CN117317325B - Proton transmission type solid oxide fuel cell unit, battery pack and preparation method - Google Patents
Proton transmission type solid oxide fuel cell unit, battery pack and preparation method Download PDFInfo
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- CN117317325B CN117317325B CN202311606114.6A CN202311606114A CN117317325B CN 117317325 B CN117317325 B CN 117317325B CN 202311606114 A CN202311606114 A CN 202311606114A CN 117317325 B CN117317325 B CN 117317325B
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- 239000000446 fuel Substances 0.000 title claims abstract description 71
- 239000007787 solid Substances 0.000 title claims abstract description 49
- 230000005540 biological transmission Effects 0.000 title abstract description 24
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 238000000576 coating method Methods 0.000 claims abstract description 238
- 239000011248 coating agent Substances 0.000 claims abstract description 229
- 229910052751 metal Inorganic materials 0.000 claims abstract description 100
- 239000002184 metal Substances 0.000 claims abstract description 100
- 239000003792 electrolyte Substances 0.000 claims abstract description 68
- 230000008021 deposition Effects 0.000 claims description 42
- 239000000843 powder Substances 0.000 claims description 36
- 238000005507 spraying Methods 0.000 claims description 27
- 238000005137 deposition process Methods 0.000 claims description 22
- 238000007750 plasma spraying Methods 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 14
- 230000007423 decrease Effects 0.000 claims description 3
- 239000010410 layer Substances 0.000 abstract description 41
- 238000007789 sealing Methods 0.000 abstract description 15
- 239000011247 coating layer Substances 0.000 abstract description 14
- 239000000178 monomer Substances 0.000 abstract description 12
- 238000000151 deposition Methods 0.000 description 30
- 239000002737 fuel gas Substances 0.000 description 27
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 9
- 239000001301 oxygen Substances 0.000 description 9
- 229910052760 oxygen Inorganic materials 0.000 description 9
- 239000002245 particle Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000011148 porous material Substances 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- 230000009286 beneficial effect Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000007921 spray Substances 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 238000010285 flame spraying Methods 0.000 description 3
- 238000010248 power generation Methods 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 230000002093 peripheral effect Effects 0.000 description 2
- 150000003384 small molecules Chemical class 0.000 description 2
- RJBSIFOTJSUDHY-UHFFFAOYSA-N [O-2].[Fe+2].[Co+2].[Sr+2].[La+3] Chemical compound [O-2].[Fe+2].[Co+2].[Sr+2].[La+3] RJBSIFOTJSUDHY-UHFFFAOYSA-N 0.000 description 1
- QERIHWANWDAFDF-UHFFFAOYSA-N [O-2].[Y+3].[Zr+4].[Ce+3].[Ba+2].[O-2].[O-2].[O-2].[O-2].[O-2] Chemical compound [O-2].[Y+3].[Zr+4].[Ce+3].[Ba+2].[O-2].[O-2].[O-2].[O-2].[O-2] QERIHWANWDAFDF-UHFFFAOYSA-N 0.000 description 1
- -1 anode Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- VNNRSPGTAMTISX-UHFFFAOYSA-N chromium nickel Chemical compound [Cr].[Ni] VNNRSPGTAMTISX-UHFFFAOYSA-N 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000010891 electric arc Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 229910001120 nichrome Inorganic materials 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 229910000623 nickel–chromium alloy Inorganic materials 0.000 description 1
- 229910002119 nickel–yttria stabilized zirconia Inorganic materials 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 238000005240 physical vapour deposition Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000004449 solid propellant Substances 0.000 description 1
- 238000009718 spray deposition Methods 0.000 description 1
Classifications
-
- 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
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
- H01M8/1213—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the electrode/electrolyte combination or the supporting material
- H01M8/122—Corrugated, curved or wave-shaped MEA
-
- 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
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/023—Porous and characterised by the material
- H01M8/0232—Metals or alloys
-
- 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
- H01M8/24—Grouping of fuel cells, e.g. stacking of fuel cells
- H01M8/241—Grouping of fuel cells, e.g. stacking of fuel cells with solid or matrix-supported electrolytes
- H01M8/2425—High-temperature cells with solid electrolytes
-
- 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
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
- H01M2008/1293—Fuel cells with solid oxide electrolytes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Fuel Cell (AREA)
Abstract
The invention belongs to the field of fuel cells, and in particular relates to a proton transmission type solid oxide fuel cell monomer, a battery pack and a preparation method, wherein the monomer comprises the following components: a current collector provided with a groove extending from one side to the other side of the current collector; the porous metal coating is positioned in the groove and covers the bottom of the groove, holes in the porous metal coating are mutually communicated, the aperture is in the micro-nano to micro-micro level, and the porosity is 10% -50%; an anode coating within the recess, covering the porous metal coating; an electrolyte coating layer, which is partially located in the groove, which covers the anode layer, and the edge of which extends onto the surface of the current collector at the edge of the groove, which covers the surface of the current collector at the edge of the groove; and the cathode coating and the anode coating are respectively positioned at two sides of the electrolyte coating, and are correspondingly arranged relative to the electrolyte coating. The solid oxide fuel cell unit has small volume and weight and can realize self-sealing.
