CN114622231A - Ceramic hydrogen pump and hydrogen purification device of hydrogen-oxygen fuel cell - Google Patents
Ceramic hydrogen pump and hydrogen purification device of hydrogen-oxygen fuel cell Download PDFInfo
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- CN114622231A CN114622231A CN202210336133.0A CN202210336133A CN114622231A CN 114622231 A CN114622231 A CN 114622231A CN 202210336133 A CN202210336133 A CN 202210336133A CN 114622231 A CN114622231 A CN 114622231A
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- 239000001257 hydrogen Substances 0.000 title claims abstract description 108
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 108
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 83
- 239000000919 ceramic Substances 0.000 title claims abstract description 39
- 239000000446 fuel Substances 0.000 title claims abstract description 15
- 238000000746 purification Methods 0.000 title claims abstract description 11
- 239000001301 oxygen Substances 0.000 title claims description 11
- 229910052760 oxygen Inorganic materials 0.000 title claims description 11
- 239000003792 electrolyte Substances 0.000 claims abstract description 59
- 239000007789 gas Substances 0.000 claims abstract description 58
- 239000012528 membrane Substances 0.000 claims abstract description 40
- 239000000463 material Substances 0.000 claims description 19
- 150000002431 hydrogen Chemical class 0.000 claims description 12
- 229910045601 alloy Inorganic materials 0.000 claims description 9
- 239000000956 alloy Substances 0.000 claims description 9
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 claims description 9
- 239000010935 stainless steel Substances 0.000 claims description 8
- 229910001220 stainless steel Inorganic materials 0.000 claims description 8
- 239000002131 composite material Substances 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 229910003389 CeO2-δ Inorganic materials 0.000 claims description 3
- 229910003385 CeO2–δ Inorganic materials 0.000 claims description 3
- 229910003411 CeO2−δ Inorganic materials 0.000 claims description 3
- 239000003595 mist Substances 0.000 claims description 3
- 238000007599 discharging Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- -1 hydrogen ions Chemical class 0.000 abstract description 22
- 239000012466 permeate Substances 0.000 abstract description 4
- 210000004027 cell Anatomy 0.000 description 10
- 238000007789 sealing Methods 0.000 description 8
- 230000000712 assembly Effects 0.000 description 6
- 238000000429 assembly Methods 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 230000006399 behavior Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 210000000170 cell membrane Anatomy 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 230000009471 action Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
- C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
- C25B9/19—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
- C25B9/60—Constructional parts of cells
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
- H01M8/0606—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants
- H01M8/0656—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants by electrochemical means
Abstract
The invention discloses a ceramic hydrogen pump and a hydrogen purification device of an oxyhydrogen fuel cell, wherein the ceramic hydrogen pump comprises a pump body module, the pump body module comprises a positive electrode assembly, an electrolyte membrane and a negative electrode assembly which are sequentially arranged along a first direction, hydrogen in mixed gas is dissociated by the positive electrode assembly to generate hydrogen ions, the electrolyte membrane enables the hydrogen ions to permeate and reach the negative electrode assembly, and the negative electrode assembly reduces the hydrogen ions to generate the hydrogen.
Description
Technical Field
The invention relates to the technical field of hydrogen-oxygen fuel cells, in particular to a ceramic hydrogen pump and a hydrogen purification device of the hydrogen-oxygen fuel cell.
Background
The hydrogen-oxygen fuel cell membrane electrode comprises a catalytic layer, a diffusion layer, a proton exchange membrane and the like, and during the reaction process, if impurities such as sulfide and the like in hydrogen gas are toxic to a platinum-carbon catalyst, the activity of the catalyst is reduced, the power of the fuel cell is reduced, the service life of the fuel cell is shortened, and the like. There are various ways to purify hydrogen, and in the prior art, a ceramic hydrogen pump can be used to purify hydrogen, and generally comprises an electrolyte, a cathode and an anode, wherein the electrolyte can conduct protons. Under the drive of electric power, hydrogen is dissociated into protons at the positive electrode and is transmitted to the negative electrode through the electrolyte membrane, and the protons are electronically combined with an external circuit at the negative electrode to generate hydrogen. In order to meet the high flux requirement of practical application, a hydrogen pump monomer, a negative current collector, a positive current collector, a connector and the like are often packaged in series at the temperature of 800-. In addition, different thermal expansion behaviors among the hydrogen pump monomer, the sealing element and the connecting body increase the risk of sealing failure, and the service life and the reliability of the high-power hydrogen pump module are influenced.
