CN111233467A - Oxide-doped scandium-zirconium powder and preparation method thereof - Google Patents
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Abstract
The invention provides an oxide-doped scandium-zirconium powder and a preparation method thereof. The method comprises the following steps: s1, mixing the scandium-containing zirconium solution with the acid solution of the doped metal oxide to obtain a scandium-zirconium mixed solution; wherein the metal element in the doped metal oxide is one or more of rare earth elements, alkaline earth metal elements, aluminum elements and bismuth elements except scandium elements; s2, adding a precipitator into the scandium-zirconium mixed solution to adjust the pH value of the system to 7-11, and carrying out precipitation reaction to obtain a scandium-zirconium precursor solution; s3, filtering the scandium-zirconium precursor solution to obtain a precipitate; then washing and drying the precipitate in sequence to obtain a scandium-zirconium precursor; and S4, calcining the scandium-zirconium precursor to obtain the scandium-zirconium powder doped with the oxide. By utilizing the preparation method provided by the invention, the problem of insufficient stability of the phase structure of the scandium-zirconium powder prepared in the prior art is effectively solved, and the scandium-zirconium powder doped with the oxide with the cubic phase as the main phase is obtained.
Description
Technical Field
The invention relates to the technical field of solid electrolyte materials, in particular to an oxide-doped scandium-zirconium powder and a preparation method thereof.
Background
The Solid Oxide Fuel Cell (SOFC) belongs to the third-generation fuel cell from the technical aspect, is an all-solid-state novel power generation device which directly and efficiently converts chemical energy stored in fuel and oxidant into electric energy, has the advantages of high energy conversion rate, strong fuel adaptability, environmental friendliness and the like, is more and more attracted by people, and has wide application prospect. The SOFC technology is industrialized in developed countries, such as Bloom Energy corporation in the united states, but in China, the development of SOFC has a certain gap with developed countries in europe and america.
The core component of an SOFC is a solid electrolyte. At present, most SOFCs use 6-10% Yttria Stabilized Zirconia (YSZ) as a solid electrolyte, which has high oxygen ion conductivity at high temperature (1000 ℃) but no electronic conductivity, and also has high chemical and physical stability, high mechanical strength, high thermal stability, very low chemical reactivity with other battery components, easy processability, moderate price and the like. However, YSZ materials also have certain limitations, and the operating temperature of the SOFC using YSZ as an electrolyte is generally 1000 ℃ or higher, which not only increases the investment and production cost of the SOFC, but also brings stability problems, such as oxidation of the connection plates, failure of sealing, electrode poisoning, etc., which affects the overall life of the cell stack and hinders practical application. Therefore, the work temperature is reduced to the medium temperature (500-800 ℃) which is the trend of the SOFC development at present. However, lowering the operating temperature lowers the ionic conductivity of the electrolyte and does not meet the requirements of medium and low temperature operation.
The scandia-stabilized zirconia (ScSZ) is the electrolyte material with the highest ion conductivity in the existing zirconium-based solid electrolyte, and can also be called scandium-zirconiumPowder having an electrical conductivity of about 0.12S-cm at 800 deg.C-12 times of the conductivity of YSZ, therefore, the defect of low electrolyte conductivity of YSZ at medium temperature can be solved to a great extent. Besides, the material and YSZ belong to zirconia-based materials, has similar chemical properties and high-temperature properties, and is convenient for selecting matched electrode materials, so that the material can replace YSZ electrolyte under the condition of not changing the preparation conditions of the existing process and becomes the preferred electrolyte of the intermediate-temperature SOFC.
At present, the preparation method of scandium-zirconium powder mainly comprises a solid-phase crushing method, a hydrothermal method, a sol-gel method and a coprecipitation method. 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 hydrothermal method has the advantages of high product purity, high crystallinity, uniform powder particle size, good sintering performance and the like, but generally has high requirements on equipment, complex operation and larger energy consumption, and is not suitable for industrialization. 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 is characterized in that a solution contains two or more cations which exist in the solution in a homogeneous phase, a precipitator is added, and precipitates with various uniform components can be obtained after precipitation reaction.
However, at present, the scandium-zirconium powder is difficult to obtain a fully stable cubic phase at room temperature, and most of the synthesized scandium-zirconium powder is accompanied by a tetragonal phase, a rhombohedral phase and other mixed phases, so that the electrolyte structure and the conductivity are affected. For the above reasons, there is a need to provide a new preparation process of scandium-zirconium powder, so as to increase the proportion of stable cubic phase and reduce the proportion of impurity phases such as tetragonal phase and rhombohedral phase.
Disclosure of Invention
The invention mainly aims to provide an oxide-doped scandium-zirconium powder and a preparation method thereof, and aims to solve the problem that the stability of the phase structure of the scandium-zirconium powder prepared in the prior art is insufficient.
In order to achieve the above object, according to an aspect of the present invention, there is provided a method for preparing an oxide-doped scandium-zirconium powder, including the steps of: s1, mixing the scandium-containing zirconium solution with the acid solution of the doped metal oxide to obtain a scandium-zirconium mixed solution; wherein the metal element in the doped metal oxide is one or more of rare earth elements, alkaline earth metal elements, aluminum elements and bismuth elements except scandium elements; s2, adding a precipitator into the scandium-zirconium mixed solution to adjust the pH value of the system to 7-11, and carrying out precipitation reaction to obtain a scandium-zirconium precursor solution; s3, filtering the scandium-zirconium precursor solution to obtain a precipitate; then washing and drying the precipitate in sequence to obtain a scandium-zirconium precursor; and S4, calcining the scandium-zirconium precursor to obtain the scandium-zirconium powder doped with the oxide.
Further, the doped metal oxide is one or more of cerium oxide, yttrium oxide, ytterbium oxide, bismuth oxide and aluminum oxide.
