CN109980238B - Manufacturing method of membrane electrode structure and fuel cell - Google Patents
Manufacturing method of membrane electrode structure and fuel cell Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8803—Supports for the deposition of the catalytic active composition
- H01M4/881—Electrolytic membranes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8825—Methods for deposition of the catalytic active composition
- H01M4/8828—Coating with slurry or ink
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- 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
- H01M8/1004—Fuel cells with solid electrolytes characterised by membrane-electrode assemblies [MEA]
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Fuel Cell (AREA)
Abstract
A manufacturing method of a membrane electrode structure and a fuel cell belong to the field of fuel cells. The membrane electrode structure includes a first electrode, an electrolyte layer, and a second electrode. A network partition structure is distributed in the first electrode and/or the second electrode. The thermal expansion coefficient of the network partition structure is equal to or less than that of the electrolyte layer. The manufacturing method comprises the following steps: an intermediate body is provided that includes an electrolyte layer, and a network partition structure formed on a first surface and/or a second surface of the electrolyte layer, the network partition structure partitioning the first surface and/or the second surface of the electrolyte layer into a void region and a coverage region. Forming a first electrode made of a first electrode material on a first surface side of the intermediate body, and forming a second electrode made of a second electrode material on a second surface side of the intermediate body; the first electrode material and/or the second electrode material covers the void region and/or the coverage region. The method improves the yield of the fuel cell in a simpler and easier way.
Description
Technical Field
The invention relates to the field of fuel cells, in particular to a manufacturing method of a membrane electrode structure and a fuel cell.
Background
With the rapid development of the mobile internet and the internet of things, various portable mobile devices (such as a palm computer, a mobile phone, various wearable devices such as a watch, and various electronic machines) are becoming more and more popular. In use, such devices often involve endurance problems, i.e. insufficient power. With the development of semiconductor technology, various devices are being miniaturized. The use of fuel cells with unique properties for the power source of these devices has promising promise.
Fuel cells are devices that convert chemical energy of a chemical reaction directly into electrical energy. Which uses fuel and oxidant as power generation raw materials. There are many types of fuel cells and various methods of classification.
As an important class of Fuel cells, Fuel cells (SOFC) have their own unique advantages. And accordingly, the service performance and the value are excellent. For example, fuel cells have relatively high operating temperatures (e.g., 800-1000 ℃). The fuel cell is an all-solid-state device, and only two-phase (gas-solid) reaction is involved in the fuel reaction process, so that the structure can be simplified to a certain extent without complicated electrolyte management.
Some SOFCs currently have a thin film structural design. The fabrication process of such an SOFC needs to be specifically examined, and the use thereof has a problem in combination with conditions such as the operating temperature. These have limited further development of plate-type SOFCs.
Generally, one of the main problems of SOFCs is: plate-type SOFCs tend to exhibit conditions that are prone to crack formation, cracking, peeling, etc. during actual manufacturing and use.
The information disclosed in this background section is only for enhancement of understanding of the general background of the invention and should not be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person skilled in the art.
Disclosure of Invention
Based on the shortcomings of the prior art, the present invention provides a method for fabricating a membrane electrode structure and a fuel cell, so as to partially or completely improve or even solve the above problems.
The invention is realized by the following steps:
in a first aspect, examples of the invention provide a method of making a membrane electrode structure.
The membrane electrode structure can be used in a fuel cell, such as a fuel cell.
The membrane electrode structure includes a first electrode, an electrolyte layer, and a second electrode that are sequentially stacked.
The electrolyte layer is formed by extending from the first surface to the second surface.
The first electrode is located on the first surface side of the electrolyte layer, and the second electrode is located on the second surface side of the electrolyte layer.
A network partition structure is distributed in the first electrode and/or the second electrode, and the thermal expansion coefficient of the network partition structure is less than or equal to that of the electrolyte layer;
the manufacturing method comprises the following steps:
providing an intermediate body, wherein the intermediate body comprises an electrolyte layer and a network partitioning structure formed on the first surface and/or the second surface of the electrolyte layer, and the network partitioning structure partitions the first surface and/or the second surface of the electrolyte layer into a vacant region and a coverage region;
forming a first electrode made of a first electrode material on a first surface side of the intermediate body, and forming a second electrode made of a second electrode material on a second surface side of the intermediate body;
the first electrode material and/or the second electrode material covers the void region and/or the covered region.