Description
Technical Field
The invention belongs to the technical field of fuel cells, and particularly relates to a proton transmission type solid oxide fuel cell monomer, a battery pack and a preparation method.
Background
The fuel cell is a power generation device for directly converting chemical energy of fuel into electric energy, and is rapidly developed in the new energy fields of fuel cell electric vehicles, fixed power supplies and the like. A Solid Oxide Fuel Cell (SOFC) belongs to a third generation fuel cell, is an all-solid-state chemical power generation device for directly converting chemical energy stored in fuel and oxidant into electric energy at medium and high temperature with high efficiency and environmental friendliness, and is an important development direction of the fuel cell because of high power generation efficiency, slow attenuation and excellent comprehensive performance.
The structure of the solid oxide fuel cell mainly comprises three types of tubular, flat and integral type, wherein the flat type is a development trend of the SOFC due to high power density and low manufacturing cost, but the flat type fuel cell has large sealing area and difficult high-temperature sealing.
Currently, the SOFC is developing towards the working temperature below 700 ℃, the traditional high-temperature SOFC can only adopt ceramic support, the cell volume is large, the toughness is poor, metal support with stronger toughness is used, the flat solid oxide fuel cell unit mainly comprises a current collector flat plate provided with a fuel gas flow channel, a porous metal support layer, an anode layer, an electrolyte layer and a cathode layer, in order to enable the porous metal support layer to effectively support the anode layer, the electrolyte layer and the cathode layer above, the thickness of the porous metal support layer is required to be more than 0.8mm, the volume and the weight of the flat solid fuel cell unit are increased by the porous metal support layer, and on the premise that the volume and the weight of the single cell are large, a plurality of single cells are formed into a fuel cell unit in various modes (series connection, parallel connection and series connection), so that the fuel cell unit is very inconvenient when the fuel cell unit is applied to mobile systems such as automobiles and unmanned aerial vehicles.
Disclosure of Invention
The invention aims to overcome the defects of difficult sealing and large volume and weight of a flat solid oxide fuel cell unit in the prior art, and provides a proton transmission type solid oxide fuel cell unit, a battery pack and a preparation method.
In order to achieve the above object, in a first aspect, the present invention provides a proton-transporting solid oxide fuel cell unit comprising:
a current collector provided with a groove extending from one side to the other side of the current collector;
the porous metal coating is positioned in the groove and covers the bottom of the groove, holes in the porous metal coating are communicated with each other, the aperture is in the micro-nano to micro-micro level, and the porosity is 10% -50%;
an anode coating within the recess that covers the porous metal coating;
an electrolyte coating partially within the recess, covering the anode coating, with an edge portion extending onto a surface of the current collector at the recess edge, covering a surface of the current collector at the recess edge;
and the cathode coating is positioned in the groove, the cathode coating and the anode coating are respectively positioned at two sides of the electrolyte coating, and the cathode coating and the anode coating are correspondingly arranged relative to the electrolyte coating.
In some preferred embodiments, the cross-section of the groove is trapezoidal, and the area of the longitudinal section of the groove gradually decreases from the top of the groove to the bottom of the groove.
Preferably, the included angle between the bottom surface and the side surface of the groove is not smaller than 120 degrees.
In some preferred embodiments, the edges of the anodic coating extend onto the sides of the grooves.
In some preferred embodiments, the porous metal coating has a thickness of 50 μm to 150 μm.
In some preferred embodiments, the anode, electrolyte and cathode coatings have a thickness of 5 μm to 50 μm, respectively, and the anode, electrolyte and cathode coatings have porosities of 5% to 30%, 0.5% to 5% and 5% to 30%, respectively.
In a second aspect, the present invention provides a battery pack formed by connecting solid oxide fuel cells according to the first aspect in series, wherein the battery pack is formed by connecting at least two solid oxide fuel cells in series, and the connection is performed in such a way that one side of one cell facing away from a groove contacts with one side of another cell facing away from the groove, and the contact is that the side facing away from the groove contacts with an electrolyte coating on the surface of a current collector at the edge of the groove on the side of the groove.
In a third aspect, the present invention provides a method for preparing the solid oxide fuel cell unit according to the first aspect, the method comprising:
performing first deposition treatment on the bottom of the groove of the current collector to obtain a porous metal coating; the conditions of the first deposition process include: carrying out the first deposition treatment by adopting plasma spraying, wherein when the granularity of the metal powder is 20-40 mu m, the spraying power is 15-25 kw, and when the granularity of the metal powder is 41-70 mu m, the spraying power is 26-35 kw;
performing second deposition treatment on the porous metal coating to obtain an anode coating;
performing a third deposition treatment on the anode coating to obtain an electrolyte coating, wherein the deposition process of the third deposition treatment extends to the surface of the current collector at the edge of the groove;
and carrying out fourth deposition treatment on the electrolyte coating and the area corresponding to the anode coating to obtain a cathode coating.
