CN114907100B - Instant synthesis process of Ba matrix sub-conductor electrolyte - Google Patents

Instant synthesis process of Ba matrix sub-conductor electrolyte Download PDF

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CN114907100B
CN114907100B CN202210545479.1A CN202210545479A CN114907100B CN 114907100 B CN114907100 B CN 114907100B CN 202210545479 A CN202210545479 A CN 202210545479A CN 114907100 B CN114907100 B CN 114907100B
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electrolyte
matrix
subconductor
ions
powder
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CN114907100A (en
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张新波
鲍迪
王芳
赵银雷
黄岗
刘建伟
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Changchun Institute of Applied Chemistry of CAS
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Abstract

The invention provides a preparation method of Ba matrix sub-conductor electrolyte, which comprises the following steps of firstly ball milling metal oxide and carbonate to obtain wet milling mixed materials; then shaping the wet-milling mixed material obtained in the steps to obtain a powder tabletting; and then placing the powder pressed sheet obtained in the steps between metal heating sheets in a protective atmosphere, and carrying out electrifying heating and heat preservation on the metal heating sheets to obtain the sintered Ba matrix subconductor electrolyte. The preparation and densification sintering method of the instant proton conductor can also adjust the application value of current, improve the sintering parameters of the Ba matrix subconductor electrolyte, and quickly synthesize the electrolyte so as to reduce the loss of volatilized Ba element. The preparation process is simple, the energy utilization rate is high, the equipment is simple, the synthesis conditions are simplified, the stability, the repeatability and the controllability are good, and the method can be used for batch preparation processes such as rapid synthesis and reaction sintering of the Ba matrix subconductors.

Description

Instant synthesis process of Ba matrix sub-conductor electrolyte
Technical Field
The invention belongs to the technical field of synthesis of Ba matrix sub-conductor electrolyte, relates to a preparation method of Ba matrix sub-conductor electrolyte, and in particular relates to an instantaneous synthesis process of Ba matrix sub-conductor electrolyte.
Background
Proton conducting solid oxide fuel cells/cells have been of great interest for use because proton conducting electrolytes have higher ionic conductivity at medium to low temperatures than oxygen ions and proton transfer has a lower activation energy than oxygen ions. Current research on proton conducting electrolytes has focused on the cubic perovskite barium-based material system (BaCeO 3 、BaZrO 3 Etc.) as potential proton conductors by means of trivalent cation incorporation, such as yttrium ions (Y 3+ ) Ytterbium ion (Yb) 3+ ) Oxygen vacancies are formed in the Ba-based perovskite,when the electrolyte is in an atmosphere containing hydrogen or water vapor, water combines with oxygen vacancies to form interstitial protons, which in turn convert the conduction of oxygen defects to interstitial proton conduction by dissociative adsorption of water.
With the development of proton conducting electrolyte further toward industrialization, how to realize batch preparation and sintering of Ba matrix subconductors in a short time has become a continuously pursuing goal of inorganic chemistry and material scientists. Currently, sintering processes including microwave sintering, spark plasma sintering, and flash sintering have been applied to the sintering of proton conductors. The microwave-assisted sintering utilizes the microwave absorption characteristic of the material to heat, but the material without the microwave characteristic cannot be sintered, so that the application range of the material is limited; spark plasma sintering techniques require custom-made molds to compress the ceramic during sintering, which makes sintering three-dimensional porous structures difficult and mass processing difficult. Flash firing is a current-assisted sintering technique, which requires the use of expensive platinum electrodes, and the non-uniformity of sintering seriously hinders the industrialization process, so that in order to make the current flow uniformly through the sample, the sample used for the flash firing test is mostly in the shape of a long and thin strip or rod, and uniform sintering of the block or wafer is difficult to realize. The traditional sintering method is a kiln and a heat radiation method of a resistance wire, and involves multiple steps of heating, heat preservation, cooling and the like, the preparation and sintering of the ceramic material can be completed in a few hours, the energy loss is huge, the efficiency is low, the sintering time is overlong, the loss of volatile Ba element is further caused, and the material composition and the particle size distribution are uneven. In addition, there are also prior studies showing that the addition of sintering aids or chemico-physical methods to prepare nano-powders increases the surface activity and promotes sintering, however, these methods can lead to a decrease in the electrolyte conductivity, affecting the dense sintering of ceramic materials.