In the above manufacturing process, in an example, a network partition structure is manufactured between the electrode and the electrolyte layer. A network partitioning structure may be used to partition the electrodes.
By such means, the electrode of the complete continuum structure is physically divided into a plurality of sections by the network division structure, and the network division structure can be used as a boundary between the sections.
Since the electrode is divided into a plurality of parts, the thermal expansion of the electrode is well dispersed and suppressed during the manufacturing and using processes of the fuel cell, so that the stress of the thermal expansion is dispersed and partially unloaded, thereby facilitating the matching between the electrolyte layer and the electrode, and avoiding mutual falling and separation due to too large difference of deformation (such as thermal expansion) of the electrolyte layer and the electrode.
With reference to the first aspect, in a first possible embodiment of the present invention, the method for making the intermediate comprises:
and manufacturing a network division structure on the first surface and/or the second surface by taking the electrolyte layer as a support.
The electrolyte layer has proper structural stability, and can keep the shape and the structural stability in the manufacturing process of the membrane electrode structure, so that the electrolyte layer can be used as an attachment matrix of other components (a first electrode, a second electrode and a network division structure) and provides a point of force, and the arrangement and the manufacture of other structures and functional layers in the membrane electrode structure are facilitated.
With reference to the first possible implementation manner of the first aspect, in a second possible implementation manner of the first aspect, the method for manufacturing the electrolyte layer includes:
molding a material for making the electrolyte into a desired shape in a fluid state or a viscous fluid state and curing;
optionally, the electrolyte is made of a material that is shaped into a desired shape in a solid state, optionally hardened.
Since the electrolyte layer serves as a support, it can be selected to be made solid. The manufacturing method of the compound has certain differences according to different raw materials.
For example, when the raw material from which the electrolyte is made is a solid having an appropriate hardness, it may be directly made (cut, stamped, molded, etc.) into a desired shape and then hardened to a desired hardness according to an optional hardening operation.
For example, when the starting material from which the electrolyte is made is in a fluid or viscous fluid state, it can be readily shaped (e.g., by constraining the shape with a mold) and then cured by suitable means and means to give it a defined and stable shape capable of supporting other structural layers.
In combination with the second possible implementation manner of the first aspect, in a third possible implementation manner of the first aspect, a method for molding a manufacturing material of an electrolyte into a desired shape in a fluid state or a viscous fluid state and curing the manufacturing material includes: tape casting and extrusion molding.
As described above, if the electrolyte layer is made of a different material, it is necessary to form the support by selecting a corresponding process. For example, the solid feedstock can be formed by extrusion; the fluid or viscous fluid feedstock may be cast or extruded and cured in a suitable manner.
With reference to the first, second, or third possible implementation manner of the first aspect, in a fourth possible implementation manner of the first aspect, the method for manufacturing the network partition structure on the first surface and/or the second surface by using the electrolyte layer as a support includes:
and transferring the manufacturing material of the network partition structure to a support body by using a fluid or a viscous fluid, and solidifying the manufacturing material of the network partition structure.
The network partition structure is used in a fluid or viscous fluid form, so that the forming is facilitated, and the operation is simpler and more convenient.
With reference to the fourth possible implementation manner of the first aspect, in a fifth possible implementation manner of the first aspect, the method for transferring the material for manufacturing the network partition structure to the support body in a fluid or viscous fluid includes: ceramic ink-jet, screen printing.
In order to form the electrolyte layer by using the fluid or viscous fluid electrolyte, a ceramic printing or screen printing method may be used.
With reference to the first aspect, in a sixth possible implementation manner of the first aspect, the method for manufacturing the first electrode made of the first electrode material on the first surface side of the intermediate body includes: the first electrode material is transferred to the first surface side of the intermediate body in a fluid or viscous fluid state, and the first electrode material is cured.
The first electrode is treated in a fluid and viscous fluid manner as required and transferred to the intermediate body surface. Therefore, the manufacturing process of the electrode can be simplified, and the efficiency can be improved.
With reference to the first aspect or the sixth possible implementation manner of the first aspect, in a seventh possible implementation manner of the first aspect, the method for manufacturing the second electrode made of the second electrode material on the second surface side of the intermediate body includes: the second electrode material is transferred to the first surface side of the intermediate body in a fluid or viscous fluid state, and the second electrode material is cured.
