CN102500368B - Ru-Hf-Sn ternary oxide active material and preparation method thereof - Google Patents
Ru-Hf-Sn ternary oxide active material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses an Ru-Hf-Sn ternary oxide active material and a preparation method thereof; RuCl3, HfCl4 and SnCl4 or SnCl2 serve as source substances, are respectively dissolved in ethanol, mixed uniformly and prepared into active slurry; and the active slurry is heated, evaporated, heated, cured, oxidized and sintered, and the Ru-Hf-Sn ternary oxide active material is obtained. The electrocatalysis performance of the active material is significantly improved compared with an Ru-Hf binary oxide active material, and the preparation method is simple, the operability is high, raw materials are easily available and the cost is low.
Description
Technical field
The invention belongs to the electrode material field of Applied Electrochemistry and energy industry, relate to a kind of material with high electrocatalysis characteristic and preparation method thereof, be specifically related to Ru-Hf-Sn ternary oxide active material 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 obviously reduce the consumption of noble metal, thereby reduce costs.The most common activating oxide has binary or the multivariant oxide materials such as Ti-Ru, Sn-Ru take titanium and tin as carrier, Ti-Ru-Ir, Sn-Ru-Ir, Sn-Ru-Ti.Adopting the oxide that has a different crystal structure with ruthenic oxide is that carrier is that people explore the important topic how further to reduce costs, other carrier of research also have 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 to systematic research, if find to control the crystal formation of oxide, will likely obtain novel mixed oxide active material.Hafnium oxide belongs to high-k material, adds this element and often is unfavorable for activity, and the research of this team is found, adopted suitable technology of preparing can obtain to have the oxide of cubic structure.It is mixed with ruthenic oxide, can prepare the material with high electrocatalysis characteristic, patent of invention (" a kind of Hf of containing oxide active material and preparation method thereof " application number 201110110826.X) has been applied in this invention.On this basis, this team finds, adopts and adds SnO
2Method, can obtain the more superior active material of Performance Ratio Ru-Hf binary oxide.
Summary of the invention
The object of the present invention is to provide a kind of Ru-Hf-Sn ternary oxide active material and preparation method thereof, this active material has more superior combination property than Ru-Hf binary oxide, and the preparation method is simple, and workable, raw material is easy to get, and cost is low.
For achieving the above object, the present invention adopts following technical scheme:
The oxide that contains Ru, Hf and Sn in Ru-Hf-Sn ternary oxide active material of the present invention.
In described active material, the mol ratio of Ru and Hf is 1:1.The molar content of Hf+Ru >=50% in described active material.In described active material, the mol ratio of Hf+Ru and Sn is 50-90: 10-50.In described active material, the mol ratio of Hf+Ru and Sn is 70: 30.
Described preparation method's concrete steps are as follows:
1) preparation of active slurry: active component is with RuCl
3For the source material, nonactive constituent element Hf is with HfCl
4For the source material, add element S n with SnCl
4Or SnCl
2For the source material; Mol ratio by Hf+Ru and Sn takes each source material, is dissolved in respectively ethanol, treats that abundant dissolving and mixing obtains active slurry;
2) sintering of active slurry: by the described active slurry of step 1), through 80 ~ 100 ℃ of heating evaporations to drying regime, again after 120 ~ 180 ℃ were heating and curing 10-30 minute, oxidation and sinter 1-2 hour in the batch-type furnace of 250 ~ 400 ℃, come out of the stove cooling, namely make described Ru-Hf-Sn ternary oxide active material.
Remarkable advantage of the present invention is:
(1) the present invention is by adopting suitable preparation technology, institutional framework that can stable coatings, and crystal grain thinning, thus can obtain the highly active Ru of containing oxide.By technique of the present invention, can obtain the oxide active material of ternary, for electrode material provides a kind of new Composition Design scheme.Due to the base metal element Hf and the Sn that contain high level, make the cost of electrode material greatly descend.
(2) adopt preparation technology of the present invention to solve to adopt the defect 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 the mixing of three kinds of ions, the final activated centre that obtains the institutional framework of high degree of dispersion and highly distribute, thus increased substantially the electro catalytic activity that contains the Ru oxide material.
(3) raw materials of the present invention's selection is simple, be easy to get, and 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, the Ru-Hf-Sn ternary oxide active material of acquisition, cost is very low, technique is simple, feasible, has reached practical and industrialized condition.
