CN111689777A - Symmetric ceramic hydrogen pump capable of realizing hydrogen purification in complex scene and preparation method thereof - Google Patents
Symmetric ceramic hydrogen pump capable of realizing hydrogen purification in complex scene and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a ceramic hydrogen pump capable of realizing hydrogen purification in a complex scene, which has a symmetrical structure and sequentially comprises the following components from left to right: a first porous electrode support layer, a dense electrolyte layer, and a second porous electrode support layer; the component of the compact electrolyte layer is a proton conductor, and the proton conductor is AB1‑ xMxO3‑1、Ln2B2‑xMxO7‑1、A2In2‑yDyO5+1And Ln6‑zW1‑iMoiO12‑2One or more of (a) or (b); the components of the porous electrode support layer include a proton conductor and an electron conductor having catalytic properties; proton transference number of the proton conductor
Approximately 1, oxygen ion transport number
Near 0, electron transport number
Is close to 0; electron conductivity of the electron conductor of the porous electrode support layer
>10S/cm, the proton conductor material is the same as the electrolyte layer. The invention reduces the resistance of bulk phase proton transmission, reduces the resistance of gas diffusion and reduces the energy barrier of electrochemical reaction.
Description
Technical Field
The invention relates to a symmetrical ceramic hydrogen pump for hydrogen separation in a complex scene, in particular to the field of electrochemical hydrogen energy.
Background
The hydrogen is used as a secondary energy source which has wide source, cleanness, no carbon, flexibility, high efficiency and rich application scene, is an ideal interconnection medium for promoting the clean and high-efficiency utilization of the traditional fossil energy and supporting the large-scale development of renewable energy, and is also the best choice for realizing large-scale deep decarburization in the fields of transportation, industry, buildings and the like. Hydrogen energy and fuel cells are becoming important directions of the global energy technology revolution.
At present, the hydrogen production industry mainly has the following three mature technical routes: firstly, reforming fossil energy represented by coal and natural gas to prepare hydrogen; hydrogen is produced from industrial byproduct gas represented by coke oven tail gas, chlor-alkali tail gas and propane dehydrogenation; thirdly, hydrogen is produced by electrolyzing water, and the annual hydrogen production scale accounts for about 3 percent. The technical routes of direct hydrogen production by biomass, hydrogen production by solar photocatalytic water decomposition and the like are still in the experimental development stage, the yield needs to be further improved, and the industrial-scale hydrogen production requirement is not met.
At present, hydrogen production modes applied in large scale in industry are concentrated on hydrogen production by reforming fossil energy and hydrogen production by industrial byproduct gas, but hydrogen produced by the two hydrogen production modes contains a large amount of impurity gases, such as 10-20% of CH4，2%~5%CO2，5%~9%CO，2%~6%H2S, etc., therefore, to satisfyThe practical application needs further separation and purification. The separation and purification technology applied in large scale at present is Pressure Swing Adsorption (PSA), but the technology has some disadvantages due to its own characteristics, for example, the technology can only be applied to scenes with higher hydrogen concentration (not less than 50%), and the recovery rate of hydrogen is low (-20%).
As a relatively new and rapidly developed technology, the ceramic membrane separation technology has inherent advantages in the aspects of energy conservation, low cost, environmental protection and the like compared with the traditional separation technology. In addition, membrane separation techniques can be readily combined with other separation techniques to improve the efficiency and economics of the separation process. The ceramic hydrogen separation membrane is divided into a mixed proton-electron conductor hydrogen permeation membrane, a mixed oxygen ion-electron conductor oxygen permeation membrane and a proton conductor ceramic membrane hydrogen pump, wherein the mixed proton-electron conductor hydrogen permeation membrane has a wide research range, for example, refer to CN107096394A, CN101585703A, CN109133919A, etc., and the research results have achieved certain results. However, because the driving force of the hydrogen permeable membrane of the mixed proton-electron conductor is the hydrogen partial pressure difference on two sides of the membrane, the mixed proton-electron conductor can only be used for separating and purifying hydrogen in hydrogen mixed gas with higher concentration, and the hydrogen separation rate is lower than 1mL cm-2·min-1In addition, the application scenes of the researches are all hydrogen-inert gas (such as nitrogen, argon, helium and the like), and the hydrogen purification method is not suitable for hydrogen production by reforming or hydrogen purification in industrial by-product tail gas; researches on the application of the mixed oxygen ion-electron conductive oxygen permeable membrane in hydrogen separation and purification are rare, and only reports in CN108117389A and CN109836153A show that although the hydrogen separation rate is high, the hydrogen separation in the mixed gas is realized by means of high-temperature water decomposition, and whether the mixed gas can be applied to actual industrial application scenes or not is still to be verified.