The first electrode is treated in a fluid and viscous fluid manner as required and transferred to the intermediate body surface. Therefore, the manufacturing process of the electrode can be simplified, and the efficiency can be improved. Because the first electrode and the second electrode are used in a fluid or viscous fluid mode, the multiplexing of the equipment can be realized to a certain extent, and the complexity of manufacturing the equipment is simplified.
With reference to the seventh possible implementation manner of the first aspect, in an eighth possible implementation manner of the first aspect, the method for transferring the first electrode material to the first surface side of the intermediate body in a fluid or viscous fluid state includes: coating;
the method of transferring the second electrode material to the first surface side of the intermediate body in a fluid or viscous fluid state includes: and (4) coating.
Transferring the first electrode material and the second electrode material by means of coating is an easy to implement and simple method.
In a second aspect, an example of the invention provides a fuel cell.
The fuel cell comprises the membrane electrode structure manufactured by the manufacturing method of the membrane electrode structure.
In the process of manufacturing a fuel cell, the above method of manufacturing a membrane electrode structure is applied to divide/partition the anode into a plurality of portions. The parts are partially or completely separated by the network partition structure (taking the network partition structure as a boundary), so that the thermal expansion stress and deformation of the anode can be well weakened and dispersed, the thermal expansion of the electrolyte layer is properly matched, and the cracking and falling of the membrane electrode structure are further avoided.
Has the advantages that:
the method for manufacturing the membrane electrode structure provided by the embodiment of the invention divides the electrode (the first electrode and/or the second electrode) in the membrane electrode structure, so that the electrode of the complete continuum structure is divided into a plurality of parts. And, adjacent two parts among the plurality of parts may be structured as a boundary by network division. In this way, due to the arrangement of the network dividing structure, it is possible to partially or completely correct the thermal expansion mismatch between the electrode and the electrolyte layer, and therefore, the problem that the two are not likely to come off each other due to a large difference in thermal expansion deformation is not likely to occur.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below.
FIG. 1 is a schematic diagram of a first viewing angle of a first film electrode structure in an example of the invention;
FIG. 2 is a schematic diagram showing the membrane electrode structure of FIG. 1 from a second perspective;
FIG. 3 is a schematic diagram of a second viewing angle of a second film electrode structure in an example of the invention;
FIG. 4 is a schematic diagram of a third membrane electrode assembly according to an example of the present invention from a second perspective;
FIG. 5 is a schematic diagram of a fourth membrane electrode structure in an example of the invention from a second viewing angle;
fig. 6 is a schematic diagram illustrating a fifth film electrode structure according to an exemplary embodiment of the present invention from a first viewing angle.
Icon: 100-a membrane electrode structure; 102-a cathode; 103-an electrolyte layer; 104-an anode; 105-dividing the material layer; 1041 a-region; 1051 a-line segment; 1041 b-region; 1051 b-line segment; 1041 c-region; 1051 c-segmenting the material segments; 1041 d-region; 1051 d-dividing the material segments; 200-a membrane electrode structure; 204-anode; 205-dividing the material layer.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The following is a detailed description of a method for manufacturing a membrane electrode structure and a fuel cell according to an embodiment of the present invention:
in the process of implementing the invention, the inventor finds out through research that the fuel cell has unique advantages, but has certain problems to be solved.
For example, during the manufacturing and use (repeated start-up) of the battery, the problems of cracking, structural layer peeling (such as separation of the electrode and the electrolyte) and the like are easy to occur.
Such problems are manifested both during the manufacturing process and during the use process. With respect to such problems, it is generally considered in the related research and technology that this is caused by weak bonding between layers of different structures (e.g., electrode and electrolyte). However, the inventors have found in further studies that one of the main causes of this problem is the mismatch problem between different structural layers. For example, because of the thermal expansion (the main factor) and the degree of shrinkage caused by cooling between different structural layers, the two cannot be matched well when relative deformation (expansion) occurs. The substance having a large thermal expansion coefficient and the substance having a small thermal expansion coefficient cause stress accumulation due to the difference in expansion, and the joint surfaces may be separated from each other.
For example, in some fuel cells, the problems are: the perovskite cathodes such as LSC, LSCF, SSC and the like have higher catalytic activity and conductivity at medium and low temperature, but the thermal expansion coefficient is obviously higher than that of the electrolyte. Alternatively, its anodic problem: as the Ni content increases, the thermal expansion coefficient of the Ni metal anode increases. In order to maintain a good thermal expansion match, lower Ni contents are often used and the conductivity of the anode decreases.
