CN212315954U - Device for preparing scandium-zirconium powder - Google Patents

Abstract

The utility model provides a device of preparation scandium zirconium powder. The device comprises a first supply unit, a second supply unit, a third supply unit, a first mixing unit, a fourth supply unit, a microwave or ultrasonic reactor, a filtering unit, a washing unit, a drying unit and a calcining unit, wherein the microwave or ultrasonic reactor is respectively connected with the first mixing unit and the fourth supply unit and is used for carrying out coprecipitation reaction on a scandium-zirconium mixed solution under the condition of microwave heating or ultrasonic waves so as to obtain a precipitated material; and the filtering unit is connected with an outlet of the microwave or ultrasonic reactor, the washing unit is connected with an outlet of the filtering unit, the drying unit is connected with an outlet of the washing unit, and the calcining unit is connected with an outlet of the drying unit. The utility model discloses utilize microwave or ultrasonic wave to assist coprecipitation method preparation scandium zirconium powder body, effectively solved the easy problem of gathering of coprecipitation method among the prior art, correspondingly help improving its conductivity as the solid electrolyte powder body.

Description

Device for preparing scandium-zirconium powder

Technical Field

The utility model relates to a solid electrolyte material technical field particularly, relates to a device of preparation scandium zirconium powder.

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.

Scandia-stabilized zirconia (ScSZ), which is the highest ionic conductivity electrolyte material in the current zirconium-based solid electrolytes, is also called scandium-zirconium powder, and has a conductivity of about 0.12S-cm at 800 ℃^-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 the ScSZ electrolyte 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 uniform precipitates of various components can be obtained after precipitation reaction. However, the coprecipitation method has the disadvantages that agglomeration is easy to occur in the preparation process, the sintering temperature of the ceramic is high, the sintering performance is poor and the like, and the application performance of the powder, such as the reduction of the conductivity, is seriously influenced.

SUMMERY OF THE UTILITY MODEL

A primary object of the present invention is to provide a device for preparing scandium-zirconium powder, which solves the problem of easy agglomeration in the prior art that scandium-zirconium powder is prepared by coprecipitation method.

In order to achieve the above object, according to an aspect of the present invention, there is provided an apparatus for preparing scandium-zirconium powder, including: a first supply unit for supplying a polyalkenyl alcohol-based high-molecular polymer, an ammonium salt of a polyalkenyl alcohol, a polyalkanol-based high-molecular polymer, a polyalkenyl acid-based high-molecular polymer, an ammonium salt of a polyalkenyl acid, or a monohydric aliphatic alcohol of C2 to C6 as a dispersant; a second supply unit for supplying a solution containing scandium ions and zirconium ions; a third supply unit including a doped metal oxide supply bin for supplying a doped metal oxide, a metal element of the doped metal oxide being a rare earth element other than scandium, an aluminum element, or a bismuth element, an acid solution supply unit for supplying an acid, and a dissolving unit connected to the doped metal oxide supply bin and the acid solution supply unit, respectively, for dissolving the doped metal oxide in the acid to form a doped metal acid solution; the first mixing unit is respectively connected with the first supply unit, the second supply unit and the dissolving unit and is used for mixing the dispersing agent, the doped metal acid solution and the solution containing scandium ions and zirconium ions to obtain a scandium-zirconium mixed solution; a fourth supply unit for supplying a precipitant; the microwave or ultrasonic reactor is respectively connected with the first mixing unit and the fourth supply unit and is used for carrying out coprecipitation reaction on the scandium-zirconium mixed solution under the condition of microwave heating or ultrasonic waves to obtain a precipitated material; the filtering unit is connected with an outlet of the microwave or ultrasonic reactor and is used for filtering the precipitated materials to obtain precipitated colloid; the washing unit is connected with the outlet of the filtering unit and is used for washing the precipitated colloid to obtain a washing colloid; the drying unit is connected with the outlet of the washing unit and is used for drying the washing colloid to obtain a dry material; and the calcining unit is connected with the outlet of the drying unit and is used for calcining the dry materials to obtain scandium-zirconium powder.

Further, the washing unit includes first washing unit and the second washing unit of establishing ties and setting between filter unit and drying unit, and first washing unit still is provided with the water inlet, and the second washing unit still is provided with the alcohol import, and the washing unit still includes: the water supply unit is connected with the water inlet; and the alcohol supply unit is connected with the alcohol inlet.

Further, the drying unit is a freeze dryer.

Further, the filtration unit is a centrifuge or a filter press.

Further, the second supply unit includes: a scandium-containing solution supply unit for supplying an aqueous solution of scandium chloride or scandium nitrate; a zirconium-containing solution supply unit for supplying an aqueous solution of zirconium chloride, zirconium nitrate, zirconium oxychloride or zirconium oxynitrate; and the second mixing unit is respectively connected with the scandium-containing solution supply unit and the zirconium-containing solution supply unit and is used for mixing the solutions supplied by the scandium-containing solution supply unit and the zirconium-containing solution supply unit to form a scandium-zirconium mixed solution, and an outlet of the second mixing unit is connected with an inlet of the first mixing unit.

Further, the device also comprises a pH detection unit, and the pH detection unit is used for detecting the pH value of the reaction system in the microwave reactor.

Furthermore, the device also comprises a precipitant flow control meter, wherein the precipitant flow control meter is arranged on a pipeline connected with the fourth supply unit and the microwave or ultrasonic reactor, and is used for adjusting the flow of the precipitant according to the detection result of the pH detection unit so as to maintain the pH value of the reaction system at 7-11.

Further, the fourth supply unit is for supplying a sodium hydroxide solution, an ammonium bicarbonate solution, or ammonia water as a precipitant.

Furthermore, a stirring device is also arranged in the microwave or ultrasonic reactor.

Use the utility model discloses a device, after placing scandium zirconium mixed solution in microwave or ultrasonic reactor, to wherein adding the precipitant and carrying out precipitation reaction. And then, filtering, washing, drying and calcining the obtained scandium-zirconium precursor solution to obtain scandium-zirconium powder. The microwave-assisted method has the advantages of simplicity, rapidness, high efficiency, greenness and the like, and the microwave heating mode from inside to outside ensures that a reaction system is heated quickly and uniformly, can effectively prevent the agglomeration of nano powder, and has a complete crystal structure of a product. Therefore, the sample prepared by the microwave synthesis method has the excellent characteristics of higher purity, narrower particle size distribution, more uniform shape and the likeAnd (4) sex. Ultrasonic wave means that the frequency range is 2 x 10⁴～1×10⁹The Hz sound wave has the wave speed of about 1500m/s, which exceeds the upper limit of the hearing of people, and the ultrasonic wave is a wave form and can be used as a carrier for detecting and loading information; meanwhile, the ultrasonic wave is an energy form, the ultrasonic wave can accelerate chemical reaction or trigger a new reaction channel, and the ultrasonic wave interacts with a medium in the propagation process to generate an ultrasonic effect. The utility model discloses carry out precipitation reaction in microwave or ultrasonic reactor, effectively improved the problem that coprecipitation in-process precipitation colloid easily reunited. Meanwhile, after the precipitate is obtained, firstly, washing with water and then washing with alcohol to enable the organic groups to replace non-bridging hydroxyl groups on the surfaces of the colloidal particles of the zirconium scandium precipitate, so that the agglomeration of powder in drying and calcining can be further reduced. Based on the reason in above several aspects, the utility model discloses utilize microwave or ultrasonic wave to assist coprecipitation method preparation scandium zirconium powder body, effectively solved the easy problem of gathering of coprecipitation method among the prior art, correspondingly help improving its conductivity as solid electrolyte powder body.

Drawings

The accompanying drawings, which form a part of the present application, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, 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 block diagram of a device for preparing scandium-zirconium powder according to an embodiment of the present invention.