The proton conductor ceramic membrane hydrogen pump is an electrochemical hydrogen pump, and the driving force for separation and purification comes from an external electric field, so that the proton conductor ceramic membrane hydrogen pump can be applied to separation and purification of mixed gas with lower hydrogen concentration; in order to ensure the normal operation of the ceramic membrane hydrogen pump, the compact electrolyte has excellent chemical stability, thermal stability and good proton conductivity, and meanwhile, the contact condition of a three-phase interface is improved, the active area is increased, the contact resistance is reduced, and the energy consumption loss in the operation of the electrochemical hydrogen pump is reduced by optimizing the electrode structure. In addition, the solution of the stability of hydrogen separation and purification of the ceramic hydrogen pump in a carbon-containing atmosphere is also crucial to the realization of large-scale industrial application. Although proton conductor ceramic membrane hydrogen pumps have many of the above advantages, no successful research results have been found. CN107354479A proposes a method for preparing ceramic hydrogen pump anode by ordered hydrothermal method, but does not give specific device and hydrogen separation performance in practical application.
Disclosure of Invention
The invention aims to provide a symmetrical ceramic hydrogen pump capable of realizing hydrogen purification in a complex scene, which reduces the resistance of bulk phase proton transmission, the resistance of gas diffusion and the energy barrier of electrochemical reaction; meanwhile, the preparation method of the symmetrical ceramic hydrogen pump capable of realizing hydrogen purification in a complex scene is provided.
In order to achieve the purpose, the invention adopts the technical scheme that: the utility model provides a can realize ceramic hydrogen pump of hydrogen purification under complicated scene, ceramic hydrogen pump has symmetrical structure, includes from left to right in proper order: a first porous electrode support layer, a dense electrolyte layer, and a second porous electrode support layer;
the component of the dense electrolyte layer is a proton conductor, which should be AB1-xMxO3-1、Ln2B2-xMxO7-1、A2In2-yDyO5+1And Ln6-zW1-iMoiO12-2The compound is formed by one or more of A, B, D, L, B, Sm, Mn, Nd, Tb, Eu, Tm, In and Gd, D is at least one of Sc, Lu, Yb, Y, Dy, Gd and Sm, Ln is at least one of La, Nd, Gd and Er, x is more than or equal to 0 and less than 0.3, Y is more than or equal to 0 and less than 1, z is more than or equal to 0 and less than 1, i is more than or equal to 0 and less than 0.3, 1 is more than or equal to 0 and less than 0.5, and 2 is more than or equal to 0 and less than 1;
the components of the porous electrode support layer include a proton conductor and an electron conductor having catalytic properties; the proton conducting wireProton transference number of body
Approximately 1, oxygen ion transport number
Near 0, electron transport number
Is close to 0; electron conductivity of the electron conductor of the porous electrode support layer
>10S/cm, the proton conductor material is the same as the electrolyte layer, and the electron conductor is at least one of metal Ni, Co, Fe, Cu or 430L metal alloy.
The technical scheme of further improvement in the technical scheme is as follows:
1. in the above scheme, the porous electrode support layer has a bimodal pore structure, in which micropores and nanopores coexist.
2. In the scheme, the micron aperture in the porous electrode supporting layer is 1-10 mu m, and the nano aperture in the porous electrode supporting layer is 1-100 nm.
3. In the scheme, the thickness of the compact electrolyte layer is 10-40 mu m.
4. In the scheme, the thickness of the porous electrode supporting layer is 150-400 mu m.
5. In the above scheme, the thicknesses and sizes of the first porous support layer and the second porous support layer are the same.
6. In the above scheme, the mass ratio of the electron conductor to the proton conductor in the porous electrode support layer is 2: 1-1: 2.
7. in the scheme, the porosity of the porous electrode supporting layer is 10-30%.
8. In the above scheme, the nanopores in the porous electrode support layer are formed by in-situ low-temperature reduction under kinetic control.