In some preferred embodiments, the second deposition process and the fourth deposition process are performed using plasma spraying, and the conditions of the second deposition process and the fourth deposition process include: the spraying power is 25-35 kw, and the powder feeding speed is 20-35 g/min.
In some preferred embodiments, the third deposition process is performed using plasma spraying, and the conditions of the third deposition process include: the spraying power is 40-50 kw, and the powder feeding speed is 10-15 g/min.
The proton transmission type solid oxide fuel cell unit is characterized in that a groove extending from one side to the other side is formed in a current collector, a porous metal coating, an anode coating, an electrolyte coating and a cathode coating are sequentially arranged in the groove, the porous metal coating is in a coating form, holes with the pore diameters ranging from micro-nanometers to micrometers are formed in the porous metal coating and can transmit fuel gas, and the porous metal layer, the anode layer, the electrolyte layer and the cathode layer are all positioned in the groove and do not protrude to the outside of the current collector.
According to the fuel cell, the edge of the electrolyte coating extends to the surface of the current collector at the edge of the groove, so that the direct contact of fuel cell gas and oxygen can be blocked, namely, the fuel gas can only circulate in the porous metal coating and the anode coating, the oxygen can only circulate in the cathode coating and the upper part of the cathode coating, an additional sealing layer is not needed, a self-sealing effect is formed, the peripheral sealing process of the porous metal coating, the anode coating and the cathode coating can be omitted, the overall sealing difficulty of the cell is reduced, and the preparation process is simplified.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed in the embodiments will be briefly described below, it being understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and other related drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
Fig. 1 is a schematic structural diagram of one embodiment of a proton transmissive solid oxide fuel cell unit of the present invention.
Description of the reference numerals
1. A current collector; 101. a groove; 2. a porous metal coating; 3. an anode coating; 4. an electrolyte coating; 5. and (5) cathode coating.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
In this document, unless otherwise indicated, terms of orientation such as "upper, lower, left, right" and "upper" are used generally to refer to the orientation understanding shown in the drawings and in practice, and "inner, outer" are intended to refer to the inner, outer of the outline of the component.
In the description of the present invention, it should be understood that the terms "center", "longitudinal", "lateral", "length", "width", "thickness", "upper", "lower", "front", "rear", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer", "clockwise", "counterclockwise", "axial", "radial", "circumferential", etc. indicate orientations or positional relationships based on the orientations or positional relationships shown in the drawings are merely for convenience in describing the present invention and simplifying the description, and do not indicate or imply that the device or element being referred to must have a specific orientation, be configured and operated in a specific orientation, and therefore should not be construed as limiting the present invention.
In the present invention, unless explicitly specified and limited otherwise, the terms "mounted," "connected," "secured," and the like are to be construed broadly, and may be, for example, fixedly connected, detachably connected, or integrally formed; can be mechanically or electrically connected; can be directly connected or indirectly connected through an intermediate medium, and can be communicated with the inside of two elements or the interaction relationship of the two elements. The specific meaning of the above terms in the present invention can be understood by those of ordinary skill in the art according to the specific circumstances.
In the present invention, unless expressly stated or limited otherwise, a first feature "up" or "down" a second feature may be the first and second features in direct contact, or the first and second features in indirect contact via an intervening medium. Moreover, a first feature being "above," "over" and "on" a second feature may be a first feature being directly above or obliquely above the second feature, or simply indicating that the first feature is level higher than the second feature. The first feature being "under", "below" and "beneath" the second feature may be the first feature being directly under or obliquely below the second feature, or simply indicating that the first feature is less level than the second feature.
The inventor of the present invention has studied and found that the sealing of the existing flat solid oxide fuel cell unit is difficult, and the fuel cell unit has large volume and weight.
In this regard, in a first aspect, the present invention provides a proton transmissive solid oxide fuel cell unit comprising:
a current collector 1 provided with a groove 101, the groove 101 extending from one side of the current collector 1 to the other side;
the porous metal coating 2 is positioned in the groove 101 and covers the bottom of the groove 101, holes in the porous metal coating are communicated with each other, the aperture is in the micro-nano to micro-micro level, and the porosity is 10% -50%;
an anode coating 3 located within the recess 101, which covers the porous metal coating 2;
an electrolyte coating layer 4, which is partially located in the groove 101, covers the anode coating layer 3, and the edge of which extends onto the surface of the current collector 1 at the edge of the groove 101, and covers the surface of the current collector 1 at the edge of the groove 101;
and the cathode coating 5 is positioned in the groove 101, the cathode coating 5 and the anode coating 3 are respectively positioned at two sides of the electrolyte coating 4, and the cathode coating 5 and the anode coating 3 are correspondingly arranged relative to the electrolyte coating.
The proton transmission type solid oxide fuel cell is characterized in that the current collector is provided with the grooves extending from one side to the other side, and the porous metal coating, the anode coating, the electrolyte coating and the cathode coating are sequentially arranged in the grooves. The invention adopts a coating mode to prepare the solid oxide fuel cell monomer, the porous metal coating, the anode coating, the electrolyte coating and the cathode coating, the total thickness of the four coatings can be controlled within 300 micrometers, and the overall thickness and the weight of the fuel cell monomer can be obviously reduced.
