CN108794001B - Modified ZrO2Preparation method of base solid composite electrolyte ceramic material - Google Patents

Abstract

Modified ZrO₂A preparation method of a solid composite electrolyte ceramic material relates to the technical field of solid electrolyte ceramic material preparation. Weighing zirconium nitrate, cerium nitrate and copper nitrate, adding into distilled water, adding citric acid, and fully stirring to dissolve; adding ethylene glycol into the mixed solution, and performing ultrasonic treatment to uniformly disperse the ethylene glycol; after adjusting the pH value of the solution, heating and stirring the solution in a constant-temperature water bath until sol is formed, and standing the solution to form gel; drying the gel, calcining, and grinding to obtain an electrolyte powder material after calcining; adding PVA for granulation, pressing into tablets under pressure, and sintering in a programmed heating furnace to obtain ZrO₂The base solid composite electrolyte ceramic material. The invention adopts an ultrasonic-assisted sol-gel method to prepare the solid electrolyte, and cerium oxide and copper oxide are doped in the zirconia base to produce cerium oxide and copper oxide, so that the conductivity of the zirconia base is expected to be improved.

Description

Modified ZrO2Preparation method of base solid composite electrolyte ceramic material

Technical Field

The invention relates toThe technical field of solid electrolyte ceramic material preparation, in particular to modified ZrO₂A preparation method of a base solid composite electrolyte ceramic material.

Background

The essence of Solid Oxide Fuel Cells (SOFCs) is to convert chemical energy that is difficult to use or very inefficient to use in Fuel into electrical energy that can be conveniently used by people. The interior of the solid fuel cell is formed by connecting a large number of small cells. Each of the small cells is constructed by a cathode, an anode, a separator and an electrolyte, and a connector. In a solid oxide fuel cell, the most important is the electrolyte, which is mostly made of oxide ceramics, which generally have excellent electrical properties. In SOFCs, the electrolyte is very important because it serves as a channel connecting the electrodes to allow conduction of electrons between them, and therefore the requirements for the electrolyte ceramic materials of SOFCs are very strict.

The general working process of the solid fuel cell is that firstly, fuel enters from the anode, reacts at the anode, releases energy, is converted into current, and provides electric energy for external electronic components, and what is used for carrying electronic communication inside is electrolyte. Oxygen enters from the cathode to provide oxygen ions. Since electrons are exchanged through the electrolyte inside, the conductivity of the electrolyte is required to be high.

Monoclinic ZrO₂Tetragonal ZrO without conductivity₂The electrical conductivity is very low, so that doped cubic ZrO is generally used₂As an electrolyte material. Numerous studies have shown that: through the direction of ZrO₂Doped with some divalent or trivalent alkaline earth metal oxides (e.g. CaO, MgO, Y)₂O₃、Sc₂O₃、Yb₂O₃、CeO₂) Etc. to form cubic phase solid solution, and substituting trivalent or divalent rare earth ions for Zr⁴⁺So that the alloy is cubic from room temperature to high temperature, and oxygen vacancy is increased to improve the oxygen ion conductivity of the alloy.

In general, zirconia-based electrolytes are expected to be the most commercially valuableA high temperature oxide fuel cell. ZrO in general₂The base solid electrolyte material operates at a relatively high temperature (typically around 1000 c), and at 1000 c, its electrical conductivity is high, but it also has problems such as slow decomposition of the material, interphase diffusion, corrosion of the metal connection material, and the like. In addition, O at about 800 deg.C^2-The conductivity is still low compared to other types of solid electrolyte materials. In order to increase the conductivity of the material, researchers have never been stopped, they have been working on ZrO₂The doping modification aspect of (a) has been studied in large numbers and has achieved a number of results. Research results show that the addition of some dopants can greatly improve the conductivity of the zirconia base.

ZrO preparation by adopting traditional high-temperature solid phase method₂-CeO₂-CuO composite materials, which generally need to be sintered at a temperature above 1500 ℃, are liable to cause volatilization of CuO components in the raw materials, resulting in ZrO₂Or precipitation of other foreign phases, it is difficult to obtain a pure phase and the composition becomes difficult to control. The invention adopts an ultrasonic-assisted sol-gel method to prepare ZrO₂The sol-gel method based solid composite electrolyte ceramic material is widely used due to simple and convenient operation, uniform and smaller particle size of the obtained powder, good performance, easy operation in the experimental process and good repeatability.

