CN114907100A - Instantaneous synthesis process of Ba-matrix sub-conductor electrolyte - Google Patents

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

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CN114907100A
CN114907100A CN202210545479.1A CN202210545479A CN114907100A CN 114907100 A CN114907100 A CN 114907100A CN 202210545479 A CN202210545479 A CN 202210545479A CN 114907100 A CN114907100 A CN 114907100A
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electrolyte
sintering
ions
powder
matrix
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CN114907100B (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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Changchun Institute of Applied Chemistry of CAS
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Abstract

The invention provides a preparation method of a Ba-matrix sub-conductor electrolyte, which comprises the following steps of firstly, carrying out ball milling on metal oxide and carbonate to obtain a wet-milled mixed material; then, the wet-grinding mixed material obtained in the step is molded to obtain powder tablets; and then placing the powder pressing sheet obtained in the step between metal heating sheets in a protective atmosphere, electrifying and heating the metal heating sheets, and preserving heat to obtain the sintered Ba-based proton conductor electrolyte. The method for preparing the instantaneous proton conductor and densifying and sintering provided by the invention can also adjust the applied value of current, improve the sintering parameters of the Ba-based proton conductor electrolyte, and quickly synthesize the Ba-based proton conductor electrolyte to reduce the loss of volatile Ba elements. And the preparation process is simple, the energy utilization rate is high, the equipment is simple, the synthesis condition is simplified, and the method has good stability, repeatability and controllability, and can be used for batch preparation processes such as rapid synthesis and reactive sintering of Ba substrate sub-conductors.

Description

Instantaneous synthesis process of Ba-matrix sub-conductor electrolyte
Technical Field
The invention belongs to the technical field of Ba matrix sub-conductor electrolyte synthesis, relates to a preparation method of a Ba matrix sub-conductor electrolyte, and particularly relates to an instantaneous synthesis process of the Ba matrix sub-conductor electrolyte.
Background
Since the proton conducting electrolyte has higher ion conductivity than oxygen ions at medium and low temperatures and the migration of protons has lower activation energy than oxygen ions, the application of the proton conducting solid oxide fuel cell/electrolytic cell is of great interest. Research on proton conducting electrolytes is currently focused on cubic perovskite barium-based material systems (BaCeO) 3 、BaZrO 3 Etc.), as potential proton-type conductors, by means of trivalent cation incorporation, e.g. yttrium ion (Y) 3+ ) Ytterbium ion (Yb) 3+ ) When the electrolyte is in an atmosphere containing hydrogen or water vapor, water combines with the oxygen vacancies to form interstitial protons, and the conduction of oxygen defects is converted into the conduction of the interstitial protons by dissociative adsorption of water.
With the development of proton conducting electrolytes toward industrialization, how to implement batch preparation and sintering of Ba matrix sub-conductors in a short time has become a continuous pursuit target of inorganic chemistry and material scientists. At present, sintering processes including microwave sintering, spark plasma sintering, and flash firing have been applied to 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; the spark plasma sintering technique requires the use of a custom mold to compress the ceramic during sintering, which makes sintering three-dimensional porous structures difficult and makes batch processing difficult. Flash sintering is used as a current-assisted sintering technology, an expensive platinum electrode is required, the non-uniformity of sintering seriously hinders the industrialization process, and in order to enable current to uniformly flow through a sample, the sample for flash sintering test is mainly in a slender strip shape or a rod shape, so that uniform sintering of a block or a wafer is difficult to realize. The traditional sintering mode is a heat radiation method of a kiln and a resistance wire, and relates to multiple steps of heating, heat preservation, cooling and the like, the preparation and sintering of the ceramic material can be completed within hours, the energy loss is huge, the efficiency is low, the sintering time is too long, the loss of volatile Ba element is further caused, and the material composition and the particle size are not uniformly distributed. In addition, the existing research shows that the surface activity is improved and the sintering is promoted by adding a sintering aid or preparing nano powder by a chemical physical method, however, the methods can cause the reduction of the electrolyte conductivity and influence the densification and sintering of the ceramic material.
