salt as the source material, and Hf: the Hf+Ru molar ratio is 3 ~ 7: 10;
Described Ru salt comprises RuCl
3, described Hf salt is HfCl
4, HfOCl
2Or HfO (NO
3)
2In any one;
Its preparation method comprises the steps:
1) preparation of active slurry: the active component of active slurry is with RuCl
3Be the source material, nonactive constituent element is with HfCl
4, HfOCl
2Or HfO (NO
3)
2In any one be the source material, according to described Hf: the Hf+Ru molar ratio takes by weighing each source material, and is dissolved in respectively in the alcoholic solution, after each source material of solid fully dissolves the two is mixed, and obtains active slurry;
2) sintering: with above-mentioned active slurry, through 80 ~ 100 ℃ of heating evaporations, again through 120 ~ 180 ℃ be heating and curing after, oxidation and sinter in 250 ~ 400 ℃ batch-type furnace, the cooling of coming out of the stove becomes the active material of the described Hf of containing oxide;
The molar concentration of the solute after mixing in the described step 1) is 2-3mol/L;
Alcoholic solution in the described step 1) comprises ethanol, isopropyl alcohol, n-butanol.
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| CN103693621B (en) * | 2012-09-27 | 2015-07-22 | 北京有色金属研究总院 | Preparation method of high-purity hafnium oxychloride |
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