Disclosure of Invention
The invention mainly aims to provide a ceramic hydrogen pump, which aims to solve the problems of complex structure, easy failure of sealing and the like in the prior art when a high-power hydrogen pump module is adopted for hydrogen purification, and further improve the service life and reliability of the hydrogen pump module.
In order to achieve the above object, the present invention provides a ceramic hydrogen pump comprising:
including pump body module, pump body module includes anodal subassembly, electrolyte diaphragm and the negative pole subassembly that sets gradually along the first direction, anodal subassembly is used for dissociating the hydrogen in the mist and produces hydrogen ion, the electrolyte diaphragm is used for supplying hydrogen ion sees through, the negative pole subassembly is used for reducing hydrogen ion and produces hydrogen, wherein, anodal subassembly the electrolyte diaphragm reaches negative pole subassembly integrated into one piece sets up.
Optionally, the positive electrode assembly includes a positive electrode connector, a positive electrode current collector, and a positive electrode, which are sequentially disposed, and the positive electrode is disposed adjacent to the electrolyte membrane;
the negative electrode assembly comprises a negative electrode connector, a negative electrode current collector and a negative electrode which are sequentially arranged, and the negative electrode is arranged adjacent to the electrolyte diaphragm;
the positive electrode connector, the positive electrode current collector, the positive electrode, the electrolyte film, the negative electrode current collector and the negative electrode connector are sintered into a whole.
Optionally, the positive electrode and/or the negative electrode is made of a material including a metal, an alloy, an electron conductive oxide, and an oxygen ion/proton-electron mixed conductive oxide; and/or the presence of a gas in the gas,
the thickness of the positive electrode and/or the negative electrode is H2, wherein H2 is more than or equal to 0.1mm and less than or equal to 1mm, and the porosity of the positive electrode and/or the negative electrode is 0.1-70%; and/or the presence of a gas in the gas,
the positive connector and/or the negative connector are made of high-temperature alloy, conductive oxide or conductive composite ceramic, and the coefficient of thermal expansion of the material of the positive connector and/or the negative connector is T1Coefficient of thermal expansion T of the electrolyte membrane2Wherein-30% or less of (T)1-T2)/T2Less than or equal to 30 percent; and/or the presence of a gas in the gas,
the thickness of the positive electrode connector and/or the negative electrode connector is H3, wherein H3 is more than or equal to 0.2mm and less than or equal to 3 mm; and/or the presence of a gas in the gas,
the positive current collector and/or the negative current collector are made of metal, alloy, conductive oxide or conductive composite ceramic.
Optionally, the positive electrode and/or the negative electrode is made of a material including Ni, Fe, Co, FeNi3、Ce1- xSmxO2–δ、Ni-Ce1-xSmxO2–δ、Ni-Ce1-xGdxO2–δ、(La1-xSrx)(Cr1-yFey)O3–δ、(La1-xSrx)(Cr1-yMny)O3–δ、(La1-xSrx)TiO3–δ、La2-xSrxFe2-y-zNiyMozO6-δIn at leastWherein 0 is<x<1，0<y<1，0<z<1，0<δ<1; (ii) a And/or the presence of a gas in the gas,
the positive connector and/or the negative connector are made of stainless steel 430L, stainless steel 446, stainless steel Crofer, (La) or a mixture thereof1-xSrx)TiO3–δAnd La2-xSrxFe2-y-zNiyMozO6-δAt least one of (1) and (b), wherein, 0<x<1，0<y<1，0<z<1，0<δ<1; and/or the presence of a gas in the gas,
the positive current collector and/or the negative current collector are made of materials including Ni, Fe, Co and FeNi3、430L、446、Crofer、Ni-Ce1-xSmxO2–δ、Ni-Ce1-xGdxO2–δ、(La1-xSrx)(Cr1-yFey)O3–δ、(La1-xSrx)(Cr1-yMny)O3–δAnd (La)1-xSrx)TiO3–δ、La2-xSrxFe2-y-zNiyMozO6-δAt least one of (1) and (b), wherein, 0<x<1，0<y<1，0<z<1，0<δ<1。
Optionally, the positive electrode assembly is formed with a first vessel opening towards the electrolyte membrane and a first gas inlet channel communicated with the first vessel, and the first gas inlet channel is used for enabling mixed gas to enter the first vessel;
the negative electrode component is provided with a second containing groove arranged towards the electrolyte membrane and a second gas outlet channel communicated with the second containing groove, and the second gas outlet channel is used for discharging hydrogen generated by the second containing groove.