Disclosure of Invention

Aiming at the technical problems in the prior art, the invention provides modified ZrO₂A preparation method of a base solid composite electrolyte ceramic material. Modified ZrO obtained₂The base solid composite electrolyte ceramic material has excellent conductivity.

In order to achieve the purpose, the technical scheme adopted by the invention is as follows: modified ZrO₂The preparation method of the base solid composite electrolyte ceramic material comprises the following steps:

firstly, according to a target sample (ZrO)₂)_0.89(CeO₂)_x(CuO)_0.11-xWeighing zirconium nitrate, cerium nitrate and copper nitrate, adding the zirconium nitrate, the cerium nitrate and the copper nitrate into 30ml of distilled water, then adding citric acid, and fully stirring to dissolve the citric acid;

adding ethylene glycol into the mixed solution, and then putting the solution into an ultrasonic cleaning machine for ultrasonic treatment to uniformly disperse the ethylene glycol;

thirdly, titrating the solution by taking dilute ammonia water as a pH regulator, and regulating the pH value of the solution to 7;

heating and stirring in a water bath with constant temperature of 80 ℃ until sol is formed, and standing for a period of time to form gel;

fifthly, putting the gel into an oven to be dried for 24 hours, taking out the gel, putting the gel into a muffle furnace to be calcined for 10 hours at 700 ℃, cooling the gel to room temperature after the calcination is finished, taking out the crucible, and fully grinding the powder to ultrafine powder to obtain (ZrO)₂)_0.89(CeO₂)_x(CuO)_0.11-xAn electrolyte powder material;

sixthly, adding PVA into the obtained superfine powder for granulation, wherein during the granulation, sufficient grinding is ensured to ensure that the powder and the PVA are uniformly mixed; pressing the powder into tablets under the pressure of 14 Mpa; putting the pressed and formed sheet into a temperature programming furnace for sintering, and preserving the heat for 200 minutes at 1350 ℃ to obtain ZrO₂Solid based composite electrolyte ceramic material (ZrO)₂)_0.89(CeO₂)_x(CuO)_0.11-xAnd (5) ceramic plates.

As a preferable embodiment of the production method of the present invention, a target sample (ZrO)₂)_0.89(CeO₂)_x(CuO)_0.11-xWherein x is 0 to 0.10. The molar mass of citric acid is 1.5 times of the amount of metal ions contained in the component, and the weight of ethylene glycol is 1.2 times of the weight of citric acid.

Compared with the prior art, the invention has the beneficial effects that:

the invention is realized by applying the material to a solid oxide fuel cell (ZrO)₂)_0.89(CeO₂)_x(CuO)_0.11-xSix components of a ternary system (x is 0, 0.02, 0.04, 0.06, 0.08 and 0.10) are explored, an ultrasonic-assisted sol-gel method is adopted to prepare a solid electrolyte, and cerium oxide and copper oxide are doped in a zirconia base to produce cerium oxide and copper oxide, so that the conductivity of the zirconia base is expected to be improved. The preparation method comprises the steps of preparing sol, drying, roasting, grinding to prepare superfine powder, then carrying out compression molding, and sintering the molded sampleAnd (5) manufacturing the electrolyte ceramic chip. The obtained xerogel powder and corresponding ZrO are tested by infrared and thermogravimetric differential scanning calorimetry, XRD, scanning electron microscope and alternating current impedance test₂-CeO₂The properties of the composite material were characterized. The experimental results show that (ZrO) is prepared₂)_0.89(CeO₂)_x(CuO)_0.11-xThe conductivity of the system is lower, but relatively speaking, it can be seen that with CeO₂The content is increased, and the conductivity is improved: 0.00375S cm at 800 deg.C when x is 0^-10.00665S cm when x is increased to 0.10^-1。

Drawings

FIG. 1 is (ZrO) obtained in example 1₂)_0.89(CeO₂)_x(CuO)_0.11-xXRD pattern of electrolyte powder material.

FIG. 2 is an infrared spectrum of xerogel powder with different doping ratios.

FIG. 3 is (ZrO)₂)_0.89(CeO₂)_0.10(CuO)_0.01TG-DSC thermogram of xerogel.

FIG. 4 shows (ZrO)₂)_0.89(CeO₂)_0.1(CuO)_0.01And impedance spectrograms of the electrolyte samples obtained at different temperatures.

Fig. 5 is a graph of the conductivity of different component electrolyte samples.