(4) Ru-Hf-Sn ternary oxide active material of the present invention has than existing RuO
2The electro catalytic activity that material is much higher, its stability and electro catalytic activity are also than RuO
2-HfO
2Be significantly improved, can be applied to electrochemistry parts and the devices such as aqueous solution electrolysis, electrochemical capacitance, organic solution electrolysis, fuel cell.
The accompanying drawing explanation
Fig. 1 is RuO
2Mixed oxide coating anode is at 0.5NH
2SO
4In in sweep speed, be the cyclic voltammetry curve of testing under 20mV/s.
Fig. 2 is Ru
0.35Hf
0.35Sn
0.30O
2Mixed oxide and Ru
0.5Hf
0.5O
2Mixed oxide coating anode is at 0.5NH
2SO
4In in sweep speed, be the cyclic voltammetry curve of testing under 20mV/s.
The specific embodiment
Thermolysis process is totally adopted in the preparation of Ru-Hf-Sn ternary oxide active material of the present invention.Concrete implementation step and mode are:
1) preparation of active slurry:
Active component is with RuCl
3For the source material, nonactive constituent element Hf adopts HfCl
4For the source material, Sn adopts SnCl
4Or SnCl
2For the source material.By above-mentioned (Hf+Ru): the Sn molar ratio takes each source material, and is dissolved in respectively ethanol, after solid medicine fully dissolves ethanol, they is mixed, and with magnetic stirrer, mixes standing 12h;
2) sintering of active slurry:
The active slurry that will contain hafnium, after 80 ~ 100 ℃ of heating evaporations, then after 120 ~ 180 ℃ are heating and curing, move in batch-type furnace, oxidation and sinter is 1 ~ 2 hour at the temperature of 250 ~ 400 ℃, comes out of the stove cooling, namely becomes and contains Hf, Ru, Sn ternary oxide active material powder.
3) preparation of active electrode material:
The preparation of active electrode material, can adopt the active slurry after being heating and curing, and batch-type furnace is directly inserted in repressed moulding, and oxidation and sinter is 1 ~ 2 hour at the temperature of 250 ~ 400 ℃, comes out of the stove cooling, namely becomes the oxide active electrode material of ternary; Also active powder (or slurry) can be sneaked into to other and support material (as inorganic material, material with carbon element etc.), mix compressing rear sintering, the active material powder is distributed in and support between material, become the electrode material of support type ternary active oxide; Also can be coated on the metal materials such as titanium material containing the active slurry gradation, be heating and curing, in the batch-type furnace of 250 ~ 400 ℃, oxidation and sinter is 10 minutes, come out of the stove cooling, and the heat treatment of finally annealing under 250 ~ 400 ℃ in batch-type furnace.Namely become the ternary oxide active coated Ti.
The present invention is to add Sn as additive by the composition characteristic of the active material of the ternary oxide of above-mentioned enforcement acquisition.Because at RuO
2-SnO
2In oxide, add again a considerable amount of Sn, made the content of noble ruthenium can relative reduce, to reducing material cost, played direct effect.
The present invention is to have very high electro catalytic activity by the performance characteristics of the ternary active material 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 by the active electrode material that contains hafnium and the pure RuO that obtain
2Electrode material carries out the contrast experiment, and 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
2Left and right, and adopt prepared by ternary oxide all contain the Q* of the active electrode material of hafnium can 1200 ~ 1700 mC/cm
2Left and right, not only its electro catalytic activity is than conventional RuO
2Electrode has increased significantly, and has adopted the base metal raw material, and 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 accompanying drawing 2
0.35Ru
0.35Sn
0.3O
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.Can find out simultaneously, the Area Ratio that the volt-ampere curve of ternary oxide electrode surrounds does not add the area that the volt-ampere curve of the binary oxide electrode of Sn surrounds and significantly improves, and demonstrates superior electrocatalysis characteristic.
Below describe three examples of implementation of the present invention in detail, but the present invention not only is limited to this.
