CN111205088A - Method for preparing scandia-stabilized zirconia powder by hydrothermal method and scandia-stabilized zirconia powder prepared by method - Google Patents
Method for preparing scandia-stabilized zirconia powder by hydrothermal method and scandia-stabilized zirconia powder prepared by method Download PDFInfo
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Abstract
The invention provides a method for preparing scandia-stabilized zirconia powder by a hydrothermal method and the scandia-stabilized zirconia powder prepared by the method. The method comprises the following steps: s1, mixing the scandium-containing solution, the zirconium-containing solution and urea to obtain a mixed solution; s2, placing the mixed solution in a hydrothermal kettle, and carrying out hydrothermal reaction at the temperature of 100-250 ℃ to obtain a scandium-zirconium precursor solution; s3, filtering, washing and drying the scandium-zirconium precursor solution to obtain a scandium-zirconium precursor solid; and S4, calcining the scandium-zirconium precursor solid to obtain the scandia-stabilized zirconia powder. The method provided by the invention effectively solves the problems of high impurity content, serious agglomeration, large particle size, high raw material cost and the like in the preparation of the scandia-stabilized zirconia in the prior art.
Description
Technical Field
The invention relates to the technical field of solid electrolyte materials, in particular to a method for preparing scandia-stabilized zirconia powder by a hydrothermal method and the scandia-stabilized zirconia powder prepared by the method.
Background
Solid Oxide Fuel Cells (SOFC) are an efficient and clean energy conversion device, and electrolytes as a key component thereof are currently the focus of research. The operating temperature of the conventional yttria-stabilized zirconia (YSZ) electrolyte is generally high at 1000 ℃ or above to obtain high electric energy conversion efficiency, and such high operating temperature can cause serious problems of interface reaction, battery component failure and the like. Scandium oxide stabilized zirconia (ScSZ) is an electrolyte material with the highest ionic conductivity in the existing zirconium-based solid electrolyte, and the conductivity is about 2 times of the conductivity of YSZ at 800 ℃, so that the scandium oxide stabilized zirconia (ScSZ) becomes a preferred medium-low temperature electrolyte. The chemical composition, morphology, size and the like of the ScSZ powder directly influence the performance of the electrolyte ceramic, and the ScSZ powder plays an important role in the research of the ScSZ electrolyte ceramic material. For example, the monodisperse superfine ScSZ powder can reduce the sintering temperature of the electrolyte ceramic, improve the mechanical property of the electrolyte ceramic and improve the conductivity of the electrolyte ceramic. Therefore, the preparation of the ultrafine ScSZ powder with good dispersibility has important and long-term significance.
At present, the preparation method of the superfine ScSZ electrolyte powder mainly comprises a solid-phase crushing method, a sol-gel method, a coprecipitation method, a hydrothermal method and the like. The preparation methods have different principles and different operation modes, and the obtained products have great differences in appearance and performance. The solid phase crushing method has simple process, less pollution in the production process, good filling property, low cost and easy large-scale production, but can cause the pollution of powder, and the granularity after ball milling is relatively large. The sol-gel method can obtain the uniformity of the molecular level in a short time and realize the uniform doping on the molecular level, but the raw materials required by the sol-gel method are expensive, generally need to use an organic solvent, have certain toxicity to human bodies and are easy to harden. The coprecipitation method has the advantages of simple preparation process, low cost, easy industrialization and the like, but the coprecipitation method has the disadvantages of high sintering temperature, poor sintering performance and the like of ceramics due to easy agglomeration in the preparation process, and the application performance of the powder is seriously influenced.
Disclosure of Invention
The invention mainly aims to provide a method for preparing scandia-stabilized zirconia powder by a hydrothermal method and the scandia-stabilized zirconia powder prepared by the method, so as to solve the problems of high impurity content, serious agglomeration, large particle size, high raw material cost and the like in the preparation of scandia-stabilized zirconia in the prior art.