Proton-transporting solid oxidationIn the solid oxide fuel cell, small molecular fuel gas is continuously introduced into the anode side of the solid oxide fuel cell, for example: hydrogen, ammonia and the like, the surface of the anode with the catalysis function adsorbs fuel gas, electrons and hydrogen protons are generated by decomposition of the anode layer, the electrons flow to the cathode through an external circuit, the hydrogen protons are diffused to the interface between the anode layer and the electrolyte layer through the porous structure of the anode, and the hydrogen protons are further diffused in the electrolyte layer under the action of chemical potential; oxygen or air is continuously introduced into one side of the cathode of the solid oxide fuel cell, and oxygen is adsorbed on the surface of the cathode with a porous structure, so that O is caused by the catalytic action of the cathode 2 The electrons of the external circuit are changed into O 2- And reacts with hydrogen protons at the interface between the cathode and the electrolyte to form water.
According to the proton transmission type solid oxide fuel cell monomer, the porous metal layer is in a coating form, the holes in the porous metal coating are mutually communicated, the aperture is in the order of micro-nanometers to micrometers, the porosity is 10% -50% (the detection method of the porosity is a metallographic test method), the inventor finds that after small molecular fuel gas such as hydrogen, ammonia and the like is introduced into the holes of the porous metal coating, the fuel gas can be uniformly distributed in the holes of the porous metal coating and reaches the anode coating, one possible explanation is that the apertures of the holes in the porous metal coating are in the order of micro-nanometers to micrometers, the apertures are smaller, the small molecular fuel gas can easily flow through multiple channels, and the small molecular fuel gas can easily reach the anode coating due to the fact that the porous metal layer is in the coating form. The battery monomer is a proton transmission type solid oxide fuel battery monomer, water vapor is generated on the cathode side and is discharged through a channel above the cathode coating, the water vapor does not enter the porous metal layer, the drainage of the water vapor is not influenced, the water vapor does not enter the porous metal layer, and the transmission of micromolecular fuel gas in the porous metal layer is not influenced by the water vapor. Taking fuel gas as ammonia gas for example, the ammonia gas is decomposed into hydrogen protons, electrons and nitrogen gas in the anode coating, the hydrogen protons are transmitted to the interface between the anode layer and the electrolyte layer, the electrons are transmitted downwards through the porous metal layer, the nitrogen gas returns to enter the porous metal coating, and the nitrogen gas can not prevent the transmission of the small-molecule fuel gas in the communication holes in the porous metal layer, but can promote the transmission of the small-molecule fuel gas. The proton transmission type solid oxide fuel cell monomer adopts a porous metal coating with mutually communicated holes with the pore diameter of micro-nanometer to micron level to replace the structure of a fuel gas flow channel and a porous metal support body, adopts the porous metal layer in the form of the coating, can increase the transmission efficiency of fuel gas on the basis of ensuring that the fuel gas uniformly distributes to reach an anode coating, improves the cell performance, can reduce the volume and the weight of the proton transmission type solid oxide fuel cell monomer, and does not need to carry out a flow channel processing technology. The porosity of the porous metal coating 2 is not lower than 10%, so that the transmission efficiency of fuel gas can be improved, the fuel gas can uniformly reach the anode coating after being uniformly distributed in the porous metal coating, the porosity of the porous metal coating 2 is not higher than 50%, and the strength of the porous metal coating can be ensured. The porosity of the porous metal coating of the present invention may specifically be, for example, 10%, 20%, 30%, 40% and 50%.
The edge of the electrolyte coating extends to the surface of the current collector at the edge of the groove, so that the direct contact of fuel cell gas and oxygen can be blocked, namely, the fuel gas can only circulate in the porous metal coating and the anode coating, the oxygen can only circulate on the cathode coating and the upper part of the cathode coating, an extra sealing layer is not needed, a self-sealing effect is formed, the peripheral sealing process of the porous metal coating, the anode coating and the cathode coating can be omitted, the overall sealing difficulty of the cell is reduced, and the preparation process is simplified.
The electrolyte coating covers the surface of the current collector 1 at the edge of the groove, namely the electrolyte coating covers the whole surface of the current collector at the edge of the groove, and the battery cells are stacked, so that adjacent current collectors are not in direct contact, and short circuits can be avoided.