Therefore, how to find a more suitable sintering mode, solve the above problems existing in the existing sintering mode, meet the requirement of rapid batch preparation of modern ceramics, and become one of the problems to be solved by many prospective researchers in the industry.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide a method for preparing a Ba matrix subconductor electrolyte, in particular to a process for instantaneously synthesizing a Ba matrix subconductor electrolyte. And the preparation process is simple, has good stability, repeatability and controllability, and has good industrial application prospect in the fields of batch preparation and sintering of Ba matrix subconductors.
The invention provides a preparation method of a Ba matrix subconductor electrolyte, which comprises the following steps:
1) Ball milling is carried out on the metal oxide and the carbonate to obtain a wet milling mixed material;
2) Shaping the wet-grinding mixed material obtained in the steps to obtain a powder tablet;
3) And (3) placing the powder pressed sheet obtained in the steps between metal heating sheets in a protective atmosphere, and carrying out electrifying heating and heat preservation on the metal heating sheets to obtain the sintered Ba matrix subconductor electrolyte.
Preferably, the metal oxide includes an oxide of a doping element and/or an oxide of Ba;
the carbonate comprises a carbonate of a doping element and/or a carbonate of Ba;
at least one of the metal oxide and the carbonate is a Ba-based material;
the doping element comprises a cation doping.
Preferably, the cations include one or more of yttrium ions, ytterbium ions, cerium ions, zirconium ions, titanium ions, neodymium ions, scandium ions, zinc ions, samarium ions, and indium ions;
in the ball milling process, a solvent is also added;
the solvent comprises one or more of ethanol, acetone, butanone and xylene;
the solvent is used in an amount to wet the powder.
Preferably, the ball-milling ball material ratio is (10-20): 1, a step of;
the rotation speed of the ball milling is 200-800 rpm;
the ball milling time is 1-6 hours.
Preferably, the wet grinding further comprises a step of washing and/or drying;
the diameter of the powder tabletting is 0.5-3 cm;
the thickness of the powder pressed sheet is 0.05-0.3 cm.
Preferably, the metal heating sheet comprises a high temperature resistant metal heating sheet;
the metal heating plate is made of tungsten and/or molybdenum;
the metal heating plate is provided with a tab, and the tab is connected with an external power supply.
Preferably, the voltage of the electrified heating is 1-40V;
the current for electrifying and heating is 1-200A;
the time of the electrifying and heating is more than or equal to 0.1 second;
the temperature after the electric heating is 25-3000 ℃.
Preferably, the voltage of the heat preservation is 1-40V;
the heat-preserving current is 1-200A;
the heat preservation time is more than or equal to 0.1 second;
the temperature of the heat preservation is 25-3000 ℃.
Preferably, the sintered Ba matrix subconductor electrolyte is a densely sintered Ba matrix subconductor electrolyte;
the porosity of the sintered Ba matrix subconductor electrolyte is less than or equal to 5 percent.
Preferably, the Ba matrix subconductor electrolyte comprises one or more of barium zirconate, barium cerium, doped barium zirconate, and doped barium cerium;
the doped element comprises cation doping;
the cations include trivalent cations.
The invention provides a preparation method of Ba matrix sub-conductor electrolyte, which comprises the following steps of firstly ball milling metal oxide and carbonate to obtain wet milling mixed materials; then shaping the wet-milling mixed material obtained in the steps to obtain a powder tabletting; and then placing the powder pressed sheet obtained in the steps between metal heating sheets in a protective atmosphere, and carrying out electrifying heating and heat preservation on the metal heating sheets to obtain the sintered Ba matrix subconductor electrolyte. Compared with the prior art, the sintering scheme of the electrolyte for the Ba matrix subconductor has the advantages of long existing time, high power consumption, complex instrument and high cost; the long-time high-temperature sintering causes the problems of coarsening of particle size, volatilization of elements, reduction of proton conductivity and the like.