Furthermore, the cation concentration in the scandium-zirconium mixed solution is 0.01-2 mol/L, preferably 0.1-1 mol/L.
Further, in step S1, a dispersant is simultaneously added to the system to obtain a scandium-zirconium mixed solution, wherein the dispersant is a polyalcohols polymer, an ammonium salt of a polyalcohols, a polyalcohols polymer, an ammonium salt of a polyalkenoic acid, C2To C6One or more of the monohydric aliphatic alcohols of (a); preferably, the polyalkenyl high molecular polymer is polyvinyl alcohol and/or polypropylene alcohol; the ammonium salt of the polyvinyl alcohol is polyvinyl alcohol ammonium and/or polypropylene alcohol ammonium; the polymeric polyol high molecular polymer is one or more of polyethylene glycol and polytetramethylene glycol; the polyolefin high molecular polymer is one or more of polyacrylic acid, polymethacrylic acid and polyethylacrylic acid; the ammonium salt of the polyenoic acid is one or more of ammonium polyacrylate, ammonium polymethacrylate and ammonium polyethylacrylate; c2To C6The monohydric aliphatic alcohol is one or more of ethanol, n-propanol, isopropanol, n-butanol, isobutanol, n-pentanol and isoamylol; more preferably, the dispersant isOne or more of polyvinyl alcohol, ammonium polyacrylate, polyethylene glycol, polyacrylic acid, ammonium polyacrylate, ammonium polymethacrylate, ethanol and propanol.
Furthermore, in the scandium-zirconium mixed solution, the molar ratio of scandium ions is 8 to 13% relative to the total molar ratio of metal ions corresponding to scandium ions, zirconium ions and doped metal oxide, and the molar ratio of metal ions corresponding to doped metal oxide is 0.5 to 5%; preferably, the addition amount of the dispersing agent is 1-10% of the total weight of the solute of the scandium-containing zirconium-containing solution; more preferably, in the scandium-zirconium mixed solution, the molar ratio of scandium ions is 8.5 to 12% relative to the total molar ratio of metal ions corresponding to scandium ions, zirconium ions and doped metal oxide, and the molar ratio of metal ions corresponding to doped metal oxide is 0.7 to 3%; the addition amount of the dispersing agent is 2-9% of the total weight of the solute of the scandium-containing zirconium-containing solution.
Further, the scandium-containing zirconium-containing solution is formed by mixing a scandium-containing solution and a zirconium-containing solution, and 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 precipitant is one or more of ammonia water, ammonium bicarbonate, sodium hydroxide and urea.
Further, in step S2, the temperature of the precipitation reaction is 30-95 ℃, and the stirring speed is 100-2000 r/min.
Further, in the step S4, in the process of calcining the scandium-zirconium precursor, the calcining temperature is 600 to 1200 ℃, and the calcining time is 1 to 10 hours; preferably, the washing process comprises water washing and alcohol washing in sequence, more preferably alcohol; preferably, the drying temperature in the drying process is 80-200 ℃.
According to another aspect of the invention, the oxide-doped scandium-zirconium powder prepared by the preparation method is also provided.
The invention discloses an oxide-doped scandium-zirconium powder, which is prepared by adding an acid solution doped with metal oxide into a scandium-containing zirconium-containing solution before a coprecipitation step, and doping metal ions,Both scandium ions and zirconium ions are converted into precipitates. And then calcining to obtain a precipitate, wherein the precipitate forms doped metal oxide, scandium oxide and zirconium oxide composite powder. The metal element in the doped metal oxide is one or more of rare earth element, alkaline earth element, aluminum element and bismuth element except scandium element, the ionic radius of the metal element is similar to that of zirconium ion, and ZrO is doped with the metal element2Doped with scandium oxide and rare earth oxides other than scandium, or aluminum oxide, bismuth oxide, etc., optionally with Zr4+Forming cubic phase solid solution, making it cubic phase from room temperature to high temperature, entering into crystal lattice to cause certain crystal lattice distortion, increasing oxygen vacancy, and improving oxygen ion conductivity. Meanwhile, a part of scandium oxide is replaced by rare earth oxide or aluminum oxide, bismuth oxide and the like, so that the cost of the fuel cell can be reduced.
In a word, the preparation method effectively solves the problem that the scandium-zirconium powder prepared in the prior art is insufficient in phase structure stability, and the scandium-zirconium powder doped with the oxide with the cubic phase as the main phase is obtained.
Drawings
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 flow chart of a method for preparing an oxide-doped scandium-zirconium powder according to an embodiment of the present invention;
fig. 2 shows a flow chart of a method for preparing an oxide-doped scandium-zirconium powder according to another embodiment of the present 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 section, the scandium-zirconium powders prepared in the prior art have insufficient stability.
In order to solve the problem, the invention provides a preparation method of an oxide-doped scandium-zirconium powder, as shown in fig. 1, the preparation method comprises the following steps: s1, mixing the scandium-containing zirconium solution with the acid solution of the doped metal oxide to obtain a scandium-zirconium mixed solution; wherein the metal element in the doped metal oxide is one or more of rare earth elements, alkaline earth metal elements, aluminum elements and bismuth elements except scandium elements; s2, adding a precipitator into the scandium-zirconium mixed solution to adjust the pH value of the system to 7-11, and carrying out precipitation reaction to obtain a scandium-zirconium precursor solution; s3, filtering the scandium-zirconium precursor solution to obtain a precipitate; then washing and drying the precipitate in sequence to obtain a scandium-zirconium precursor; and S4, calcining the scandium-zirconium precursor to obtain the scandium-zirconium powder doped with the oxide.