In this regard, the inventors believe that the above problems can be ameliorated or alleviated by adjusting the thermal expansion coefficients (deformation, e.g. expansion, contraction) of the different structural layers.
Although this may be adjusted by the selection of materials, merely changing the materials may cause some properties (e.g., power, stability, etc.) of the battery itself to be deteriorated, considering the characteristics of the battery itself, such as electrode reaction, working environment (indoor or outdoor at high or low temperature), etc.
In other words, merely adjusting the materials of the electrodes and/or electrolyte to achieve thermal expansion matching may cause other problems, such that such attempts may not be desirable or better alternatives.
In view of the above, in the present example, the inventors have attempted to improve the membrane electrode structure of a fuel cell.
In an example, the electrode is divided into a plurality of regions which are smaller than the original size, a network division structure is constructed at the boundary of adjacent regions of the plurality of regions, and the network division structure is used as the boundary of the two adjacent regions.
Due to the existence of the network partition structure as a boundary, the structural integrity of the electrode as a whole is broken, and its deformation (volume expansion or contraction) as a whole is dispersed in each region to become smaller deformation. Thus, the thermal expansion deformation stress of the electrode is released and is not easily separated from the electrolyte. At the same time, since the coefficient of thermal expansion of the dividing material layer is appropriately selected, it is also less prone to large volume changes and thus is more compatible with the electrolyte and the electrodes.
In some examples of the invention, such membrane electrode structures and methods of making the same may be briefly described as follows:
the membrane electrode structure includes a first electrode, an electrolyte layer, and a second electrode that are sequentially stacked.
The electrolyte layer is formed by extending from the first surface to the second surface and is positioned between the first electrode and the second electrode. Alternatively, the first electrode is located on the first surface side of the electrolyte layer, and the second electrode is located on the second surface side of the electrolyte layer.
As an example of the electrode division, a network division structure is distributed in the first electrode and/or the second electrode, and a thermal expansion coefficient of the network division structure is equal to or less than a thermal expansion coefficient of the electrolyte layer.
In other words, in some examples, only the first electrode in the membrane electrode structure has a network partition structure. In other examples, only the second electrode in the membrane electrode structure has a network partition structure. Alternatively, in other examples, the membrane electrode structure has a network partition structure for each of the first electrode and the second electrode.
Based on the membrane electrode structure, the manufacturing method comprises the following steps: an intermediate body is provided, the intermediate body including an electrolyte layer, a network partition structure formed on a first surface and/or a second surface of the electrolyte layer, the network partition structure partitioning the first surface and/or the second surface of the electrolyte layer into a void region and a coverage region. A first electrode made of a first electrode material is formed on a first surface side of the intermediate body, and a second electrode made of a second electrode material is formed on a second surface side of the intermediate body. The first electrode material and/or the second electrode material covers the void region and/or the coverage region.
In a first possible example, a method of fabricating a membrane electrode structure includes: an intermediate body is provided, the intermediate body including an electrolyte layer, a network partition structure formed on a first surface of the electrolyte layer, the network partition structure partitioning the first surface of the electrolyte layer into a void region and a coverage region. A first electrode made of a first electrode material is formed on a first surface side of the intermediate body, and a second electrode made of a second electrode material is formed on a second surface side of the intermediate body. The first electrode material covers the void region (which may also be a covered region).
Or the manufacturing method of the membrane electrode structure comprises the following steps: an intermediate body is provided, the intermediate body including an electrolyte layer, a network partition structure formed on a first surface of the electrolyte layer, the network partition structure partitioning the first surface of the electrolyte layer into a void region and a coverage region. A first electrode made of a first electrode material is formed on a first surface side of the intermediate body, and a second electrode made of a second electrode material is formed on a second surface side of the intermediate body. The first electrode material covers the void region and the covered region.
In a second possible example, a method of fabricating a membrane electrode structure includes: providing an intermediate body, wherein the intermediate body comprises an electrolyte layer and a network dividing structure formed on the second surface of the electrolyte layer, and the network dividing structure divides the second surface of the electrolyte layer into a vacant area and a coverage area. A first electrode made of a first electrode material is formed on a first surface side of the intermediate body, and a second electrode made of a second electrode material is formed on a second surface side of the intermediate body. The second electrode material covers the void region (which may also be a covered region).