The invention creatively provides a preparation method of a Ba matrix sub-conductor electrolyte, which is a preparation and densification sintering method of a transient proton conductor, and innovates the traditional sintering method, directly applies current to a heating belt, instantly heats the synthesis of a Ba matrix sub-conductor electrolyte block and/or powder in a high-temperature environment formed by heat radiation of the heating belt and adjacent to the surface of a material, and is based on Q=I 2 Rt, the applied value of current can be regulated, the sintering parameter of the Ba matrix subconductor electrolyte can be improved, and more importantly, the loss of volatilized Ba element can be reduced by rapid synthesis. The instantaneous synthesis and densification sintering process provided by the invention can be applied to batch preparation of Ba matrix sub-conductor electrolyte, and can meet the requirement of rapid batch preparation of modern ceramics.
According to the method for batch instantaneous synthesis and rapid compact sintering of the Ba matrix subconductor electrolyte, provided by the invention, a heat radiation effect is generated by applying a large current to the conductive heating belt, and the material causes abrupt change of the arrangement mode of atoms in the instantaneous temperature rise/fall process, so that the physicochemical properties of the material are affected. The long-time sintering mode relative to the kiln is very valuable for basic research and various applications. The preparation process is simple, the energy utilization rate is high, the equipment is simple, the synthesis condition is simplified, the stability, the repeatability and the controllability are good, the method can be used in the fields of batch preparation and sintering such as rapid synthesis and reaction sintering of the volatile Ba matrix sub-conductor, and the method has good industrial application prospect.
Experimental results show that the preparation method provided by the invention can enable BaCeO to be prepared within tens of seconds 3 -BaZrO 3 The proton conductor is successfully synthesized, the obtained product has high purity, the reaction method is easy to repeat, and the preparation time and the power consumption of the material powder are greatly reduced.
Drawings
FIG. 1 is a schematic diagram of a reaction apparatus for transient sintering proton conductor electrolyte provided by the present invention;
FIG. 2 is an XRD diffraction pattern of the initial reaction starting material provided in example 1 of the present invention;
FIG. 3 shows BaCe synthesized in example 1 of the present invention 0.7 Zr 0.1 Y 0.1 Yb 0.1 O 3-δ XRD diffractogram of (2);
FIG. 4 shows BaCe synthesized in example 1 of the present invention 0.7 Zr 0.1 Y 0.1 Yb 0.1 O 3-δ SEM images of (a);
FIG. 5 is a temperature profile of the process of synthesizing Ba-based subconductor electrolyte according to example 1 of the present invention;
FIG. 6 shows BaCe synthesized in example 2 of the present invention 0.7 Zr 0.1 Y 0.1 Yb 0.1 O 3-δ XRD diffractogram of (2);
FIG. 7 shows BaCe synthesized in example 2 of the present invention 0.7 Zr 0.1 Y 0.1 Yb 0.1 O 3-δ SEM images of (a);
FIG. 8 shows BaCe synthesized in example 3 of the present invention 0.7 Zr 0.1 Y 0.1 Yb 0.1 O 3-δ SEM scanning electron microscopy of (c);
FIG. 9 is a temperature profile of the synthesis of Ba-based subconductor electrolyte according to example 3 of the present invention.
Detailed Description
For a further understanding of the present invention, preferred embodiments of the invention are described below in conjunction with the examples, but it should be understood that these descriptions are merely intended to illustrate further features and advantages of the invention and are not limiting of the invention claims.
All the raw materials of the present invention are not particularly limited in their sources, and may be purchased on the market or prepared according to conventional methods well known to those skilled in the art.
The raw material used in the present invention is not particularly limited in purity, and the present invention is preferably analytically pure or a purity conventional in the sintering field of Ba matrix subconductor electrolytes.
All the materials of the invention, the brands and abbreviations of which belong to the conventional brands and abbreviations in the field of the related application are clear and definite, and the person skilled in the art can purchase from the market or prepare by the conventional method according to the brands, abbreviations and the corresponding application.