Optionally, the depth of the first container and/or the second container along the thickness direction of the electrolyte membrane is H, wherein H is more than or equal to 0.1mm and less than or equal to 3 mm.
Optionally, the pump body module sets up a plurality ofly, and is a plurality of the pump body module is followed first direction sets gradually, two adjacent pump body modules, one the first groove of holding of positive pole subassembly and another the first inlet channel of positive pole subassembly is linked together, perhaps, one the second of negative pole subassembly holds the groove and another the second exhaust channel of negative pole subassembly is linked together.
Optionally, the pump body module sets up a plurality ofly, and is a plurality of the pump body module is followed first direction sets gradually, two adjacent in the pump body module, one the positive pole subassembly of pump body module is connected with another the negative pole subassembly electricity of pump body module.
Optionally, the electrolyte separator is made of CeO2–δ、LaGaO3–δ、BaCeO3–δ、BaZrO3–δ、BaZr1-x-yCexYyO3–δ、Sr2Sc1+xNb1–xO6–δ、La5.5WO11.25-δAnd Ba3Ca1+xNb2–xO9At least one of (1) and (b), wherein, 0<x<1，0<δ<1; and/or the presence of a gas in the atmosphere,
the thickness of the electrolyte membrane is T1Wherein, H1 is more than or equal to 1 μm and less than or equal to 100 μm.
In order to achieve the above object, the present invention provides a hydrogen purification apparatus for hydrogen-oxygen fuel cell, comprising the ceramic hydrogen pump as described above, the ceramic hydrogen pump comprising:
including pump body module, pump body module includes anodal subassembly, electrolyte diaphragm and the negative pole subassembly that sets gradually along the first direction, anodal subassembly is used for dissociating the hydrogen in the mist and produces hydrogen ion, the electrolyte diaphragm is used for supplying hydrogen ion sees through, the negative pole subassembly is used for reducing hydrogen ion and produces hydrogen, wherein, anodal subassembly the electrolyte diaphragm reaches negative pole subassembly integrated into one piece sets up.
In the technical scheme provided by the invention, the pump body module comprises a positive electrode assembly, an electrolyte membrane and a negative electrode assembly which are sequentially arranged along a first direction, hydrogen in mixed gas is dissociated by the positive electrode assembly to generate hydrogen ions, the electrolyte membrane enables the hydrogen ions to permeate and reach the negative electrode assembly, and the negative electrode assembly reduces the hydrogen ions to generate the hydrogen.
Drawings
In order to more clearly illustrate the embodiments or technical solutions of the present invention, the drawings used in the embodiments or technical solutions of the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the structures shown in the drawings without creative efforts.
FIG. 1 is a schematic structural diagram of one embodiment of a ceramic hydrogen pump provided by the present invention;
fig. 2 is an exploded view of the ceramic hydrogen pump of fig. 1.
The reference numbers illustrate:
| reference numerals | Name (R) | Reference numerals | Name (R) |
| 100 | |
12 | Electrolyte separator |
| 1 | |
13 | |
| 11 | |
131 | |
| 111 | |
132 | Negative |
| 112 | Positive |
133 | |
| 113 | |
134 | The |
| 114 | The first containing |
135 | Second |
| 115 | First |
136 | Second |
| 116 | First air outlet channel |
The implementation, functional features and advantages of the objects of the present invention will be further explained with reference to the accompanying drawings.
Detailed Description
The technical solutions in the embodiments of the present invention will be described clearly and completely with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
It should be noted that, if directional indications (such as up, down, left, right, front, and back … …) are involved in the embodiment of the present invention, the directional indications are only used to explain the relative positional relationship between the components, the movement situation, and the like in a specific posture (as shown in the drawing), and if the specific posture is changed, the directional indications are changed accordingly.
In addition, if there is a description relating to "first", "second", etc. in the embodiments of the present invention, the description of "first", "second", etc. is for descriptive purposes only and is not to be construed as indicating or implying relative importance or to implicitly indicate the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include at least one such feature. In addition, the meaning of "and/or" appearing throughout includes three juxtapositions, exemplified by "A and/or B" including either A or B or both A and B. In addition, technical solutions between the embodiments may be combined with each other, but must be based on the realization of the technical solutions by a person skilled in the art, and when the technical solutions are contradictory to each other or cannot be realized, such a combination should not be considered to exist, and is not within the protection scope of the present invention.