Or the manufacturing method of the membrane electrode structure comprises the following steps: providing an intermediate body, wherein the intermediate body comprises an electrolyte layer and a network dividing structure formed on the second surface of the electrolyte layer, and the network dividing structure divides the second surface of the electrolyte layer into a vacant area and a coverage area. A first electrode made of a first electrode material is formed on a first surface side of the intermediate body, and a second electrode made of a second electrode material is formed on a second surface side of the intermediate body. The second electrode material covers the void region and the covered region.
In a third possible example, a method of making a membrane electrode structure includes: providing an intermediate body, wherein the intermediate body comprises an electrolyte layer and a network partitioning structure formed on a first surface and a second surface of the electrolyte layer, and the network partitioning structure partitions the first surface and the second surface of the electrolyte layer into a blank region and a coverage region. A first electrode made of a first electrode material is formed on a first surface side of the intermediate body, and a second electrode made of a second electrode material is formed on a second surface side of the intermediate body. The first electrode material and the second electrode material cover the electrolyte layer in a void region (may be a covered region) on the first surface side and a void region (may be a covered region) on the second surface side, respectively.
Or the manufacturing method of the membrane electrode structure comprises the following steps: providing an intermediate body, wherein the intermediate body comprises an electrolyte layer and a network dividing structure formed on a first surface and a second surface of the electrolyte layer, and the network dividing structure divides the first surface and the second surface of the electrolyte layer into a vacant area and a coverage area. A first electrode made of a first electrode material is formed on a first surface side of the intermediate body, and a second electrode made of a second electrode material is formed on a second surface side of the intermediate body. The first electrode material and the second electrode material cover the electrolyte layer in a void region and a coverage region on the first surface side and a void region and a coverage region on the second surface side, respectively.
Generally, in a fuel cell, a first electrode may be implemented as an anode for preparation and use; accordingly, the second electrode may be implemented as a cathode to be prepared and used. After the network structure is fabricated, the anode or cathode is optionally fabricated in a different desired order. For example, after the network partition structure is formed on the first surface of the electrolyte layer, the cathode is formed on the second surface of the electrolyte layer, and then the anode is formed on the first surface side of the electrolyte layer. Alternatively, after the network partition structure is formed on the first surface of the electrolyte layer, the anode is formed on the first surface of the electrolyte layer, and then the anode is formed on the second surface side of the electrolyte layer. When the network partition structure on the surface of the electrolyte layer has other distribution modes as described above, the order of manufacturing the anode and the cathode can be selected accordingly.
In order to more clearly illustrate the method of fabricating the membrane electrode structure, the membrane electrode structure and the method of fabricating the same are more fully described in the examples.
Taking as an example the division of a first electrode (e.g. an anode; correspondingly, a second electrode may be a cathode), the membrane electrode structure comprises a cathode, an electrolyte layer and an anode, which are arranged in a stack in that order. A network partition structure is distributed in the anode. And the coefficient of thermal expansion of the network dividing structure is equal to or less than the coefficient of thermal expansion of the electrolyte layer. As an alternative implementation, such a membrane electrode structure 100 may be illustrated by fig. 1, which includes a cathode 102, an electrolyte layer 103, an anode 104, and a separator material layer 105 distributed in the anode 104.
It should be noted that the thickness of each structural layer (extending from the cathode 102 to the anode 104) in fig. 1 is merely an exemplary illustration, which does not mean that the thickness of each functional layer of the membrane electrode structure prepared by the method provided by the present invention needs to be designed and manufactured in the manner shown in fig. 1. For example, in fig. 1, the thickness of the cathode 102 is greater than the thickness of the anode 104, and in other examples of the invention, the thickness of the cathode 102 may be less than (or equal to) the thickness of the anode 104.
Fig. 2 is a schematic structural view of the membrane electrode assembly 100 of fig. 1 in a plan view (from the anode toward the cathode). Referring to fig. 1 and 2, in fig. 2, the black portion is the anode 104, and the white portion is the partition material layer 105. As is apparent, in fig. 2, the anode 104 includes 16 fine black regions. The divided material layer 105 includes 3 × 3-9 line segments 1051a distributed in a vertical and horizontal (three vertical and three horizontal) manner at intervals. The anode 104 is divided into 16 finer regions 1041a by 9 line segments constituting the dividing material layer 105, and the line segment 1051a (which may be a part thereof) is used as a boundary between two adjacent regions 1041 a.