Wherein the figures include the following reference numerals:

10. a first supply unit; 20. a second supply unit; 30. a third supply unit; 31. a doped metal oxide supply bin; 32. an acid solution supply unit; 33. a dissolving unit; 40. a first mixing unit; 50. a fourth supply unit; 60. a microwave or ultrasonic reactor; 70. a filtration unit; 80. a washing unit; 81. a first washing unit; 82. a second washing unit; 83. A water supply unit; 84. an alcohol supply unit; 90. a drying unit; 100. a calcination unit.

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 accompanying drawings in conjunction with embodiments.

As described in the background section, there is a problem of easy agglomeration in the preparation of scandium-zirconium powder by using a coprecipitation method in the prior art.

In order to solve the problem, the present invention provides an apparatus for preparing scandium-zirconium powder, as shown in fig. 1, the apparatus comprises a first supply unit 10, a second supply unit 20, a third supply unit 30, a first mixing unit 40, a fourth supply unit 50, a microwave or ultrasonic reactor 60, a filtering unit 70, a washing unit 80, a drying unit 90, and a calcining unit 100; the first supply unit 10 is used for supplying polyalkenyl alcohol high-molecular polymer, ammonium salt of polyalkenyl alcohol, polyalkenyl alcohol high-molecular polymer, polyalkenyl acid high-molecular polymer, ammonium salt of polyalkenyl acid or monohydric aliphatic alcohol of C2-C6 as dispersing agent; the second supply unit 20 is for supplying a solution containing scandium ions and zirconium ions; the third supply unit 30 includes a doped metal oxide supply bin 31 for supplying a doped metal oxide of which metal element is a rare earth element other than scandium, an aluminum element, or a bismuth element, an acid solution supply unit 32 for supplying an acid, and a dissolving unit 33 connected to the doped metal oxide supply bin 31 and the acid solution supply unit 32, respectively, for dissolving the doped metal oxide in the acid to form a doped metal acid solution; the first mixing unit 40 is respectively connected with the first supply unit 10, the second supply unit 20 and the dissolving unit 33, and is used for mixing the dispersing agent, the doped metal acid solution and the solution containing scandium ions and zirconium ions to obtain a scandium-zirconium mixed solution; the fourth supply unit 50 is for supplying a precipitant; the microwave or ultrasonic reactor 60 is respectively connected with the first mixing unit 40 and the fourth supply unit 50, and is used for carrying out coprecipitation reaction on the scandium-zirconium mixed solution under the condition of microwave heating or ultrasonic wave to obtain a precipitated material; the filtering unit 70 is connected to an outlet of the microwave or ultrasonic reactor 60, and is used for filtering the precipitated material to obtain a precipitated colloid; the washing unit 80 is connected to an outlet of the filtering unit 70, and is used for washing the precipitated colloid to obtain a washing colloid; the drying unit 90 is connected with the outlet of the washing unit 80 and is used for drying the washing colloid to obtain dry materials; the calcining unit 100 is connected with the outlet of the drying unit 90 and is used for calcining the dry materials to obtain the doped scandium-zirconium powder body.

The utility model provides a device of preparation scandium zirconium powder, specifically: after the dispersing agent in the first supply unit, the solution containing scandium ions and zirconium ions in the second supply unit and the doped metal acid solution prepared by the third supply unit are mixed in the first mixing unit, the formed scandium-zirconium mixed solution is subjected to coprecipitation reaction in a microwave or ultrasonic reactor. In the process, the microwave reactor can heat the reaction system from inside to outside through microwaves, so that the reaction system is heated quickly and uniformly, the agglomeration of the nano powder can be effectively prevented, and the crystal structure of the product is complete. The ultrasonic wave can accelerate chemical reaction or trigger a new reaction channel, and the ultrasonic wave interacts with a medium in the propagation process to generate an ultrasonic effect. Meanwhile, the added dispersing agent is a nonionic high-molecular polymer or ammonium salt thereof, or a micromolecular monohydric aliphatic alcohol, contains hydrophilic groups, and can improve the dispersibility of scandium ions and zirconium ions in the 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 in the initial stage of the reaction, the steric hindrance of the organic additive significantly reduces the rate of particle formation, making the reaction process more uniform, thereby effectively preventing or reducing the formation of agglomerates in the powder. In addition, the acid solution doped with the metal oxide and supplied by the third supply unit also participates in the coprecipitation reaction, during which the doped metal ions and the scandium-zirconium ions react to form a precipitated colloid, and then the precipitated colloid is dried and calcined to form a doped scandium-zirconium powder, so that the proportion of cubic phases in the powder is increased, and the phase structure stability of the powder is improved.

In summary, the doped scandium-zirconium powder prepared by the device provided by the utility model has narrower particle size distribution and more uniform shape due to the use of the dispersing agent and the microwave or ultrasonic reactor, and stabilizes the cubic phase structure due to the introduction of the doped metal. Therefore, the utility model discloses the doped scandium zirconium powder body of preparation is high through sintering back density, and the conductivity is high.

The acid solution supply unit 32 supplies hydrochloric acid, sulfuric acid, nitric acid, or the like.

The above washing process may be water washing, and in order to further improve the washing effect, in a preferred embodiment, the washing unit 80 includes a first washing unit 81 and a second washing unit 82 which are serially disposed between the filtering unit 70 and the drying unit 90, the first washing unit 81 is further provided with a water inlet, the second washing unit 82 is further provided with an alcohol inlet, and the washing unit 80 further includes: a water supply unit 83 connected to the water inlet; an alcohol supply unit 84 connected to the alcohol inlet. Therefore, the scandium-zirconium precipitated colloid can be washed by water firstly and then washed by alcohol, and organic groups can replace non-bridging hydroxyl groups on the surface of the precipitated colloid particles by using the alcohol washing, so that the method is favorable for avoiding the aggregation of nano particles easily caused by the combination effect of the surface tension of water on the particles, particularly during high-temperature drying, and further reducing the aggregation of powder during drying and calcining. In the actual operation process, water washing and alcohol washing can be performed for multiple times, for example, the water washing is performed for 3-5 times, and the alcohol washing is performed for 1-3 times.

In a preferred embodiment, the drying unit 90 is a freeze dryer. Compared with other drying forms, the low-temperature freeze drying is carried out by adopting a freeze dryer, which is beneficial to further preventing the washed colloid from agglomerating, so that the dispersibility of the final doped scandium-zirconium powder can be further improved. The above-described filtration unit 70 may take a form commonly used in the art, and in a preferred embodiment, the filtration unit 70 is a centrifuge or a filter press. Centrifugal filtration and filter pressing filtration are adopted, so that solid-liquid separation is more sufficient.

The scandium-containing zirconium-containing solution may be of a type commonly used in the art, and in a preferred embodiment, the second supply unit 20 includes: a scandium-containing solution supply unit for supplying an aqueous solution of scandium chloride or scandium nitrate; a zirconium-containing solution supply unit for supplying an aqueous solution of zirconium chloride, zirconium nitrate, zirconium oxychloride or zirconium oxynitrate; and the second mixing unit is respectively connected with the scandium-containing solution supply unit and the zirconium-containing solution supply unit and is used for mixing the solutions supplied by the scandium-containing solution supply unit and the zirconium-containing solution supply unit to form a scandium-zirconium mixed solution, and the outlet of the second mixing unit is connected with the inlet of the first mixing unit 40. 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.

In order to stabilize the coprecipitation process and improve the precipitation effect, the apparatus preferably further includes a pH detection unit for detecting a pH value of the reaction system in the microwave or ultrasonic reactor 60. Thus, the pH value of the reaction system can be detected in real time by the pH detection unit, so that the reaction system is maintained in a stable state, and the progress of the precipitation reaction can be promoted. More preferably, the apparatus further comprises a precipitant flow control meter disposed on a pipeline connecting the fourth supply unit 50 and the microwave or ultrasonic reactor 60, and the precipitant flow control meter is configured to adjust the flow rate of the precipitant according to the detection result of the pH detection unit to maintain the pH of the reaction system at 7-11. The pH value is maintained at 7-11, and the coprecipitation reaction effect is better.

