CN110171968B - High-performance solid electrolyte and preparation method thereof - Google Patents

High-performance solid electrolyte and preparation method thereof Download PDF

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CN110171968B
CN110171968B CN201910485185.2A CN201910485185A CN110171968B CN 110171968 B CN110171968 B CN 110171968B CN 201910485185 A CN201910485185 A CN 201910485185A CN 110171968 B CN110171968 B CN 110171968B
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包金小
阮飞
刘国奇
谢敏
郜建全
周芬
关丽丽
宋希文
安胜利
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Inner Mongolia University of Science and Technology
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Abstract

The invention relates to a high-performance solid electrolyte and a preparation method thereof, wherein the chemical expression of the electrolyte is CaHf1‑ xRExO3‑αWith CaCO3、HfO2And rare earth oxide RE2O3The high-performance solid electrolyte is prepared by the technical routes of pretreatment, proportioning, pre-grinding, pre-sintering, crushing, final grinding and final sintering. The electrolyte has the advantages of high density, high conductivity, high proton transference number, wide proton conducting range, high temperature stability, high chemical stability, high corrosion resistance and other advantages, and has excellent comprehensive performance. The method is used in the technical fields of electrochemical hydrogen sensors, solid oxide fuel cells, hydrogen and heavy hydrogen extraction and preparation, hydrogen isotope concentration, organic matter hydrogenation and dehydrogenation, electrochemical synthesis of ammonia and methanol and the like, and can solve the problems of low density, low conductivity, narrow proton conduction range, low proton transference number, poor chemical stability and high-temperature stability and the like of the conventional solid electrolyte.

Description

High-performance solid electrolyte and preparation method thereof
Technical Field
The invention relates to the technical field of electrochemical materials, in particular to a high-performance solid electrolyte and a preparation method thereof.
Background
Since the early 80 s of the twentieth century, the rare earth-doped perovskite-structured solid electrolyte is found to have proton conductivity in a high-temperature water vapor or hydrogen-containing atmosphere, and is widely concerned by experts and scholars at home and abroad due to higher chemical stability and good proton conductivity, and in recent years, with the deep development of relevant theories and technologies of solid electrolytes, the perovskite-type solid electrolyte shows great application value and wide development prospects in the technical fields of electrochemical hydrogen sensors, solid oxide fuel cells, hydrogen and heavy hydrogen extraction and preparation, hydrogen isotope concentration, organic matter hydrogenation and dehydrogenation, electrochemical synthesis of ammonia and methanol and the like.
The ideal perovskite structure belongs to the cubic system and its chemical formula can be expressed as ABO3With CaTiO3For example, wherein O2-At the face center position of the cubic lattice, Ca2+At the apex of the cubic lattice, Ti4+Located in the oxygen octahedral interstitial sites of the cubic lattice.
The perovskite structure has a relatively stable cubic symmetry structure and has high stability. And the change of the radius of the B-site ions in a larger range can be tolerated, when the + 4-valent ions of the B site are doped with the + 3-valent rare earth element RE with a larger radius, according to the defect chemical theory, in order to keep the electric neutrality, oxygen vacancies are generated in the perovskite crystal structure, and the proper oxygen vacancy concentration provides conditions for the conduction of protons, so that the perovskite structure solid electrolyte has good proton conductivity.
Because the oxygen vacancy generated in the perovskite type solid electrolyte crystal structure is related to the doping amount of the rare earth element, in the actual doping process, the doping amount of the rare earth element must be reasonably controlled, the doping amount is too low, the proton conductivity of the solid electrolyte is too low, and the doping amount of the rare earth element is too high, so that a second phase is generated, and the improvement of the proton conductivity is not facilitated. In addition, the perovskite-structure solid electrolyte adopting different rare earth elements doped with the same component or the perovskite-structure solid electrolyte adopting the same rare earth element doped with different components has obvious differences in various performances such as chemical stability, proton conductivity and the like, and in order to explore the perovskite-type solid electrolyte with excellent comprehensive performance, researchers at home and abroad carry out a large amount of related research works, and the perovskite-type solid electrolyte which is researched more at present mainly hasComprising CaZrO3、BaZrO3、SrCeO3、BaCeO3、SrTiO3And the like.
CaZrO3The system is generally made by singly doping or co-doping CaZrO with elements such as In, Ga, Sc and the like3The solid electrolyte has relatively pure proton conductivity at relatively low temperature, relatively high proton transference number, relatively high chemical stability and heat shock resistance, relatively high sintering temperature and proton conductivity higher than SrCeO3The system is 2 orders of magnitude lower.
BaZrO3A system which is singly doped or codoped with BaZrO of In, Y, Sc and other elements3The prepared solid electrolyte has stable lattice structure, high mechanical strength and chemical stability, good reduction resistance, and good stability in CO2Has high stability, high melting point and small expansion coefficient in an acidic atmosphere, but has higher sintering temperature and lower electric conductivity than SrCeO3Is 1-2 orders of magnitude, and has a proton transfer activation energy higher than SrCeO3High.
SrCeO3The system is generally formed by singly doping or co-doping elements such as Yb, Sc, Y, Tm, Ga, In, Sm, Dy and the like with SrCeO3The solid electrolyte prepared from the matrix has the conductivity activation energy generally smaller than 1eV, and in the structural aspect, oxygen ion migration can be inhibited due to the fact that crystal lattices of an orthogonal structure of the solid electrolyte are greatly distorted, so that the oxygen ion conductivity is reduced, and therefore the solid electrolyte has purer proton conductivity, and the proton migration number is close to 1 in a high-temperature hydrogen atmosphere. But the system is combined with BaCeO3System analogous to CO2And the like, and thus, the acid gas is less chemically stable because of the tendency to react.