In order to achieve the above object, according to an aspect of the present invention, there is provided a method for preparing scandia-stabilized zirconia powder by a hydrothermal method, comprising the steps of: s1, mixing the scandium-containing solution, the zirconium-containing solution and urea to obtain a mixed solution; s2, placing the mixed solution in a hydrothermal kettle, and carrying out hydrothermal reaction at the temperature of 100-250 ℃ to obtain a scandium-zirconium precursor solution; s3, filtering, washing and drying the scandium-zirconium precursor solution to obtain a scandium-zirconium precursor solid; and S4, calcining the scandium-zirconium precursor solid to obtain the scandia-stabilized zirconia powder.
Further, the total molar concentration of scandium ions and zirconium ions in the mixed solution is 0.01-1.5 mol/l.
Further, the ratio of the total number of moles of scandium ions and zirconium ions to the number of moles of urea in the mixed solution is 1:15 to 50, preferably 1:25 to 35.
Further, the scandium-containing solution is an aqueous solution of scandium chloride or scandium nitrate; the zirconium-containing solution is an aqueous solution of zirconium chloride, zirconium nitrate, zirconium oxychloride or zirconium oxynitrate.
Further, the temperature of the hydrothermal reaction is 120-180 ℃.
Further, in step S4, the temperature for calcining the scandium-zirconium precursor solid is 450 to 1200 ℃, and the calcining time is 1 to 10 hours.
Furthermore, the reaction time of the hydrothermal reaction is 6-36 h.
Further, the ratio of the number of moles of scandium ions to the total number of moles of scandium ions and zirconium ions in the mixed solution is 8 to 13%.
According to another aspect of the invention, the scandia-stabilized zirconia powder prepared by the preparation method is also provided.
The invention provides a method for preparing scandia-stabilized zirconia powder by a hydrothermal method, which comprises the following steps: s1, mixing the scandium-containing solution, the zirconium-containing solution and urea to obtain a mixed solution; s2, placing the mixed solution in a hydrothermal kettle, and carrying out hydrothermal reaction at the temperature of 100-250 ℃ to obtain a scandium-zirconium precursor solution; s3, filtering, washing and drying the scandium-zirconium precursor solution to obtain a scandium-zirconium precursor solid; and S4, calcining the scandium-zirconium precursor solid to obtain the scandia-stabilized zirconia powder.
The hydrothermal method has the advantages of high product purity, high crystallinity, uniform powder particle size, good sintering performance and the like. In particular, the invention adds urea into scandium-containing and zirconium-containing solution, and the urea (CO (NH) is added in hydrothermal environment2)2) The ammonia gas is ionized into ammonia radicals and hydroxide radicals in the aqueous solution, and the hydroxide radicals are in the slow release process, so that the rate of generating precipitates through the reaction of scandium ions and zirconium ions with the hydroxide radicals is slow, uniform nucleation is realized, the agglomeration of particles is slowed, the size of the generated particles is small, and the dispersibility of scandium-zirconium precursor solids is good. And secondly, the scandium oxide stabilized zirconia powder which is uniform in particle size, small in size and good in dispersion can be obtained through calcination, the impurity content in the powder is low, and the powder is high in density and high in conductivity after sintering.
In a word, the method provided by the invention effectively solves the problems of high impurity content, serious agglomeration, large particle size, high raw material cost and the like in the preparation of the scandia-stabilized zirconia in the prior art.
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The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate embodiments of the invention and, together with the description, serve to explain the invention and not to limit the invention. In the drawings:
fig. 1 shows a schematic flow diagram of a method for preparing scandia-stabilized zirconia powder by a hydrothermal method according to an embodiment of the invention.
Detailed Description
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail below with reference to the embodiments with reference to the attached drawings.
As described in the background art, the problems of high impurity content, serious agglomeration, large particle size, high raw material cost and the like in the preparation of scandia-stabilized zirconia in the prior art are solved.