The precipitant may be a precipitant commonly used in the co-precipitation process, and in order to further improve the co-precipitation effect, in a preferred embodiment, the fourth supply unit 50 is configured to supply a sodium hydroxide solution, an ammonium bicarbonate solution, or ammonia water as the precipitant. Specifically, a sodium hydroxide solution with the concentration of 50-120 g/L, an ammonium bicarbonate solution with the concentration of 5-20 g/L or 5-25 wt% ammonia water can be adopted as a precipitator.

In order to further prevent the agglomeration of the crystal nuclei during the precipitation, it is preferable that a stirring device is further provided in the microwave or ultrasonic reactor 60.

According to another aspect of the present invention, there is provided a method for preparing scandium-zirconium powder, the method comprising the steps of: mixing the scandium-containing solution and the zirconium-containing solution to obtain a scandium-zirconium mixed solution; placing the scandium-zirconium mixed solution in a microwave reactor or an ultrasonic reactor, adding a precipitator into the scandium-zirconium mixed solution under the action of microwave heating or ultrasonic waves, and adjusting the pH value of the system to 7-11 so as to perform precipitation reaction on the system, thereby obtaining a scandium-zirconium precursor solution; filtering the scandium-zirconium precursor solution to obtain a precipitate; then washing, washing with alcohol and drying the precipitate in sequence to obtain a scandium-zirconium precursor; and calcining the scandium-zirconium precursor to obtain scandium-zirconium powder.

The microwave-assisted method has the advantages of simplicity, rapidness, high efficiency, greenness and the like, and the microwave heating mode from inside to outside ensures that a reaction system is heated quickly and uniformly, can effectively prevent the agglomeration of nano powder, and has a complete crystal structure of a product. Therefore, the sample prepared by the microwave synthesis method has the excellent characteristics of higher purity, narrower particle size distribution, more uniform shape and the like. Ultrasonic wave means that the frequency range is 2 x 10⁴～1×10⁹The Hz sound wave has the wave speed of about 1500m/s, which exceeds the upper limit of the hearing of people, and the ultrasonic wave is a wave form and can be used as a carrier for detecting and loading information; meanwhile, the ultrasonic wave is an energy form, the ultrasonic wave can accelerate chemical reaction or trigger a new reaction channel, and the ultrasonic wave interacts with a medium in the propagation process to generate an ultrasonic effect. The utility model discloses carry out precipitation reaction in microwave or ultrasonic reactor, effectively improved the problem that coprecipitation in-process precipitation colloid easily reunited. Meanwhile, after the precipitate is obtained, firstly, washing with water and then washing with alcohol to enable the organic groups to replace non-bridging hydroxyl groups on the surfaces of the colloidal particles of the zirconium scandium precipitate, so that the agglomeration of powder in drying and calcining can be further reduced. Based on the reasons in the aspects above, the utility model discloses utilize microwave or ultrasonic wave to assist coprecipitation method preparation scandium zirconium powder body, effectively solved the easy reunion problem of coprecipitation method among the prior art, correspondingly help improving it as solid electrolyteThe electrical conductivity of the powder.

In a preferred embodiment, during the preparation of the scandium-zirconium mixed solution, an acid solution of a doped metal oxide is added to the system at the same time, wherein the metal element in the doped metal oxide is one or more of a rare earth element other than scandium element, an aluminum element and a bismuth element. In the coprecipitation process, metal ions, scandium ions and zirconium ions are doped to form coprecipitation colloid, and then, after calcination, the doped metal atoms and scandium atoms can partially replace the positions of the zirconium atoms to form doped scandium-zirconium powder. And because the ionic radius of the doped metal element is similar to that of zirconium ion, the doped metal element can be formed into ZrO₂Doped 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. Therefore, the problem of unstable phase structure of the scandium-zirconium powder can be effectively solved by adding the acid solution doped with the metal oxide, so that the doped scandium-zirconium powder with more stable phase structure is obtained, and the powder has better conductivity correspondingly. Preferably, the doped metal oxide is one or more of cerium oxide, yttrium oxide, bismuth oxide and aluminum oxide.

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 a preferred embodiment, during the preparation of the scandium-zirconium mixed solution, a dispersant is simultaneously added into the system, wherein the dispersant is a polyalkenyl alcohol high polymer, an ammonium salt of polyalkenyl alcohol, a polyatomic alcohol high polymer, a polyalkenyl acid high polymer, an ammonium salt of polyalkenyl acid, C₂To C₆One or more of the monohydric aliphatic alcohols of (a). The dispersants are nonionic high molecular polymers or ammonium salts thereof, or small molecular monohydric aliphatic alcohols, contain hydrophilic groups, and can improve scandium ions and zirconium ions in solutionDispersion in (2) medium. 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 in the initial stage of the reaction, the steric hindrance of the organic additive obviously reduces the formation rate of the particles, so that the reaction process is more uniformly carried out, and the formation of aggregates in the powder is effectively further prevented or reduced.

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 order to further improve the microwave and ultrasonic-assisted dispersion effect, in a preferred embodiment, when the precipitation reaction is carried out in a microwave reactor, the power of the microwave reactor is 10-1000W, the reaction temperature of the precipitation reaction is 30-250 ℃, and the stirring speed is 100-2500 r/min; when the precipitation reaction is carried out in the ultrasonic reactor, the ultrasonic power of the ultrasonic reactor is 200-2000W, preferably 500-1500W, the reaction temperature of the precipitation reaction is 30-95 ℃, and the reaction time is 0.5-10 h. The precipitation reaction is carried out under such conditions, which contributes to further improvement of the precipitation efficiency.

The scandium-containing zirconium-containing solution may be of the type commonly used in coprecipitation preparation 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 after precipitation reaction, the coprecipitation effect is good. In particular, the above types of scandium-containing zirconium-containing solutions have a more suitable particle formation rate when the coprecipitation reaction is performed under the above conditions, which contributes to further improving the uniformity of the powder and preventing agglomeration.

In a preferred embodiment, the cation concentration in the scandium-zirconium mixed solution is 0.01 to 2 mol/L. The cation concentration is in the range, the scandium ions and the zirconium ions have better dispersibility, and the coprecipitation process has better agglomeration inhibition capability and precipitation efficiency. More preferably, the cation concentration in the scandium-zirconium mixed solution is 0.1 to 0.5 mol/L.

In order to improve the doping effect, improve the structural stability of the scandium-zirconium powder, and improve the electrical conductivity and mechanical properties, in a preferred embodiment, in the scandium-zirconium mixed solution, the mole ratio of scandium ions is 8 to 13% relative to the total mole number of metal ions corresponding to scandium ions, zirconium ions and the doped metal oxide in the scandium-zirconium mixed solution, and the mole number of metal ions corresponding to the doped metal oxide is 0.25 to 5%; preferably, in the scandium-zirconium mixed solution, the ratio of the number of moles of scandium ions to the total number of moles of metal ions corresponding to scandium ions, zirconium ions, and the doped metal oxide is 9 to 11%, and the number of moles of metal ions corresponding to the doped metal oxide is 0.5 to 1.5%.

In a preferred embodiment, the amount of the dispersant added is 1 to 10%, preferably 2 to 6% of the total weight of the solute of the scandium-containing zirconium-containing solution. The addition amount of the dispersing agent is in the range, the dispersity of scandium ions and zirconium ions is better, the excessive dispersing agent is favorable for avoiding the over-slow precipitation reaction speed, and the coprecipitation process has better agglomeration inhibition capability and precipitation efficiency.

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.

In a preferred embodiment, 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, alcohol is adopted in the alcohol washing process, and the drying temperature in the drying process is 80-200 ℃.

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.

Microwave assisted co-precipitation

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, and the scandium-zirconium mixed solution is obtained by mixing and stirring the solution, wherein the cation concentration of the scandium-zirconium mixed solution is 1.5mol/l, and the scandium ion is 10% of the total mole number of the scandium ion and the zirconium ion.

Coprecipitation: and (3) placing the mixed solution into a microwave reactor, wherein the reaction temperature is 80 ℃, the stirring speed is 200r/min, the microwave power is 500W, and adding ammonia water to adjust the pH value of the scandium-zirconium mixed solution to 9 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 2:

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, and the scandium-zirconium mixed solution is obtained by mixing and stirring the solution, wherein the cation concentration of the scandium-zirconium mixed solution is 2mol/l, and scandium ions are 8% of the total molar number of scandium ions and zirconium ions.