The dividing material layer 105 may also have other types of arrangements to enable the anode to be divided into various forms, and such divisions may be illustrated in fig. 3 to 5.
Referring to fig. 1 and 3, as shown in fig. 3, the anode 104 is divided into a plurality of finer honeycomb-like regions 1041b by a plurality of line segments constituting the dividing material layer 105, and the line segment 1051b (which may be a part thereof) is used as a boundary between two adjacent regions 1041 c.
Referring to fig. 4 in conjunction with fig. 1 and 4, the example of fig. 4 is that the gray black portion is a region 1041c of the anode, which is divided into regions, and has a substantially regular quadrilateral structure and is a discrete body. The white portion is a divided material segment 1051c in the divided material layer, is substantially a combination of a plurality of line segments, and is a continuous body.
Referring to fig. 5 in conjunction with fig. 1 and 5, the example of fig. 5 is that the gray black portion is a region 1041d of the anode, which is divided into regions, has a substantially regular quadrilateral structure, and is a continuous body. The white portion is a divided material segment 1051d in the divided material layer, and is substantially a cross-shaped structure in which two line segments are combined, and a plurality of the cross-shaped structures are arranged at intervals and are discrete bodies.
In the above membrane electrode structure, the anode is divided by the network dividing structure of different structures, and thus, the anode exhibits different dividing manners. The thickness of the network partition structure is equal to the thickness of the anode (the length extending from the cathode to the anode). Of course, the thickness of the network dividing structure may not be equal to the thickness of the anode. For example, the thickness of the network partition structure is greater than the thickness of the anode. Alternatively, the thickness of the network partition structure is smaller than that of the anode, and such an example can be illustrated in fig. 6, which will be mentioned later.
The above membrane electrode structure 100 can be fabricated by the following method.
The manufacturing method comprises the following steps:
an intermediate body is provided, the intermediate body including an electrolyte layer, a network partition structure formed on a first surface and/or a second surface of the electrolyte layer, the network partition structure partitioning the first surface and/or the second surface of the electrolyte layer into a void region and a coverage region.
The intermediate can be prefabricated and directly used when manufacturing the membrane electrode structure; alternatively, the intermediate is prepared in situ during the fabrication of the membrane electrode structure. Generally, pre-fabrication and inspection to obtain high quality and consistent intermediates is an alternative solution based on the needs of mass production and quality control.
In the membrane electrode structure shown in fig. 1 and 2, the anode is divided, and thus the membrane electrode structure can be described by being supported by the electrolyte layer and divided by the anode. Alternatively, the method of making an intermediate comprises: and manufacturing a network division structure on the first surface and/or the second surface by taking the electrolyte layer as a support. Since the electrolyte layer is a support, it has appropriate structural strength and stability as the name suggests, so that it is possible to improve appropriate supporting force. In other words, the electrolyte layer can provide a stable fabrication force for other structures and members in the membrane electrode structure to maintain the membrane electrode structure with a desired profile structure.
The method for manufacturing the electrolyte layer can be distinguished according to different manufacturing raw materials. The method for manufacturing the electrolyte layer comprises the following steps: molding a material for making the electrolyte into a desired shape in a fluid state or a viscous fluid state and curing; alternatively, the material from which the electrolyte is made is molded into a desired shape in a solid state, optionally hardened.
For example, when the raw material for producing the electrolyte layer is a fluid or viscous fluid, the method for producing the electrolyte layer includes: the manufacturing material of the electrolyte layer is molded into a desired shape in a fluid state or a viscous fluid state and cured. That is, the electrolyte layer is made of a material that is dispersed with a suitable dispersant to obtain a fluid or viscous fluid, which is then transferred to a mold or container and allowed to solidify to maintain the desired shape.
Alternatively, the method of molding and solidifying the starting material for the electrolyte layer in a fluid state or a viscous fluid state into a desired shape includes: tape casting or extrusion molding. For example, in the case of a flat cell, when the electrolyte layer has a flat plate-like structure, the production raw material may be poured into a flat plate-like container or tank or a mold, and then cured by means of, for example, heating, sintering, or the like. In the case of the tube-type battery, when the electrolyte layer has a tubular structure, the production raw material may be produced by extrusion. In an example, the electrolyte layer (sheet) may be made of a material selected from rare earth-doped ceria or rare earth-doped zirconia (the rare earth element may be cerium, lanthanum, gadolinium, or the like). In one example, the electrolyte layer is formed as a thin film, and the thickness of the electrolyte layer can be set as desired, for example, 1 to 50 micrometers, or 2 to 44 micrometers, or 10 to 33 micrometers.