BaCeO3The system is formed by singly doping or co-doping BaCeO with Y, Yb, Gd, Nd, Sm and other elements3The prepared solid electrolyte is a material with higher conductivity in the perovskite type solid electrolyte found at present, and the conductivity activation energy is about 0.5-0.6 eV. The solid electrolyte of the system belongs to a mixed ion conductor, the conductivity is more complex, generally, the oxygen ion conductivity is dominant at the temperature of more than 800 ℃, and the proton conductivity is dominant at the temperature of less than 800 ℃. The electrolyte of the system is strong in alkalinity, butPoor mechanical strength and chemical stability, and easy reaction with CO2And the acid gas is subjected to chemical reaction.
SrTiO3The system can be singly doped or codoped with SrTiO by In, Yb, Ga, Y and other elements3The system has better mechanical strength and chemical stability, and is formed at high temperature and CO2The stability in the acidic atmosphere is far higher than that of SrCeO3The system can still maintain higher proton conductivity at the temperature higher than 900 ℃, but the conductivity of the series of solid electrolytes is higher than that of SrCeO3Is 1-2 orders of magnitude lower and has a proton transfer activation energy higher than SrCeO3Is high.
In summary, the research and development of perovskite proton conductive solid electrolyte materials at home and abroad have been advanced to a certain extent, especially for CaZrO3、BaZrO3、SrCeO3、BaCeO3、SrTiO3The preparation, structure characterization and performance test of the solid electrolyte of the same system are systematically and deeply studied, and representative patents obtained at home and abroad in the field mainly comprise German invention patent (DE19535922), US invention patent (US 2009016933), Chinese invention patent (CN101445395), Chinese invention patent (CN101119A), Chinese invention patent (CN101752585A), Chinese invention patent (CN102442818A), Chinese invention patent (CN102603299A), Chinese invention patent (CN101215644A), Chinese invention patent (CN104968632A), Chinese invention patent (CN108370041A), Chinese invention patent (CN1491420A) and the like.
Although the research and development of perovskite type proton conductive solid electrolyte have been developed to a certain extent at present, many perovskite type solid electrolyte systems developed at present mostly adopt the traditional preparation process, and due to the defects of low electrolyte density, lower conductivity, narrow proton conductive temperature range, low proton transference number, poor chemical stability, poor high-temperature stability and the like, the perovskite type solid electrolyte systems cannot be practically applied to electrochemical hydrogen sensors, solid oxide fuel cells, hydrogen and heavy hydrogen extraction preparation, hydrogen isotope concentration, organic matter hydrogenation and heavy hydrogen extraction preparation, and the like with high requirements on comprehensive properties such as proton conductivity, chemical stability and the likeDehydrogenation, electrochemical synthesis of ammonia and methanol, etc. For example, In, which is more successful even In the field of high-temperature metal melt electrochemical hydrogen sensors2O3Doped CaZrO3Is a solid electrolyte, and has a dopant In used for synthesizing probe material2O3Poor stability and In generation at high temperature2O3(s)→In2O(g)+O2(g)The material preparation process has poor repeatability, the sensor has poor high-temperature measurement accuracy and the like due to decomposition reaction.
Disclosure of Invention
The invention aims to provide a high-performance solid electrolyte to solve the problems of low electrolyte density, low conductivity, narrow proton conduction range, low proton transference number, poor chemical stability and high-temperature stability and the like of the conventional solid electrolyte.
The scheme adopted by the invention for solving the technical problems is as follows:
the high-performance solid electrolyte provided by the invention is a calcium hafnate-based solid electrolyte for analyzing pure CaCO3、HfO2And RE2O3Is prepared from raw materials through optimized high-temperature solid-phase reaction, and the chemical composition can be expressed as CaHf1-xRExO3-αWherein x is 0.01 to 0.6.
The rare earth oxide RE2O3And RE is at least one element of Sc, Lu, Yb, Tm, Er, Ho, Dy, Tb, Gd, Eu, Sm and Pm.
When singly doped, it has the chemical formula of CaHf1-xRExO3-α. The rare earth dopant can also be more than two, such as two, three, four, etc., when the rare earth dopant is two or more, the chemical formula of the synthesized solid electrolyte follows the principle of the general formula but is not limited by CaHf1-xRExO3-αTo the extent that, for example, the solid electrolyte chemistry resulting from doping with Yb having a mole fraction of y and Sc having a mole fraction of z can be expressed as CaHf1-y-zYbySczO3-αFor other cases where two or more dopants are usedAnd so on.
In addition, the doping amount of the rare earth elements can be generally selected within the range of x being 0.01-0.6, and the actual doping amount of each element is not more than that of CaHfO3In the case of co-doping of a plurality of elements, the doping amount of each element may vary, and the doping amount of each element needs to be adjusted as appropriate.
The results of the previous research on the team show that CaHfO3The perovskite type perovskite-type ceramic material belongs to a typical simple perovskite structure, has a stable cubic symmetric crystal structure, and is high in melting point and mechanical strength. In an air atmosphere, CO2Atmosphere, O2Atmosphere, H2O and H2Has higher stability and good chemical stability in the atmosphere, the crystal structure can tolerate the change of the radius of Hf site ions in a larger range, and proper amount of + 3-valent rare earth ions are doped into CaHfO3The + 4-valence Hf site in the crystal structure, CaHfO according to the defect chemistry theory, for maintaining electric neutrality3Oxygen vacancy is generated in the crystal structure, and the generated oxygen vacancy provides conditions for proton conduction, so that CaHfO3The base solid electrolyte has good proton conductivity.
The solid electrolyte has higher proton conductivity, higher high-temperature stability and chemical stability, higher corrosion resistance and better mechanical strength, is an ideal proton conductive solid electrolyte used in the technical fields of electrochemical hydrogen sensors, solid oxide fuel cells, hydrogen and heavy hydrogen extraction and preparation, hydrogen isotope concentration, organic matter hydrogenation and dehydrogenation, electrochemical synthesis of ammonia and methanol and the like, and solves the problems of low density, low conductivity, narrow proton conductive range, low proton transference number, poor chemical stability and high-temperature stability and the like of the conventional proton conductive solid electrolyte.