Coprecipitation: and (3) placing the mixed solution into a microwave reactor, wherein the reaction temperature is 30 ℃, the stirring speed is 100r/min, the microwave power is 1000W, and adding ammonium bicarbonate 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 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 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, and the scandium-zirconium mixed solution is obtained by mixing and stirring the solution, wherein the cation concentration of the scandium-zirconium mixed solution is 1mol/l, and the scandium ion is 13% of the total molar number of the scandium ion and the zirconium ion.

Coprecipitation: and (3) placing the mixed solution into a microwave reactor, wherein the reaction temperature is 250 ℃, the stirring speed is 1000r/min, the microwave power is 200W, and adding ammonia water 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 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 4:

preparing a reaction solution: dissolving zirconium oxychloride in water to obtain the oxychlorideZirconium solution, adding Sc₂O₃The scandium chloride solution is prepared by dissolving in hot hydrochloric acid, and the scandium and zirconium mixed solution is obtained by mixing and stirring the solution, wherein the cation concentration of the scandium and zirconium mixed solution is 0.1mol/l, and scandium ions are 10% of the total molar number of scandium ions and zirconium ions.

Coprecipitation: and (3) placing the mixed solution into a microwave reactor, wherein the reaction temperature is 60 ℃, the stirring speed is 2500r/min, the microwave power is 800W, and adding ammonia water-ammonium bicarbonate 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 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 5:

preparing a reaction solution: dissolving zirconyl nitrate in water to obtain zirconyl nitrate solution, and adding Sc₂O₃Dissolving the scandium nitrate solution in hot nitric acid to prepare a scandium nitrate solution, and mixing and stirring the solution to obtain a scandium-zirconium mixed solution, wherein the cation concentration of the scandium-zirconium mixed solution is 0.01mol/l, and scandium ions are 10% of the total molar number of scandium ions and zirconium ions.

Coprecipitation: and (3) placing the mixed solution into a microwave reactor, wherein the reaction temperature is 70 ℃, the stirring speed is 500r/min, the microwave power is 10W, and adding urea to adjust the pH value of the scandium-zirconium mixed solution to 11 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 6:

preparing a reaction solution: dissolving zirconium oxychloride in water to obtain zirconium oxychloride solution, and adding Sc₂O₃Dissolving the scandium chloride solution in hot hydrochloric acid to prepare a scandium chloride solution, mixing and stirring the solution for 1h to obtain a scandium-zirconium mixed solution, wherein the scandium-zirconium mixed solutionHas a cation concentration of 0.5mol/l and a scandium ion of 9% of the total molar amount of scandium ion and zirconium ion.

Coprecipitation: and (3) placing the mixed solution into a microwave reactor, wherein the reaction temperature is 180 ℃, the stirring speed is 1000r/min, the microwave power is 600W, and adding ammonia water-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 800 ℃ for 3h 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 is prepared by dissolving in hot hydrochloric acid, and the scandium-zirconium mixed solution is obtained by mixing and stirring the solution, wherein the cation concentration of the scandium-zirconium mixed solution is 2mol/l, and scandium ions are 11% of the total molar number of scandium ions and zirconium ions.

Coprecipitation: and (3) placing the mixed solution into a microwave reactor, wherein the reaction temperature is 150 ℃, the stirring speed is 300r/min, the microwave power is 100W, 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. 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 8:

preparing a reaction solution: dissolving zirconyl nitrate in water to obtain zirconyl nitrate solution, and adding Sc₂O₃Dissolving the scandium nitrate solution in hot nitric acid to prepare a scandium nitrate solution, and mixing and stirring the solution to obtain a scandium-zirconium mixed solution, wherein the cation concentration of the scandium-zirconium mixed solution is 1mol/l, and scandium ions are 12% of the total molar number of scandium ions and zirconium ions.

Coprecipitation: and (3) placing the mixed solution into a microwave reactor, wherein the reaction temperature is 100 ℃, the stirring speed is 1500r/min, the microwave power is 300W, and adding urea to adjust the pH value of the scandium-zirconium mixed solution to 8.5 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.

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, and the scandium-zirconium mixed solution is obtained by mixing and stirring the solution, wherein the cation concentration of the scandium-zirconium mixed solution is 1.5mol/l, and the scandium ion is 10% of the total mole number of the scandium ion and the zirconium ion.

Coprecipitation: and (3) placing the mixed solution in a constant-temperature water bath, wherein the reaction temperature is 80 ℃, the stirring speed is 200r/min, the microwave power is 500W, and adding ammonia water to adjust the pH value of the scandium-zirconium mixed solution to 9 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 differs from example 1 in that no microwave reactor was used.

The agglomerated particle diameters of the scandia-stabilized zirconia powders prepared in examples 1 to 8 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 8 and comparative example 1) were measured by an ac impedance spectroscopy, and the results of the measurements are shown in table 1.

TABLE 1

Group of	Agglomerate diameter d50 (. mu.m)	Conductivity at 800 ℃ (μ S/cm)
			Example 1	0.32	195
Example 2	0.36	205
			Example 3	0.35	199
Example 4	0.28	207
			Example 5	0.32	204
Example 6	0.34	198
			Example 7	0.3	210
Example 8	0.38	202
			Comparative example 1	0.78	169

In a word, the microwave has very strong penetrability and excellent selectivity, the heating mode of the system is bulk heating, the heating medium absorbs microwave energy at the same time, so that the heating is rapid and uniform, the agglomeration of the nano powder can be effectively prevented, and the crystal structure of the product is complete, so that the powder prepared by adopting the microwave-assisted coprecipitation method has uniform granularity, good dispersibility and small particle size. The utility model provides a preparation method of scandium zirconium powder simple process, with low costs, easily realize industrial production to the scandium zirconium powder body of preparation has good dispersibility, particle size distribution even, and the particle diameter is little, and the density is high after the sintering, and the conductivity is high.

Microwave assisted co-precipitation + doped oxides

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, 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 into a microwave reactor, wherein the reaction temperature is 90 ℃, the stirring speed is 300r/min, the microwave power is 700W, 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 by alcohol for three times, and dried at 100 ℃ to prepare scandium-zirconium precursor powder.

And (3) calcining: and calcining the prepared scandium-zirconium precursor solid at 800 ℃ for 5 hours 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、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 2mol/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 into a microwave reactor, wherein the reaction temperature is 30 ℃, the stirring speed is 1000r/min, the microwave power is 1000W, and adding ammonium bicarbonate to adjust the pH value of the scandium-zirconium mixed solution to 9 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 by alcohol for three times, and dried at 80 ℃ to prepare scandium-zirconium precursor powder.

And (3) calcining: and calcining the prepared scandium-zirconium precursor solid at 1200 ℃ for 1h 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、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 1mol/l, the molar ratio of scandium ions is 13% relative to the total molar ratio of scandium ions, zirconium ions and yttrium ions, and the molar ratio of yttrium ions is 0.5%.

Coprecipitation: and (3) placing the mixed solution into a microwave reactor, wherein the reaction temperature is 80 ℃, the stirring speed is 100r/min, the microwave power is 200W, 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^-Then the mixture is washed by alcohol for three times,drying at 100 ℃ to obtain scandium-zirconium precursor powder.

And (3) calcining: and calcining the prepared scandium-zirconium precursor solid at 1100 ℃ for 3h to obtain the scandium-zirconium powder.

Example 12:

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 into a microwave reactor, wherein the reaction temperature is 240 ℃, the stirring speed is 2500r/min, the microwave power is 300W, and adding ammonia water-ammonium bicarbonate 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 by alcohol for three times, and dried at 200 ℃ to prepare scandium-zirconium precursor powder.

And (3) calcining: and calcining the prepared scandium-zirconium precursor solid at 600 ℃ for 10h to obtain the scandium-zirconium powder.