Therefore, how to find a more suitable sintering method, solve the above problems of the existing sintering method, and meet the requirement of rapid batch preparation of modern ceramics has become one of the many problems to be solved by 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-based sub-conductor electrolyte, and in particular, to a transient synthesis process of a Ba-based sub-conductor electrolyte, which can rapidly realize transient synthesis and reactive sintering of a Ba-based sub-conductor electrolyte by applying a large current to a conductive heating band to generate a heat radiation effect. 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 substrate sub-conductors.
The invention provides a preparation method of a Ba-matrix sub-conductor electrolyte, which comprises the following steps:
1) carrying out ball milling on metal oxide and carbonate to obtain a wet milling mixed material;
2) molding the wet-milled mixed material obtained in the step to obtain powder tablets;
3) and placing the powder pressed sheet obtained in the step between metal heating sheets in a protective atmosphere, electrifying and heating the metal heating sheets, and preserving heat to obtain the sintered Ba-based proton conductor electrolyte.
Preferably, the metal oxide comprises an oxide of a doping element and/or an oxide of Ba;
the carbonate comprises a doped element carbonate and/or a Ba carbonate;
at least one of the metal oxide and the carbonate is a Ba-based material;
the doping element comprises a cationic doping.
Preferably, the cation comprises 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;
in the ball milling process, a solvent is also added;
the solvent comprises one or more of ethanol, acetone, butanone and xylene;
the dosage of the solvent is soaking powder.
Preferably, the ball-milling ball-material ratio is (10-20): 1;
the rotation speed of the ball mill is 200-800 rpm;
the ball milling time is 1-6 hours.
Preferably, the wet grinding further comprises a washing and/or drying step;
the diameter of the powder tablet is 0.5-3 cm;
the thickness of the powder tablet is 0.05-0.3 cm.
Preferably, the metal heating plate comprises a high-temperature-resistant metal heating plate;
the metal heating sheet is made of tungsten and/or molybdenum;
and the metal heating sheet is provided with a lug which is connected with an external power supply.
Preferably, the voltage for electrifying and heating is 1-40V;
the current for electrifying and heating is 1-200A;
the time of the electrifying heating is more than or equal to 0.1 second;
the temperature after the electrification heating is 25-3000 ℃.
Preferably, the voltage for 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 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 sub-conductor electrolyte is less than or equal to 5 percent.
Preferably, the Ba matrix sub-conductor electrolyte comprises one or more of barium zirconate, barium cerate, doped barium zirconate, and doped barium cerate;
the doped element comprises a cationic doping;
the cation comprises a trivalent cation.
The invention provides a preparation method of a Ba-matrix sub-conductor electrolyte, which comprises the following steps of firstly, carrying out ball milling on metal oxide and carbonate to obtain a wet-milled mixed material; then, the wet-grinding mixed material obtained in the step is molded to obtain powder tablets; and then placing the powder pressing sheet obtained in the step between metal heating sheets in a protective atmosphere, electrifying and heating the metal heating sheets, and preserving heat to obtain the sintered Ba-based proton conductor electrolyte. Compared with the prior art, the sintering scheme of the traditional Ba-matrix sub-conductor electrolyte has the advantages of long existing time, large 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 conduction performance and the like.
The invention creatively provides a preparation method of a Ba matrix subconductor electrolyte, which is a method for preparing an instantaneous proton conductor and densifying and sintering, and innovatively relates to the traditional sintering method 2 Rt, and can also adjust the applied value of current, improve the sintering parameters of the Ba-matrix subconductor electrolyte, and more importantly, rapidly synthesize the Ba-matrix subconductor electrolyteThe loss of Ba element is less volatilized. The instantaneous synthesis and densification sintering process provided by the invention can be applied to the batch preparation of Ba-matrix sub-conductor electrolytes and meets the requirement of the rapid batch preparation of modern ceramics.
According to the batch instantaneous synthesis and rapid compact sintering method of the Ba substrate sub-conductor electrolyte, provided by the invention, a heat radiation effect is generated by applying a large current to the conductive heating band, and the material is subjected to mutation of an atom arrangement mode in an instantaneous temperature rising/reducing process, so that the physical and chemical properties of the material are influenced. Compared with a long-time sintering mode of a furnace kiln, the method is very valuable for basic research and various applications. And the preparation process is simple, the energy utilization rate is high, the equipment is simple, the synthesis condition is simplified, and the method has good stability, repeatability and controllability, can be used in the fields of batch preparation and sintering, such as rapid synthesis, reaction sintering and the like of the volatile Ba substrate sub-conductor, and has good industrial application prospect.