The hydrogen-oxygen fuel cell membrane electrode comprises a catalytic layer, a diffusion layer, a proton exchange membrane and the like, and during the reaction process, if impurities such as sulfide and the like in hydrogen gas are toxic to a platinum-carbon catalyst, the activity of the catalyst is further reduced, the power of the fuel cell is reduced, the service life of the fuel cell is shortened, and the like. There are various ways to purify hydrogen, and in the prior art, a ceramic hydrogen pump can be used to purify hydrogen, and generally comprises an electrolyte, a cathode and an anode, wherein the electrolyte can conduct protons. Under the drive of electric power, hydrogen is dissociated into protons at the positive electrode and is transmitted to the negative electrode through the electrolyte membrane, and the protons are electronically combined with an external circuit at the negative electrode to generate hydrogen. In order to meet the high flux requirement of practical application, a hydrogen pump monomer, a negative current collector, a positive current collector, a connector and the like are often packaged in series at the temperature of 800-. In addition, different thermal expansion behaviors among the hydrogen pump monomer, the sealing element and the connecting body increase the risk of sealing failure, and the service life and the reliability of the high-power hydrogen pump module are influenced.
The invention provides a ceramic hydrogen pump, wherein fig. 1 to 2 are schematic structural diagrams of an embodiment of the ceramic hydrogen pump provided by the invention.
Referring to fig. 1 to 2, the ceramic hydrogen pump 100 includes a pump module 1, the pump module 1 includes a positive electrode assembly 11, an electrolyte membrane 12 and a negative electrode assembly 13 sequentially disposed along a first direction, the positive electrode assembly 11 is configured to dissociate hydrogen gas in a mixed gas to generate hydrogen ions, the electrolyte membrane 12 is configured to allow the hydrogen ions to permeate through, the negative electrode assembly 13 is configured to reduce the hydrogen ions to generate hydrogen gas, and the positive electrode assembly 11, the electrolyte membrane 12 and the negative electrode assembly 13 are integrally formed.
In the above implementation manner, the pump module 1 includes the positive electrode assembly 11, the electrolyte membrane 12 and the negative electrode assembly 13 that set gradually along the first direction, through the hydrogen in the mixed gas is dissociated to generate hydrogen ions by the positive electrode assembly 11, the electrolyte membrane 12 makes the hydrogen ions permeate through and reach the negative electrode assembly 13, the negative electrode assembly 13 is used for reducing the hydrogen ions to generate hydrogen, and because in this embodiment, the positive electrode assembly 11, the electrolyte membrane 12 and the negative electrode assembly 13 are integrally formed, the problems that in the prior art, the positive electrode assembly 11, the electrolyte membrane 12 and the negative electrode assembly 13 cause sealing failure due to different thermal expansion behaviors, and the service life and reliability of the high-power hydrogen pump module are affected are solved.
Specifically, referring to fig. 2, the positive electrode assembly 11 includes a positive electrode connector 111, a positive electrode current collector 112 and a positive electrode 113 that are sequentially disposed, the positive electrode 113 is disposed adjacent to the electrolyte membrane 12, the negative electrode assembly 13 includes a negative electrode connector 131, a negative electrode current collector 132 and a negative electrode 133 that are sequentially disposed, the negative electrode 133 is disposed adjacent to the electrolyte membrane 12, and by sintering the positive electrode connector 111, the positive electrode current collector 112, the positive electrode 113, the electrolyte membrane 12, the negative electrode 133, the negative electrode current collector 132 and the negative electrode connector 131 into a whole, a sealing member is not needed, so that the sealing performance and reliability of the ceramic hydrogen pump 100 are improved.
Further, when the ceramic hydrogen pump 100 works, the positive electrode 113 needs to be electrically connected to a positive electrode of an external power supply, and the negative electrode 133 needs to be electrically connected to a negative electrode of the external power supply, for this reason, the positive electrode 113 and/or the negative electrode 133 are made of a material including a metal, an alloy, an electron conductive oxide, and an oxygen ion/proton-electron mixed conductive oxide.