Another object of the present invention is to provide a method for preparing a high-performance solid electrolyte, comprising the steps of:
s1: pretreatment, taking analytically pure CaCO respectively3And rare earth oxide RE2O3Drying to remove water in the raw materials; in addition, take HfO2Pretreating the mixture at a certain temperature;
s2: proportioning, namely mixing the CaCO dried in the step S13And rare earth oxide RE2O3And pretreated HfO2According to the solid electrolyte to be synthesized, CaHf1-xRExO3-αAccurately weighing each raw material to prepare the ingredients;
s3: pre-grinding, namely uniformly mixing the raw materials weighed in the step S2, then ball-milling by taking deionized water as a medium, then adding a dispersing agent into the deionized water as a medium for sand grinding, and then spray-drying and sieving to obtain nano-scale mixed powder;
s4: pre-sintering, namely placing the mixed powder prepared in the step S3 into a sintering furnace for sintering, raising the sintering temperature to 800-1300 ℃ at the temperature rise rate of 25-300 ℃/min in the sintering process, preserving the temperature for 5-35 min, then cutting off a power supply, cooling the mixed powder to room temperature along with the furnace to finish pre-sintering, and applying different axial pressures to the mixed powder in stages in the sintering process;
s5: crushing, namely crushing the sample obtained by pre-sintering in the step S4, performing coarse grinding after crushing to obtain powder, and performing strong magnetic treatment on the powder to prevent iron-containing impurities from being introduced in the crushing process;
s6: performing final grinding, namely performing ball milling on the powder subjected to the strong magnetic treatment in the step S5 by taking deionized water as a medium, then adding a dispersing agent into the deionized water as the medium, performing sand milling, and performing spray drying and sieving to obtain nano-scale mixed powder again;
s7: and (4) final sintering, namely putting the mixed powder obtained in the step S6 into a sintering furnace again for sintering, raising the sintering temperature to 1400-1600 ℃ at the temperature rise rate of 20-250 ℃/min in the sintering process, then preserving the heat for 10-40 min, cutting off a power supply, cooling to room temperature along with the furnace to finish final sintering, and applying different axial pressures to the mixed powder in stages in the sintering process.
Further, in step S1, CaCO3And rare earth oxide RE2O3The drying method comprises the following steps: raising the drying temperature to 300-900 ℃ at a temperature raising rate of 2-10 ℃/min, then preserving heat for 2-7 h, and then carrying out heat preservationCooling the furnace; in step S1, HfO2The pretreatment method comprises the following steps: raising the pretreatment temperature to 1100-1200 ℃ at a temperature rise rate of 2-10 ℃/min, then preserving heat for 3-10 h, and then cooling along with the furnace
Further, in step S3, the ball milling parameters of the pre-milled raw materials are: the adding amount of the deionized water is 50-80 wt.%, the adopted ball milling tool is made of agate materials, the mass ratio of ball materials is 3:1, the rotating speed is 200-500 r/min, and the ball milling time is 20-90 h.
Further, in step S3, the sanding parameters of the pre-grinding are: the adding amount of deionized water is 50-80 wt.%, the adding amount of dispersant ammonium polymethacrylate is 20-60% of the content of powder, the rotating speed is 1000-2500 r/min, sanding is carried out for 1-10 h, and spray drying parameters are as follows: the inlet temperature is 220-250 ℃, the outlet temperature is 90-120 ℃, the rotating speed is 2000-12000 r/min, and the negative pressure is-20 to-120 kPa.
Further, in step S4, applying different axial pressure parameters to the mixed powder in stages is: pre-pressurizing to 4-8 MPa before sintering, pressurizing to 9-15 MPa at the beginning of sintering, pressurizing to 20-30 MPa at the middle temperature rise stage, and maintaining the pressure to 35-70 MPa after the sintering temperature is reached at the later stage.
Further, the ball milling parameters of the final milling in step S6 are: the adding amount of the deionized water is 50-80 wt.%, the adopted ball milling tool is made of agate materials, the mass ratio of ball materials is 3:1, the rotating speed is 200-500 r/min, and the ball milling time is 20-90 h.
Further, the sanding parameters for the final grinding in step S6 are: the adding amount of deionized water is 50-80 wt.%, the adding amount of dispersant ammonium polymethacrylate is 30-70% of the content of powder, the rotating speed is 1000-2500 r/min, sanding is carried out for 1-10 h, and spray drying parameters are as follows: the inlet temperature is 220-250 ℃, the outlet temperature is 90-120 ℃, the rotating speed is 1000-10000 r/min, and the negative pressure is-10 to-100 kPa.
Further, in step S7, the parameters of applying different axial pressures to the mixed powder in stages are: pre-pressurizing to 3-6 MPa before sintering, starting sintering and pressurizing to 8-12 MPa, pressurizing to 15-25 MPa in the middle temperature rise stage, and maintaining the pressure to 30-60 MPa after the sintering temperature is reached in the later stage.
The invention uses CaHfO3Is used as a matrix and is provided with a plurality of groups of nano-particles,with rare earth oxide RE2O3As a dopant, a proton-conducting solid electrolyte was prepared, due to CaHfO3The matrix material is of a perovskite structure (the crystal structure is shown in figure 1), the crystal structure is stable, and the crystal structure is a high-temperature-resistant material with excellent comprehensive performance, so that the prepared solid electrolyte inherits the advantages of the matrix material, has the advantages of high melting point, good chemical stability, high-temperature stability and the like, and can adapt to high temperature, air atmosphere, CO and the like2Atmosphere, O2Atmosphere, H2O and H2Atmosphere, etc.