All processes of the present invention, the abbreviations of which are conventional in the art, are each well-defined in the art of their relevant use, and the skilled artisan will be able to understand the conventional process steps thereof based on the abbreviations.
The invention provides a preparation method of a Ba matrix subconductor electrolyte, which comprises the following steps:
1) Ball milling is carried out on the metal oxide and the carbonate to obtain a wet milling mixed material;
2) Shaping the wet-grinding mixed material obtained in the steps to obtain a powder tablet;
3) And (3) placing the powder pressed sheet obtained in the steps between metal heating sheets in a protective atmosphere, and carrying out electrifying heating and heat preservation on the metal heating sheets to obtain the sintered Ba matrix subconductor electrolyte.
Firstly, ball milling is carried out on metal oxide and carbonate to obtain wet milling mixed materials.
In the present invention, the metal oxide preferably includes an oxide of a doping element and/or an oxide of Ba, more preferably an oxide of a doping element or an oxide of Ba.
In the present invention, the carbonate preferably includes a carbonate of a doping element and/or a carbonate of Ba, more preferably a carbonate of a doping element or a carbonate of Ba.
In the present invention, at least one of the metal oxide and the carbonate is a Ba-based material.
In the present invention, the doping element preferably includes cation doping.
In the present invention, the cation preferably includes one or more of yttrium ion, ytterbium ion, cerium ion, zirconium ion, titanium ion, neodymium ion, scandium ion, zinc ion, samarium ion, and indium ion, and more preferably yttrium ion, ytterbium ion, cerium ion, zirconium ion, titanium ion, neodymium ion, scandium ion, zinc ion, samarium ion, or indium ion.
In the present invention, the cation preferably includes a trivalent cation.
In the present invention, a solvent is preferably added during the ball milling process.
In the present invention, the solvent preferably includes one or more of ethanol, acetone, butanone, and xylene, more preferably ethanol, acetone, butanone, or xylene.
In the present invention, the solvent is preferably used in an amount of wet powder.
In the invention, the ball-milling ball material ratio is preferably (10-20): 1, more preferably (12 to 18): 1, more preferably (14 to 16): 1.
in the present invention, the rotational speed of the ball mill is preferably 200 to 800rpm, more preferably 300 to 700rpm, and still more preferably 400 to 600rpm.
In the present invention, the time of the ball milling is preferably 1 to 6 hours, more preferably 2 to 5 hours, and still more preferably 3 to 4 hours.
The wet-grinding mixed material obtained in the steps is molded to obtain the powder tabletting.
In the present invention, the wet-milling is preferably followed by a washing and/or drying step, more preferably a washing or drying step.
In the present invention, the diameter of the powder compact is preferably 0.5 to 3cm, more preferably 1 to 2.5cm, and still more preferably 1.5 to 2cm.
In the present invention, the thickness of the powder compact is preferably 0.05 to 0.3cm, more preferably 0.1 to 0.2cm.
Finally, placing the powder pressed sheet obtained in the steps between metal heating sheets in protective atmosphere, and carrying out electrifying heating and heat preservation on the metal heating sheets to obtain the sintered Ba matrix subconductor electrolyte.
In the present invention, the metal heating sheet preferably includes a high temperature resistant metal heating sheet. In particular, the temperature of the high temperature resistance is preferably less than the melting point of the metal sheet, for example, the maximum temperature may be 3000 ℃.
In the present invention, the material of the metal heating plate preferably includes tungsten and/or molybdenum, and more preferably tungsten or molybdenum.
In the invention, the metal heating plate is preferably provided with a tab, and the tab is connected with an external power supply.
In the present invention, the voltage for the electric heating is preferably 1 to 40V, more preferably 5 to 30V, and still more preferably 15 to 20V.
In the present invention, the current for the energization heating is preferably 1 to 200A, more preferably 10 to 160A, and still more preferably 50 to 120A.
In the present invention, the time of the energization heating is preferably 0.1 seconds or longer. Specifically, the time period may be 0.1s to 10min, more preferably 0.2 to 60s, still more preferably 0.3 to 30s, still more preferably 0.5 to 10s.