Specifically, the positive electrode 113 and/or the negative electrode 133 are made of materials including Ni, Fe, Co, FeNi3、Ce1-xSmxO2–δ、Ni-Ce1-xSmxO2–δ、Ni-Ce1-xGdxO2–δ、(La1-xSrx)(Cr1-yFey)O3–δ、(La1-xSrx)(Cr1-yMny)O3–δ、(La1-xSrx)TiO3–δ、La2-xSrxFe2-y-zNiyMozO6-δAt least one of them. In the above-mentioned material, the value ranges of x, y, delta and z are 0<x<0.5，0<y<0.5，0<δ<1，0<z<0.5. Of course, in other embodiments, values of x, y, δ, and z may be selected as needed, which is not limited in this application.
Specifically, the thickness of the positive electrode 113 and/or the negative electrode 133 is H2, wherein H2 is 0.1mm or more and 1mm or less, and the arrangement is such that the weight of the positive electrode 113 and/or the negative electrode 133 is reduced on the premise that the strength of the positive electrode 113 and/or the negative electrode 133 is satisfied. The porosity of the positive electrode 113 and/or the negative electrode 133 is 0.1% -70%, and the arrangement is such that the positive electrode 113 adsorbs hydrogen as much as possible on the premise that the strength of the positive electrode 113 and/or the negative electrode 133 is satisfied, so that hydrogen ions are dissociated under the action of a catalyst, and the negative electrode 133 adsorbs electrons and hydrogen ions to react as much as possible, so that a large amount of hydrogen is generated.
Specifically, the material of the positive electrode connector 111 and/or the negative electrode connector 131 includes a high temperature alloy, a conductive oxide, or a conductive composite ceramic, and the coefficient of thermal expansion of the material of the positive electrode connector 111 and/or the negative electrode connector 131 is T1Coefficient of thermal expansion T of said electrolyte separator 122Wherein-30% or less (T)1-T2)/T2Less than or equal to 30 percent, so that the thermal expansion coefficient of the material of the anode connector 111 and/or the cathode connector 131 is close to that of the electrolyte membrane 12, thereby avoiding the expansion deformation of the anode connector 111 and/or the cathode connector 131 and the electrolyte membrane 12 caused by overhigh temperature when the ceramic hydrogen pump 100 works, and reducing the reliability and the service life of the ceramic hydrogen pump 100.
Further, the positive electrode connector 111 and/or the negative electrode connector 131 is made of stainless steel 430L or stainless steelSteel 446, stainless steel Crofer, (La)1-xSrx)TiO3–δAnd La2-xSrxFe2-y-zNiyMozO6-δAt least one of the positive electrode connector 111 and the negative electrode connector 131 is arranged in such a way that the positive electrode connector 111 and/or the negative electrode connector 131 is electrically conductive and directly electrically connected with an external power supply, and the structure is simple. In the above-mentioned material, the value ranges of x, y, delta and z are 0<x<0.5，0<y<0.5，0<δ<1，0<z<0.5. Of course, in other embodiments, the values of x, y, δ, and z may be selected as needed, and the present application does not limit this.
Specifically, the thickness of the positive electrode connector 111 and/or the negative electrode connector 131 is H3, wherein H3 is 0.2mm or more and 3mm or less, within this thickness range, so that the weight of the positive electrode connector 111 and/or the negative electrode connector 131 is reduced while the strength of the positive electrode connector 111 and/or the negative electrode connector 131 is satisfied.
Specifically, the positive electrode current collector 112 and/or the negative electrode current collector 132 may be made of a metal, an alloy, a conductive oxide, or a conductive composite ceramic.
Further, the positive electrode current collector 112 and/or the negative electrode current collector 132 are made of materials including Ni, Fe, Co, FeNi3、430L、446、Crofer、Ni-Ce1-xSmxO2–δ、Ni-Ce1-xGdxO2–δ、(La1-xSrx)(Cr1-yFey)O3–δ、(La1-xSrx)(Cr1-yMny)O3–δAnd (La)1-xSrx)TiO3–δ、La2-xSrxFe2-y-zNiyMozO6-δAt least one of them. In the above-mentioned material, the value ranges of x, y, delta and z are 0<x<0.5，0<y<0.5，0<δ<1，0<z<0.5. Of course, in other embodiments, values of x, y, δ, and z may be selected as needed, which is not limited in this application.