The method provided by the invention is used for preparing the oxide-doped scandium-zirconium powder, and specifically comprises the steps of adding an acid solution doped with a metal oxide into a scandium-containing zirconium-containing solution before a coprecipitation step, and converting doped metal ions, scandium ions and zirconium ions into precipitates after coprecipitation. And calcining to obtain a precipitate, wherein the precipitate forms a doped metal oxide, scandium oxide and zirconium oxide composite powder, in the high-temperature calcining process, the phase structure in the powder is gradually stabilized, and metal ions in the doped metal oxide and scandium ions in the scandium oxide can partially replace the positions of zirconium ions to form a cubic phase solid solution. The metal elements in the adopted doped metal oxide are one or more of rare earth elements, alkaline earth elements, aluminum elements and bismuth elements except scandium elements, the ionic radius of the metal elements is close to that of zirconium ions, the proportion of stable cubic phases in the doped powder is higher, the number of impure phases is less, the integral phase structure of the powder is more stable, and the powder has good conductivity. In a word, the preparation method effectively solves the problem that the scandium-zirconium powder prepared in the prior art is insufficient in phase structure stability, and the scandium-zirconium powder doped with the oxide with the cubic phase as the main phase is obtained.
The acid solution of the doped metal oxide is formed by dissolving the doped metal oxide in acid, and for example, hydrochloric acid, sulfuric acid, nitric acid, etc. may be used.
In order to obtain scandium-zirconium powder with a more stable phase structure, in a preferred embodiment, the doped metal oxide is one or more of cerium oxide, yttrium oxide, ytterbium oxide, bismuth oxide and aluminum oxide. The oxides are used as doped oxides of scandium-zirconium powder, the cubic phase proportion in the powder is higher, the structure is more stable, and therefore the performances such as conductivity and the like are better.
In a preferred embodiment, the cation concentration in the scandium-zirconium mixed solution is 0.01 to 2 mol/L. Therefore, the distances of all cations in the mixed solution are proper, the generation of precipitates in the coprecipitation process has time difference, the formation of agglomeration is favorably reduced, and the dispersibility of the final powder can be improved. Meanwhile, the method is also beneficial to improving the precipitation efficiency of each metal ion. More preferably, the cation concentration in the scandium-zirconium mixed solution is 0.1 to 1 mol/L.
In a preferred embodiment, as shown in fig. 2, in step S1, a dispersant is simultaneously added to the system to obtain a scandium-zirconium mixed solution, wherein the dispersant is a polyalkenyl alcohol polymer, an ammonium salt of a polyalkenyl alcohol, a polyalkanol polymer, a polyalkanoic acid polymer, an ammonium salt of a polyalkenoic acid, C2To C6One or more of the monohydric aliphatic alcohols of (a). The dispersing agents are nonionic high molecular polymers or ammonium salts thereof, or micromolecular monohydric aliphatic alcohols, contain hydrophilic groups, and can improve the dispersibility of scandium ions and zirconium ions in a solution. In particular, the macromolecules of the former types are in a stretched state in water, and can form an organic polymer film on the surface of the precipitated particles to prevent association and aggregation among the particles, thereby eliminating and reducing the agglomeration of powder. And the high molecular polymer is adsorbed on the surfaces of zirconium and scandium to form a protective layer, so that aggregation and bonding among particles are prevented in space, and meanwhile, electrostatic repulsion is increased, and repulsion among particles is obviously improved. The magnitude of electrostatic repulsion between particles is decisive for the magnitude of the repulsion between particles. Therefore, after the precipitated particles formed at the initial stage of the reaction, the steric hindrance of the organic additive significantly reduces the rate of formation of the particles, making the reaction process more uniform, thereby effectively preventing or reducing the occurrence of the precipitation of the particlesThe formation of aggregates in the powder is reduced. Therefore, the operation effectively solves the agglomeration problem in the coprecipitation process, and the scandium-zirconium powder with good dispersion is obtained, which is more favorable for improving the conductivity of the scandium-zirconium powder.
In order to further improve the dispersing effect of the dispersing agent and solve the agglomeration problem in the coprecipitation process to obtain scandium-zirconium powder with better dispersibility, in a preferred embodiment, the polyalcohols high molecular polymer is polyvinyl alcohol and/or polypropylene alcohol; the ammonium salt of the polyvinyl alcohol is polyvinyl alcohol ammonium and/or polypropylene alcohol ammonium; the polymeric polyol high molecular polymer is one or more of polyethylene glycol and polytetramethylene glycol; the polyolefin high molecular polymer is one or more of polyacrylic acid, polymethacrylic acid and polyethylacrylic acid; the ammonium salt of the polyenoic acid is one or more of ammonium polyacrylate, ammonium polymethacrylate and ammonium polyethylacrylate; c2To C6The monohydric aliphatic alcohol is one or more of ethanol, n-propanol, isopropanol, n-butanol, isobutanol, n-pentanol and isoamylol. More preferably, the dispersant is polyvinyl alcohol (PVA), ammonium polyacrylate, polyethylene glycol (PEG), polyacrylic acid (PAA), ammonium Polyacrylate (PAANH)4) One or more of ammonium polymethacrylate, ethanol and propanol.
In a preferred embodiment, the scandium-zirconium mixed solution has a scandium ion molar ratio of 8 to 13% and a metal ion molar ratio of 0.5 to 5% relative to the total molar ratio of scandium ions, zirconium ions and metal ions corresponding to the doped metal oxide, for the purpose of improving the doping effect, improving the structural stability of the scandium-zirconium powder phase, improving the electrical conductivity, and the like. Preferably, the addition amount of the dispersing agent is 1-10% of the total weight of the scandium-zirconium mixed solution. The addition amount of the dispersing agent is controlled within the range, the dispersity of scandium ions, zirconium ions and doped metal ions is better, the excessive dispersing agent is favorably avoided to cause the over-slow precipitation reaction speed, and the coprecipitation process has better agglomeration inhibition capability and precipitation efficiency. More preferably, in the scandium-zirconium mixed solution, the molar ratio of scandium ions is 8.5 to 12% relative to the total molar ratio of metal ions corresponding to scandium ions, zirconium ions and doped metal oxide, and the molar ratio of metal ions corresponding to doped metal oxide is 0.7 to 3%; the addition amount of the dispersing agent is 2-9% of the total weight of the scandium-zirconium mixed solution.