Example 13:

preparing a reaction solution: dissolving zirconyl nitrate in water to obtain zirconyl nitrate solution, and adding Sc₂O₃、CeO₂The scandium nitrate and the cerium nitrate are dissolved in hot nitric acid to prepare a scandium nitrate and cerium nitrate solution, and the solutions 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 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 into a microwave reactor, wherein the reaction temperature is 170 ℃, the stirring speed is 500r/min, the microwave power is 30W, 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 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 scandium-zirconium precursor powder.

And (3) calcining: and calcining the prepared scandium-zirconium precursor solid at 800 ℃ for 5 hours 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、Bi₂O₃Dissolving in hot hydrochloric acid to obtain scandium chloride and bismuth chloride solution, wherein the Sc is₂O₃The content of (B) is 9 mol%, said Bi₂O₃Is 1.5 mol%, and the above solution is mixed and stirred to obtain a scandium-zirconium mixed solution, wherein the cation concentration of the scandium-zirconium mixed solution is 0.5mol/l, the molar ratio of scandium ions is 9% and the molar ratio of bismuth ions is 1.5% with respect to the total molar ratio of scandium ions, zirconium ions and bismuth ions.

Coprecipitation: and (3) placing the mixed solution into a microwave reactor, wherein the reaction temperature is 80 ℃, the stirring speed is 700r/min, the microwave power is 1000W, and adding ammonia water-sodium hydroxide to adjust the pH value of the scandium-zirconium mixed solution to 9.5 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 by alcohol for three times, and dried at 100 ℃ to prepare scandium-zirconium precursor powder.

And (3) calcining: and calcining the prepared scandium-zirconium precursor solid at 800 ℃ for 3h to obtain the scandium-zirconium powder.

Example 15:

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 2mol/l, the mole ratio of scandium ions is 10% relative to the total mole ratio of scandium ions, zirconium ions and Ce ions, and the mole ratio of Ce ions is 1%.

Coprecipitation: placing the mixed solution in a microwave reactor, and reactingAnd (3) adjusting the pH value of the scandium-zirconium mixed solution to 8 by adding sodium hydroxide at the temperature of 150 ℃, the stirring speed of 1000r/min and the microwave power of 200W 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 by alcohol for three times, and dried at 100 ℃ to prepare scandium-zirconium precursor powder.

And (3) calcining: and calcining the prepared scandium-zirconium precursor solid at 1100 ℃ for 5 hours to obtain the scandium-zirconium powder.

Example 16:

preparing a reaction solution: dissolving zirconyl nitrate in water to obtain zirconyl nitrate solution, and adding Sc₂O₃、CeO₂The scandium nitrate and the cerium nitrate are dissolved in hot nitric acid to prepare a scandium nitrate and cerium nitrate solution, and the solutions are mixed and stirred to obtain a scandium-zirconium mixed solution, wherein the cation concentration of the scandium-zirconium mixed solution is 1mol/l, the molar ratio of scandium ions is 12% 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 into a microwave reactor, wherein the reaction temperature is 100 ℃, the stirring speed is 100r/min, the microwave power is 500W, and adding urea to adjust the pH value of the scandium-zirconium mixed solution to 9 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 120 ℃ to obtain scandium-zirconium precursor powder.

And (3) calcining: and calcining the prepared scandium-zirconium precursor solid at 800 ℃ for 7 hours to obtain the scandium-zirconium powder.

The phase structure of the scandia-stabilized zirconia powder prepared in examples 9 to 16 was analyzed by X-ray diffraction, the agglomerate particle size was measured by a laser particle size analyzer, and the conductivity of the scandia-stabilized zirconia electrolyte ceramic sheet (the ceramic sheet was prepared by tape casting and sintering the scandia-stabilized zirconia powder prepared in examples 9 to 16) was measured by an ac impedance spectroscopy, and the results of the measurements are shown in table 2.

TABLE 2

Group of	Cubic phase content (%)	Agglomerate diameter d50 (. mu.m)	Conductivity at 800 ℃ (μ S/cm)
				Example 9	98.7	0.37	206
Example 10	98.5	0.34	200
				Example 11	99.2	0.29	208
Example 12	99.4	0.35	210
				Example 13	99.3	0.4	212
Example 14	99	0.32	201
				Example 15	99.4	0.33	203
Example 16	99.7	0.39	202

Microwave-assisted coprecipitation plus dispersing agent

Example 17:

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 above solutions are mixed, and dispersant polyethylene glycol (1 wt% of the total mass of zirconium oxychloride and scandium chloride) is added for mixing and stirring to obtain the scandium-zirconium mixed solution, wherein the cation concentration of the scandium-zirconium mixed solution is 1.5mol/l, and scandium ions are 10% of the total molar amount of scandium ions and zirconium ions.

Coprecipitation: and (3) placing the mixed solution into a microwave reactor, wherein the reaction temperature is 50 ℃, the stirring speed is 500r/min, the microwave power is 700W, and adding ammonia water to adjust the pH value of the scandium-zirconium mixed solution to 9 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 18:

preparing a reaction solution: dissolving zirconium oxychloride in water to obtainZirconium oxychloride solution, Sc₂O₃The scandium chloride solution is prepared by dissolving in hot hydrochloric acid, the above solutions are mixed, and dispersant polyvinyl alcohol (PVA) (which is 5 wt% of the total mass of zirconium oxychloride and scandium chloride) is added for mixing and stirring to obtain scandium-zirconium mixed solution, wherein the cation concentration of the scandium-zirconium mixed solution is 2mol/l, and scandium ions are 8% of the total mole number of scandium ions and zirconium ions.

Coprecipitation: and (3) placing the mixed solution into a microwave reactor, wherein the reaction temperature is 130 ℃, the stirring speed is 2000r/min, the microwave power is 1000W, and adding ammonium bicarbonate 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 80 ℃ 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 19:

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 above solutions are mixed, and polyacrylic acid (10 wt% of the total mass of zirconium oxychloride and scandium chloride) as a dispersant is added, mixed and stirred to obtain a scandium-zirconium mixed solution, wherein the cation concentration of the scandium-zirconium mixed solution is 1mol/l, and scandium ions are 13% of the total mole number of scandium ions and zirconium ions.

Coprecipitation: and (3) placing the mixed solution into a microwave reactor, wherein the reaction temperature is 80 ℃, the stirring speed is 100r/min, the microwave power is 200W, 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 1200 ℃ for 1h to obtain the scandium-zirconium powder.

Example 20:

preparing a reaction solution: dissolving zirconium oxychloride in water to obtain oxygenZirconium chloride solution, Sc₂O₃Dissolving in hot hydrochloric acid to prepare a scandium chloride solution, mixing the solutions, adding a dispersant polyallyl ammonium (which is 3 wt% of the total mass of zirconium oxychloride and scandium chloride), mixing and stirring to obtain a scandium-zirconium mixed solution, wherein the cation concentration of the scandium-zirconium mixed solution is 0.1mol/l, and scandium ions are 10% of the total molar amount of scandium ions and zirconium ions.

Coprecipitation: and (3) placing the mixed solution into a microwave reactor, wherein the reaction temperature is 250 ℃, the stirring speed is 200r/min, the microwave power is 50W, and adding ammonia water-ammonium bicarbonate 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 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 21:

preparing a reaction solution: dissolving zirconyl nitrate in water to obtain zirconyl nitrate solution, and adding Sc₂O₃Dissolving the scandium nitrate solution in hot nitric acid to prepare a scandium nitrate solution, mixing the solutions, adding a dispersant of poly (ammonium methacrylate) (which is 4 wt% of the total mass of the zirconyl nitrate and the scandium nitrate), mixing and stirring to obtain a scandium-zirconium mixed solution, wherein the cation concentration of the scandium-zirconium mixed solution is 0.01mol/l, and the scandium ions are 10% of the total molar number of the scandium ions and the zirconium ions.