In order to solve the above problems, the present invention provides a method for preparing scandia-stabilized zirconia powder by a hydrothermal method, as shown in fig. 1, the method comprising the following steps: s1, mixing the scandium-containing solution, the zirconium-containing solution and urea to obtain a mixed solution; s2, placing the mixed solution in a hydrothermal kettle, and carrying out hydrothermal reaction at the temperature of 100-250 ℃ to obtain a scandium-zirconium precursor solution; s3, filtering, washing and drying the scandium-zirconium precursor solution to obtain a scandium-zirconium precursor solid; and S4, calcining the scandium-zirconium precursor solid to obtain the scandia-stabilized zirconia powder.
The hydrothermal method has the advantages of high product purity, high crystallinity, uniform powder particle size, good sintering performance and the like. In particular, the invention adds urea into scandium-containing and zirconium-containing solution, and the urea (CO (NH) is added in hydrothermal environment2)2) The ammonia gas is ionized into ammonia radicals and hydroxide radicals in the aqueous solution, and the hydroxide radicals are in the slow release process, so that the rate of generating precipitates through the reaction of scandium ions and zirconium ions with the hydroxide radicals is slow, uniform nucleation is realized, the agglomeration of particles is slowed, the size of the generated particles is small, and the dispersibility of scandium-zirconium precursor solids is good. And secondly, the scandium oxide stabilized zirconia powder which is uniform in particle size, small in size and good in dispersion can be obtained through calcination, the impurity content in the powder is low, and the powder is high in density and high in conductivity after sintering.
In a word, the method provided by the invention effectively solves the problems of high impurity content, serious agglomeration, large particle size, high raw material cost and the like in the preparation of the scandia-stabilized zirconia in the prior art.
In a preferred embodiment, the total molar concentration of scandium ions and zirconium ions in the mixed solution is 0.01 to 1.5 mol/l. Therefore, the distribution sparsity of scandium ions and zirconium ions in the mixed solution is more matched with the slow release speed of hydroxyl, the stable proceeding of the reaction is more facilitated, and the occurrence of agglomeration is reduced. In order to further improve the dispersibility during the hydrothermal reaction, the ratio of the total mole number of scandium ions and zirconium ions to the mole number of urea in the mixed solution is more preferably 1:15 to 50, and preferably 1:25 to 35. Thus, on the one hand, the reaction process is more stable, and on the other hand, the full reaction of scandium ions and zirconium ions is facilitated.
In a preferred embodiment, the mixed solution contains scandium ions in an amount of 8 to 13 mol% based on the total mol number of scandium ions and zirconium ions. The scandium ion ratio is within the above range, and the obtained scandia-stabilized zirconia powder has a more stable cubic phase structure, which contributes to further improvement of the electrical conductivity.
The scandium-containing zirconium-containing solution may be of the type commonly used in hydrothermal processes, and in a preferred embodiment, the scandium-containing solution is an aqueous solution of scandium chloride or scandium nitrate; the zirconium-containing solution is an aqueous solution of zirconium chloride, zirconium nitrate, zirconium oxychloride or zirconium oxynitrate. Scandium chloride, scandium nitrate, zirconium chloride, zirconium nitrate, zirconium oxychloride and zirconium oxynitrate have good solubility in water, and have good reaction effect after hydrothermal reaction. And the scandium-containing zirconium-containing solution is acidic.
In order to complete the hydrothermal reaction more fully and control the hydroxyl release rate more effectively to better match the precipitation rate, in a preferred embodiment, the temperature of the hydrothermal reaction is 120-180 ℃. More preferably, the reaction time is 6-36 h.
The calcination process may adopt a common process in the field, and in a preferred embodiment, in step S4, the temperature for calcining the scandium-zirconium precursor solid is 450 to 1200 ℃, and the calcination time is 1 to 10 hours. Therefore, scandium-zirconium precursor solid can be more fully calcined, and meanwhile, the stability of a phase state is facilitated, so that the performance of the powder is further improved.