After the electrolyte layer is obtained, a network partition structure is optionally fabricated on the first surface and/or the second surface thereof. The method for manufacturing the network partition structure on the first surface and/or the second surface by taking the electrolyte layer as a support comprises the following steps: and transferring the manufacturing material of the network partition structure to a support body by using a fluid or a viscous fluid, and solidifying the manufacturing material of the network partition structure. The method for transferring the material for manufacturing the network partition structure to the support body by fluid or viscous fluid comprises the following steps: ceramic ink-jet, screen printing. In an example, as shown in fig. 1, a network partition structure is fabricated on a first surface of an electrolyte layer.
It should be understood that the raw material for making the network dividing structure is not attached to the surface of the electrolyte layer in a completely covering manner, since it is necessary to divide the anode by using the network dividing structure. Conversely, part of the surface of the electrolyte layer is covered, while the other part is uncovered. In the example, as shown in fig. 2, the starting material for making the network partition structure is formed on the surface of the electrolyte layer in a crisscross manner.
The network partitioning structure may be selected differently according to the type of battery. For example, rare earth doped ceria or rare earth doped zirconia, alumina, Mg-Al spinel, silicates, and the like. In the example, the network partition structure is chosen to be an oxide. The preparation method comprises the steps of processing raw materials in the form of dispersion liquid, and transferring the raw materials to the surface of an electrolyte layer of an intermediate body by means of screen printing, ceramic ink-jet printing and the like. The above-fabricated network partition structure may have a suitable thickness, for example, a thickness of 1 to 50 μm; or 3-46 μm; or 12-38 μm; or 20 to 50 μm.
After the electrolyte layer and the network partition structure are fabricated, a first electrode (e.g., an anode) and a second electrode (e.g., a cathode) are fabricated, respectively, in an optional order as needed. That is, the first electrode made of the first electrode material is formed on the first surface side of the intermediate body, and the second electrode made of the second electrode material is formed on the second surface side of the intermediate body, so that the first electrode material and/or the second electrode material covers the vacant region and/or the covered region.
In an example, an anode is fabricated on a first surface of the electrolyte layer such that the anode covers a void area of the electrolyte layer. The method of forming a first electrode made of a first electrode material on the first surface side of the intermediate body includes: the first electrode material is transferred to the first surface side of the intermediate body in a fluid or viscous fluid state, and the first electrode material is cured. In an example, a method of transferring a first electrode material to a first surface side (anode side) of an intermediate body in a fluid or viscous fluid state includes coating.
In some examples, the anode may be selected to be an electrode made from elemental nickel or a cermet electrode made from a nickel alloy (Ni alloys include Ni-Co, Ni-Fe, Ni-Pt, etc., with the Ni or Ni alloy then forming a cermet with ceria/zirconia, etc. in a cermet, the volume fraction of metal is between 20-80%).
Wherein the anode material covers both the electrolyte layer and the network dividing structure when the anode material is bonded to the electrolyte layer and the network dividing structure surface, optionally by brushing. In such an example, the anode includes a first cover portion covering the electrolyte layer and a second cover portion covering the network partition structure, as shown in fig. 6. The membrane electrode structure 200 includes a cathode 102, an electrolyte layer 103, an anode 204, and a separator layer 205 distributed in the anode 204. Because the anode covers the network partition structure, the anode is a continuous body, and the thickness of the anode is larger than that of the network partition structure.
In other examples, the anode material may only cover the electrolyte layer and not the network partition structure, such as shown in fig. 1. In fig. 1, the anode 104 and the partition material layer 105 have the same thickness. It is understood that in other examples, the thickness of the anode 104 may be less than the thickness of the dividing material layer 105; alternatively, the thickness of the anode 104 may be larger than the thickness of the partition material layer 105.