The scandium-containing zirconium-containing solution may be of a type commonly used in coprecipitation production methods, and in a preferred embodiment, the scandium-containing zirconium-containing solution is a mixture of a scandium-containing solution and a zirconium-containing solution, and 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 after precipitation reaction, the coprecipitation effect is good. After the dispersing agent is used for dispersing, the scandium ions and the zirconium ions have better dispersibility, and have more proper particle forming rate in the coprecipitation process.
The precipitant can be one or more of ammonia, ammonium bicarbonate, sodium hydroxide and urea, and in order to further improve the coprecipitation effect, in a preferred embodiment, the precipitant includes but is not limited to ammonia, ammonium bicarbonate, sodium hydroxide and urea. More preferably, in step S2, the temperature of the precipitation reaction is 30-95 ℃, and the stirring speed is 100-2000 r/min.
In a preferred embodiment, in the step S4, in the process of calcining the scandium-zirconium precursor, the calcining temperature is 600 to 1200 ℃, and the calcining time is 1 to 10 hours. With this calcination condition, the precipitated colloid can be more sufficiently converted into scandia-stabilized zirconia powder, and stable formation of a phase structure can be promoted. Preferably, the drying temperature in the drying process is 80-200 ℃.
Preferably, the washing process comprises water washing and alcohol washing in sequence, more preferably alcohol. After the precipitate is obtained by filtering, washing with water and then with alcohol to replace non-bridging hydroxyl on the surface of the colloidal particles of the zirconium scandium precipitate by organic groups, thereby further reducing the agglomeration of powder during drying and calcining.
According to another aspect of the invention, the oxide-doped scandium-zirconium powder prepared by the preparation method is also provided. The powder has a stable cubic phase structure, less impure phases, more stable structure compared with the traditional scandium-zirconium powder, and correspondingly good conductivity.
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 Sc2O3、CeO2The scandium chloride and the cerium chloride are dissolved in hot hydrochloric acid to prepare a scandium chloride and cerium chloride solution, and the scandium chloride and the cerium chloride solution are mixed and stirred to obtain a scandium-zirconium mixed solution, wherein the cation concentration of the scandium-zirconium mixed solution is 1.5mol/L, the molar ratio of scandium ions is 10% relative to the total molar ratio of scandium ions, zirconium ions and Ce ions, and the molar ratio of Ce ions is 1%.
Coprecipitation: and (3) placing the mixed solution in a constant-temperature water bath kettle, wherein the reaction temperature is 50 ℃, the stirring speed is 200r/min, and adding ammonia water to adjust the pH value of the scandium-zirconium mixed solution to 9 to obtain a scandium-zirconium precursor solution. And filtering, washing and drying the prepared scandium-zirconium precursor solution to obtain a scandium-zirconium precursor.
And (3) calcining: and calcining the prepared scandium-zirconium precursor solid at 800 ℃ for 5 hours to obtain the scandium-zirconium powder.
Example 2:
preparing a reaction solution: dissolving zirconium oxychloride in water to obtain zirconium oxychloride solution, and adding Sc2O3、CeO2The scandium chloride and the cerium chloride are dissolved in hot hydrochloric acid to prepare a scandium chloride and cerium chloride solution, and the scandium chloride and the cerium chloride solution are mixed and stirred to obtain a scandium-zirconium mixed solution, wherein the cation concentration of the scandium-zirconium mixed solution is 0.01mol/l, the molar ratio of scandium ions is 8% relative to the total molar ratio of scandium ions, zirconium ions and Ce ions, and the molar ratio of Ce ions is 5%.
Coprecipitation: and (3) placing the mixed solution in a constant-temperature water bath kettle, wherein the reaction temperature is 30 ℃, the stirring speed is 500r/min, and adding ammonia water to adjust the pH value of the scandium-zirconium mixed solution to 11 to obtain a scandium-zirconium precursor solution. And filtering, washing and drying the prepared scandium-zirconium precursor solution to obtain a scandium-zirconium precursor.
And (3) calcining: and calcining the prepared scandium-zirconium precursor solid at 1200 ℃ for 1h to obtain the scandium-zirconium powder.
Example 3:
preparing a reaction solution: dissolving zirconium oxychloride in water to obtain zirconium oxychloride solution, and adding Sc2O3、Al2O3The scandium chloride and aluminum chloride solutions were prepared by dissolving in hot hydrochloric acid, and the solutions were mixed and stirred to obtain a scandium-zirconium mixed solution having a cation concentration of 0.1mol/l, a molar ratio of scandium ions of 10% relative to the total molar number of scandium ions, zirconium ions, and aluminum ions, and a molar ratio of aluminum ions of 1.5%.
Coprecipitation: and (3) placing the mixed solution in a constant-temperature water bath kettle, wherein the reaction temperature is 95 ℃, the stirring speed is 100r/min, and adding ammonia water to adjust the pH value of the scandium-zirconium mixed solution to 8.5 to obtain a scandium-zirconium precursor solution. And filtering, washing and drying the prepared scandium-zirconium precursor solution to obtain a scandium-zirconium precursor.