The invention has a wide range of alternatives to the form of the groove 101, and the cross section of the groove 101 may be rectangular or trapezoidal, for example. In some preferred embodiments, referring to fig. 1, the cross section of the groove 101 is trapezoidal, and the area of the longitudinal section of the groove 101 gradually decreases from the top of the groove 101 to the bottom of the groove 101. Under the preferred scheme, the grooves are opened outwards, so that the timely discharge of water vapor on the cathode side is facilitated, the uniform spray deposition of a porous metal coating, an anode coating, an electrolyte coating and a cathode coating is facilitated, the deposition of a compact electrolyte coating is also facilitated, the direct contact of fuel cell gas and oxygen is effectively isolated, further preferably, the included angle between the bottom surface and the side surface of the groove 101 is not less than 120 degrees, and the included angle between the side surface of the groove 101 and the surface of the current collector 1 at the edge of the groove 101 is not less than 120 degrees. In this preferred embodiment, it is advantageous to deposit porous metal, anode, electrolyte and cathode coatings in the corner regions of the sides and bottom of the groove and in the edge regions of the groove.
In some preferred embodiments, the edges of the anodic coating 3 extend onto the sides of the recess 101. According to the fuel cell provided by the invention, the edge of the anode coating extends to the side surface of the groove, the cathode coating and the anode coating are respectively positioned at two sides of the electrolyte coating, and the cathode coating and the anode coating are correspondingly arranged, so that the working efficiency of the cell can be improved.
In some preferred embodiments, the porous metal coating 2 has a thickness of 50 μm to 150 μm. In the invention, the porous metal coating 2 is positioned in the groove 101 and covers the bottom of the groove 101, and the porous metal coating with the thickness of micron order can be adopted.
In some preferred embodiments, the anode, electrolyte and cathode coatings have a thickness of 5 μm to 50 μm, respectively, and the anode, electrolyte and cathode coatings have porosities of 5% to 30%, 0.5% to 5% and 5% to 30%, respectively. Under the preferred scheme, the thicknesses of the anode coating, the electrolyte coating and the cathode coating are not less than 5 mu m, which is more beneficial to avoiding the local leakage spray phenomenon of the anode coating, the electrolyte coating and the cathode coating, and the anode coatingThe thickness of the electrolyte coating and the cathode coating is not higher than 50 mu m, which is more beneficial to reducing the volume and weight of the fuel cell unit. The thickness of the anode coating is not higher than 50 mu m, the anode coating is also more beneficial to improving the transmission efficiency of the hydrogen protons to the interface between the anode layer and the electrolyte layer after the fuel gas is decomposed into the hydrogen protons and electrons in the anode layer, improving the transmission efficiency of electrons, improving the working efficiency of the battery, ensuring that the thickness of the electrolyte coating is not lower than 5 mu m, being more beneficial to improving the sealing effect of the fuel battery, blocking the direct contact of the fuel battery gas and oxygen and avoiding the failure of the battery. The thickness of the electrolyte coating is not higher than 50 mu m, which is also more beneficial to improving the transmission efficiency of hydrogen protons from the interface of the anode coating and the electrolyte layer to the interface of the electrolyte coating and the cathode coating, and the thickness of the cathode coating is not higher than 50 mu m, which is also more beneficial to improving O 2- And improves the transmission efficiency of the water vapor and the discharge effect of the water vapor. The porosity of the anode coating is not lower than 5%, the efficiency and uniformity of the interface transmission of hydrogen protons to the anode layer and the electrolyte layer are improved, the porosity is not higher than 30%, the strength of the anode layer is ensured, the porosity of the electrolyte layer is not higher than 5%, defects are reduced, the ion conductivity of the electrolyte coating is improved, the fuel cell is effectively sealed to fully isolate the fuel gas side and the oxygen side, the strength of the electrolyte coating is improved, the porosity of the cathode coating is not higher than 30%, the strength of the cathode coating is improved, the strength of the cathode coating is not lower than 5%, and the water vapor discharge effect is improved.
In a second aspect, the present invention provides a battery pack formed by connecting solid oxide fuel cells according to the first aspect in series, wherein the battery pack is formed by connecting at least two solid oxide fuel cells in series, and the connection is performed in such a way that one side of one cell facing away from a groove contacts with one side of the other cell facing away from the groove, and the contact is that the side facing away from the groove contacts with an electrolyte coating on the surface of a current collector at the edge of the groove on the side of the groove.
The battery pack of the present invention is constructed by connecting the solid oxide fuel cells of the first aspect in series, and the weight and the volume of the battery pack are reduced, and since the edge portion of the electrolyte coating 4 of the solid oxide fuel cell extends onto the surface of the current collector 1 at the edge of the recess 101 and covers the surface of the current collector 1 at the edge of the recess 101, it is possible to prevent a short circuit between the cells.
In a third aspect, the present invention provides a method for preparing the solid oxide fuel cell unit according to the first aspect, the method comprising:
performing first deposition treatment on the bottom of the groove 101 of the current collector 1 to obtain a porous metal coating 2; the conditions of the first deposition process include: carrying out the first deposition treatment by adopting plasma spraying, wherein when the granularity of the metal powder is 20-40 mu m, the spraying power is 15-25 kw, and when the granularity of the metal powder is 41-70 mu m, the spraying power is 26-35 kw;
performing a second deposition treatment on the porous metal coating 2 to obtain an anode coating 3;
performing a third deposition treatment on the anode coating 3 to obtain an electrolyte coating 4, wherein the deposition process of the third deposition treatment extends to the surface of the current collector 1 at the edge of the groove 101;
a fourth deposition treatment is performed on the electrolyte coating layer 4 on the area corresponding to the anode coating layer 3, resulting in a cathode coating layer 5.