The invention also provides a preparation method of the symmetrical ceramic hydrogen pump capable of realizing hydrogen purification in a complex scene, which comprises the following steps:
step one, preparing a symmetrical ceramic hydrogen pump green compact by a 'tape casting-laminating-hot pressing' process, wherein a pore-forming agent and electronic conductor powder are not added into a compact electrolyte tape casting membrane, and the powder of a porous electrode layer tape casting membrane consists of proton conductor powder, electronic conductor powder and a pore-forming agent;
and step two, sintering the green body at 1380-1450 ℃ for 4-6 hours to obtain the symmetrical ceramic hydrogen pump.
Due to the application of the technical scheme, compared with the prior art, the invention has the following advantages:
the invention can realize the symmetric ceramic hydrogen pump of hydrogen purification under the complicated scene and its preparation method, its ceramic membrane hydrogen pump has "porous electrode | dense electrolyte | porous electrode" symmetrical sandwich structure, wherein the thinning of the electrolyte of the dense layer has reduced the resistance of proton transmission of the bulk phase, the nanometer hole coexists with micron hole in the porous electrode, wherein the micron hole is favorable to the diffusion transmission of the gas, has reduced the resistance of gas diffusion; meanwhile, the existence of the nano holes provides more reaction sites, the active area of the reaction is increased, the contact condition of a three-phase interface is improved, and the energy barrier of the electrochemical reaction is reduced; the pore size distribution of the bimodal structure greatly reduces the polarization impedance of the ceramic membrane in the operation process, and the reduction of the electrolyte layer reduces the ohmic impedance, so that the ceramic membrane hydrogen pump has good hydrogen separation and purification performance even at a lower operation temperature; the reduction in operating temperature suppresses the carbonaceous fuel (e.g., CH)4) The problem of performance attenuation caused by carbon deposition is solved through the cracking reaction; the symmetric structure is more beneficial than the asymmetric structure when a large-size device is prepared; in addition, the proton conductor used by the symmetrical ceramic membrane hydrogen pump has good thermochemical stability, so that the symmetrical ceramic hydrogen pump is suitable for extreme conditions of hydrogen separation and purification of H2, CH4 and CO2 mixed gas, and more meets the actual industrial application requirements.
Drawings
FIG. 1 shows a SEM image of a symmetric ceramic membrane hydrogen pump cross-section sandwich structure prepared in one embodiment of the present invention;
FIG. 2 shows an SEM image of a porous electrode layer on the surface of a symmetric ceramic membrane hydrogen pump prepared in one embodiment of the invention;
FIG. 3 shows a symmetric ceramic membrane hydrogen pump prepared in one embodiment of the present invention at 10% H2-90%CH4Hydrogen separation performance in the mixed gas;
FIG. 4 shows a symmetric ceramic membrane hydrogen pump prepared in one embodiment of the present invention at 10% H2-90%CO2Hydrogen separation performance in the mixed gas;
fig. 5 shows the long term stability of the operation of the symmetric ceramic membrane hydrogen pump prepared in the embodiment of the present invention.
Detailed Description
The invention is further described below with reference to the following examples:
the present invention is further illustrated by the following examples, which are to be understood as merely illustrative and not restrictive.
In the present disclosure, a symmetric ceramic membrane hydrogen pump structure includes: a dense electrolyte layer, and porous electrode support layers (including a first porous electrode support layer and a second porous electrode support layer) positioned on both sides of the dense electrolyte layer.
In one embodiment of the present invention, the composition of the dense electrolyte layer is a proton conductor (e.g., BaZr)0.8Y0.2O3-、BaCe0.8Y0.2O3-、BaZr0.1Ce0.7Y0.2O3-And the oxygen deficiency position is equal to or more than 0 and less than 0.5). In an alternative embodiment, the thickness of the dense electrolyte layer may be 1 to 100 μm, preferably 10 to 40 μm.