In another aspect of the present invention, a scandia-stabilized zirconia powder prepared by the above preparation method is also provided. As described above, according to the method of the present invention, a hydrothermal method is adopted, and the characteristic that urea is decomposed under a high temperature acidic condition so as to slowly release hydroxyl groups is combined, such that problems of large particle size, agglomeration and the like are effectively solved, a scandia-stabilized zirconia powder with good dispersibility, uniform particle size and small size is obtained, and a ceramic plate formed by sintering the powder is used as a solid electrolyte, such that the ceramic plate has good conductivity, and the performance of a solid oxide fuel cell can be effectively improved.
The present application is described in further detail below with reference to specific examples, which should not be construed as limiting the scope of the invention as claimed.
Example 1:
preparing a reaction solution: dissolving zirconium oxychloride in water to obtain zirconium oxychloride solution, and adding Sc2O3The scandium chloride solution is prepared by dissolving in hot hydrochloric acid, the solutions are mixed, and urea (the molar ratio of cation to urea is 1:30) is added for mixing and stirring to prepare the scandium-zirconium mixed solution, wherein the cation concentration of the scandium-zirconium mixed solution is 0.5mol/l, and the molar ratio of scandium ions is 10% relative to the total molar ratio of scandium ions and zirconium ions.
Hydrothermal reaction: and (3) placing the mixed solution into a polytetrafluoroethylene hydrothermal reaction kettle, reacting at the temperature of 150 ℃ for 12 hours, cooling to room temperature after the reaction is finished, filtering, washing and drying to obtain scandium-zirconium precursor solid.
And (3) calcining: and calcining the prepared scandium-zirconium precursor solid at 900 ℃ for 5 hours to obtain the scandium oxide-stabilized zirconia powder.
Example 2:
preparing a reaction solution: dissolving zirconium oxychloride in water to obtain zirconium oxychloride solution, and adding Sc2O3Dissolving in hot hydrochloric acid to obtain scandium chloride solution, mixing the above solutions, adding urea (the molar ratio of cation to urea is 1:50), mixing and stirring to obtain scandium-zirconium mixed solution, wherein the cation concentration of the scandium-zirconium mixed solution is 1.5mol/l, the molar ratio of scandium ions relative to the total molar ratio of scandium ions and zirconium ions was 8%.
Hydrothermal reaction: and (3) placing the mixed solution into a polytetrafluoroethylene hydrothermal reaction kettle, reacting at 100 ℃ for 36 hours, cooling to room temperature after the reaction is finished, filtering, washing and drying to obtain scandium-zirconium precursor solid.
And (3) calcining: and calcining the prepared scandium-zirconium precursor solid at 450 ℃ for 10h to obtain the scandium oxide-stabilized zirconia powder.
Example 3:
preparing a reaction solution: dissolving zirconium oxychloride in water to obtain zirconium oxychloride solution, and adding Sc2O3The scandium chloride solution is prepared by dissolving in hot hydrochloric acid, the solutions are mixed, and urea (the molar ratio of cation to urea is 1:35) is added for mixing and stirring to prepare the scandium-zirconium mixed solution, wherein the cation concentration of the scandium-zirconium mixed solution is 0.01mol/l, and the molar ratio of scandium ions is 13% relative to the total molar ratio of scandium ions and zirconium ions.
Hydrothermal reaction: and (3) placing the mixed solution into a polytetrafluoroethylene hydrothermal reaction kettle, reacting at 200 ℃ for 6 hours, cooling to room temperature after the reaction is finished, filtering, washing and drying to obtain scandium-zirconium precursor solid.
And (3) calcining: and calcining the prepared scandium-zirconium precursor solid at 1200 ℃ for 1h to obtain the scandium oxide-stabilized zirconia powder.