And (3) calcining: and calcining the prepared scandium-zirconium precursor solid at 600 ℃ for 10h to obtain the scandium-zirconium powder.
Example 4:
preparing a reaction solution: dissolving zirconium oxychloride in water to obtain zirconium oxychloride solution, and adding Sc2O3、CeO2The scandium chloride and the cerium chloride are dissolved in hot hydrochloric acid to prepare a scandium chloride and cerium chloride solution, and the scandium chloride and the cerium chloride solution are mixed and stirred to obtain a scandium-zirconium mixed solution, wherein the cation concentration of the scandium-zirconium mixed solution is 0.05mol/l, the molar ratio of scandium ions is 10% relative to the total molar ratio of scandium ions, zirconium ions and Ce ions, and the molar ratio of Ce ions is 1%.
Coprecipitation: and (3) placing the mixed solution in a constant-temperature water bath kettle, wherein the reaction temperature is 50 ℃, the stirring speed is 1000r/min, and adding urea to adjust the pH value of the scandium-zirconium mixed solution to 10 to obtain a scandium-zirconium precursor solution. And filtering, washing and drying the prepared scandium-zirconium precursor solution to obtain a scandium-zirconium precursor.
And (3) calcining: and calcining the prepared scandium-zirconium precursor solid at 800 ℃ for 5 hours to obtain the scandium-zirconium powder.
Example 5:
preparing a reaction solution: dissolving zirconium oxychloride in water to obtain zirconium oxychloride solution, and adding Sc2O3、Bi2O3The scandium chloride and bismuth chloride solution is prepared by dissolving in hot hydrochloric acid, and the scandium-zirconium mixed solution is obtained by mixing and stirring the above solutions, wherein the cation concentration of the scandium-zirconium mixed solution is 0.5mol/l, the molar ratio of scandium ions is 9% relative to the total molar ratio of scandium ions, zirconium ions and bismuth ions, and the molar ratio of bismuth ions is 2%.
Coprecipitation: and (3) placing the mixed solution in a constant-temperature water bath kettle, wherein the reaction temperature is 80 ℃, the stirring speed is 2000r/min, and adding ammonia water-sodium hydroxide to adjust the pH value of the scandium-zirconium mixed solution to 7 to obtain a scandium-zirconium precursor solution. And filtering, washing and drying the prepared scandium-zirconium precursor solution to obtain a scandium-zirconium precursor.
And (3) calcining: and calcining the prepared scandium-zirconium precursor solid at 800 ℃ for 3h to obtain the scandium-zirconium powder.
Example 6:
preparing a reaction solution: dissolving zirconium oxychloride in water to obtain zirconium oxychloride solution, and adding Sc2O3、Y2O3The scandium chloride and yttrium chloride solution is prepared by dissolving in hot hydrochloric acid, and the scandium-zirconium mixed solution is obtained by mixing and stirring the above solutions, wherein the cation concentration of the scandium-zirconium mixed solution is 2mol/l, the molar ratio of scandium ions is 10% relative to the total molar ratio of scandium ions, zirconium ions and yttrium ions, and the molar ratio of yttrium ions is 1%.
Coprecipitation: and (3) placing the mixed solution in a constant-temperature water bath kettle, wherein the reaction temperature is 30 ℃, the stirring speed is 1500r/min, and adding sodium hydroxide to adjust the pH value of the scandium-zirconium mixed solution to 9.5 to obtain a scandium-zirconium precursor solution. And filtering, washing and drying the prepared scandium-zirconium precursor solution to obtain a scandium-zirconium precursor.
And (3) calcining: and calcining the prepared scandium-zirconium precursor solid at 1100 ℃ for 5 hours to obtain the scandium-zirconium powder.
Example 7:
preparing a reaction solution: dissolving zirconium oxychloride in water to obtain zirconium oxychloride solution, and adding Sc2O3The scandium chloride solution was prepared by dissolving magnesium chloride in hot hydrochloric acid, the magnesium chloride solution was prepared by dissolving magnesium chloride in water, and the solutions were mixed and stirred to obtain a scandium-zirconium mixed solution, wherein the cation concentration of the scandium-zirconium mixed solution was 1.5mol/l, the molar ratio of scandium ions was 10% relative to the total molar ratio of scandium ions, zirconium ions, and magnesium ions, and the molar ratio of magnesium ions was 1%.
Coprecipitation: and (3) placing the mixed solution in a constant-temperature water bath kettle, wherein the reaction temperature is 50 ℃, the stirring speed is 200r/min, and adding ammonia water to adjust the pH value of the scandium-zirconium mixed solution to 9 to obtain a scandium-zirconium precursor solution. And filtering, washing and drying the prepared scandium-zirconium precursor solution to obtain a scandium-zirconium precursor.
And (3) calcining: and calcining the prepared scandium-zirconium precursor solid at 800 ℃ for 5 hours to obtain the scandium-zirconium powder.
Example 7 differs from example 1 in that the additive is magnesium oxide.
Example 8:
preparing a reaction solution: dissolving zirconium oxychloride in water to obtain zirconium oxychloride solution, and adding Sc2O3、CeO2The method comprises the steps of dissolving scandium chloride and cerium chloride in hot hydrochloric acid to obtain a solution, mixing the solution, adding polyethylene glycol (which is 1 wt% of the total solute mass of the mixed solution) serving as a dispersant, and mixing and stirring to obtain a scandium-zirconium mixed solution, wherein the cation concentration of the scandium-zirconium mixed solution is 1.5mol/l, the molar ratio of scandium ions is 10% relative to the total molar ratio of scandium ions, zirconium ions and Ce ions, and the molar ratio of Ce ions is 1%.