In the present invention, the temperature after the electric heating is preferably 25 to 3000 ℃, more preferably 1000 to 2500 ℃, and still more preferably 150 to 2000 ℃.
In the present invention, the time for the heat preservation is preferably 0.1 seconds or longer. Specifically, the time period may be 0.1s to 10min, more preferably 0.2 to 60s, still more preferably 0.3 to 30s, still more preferably 0.5 to 20s.
In the present invention, the temperature of the heat preservation is preferably 25 to 3000 ℃, more preferably 1000 to 2500 ℃, still more preferably 150 to 2000 ℃.
In the present invention, the sintered Ba matrix subconductor electrolyte is preferably a densely sintered Ba matrix subconductor electrolyte.
In the present invention, the porosity of the sintered Ba matrix subconductor electrolyte is preferably 5% or less, more preferably 4% or less, and still more preferably 2% or less.
In the invention, the metal heating sheet is electrified and heated and insulated, namely, the process of instantaneous synthesis and densification sintering is included. Specifically, the preparation method of the Ba matrix subconductor electrolyte preferably comprises the synthesis and sintering processes of the Ba matrix subconductor electrolyte.
In the present invention, the Ba matrix subconductor electrolyte preferably comprises a volatile Ba matrix subconductor.
In the present invention, the Ba-matrix subconductor electrolyte preferably includes one or more of barium zirconate, barium cerium, doped barium zirconate, and doped barium cerium, more preferably barium zirconate, barium cerium, doped barium zirconium, or doped barium cerium.
The invention is a complete and refined integral technical proposal, better ensures the stable and controllable synthesis of the Ba matrix sub-conductor electrolyte, further improves the sum parameters of the Ba matrix sub-conductor electrolyte, and the preparation method of the Ba matrix sub-conductor electrolyte comprises the following steps:
1) Weighing raw material oxide and carbonate powder according to the molar ratio of metal elements, putting the raw material oxide and carbonate powder into a planetary ball milling tank, adding a small amount of absolute ethyl alcohol (wetting powder), adding grinding balls, adjusting the ball milling rotating speed to 200-800 rpm and the time to 1-6 hours according to the ball material ratio of 10-20:1, carrying out wet milling and mixing, taking out the powder after the wet milling and mixing, washing, and placing the powder into an oven at 80 ℃ for drying for later use;
2) Taking the dried powder, and carrying out batch stamping forming by using a powder tabletting machine;
3) Transferring the formed solid sheet into an argon inert atmosphere box, clamping the solid sheet between two metal heating sheets (tungsten and molybdenum), fixing a clamp, connecting an electrode and a tab, and ensuring that the clamp is contacted with the electrode;
4) Adjusting the applied voltage to be 0.1-40V, the current to be 0.1-200A and the time to be 0.1-60 seconds through an external power supply, and preserving the heat to be 0.1-200A and the time to be 0.1-60 seconds to prepare the material;
5) The material is heated rapidly, the surface of the material is red, the applied current and time are regulated, and after the high temperature condition is maintained for seconds, the material is recovered to the normal color, and the Ba matrix subconductor electrolyte is obtained.
The material can also be subjected to X-ray diffraction and electron scanning microscopic image analysis to characterize the purity and surface morphology of the material.
The invention also provides a preparation device of the Ba matrix subconductor electrolyte, which preferably comprises:
the sealing box body and the clamp arranged in the sealing box body.
One or more metal heating plates disposed on one side of the fixture and one or more metal heating plates disposed on the other side of the fixture.
The metal heating plates arranged on the two sides of the clamp are correspondingly arranged to form a group of metal heating plates.
And the group of metal heating plates are used for placing powder pressing plates.
The fixture is provided with at least one pair of lugs.
The pair of tabs are distally disposed on the clamp.
The pair of tabs are connected by a wire.
An external power supply and a current-voltage sensor are arranged on the lead.
And a temperature and humidity sensor is arranged in the sealed box body.
The sealed box body is connected with a vacuum device.
The sealed housing is connected to a source of protective gas.
Referring to fig. 1, fig. 1 is a schematic diagram of a reaction apparatus for instantaneously sintering a proton conductor electrolyte according to the present invention.