Example 4:
preparing a reaction solution: dissolving zirconyl nitrate in water to obtain zirconyl nitrate solution, and mixing Sc2O3The scandium nitrate solution is prepared by dissolving in hot nitric acid, the solutions are mixed, and urea (the molar ratio of the cation to the urea is 1:10) is added for mixing and stirring to prepare the scandium-zirconium mixed solution, wherein the cation concentration of the scandium-zirconium mixed solution is 0.1mol/l, and the molar ratio of scandium ions is 11% relative to the total molar ratio of scandium ions and zirconium ions.
Hydrothermal reaction: and (3) placing the mixed solution into a polytetrafluoroethylene hydrothermal reaction kettle, reacting at 160 ℃ for 36 hours, cooling to room temperature after the reaction is finished, filtering, washing and drying to obtain scandium-zirconium precursor solid.
And (3) calcining: and calcining the prepared scandium-zirconium precursor solid at 850 ℃ for 5h to obtain the scandium oxide-stabilized zirconia powder.
Example 5:
preparing a reaction solution: dissolving zirconium oxychloride in water to obtain zirconium oxychloride solution, and adding Sc2O3The scandium chloride solution is prepared by dissolving in hot hydrochloric acid, the solutions are mixed, urea (the molar ratio of cation to urea is 1:30) is added, and the mixture is mixed and stirred to prepare the scandium-zirconium mixed solution, wherein the cation concentration of the scandium-zirconium mixed solution is 2mol/l, and the molar ratio of scandium ions is 10% relative to the total molar ratio of scandium ions and zirconium ions.
Hydrothermal reaction: and (3) placing the mixed solution into a polytetrafluoroethylene hydrothermal reaction kettle, reacting at the temperature of 150 ℃ for 12 hours, cooling to room temperature after the reaction is finished, filtering, washing and drying to obtain scandium-zirconium precursor solid.
And (3) calcining: and calcining the prepared scandium-zirconium precursor solid at 900 ℃ for 5 hours to obtain the scandium oxide-stabilized zirconia powder.
Example 6:
preparing a reaction solution: dissolving zirconium oxychloride in water to obtain zirconium oxychloride solution, and adding Sc2O3The scandium chloride solution is prepared by dissolving in hot hydrochloric acid, the solutions are mixed, and urea (the molar ratio of cation to urea is 1:10) is added for mixing and stirring to prepare the scandium-zirconium mixed solution, wherein the cation concentration of the scandium-zirconium mixed solution is 0.5mol/l, and the molar ratio of scandium ions is 10% relative to the total molar ratio of scandium ions and zirconium ions.
Hydrothermal reaction: and (3) placing the mixed solution into a polytetrafluoroethylene hydrothermal reaction kettle, reacting at the temperature of 150 ℃ for 12 hours, cooling to room temperature after the reaction is finished, filtering, washing and drying to obtain scandium-zirconium precursor solid.
And (3) calcining: and calcining the prepared scandium-zirconium precursor solid at 900 ℃ for 5 hours to obtain the scandium oxide-stabilized zirconia powder.
Example 7:
preparing a reaction solution: the method comprises the steps of dissolving zirconium sulfate in water to obtain a zirconium sulfate solution, dissolving scandium sulfate in water to obtain a scandium sulfate solution, mixing the solutions, adding urea (the molar ratio of cations to urea is 1:30), mixing and stirring to obtain a scandium-zirconium mixed solution, wherein the cation concentration of the scandium-zirconium mixed solution is 0.5mol/l, and the molar ratio of scandium ions is 10% relative to the total molar ratio of scandium ions and zirconium ions.
Hydrothermal reaction: and (3) placing the mixed solution into a polytetrafluoroethylene hydrothermal reaction kettle, reacting at the temperature of 150 ℃ for 12 hours, cooling to room temperature after the reaction is finished, filtering, washing and drying to obtain scandium-zirconium precursor solid.