Coprecipitation: and (3) placing the mixed solution in a constant-temperature water bath kettle, wherein the reaction temperature is 50 ℃, the stirring speed is 300r/min, and adding ammonia water to adjust the pH value of the scandium-zirconium mixed solution to 7 to obtain a scandium-zirconium precursor solution. Filtering the prepared scandium-zirconium precursor solution, and repeatedly washing with water until no Cl exists-And then washed with alcohol for three times, and dried at 100 ℃ to prepare the scandium-zirconium precursor.
And (3) calcining: and calcining the prepared scandium-zirconium precursor solid at 800 ℃ for 5 hours to obtain the scandium-zirconium powder.
Example 9:
preparing a reaction solution: dissolving zirconium oxychloride in water to obtain zirconium oxychloride solution, and adding Sc2O3、CeO2The scandium chloride and the cerium chloride are dissolved in hot hydrochloric acid to prepare a scandium chloride and cerium chloride solution, the solutions are mixed, and a dispersing agent polyvinyl alcohol (PVA) (which is 5 wt% of the total solute mass of the mixed solution) is added for mixing and stirring to obtain a scandium-zirconium mixed solution, wherein the cation concentration of the scandium-zirconium mixed solution is 0.01mol/l, the mole ratio of scandium ions is 8% relative to the total mole ratio of scandium ions, zirconium ions and Ce ions, and the mole ratio of Ce ions is 2%. .
Coprecipitation: and (3) placing the mixed solution in a constant-temperature water bath kettle, wherein the reaction temperature is 30 ℃, the stirring speed is 600r/min, and adding ammonium bicarbonate to adjust the pH value of the scandium-zirconium mixed solution to 8 to obtain a scandium-zirconium precursor solution. Filtering the prepared scandium-zirconium precursor solution, and repeatedly washing with water until no Cl exists-And then washed with alcohol for three times, and dried at 80 ℃ to prepare the scandium-zirconium precursor.
And (3) calcining: and calcining the prepared scandium-zirconium precursor solid at 1200 ℃ for 1h to obtain the scandium-zirconium powder.
Example 10:
preparing a reaction solution: dissolving zirconium oxychloride in water to obtain zirconium oxychloride solution, and adding Sc2O3、Y2O3The scandium chloride and yttrium chloride solution is prepared by dissolving in hot hydrochloric acid, the above solutions are mixed, and dispersant polyacrylic acid (10 wt% of total solute mass of the mixed solution) is added for mixing and stirring to obtain scandium-zirconium mixed solution, wherein cation concentration of the scandium-zirconium mixed solution is 1mol/l, relative to total mole number of scandium ions, zirconium ions and yttrium ions, mole number of scandium ions is 13%, and mole number of yttrium ions is 0.5%.
Coprecipitation: and (3) placing the mixed solution in a constant-temperature water bath kettle, wherein the reaction temperature is 80 ℃, the stirring speed is 1000r/min, and adding ammonia water-ammonium bicarbonate to adjust the pH value of the scandium-zirconium mixed solution to 9 to prepare a scandium-zirconium precursor solution. Filtering the prepared scandium-zirconium precursor solution, and reacting with waterRepeatedly washing until no Cl is formed-And then washed with alcohol for three times, and dried at 100 ℃ to prepare the scandium-zirconium precursor.
And (3) calcining: and calcining the prepared scandium-zirconium precursor solid at 1000 ℃ for 3h to obtain the scandium-zirconium powder.
Example 11:
preparing a reaction solution: dissolving zirconium oxychloride in water to obtain zirconium oxychloride solution, and adding Sc2O3、Al2O3The scandium chloride and aluminum chloride solution is prepared by dissolving in hot hydrochloric acid, the above solutions are mixed, and dispersant polyallyl alcohol ammonium (3 wt% of the total solute mass of the mixed solution) is added to be mixed and stirred to obtain scandium-zirconium mixed solution, wherein the cation concentration of the scandium-zirconium mixed solution is 0.1mol/l, the mole ratio of scandium ions is 10% relative to the total mole ratio of scandium ions, zirconium ions and aluminum ions, and the mole ratio of aluminum ions is 1.5%.
Coprecipitation: and (3) placing the mixed solution in a constant-temperature water bath kettle, wherein the reaction temperature is 95 ℃, the stirring speed is 400r/min, and adding ammonia water to adjust the pH value of the scandium-zirconium mixed solution to 11 to obtain a scandium-zirconium precursor solution. Filtering the prepared scandium-zirconium precursor solution, and repeatedly washing with water until no Cl exists-And then washed with alcohol for three times, and dried at 200 ℃ to prepare the scandium-zirconium precursor.
And (3) calcining: and calcining the prepared scandium-zirconium precursor solid at 600 ℃ for 10h to obtain the scandium-zirconium powder.
Example 12:
preparing a reaction solution: dissolving zirconyl nitrate in water to obtain zirconyl nitrate solution, and adding Sc2O3、CeO2The method comprises the steps of dissolving scandium nitrate and cerium nitrate in hot nitric acid to obtain a solution, mixing the solution, adding a dispersant of ammonium polymethacrylate (accounting for 4 wt% of the total solute mass of the mixed solution), and mixing and stirring to obtain a scandium-zirconium mixed solution, wherein the cation concentration of the scandium-zirconium mixed solution is 0.05mol/l, the molar ratio of scandium ions is 10% relative to the total molar ratio of scandium ions, zirconium ions and Ce ions, and the molar ratio of Ce ions is 1%.
Coprecipitation: and (3) placing the mixed solution in a constant-temperature water bath kettle, wherein the reaction temperature is 50 ℃, the stirring speed is 1500r/min, and adding urea to adjust the pH value of the scandium-zirconium mixed solution to 9.5 to prepare a scandium-zirconium precursor solution. And filtering the prepared scandium-zirconium precursor solution, repeatedly washing with water until no nitrate radical exists, washing with alcohol for three times, and drying at 100 ℃ to obtain the scandium-zirconium precursor.