In one embodiment of the invention, the composition of the porous electrode support layer comprises a proton conductor (e.g., BaZr)0.8Y0.2O3-、BaCe0.8Y0.2O3-、BaZr0.1Ce0.7Y0.2O3-Etc., oxygen deficiency, 0. ltoreq. 0.5) and an electron conductor having catalytic properties (e.g., metals Ni, Co, Fe, Cu, etc.). Wherein the content of the first and second substances,the mass ratio of the proton conductor to the electron conductor may be 2:1 to 1:2, preferably 60: 40. in alternative embodiments, the porosity of the porous electrode support layer may be between 10% and 90%, preferably between 10% and 30%. In an alternative embodiment, the thickness of the porous electrode support layer may be 1 to 1000 μm, preferably 150 to 400 μm. It should be noted that, although the first porous electrode supporting layer and the second porous electrode supporting layer both belong to the porous electrode layers, the components and the porosities of the first porous electrode supporting layer and the second porous electrode supporting layer are not limited to be completely consistent, and only the requirements of serving as the porous electrode supporting layer under the symmetric structure need to be satisfied.
In one embodiment of the present invention, the ceramic membrane hydrogen pump may have a size of at least 10cm × 10cm × 0.55 to 1.05mm (e.g., 12cm × 12cm × 0.55 mm).
In one embodiment of the invention, the ceramic membrane hydrogen pump is prepared by adopting a casting and sintering mode. The following exemplarily illustrates a method for producing a proton conductor ceramic membrane hydrogen pump.
And (4) preparing a compact electrolyte layer membrane. And casting the compact electrolyte layer slurry into a membrane by adopting a casting process. The compact electrolyte layer slurry comprises proton conductor powder, a dispersing agent, a binder, a plasticizer and a solvent.
And preparing the porous electrode layer membrane. And casting the porous electrode supporting layer slurry into a membrane by adopting a casting process. The porous electrode supporting layer slurry comprises proton conductor powder, electronic conductor powder, a pore-forming agent, a dispersing agent, a binder, a plasticizer and a solvent.
And (3) laminating at least three porous electrode supporting layer membranes/at least one compact electrolyte layer membrane/at least three porous electrode supporting layer membranes, and pressing to obtain the ceramic membrane hydrogen pump blank.
And sintering the symmetrical ceramic membrane hydrogen pump blank at 1380-1450 ℃ for 4-6 hours to obtain the proton conductor ceramic membrane hydrogen pump.
In the present disclosure, due to the special electrode structure and the thin electrolyte layer, the electrochemical impedance during the operation of the hydrogen pump is reduced, thereby reducing power consumption. And the preparation process is simple and the preparation cost is low.
The present invention will be described in detail by way of examples. It is also to be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the invention, and that certain insubstantial modifications and adaptations of the invention by those skilled in the art may be made in light of the above teachings. The specific process parameters and the like of the following examples are also only one example of suitable ranges, i.e., those skilled in the art can select the appropriate ranges through the description herein, and are not limited to the specific values exemplified below.
Example 1
Preparation of functional layer membrane slurry
The dense electrolyte layer slurry was prepared as follows: 30g of BaZr are weighed0.1Ce0.7Y0.2O3-(BZCY) powder, taking absolute ethyl alcohol and butanone as solvents (11 g of absolute ethyl alcohol and 11g of butanone), adding a proper amount of dispersant (1.5 g of triethanolamine), putting the mixture into a roller ball mill for ball milling for 24 hours, then adding a proper amount of additive (4.7 g of polyvinyl butyral and 2.12g of dibutyl phthalate) into the mixture, putting the mixture into the roller ball mill for ball milling for 24 hours, and preparing proper dense electrolyte layer slurry.
The preparation process of the porous electrode supporting layer slurry is as follows: 16g of BaZr are weighed0.1Ce0.7Y0.2O3-The preparation method comprises the following steps of mixing powder, 24g of NiO powder, 7.5g of glutinous rice powder and 2.5g of graphite powder, adding a proper amount of dispersing agent (triethanolamine 2 g) into absolute ethyl alcohol and butanone serving as solvents (absolute ethyl alcohol 15g and butanone 15 g), ball-milling the mixture in a roller ball mill for 24 hours, adding a proper amount of additives (polyvinyl butyral 4.64g and dibutyl phthalate 3.86 g) into the mixture, and ball-milling the mixture in the roller ball mill for 24 hours to prepare proper porous electrode layer slurry.