The positive electrode assembly 11 is formed with a first container 114 with an opening facing the electrolyte membrane 12 and a first gas inlet channel 115 communicated with the first container 114, the negative electrode assembly 13 is formed with a second container 134 with an opening facing the electrolyte membrane 12 and a second gas outlet channel 135 communicated with the second container 134, the first gas inlet channel 115 is used for conveying mixed gas into the first container 114, the mixed gas contains hydrogen, the mixed gas enters the first container 114, the positive electrode assembly 11 dissociates the hydrogen in the mixed gas to generate hydrogen ions, the generated hydrogen ions pass through the electrolyte membrane 12 and enter the second container 134, the hydrogen ions in the second container 134 react with electrons provided by the negative electrode assembly 13 to generate hydrogen, and the regenerated hydrogen is discharged through the second gas outlet channel 135, thereby achieving the purification of hydrogen.
In order to facilitate the discharge of the purified hydrogen, in an embodiment, the positive electrode assembly 11 further forms a first gas outlet channel 116, the first gas outlet channel 116 is communicated with the first container 114, and after the reaction of the mixed gas entering the first container 114 is finished, the reacted mixed gas is discharged from the first gas outlet channel 116. The negative electrode assembly 13 further has a second air inlet channel 136, the second air inlet channel 136 is communicated with the second container 134, and hydrogen is delivered into the second container 134 through the first air inlet channel 115, so that the pressure of the hydrogen in the second container 134 is increased, and the hydrogen generated by the reaction is discharged.
In order to facilitate the discharge of purified hydrogen, in another embodiment, the second outlet channel 135 is connected to a negative pressure device, so that the hydrogen generated in the second vessel is sucked out by generating a pressure difference between the first vessel 114 and the inlet of the negative pressure device.
It should be noted that, the kind of the negative pressure device may be various, for example, the negative pressure device may be a negative pressure vacuum pump, a suction pump, etc., and since the technology of the negative pressure vacuum pump and the suction pump is mature, the detailed structure and the operation principle of the negative pressure vacuum pump and the suction pump are not further described in this application.
Specifically, the depth of the first container 114 and/or the second container 134 in the thickness direction of the electrolyte membrane 12 is H, wherein H is greater than or equal to 0.1mm and less than or equal to 3mm, and thus the gas flow rate of the first container 114 and/or the second container is increased on the premise of ensuring the performance of the positive electrode assembly 11 and/or the negative electrode assembly 13.
In order to increase the power of the ceramic hydrogen pump 100, referring to fig. 2, the pump modules 1 are provided in plurality, the pump modules 1 are provided in the first direction, and in two adjacent pump modules 1, the first receiving groove 114 of one positive electrode assembly 11 is communicated with the first air inlet channel 115 of another positive electrode assembly 11, or the second receiving groove 134 of one negative electrode assembly 13 is communicated with the second air outlet channel 135 of another negative electrode assembly 13, so that when the first receiving groove 114 of the positive electrode assembly 11 is communicated with the first air inlet channel 115 of another positive electrode assembly 11, the first receiving grooves 114 of the positive electrode assemblies 11 are arranged in series, that is, when the mixed gas enters the first receiving groove 114 of the positive electrode assembly 11 from the first air inlet channel 115 of the positive electrode assembly 11 at the front end of the series, the mixed gas in the first receiving groove 114 reaches the plurality of positive electrode assemblies 11 in sequence along the flow path of the series And hydrogen ions are dissociated from the plurality of first containers 114 by the corresponding positive electrode assemblies 11, the hydrogen ions then pass through the electrolyte membrane 12 to reach the corresponding second vessel 134, the hydrogen ions react with the electrons provided by the negative electrode assembly 13 in the second vessel 134 to generate hydrogen gas, since the second container 134 of one of the negative electrode assemblies 13 is communicated with the second outlet channel 135 of the other one of the negative electrode assemblies 13, the second tanks 134 of the plurality of negative electrode assemblies 13 are arranged in series, and hydrogen gas generated from the second tank 134 of the first negative electrode assembly 13 can sequentially pass through the plurality of second tanks 134 arranged in series along the series flow path, and finally exits from second outlet channel 135 of second container 134 of the last-end negative electrode assembly 13 in series, since a plurality of the second vessel 134 are arranged in series, the pressure of the discharged hydrogen gas is increased.
It should be noted that, in the above description, the head end is the pump body module 1 which is contacted first along the gas, and the tail end is the pump body module 1 which is contacted last along the gas, of course, in other embodiments, the head end and the tail end may be set according to the needs, and the present application is not limited thereto.