The invention mainly adopts the grinding method of combining common ball milling and high-performance sand milling to finish powder grinding, and the powder granularity can reach the level of nanometer level, the specific surface area is large, and the reaction activity is high. Wherein, ammonium polymethacrylate dispersant is added in the sanding link, so as to ensure that the grinded powder is uniformly dispersed. The spray drying process is adopted for drying the powder, the agglomeration of the powder can be inhibited to the greatest extent, and the deionized water is used as a medium for grinding, so that the safety of spray drying can be ensured. Different axial pressures are applied to the mixed powder in different stages in the pre-sintering and the final sintering, so that the powder particles are in closer contact, the sintering is promoted, and the density of the material is improved. The process can ensure the full implementation of the solid-phase reaction and the sintering process, and the prepared proton conductive solid electrolyte has good crystallinity, high density, stable performance, low defective rate and good repeatability.
The invention prepares the rare earth element doped calcium hafnate-based high-performance solid electrolyte based on an optimized solid-phase reaction method, a large amount of experiments are searched and optimized on the temperature schedule of the sintering process in the early period, and the formulated presintering and final sintering temperature schedule can synthesize CaHfO with excellent performance3The temperature regime of the base solid electrolyte (shown in figure 2 by the XRD pattern of the sample prepared in example 5) can ensure that the solid solution and sintering processes are sufficiently performed, and can inhibit the excessive growth of crystal grains during sintering to reduce the overall performance of the material.
The invention adopts SPS sintering technology, and prepares the high-temperature solid electrolyte through presintering and final sintering under different temperature systems, the prepared high-temperature solid electrolyte has very high density (figure 3 shows that the relative density of 4 groups of samples prepared by adopting example 4 is more than 98 percent), and the crystal grains are uniform and fine, so the prepared proton conductive solid electrolyte has good high-temperature stability and corrosion resistance (figure 4 shows that the electromotive force of the samples prepared by adopting example 3 in high-temperature hydrogen atmosphere, and the long-time working signal under high temperature has no obvious attenuation).
The invention uses rare earth oxide to dope CaHfO3The prepared high-temperature proton conductive solid electrolyte has high conductivity, particularly high proton conductivity in water vapor and hydrogen atmosphere (fig. 5 shows that the conductivity of samples prepared by adopting example 1 under different conditions is shown), wide proton conductive temperature range (fig. 6 shows that the solid electrolyte prepared by adopting example 2 has H/D isotope effect under different temperatures and has isotope effect in the tested temperature range), high proton transference number, no obvious attenuation phenomenon when the electromotive force is tested for a long time at high temperature, and the measured value is very close to the theoretical calculated value (as shown in fig. 4), and can be used for electrochemical hydrogen sensors, solid oxide fuel cells, hydrogen and heavy hydrogen extraction preparation, hydrogen isotope concentration, organic matter hydrogenation and dehydrogenation, electrochemical synthesis of ammonia and methanol and the like, proton conductivity of solid electrolyte, The chemical stability and other comprehensive performance requirements are higher.
Drawings
FIG. 1CaHfO3A schematic diagram of a crystal structure;
FIG. 2 is an XRD pattern of the sample prepared in example 5;
FIG. 3 relative compactness of a sample prepared using example 4;
FIG. 4 shows the electromotive force in a high-temperature hydrogen atmosphere of the sample prepared in example 3;
FIG. 5 conductivity under different conditions using samples prepared in example 1;
FIG. 6 shows the H/D isotope effects at different temperatures of the solid electrolyte prepared in example 2.
Detailed Description
The following examples are provided to further illustrate the present invention for better understanding, but the present invention is not limited to the following examples.
Example 1
Weighing a certain amount of analytically pure CaCO3And rare earth oxide Sc2O3Respectively placing the raw materials into a corundum sagger with a cover, placing the corundum sagger into a high-temperature furnace, heating to 500 ℃ at the heating rate of 4 ℃/min, preserving heat for 4 hours, drying the moisture in the raw materials, then cooling to room temperature along with the furnace, and grinding by an agate mortar to obtain powder for later use. Separately weighing a certain amount of analytically pure HfO2Placing the mixture into a corundum sagger with a cover, placing the corundum sagger into a high-temperature furnace, heating to 1100 ℃ at the heating rate of 4 ℃/min, preserving heat for 4 hours, drying water in the raw materials, carrying out high-temperature treatment on the raw materials, then cooling to room temperature along with the furnace, and grinding by an agate mortar to obtain powder for later use.
According to the molar ratio of CaCO3：Hf2O3：Sc2O3Weighing a proper amount of dried and high-temperature pretreated powder respectively according to the proportion of 20:9:1, mixing and loading the powder into a ball mill tank, adding 50 wt.% of deionized water, adding agate grinding balls, wherein the mass ratio of the ball materials is 3:1, then filling the ball mill tank into a planetary ball mill, setting the rotating speed to be 480r/min, carrying out ball milling for 24h, then transferring the slurry into a sand mill, adding an ammonium polymethacrylate dispersing agent according to 25% of the content of the powder, carrying out sand milling for 3h at the rotating speed of 2000r/min, transferring the obtained slurry into a spray dryer, setting the inlet temperature to be 220 ℃, the outlet temperature to be 100 ℃, the rotating speed to be 2200r/min, drying the slurry at the negative pressure of-20 kPa, and sieving to obtain pre-milled powder.
Weighing a certain amount of the pre-ground powder, putting the pre-ground powder into a graphite die with the inner diameter of 50mm, putting the graphite die into an SPS sintering furnace, respectively setting pre-pressurization of 4MPa before sintering, pressurization of 9MPa at the beginning of sintering, pressurization of 20MPa at the middle temperature rise stage, pressure maintenance of 35MPa after the sintering temperature is reached at the later stage, heating to 1200 ℃ at the heating rate of 100 ℃/min, heat preservation for 10min, and then cutting off a power supply to cool to room temperature along with the furnace to finish pre-sintering.
And (3) crushing a certain amount of the sample obtained by pre-sintering by using a special crusher, coarsely grinding by using an agate mortar after crushing, and then performing strong magnetic treatment on the powder by using self-made strong magnetic treatment equipment to prevent iron-containing impurities from being introduced in the crushing process.