Experimental results show that the preparation method provided by the invention can ensure that the BaCeO can be obtained 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 view of a reaction apparatus for instantaneously sintering a proton conductor electrolyte according to the present invention;
FIG. 2 is an XRD diffractogram of the initial reaction feed 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 (a);
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 picture of (1);
FIG. 5 is a temperature profile of the process of synthesizing a Ba matrix 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 (a);
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 picture of (1);
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 Scanning electron microscope images of SEM;
fig. 9 is a temperature profile of the process of synthesizing Ba-host subconductor electrolyte in example 3 of the present invention.
Detailed Description
For a further understanding of the invention, reference will now be made to the preferred embodiments of the invention by way of example, and it is to be understood that the description is intended to further illustrate features and advantages of the invention, and not to limit the scope of the claims.
All starting materials for the present invention, without particular limitation as to their source, may be purchased commercially 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 pure analytically or in purity conventional in the field of sintering of Ba-based daughter conductor electrolytes.
All the materials of the invention, the marks and the acronyms thereof belong to the conventional marks and the acronyms in the field, each mark and the acronyms are clear and definite in the field of the related application, and the technical personnel in the field can purchase the materials from the market or prepare the materials by the conventional method according to the marks, the acronyms and the corresponding application.
All the processes of the invention, the abbreviations thereof belong to the common abbreviations in the art, each abbreviation is clear and definite in the field of its associated use, and the ordinary process steps thereof can be understood by those skilled in the art from the abbreviations.
The invention provides a preparation method of a Ba-matrix sub-conductor electrolyte, which comprises the following steps:
1) carrying out ball milling on metal oxide and carbonate to obtain a wet milling mixed material;
2) molding the wet-milled mixed material obtained in the step to obtain powder tablets;
3) and placing the powder pressed sheet obtained in the step between metal heating sheets in a protective atmosphere, electrifying and heating the metal heating sheets, and preserving heat to obtain the sintered Ba-based proton conductor electrolyte.
The invention firstly ball-mills the metal oxide and the carbonate to obtain a wet-milling mixed material.
In the present invention, the metal oxide preferably includes an oxide of a doping element and/or an oxide of Ba, and 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, and 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 cationic doping.
In the present invention, the cation preferably includes one or more of an yttrium ion, an ytterbium ion, a cerium ion, a zirconium ion, a titanium ion, a neodymium ion, a scandium ion, a zinc ion, a samarium ion, and an indium ion, and more preferably an yttrium ion, a ytterbium ion, a cerium ion, a zirconium ion, a titanium ion, a neodymium ion, a scandium ion, a zinc ion, a samarium ion, or an 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.
In the present invention, the solvent preferably includes one or more of ethanol, acetone, butanone and xylene, and 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-to-material ratio of the ball mill is preferably (10-20): 1, more preferably (12-18): 1, more preferably (14 to 16): 1.
in the invention, the rotation speed of the ball mill is preferably 200-800 rpm, more preferably 300-700 rpm, and more preferably 400-600 rpm.
In the present invention, the time for 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 step is molded to obtain the powder tablet.
In the present invention, the wet-milling preferably comprises a washing and/or drying step, more preferably a washing or drying step.
In the invention, the diameter of the powder tablet is preferably 0.5-3 cm, more preferably 1-2.5 cm, and more preferably 1.5-2 cm.
In the present invention, the thickness of the powder tablet is preferably 0.05 to 0.3cm, and more preferably 0.1 to 0.2 cm.
Finally, placing the powder pressing sheet obtained in the step between metal heating sheets in a protective atmosphere, and carrying out power-on heating and heat preservation on the metal heating sheets to obtain the sintered Ba matrix sub-conductor electrolyte.
In the present invention, the metal heating sheet preferably includes a high temperature resistant metal heating sheet. Specifically, the temperature of the high temperature resistance is preferably less than the melting point of the metal sheet, and 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 sheet is preferably provided with a tab, and the tab is connected with an external power supply.