FIG. 6 is an Arrhenius plot of temperature and conductivity for samples of different compositions.

FIG. 7 shows (ZrO) sintered at 1350 ℃₂)_0.89(CeO₂)_0.1(CuO)_0.01SEM images of samples at different magnifications.

Detailed Description

Modified ZrO of the present invention by referring to examples and drawings₂The preparation method of the base solid composite electrolyte ceramic material is further detailed.

Example 1

Modified ZrO₂The preparation method of the base solid composite electrolyte ceramic material comprises the following steps:

①、according to the target sample (ZrO)₂)_0.89(CeO₂)_x(CuO)_0.11-xThe stoichiometric ratio of (A) is that zirconium nitrate, cerium nitrate and copper nitrate are weighed and added into 30ml of distilled water, then citric acid is added, and the mixture is fully stirred to be dissolved. The experiments total 6 groups, x is respectively taken from 0, 0.02, 0.04, 0.06, 0.08 and 0.10. For each set of experiments, the molar mass of citric acid was 1.5 times the amount of metal ions contained in the component.

And secondly, adding glycol (the weight is 1.2 times of that of the citric acid) into the mixed solution, and then putting the solution into an ultrasonic cleaning machine for ultrasonic treatment to uniformly disperse the glycol.

And thirdly, titrating the solution by taking the dilute ammonia water as a pH regulator, and regulating the pH value of the solution to 7.

Heating and stirring in a water bath with constant temperature of 80 ℃ until sol is formed, and standing for a period of time to form gel.

Fifthly, putting the gel into an oven to be dried for 24 hours, taking out the gel, putting the gel into a muffle furnace to be calcined for 10 hours at 700 ℃, cooling the gel to room temperature after the calcination is finished, taking out the crucible, and fully grinding the powder to ultrafine powder to obtain (ZrO)₂)_0.89(CeO₂)_x(CuO)_0.11-xAn electrolyte powder material.

Sixthly, adding PVA into the obtained superfine powder for granulation, wherein during the granulation, sufficient grinding is ensured to ensure that the powder and the PVA are uniformly mixed; pressing the powder into tablets under the pressure of 14 Mpa; putting the pressed and formed sheet into a temperature programming furnace for sintering, and preserving the heat for 200 minutes at 1350 ℃ to obtain ZrO₂Solid based composite electrolyte ceramic material (ZrO)₂)_0.89(CeO₂)_x(CuO)_0.11-xAnd (5) ceramic plates.

Example 2

(ZrO₂)_0.89(CeO₂)_x(CuO)_0.11-xPerformance characterization of ceramic wafers

1. X-ray diffraction analysis

The diffraction patterns generated by crystals with different atomic arrangements are generally different, and the diffraction geometry and intensity are two aspects of measuring a series of information such as crystal structures, and the information such as lattice structures, unit cell sizes and shapes related to the crystals can be calculated from the diffraction geometries and intensities.

According to the diffraction conditions, the bragg formula is utilized: the lattice constant of the sample can be calculated from the measured specific wavelength λ by using 2dsin θ ═ n λ.

FIG. 1 is (ZrO) obtained in example 1₂)_0.89(CeO₂)_x(CuO)_0.11-xXRD pattern of electrolyte powder material. From FIG. 1, it is apparent that the three strong peaks correspond to the crystal plane indexes (011), (020) and (121). The other weaker diffraction peaks correspond to the crystal face indexes (110), (111), (200), (002) and the like. And when CeO₂When the doping amount of (A) is 0 mol%, 2 mol% or 4 mol%, the diffraction pattern of the component and ZrO₂The monoclinic structure PDF #37-1484 is relatively good, the majority of the crystal phase of the material is monoclinic zirconia, and the minority of the crystal phase of the material is tetragonal zirconia, which indicates that CeO₂The doping amount is 0 or less, and when the doping amount of CuO is large, a small amount of stabilized zirconia is generated. The ZrO₂The composite material is mainly monoclinic phase ZrO₂. When CeO is present₂At doping levels of 6 mol% and 8 mol%, the crystal structure is mainly tetragonal phase and cubic phase, accompanied by CeO₂The monoclinic phase gradually disappears when the doping amount is increased, and when the doping amount is 10 mol%, the diffraction pattern is corresponding to the square structure PDF #50-1089 card well, and ZrO is₂-CeO₂The phase structure of the-CuO composite is mainly tetragonal phase and secondly cubic phase, which indicates that Ce is in the form of a cubic phase⁴⁺And Cu²⁺Has been mostly incorporated into ZrO₂In the crystal structure, a solid solution was formed, and the tetragonal system could be stably maintained at room temperature, which indicates that Cu²⁺Synergistic Ce⁴⁺Plays a role in stabilizing ZrO₂The function of (1).