Embodiment 1
The active slurry preparation of ternary mixed oxide material, with RuCl
3, HfCl
4And SnCl
4Or SnCl
2For the source material.In Hf: Ru: the Sn mol ratio is the ratio of 60: 60: 20, takes each source material, and is dissolved in respectively ethanolic solution, after solid medicine fully dissolves, they are mixed, adopt sonic oscillation to make it dispersed, make the concentration of solute be controlled at 2 mol/L left and right, and standing 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.By above-mentioned active slurry, with the brush pen, be coated on pretreated titanium plate, through 80 ~ 100 ℃ of heating evaporations, again through 120 ~ 180 ℃ after under infrared light, being heating and curing, oxidation 10min in the batch-type furnace of 270 ℃, 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, the 1h that anneals under 270 ℃ after applying for the last time and drying, come out of the stove cooling.The employing electrochemical workstation is measured, and the Q* of the active electrode material that obtains is 1360 mC/cm
2Left and right.
Embodiment 2
In Hf: Ru: the Sn mol ratio is the ratio of 35: 35: 30, takes each source material, and is dissolved in respectively ethanolic solution, after solid medicine fully dissolves, they are mixed, adopt sonic oscillation to make it dispersed, make the concentration of solute be controlled at 2 mol/L left and right, and standing 12h, be mixed with slurry.。By above-mentioned active slurry, with the brush pen, be coated on pretreated titanium plate and (see example 1), through 80 ~ 100 ℃ of heating evaporations, again through 120 ~ 180 ℃ after under infrared light, being heating and curing, oxidation 10min in the batch-type furnace of 280 ℃, 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, the 1h that anneals under 280 ℃ after applying for the last time and drying, come out of the stove cooling.The employing electrochemical workstation is measured, and the Q* of the active electrode material of the ternary oxide that obtains is 1800 mC/cm
2.
Embodiment 3
In Hf: Ru: the Sn mol ratio is the ratio of 25: 25: 50, takes each source material, and is dissolved in respectively ethanolic solution, after solid medicine fully dissolves, they are mixed, adopt sonic oscillation to make it dispersed, make the concentration of solute be controlled at 3 mol/L left and right, and standing 10h, be mixed with masking liquid.By above-mentioned active slurry, with the brush pen, be coated on pretreated titanium plate and (see example 1), through 80 ~ 100 ℃ of heating evaporations, again through 120 ~ 180 ℃ after under infrared light, being heating and curing, oxidation 10min in the batch-type furnace of 300 ℃, 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, the 1h that anneals under 300 ℃ after applying for the last time and drying, come out of the stove cooling.The employing electrochemical workstation is measured, and the Q* of the ternary oxide active electrode material that obtains is 1120 mC/cm
2.
The foregoing is only preferred embodiment of the present invention, all equalizations of doing according to the present patent application the scope of the claims change and modify, and all should belong to covering scope of the present invention.
Claims (1)
1. the preparation method of a Ru-Hf-Sn ternary oxide active material, is characterized in that: the oxide that contains Ru, Hf and Sn in described active material;
In described active material, the mol ratio of Ru and Hf is 1:1;
In described active material, the mol ratio of Hf+Ru and Sn is 5-9: 1-5;
Preparation method's concrete steps are as follows:
1) preparation of active slurry: active component is with RuCl
3For the source material, nonactive constituent element Hf is with HfCl
4For the source material, add element S n with SnCl
4Or SnCl
2For the source material; Mol ratio by Hf+Ru and Sn takes each source material, is dissolved in respectively ethanol, treats that abundant dissolving and mixing obtains active slurry;
2) sintering of active slurry: by the described active slurry of step 1), through 80 ~ 100 ℃ of heating evaporations to drying regime, again after 120 ~ 180 ℃ were heating and curing 10-30 minute, oxidation and sinter 1-2 hour in the batch-type furnace of 250 ~ 400 ℃, come out of the stove cooling, namely make described Ru-Hf-Sn ternary oxide active material.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102060327A (en) * | 2010-11-30 | 2011-05-18 | 福州大学 | Active material of Ru-containing stable zirconium oxide and preparation method thereof |
| CN102225334A (en) * | 2011-04-29 | 2011-10-26 | 福州大学 | Active material containing Hf (hydrogen fluoride) oxide and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102060327A (en) * | 2010-11-30 | 2011-05-18 | 福州大学 | Active material of Ru-containing stable zirconium oxide and preparation method thereof |
| CN102225334A (en) * | 2011-04-29 | 2011-10-26 | 福州大学 | Active material containing Hf (hydrogen fluoride) oxide and preparation method thereof |
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