In the present invention, the voltage for the electrical 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 electric heating is preferably 1 to 200A, more preferably 10 to 160A, and still more preferably 50 to 120A.
In the present invention, the time for the energization heating is preferably 0.1 second or more. Specifically, the time period may be 0.1 to 10min, more preferably 0.2 to 60s, still more preferably 0.3 to 30s, still more preferably 0.5 to 10 s.
In the invention, the temperature after the electrification heating is preferably 25-3000 ℃, more preferably 1000-2500 ℃, and more preferably 150-2000 ℃.
In the present invention, the time for the heat-retention is preferably 0.1 seconds or more. Specifically, the time period may be 0.1 to 10min, more preferably 0.2 to 60s, still more preferably 0.3 to 30s, still more preferably 0.5 to 20 s.
In the invention, the heat preservation temperature is preferably 25-3000 ℃, more preferably 1000-2500 ℃, and more preferably 150-2000 ℃.
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 plate is electrified, heated and insulated, namely the process comprises instantaneous synthesis and densification sintering. 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 sub-conductor electrolyte preferably includes one or more of barium zirconate, barium cerate, doped barium zirconate, and doped barium cerate, more preferably barium zirconate, barium cerate, doped barium zirconate, or doped barium cerate.
The invention is a complete and detailed integral technical scheme, better ensures the stable and controllable synthesis of the Ba matrix subconductor electrolyte, and further improves the sum parameters of the Ba matrix subconductor electrolyte, and the preparation method of the Ba matrix subconductor electrolyte can specifically comprise 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 (only the powder is soaked), adding grinding balls, adjusting the ball milling rotation speed to be 200-800 rpm and the time to be 1-6 hours at a ball-material ratio of 10-20: 1, carrying out wet milling and mixing, taking out the powder after finishing, washing, and drying in an oven at 80 ℃ for later use;
2) taking the dried powder, and performing batch punch 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 and the heat preservation current to be 0.1-200A and the time to be 0.1-60 seconds by an external power supply to prepare the material;
5) and (3) rapidly heating the material, enabling the surface of the material to be red, adjusting the applied current and time, and keeping the high-temperature condition for a plurality of seconds, and then enabling the material to recover to the normal color to obtain the Ba-based daughter conductor electrolyte.
The material can be subjected to X-ray diffraction and electron scanning microscopic image analysis to characterize the purity and surface morphology of the material.
The present invention also provides a device for preparing a Ba-host conductor electrolyte, preferably comprising:
the device comprises a sealed box body and a clamp arranged in the sealed 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 sheets arranged on the two sides of the clamp are correspondingly arranged to form a group of metal heating sheets.
And the group of metal heating plates are used for placing powder pressing sheets.
The clamp is provided with at least one pair of tabs.
The pair of tabs are arranged at the far end of the clamp.
The pair of tabs are connected through a wire.
And an external power supply and a current and 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 box body is connected with a protective gas source.
Referring to fig. 1, fig. 1 is a schematic view 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 tab 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 and voltage sensor 9, an external power supply 10 and a temperature and humidity sensor 11.
The invention provides a transient synthesis process of Ba matrix subconductor electrolyte, which is a method for preparing transient proton conductor and densifying and sintering, and innovating the traditional sintering method, wherein current is directly applied to a heating band, and synthesis of Ba matrix subconductor electrolyte blocks and/or powder is instantaneously heated by heat radiation of the heating band in a high-temperature environment formed adjacent to the surface of a material, and the process is based on Q ═ I 2 Rt, and also adjusting the applied value of current, improving the sintering parameters of Ba matrix subconductor electrolyte, and more importantly, rapidly synthesizing to reduce the loss of volatile Ba element. The instantaneous synthesis and densification sintering process provided by the invention can be applied to the batch preparation of Ba-matrix sub-conductor electrolytes and meets the requirement of the rapid batch preparation of modern ceramics.