Pure cubic phase is ion-conductive, has very high conductivity, but has poor mechanical strength and is easy to crack in high-temperature sintering; whereas pure tetragonal phase has high mechanical strength but low electrical conductivity. Thus, if the electrolyte crystal structure can possess both cubic and tetragonal phases, good conductivity and mechanical properties can be combined.

(ZrO) sintered at 700 ℃ by Jade software₂)_0.89(CeO₂)_0.1(CuO)_0.01Processing the powder by utilizing a Debye-Xiele formula:

in the formula, D: grain radius (nm); k: scherrer constant (0.89); λ: the wavelength of X-rays (λ 0.154056 nm); θ: diffraction angle; beta: corresponding to the full width at half maximum of the diffraction peak. The resulting grain radius data is shown in table 1:

TABLE 1 data for the major diffraction peaks

2. Density measurement

The porosity was measured by the archimedes drainage method. The calculation formula is as follows:

in the formula: m is₀Dry weight, m₁The weight in hanging (mass of the sample suspended in water after saturation), m₂Wet weight (mass of sample after saturation by water absorption), p is porosity. The calculation results are shown in table 2.

TABLE 2 summary of porosity for each sample of doping ratio

From the porosity data, the relative density of the 1350 ℃ sintered sample is only partially greater than 95%, which may be caused by the following factors: firstly, errors exist in observation by using a pH test paper in the pH adjusting process, so that the sizes of particles prepared by a sol-gel method are inconsistent, further the sintering density is influenced, secondly, some components are insufficiently ground in the granulating process, and finally, the density is different due to uneven temperature caused by different positions in a hearth of a high-temperature furnace where a sample is located in the sintering process. For electrolytes, higher densification is more beneficial for improved electrical performance because asymmetric pores may alter the transport mechanism of oxygen ions and reduce conductivity.

3. Infrared testing

The intensity of infrared is a qualitative and temporal quantitative identification of the presence of a chemical substance or functional group, and its stress, strain, crystallinity and heterogeneity can also be known from the absorption peak width and transition point.

FIG. 2 is an infrared spectrum of xerogel powder with different doping ratios. 3436cm when x is 0.00, 0.02, 0.08, 0.10^-1、1618cm^-1、1396cm^-1、1093cm^-1、920cm^-1、860cm^-1、685cm^-1There is a distinct characteristic absorption peak at the location. When x is 0.04, 0.06, the infrared test curve tends to be smooth. In addition, the wavelength is 1400-2400 cm^-1The wider curve in between, which may be a problem due to improper use of the test machine.

In the absorption peak on the graph, at 3436cm^-1The absorption peak at this point is broad, and it is known that this is contraction vibration of O-H associated with hydrogen bonds. The reason for this absorption peak may be the following: firstly, the sample also has a certain amount of crystal water; and secondly, water in the surrounding environment enters the sample when the sample is prepared for testing. Thirdly, hydroxyl groups should be present in the added ethylene glycol. 1618cm^-1And COO^-The antisymmetric stretching vibration peak of the vibration plate corresponds to the antisymmetric stretching vibration peak of the vibration plate. NO^- ₃The antisymmetric telescopic vibration peak of (1) corresponds to 1396cm^-1Here, the presence of this characteristic peak demonstrates the presence of NO₃ ^-In a gel, 1093cm^-1Probably due to the stretching vibration peak of C-O. 920cm^-1Is a characteristic absorption peak of C-O-C, and the existence of the characteristic peak indicates that the esterification reaction exists in the process of forming the gel. 860cm^-1、 685cm^-1、534cm^-1The absorption peak present at a position can be attributed to O-M (where M may be Ce)⁴⁺、Cu²⁺、Zr⁴⁺) The characteristic peak of stretching vibration, free COOH, is also not shown in the figure, indicating that the doped ions and complexing agent are completely bound.