Preparation of symmetric ceramic membrane hydrogen pump
Casting the slurry into membranes by adopting a casting process, then cutting each membrane into membranes of 15mm to 15mm, and supporting 3 porous electrode supporting layers |1 compact electrolyte layers |3 porous electrode supporting layersLaminated together and pressed in a warm isostatic press to form a green body. And then sintering the mixture for 4 hours at 1400 ℃ to prepare the proton conductor ceramic membrane hydrogen pump. The prepared ceramic membrane hydrogen pump is 10% H at 500 DEG C2Reducing for 10 hours under atmosphere to obtain a ceramic membrane hydrogen pump with bimodal pore size distribution, wherein the size of the symmetric ceramic hydrogen pump is about 12cm × 12cm, the thickness is about 0.55mm, and the flatness is relatively good, the microscopic morphology of the section SEM of the symmetric ceramic hydrogen pump is shown in figure 1, the thickness of a compact electrolyte layer is about 10 mu m, no open pores exist, and the compactness is good, the surface SEM surrounding morphology of the symmetric ceramic hydrogen pump is shown in figure 2, the size of Ni particles is about 3 mu m, a plurality of nano pores (about 70 nm) are distributed on the Ni particles, active sites of reaction are increased, the polarization impedance of the hydrogen pump work is reduced, the size of BZCY crystal grains is about 1.5 mu m to 2 mu m, a plurality of micro pores (about 2 mu m) are distributed between the Ni particles and the BZCY particles, a passage for gas transmission between electrodes is provided, the gas diffusion impedance of the hydrogen pump work is reduced, and the prepared symmetric ceramic membrane hydrogen pump is tested well2-CH4Separating and purifying hydrogen from the mixed gas, and introducing 80 mL/min into one side of the mixed gas-110% of H2-90%CH4Introducing mixed gas into the other side of the reactor, and introducing 70 mL-min-1100% H of2Under the action of an external electric field, H is converted into2From 10% H2-90%CH4One side is pumped to the pure hydrogen side, and the flow rate of the pure hydrogen side outlet gas and 10% H are tested2-90%CH4The flow rate and the content of the side outlet were calculated to calculate the separation and purification rate and the current efficiency at the corresponding pump voltage, and the results are shown in fig. 3. It can be seen that the hydrogen separation rate and the recovery rate of the hydrogen gas are increased along with the increase of the pump hydrogen voltage, when the pump hydrogen voltage is lower than 0.51V, the Faraday efficiency is higher than 95%, that is, the consumed electric energy is almost completely used for the separation and purification of the hydrogen gas, no extra loss is generated, and the hydrogen separation rate can reach 2.36 mL-cm at the moment-2·min-1The recovery rate of hydrogen reaches 25%. The hydrogen pumping voltage is further increased, the Faraday efficiency is reduced, and when the voltage is increased to 1.32V, the separation rate of the hydrogen reaches 3.65 mL-cm-2·min-1The recovery rate of hydrogen is improved to 40%, and the Faraday efficiency reaches 74%.
Example 2
Preparation of functional layer membrane slurry
The dense electrolyte layer slurry was prepared as follows: 30g of BaZr are weighed0.8Y0.2O3-(BZY) powder is prepared by taking absolute ethyl alcohol and butanone as solvents (11 g of absolute ethyl alcohol and 11g of butanone), adding a proper amount of dispersant (1.5 g of triethanolamine), putting the mixture into a roller ball mill for ball milling for 24 hours, then adding a proper amount of additive (4.7 g of polyvinyl butyral and 2.12g of dibutyl phthalate) into the mixture, putting the mixture into the roller ball mill for ball milling for 24 hours, and preparing proper dense electrolyte layer slurry.
The preparation process of the porous electrode supporting layer slurry is as follows: 16g of BaZr are weighed0.8Y0.2O3-The preparation method comprises the following steps of mixing powder, 24g of NiO powder, 7.5g of glutinous rice powder and 2.5g of graphite powder, adding a proper amount of dispersing agent (triethanolamine 2 g) into absolute ethyl alcohol and butanone serving as solvents (absolute ethyl alcohol 15g and butanone 15 g), ball-milling the mixture in a roller ball mill for 24 hours, adding a proper amount of additives (polyvinyl butyral 4.64g and dibutyl phthalate 3.86 g) into the mixture, and ball-milling the mixture in the roller ball mill for 24 hours to prepare proper porous electrode layer slurry.