The device comprises a power line 1, an atmosphere box 2, a lug 3, a clamp 4, a metal heating plate 5, a sintered ceramic plate 6, a vacuum pump 7, a gas steel cylinder 8, a current-voltage sensor 9, an external power supply 10 and a temperature-humidity sensor 11.
The invention provides a transient synthesis process of Ba matrix sub-conductor electrolyte, which is a method for preparing and densification sintering of transient proton conductor, and the invention innovates the traditional sintering method, directly applies current on a heating belt, and instantly adds in the high temperature environment formed by the heat radiation of the heating belt and the adjacent material surfaceSynthesis of hot Ba-based subconductor electrolyte blocks and/or powders and based on q=i 2 Rt, the applied value of current can be regulated, the sintering parameter of the Ba matrix subconductor electrolyte can be improved, and more importantly, the loss of volatilized Ba element can be reduced by rapid synthesis. The instantaneous synthesis and densification sintering process provided by the invention can be applied to batch preparation of Ba matrix sub-conductor electrolyte, and can meet the requirement of rapid batch preparation of modern ceramics.
According to the method for batch instantaneous synthesis and rapid compact sintering of the Ba matrix subconductor electrolyte, provided by the invention, a heat radiation effect is generated by applying a large current to the conductive heating belt, and the material causes abrupt change of the arrangement mode of atoms in the instantaneous temperature rise/fall process, so that the physicochemical properties of the material are affected. The long-time sintering mode relative to the kiln is very valuable for basic research and various applications. The preparation process is simple, the energy utilization rate is high, the equipment is simple, the synthesis condition is simplified, the stability, the repeatability and the controllability are good, the method can be used in the fields of batch preparation and sintering such as rapid synthesis and reaction sintering of Ba matrix subconductors, and the method has good industrial application prospects.
Experimental results show that the preparation method provided by the invention can enable BaCeO to be prepared within tens of seconds 3 -BaZrO 3 The proton conductor is successfully synthesized, the obtained product has high purity, the reaction method is easy to repeat, and the preparation time and the power consumption of the material powder are greatly reduced.
For further explanation of the present invention, the following describes in detail a preparation method of a Ba matrix subconductor electrolyte provided by the present invention with reference to examples, but it should be understood that these examples are implemented on the premise of the technical solution of the present invention, and detailed implementation and specific operation procedures are given only for further explanation of the features and advantages of the present invention, and not limitation of the claims of the present invention, and the scope of protection of the present invention is not limited to the following examples.
Example 1
Y and Yb co-doped BaCeO 3 -BaZrO 3 Solid solution (BaCe) 0.7 Zr 0.1 Y 0.1 Yb 0.1 O 3-δ ) Is prepared from
1) Weighing BaCO according to the molar ratio of metal elements 3 、CeO 2 、ZrO 2 、Y 2 O 3 、Yb 2 O 3 Placing the powder into a planetary ball milling tank, adding a small amount of absolute ethyl alcohol (soaking the powder), adding grinding balls, adjusting the ball milling rotation speed and time according to the ball material ratio of 15:1, performing wet milling and mixing, taking out the powder after the wet milling and mixing, washing, and placing the powder into an oven at 80 ℃ for drying for later use;
2) Taking the dried powder, and carrying out batch stamping forming by using a powder tabletting machine, wherein the apparent pressure is 10MPa;
3) Transferring the formed solid sheet into an argon inert atmosphere box, clamping the solid sheet between two metal heating sheets (tungsten and molybdenum), connecting wires, and ensuring that the clamp is contacted with an electrode;
4) The applied voltage was adjusted to 40V, current 30A and time 10 seconds.
5) The sample is heated rapidly, the temperature reaches 2000 ℃ in a few seconds, the surface is red due to high-temperature sintering, the block explodes, and the material is white powder after cooling;
XRD and SEM tests on the material prove that BaCe 0.7 Zr 0.1 Y 0.1 Yb 0.1 O 3-δ Successful synthesis, however, the local temperature rise is too fast due to the overlarge temperature rise current, and the compact sintering of the block material cannot be realized.