And (3) calcining: and calcining the prepared scandium-zirconium precursor solid at 900 ℃ for 5 hours to obtain the scandium oxide-stabilized zirconia powder.
Comparative example 1:
preparing a reaction solution: dissolving zirconium oxychloride in water to obtain zirconium oxychloride solution, and adding Sc2O3The scandium chloride solution is prepared by dissolving in hot hydrochloric acid, the solutions are mixed, and urea (the molar ratio of cation to urea is 1:30) is added for mixing and stirring to prepare the scandium-zirconium mixed solution, wherein the cation concentration of the scandium-zirconium mixed solution is 0.5mol/l, and the molar ratio of scandium ions is 10% relative to the total molar ratio of scandium ions and zirconium ions.
Hydrothermal reaction: and (3) placing the mixed solution into a polytetrafluoroethylene hydrothermal reaction kettle, reacting at 80 ℃ for 12h, cooling to room temperature after the reaction is finished, filtering, washing and drying to obtain scandium-zirconium precursor solid.
And (3) calcining: and calcining the prepared scandium-zirconium precursor solid at 900 ℃ for 5 hours to obtain the scandium oxide-stabilized zirconia powder.
The agglomerated particle diameters of the scandia-stabilized zirconia powders prepared in examples 1 to 7 and comparative example 1 were measured by a laser particle size analyzer, and the electric conductivities of the scandia-stabilized zirconia electrolyte ceramic sheets (the ceramic sheets were prepared by tape casting and sintering the scandia-stabilized zirconia powders prepared in examples 1 to 7 and comparative example 1) were measured by an ac impedance spectroscopy, and the results of the measurements are shown in table 1.
TABLE 1
Comparative example 1 no product was obtained.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A method for preparing scandia-stabilized zirconia powder by a hydrothermal method is characterized by comprising the following steps:
s1, mixing the scandium-containing solution, the zirconium-containing solution and urea to obtain a mixed solution;
s2, placing the mixed solution in a hydrothermal kettle, and carrying out hydrothermal reaction at the temperature of 100-250 ℃ to obtain a scandium-zirconium precursor solution;
s3, filtering, washing and drying the scandium-zirconium precursor solution to obtain a scandium-zirconium precursor solid;
s4, calcining the scandium-zirconium precursor solid to obtain the scandia-stabilized zirconia powder.
2. The method according to claim 1, wherein the total molar concentration of scandium ions and zirconium ions in the mixed solution is 0.01-1.5 mol/l.
3. The method according to claim 2, wherein the ratio of the total number of moles of the scandium ions and the zirconium ions to the number of moles of the urea in the mixed solution is 1:15 to 50.
4. The method according to claim 2, wherein the ratio of the total number of moles of the scandium ions and the zirconium ions to the moles of the urea in the mixed solution is 1:25 to 35.
5. The method according to any one of claims 1 to 4, wherein the scandium-containing solution is an aqueous solution of scandium chloride or scandium nitrate; the zirconium-containing solution is an aqueous solution of zirconium chloride, zirconium nitrate, zirconium oxychloride or zirconium oxynitrate.
6. The method according to any one of claims 1 to 4, wherein the temperature of the hydrothermal reaction is 120 to 180 ℃.
7. The method according to any one of claims 1 to 4, wherein in the step S4, the temperature for calcining the scandium-zirconium precursor solid is 450 to 1200 ℃, and the calcining time is 1 to 10 hours.
8. The method according to any one of claims 1 to 4, wherein the reaction time of the hydrothermal reaction is 6-36 h.
9. The method according to claim 2 or 3, wherein the molar amount of scandium ions in the mixed solution is 8 to 13% relative to the total molar amount of scandium ions and zirconium ions.
10. A scandia-stabilized zirconia powder prepared by the method of any one of claims 1 to 9.
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