Weighing a proper amount of powder subjected to strong magnetic treatment, filling the powder into a ball mill tank, adding 50 wt.% of deionized water, adding agate grinding balls, wherein the mass ratio of the balls to the materials is 3:1, filling the ball mill tank into a planetary ball mill, setting the rotating speed to be 450r/min, carrying out ball milling for 25h, then transferring the slurry into a sand mill, adding an ammonium polymethacrylate dispersing agent according to 30% of the content of the powder, carrying out sand milling for 4h at the rotating speed of 1500r/min, transferring the obtained slurry into a spray dryer, setting the inlet temperature to be 225 ℃, the outlet temperature to be 115 ℃, the rotating speed to be 2000r/min, drying the slurry at the negative pressure of-25 kPa, and sieving after drying to obtain the final-milled powder.
Weighing a certain amount of the finally ground powder, putting the finally ground powder into a graphite mold with the inner diameter of 16mm, putting the graphite mold into an SPS sintering furnace, respectively setting pre-pressurization of 3MPa, starting sintering pressurization of 8MPa, pressurizing at a medium-stage temperature rise stage of 15MPa, maintaining the axial pressure of 30MPa after reaching the sintering temperature at a later stage, raising the temperature to 1400 ℃ at the temperature rise rate of 100 ℃/min, preserving heat for 10min, then cutting off a power supply, cooling to room temperature along with the furnace, and preparing the CaHf0.9Sc0.1O3-αA solid electrolyte.
Example 2
Weighing a certain amount of analytically pure CaCO3And rare earth oxide Lu2O3Respectively placing the raw materials into a corundum sagger with a cover, placing the corundum sagger into a high-temperature furnace, heating to 600 ℃ at the heating rate of 5 ℃/min, preserving heat for 5 hours, drying water in the raw materials, then cooling to room temperature along with the furnace, and grinding by an agate mortar to obtain powder for later use. Separately weighing a certain amount of analytically pure HfO2Placing the mixture into a corundum sagger with a cover, placing the corundum sagger into a high-temperature furnace, heating to 1200 ℃ at the heating rate of 5 ℃/min, preserving heat for 5 hours, drying water in the raw materials, carrying out high-temperature treatment on the raw materials, then cooling to room temperature along with the furnace, and grinding by an agate mortar to obtain powder for later use.
According to the molar ratio of CaCO3：Hf2O3：Lu2O3Taking a proper amount of dried and high-temperature pretreated powder respectively according to the proportion of 20:8.5:1.5, mixing and loading the powder into a ball mill tank, adding 60 wt.% of deionized water, adding agate grinding balls, wherein the mass ratio of the ball materials is 3:1, then loading the ball mill tank into a planetary ball mill, setting the rotating speed to 460r/min, carrying out ball milling for 48 hours, then transferring the slurry into a sand mill, adding an ammonium polymethacrylate dispersing agent according to 30% of the content of the powder, carrying out sand milling at the rotating speed of 2000r/min for 4 hours, transferring the obtained slurry into a spray dryer, setting the inlet temperature to 230 ℃, the outlet temperature to 110 ℃, the rotating speed to 2500r/min, drying the slurry at the negative pressure of-30 kPa, and sieving to obtain pre-milled powder.
Weighing a certain amount of the pre-ground powder, putting the pre-ground powder into a graphite die with the inner diameter of 50mm, putting the graphite die into an SPS sintering furnace, respectively setting pre-pressurization of 5MPa, starting sintering and pressurizing by 10MPa, heating up to 25MPa in the middle heating stage, maintaining the axial pressure of 40MPa after the sintering temperature is reached in the later stage, heating up to 1300 ℃ at the heating rate of 200 ℃/min, preserving heat for 15min, and then cutting off a power supply to cool to room temperature along with the furnace to finish pre-sintering.
And (3) crushing a certain amount of the sample obtained by pre-sintering by using a special crusher, coarsely grinding by using an agate mortar after crushing, and then performing strong magnetic treatment on the powder by using self-made strong magnetic treatment equipment to prevent iron-containing impurities from being introduced in the crushing process.
Weighing a proper amount of powder subjected to strong magnetic treatment, putting the powder into a ball mill tank, adding 60 wt.% of deionized water, adding agate grinding balls, wherein the mass ratio of the balls to the materials is 3:1, putting the ball mill tank into a planetary ball mill, setting the rotating speed at 470r/min, carrying out ball milling for 50h, then transferring the slurry into a sand mill, adding an ammonium polymethacrylate dispersing agent according to 45% of the content of the powder, carrying out sand milling for 5h at the rotating speed of 2200r/min, transferring the obtained slurry into a spray dryer, setting the inlet temperature at 235 ℃, the outlet temperature at 120 ℃, the rotating speed at 2500r/min, and drying the slurry at the negative pressure of-35 kPa, and sieving the dried slurry to obtain the final-milled powder.
Weighing a certain amount of the finally ground powder, putting the finally ground powder into a graphite mold with the inner diameter of 16mm, placing the finally ground powder into an SPS sintering furnace, respectively setting the pre-pressurization to be 3.5MPa, the initial sintering pressurization to be 8.5MPa, and the middle stagePressurizing at 16MPa in the temperature rise stage, maintaining the axial pressure of 32MPa after the sintering temperature is reached in the later stage, raising the temperature to 1500 ℃ at the temperature rise rate of 150 ℃/min, preserving the temperature for 15min, cutting off a power supply, cooling to room temperature along with the furnace, and preparing the CaHf0.85Lu0.15O3-αA solid electrolyte.