And (3) calcining: and calcining the prepared scandium-zirconium precursor solid at 800 ℃ for 5 hours to obtain the scandium-zirconium powder.
Example 13:
preparing a reaction solution: dissolving zirconium oxychloride in water to obtain zirconium oxychloride solution, and adding Sc2O3、Bi2O3The scandium chloride and bismuth chloride solution is prepared by dissolving in hot hydrochloric acid, the above solutions are mixed, and a dispersant ethanol (7 wt% of the total solute mass of the mixed solution) is added for mixing and stirring to obtain a scandium-zirconium mixed solution, wherein the cation concentration of the scandium-zirconium mixed solution is 0.5mol/l, the mole ratio of scandium ions is 9% relative to the total mole ratio of scandium ions, zirconium ions and bismuth ions, and the mole ratio of bismuth ions is 5%.
Coprecipitation: and (3) placing the mixed solution in a constant-temperature water bath kettle, wherein the reaction temperature is 80 ℃, the stirring speed is 2000r/min, and adding ammonia water-sodium hydroxide to adjust the pH value of the scandium-zirconium mixed solution to 8.5 to obtain a scandium-zirconium precursor solution. Filtering the prepared scandium-zirconium precursor solution, and repeatedly washing with water until no Cl exists-And then washed with alcohol for three times, and dried at 100 ℃ to prepare the scandium-zirconium precursor.
And (3) calcining: and calcining the prepared scandium-zirconium precursor solid at 800 ℃ for 3h to obtain the scandium-zirconium powder.
Example 14:
preparing a reaction solution: dissolving zirconium oxychloride in water to obtain zirconium oxychloride solution, and adding Sc2O3、CeO2Dissolving in hot hydrochloric acid to obtain scandium chloride and cerium chloride solutions, mixing the solutions, adding dispersant ammonium polyacrylate (1 wt% of the total solute mass of the mixed solution), and mixing and stirring to obtain scandium-zirconium mixed solution, wherein the cation concentration of the scandium-zirconium mixed solution is 2mol/l relative to scandium ions, zirconium ions and Ce ionsThe total molar number of moles of scandium ion was 10%, and the molar number of moles of Ce ion was 1%.
Coprecipitation: and (3) placing the mixed solution in a constant-temperature water bath kettle, wherein the reaction temperature is 60 ℃, the stirring speed is 200r/min, and adding sodium hydroxide to adjust the pH value of the scandium-zirconium mixed solution to 10 to obtain a scandium-zirconium precursor solution. Filtering the prepared scandium-zirconium precursor solution, and repeatedly washing with water until no Cl exists-And then washed with alcohol for three times, and dried at 100 ℃ to prepare the scandium-zirconium precursor.
And (3) calcining: and calcining the prepared scandium-zirconium precursor solid at 1100 ℃ for 5 hours to obtain the scandium-zirconium powder.
Example 15:
preparing a reaction solution: dissolving zirconyl nitrate in water to obtain zirconyl nitrate solution, and adding Sc2O3、CeO2The method comprises the steps of dissolving scandium nitrate and cerium nitrate in hot nitric acid to obtain a solution, mixing the solution, adding a dispersant propanol (which is 5 wt% of the total solute mass of the mixed solution), mixing and stirring to obtain a scandium-zirconium mixed solution, wherein the cation concentration of the scandium-zirconium mixed solution is 1mol/l, the mole ratio of scandium ions is 12% relative to the total mole ratio of scandium ions, zirconium ions and Ce ions, and the mole ratio of Ce ions is 0.5%.
Coprecipitation: and (3) placing the mixed solution in a constant-temperature water bath kettle, wherein the reaction temperature is 30 ℃, the stirring speed is 100r/min, and adding urea to adjust the pH value of the scandium-zirconium mixed solution to 8 to obtain a scandium-zirconium precursor solution. And filtering the prepared scandium-zirconium precursor solution, repeatedly washing with water until no nitrate radical exists, washing with alcohol for three times, and drying at 120 ℃ to obtain the scandium-zirconium precursor.
And (3) calcining: and calcining the prepared scandium-zirconium precursor solid at 800 ℃ for 7 hours to obtain the scandium-zirconium powder.
Example 16:
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, dissolving calcium chloride in water to obtain calcium chloride solution, mixing the above solutions, and adding dispersant polyethylene glycol (for mixing)1 wt% of the total solute mass of the solution) to obtain a scandium-zirconium mixed solution, wherein the cation concentration of the scandium-zirconium mixed solution is 1.5mol/l, the mole ratio of scandium ions is 10% and the mole ratio of calcium ions is 1% relative to the total mole ratio of scandium ions, zirconium ions and calcium ions.
Coprecipitation: and (3) placing the mixed solution in a constant-temperature water bath kettle, wherein the reaction temperature is 50 ℃, the stirring speed is 300r/min, and adding ammonia water to adjust the pH value of the scandium-zirconium mixed solution to 7 to obtain a scandium-zirconium precursor solution. Filtering the prepared scandium-zirconium precursor solution, and repeatedly washing with water until no Cl exists-And then washed with alcohol for three times, and dried at 100 ℃ to prepare the scandium-zirconium precursor.
And (3) calcining: and calcining the prepared scandium-zirconium precursor solid at 800 ℃ for 5 hours to obtain the scandium-zirconium powder.
Comparative example 1
Preparing a reaction solution: dissolving zirconium oxychloride in water to obtain zirconium oxychloride solution, and adding Sc2O3The scandium chloride solution was dissolved in hot hydrochloric acid to prepare a scandium chloride solution, and the solution was mixed and stirred to obtain a scandium-zirconium mixed solution, in which the cation concentration of the scandium-zirconium mixed solution was 1.5mol/L and the molar ratio of scandium ions was 10% relative to the total molar ratio of scandium ions and zirconium ions.