4. Thermal analysis

Thermogravimetry (TG) is a technique for detecting the change of the mass of a substance to be measured with time or temperature at a programmed temperature. The differential scanning calorimetry method is used for researching the relationship between the heat flow difference and the temperature between the object to be tested and the reference object, and can be embodied by the heat absorption rate or the heat release rate at any moment.

FIG. 3 is (ZrO)₂)_0.89(CeO₂)_0.10(CuO)_0.01And (3) a TG-DSC thermal analysis curve of the xerogel, wherein the test condition is nitrogen atmosphere, and the heating rate is set to be 10 ℃/min. From FIG. 3, the reaction process is divided into three stages: from 25 ℃ to 180 ℃ is the first weight loss stage, with a weight loss of about 12%. According to experimental analysis, the dry gel precursor is mainly caused by moisture and partial evaporation of organic matters. The second weight loss stage is 180-500 deg.c, and it can be seen that the TG curve has descending trend from fast to slow and the weight loss of the sample is about 38%. The DSC curve of the second stage shows an exothermic peak at T-250 ℃ and T-375 ℃, which is probably caused by the oxidation-reduction reaction exothermicity of organic matters, nitrates or metal ions in the system under the heating environment of the precursor. The final third stage, i.e. after 480 ℃ the sample tended to be constant weight, about 50%, and the final phase was known to form and tended to stabilize.

5. Electrical Performance testing

The AC impedance spectrum is used to measure the impedance of the battery and the perturbation frequency.

The impedance analyzer used in the laboratory mainly measures the relation between impedance and frequency, total resistance of the sample is analyzed by Zsimpwin impedance analysis software, and the conductivity of the sample can be obtained through formula calculation. The calculation formula is as follows:

in the formula, σ: electrical conductivity; l: the thickness of the sample; s: cross-sectional area of the sample.

The conductivity and temperature conform to the arrhenius theory and satisfy the following formula:

wherein A is a characteristic constant; t is absolute temperature; ea is activation energy; r is gas constant.

5.1 spectrum of AC impedance

FIG. 4 shows (ZrO)₂)_0.89(CeO₂)_0.1(CuO)_0.01The impedance spectrum of the electrolyte sample is obtained at different temperatures, and the test is carried out in an air atmosphere. The figure shows 4 impedance spectra at different temperatures, and it can be seen that the impedance spectra at 500 ℃ and 600 ℃ contain 3 arcs with different frequencies, which correspond to the grain resistance, the grain boundary resistance and the electrode interface resistance. The core of EIS is to distinguish the processes of different speeds during the electrochemical reaction by a change in frequency, the high frequency region being associated with the grain boundaries of the electrolyte, and the resistance at intermediate frequencies possibly being due to the dissociation resistance of oxygen ions and the charge transfer at the interface. At low frequencies, where the electrochemical reaction is the slowest, mainly due to diffusion processes. In addition, as the temperature increases to 700 ℃ to 800 ℃, the arc shrinks and the polarization resistance disappears, leaving only the grain boundary resistance in this range.

5.2 conductivity at different temperatures

The total resistance of the electrolyte (total resistance-grain resistance + grain boundary resistance) can be measured by an electrochemical impedance analyzer, the measured temperature range is 400-800 ℃, and the data can be analyzed by zsimwin software to obtain the following table 3:

TABLE 3 (ZrO)₂)_0.89(CeO₂)_0.1(CuO)_0.01Analysis of electrical property data

From the above table, the number of increases in conductivity with temperature of the other components can be calculatedAccording to the summary, as shown in fig. 5, which is obtained by Origin mapping, the conductivity of the whole system shows an increasing trend with the temperature, and as can be seen from the impedance spectrum, as the temperature increases, the resistance of crystal grains and grain boundaries is continuously reduced, the oxygen ion moving rate is accelerated, and thus the conductivity is continuously increased. The conductivity of the 800 ℃ zirconia ceria composite sample was highest, about 0.0067S-cm when x was 0.10^-1As a whole, with Ce⁴⁺The doping amount of the material is increased, and the conductivity of the material is slightly improved.

The relationship between the conductivity and the temperature satisfies an arrhenius curve, and the expression thereof is as follows:

in the formula, σ₀: pre-finger factor, K: boltzmann constant, Ea: activation energy.