Coprecipitation: and (3) placing the mixed solution into a microwave reactor, wherein the reaction temperature is 70 ℃, the stirring speed is 1000r/min, the microwave power is 500W, and adding urea to adjust the pH value of the scandium-zirconium mixed solution to 10 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 22:

preparing a reaction solution: dissolving zirconium oxychloride in waterObtaining zirconium oxychloride solution, and adding Sc₂O₃The scandium chloride solution is prepared by dissolving in hot hydrochloric acid, the above solutions are mixed, and a dispersant ethanol (7 wt% of the total mass of zirconium oxychloride and scandium chloride) 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, and scandium ions are 9% of the total molar amount of scandium ions and zirconium ions.

Coprecipitation: and (3) placing the mixed solution into a microwave reactor, wherein the reaction temperature is 30 ℃, the stirring speed is 1500r/min, the microwave power is 400W, and adding ammonia water-sodium hydroxide to adjust the pH value of the scandium-zirconium mixed solution to 9.5 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 23:

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 above solutions are mixed, and dispersant ammonium polyacrylate (1 wt% of the total mass of zirconium oxychloride and scandium chloride) is added for mixing and stirring to obtain the scandium-zirconium mixed solution, wherein the cation concentration of the scandium-zirconium mixed solution is 2mol/l, and scandium ions are 11% of the total mole number of scandium ions and zirconium ions.

Coprecipitation: and (3) placing the mixed solution into a microwave reactor, wherein the reaction temperature is 150 ℃, the stirring speed is 700r/min, the microwave power is 500W, and adding 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 1100 ℃ for 5 hours to obtain the scandium-zirconium powder.

Example 24:

preparing a reaction solution: dissolving zirconyl nitrate inObtaining zirconyl nitrate solution in water, and adding Sc₂O₃Dissolving the scandium nitrate solution in hot nitric acid to obtain a scandium nitrate solution, mixing the scandium nitrate solution and adding a dispersant propanol (which is 5 wt% of the total mass of the zirconyl nitrate and the scandium nitrate), mixing and stirring to obtain a scandium-zirconium mixed solution, wherein the cation concentration of the scandium-zirconium mixed solution is 1mol/l, and the scandium ions are 12% of the total molar amount of the scandium ions and the zirconium ions.

Coprecipitation: and (3) placing the mixed solution into a microwave reactor, wherein the reaction temperature is 100 ℃, the stirring speed is 800r/min, the microwave power is 800W, and the microwave frequency is 50Hz, 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.

The agglomerate grain size of the scandia-stabilized zirconia powder prepared in examples 17 to 24 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 tape casting and sintering the scandia-stabilized zirconia powder prepared in examples 17 to 24) was measured by an ac impedance spectroscopy, and the measurement results are shown in table 3.

TABLE 3

Examples	Agglomerate particle size d50(μm)	Conductivity at 800 ℃ (μ S/cm)
			Example 17	0.22	205
Example 18	0.26	208
			Example 19	0.3	210
Example 20	0.28	217
			Example 21	0.27	204
Example 22	0.24	208
			Example 23	0.21	210
Example 24	0.23	218

Microwave-assisted coprecipitation + doped oxide + dispersing agent

Example 25:

solution preparation system and precipitant preparation system: mixing and stirring a scandium chloride solution, a zirconium oxychloride solution, a cerium chloride solution and a polyethylene glycol dispersant to obtain a scandium-zirconium mixed solution, wherein the addition amount of the dispersant is 3 wt% of the total weight of a solute of the scandium-zirconium mixed solution, the cation concentration of the scandium-zirconium mixed solution is 0.8mol/l, the molar ratio of scandium ions is 11% and the molar ratio of Ce ions is 1% relative to the total molar ratio of scandium ions, zirconium ions and Ce ions. Sodium hydroxide solution with the concentration of 100g/L is used as a precipitator.

A coprecipitation system: and respectively adding the scandium-zirconium mixed solution and a precipitator into a microwave reactor at flow rates of 10ml/min and 5ml/min for precipitation reaction, wherein the microwave power is 1000W, the microwave heating temperature is 90 ℃, the stirring speed is 1000r/min, and the pH of the system is controlled to be maintained at about 10.0, so as to obtain the scandium-zirconium precursor solution.

Mother liquor separation and filtration washing process: the mother liquor is separated by a centrifuge, washed by water for 3 times and washed by ethanol for 1 time.

And (3) drying: and drying the filter cake by adopting a low-temperature freeze drying method to prepare scandium-zirconium precursor powder.

A calcination system: and carrying out heat treatment on the prepared scandium-zirconium precursor powder for 3h under the conditions of air atmosphere and calcining temperature of 1100 ℃ to obtain scandium-zirconium powder.

Example 26:

solution preparation system and precipitant preparation system: mixing and stirring a scandium chloride solution, a zirconium oxychloride solution, a yttrium chloride solution and a polyvinyl alcohol dispersing agent to obtain a scandium-zirconium mixed solution, wherein the addition amount of the dispersing agent is 1 wt% of the total weight of a solute of the scandium-zirconium mixed solution, the cation concentration of the scandium-zirconium mixed solution is 0.1mol/l, the molar ratio of scandium ions is 10% and the molar ratio of yttrium ions is 2% relative to the total molar ratio of scandium ions, zirconium ions and yttrium ions; ammonium bicarbonate solution with the concentration of 5g/L is used as a precipitating agent.

A coprecipitation system: and adding the scandium-zirconium mixed solution and a precipitator into a microwave reactor for precipitation reaction respectively in flows of 7ml/min and 4ml/min, wherein the microwave power is 100W, the microwave heating temperature is 50 ℃, the stirring speed is 200r/min, and the pH of the system is controlled to be maintained at about 8.0, so as to obtain the scandium-zirconium precursor solution.

Mother liquor separation and filtration washing process: the mother liquor can be separated by a centrifuge or a filter press, and washed by water for 5 times and ethanol for 2 times.

And (3) drying: and drying the filter cake by adopting a low-temperature freeze drying method to prepare scandium-zirconium precursor powder.

A calcination system: and carrying out heat treatment on the prepared scandium-zirconium precursor powder for 5h under the conditions of air atmosphere and calcination temperature of 800 ℃ to obtain scandium-zirconium powder.

Example 27

Solution preparation system and precipitant preparation system: mixing and stirring a scandium nitrate solution, an zirconyl nitrate solution, a bismuth nitrate solution and a polyaluminium hydroxide dispersing agent to obtain a scandium-zirconium mixed solution, wherein the addition amount of the dispersing agent is 9 wt% of the total weight of a solute of the scandium-zirconium mixed solution, the cation concentration of the scandium-zirconium mixed solution is 1.5mol/l, the molar ratio of scandium ions is 12% and the molar ratio of bismuth ions is 0.25% relative to the total molar ratio of scandium ions, zirconium ions and bismuth ions. Sodium hydroxide solution with the concentration of 120g/L is used as a precipitator.

A coprecipitation system: and adding the scandium-zirconium mixed solution and a precipitator into a microwave reactor at flow rates of 15ml/min and 6ml/min respectively for precipitation reaction, wherein the microwave power is 500W, the microwave heating temperature is 100 ℃, the stirring speed is 100r/min, and the pH of the system is controlled to be maintained at about 11.0, so as to obtain the scandium-zirconium precursor solution.

Mother liquor separation and filtration washing process: the mother liquor is separated by a centrifuge, washed with water for 2 times and washed with ethanol for 2 times.

And (3) drying: and drying the filter cake by adopting a low-temperature freeze drying method to prepare scandium-zirconium precursor powder.

A calcination system: and carrying out heat treatment on the prepared scandium-zirconium precursor powder for 10h in an air atmosphere at the calcining temperature of 600 ℃ to obtain scandium-zirconium powder.

Example 28

Solution preparation system and precipitant preparation system: mixing and stirring a scandium chloride solution, a zirconium oxychloride solution, an aluminum chloride solution and a polyacrylic acid dispersant to obtain a scandium-zirconium mixed solution, wherein the addition amount of the dispersant is 5 wt% of the total weight of a solute of the scandium-zirconium mixed solution, the cation concentration of the scandium-zirconium mixed solution is 0.01mol/l, the molar ratio of scandium ions is 8% and the molar ratio of aluminum ions is 4% relative to the total molar ratio of scandium ions, zirconium ions and aluminum ions. Ammonium bicarbonate solution with the concentration of 20g/L is used as a precipitating agent.