Example 3
Weighing a certain amount of analytically pure CaCO3And rare earth oxide Yb2O3Respectively placing the raw materials into a corundum sagger with a cover, placing the corundum sagger into a high-temperature furnace, heating to 700 ℃ at the heating rate of 6 ℃/min, preserving heat for 4 hours, drying the moisture in the raw materials, then cooling to room temperature along with the furnace, and grinding by an agate mortar to obtain powder for later use. Separately weighing a certain amount of analytically pure HfO2Placing the mixture into a corundum sagger with a cover, placing the corundum sagger into a high-temperature furnace, heating to 1200 ℃ at the heating rate of 6 ℃/min, preserving heat for 6 hours, drying water in the raw materials, carrying out high-temperature treatment on the raw materials, then cooling to room temperature along with the furnace, and grinding by an agate mortar to obtain powder for later use.
According to the molar ratio of CaCO3：Hf2O3：Yb2O3Taking a proper amount of dried and high-temperature pretreated powder respectively according to the proportion of 20:8:2, mixing and loading the powder into a ball mill tank, adding 50 wt.% of deionized water, adding agate grinding balls, wherein the mass ratio of the ball materials is 3:1, then filling the ball mill tank into a planetary ball mill, setting the rotating speed to be 480r/min, carrying out ball milling for 24 hours, then transferring the slurry into a sand mill, adding an ammonium polymethacrylate dispersing agent according to 35% of the content of the powder, carrying out sand milling for 5 hours at the rotating speed of 2000r/min, transferring the obtained slurry into a spray dryer, setting the inlet temperature to be 240 ℃, the outlet temperature to be 120 ℃, the rotating speed to be 3000r/min, drying the slurry at the negative pressure of-50 kPa, and sieving to obtain pre-milled powder.
Weighing a certain amount of the pre-ground powder, putting the pre-ground powder into a graphite die with the inner diameter of 50mm, putting the graphite die into an SPS sintering furnace, respectively setting pre-pressurization of 6MPa, starting sintering and pressurizing at 11MPa, pressurizing at a medium temperature rise stage at 25MPa, maintaining the axial pressure at 45MPa after the sintering temperature is reached at a later stage, raising the temperature to 1300 ℃ at a temperature rise rate of 100 ℃/min, preserving heat for 20min, and then cutting off a power supply to cool to room temperature along with the furnace to finish pre-sintering.
Weighing a certain amount of the sample obtained by pre-sintering, crushing by using a special crusher, roughly grinding by using an agate mortar after crushing, and then strongly magnetic treating the powder by using self-made strong magnetic treatment equipment to prevent the introduction of iron-containing impurities in the crushing process.
Weighing a proper amount of powder subjected to strong magnetic treatment, filling the powder into a ball mill tank, adding 50 wt.% of deionized water, adding agate grinding balls, wherein the mass ratio of the balls to the materials is 3:1, filling the ball mill tank into a planetary ball mill, setting the rotating speed to be 450r/min, carrying out ball milling for 25h, then transferring the slurry into a sand mill, adding an ammonium polymethacrylate dispersing agent according to 50% of the content of the powder, carrying out sand milling for 6h at the rotating speed of 1500r/min, transferring the obtained slurry into a spray dryer, setting the inlet temperature to be 245 ℃, the outlet temperature to be 120 ℃, the rotating speed to be 2000r/min, drying the slurry at the negative pressure of-45 kPa, and sieving after drying to obtain the final-milled powder.
Weighing a certain amount of the finally ground powder, putting the finally ground powder into a graphite mold with the inner diameter of 16mm, putting the graphite mold into an SPS sintering furnace, respectively setting pre-pressurization of 3MPa, starting sintering pressurization of 8MPa, pressurizing at a medium-stage heating stage of 17MPa, maintaining the axial pressure of 35MPa after the sintering temperature is reached at a later stage, heating to 1400 ℃ at a heating rate of 100 ℃/min, preserving heat for 20min, cutting off a power supply, cooling to room temperature along with the furnace, and preparing the CaHf0.8Yb0.2O3-αA solid electrolyte.
Example 4
Weighing a certain amount of analytically pure CaCO3And rare earth oxide Tm2O3Respectively placing the raw materials into a corundum sagger with a cover, placing the corundum sagger into a high-temperature furnace, heating to 800 ℃ at the heating rate of 5 ℃/min, preserving heat for 5 hours, drying water in the raw materials, then cooling to room temperature along with the furnace, and grinding by an agate mortar to obtain powder for later use. Separately weighing a certain amount of analytically pure HfO2Placing the mixture into a corundum sagger with a cover, placing the corundum sagger into a high-temperature furnace, heating to 1100 ℃ at the heating rate of 5 ℃/min, preserving heat for 7 hours, drying water in the raw materials, carrying out high-temperature treatment on the raw materials, then cooling to room temperature along with the furnace, and grinding by an agate mortar to obtain powder for later use.
According to the molar ratio of CaCO3：Hf2O3：Tm2O3Taking a proper amount of dried and high-temperature pretreated powder respectively according to the proportion of 20:8.5:1.5, mixing and loading the powder into a ball mill tank, adding 60 wt.% of deionized water, adding agate grinding balls, wherein the mass ratio of the ball materials is 3:1, then loading the ball mill tank into a planetary ball mill, setting the rotating speed to 460r/min, carrying out ball milling for 36h, then transferring the slurry into a sand mill, adding an ammonium polymethacrylate dispersing agent according to 40% of the content of the powder, carrying out sand milling at the rotating speed of 2000r/min for 4h, transferring the obtained slurry into a spray dryer, setting the inlet temperature to 220 ℃, the outlet temperature to 110 ℃, the rotating speed to 4000r/min, drying the slurry at the negative pressure of-40 kPa, and sieving to obtain pre-milled powder.
Weighing a certain amount of the pre-ground powder, putting the pre-ground powder into a graphite die with the inner diameter of 50mm, putting the graphite die into an SPS sintering furnace, respectively setting pre-pressurization of 4MPa, starting sintering pressurization of 10MPa, pressurizing at a medium-stage heating stage of 20MPa, maintaining the axial pressure of 40MPa after the sintering temperature is reached at a later stage, heating to 1250 ℃ at a heating rate of 200 ℃/min, preserving heat for 15min, and then cutting off a power supply to cool to room temperature along with the furnace to finish pre-sintering.