Preparation of symmetric ceramic membrane hydrogen pump
And casting the slurry into membranes by adopting a casting process, then cutting each part of the membranes into membranes of 15mm x 15mm, laminating 3 porous electrode supporting layers |1 compact electrolyte layers |3 porous electrode supporting layers together, and pressing the membranes into green bodies in a warm isostatic pressing machine. And then sintering the mixture for 4 hours at 1400 ℃ to prepare the proton conductor ceramic membrane hydrogen pump. The prepared symmetrical ceramic membrane hydrogen pump is packaged and tested, and H with the hydrogen content of 10 percent is obtained2-CO2Separating and purifying hydrogen from the mixed gas, and introducing 80 mL/min into one side of the mixed gas -110% of H2-90%CO2Introducing mixed gas into the other side of the reactor, and introducing 70 mL-min -1100% H of2Under the action of an external electric field, H is converted into2From 10% H2-90%CO2One side is pumped to the pure hydrogen side, and the flow rate of the pure hydrogen side outlet gas and 10% H are tested2-90%CO2The flow rate and the content of the side outlet were calculated to calculate the separation and purification rate and the current efficiency at the corresponding pump voltage, and the results are shown in fig. 4. It can be seen that the hydrogen separation rate and the recovery rate of hydrogen increase with the increase of the pump hydrogen voltage, and when the pump hydrogen voltage is lower than 0.9V, the faradaic efficiency is higher than 95%, i.e. the consumed electric energy is almost completely used for the separation and purification of hydrogen, no extra loss is generated, and the hydrogen separation rate can reach 3.25mL cm at the moment-2·min-1The recovery rate of hydrogen reaches 35%. The hydrogen pumping voltage is further increased, the Faraday efficiency is reduced, and when the voltage is increased to 1.9V, the separation rate of the hydrogen reaches 5.17 mL-cm-2·min-1The recovery rate of hydrogen is improved to 55%, and the Faraday efficiency still exceeds 70%.
Example 3
The symmetric ceramic membrane hydrogen pump was prepared as in example 2 and tested at 10% H2-90%CO2The long-term stability of the hydrogen is separated and purified. After the prepared ceramic membrane hydrogen pump is packaged, 10% H is introduced into one side of the ceramic membrane hydrogen pump2-90%CO2Mixed gas is introduced into the other side of the reactor, and 100 percent H is introduced into the other side of the reactor2470mA · cm was applied-2The pumping hydrogen current of (2) was tested for changes in pumping hydrogen voltage and current efficiency, and the results are shown in fig. 5. It can be seen that the pump hydrogen voltage is increased in the initial stage (first 10 h) of separation and purification, slowly increased from 0.73V to 0.8V, and then maintained at 0.8V, and the current efficiency is still close to 100% in the period, indicating that the symmetric ceramic membrane hydrogen pump contains CO2The large attenuation does not occur under the long-term work of the atmosphere.
The invention discloses a proton conductor symmetric ceramic membrane hydrogen pump which can operate in a medium-low temperature range, has good hydrogen separation and purification capacity and can separate H from H2、CH4、CO2Pure hydrogen is extracted from the diluted hydrogen mixed gas of the mixed gas, the defects of the pressure swing adsorption technology can be filled in the industry, and the hydrogen in the mixed gas can be effectively separated and utilized by being applied to a distributed scene or being combined with the pressure swing adsorption technology.
The above embodiments are merely illustrative of the technical ideas and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
Claims (10)
1. The utility model provides a can realize ceramic hydrogen pump of hydrogen purification under complicated scene which characterized in that: the ceramic hydrogen pump has a symmetrical structure and sequentially comprises the following components from left to right: a first porous electrode support layer, a dense electrolyte layer, and a second porous electrode support layer;
the component of the dense electrolyte layer is a proton conductor, which should be AB1-xMxO3-1、Ln2B2-xMxO7-1、A2In2-yDyO5+1And Ln6-zW1-iMoiO12-2The compound is formed by one or more of A, B, D, L, B, Sm, Mn, Nd, Tb, Eu, Tm, In and Gd, D is at least one of Sc, Lu, Yb, Y, Dy, Gd and Sm, Ln is at least one of La, Nd, Gd and Er, x is more than or equal to 0 and less than 0.3, Y is more than or equal to 0 and less than 1, z is more than or equal to 0 and less than 1, i is more than or equal to 0 and less than 0.3, 1 is more than or equal to 0 and less than 0.5, and 2 is more than or equal to 0 and less than 1;
the components of the porous electrode support layer include a proton conductor and an electron conductor having catalytic properties; proton transference number of the proton conductor
Approximately 1, oxygen ion transport number
Near 0, electron transport number
Is close to 0; electron conductivity of the electron conductor of the porous electrode support layer
>10S/cm, the proton conductor material is the same as the electrolyte layer, and the electron conductor is at least one of metal Ni, Co, Fe, Cu or 430L metal alloy.