A coprecipitation system: and respectively adding the scandium-zirconium mixed solution and a precipitator into a microwave reactor at flow rates of 20ml/min and 10ml/min for precipitation reaction, wherein the microwave power is 400W, the microwave heating temperature is 30 ℃, the stirring speed is 500r/min, and the pH of the system is controlled to be maintained at about 8.5, so as to obtain the scandium-zirconium precursor solution.

Mother liquor separation and filtration washing process: the mother liquor is separated by a centrifuge, washed with water for 2 times and washed with ethanol for 1 time.

And (3) drying: and drying the filter cake by adopting a low-temperature freeze drying method to prepare scandium-zirconium precursor powder.

A calcination system: and carrying out heat treatment on the prepared scandium-zirconium precursor powder for 1h in an air atmosphere at the calcining temperature of 1200 ℃ to obtain scandium-zirconium powder.

Example 29

Solution preparation system and precipitant preparation system: mixing and stirring a scandium chloride solution, a zirconium oxychloride solution, a yttrium chloride solution and an ammonium polyacrylate dispersant to obtain a scandium-zirconium mixed solution, wherein the addition amount of the dispersant is 7 wt% of the total weight of a solute of the scandium-zirconium mixed solution, the cation concentration of the scandium-zirconium mixed solution is 1.0mol/l, the molar ratio of scandium ions is 9% and the molar ratio of yttrium ions is 3% relative to the total molar ratio of scandium ions, zirconium ions and yttrium ions. Ammonia water with the concentration of 25 wt% is used as a precipitating agent.

A coprecipitation system: and adding the scandium-zirconium mixed solution and a precipitator into a microwave reactor at flow rates of 25ml/min and 15ml/min respectively for precipitation reaction, wherein the microwave power is 50W, the microwave heating temperature is 250 ℃, the stirring speed is 300r/min, and the pH of the system is controlled to be maintained at about 9, so as to obtain the scandium-zirconium precursor solution.

Mother liquor separation and filtration washing process: the mother liquor is separated by a centrifuge, washed by water for 3 times and washed by ethanol for 2 times.

And (3) drying: and drying the filter cake by adopting a low-temperature freeze drying method to prepare scandium-zirconium precursor powder.

A calcination system: and carrying out heat treatment on the prepared scandium-zirconium precursor powder for 3h under the conditions of air atmosphere and the calcining temperature of 850 ℃ to obtain scandium-zirconium powder.

Example 30

Solution preparation system and precipitant preparation system: mixing and stirring a scandium chloride solution, a zirconium oxychloride solution, a ytterbium chloride solution and a propanol dispersing agent to obtain a scandium-zirconium mixed solution, wherein the addition amount of the dispersing agent is 4 wt% of the total weight of a solute of the scandium-zirconium mixed solution, the cation concentration of the scandium-zirconium mixed solution is 0.5mol/l, the molar ratio of scandium ions is 10% and the molar ratio of yttrium ions is 1% relative to the total molar ratio of scandium ions, zirconium ions and ytterbium ions. Ammonia water with the concentration of 10 wt% is used as a precipitating agent.

A coprecipitation system: and respectively adding the scandium-zirconium mixed solution and a precipitator into a microwave reactor at flow rates of 30ml/min and 10ml/min for precipitation reaction, wherein the microwave power is 800W, the microwave heating temperature is 150 ℃, the stirring speed is 600r/min, and the pH of the system is controlled to be maintained at about 7.5, so as to obtain the scandium-zirconium precursor solution.

Mother liquor separation and filtration washing process: the mother liquor is separated by a centrifuge, washed by water for 3 times and washed by ethanol for 3 times.

And (3) drying: and drying the filter cake by adopting a low-temperature freeze drying method to prepare scandium-zirconium precursor powder.

A calcination system: and carrying out heat treatment on the prepared scandium-zirconium precursor powder for 6h under the conditions of air atmosphere and calcination temperature of 1000 ℃ to obtain scandium-zirconium powder.

Example 31

Solution preparation system and precipitant preparation system: mixing and stirring a scandium chloride solution, a zirconium oxychloride solution, a yttrium chloride solution and a ammonium polymethacrylate dispersant to obtain a scandium-zirconium mixed solution, wherein the addition amount of the dispersant is 6 wt% of the total weight of a solute of the scandium-zirconium mixed solution, the cation concentration of the scandium-zirconium mixed solution is 0.05mol/l, the molar ratio of scandium ions is 11% and the molar ratio of yttrium ions is 0.5% relative to the total molar ratio of scandium ions, zirconium ions and yttrium ions. Ammonia water with the concentration of 5 wt% is used as a precipitating agent.

A coprecipitation system: and respectively adding the scandium-zirconium mixed solution and a precipitator into a microwave reactor at flow rates of 10ml/min and 7ml/min for precipitation reaction, wherein the microwave power is 300W, the microwave heating temperature is 80 ℃, the stirring speed is 700r/min, and the pH of the system is controlled to be maintained at about 10.5, so as to obtain the scandium-zirconium precursor solution.

Mother liquor separation and filtration washing process: the mother liquor is separated by a centrifuge, washed with water for 2 times and washed with ethanol for 2 times.

And (3) drying: and drying the filter cake by adopting a low-temperature freeze drying method to prepare scandium-zirconium precursor powder.

A calcination system: and carrying out heat treatment on the prepared scandium-zirconium precursor powder for 8h under the conditions of air atmosphere and calcination temperature of 700 ℃ to obtain scandium-zirconium powder.

The phase structure of the scandia-stabilized zirconia powder prepared in examples 25 to 31 was analyzed by X-ray diffraction, the agglomerate particle size was measured by a laser particle size analyzer, and the conductivity of the scandia-stabilized zirconia electrolyte ceramic sheet (the ceramic sheet was prepared by tape casting and sintering the scandia-stabilized zirconia powder prepared in examples 25 to 31) was measured by ac impedance spectroscopy, and the results of the measurements are shown in table 4.

TABLE 4

Ultrasonic assisted co-precipitation

Example 32:

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, and the scandium and zirconium mixed solution is obtained by mixing and stirring the solution, wherein the cation concentration of the scandium and zirconium mixed solution is 0.5mol/l, and scandium ions are 10% of the total molar number of scandium ions and zirconium ions.

Coprecipitation: will be mixed withAnd (3) placing the mixed solution in an ultrasonic reactor, wherein the reaction temperature is 50 ℃, the ultrasonic power is 700W, and adding ammonia water to adjust the pH value of the scandium-zirconium mixed solution to 9 for reaction for 0.5h to prepare 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 33:

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, and the scandium-zirconium mixed solution is obtained by mixing and stirring the solution, wherein the cation concentration of the scandium-zirconium mixed solution is 1.8mol/l, and the scandium ion is 8% of the total mole number of the scandium ion and the zirconium ion.

Coprecipitation: and (3) placing the mixed solution in an ultrasonic reactor, wherein the reaction temperature is 30 ℃, the ultrasonic power is 1100W, and adding ammonium bicarbonate to adjust the pH value of the scandium-zirconium mixed solution to 7 for reaction for 5h 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 34:

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, and the scandium-zirconium mixed solution is obtained by mixing and stirring the solution, wherein the cation concentration of the scandium-zirconium mixed solution is 1mol/l, and scandium ions are 12% of the total molar number of scandium ions and zirconium ions.

Coprecipitation: and (3) placing the mixed solution in an ultrasonic reactor, wherein the reaction temperature is 80 ℃, the ultrasonic power is 200W, and adding ammonia water to adjust the pH value of the scandium-zirconium mixed solution to 11 for reaction for 10h to obtain a scandium-zirconium precursor solution. The prepared scandium and zirconiumFiltering the 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 1000 ℃ for 3h to obtain the scandium-zirconium powder.