Referring to fig. 2, fig. 2 is an XRD diffractogram of the initial reaction starting material provided in example 1 of the present invention.
Referring to FIG. 3, FIG. 3 shows BaCe synthesized according to example 1 of the present invention 0.7 Zr 0.1 Y 0.1 Yb 0.1 O 3-δ Is a XRD diffractogram of (c).
Referring to FIG. 4, FIG. 4 shows BaCe synthesized according to example 1 of the present invention 0.7 Zr 0.1 Y 0.1 Yb 0.1 O 3-δ SEM images of (a).
Referring to fig. 5, fig. 5 is a temperature profile of the process of synthesizing Ba matrix subconductor electrolyte according to example 1 of the present invention.
Example 2
Y and Yb co-doped BaCeO 3 -BaZrO 3 Solid solution (BaCe) 0.7 Zr 0.1 Y 0.1 Yb 0.1 O 3-δ ) Is prepared from
1) Weighing BaCO according to the molar ratio of metal elements 3 、CeO 2 、ZrO 2 、Y 2 O 3 、Yb 2 O 3 Placing the powder into a planetary ball milling tank, adding a small amount of absolute ethyl alcohol (soaking the powder), adding grinding balls, adjusting the ball milling rotation speed and time according to the ball material ratio of 15:1, performing wet milling and mixing, taking out the powder after the wet milling and mixing, washing, and placing the powder into an oven at 80 ℃ for drying for later use;
2) Taking the dried powder, and carrying out batch stamping forming by using a powder tabletting machine, wherein the apparent pressure is 10MPa;
3) Transferring the formed solid sheet into an argon inert atmosphere box, clamping the solid sheet between two metal heating sheets (tungsten and molybdenum), connecting wires, and ensuring that the clamp is contacted with an electrode;
4) The applied voltage was adjusted to 40V, current 20A and time 10 seconds.
5) The sample is heated rapidly, the temperature reaches 1200 ℃ in a few seconds, the surface is red due to high-temperature sintering, and the material is a white block after the temperature is reduced;
XRD and SEM tests were performed on the material, although BaCe 0.7 Zr 0.1 Y 0.1 Yb 0.1 O 3-δ Successful synthesis, but with the presence of a hetero-phase (+.times.), SEM indicates that the surface did not achieve dense sintering.
Referring to FIG. 6, FIG. 6 is a block diagram of BaCe synthesized according to example 2 of the present invention 0.7 Zr 0.1 Y 0.1 Yb 0.1 O 3-δ Is a XRD diffractogram of (c).
Referring to FIG. 7, FIG. 7 shows BaCe synthesized according to example 2 of the present invention 0.7 Zr 0.1 Y 0.1 Yb 0.1 O 3-δ SEM images of (a).
Example 3
Y and Yb co-doped BaCeO 3 -BaZrO 3 Solid solution (BaCe) 0.7 Zr 0.1 Y 0.1 Yb 0.1 O 3-δ ) Is prepared from
1) Weighing BaCO according to the molar ratio of metal elements 3 、CeO 2 、ZrO 2 、Y 2 O 3 、Yb 2 O 3 Placing the powder into a planetary ball milling tank, adding a small amount of absolute ethyl alcohol (soaking the powder), adding grinding balls, adjusting the ball milling rotation speed and time according to the ball material ratio of 15:1, performing wet milling and mixing, taking out the powder after the wet milling and mixing, washing, and placing the powder into an oven at 80 ℃ for drying for later use;
2) Taking the dried powder, and carrying out batch stamping forming by using a powder tabletting machine, wherein the apparent pressure is 10MPa;
3) Transferring the formed solid sheet into an argon inert atmosphere box, clamping the solid sheet between two metal heating sheets (tungsten and molybdenum), connecting wires, and ensuring that the clamp is contacted with an electrode;
4) The applied voltage was adjusted to 40V, the current 36A and the time was 2.2 seconds, and the temperature was maintained for 17 seconds.
5) The sample is heated rapidly, the temperature reaches 1800 ℃ in a few seconds, the surface is red due to high-temperature sintering, and the material is a white block after the temperature is reduced;
XRD and SEM tests on the material showed BaCe 0.7 Zr 0.1 Y 0.1 Yb 0.1 O 3-δ Successful synthesis, SEM showed that dense sintering was achieved.