2. The ceramic hydrogen pump capable of realizing hydrogen purification under complex scenes according to claim 1, characterized in that: the porous electrode support layer has a bimodal pore structure in which micropores and nanopores coexist.
3. The ceramic hydrogen pump capable of realizing hydrogen purification under complex scenes according to claim 1 or 2, characterized in that: the micron aperture in the porous electrode supporting layer is 1-10 mu m, and the nano aperture in the porous electrode supporting layer is 1-100 nm.
4. The ceramic hydrogen pump capable of realizing hydrogen purification under complex scenes according to claim 1 or 2, characterized in that: the thickness of the compact electrolyte layer is 10-40 mu m.
5. The ceramic hydrogen pump capable of realizing hydrogen purification under complex scenes according to claim 1 or 2, characterized in that: the thickness of the porous electrode supporting layer is 150-400 mu m.
6. The ceramic hydrogen pump capable of realizing hydrogen purification under complex scenes according to claim 1 or 2, characterized in that: the thickness and size of the first porous support layer and the second porous support layer are the same.
7. The ceramic hydrogen pump capable of realizing hydrogen purification under complex scenes according to claim 1 or 2, characterized in that: the mass ratio of the electron conductor to the proton conductor in the porous electrode supporting layer is 2: 1-1: 2.
8. the ceramic hydrogen pump capable of realizing hydrogen purification under complex scenes according to claim 1 or 2, characterized in that: the porosity of the porous electrode supporting layer is 10-30%.
9. The ceramic hydrogen pump capable of realizing hydrogen purification under complex scenes according to claim 1 or 2, characterized in that: the nanopores in the porous electrode support layer are formed by kinetically-controlled in-situ low temperature reduction.
10. A preparation method of the ceramic hydrogen pump capable of realizing hydrogen purification under complex scenes is disclosed in claim 1 or 2, and is characterized in that: the method comprises the following steps:
step one, preparing a symmetrical ceramic hydrogen pump green compact by a 'tape casting-laminating-hot pressing' process, wherein a pore-forming agent and electronic conductor powder are not added into a compact electrolyte tape casting membrane, and the powder of a porous electrode layer tape casting membrane consists of proton conductor powder, electronic conductor powder and a pore-forming agent;
and secondly, sintering the green body at 1380-1450 ℃ for 4-6 hours to obtain the symmetrical ceramic hydrogen pump.
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| CN114870648A (en) * | 2022-05-17 | 2022-08-09 | 华南理工大学 | Mixed conductor hydrogen permeable membrane material and preparation method and application thereof |
| CN115646191A (en) * | 2022-11-09 | 2023-01-31 | 电子科技大学 | Hydrogen separation apparatus based on nickel-BZNY proton conductor and method of use |
| CN116924799A (en) * | 2023-07-28 | 2023-10-24 | 中国矿业大学 | Proton conductor ceramic electrochemical hydrogen pump and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103811789A (en) * | 2012-11-07 | 2014-05-21 | 中国科学院上海硅酸盐研究所 | Solid oxide fuel cell with symmetrical electrodes, and preparation method and application thereof |
-
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103811789A (en) * | 2012-11-07 | 2014-05-21 | 中国科学院上海硅酸盐研究所 | Solid oxide fuel cell with symmetrical electrodes, and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| TONGCHENG TONG等人: "Preparation and characterization of symmetrical protonic ceramic fuel cells as electrochemical hydrogen pumps", 《JOURNAL OF POWER SOURCES》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114870648A (en) * | 2022-05-17 | 2022-08-09 | 华南理工大学 | Mixed conductor hydrogen permeable membrane material and preparation method and application thereof |
| CN115646191A (en) * | 2022-11-09 | 2023-01-31 | 电子科技大学 | Hydrogen separation apparatus based on nickel-BZNY proton conductor and method of use |
| CN116924799A (en) * | 2023-07-28 | 2023-10-24 | 中国矿业大学 | Proton conductor ceramic electrochemical hydrogen pump and preparation method thereof |
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