Example 35:

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, and the scandium and zirconium mixed solution is obtained by mixing and stirring the solution, wherein the cation concentration of the scandium and zirconium mixed solution is 0.1mol/l, and scandium ions are 10% of the total molar number of scandium ions and zirconium ions.

Coprecipitation: and (3) placing the mixed solution into an ultrasonic reactor, wherein the reaction temperature is 60 ℃, the ultrasonic power is 800W, and adding ammonia water-ammonium bicarbonate to adjust the pH value of the scandium-zirconium mixed solution to 8.5 for reaction for 3h 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 36:

preparing a reaction solution: dissolving zirconyl nitrate in water to obtain zirconyl nitrate solution, and adding Sc₂O₃Dissolving the scandium nitrate solution in hot nitric acid to prepare a scandium nitrate solution, and mixing and stirring the solution to obtain a scandium-zirconium mixed solution, wherein the cation concentration of the scandium-zirconium mixed solution is 0.01mol/l, and scandium ions are 10% of the total molar number of scandium ions and zirconium ions.

Coprecipitation: and (3) placing the mixed solution in an ultrasonic reactor, wherein the reaction temperature is 70 ℃, the ultrasonic power is 500W, and adding urea to adjust the pH of the scandium-zirconium mixed solution to 9.5 for reaction for 1h 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 850 ℃ for 7h to obtain the scandium-zirconium powder.

Example 37:

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, and the scandium-zirconium mixed solution is obtained by mixing and stirring the solution, wherein the cation concentration of the scandium-zirconium mixed solution is 1.5mol/l, and the scandium ion is 9% of the total molar number of the scandium ion and the zirconium ion.

Coprecipitation: and (3) placing the mixed solution in an ultrasonic reactor, wherein the reaction temperature is 80 ℃, the ultrasonic power is 2000W, and adding ammonia water-sodium hydroxide to adjust the pH value of the scandium-zirconium mixed solution to 8.5 for reaction for 2 hours 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 38:

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, and the scandium and zirconium mixed solution is obtained by mixing and stirring the solution, wherein the cation concentration of the scandium and zirconium mixed solution is 0.8mol/l, and the scandium ion is 8% of the total mole number of the scandium ion and the zirconium ion.

Coprecipitation: and (3) placing the mixed solution in an ultrasonic reactor, wherein the reaction temperature is 50 ℃, the ultrasonic power is 1500W, and adding sodium hydroxide to adjust the pH value of the scandium-zirconium mixed solution to 8 for reaction for 1.5h 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 39:

preparing a reaction solution: dissolving zirconyl nitrate in water to obtain zirconyl nitrate solution, and adding Sc₂O₃Dissolving the scandium nitrate solution in hot nitric acid to prepare a scandium nitrate solution, and mixing and stirring the solution to obtain a scandium-zirconium mixed solution, wherein the cation concentration of the scandium-zirconium mixed solution is 1mol/l, and scandium ions are 11% of the total molar number of scandium ions and zirconium ions.

Coprecipitation: and (3) placing the mixed solution in an ultrasonic reactor, wherein the reaction temperature is 95 ℃, the ultrasonic power is 1000W, and adding urea to adjust the pH of the scandium-zirconium mixed solution to 10 for reaction for 4h 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 120 ℃ to obtain the scandium-zirconium precursor.

And (3) calcining: and calcining the prepared scandium-zirconium precursor solid at 900 ℃ for 7 hours to obtain the scandium-zirconium powder.

The agglomerate grain size of the scandia-stabilized zirconia powder prepared in examples 32 to 39 was measured by a laser particle size analyzer, and the conductivity of the scandia-stabilized zirconia electrolyte ceramic sheet (the ceramic sheet was prepared by tape casting and sintering the scandia-stabilized zirconia powder prepared in examples 32 to 39) was measured by an ac impedance spectroscopy, and the measurement results are shown in table 5.

TABLE 5

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 (9)

1. A device for preparing scandium-zirconium powder is characterized by comprising:

a first supply unit (10) for supplying a polyalkenyl alcohol-based high-molecular polymer, an ammonium salt of a polyalkenyl alcohol, a polyalkanol-based high-molecular polymer, a polyalkenyl acid-based high-molecular polymer, an ammonium salt of a polyalkenyl acid, or a monohydric aliphatic alcohol of C2 to C6 as a dispersant;

a second supply unit (20) for supplying a solution containing scandium ions and zirconium ions;

a third supply unit (30) including a doped metal oxide supply bin (31), an acid solution supply unit (32), and a dissolving unit (33), the doped metal oxide supply bin (31) being configured to supply a doped metal oxide, a metal element of the doped metal oxide being a rare earth element other than scandium element, an aluminum element, or a bismuth element, the acid solution supply unit (32) being configured to supply an acid, the dissolving unit (33) being respectively connected to the doped metal oxide supply bin (31) and the acid solution supply unit (32) and configured to dissolve the doped metal oxide in the acid to form a doped metal acid solution;

a first mixing unit (40) connected to the first supply unit (10), the second supply unit (20) and the dissolving unit (33), respectively, for mixing the dispersing agent, the doped metal acid solution and the solution containing scandium ions and zirconium ions to obtain a scandium-zirconium mixed solution;

a fourth supply unit (50) for supplying a precipitant;

a microwave or ultrasonic reactor (60) respectively connected with the first mixing unit (40) and the fourth supply unit (50) and used for carrying out coprecipitation reaction on the scandium-zirconium mixed solution under the condition of microwave heating or ultrasonic wave to obtain a precipitated material;

a filtering unit (70) connected to the outlet of the microwave or ultrasonic reactor (60) for filtering the precipitated material to obtain a precipitated colloid;

a washing unit (80) connected to an outlet of the filtering unit (70) for washing the precipitated colloid to obtain a washed colloid;

a drying unit (90) connected to the outlet of the washing unit (80) for drying the washing colloid to obtain a dry material; and

a calcination unit (100) connected to an outlet of the drying unit (90) for calcining the dry material to obtain the scandium-zirconium powder body.

2. The device according to claim 1, wherein the washing unit (80) comprises a first washing unit (81) and a second washing unit (82) arranged in series between the filtering unit (70) and the drying unit (90), the first washing unit (81) being further provided with a water inlet, the second washing unit (82) being further provided with an alcohol inlet, the washing unit (80) further comprising:

a water supply unit (83) connected to the water inlet;

an alcohol supply unit (84) connected to the alcohol inlet.

3. The apparatus according to claim 1, characterized in that said drying unit (90) is a freeze dryer.

4. The device according to claim 1, characterized in that the filtration unit (70) is a centrifuge or a filter press.

5. The device according to any one of claims 1 to 4, characterized in that said second supply unit (20) comprises:

a scandium-containing solution supply unit for supplying an aqueous solution of scandium chloride or scandium nitrate;

a zirconium-containing solution supply unit for supplying an aqueous solution of zirconium chloride, zirconium nitrate, zirconium oxychloride or zirconium oxynitrate; and

and the second mixing unit is respectively connected with the scandium-containing solution supply unit and the zirconium-containing solution supply unit and is used for mixing the solutions supplied by the scandium-containing solution supply unit and the zirconium-containing solution supply unit to form the scandium-zirconium mixed solution, and the outlet of the second mixing unit is connected with the inlet of the first mixing unit (40).

6. The apparatus according to claim 5, further comprising a pH detection unit for detecting the pH value of the reaction system in the microwave or ultrasonic reactor (60).

7. The apparatus according to claim 6, further comprising a precipitant flow control meter disposed on a line connecting the fourth supply unit (50) and the microwave or ultrasonic reactor (60), wherein the precipitant flow control meter is configured to adjust a precipitant flow according to a detection result of the pH detection unit to maintain the pH of the reaction system at 7 to 11.

8. The apparatus according to any one of claims 1 to 4, characterized in that the fourth supply unit (50) is adapted to supply sodium hydroxide solution, ammonium bicarbonate solution or ammonia water as the precipitant.

9. The device according to any of claims 1 to 4, characterized in that a stirring device is also provided in the microwave or ultrasonic reactor (60).

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