FIG. 6 is an Arrhenius plot of temperature and conductivity for samples of different compositions. As shown in fig. 6, the slope of the graph indicates that as the temperature increases, the curve increases almost linearly and has no sharp turning point, and the conductivity increases due to Cu²⁺Or Ce⁴⁺Substituted for Zr⁴⁺Charge compensation is generated to form oxygen vacancies in the unit cell, increasing the pathway for oxygen ion diffusion. In addition, the curves in all doping ratios are relatively close, which indicates that the influence of the doping ratio on the conduction mechanism is not significant, wherein the sample with the doping ratio x equal to 0.10 has the highest conductivity of 0.0067S-cm at 800 DEG C^-1The lowest activation energy is 1.24eV, and the specific data are shown in table 4:

TABLE 4 (ZrO)₂)_0.89(CeO₂)_x(CuO)_0.11-xBasic parameters of each doping ratio

6. Scanning electron microscope

The electrons emitted by the device interact with the substance, secondary electrons, auger electrons, various rays and the like are generated after the interaction, the secondary electrons, the auger electrons, the various rays and the like carry the information of the substance, and various physicochemical properties of the substance to be measured can be obtained by acquiring the information.

FIG. 7 shows (ZrO) sintered at 1350 ℃₂)_0.89(CeO₂)_0.1(CuO)_0.01SEM images of samples at different magnifications. FIGS. 7a and b show the (ZrO) grains sintered at 1350 degrees under different magnifications₂)_0.89(CeO₂)_0.1(CuO)_0.01The microscopic surface appearance of the samples is shown as a group of samples with better density and conductivity. The figure shows that the clear gaps among the grains are clear, a large number of gaps exist due to complete connection among the grains, the grain boundary is wide, the grains of the sample are small, most of the sintered body is polygonal isometric crystal composition, and the grain size is uniform. And agglomeration phenomenon occurs in part. Fig. 7c and d are SEM pictures of fracture of sintered green body under different magnifications, from which it can be seen that the trace left by the powder particles merging and growing into grains during the high-temperature sintering process. Because the grains and grain boundaries play an important role in controlling the conduction behavior in the electrolyte material system; further, the pores have an important influence on the transport of oxygen ions, and it is known from the operation principle of the electrolyte material that the transport ability of oxygen ions affects the conductivity of the material. However, as can be seen from the above analysis, the sintering temperature should be further increased to make the sample denser to increase the electrical conductivity of the composite.

The foregoing is merely exemplary and illustrative of the principles of the present invention and various modifications, additions and substitutions of the specific embodiments described herein may be made by those skilled in the art without departing from the principles of the present invention or exceeding the scope of the claims set forth herein.

Claims (2)

1. Modified ZrO₂The preparation method of the base solid composite electrolyte ceramic material is characterized by comprising the following steps:

first, a target sample (ZrO)₂)_0.89(CeO₂)_x(CuO)_0.11-xWherein x = 0.02-0.10, weighing zirconium nitrate, cerium nitrate and copper nitrate according to the stoichiometric ratio of a target sample, adding into 30ml of distilled water, then adding citric acid, and fully stirring to dissolve;

adding ethylene glycol into the mixed solution, and then putting the solution into an ultrasonic cleaning machine for ultrasonic treatment to uniformly disperse the ethylene glycol;

thirdly, titrating the solution by taking dilute ammonia water as a pH regulator, and regulating the pH value of the solution to 7;

heating and stirring in a water bath with constant temperature of 80 ℃ until sol is formed, and standing for a period of time to form gel;

fifthly, putting the gel into an oven to be dried for 24 hours, taking out the gel, putting the gel into a muffle furnace to be calcined for 10 hours at 700 ℃, cooling the gel to room temperature after the calcination is finished, taking out the crucible, and fully grinding the powder to ultrafine powder to obtain (ZrO)₂)_0.89(CeO₂)_x(CuO)_0.11-xAn electrolyte powder material;

sixthly, adding PVA into the obtained superfine powder for granulation, wherein during the granulation, sufficient grinding is ensured to ensure that the powder and the PVA are uniformly mixed; pressing the powder into tablets under the pressure of 14 Mpa; putting the pressed and formed sheet into a temperature programming furnace for sintering, and preserving the heat for 200 minutes at 1350 ℃ to obtain ZrO₂Solid based composite electrolyte ceramic material (ZrO)₂)_0.89(CeO₂)_x(CuO)_0.11-xAnd (5) ceramic plates.

2. The method according to claim 1, wherein the molar mass of citric acid is 1.5 times the amount of metal ions contained in the composition, and the weight of ethylene glycol is 1.2 times the weight of citric acid.

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