Specifically, referring to fig. 1, pump body module 1 sets up a plurality ofly, and is a plurality of pump body module 1 is followed the first direction sets gradually, adjacent two in the pump body module 1, one pump body module 1's positive pole subassembly 11 and another the negative pole subassembly 13 electricity of pump body module 1 is connected, so sets up, makes a plurality of pump body module 1 establishes ties in proper order and sets up, forms compound pump body module 1, compound body module has the both ends of relative setting, and wherein one end is provided with positive pole subassembly 11, and the other end is provided with negative pole subassembly 13, when inserting external power source, only needs to make positive pole subassembly 11 inserts the positive pole of power, negative pole subassembly 13 insert the power negative pole can, the circuit is simple.
It should be noted that, in another embodiment, in the plurality of pump body modules 1, the positive electrode assembly 11 of one pump body module 1 may be electrically connected to the positive electrode assembly 11 of another pump body module 1, and the negative electrode assembly 13 of one pump body module 1 may be electrically connected to the negative electrode assembly 13 of another pump body module 1, so as to implement parallel connection of the plurality of pump body modules 1, of course, in the plurality of pump body modules 1, the plurality of pump body modules 1 may be connected in series or in parallel, and specifically, this application does not limit this.
Specifically, the electrolyte membrane 12 is made of CeO2–δ、LaGaO3–δ、BaCeO3–δ、BaZrO3–δ、BaZr1-x-yCexYyO3–δ、Sr2Sc1+xNb1–xO6–δ、La5.5WO11.25-δAnd Ba3Ca1+xNb2–xO9At least one of them. In the above-mentioned material, the value ranges of x, y, delta and z are 0<x<0.5，0<y<0.5，0<δ<1. Of course, in other embodiments, the values of x and δ may be the rootThis is not a limitation of the present application, as may be desired.
Further, the thickness of the electrolyte membrane 12 is H1, wherein H1 is more than or equal to 1 μm and less than or equal to 100 μm, and within the thickness range, the compactness of the electrolyte membrane 12 is ensured, and the effect of transferring protons is ensured.
The invention also provides a hydrogen purification device of the oxyhydrogen fuel cell, which comprises the ceramic hydrogen pump 100, the concrete structure of the ceramic hydrogen pump 100 refers to the above embodiments, and the hydrogen purification device of the oxyhydrogen fuel cell adopts all technical schemes of all the embodiments, so that the hydrogen purification device at least has all the beneficial effects brought by all the technical schemes of all the embodiments, and the detailed description is omitted.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the scope of the present invention, and all modifications and equivalents of the present invention, which are made by the contents of the present specification and the accompanying drawings, or directly/indirectly applied to other related technical fields, are included in the scope of the present invention.
Claims (10)
1. The utility model provides a pottery hydrogen pump, its characterized in that, includes pump body module, pump body module includes anodal subassembly, electrolyte diaphragm and the negative pole subassembly that sets gradually along the first direction, anodal subassembly is used for dissociating the hydrogen among the mist and generates hydrogen ion, the electrolyte diaphragm is used for supplying hydrogen ion sees through, the negative pole subassembly is used for reducing hydrogen ion and generates hydrogen, wherein, anodal subassembly the electrolyte diaphragm reaches negative pole subassembly integrated into one piece sets up.
2. The ceramic hydrogen pump of claim 1 wherein the positive electrode assembly comprises, in order, a positive electrode connector, a positive electrode current collector, and a positive electrode disposed adjacent to the electrolyte membrane;
the negative electrode assembly comprises a negative electrode connector, a negative electrode current collector and a negative electrode which are sequentially arranged, and the negative electrode is arranged adjacent to the electrolyte diaphragm;
the positive electrode connector, the positive electrode current collector, the positive electrode, the electrolyte film, the negative electrode current collector and the negative electrode connector are sintered into a whole.