The solid oxide fuel cell monomer prepared by the preparation method has small volume and weight and can realize self-sealing. The granularity of the metal powder is not less than 20 mu m, the melting degree of the powder is more favorably controlled, the powder is prevented from being completely melted, the coating is too compact, the porosity is too low, the transmission of fuel gas in the porous metal coating is affected, the granularity of the metal powder is not more than 70 mu m, the powder deposition rate is more favorably avoided, and the bonding force of the coating is prevented from being too low. When the granularity of the metal powder is 20-40 mu m, the porous metal coating with proper pores can be prepared by adopting lower spraying power, the circulation of fuel gas is facilitated, the spraying power is not lower than 15kw, powder particles can be well melted, the porous metal layer with good binding force can be better obtained, the spraying power is not higher than 25kw, the coating is more favorable for avoiding too compact, the circulation of fuel gas is influenced, when the granularity of the metal powder is 41-70 mu m, the porous metal layer with proper pores can be prepared by adopting higher spraying power, the circulation of fuel gas is better facilitated, the spraying power is not lower than 26kw, the powder particles can be better melted, the coating with good binding force can be better obtained, the spraying power is not higher than 35kw, and the coating is more favorable for avoiding too compact, and the circulation of fuel gas is influenced. It will be appreciated that the grooves of the current collector 1 are sandblasted and cleaned prior to the first deposition process.
The porous metal coating can adopt flame spraying, electric arc spraying, plasma spraying, cladding and other coating methods to deposit metal powder or wire raw materials on the bottom 101 of the groove of the current collector 1, preferably adopts plasma spraying, and has higher coating deposition efficiency.
In some preferred embodiments, the deposition process of the second deposition process extends onto the sides of the recess 101.
The anode coating of the invention can be deposited on the porous metal coating by adopting a coating method such as flame spraying, plasma spraying and the like, preferably plasma spraying, the electrolyte coating can be deposited on the anode coating by adopting a plasma spraying, chemical or physical vapor deposition and the like, preferably plasma spraying, and the cathode coating can be deposited on the electrolyte coating by adopting a coating method such as flame spraying, plasma spraying and the like.
In some preferred embodiments, the second deposition process and the fourth deposition process are performed using plasma spraying, and the conditions of the second deposition process and the fourth deposition process include: the spraying power is 25-35 kw, and the powder feeding speed is 20-35 g/min. Under the preferred scheme, when the second deposition treatment and the fourth deposition treatment are carried out, the spraying power is not lower than 25kw, powder particles can be well melted, the coating with good binding force can be obtained more favorably, the spraying power is not higher than 35kw, the coating is more favorably prevented from being too compact, the powder feeding rate is not lower than 20g/min, the coating can form a certain pore, the gas transmission is more favorably realized, the powder feeding rate is not higher than 35g/min, and the coating with good binding force can be obtained more favorably.
In some preferred embodiments, the third deposition process is performed using plasma spraying, and the conditions of the third deposition process include: the spraying power is 40-50 kw, and the powder feeding speed is 10-15 g/min. Under the preferred scheme, during the third deposition treatment, the spraying power is not lower than 40kw, the powder particles can be well melted, the compact coating can be better obtained, the spraying power is not higher than 50kw, the workpiece is prevented from being overheated and deformed, the powder feeding speed is not lower than 10g/min, the coating can be efficiently formed, the powder feeding speed is not higher than 15g/min, the powder particles can be well melted, and the compact coating can be better obtained.
The invention will be further described in detail with reference to specific examples. The performance data involved is given as test methods.
Example 1
The preparation method of the solid oxide fuel cell monomer comprises the steps of carrying out sand blowing and cleaning treatment on a groove 101 extending from one side to the other side of a current collector 1, carrying out first deposition treatment on the bottom of the groove 101 by adopting plasma spraying to obtain a porous metal coating 2, wherein the cross section of the groove is trapezoid, the area of the longitudinal section of the groove 101 is gradually reduced from the top of the groove 101 to the bottom of the groove 101, the included angle between the bottom surface and the side surface of the groove 101 is 120 degrees, the included angle between the side surface of the groove 101 and the surface of the current collector 1 at the edge of the groove 101 is 120 degrees, the granularity of NiCr (nickel-chromium alloy) metal powder adopted by the first deposition treatment is 20-30 mu m, and the spraying power is 20kw; and (3) performing second deposition treatment on the porous metal coating 2 by adopting plasma spraying Ni-YSZ (nickel oxide plus yttrium oxide doped zirconia) to obtain an anode coating 3, wherein the spraying power of the second deposition treatment is 30kw, the powder feeding speed is 30g/min, third deposition treatment is performed on the anode coating 3 by adopting plasma spraying BZTYY (barium zirconium cerium yttrium oxide), the deposition process of the third deposition treatment extends to the surface of a current collector at the edge of the groove to obtain an electrolyte coating 4, the spraying power of the third deposition treatment is 50kw, the powder feeding speed is 15g/min, fourth deposition treatment is performed on the electrolyte coating 4 by adopting plasma spraying LSGF (lanthanum strontium cobalt iron oxide) at the area corresponding to the anode coating 3 to obtain a cathode coating 5, and the spraying power of the fourth deposition treatment is 30kw and the powder feeding speed is 30g/min.