And (3) crushing a certain amount of the sample obtained by pre-sintering by using a special crusher, coarsely grinding by using an agate mortar after crushing, and then performing strong magnetic treatment on the powder by using self-made strong magnetic treatment equipment to prevent iron-containing impurities from being introduced in the crushing process.
Weighing a proper amount of powder subjected to strong magnetic treatment, filling the powder into a ball mill tank, adding 55 wt.% of deionized water, adding agate grinding balls, wherein the mass ratio of the balls to the materials is 3:1, filling the ball mill tank into a planetary ball mill, setting the rotating speed to be 460r/min, performing ball milling for 30h, then transferring the slurry into a sand mill, adding an ammonium polymethacrylate dispersing agent according to 35% of the content of the powder, performing sand milling for 4.5h at the rotating speed of 2000r/min, transferring the obtained slurry into a spray dryer, setting the inlet temperature to be 230 ℃, the outlet temperature to be 120 ℃, the rotating speed to be 2200r/min, drying the slurry at the negative pressure of-35 kPa, and screening after drying to obtain the final-milled powder.
Weighing a certain amount of the finally ground powder, and filling the finally ground powder into a graphite mold with the inner diameter of 16mmPlacing the material in an SPS sintering furnace, respectively setting pre-pressurization of 3.5MPa, sintering and pressurization of 8.5MPa, pressurization of 15MPa in the middle temperature rise stage, maintaining the axial pressure of 30MPa after the sintering temperature is reached in the later stage, raising the temperature to 1500 ℃ at the temperature rise rate of 150 ℃/min, keeping the temperature for 25min, cutting off a power supply, cooling the furnace to room temperature, and preparing the CaHf0.85Tm0.15O3-αA solid electrolyte.
Example 5
Weighing a certain amount of analytically pure CaCO3And rare earth oxide Er2O3Respectively placing the raw materials into a corundum sagger with a cover, placing the corundum sagger into a high-temperature furnace, heating to 750 ℃ at the heating rate of 6 ℃/min, preserving heat for 6 hours, drying the moisture in the raw materials, then cooling to room temperature along with the furnace, and grinding by an agate mortar to obtain powder for later use. Separately weighing a certain amount of analytically pure HfO2Placing the mixture into a corundum sagger with a cover, placing the corundum sagger into a high-temperature furnace, heating to 1150 ℃ at the heating rate of 6 ℃/min, preserving heat for 8 hours, drying water in the raw materials, carrying out high-temperature treatment on the raw materials, then cooling to room temperature along with the furnace, and grinding by an agate mortar to obtain powder for later use.
According to the molar ratio of CaCO3：Hf2O3：Er2O3Taking a proper amount of dried and high-temperature pretreated powder respectively according to the proportion of 20:9:1, mixing and loading the powder into a ball mill tank, adding 55 wt.% of deionized water, adding agate grinding balls, wherein the mass ratio of the ball materials is 3:1, then filling the ball mill tank into a planetary ball mill, setting the rotating speed to 470r/min, ball milling for 30h, then transferring the slurry into a sand mill, adding an ammonium polymethacrylate dispersing agent according to 25% of the content of the powder, sanding for 3.5h at the rotating speed of 2000r/min, transferring the obtained slurry into a spray dryer, setting the inlet temperature to 225 ℃, the outlet temperature to 105 ℃, the rotating speed to 3500r/min, and the negative pressure to-25 kPa, drying, and sieving to obtain pre-ground powder.
Weighing a certain amount of the pre-ground powder, putting the pre-ground powder into a graphite die with the inner diameter of 50mm, putting the graphite die into an SPS sintering furnace, respectively setting pre-pressurization of 5MPa, starting sintering and pressurizing at 11MPa, pressurizing at a medium-stage heating stage at 21MPa, maintaining the axial pressure at 35MPa after the sintering temperature is reached at a later stage, heating to 1300 ℃ at a heating rate of 100 ℃/min, preserving heat for 20min, and then cutting off a power supply to cool to room temperature along with the furnace to finish pre-sintering.
Weighing a certain amount of the sample obtained by pre-sintering, crushing by using a special crusher, roughly grinding by using an agate mortar after crushing, and then strongly magnetic treating the powder by using self-made strong magnetic treatment equipment to prevent the introduction of iron-containing impurities in the crushing process.
Weighing a proper amount of powder subjected to strong magnetic treatment, filling the powder into a ball mill tank, adding 60 wt.% of deionized water, adding agate grinding balls, wherein the mass ratio of the balls to the materials is 3:1, filling the ball mill tank into a planetary ball mill, setting the rotating speed to be 450r/min, performing ball milling for 40h, then transferring the slurry into a sand mill, adding an ammonium polymethacrylate dispersing agent according to 40% of the content of the powder, performing sand milling for 5h at the rotating speed of 2100r/min, transferring the obtained slurry into a spray dryer, setting the inlet temperature to be 235 ℃, the outlet temperature to be 120 ℃, the rotating speed to be 2500r/min, drying the slurry at the negative pressure of-25 kPa, and sieving after drying to obtain the final-ground powder.
Weighing a certain amount of the finally ground powder, filling the finally ground powder into a graphite die with the inner diameter of 16mm, placing the graphite die into an SPS sintering furnace, respectively setting pre-pressurization of 3MPa, starting sintering pressurization of 8MPa, pressurizing at a medium-stage temperature rise stage of 17MPa, maintaining the axial pressure of 32MPa after the sintering temperature is reached at a later stage, raising the temperature to 1450 ℃ at the temperature rise rate of 150 ℃/min, preserving heat for 20min, cutting off a power supply, cooling to room temperature along with the furnace, and preparing to obtain CaHf0.9Er0.1O3-αA solid electrolyte.