3. The ceramic hydrogen pump of claim 2 wherein the positive electrode and/or the negative electrode is made of a material comprising a metal, an alloy, an electron conducting oxide and an oxygen ion/proton-electron mixed conducting oxide; and/or the presence of a gas in the gas,
the thickness of the positive electrode and/or the negative electrode is H2, wherein H2 is more than or equal to 0.1mm and less than or equal to 1mm, and the porosity of the positive electrode and/or the negative electrode is 0.1-70%; and/or the presence of a gas in the gas,
the anode connector and/or the cathode connector are made of high-temperature alloy, conductive oxide or conductive composite ceramic, and the thermal expansion coefficient of the anode connector and/or the cathode connector is T1Coefficient of thermal expansion T of said electrolyte separator2Wherein-30% or less (T)1-T2)/T2Less than or equal to 30 percent; and/or the presence of a gas in the gas,
the thickness of the positive electrode connector and/or the negative electrode connector is H3, wherein H3 is more than or equal to 0.2mm and less than or equal to 3 mm; and/or the presence of a gas in the gas,
the positive current collector and/or the negative current collector are made of materials including metal, alloy, conductive oxide or conductive composite ceramic.
4. The ceramic hydrogen pump of claim 3 wherein the positive electrode and/or the negative electrode is made of a material comprising Ni, Fe, Co, FeNi3、Ce1-xSmxO2–δ、Ni-Ce1-xSmxO2–δ、Ni-Ce1-xGdxO2–δ、(La1-xSrx)(Cr1- yFey)O3–δ、(La1-xSrx)(Cr1-yMny)O3–δ、(La1-xSrx)TiO3–δ、La2-xSrxFe2-y-zNiyMozO6-δAt least one of (1) and (b), wherein, 0<x<1，0<y<1，0<z<1，0<δ<1; and/or the presence of a gas in the gas,
the positive connector and/or the negative connector are made of stainless steel 430L, stainless steel 446, stainless steel Crofer, (La) or a mixture thereof1-xSrx)TiO3–δAnd La2-xSrxFe2-y-zNiyMozO6-δAt least one of (A) and (B), wherein, 0<x<1，0<y<1，0<z<1，0<δ<1; and/or the presence of a gas in the gas,
the positive current collector and/or the negative current collector are made of materials including Ni, Fe, Co and FeNi3、430L、446、Crofer、Ni-Ce1-xSmxO2–δ、Ni-Ce1-xGdxO2–δ、(La1-xSrx)(Cr1-yFey)O3–δ、(La1-xSrx)(Cr1-yMny)O3–δAnd (La)1-xSrx)TiO3–δ、La2-xSrxFe2-y-zNiyMozO6-δAt least one of (1) and (b), wherein, 0<x<1，0<y<1，0<z<1，0<δ<1。
5. A ceramic hydrogen pump as set forth in claim 1, wherein the positive electrode assembly is formed with a first vessel opening toward the electrolyte membrane and a first gas inlet passage communicating with the first vessel for letting the mixed gas into the first vessel;
the negative electrode component is provided with a second containing groove arranged towards the electrolyte membrane and a second gas outlet channel communicated with the second containing groove, and the second gas outlet channel is used for discharging hydrogen generated by the second containing groove.
6. The ceramic hydrogen pump of claim 5, wherein the first and/or second groove has a groove depth H in the thickness direction of the electrolyte membrane, wherein H is 0.1 mm. ltoreq.H.ltoreq.3 mm.
7. The ceramic hydrogen pump according to claim 6, wherein a plurality of the pump body modules are arranged, and the plurality of pump body modules are arranged in sequence along the first direction, and in two adjacent pump body modules, the first receiving groove of one positive electrode assembly is communicated with the first air inlet channel of the other positive electrode assembly, or the second receiving groove of one negative electrode assembly is communicated with the second air outlet channel of the other negative electrode assembly.
8. The ceramic hydrogen pump of claim 1, wherein a plurality of the pump body modules are arranged in sequence along the first direction, and in two adjacent pump body modules, the positive electrode component of one pump body module is electrically connected with the negative electrode component of the other pump body module.
9. A ceramic hydrogen pump as claimed in claim 1, characterized in that the electrolyte membrane is made of a material comprising CeO2–δ、LaGaO3–δ、BaCeO3–δ、BaZrO3–δ、BaZr1-x-yCexYyO3–δ、Sr2Sc1+xNb1–xO6–δ、La5.5WO11.25-δAnd Ba3Ca1+ xNb2–xO9At least one of (1) and (b), wherein, 0<x<1，0<δ<1; and/or the presence of a gas in the gas,
the thickness of the electrolyte membrane is H1, wherein H1 is more than or equal to 1 mu m and less than or equal to 100 mu m.
10. A hydrogen purification apparatus for a hydrogen-oxygen fuel cell, comprising the ceramic hydrogen pump according to any one of claims 1 to 9.
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