The solid oxide fuel cell unit prepared in the example was provided with a porous metal coating 2, an anode coating 3, an electrolyte coating 4 and a cathode coating 5 in the groove 101 from bottom to top, wherein the porous metal coating 2 covers the bottom of the groove 101, the thickness of the porous metal coating 2 is 80 μm, the pores in the porous metal coating 2 are mutually communicated, the porosity measured by a metallographic test method is 20%, the anode coating covers the porous metal coating 2 and the edge extends to the side surface of the groove 101, the thickness of the anode coating is 15 μm, the porosity is 10%, the electrolyte coating 4 covers the anode coating and the edge extends to the surface of the current collector 1 at the edge of the groove 101 and covers the surface of the current collector 1 at the edge of the groove 101, the thickness of the electrolyte coating is 15 μm, the porosity is 3%, the cathode coating 5 and the anode coating 3 are respectively positioned at two sides of the electrolyte coating 4, the cathode coating 5 and the anode coating 3 are correspondingly arranged relative to the electrolyte coating 4, the thickness of the cathode coating is 15 μm, and the porosity is 10%. The discharge power of the battery cell of the embodiment is 0.8W/cm 2 。
Example 2
The process according to example 1 is carried out, except that the anode coating covers only the porous metal coating 2, the edges of which do not extend to the sides of the groove 101. The discharge power of the battery cell of the embodiment is 0.5W/cm 2 。
Example 3
The procedure of example 1 was followed, except that the porous metal coating layer 2 of the solid oxide fuel cell was 180 μm thick, and the discharge power of the cell of this example was 0.4W/cm 2 。
Example 4
The procedure of example 1 was followed, except that the metal powder used in the first deposition treatment had a particle size of 60 μm to 70 μm and a spray power of 35kw, and the porous metal coating 2 of the solid oxide fuel cell unit was prepared to have a thickness of 130 μm, pores in the porous metal coating 2 were connected to each other, and a porosity of 15% was measured by metallographic method. The discharge power of the battery cell of the embodiment is 0.7W/cm 2 。
Comparative example 1
With reference to example 1, except that the particle size of the metal powder used for the first deposition treatment was 20 μm to 30 μm, the spray power was 30kw, and the thickness of the porous metal coating layer 2 of the prepared solid oxide fuel cell unit was 50 μm, and the porosity in the porous metal coating layer 2 was 8%. The discharge power of the battery cell of this comparative example was 0.2W/cm 2 。
Comparative example 2
With reference to example 4, except that the metal powder used in the first deposition treatment had a particle size of 60 μm to 70 μm and a spray power of 40kw, the porous metal coating layer 2 of the solid oxide fuel cell unit was prepared to have a thickness of 100 μm, the porosity in the porous metal coating layer 2 was 8.5%, and the discharge power of the cell unit of this comparative example was 0.25W/cm 2 。
The porosity of the porous metal coating layers of comparative examples 1 and 1, 4 and 2 is not less than 10%, which can improve the fuel gas transmission efficiency and the discharge power of the battery, the side portions of the anode coating layers of comparative examples 1 and 2 extend to the side surfaces of the grooves, which is more advantageous for improving the discharge power of the battery, and the thickness of the porous metal coating layers of comparative examples 1 and 3 is not more than 150 μm, which is more advantageous for improving the discharge power of the battery.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (9)
1. A proton transmissive solid oxide fuel cell unit comprising:
a current collector (1) provided with a groove (101), the groove (101) extending from one side of the current collector (1) to the other side;
the porous metal coating (2) is positioned in the groove (101) and covers the bottom of the groove (101), holes in the porous metal coating are communicated with each other, the aperture is in the micro-nano to micro-micro level, and the porosity is 10% -50%;
-an anodic coating (3) located within the recess (101) covering the porous metal coating (2);
an electrolyte coating (4) partially located within the recess (101), which covers the anode coating (3), the edges of which extend onto the surface of the current collector (1) at the edges of the recess (101), which covers the surface of the current collector (1) at the edges of the recess (101);
the cathode coating (5) is positioned in the groove (101), the cathode coating (5) and the anode coating (3) are respectively positioned at two sides of the electrolyte coating (4), and the cathode coating (5) and the anode coating (3) are correspondingly arranged relative to the electrolyte coating (4);
the solid oxide fuel cell unit does not comprise a structure in which a porous metal support layer is arranged above the gas flow channel;
the thickness of the porous metal coating (2) is 50-150 mu m;
the thicknesses of the anode coating (3), the electrolyte coating (4) and the cathode coating (5) are respectively 5-50 mu m.