According to the batch instantaneous synthesis and rapid dense sintering method of the Ba substrate sub-conductor electrolyte, provided by the invention, the heat radiation effect is generated by applying large current to the conductive heating band, and the material is subjected to sudden change of atom arrangement mode in the instantaneous temperature rise/fall process, so that the physical and chemical properties of the material are influenced. Compared with a long-time sintering mode of a furnace kiln, the method is very valuable for basic research and various applications. And the preparation process is simple, the energy utilization rate is high, the equipment is simple, the synthesis condition is simplified, and the method has good stability, repeatability and controllability, can be used in the fields of batch preparation and sintering, such as rapid synthesis, reactive sintering and the like of Ba substrate sub-conductors, and has good industrial application prospect.
The experimental results show that the preparation provided by the inventionMethod capable of making BaCeO in 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.
In order to further illustrate the present invention, the following will describe in detail a method for preparing a Ba-matrix sub-conductor electrolyte provided by the present invention with reference to the following examples, but it should be understood that these examples are carried out on the premise of the technical solution of the present invention, and the detailed embodiments and specific procedures are given, which are only for further illustrating the features and advantages of the present invention, but not for limiting 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 codoped BaCeO 3 -BaZrO 3 Solid solution (BaCe) 0.7 Zr 0.1 Y 0.1 Yb 0.1 O 3-δ ) Preparation of
1) Weighing BaCO according to the molar ratio of metal elements 3 、CeO 2 、ZrO 2 、Y 2 O 3 、Yb 2 O 3 Putting the powder into a planetary ball milling tank, adding a small amount of absolute ethyl alcohol (only the powder is soaked), adding grinding balls with a ball-material ratio of 15:1, adjusting the ball milling rotation speed and time, carrying out wet milling and mixing, taking out the powder after the ball milling rotation speed and time are adjusted, washing, and drying in an oven at 80 ℃ for later use;
2) taking the dried powder, and performing batch punch forming by using a powder tabletting machine, wherein the surface display pressure is 10 MPa;
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 a lead, and ensuring that the clamp is contacted with an electrode;
4) the applied voltage 40V, the current 30A and the time 10 seconds were adjusted.
5) As the sample is heated rapidly and reaches 2000 ℃ within seconds, the surface is red due to high-temperature sintering, the block body is exploded, and the material is white powder after being cooled;
XRD and SEM tests are carried out on the material, and BaCe is proved 0.7 Zr 0.1 Y 0.1 Yb 0.1 O 3-δ The synthesis is successful, but the temperature rise is too fast locally due to the overlarge temperature rise current, so that the dense sintering of the block material cannot be realized.
Referring to fig. 2, fig. 2 is an XRD diffractogram of the initial reaction raw material provided in example 1 of the present invention.
Referring to FIG. 3, 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 (a).
Referring to FIG. 4, 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 image of (d).
Referring to fig. 5, fig. 5 is a temperature profile of a process of synthesizing a Ba matrix subconductor electrolyte according to example 1 of the present invention.
Example 2
Y and Yb codoped BaCeO 3 -BaZrO 3 Solid solution (BaCe) 0.7 Zr 0.1 Y 0.1 Yb 0.1 O 3-δ ) Preparation of
1) Weighing BaCO according to the molar ratio of metal elements 3 、CeO 2 、ZrO 2 、Y 2 O 3 、Yb 2 O 3 Putting the powder into a planetary ball milling tank, adding a small amount of absolute ethyl alcohol (only the powder is soaked), adding grinding balls with a ball-material ratio of 15:1, adjusting the ball milling rotation speed and time, carrying out wet milling and mixing, taking out the powder after the ball milling rotation speed and time are adjusted, washing, and drying in an oven at 80 ℃ for later use;
2) taking the dried powder, and performing batch punch forming by using a powder tabletting machine, wherein the surface display pressure is 10 MPa;
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 a lead, and ensuring that the clamp is contacted with an electrode;
4) the applied voltage 40V, current 20A and time 10 seconds were adjusted.
5) The sample is heated rapidly to 1200 ℃ within seconds, the surface is red due to high-temperature sintering, and the material is a white block after being cooled;
the material was subjected to XRD and SEM tests, although BaCe 0.7 Zr 0.1 Y 0.1 Yb 0.1 O 3-δ Successful synthesis, but presence of a heterogeneous phase (═ size), SEM indicated that dense sintering was not achieved at the surface.