Coprecipitation: and (3) placing the mixed solution in a constant-temperature water bath kettle, wherein the reaction temperature is 50 ℃, the stirring speed is 200r/min, and adding ammonia water to adjust the pH value of the scandium-zirconium mixed solution to 9 to obtain a scandium-zirconium precursor solution. And filtering, washing and drying the prepared scandium-zirconium precursor solution to obtain a scandium-zirconium precursor.
And (3) calcining: and calcining the prepared scandium-zirconium precursor solid at 800 ℃ for 5 hours to obtain the scandium-zirconium powder.
The phase structures of the scandia-stabilized zirconia powders prepared in examples 1 to 16 and comparative example 1 were analyzed by X-ray diffraction, the agglomerate particle size was measured by a laser particle size analyzer, and the electric conductivity of the scandia-stabilized zirconia electrolyte ceramic sheet (the ceramic sheet was prepared by casting and sintering the scandia-stabilized zirconia powder prepared in examples 1 to 16 and comparative example 1) was measured by ac impedance spectroscopy, and the results are shown in table 1.
TABLE 1
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. The preparation method of the oxide-doped scandium-zirconium powder is characterized by comprising the following steps of:
s1, mixing the scandium-containing zirconium solution with the acid solution of the doped metal oxide to obtain a scandium-zirconium mixed solution; wherein the metal element in the doped metal oxide is one or more of a rare earth element other than scandium element, an alkaline earth metal element, an aluminum element, and a bismuth element;
s2, adding a precipitator into the scandium-zirconium mixed solution to adjust the pH value of the system to 7-11, and carrying out precipitation reaction to obtain a scandium-zirconium precursor solution;
s3, filtering the scandium-zirconium precursor solution to obtain a precipitate; then washing and drying the precipitate in sequence to obtain a scandium-zirconium precursor;
s4, calcining the scandium-zirconium precursor to obtain the oxide-doped scandium-zirconium powder.
2. The method of claim 1, wherein the doped metal oxide is one or more of cerium oxide, yttrium oxide, ytterbium oxide, bismuth oxide, and aluminum oxide.
3. The method according to claim 1, wherein the cation concentration in the scandium-zirconium mixed solution is 0.01 to 2mol/L, preferably 0.1 to 1 mol/L.
4. The method according to any one of claims 1 to 3, wherein in step S1, a dispersant is simultaneously added to the system to obtain the scandium-zirconium mixed solution, wherein the dispersant is a polyalkene alcohol polymer, an ammonium salt of a polyalkene alcohol, a polyalkene alcohol polymer, a polyalkene acid polymer, an ammonium salt of a polyalkene acid, C2To C6One or more of the monohydric aliphatic alcohols of (a);
preferably, the polyalkenyl high molecular polymer is polyvinyl alcohol and/or polypropylene alcohol; the ammonium salt of the polyenol is polyvinyl alcohol ammonium and/or polypropylene alcohol ammonium; the polymeric polyol high molecular polymer is one or more of polyethylene glycol and polytetramethylene glycol; the polyolefin high-molecular polymer is one or more of polyacrylic acid, polymethacrylic acid and polyethylacrylic acid; the ammonium salt of the polyenoic acid is one or more of ammonium polyacrylate, ammonium polymethacrylate and ammonium polyethylacrylate; said C is2To C6The monohydric aliphatic alcohol is one or more of ethanol, n-propanol, isopropanol, n-butanol, isobutanol, n-pentanol and isoamylol;
more preferably, the dispersant is one or more of polyvinyl alcohol, ammonium polyacrylate, polyethylene glycol, polyacrylic acid, ammonium polyacrylate, ammonium polymethacrylate, ethanol and propanol.
5. The method according to claim 4, wherein in the scandium-zirconium mixed solution, the molar ratio of scandium ions is 8 to 13% relative to the total molar number of scandium ions, zirconium ions, and metal ions corresponding to the doped metal oxide, and the molar number of metal ions corresponding to the doped metal oxide is 0.5 to 5%; preferably, the addition amount of the dispersing agent is 1-10% of the total weight of the solute of the scandium-containing zirconium-containing solution;
more preferably, in the scandium-zirconium mixed solution, the molar ratio of scandium ions is 8.5 to 12% with respect to the total molar number of scandium ions, zirconium ions, and metal ions corresponding to the doped metal oxide, and the molar number of metal ions corresponding to the doped metal oxide is 0.7 to 3%; the addition amount of the dispersing agent is 2-9% of the total weight of the solute of the scandium-containing zirconium-containing solution.
6. The production method according to any one of claims 1 to 5, wherein the scandium-containing zirconium-containing solution is a mixture of a scandium-containing solution and a zirconium-containing solution, and 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.
7. The method according to any one of claims 1 to 5, wherein the precipitant is one or more of ammonia water, ammonium bicarbonate, sodium hydroxide, and urea.
8. The method according to any one of claims 1 to 5, wherein in the step S2, the temperature of the precipitation reaction is 30 to 95 ℃, and the stirring speed is 100 to 2000 r/min.
9. The preparation method according to any one of claims 1 to 5, wherein in the step S4, in the process of calcining the scandium-zirconium precursor, the calcining temperature is 600 to 1200 ℃, and the calcining time is 1 to 10 hours; preferably, the washing process comprises water washing and alcohol washing which are carried out in sequence, and alcohol is more preferably adopted; preferably, the drying temperature in the drying process is 80-200 ℃.
10. An oxide-doped scandium-zirconium powder prepared by the preparation method of any one of claims 1 to 9.
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