Referring to FIG. 8, FIG. 8 is a block diagram of BaCe synthesized according to example 3 of the present invention 0.7 Zr 0.1 Y 0.1 Yb 0.1 O 3-δ SEM scanning electron microscopy of (c).
Referring to fig. 9, fig. 9 is a temperature profile of the process of synthesizing Ba matrix subconductor electrolyte according to example 3 of the present invention.
The above description of the instant synthesis process of a Ba matrix subconductor electrolyte provided by the present invention has been provided in detail, and specific examples have been provided herein to illustrate the principles and embodiments of the present invention and are provided to facilitate an understanding of the methods of the present invention and their core ideas, including the best mode, and to also enable any person skilled in the art to practice the invention, including making and using any devices or systems, and performing any incorporated methods. It should be noted that it will be apparent to those skilled in the art that various modifications and adaptations of the invention can be made without departing from the principles of the invention and these modifications and adaptations are intended to be within the scope of the invention as defined in the following claims. The scope of the patent protection is defined by the claims and may include other embodiments that occur to those skilled in the art. Such other embodiments are intended to be within the scope of the claims if they have structural elements that do not differ from the literal language of the claims, or if they include equivalent structural elements with insubstantial differences from the literal language of the claims.

Claims (9)

1. The preparation method of the Ba matrix subconductor electrolyte is characterized by comprising the following steps of:
1) Ball milling is carried out on the metal oxide and the carbonate to obtain a wet milling mixed material;
the metal oxide comprises an oxide of a doping element and/or an oxide of Ba;
the carbonate comprises a carbonate of a doping element and/or a carbonate of Ba;
at least one of the metal oxide and the carbonate is a Ba-based material;
the doping element comprises cation doping;
2) Shaping the wet-grinding mixed material obtained in the steps to obtain a powder tablet;
the wet grinding further comprises a drying step;
the diameter of the powder tabletting is 0.5-3 cm;
the thickness of the powder pressed sheet is 0.05-0.3 cm;
3) Placing the powder pressed sheet obtained in the steps between metal heating sheets in a protective atmosphere, and carrying out electrifying heating and heat preservation on the metal heating sheets to obtain sintered Ba matrix subconductor electrolyte;
the metal heating plate comprises a high-temperature-resistant metal heating plate;
the high temperature resistant temperature is less than the melting point of the metal sheet;
the metal heating plate is made of tungsten and/or molybdenum;
the current for electrifying and heating is 1-200A;
the heat-preserving current is 1-200A;
the temperature of the heat preservation is 1000-3000 ℃;
the Ba matrix subconductor electrolyte comprises one or more of barium zirconate, barium cerium, doped barium zirconate, and doped barium cerium.
2. The method of claim 1, wherein the cations include one or more of yttrium ions, ytterbium ions, cerium ions, zirconium ions, titanium ions, neodymium ions, scandium ions, zinc ions, samarium ions, and indium ions;
in the ball milling process, a solvent is also added;
the solvent comprises one or more of ethanol, acetone, butanone and xylene;
the solvent is used in an amount to wet the powder.
3. The preparation method of claim 1, wherein the ball-milled ball-material ratio is (10-20): 1, a step of;
the rotation speed of the ball milling is 200-800 rpm;
the ball milling time is 1-6 hours.
4. The method of claim 1, further comprising a step of washing after the wet milling.
5. The method of claim 1, wherein the metal heating plate is provided with a tab, and the tab is connected to an external power source.
6. The method according to claim 1, wherein the voltage for the electric heating is 1 to 40v.
7. The method according to claim 1, wherein the voltage for heat preservation is 1 to 40v.
8. The method of manufacturing according to claim 1, wherein the sintered Ba matrix subconductor electrolyte is a densely sintered Ba matrix subconductor electrolyte;
the porosity of the sintered Ba matrix subconductor electrolyte is less than or equal to 5 percent.
9. The method of claim 1, wherein the cation comprises a trivalent cation.
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