Referring to FIG. 6, 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 (a).
Referring to FIG. 7, 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 image of (d).
Example 3
Y and Yb codoped BaCeO 3 -BaZrO 3 Solid solution (BaCe) 0.7 Zr 0.1 Y 0.1 Yb 0.1 O 3-δ ) Preparation of
1) Weighing BaCO according to the molar ratio of metal elements 3 、CeO 2 、ZrO 2 、Y 2 O 3 、Yb 2 O 3 Putting the powder into a planetary ball milling tank, adding a small amount of absolute ethyl alcohol (only the powder is soaked), adding grinding balls with a ball-material ratio of 15:1, adjusting the ball milling rotation speed and time, carrying out wet milling and mixing, taking out the powder after the ball milling rotation speed and time are adjusted, washing, and drying in an oven at 80 ℃ for later use;
2) taking the dried powder, and performing batch punch forming by using a powder tabletting machine, wherein the surface display pressure is 10 MPa;
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 a lead, and ensuring that a clamp is contacted with an electrode;
4) the applied voltage 40V, the current 36A and the time 2.2 seconds and 17 seconds of heat preservation are adjusted.
5) The sample is heated rapidly to 1800 ℃ within seconds, the surface is red due to high-temperature sintering, and the material is a white block after being cooled;
XRD and SEM tests of the material show that BaCe is contained in the material 0.7 Zr 0.1 Y 0.1 Yb 0.1 O 3-δ Successful Synthesis, SEM TableThe compact sintering is realized.
Referring to FIG. 8, 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 micrograph of (g).
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 instant synthesis of a Ba-matrix subconductor electrolyte provided by the present invention has been described in detail above, and the principles and embodiments of the present invention have been described herein using specific examples, which are presented solely to aid in the understanding of the methods and concepts underlying the present invention, including the best mode, and to 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, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention. The scope of the invention 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 languages of the claims.

Claims (10)

1. A method for preparing a Ba-matrix subconductor electrolyte, comprising the steps of:
1) carrying out ball milling on metal oxide and carbonate to obtain a wet milling mixed material;
2) molding the wet-milled mixed material obtained in the step to obtain powder tablets;
3) and placing the powder pressed sheet obtained in the step between metal heating sheets in a protective atmosphere, electrifying and heating the metal heating sheets, and preserving heat to obtain the sintered Ba-based proton conductor electrolyte.
2. The production method according to claim 1, wherein the metal oxide includes an oxide of a doping element and/or an oxide of Ba;
the carbonate comprises a doped element carbonate and/or a Ba carbonate;
at least one of the metal oxide and the carbonate is a Ba-based material;
the doping element comprises a cationic doping.
3. The method of claim 2, 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 dosage of the solvent is soaking powder.
4. The preparation method of claim 1, wherein the ball-milling has a ball-to-material ratio of (10-20): 1;
the rotation speed of the ball mill is 200-800 rpm;
the ball milling time is 1-6 hours.
5. The method of claim 1, wherein the wet milling is followed by a further step of washing and/or drying;
the diameter of the powder tablet is 0.5-3 cm;
the thickness of the powder tablet is 0.05-0.3 cm.
6. The manufacturing method according to claim 1, wherein the metal heating sheet includes a high-temperature resistant metal heating sheet;
the metal heating sheet is made of tungsten and/or molybdenum;
and the metal heating sheet is provided with a lug which is connected with an external power supply.
7. The method according to claim 1, wherein the voltage for the electric heating is 1 to 40V;
the current for electrifying and heating is 1-200A;
the time of the electrifying heating is more than or equal to 0.1 second;
the temperature after the electrification heating is 25-3000 ℃.
8. The preparation method according to claim 1, wherein 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 heat preservation is 25-3000 ℃.
9. The production method 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 sub-conductor electrolyte is less than or equal to 5 percent.
10. The method of manufacturing of claim 1, wherein the Ba matrix sub-conductor electrolyte comprises one or more of barium zirconate, barium cerate, doped barium zirconate, and doped barium cerate;
the doped element comprises a cationic doping;
the cation comprises a trivalent cation.
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