2. The solid oxide fuel cell unit according to claim 1, characterized in that the cross section of the groove (101) is trapezoidal, and the area of the longitudinal section of the groove (101) gradually decreases from the top of the groove (101) to the bottom of the groove (101).
3. The solid oxide fuel cell unit according to claim 2, characterized in that the bottom surface of the groove (101) forms an angle of not less than 120 ° with the side surface.
4. The solid oxide fuel cell unit according to claim 1, characterized in that the edges of the anode coating (3) extend onto the sides of the grooves (101).
5. The solid oxide fuel cell unit according to claim 1, characterized in that the porosities of the anode coating (3), the electrolyte coating (4) and the cathode coating (5) are 5% -30%, 0.5% -5% and 5% -30%, respectively.
6. A battery pack formed by connecting solid oxide fuel cells according to any one of claim 1 to 5 in series, wherein,
the battery pack is formed by connecting at least two solid oxide fuel battery cells in series, wherein one side of the single cell, which is far away from a groove (101), is contacted with one side of the other single cell, which is far away from the groove (101), and the contact is that the side of the single cell, which is far away from the groove (101), is contacted with an electrolyte coating (4) on the surface of a current collector (1) at the edge of the groove (101) at one side of the groove (101).
7. The method for preparing a solid oxide fuel cell unit according to any one of claims 1 to 5, characterized in that the method comprises:
performing a first deposition treatment on the bottom of the groove (101) of the current collector (1) to obtain a porous metal coating (2); the conditions of the first deposition process include: carrying out the first deposition treatment by adopting plasma spraying, wherein when the granularity of the metal powder is 20-40 mu m, the spraying power is 15-25 kw, and when the granularity of the metal powder is 41-70 mu m, the spraying power is 26-35 kw;
performing a second deposition treatment on the porous metal coating (2) to obtain an anode coating (3);
-performing a third deposition treatment on the anodic coating (3) obtaining an electrolyte coating (4), the deposition process of the third deposition treatment extending onto the surface of the current collector (1) at the edges of the grooves (101);
and carrying out fourth deposition treatment on the electrolyte coating (4) and the area corresponding to the anode coating (3) to obtain a cathode coating (5).
8. The method according to claim 7, wherein the second deposition treatment and the fourth deposition treatment are performed using plasma spraying, and conditions of the second deposition treatment and the fourth deposition treatment include: the spraying power is 25-35 kw, and the powder feeding speed is 20-35 g/min.
9. The method according to claim 7, wherein the third deposition treatment is performed by plasma spraying, and conditions of the third deposition treatment include: the spraying power is 40-50 kw, and the powder feeding speed is 10-15 g/min.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5328779A (en) * | 1990-02-01 | 1994-07-12 | Medicoat Ag | Fuel cell battery and solid electrolyte fuel cells therefore |
| RU2084053C1 (en) * | 1995-09-27 | 1997-07-10 | Российский федеральный ядерный центр - Всероссийский научно-исследовательский институт технической физики | Battery of fuel elements |
| US6261710B1 (en) * | 1998-11-25 | 2001-07-17 | Institute Of Gas Technology | Sheet metal bipolar plate design for polymer electrolyte membrane fuel cells |
| CN203871425U (en) * | 2014-06-06 | 2014-10-08 | 昆山艾可芬能源科技有限公司 | Solid oxide fuel cell and cell stack |
| CN203910913U (en) * | 2014-06-06 | 2014-10-29 | 昆山艾可芬能源科技有限公司 | Novel solid oxide fuel electrode current collector |
| CN109755615A (en) * | 2019-01-24 | 2019-05-14 | 深圳市致远动力科技有限公司 | The preparation method of full solid thin film fuel cell with three-dimensional micro-nano structure |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI373880B (en) * | 2008-10-16 | 2012-10-01 | Iner Aec Executive Yuan | Solid oxide fuel cell and manufacture method thereof |
-
2023
- 2023-11-29 CN CN202311606114.6A patent/CN117317325B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5328779A (en) * | 1990-02-01 | 1994-07-12 | Medicoat Ag | Fuel cell battery and solid electrolyte fuel cells therefore |
| RU2084053C1 (en) * | 1995-09-27 | 1997-07-10 | Российский федеральный ядерный центр - Всероссийский научно-исследовательский институт технической физики | Battery of fuel elements |
| US6261710B1 (en) * | 1998-11-25 | 2001-07-17 | Institute Of Gas Technology | Sheet metal bipolar plate design for polymer electrolyte membrane fuel cells |
| CN203871425U (en) * | 2014-06-06 | 2014-10-08 | 昆山艾可芬能源科技有限公司 | Solid oxide fuel cell and cell stack |
| CN203910913U (en) * | 2014-06-06 | 2014-10-29 | 昆山艾可芬能源科技有限公司 | Novel solid oxide fuel electrode current collector |
| CN109755615A (en) * | 2019-01-24 | 2019-05-14 | 深圳市致远动力科技有限公司 | The preparation method of full solid thin film fuel cell with three-dimensional micro-nano structure |
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