While the foregoing is directed to the preferred embodiment of the present invention, other and further embodiments of the invention may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow.

Claims (8)

1. A method for preparing a high-performance solid electrolyte, characterized in that the high-performance solid electrolyte is CaHfO3As matrix, with rare earth oxide RE2O3Is a dopant with the chemical expression of CaHf x1-RE x O α3-Whereinx=0.01~0.6；
The preparation method of the high-performance solid electrolyte comprises the following preparation steps:
s1: pretreatment, taking analytically pure CaCO respectively3And rare earth oxide RE2O3Drying to remove water in the raw materials; in addition, take HfO2Pretreating the mixture at a certain temperature;
s2: proportioning, namely mixing the CaCO dried in the step S13And rare earth oxide RE2O3And pretreated HfO2According to the solid electrolyte to be synthesized, CaHf x1-RE x O α3-Accurately weighing each raw material to prepare the ingredients;
s3: pre-grinding, namely uniformly mixing the raw materials weighed in the step S2, then ball-milling by taking deionized water as a medium, then adding a dispersing agent into the deionized water as a medium for sand grinding, and then spray-drying and sieving to obtain nano-scale mixed powder;
s4: pre-sintering, namely placing the mixed powder prepared in the step S3 into a sintering furnace for sintering, raising the sintering temperature to 800-1300 ℃ at the temperature rise rate of 25-300 ℃/min in the sintering process, then preserving the heat for 5-35 min, cutting off a power supply, cooling to room temperature along with the furnace to finish pre-sintering, and applying different axial pressures to the mixed powder in stages in the sintering process;
s5: crushing, namely crushing the sample obtained by pre-sintering in the step S4, performing coarse grinding after crushing to obtain powder, and performing strong magnetic treatment on the powder to prevent iron-containing impurities from being introduced in the crushing process;
s6: performing final grinding, namely performing ball milling on the powder subjected to the strong magnetic treatment in the step S5 by taking deionized water as a medium, then adding a dispersing agent into the deionized water as the medium, performing sand milling, and performing spray drying and sieving to obtain nano-scale mixed powder again;
s7: final sintering, namely putting the mixed powder obtained in the step S6 into a sintering furnace again for sintering, raising the sintering temperature to 1400-1600 ℃ at the temperature rise rate of 20-250 ℃/min in the sintering process, then preserving the heat for 10-40 min, cutting off a power supply, cooling the mixed powder to room temperature along with the furnace to finish final sintering, and applying different axial pressures to the mixed powder in stages in the sintering process; the parameters of applying different axial pressures to the mixed powder in stages in the step are as follows: pre-pressurizing to 3-6 MPa before sintering, starting sintering and pressurizing to 8-12 MPa, pressurizing to 15-25 MPa in the middle temperature rise stage, and maintaining the pressure to 30-60 MPa after the sintering temperature is reached in the later stage.
2. The method of claim 1, wherein the rare earth oxide RE is selected from the group consisting of rare earth oxides2O3RE in the composition is at least one element of Sc, Lu, Yb, Tm, Er, Ho, Dy, Tb, Gd, Eu, Sm and Pm.
3. The method for producing a high-performance solid electrolyte as claimed in claim 1, wherein, in the step S1, CaCO3And rare earth oxide RE2O3The drying method comprises the following steps: raising the drying temperature to 300-900 ℃ at a temperature raising rate of 2-10 ℃/min, then preserving the heat for 2-7 h, and then cooling along with the furnace; in step S1, HfO2The pretreatment method comprises the following steps: and (3) raising the pretreatment temperature to 1100-1200 ℃ at a temperature raising rate of 2-10 ℃/min, then preserving the heat for 3-10 h, and then cooling along with the furnace.
4. The method for preparing a high-performance solid electrolyte according to claim 1, wherein in step S3, the ball milling parameters of the pre-milled raw materials are as follows: the adding amount of the deionized water is 50-80 wt.%, the adopted ball milling tool is made of agate materials, the mass ratio of ball materials is 3:1, the rotating speed is 200-500 r/min, and the ball milling time is 20-90 h.
5. The method for producing a high-performance solid electrolyte according to claim 1, wherein in step S3, the sanding parameters are: the adding amount of deionized water is 50-80 wt.%, the adding amount of dispersant ammonium polymethacrylate is 20-60% of the content of powder, the rotating speed is 1000-2500 r/min, sanding is carried out for 1-10 h, and spray drying parameters are as follows: the inlet temperature is 220-250 ℃, the outlet temperature is 90-120 ℃, the rotating speed is 2000-12000 r/min, and the negative pressure is-20 to-120 kPa.
6. The method for preparing a high-performance solid electrolyte according to claim 1, wherein the parameters for applying different axial pressures to the mixed powder in stages in step S4 are as follows: pre-pressurizing to 4-8 MPa before sintering, pressurizing to 9-15 MPa at the beginning of sintering, pressurizing to 20-30 MPa at the middle temperature rise stage, and maintaining the pressure to 35-70 MPa after the sintering temperature is reached at the later stage.
7. The method for preparing a high-performance solid electrolyte according to claim 1, wherein the ball milling parameters of the final milling in the step S6 are as follows: the adding amount of the deionized water is 50-80 wt.%, the adopted ball milling tool is made of agate materials, the mass ratio of ball materials is 3:1, the rotating speed is 200-500 r/min, and the ball milling time is 20-90 h.
8. The method for producing a high-performance solid electrolyte according to claim 1, wherein the sanding parameters for the final grinding in step S6 are: the adding amount of deionized water is 50-80 wt.%, the adding amount of dispersant ammonium polymethacrylate is 30-70% of the content of powder, the rotating speed is 1000-2500 r/min, sanding is carried out for 1-10 h, and spray drying parameters are as follows: the inlet temperature is 220-250 ℃, the outlet temperature is 90-120 ℃, the rotating speed is 1000-10000 r/min, and the negative pressure is-10 to-100 kPa.
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