After the electrolyte layer, the network partition structure and the anode are fabricated, the three can be combined by co-sintering, and the sintering temperature can be, for example, 1200-. Alternatively, in another example, the electrolyte layer and the network partition structure are sintered (sintering temperature is 1200 to 1500 degrees celsius) after being formed, and then sintered (sintering temperature is 1200 to 1500 degrees celsius) after the anode is formed. In the sintering method which is thus subjected to two or more times, the temperature of each sintering may be the same or may be adjusted according to actual selection. In other words, the respective structural and functional layers may be subjected to an operation of being either cured or hardened as they are being fabricated, and during which process bonding between adjacent layers is taking place. In other examples of the present invention, it is also possible to arrange layers having a desired shape (e.g., size, thickness, etc.) in a stack with the layers having appropriate bonding forces, and then perform a one-time curing operation, and achieve bonding of the layers in the process. Alternatively, each layer may be rigid and directly plastic without the need for additional hardening or curing operations; and the various may be bonded to each other by a suitable adhesive.
Next, after the electrolyte layer, the network partition structure, and the anode are fabricated and sintered to solidify and bond the different layers, a cathode is fabricated. That is, a second electrode made of a cathode material is formed on the second surface side (cathode side) of the intermediate body. The manufacturing method comprises the following steps: the second electrode material is transferred to the first surface side of the intermediate body in a fluid or viscous fluid state, and the second electrode material is cured. The method of transferring the second electrode material to the first surface side of the intermediate body in a fluid or viscous fluid state includes coating.
In some examples, the obtaining method of the cathode is freely selected according to the difference of the cathode material. In an example, the first electrode material may be selected to be a metal oxide electrode. Optionally, the metal oxide electrode is made of a ternary alloy oxide or a quaternary alloy oxide. Optionally, the metal element in the ternary alloy oxide comprises a first element combination or a second element combination, wherein the first element combination comprises samarium, strontium and cobalt, so the ternary alloy oxide can be SmxSryCoOz(SSC). Some specific examples may be Sm0.5Sr0.5Co3O3. The second element combination includes lanthanum, strontium, and cobalt, and thus. The ternary alloy oxide may be LaxSryCoOz(LSC). In some specific examples, the ternary alloy oxide may be La0.5Sr0.5CoO3. Alternatively, the cathode may be selected to be another perovskite or perovskite-like electrode, such as LaSrCoO4、LaNiO3. The metal element in the quaternary alloy oxide includes lanthanum, strontium, cobalt, and iron, such as LaxSryCoFeOz(LSCF). In some specific examples, the quaternary alloy oxide may be La1-xSrxCo0.2Fe0.8O3(wherein 0.1)<x<0.6)。
Specifically, the above first electrode material may be made in a slurry form and used, for example, by brush coating it on the surface of the network partition structure, then sintering at 900 to 1200 degrees celsius to be cured, and bonded to the electrolyte layer and/or the surface of the network partition structure.
The membrane electrode structure capable of being used for the fuel cell is manufactured based on the above manner, the problem of anode cracking is well suppressed and solved, and the yield of the electrode and the fuel cell manufactured therefrom is improved to 95% or more. The yield of the existing membrane electrode structure (the cathode and the anode are both continuous bodies, are not divided, and are not provided with a network dividing structure) and the fuel cell manufactured by the membrane electrode structure is only 40-60%.
Based on the membrane electrode structure, the fuel cell is also provided in an example, and the fuel cell comprises the membrane electrode structure manufactured by the manufacturing method. Fuel cells include fuel (e.g., hydrogen) and oxidant (oxygen) delivery structures as needed for practical use.
It should be noted that, the above is described by taking a cell of a flat plate structure as an example, and accordingly, the membrane electrode structure obtained by the foregoing method is also a flat plate or flat plate cell. In other examples, the battery may be fabricated as a tube type battery, and accordingly, the battery structure may be fabricated as a tube type. Of course, the battery may also be fabricated as a corrugated plate type, a flat tube type, or other shape battery, as desired.
Since the cell can be selected from a variety of different types, the membrane electrode structure also needs to be appropriately adjusted when different cell types are selected as targets for cell fabrication. The adjustment referred to here is an adjustment for the cell type, and the structural layer distribution (cathode, electrolyte layer, network partition structure, and anode) of the membrane electrode structure may not be adjusted, but the manufacturing process and material of each layer may be freely selected in combination.
It is understood that, as previously described, in the membrane electrode structure, in addition to the first division (dividing the cathode, undivided anode) and the second division (dividing the anode, undivided cathode) schemes, there may be a third division (dividing the anode, dividing the cathode). The above-described various division methods can be freely selected and combined with various types of batteries (flat, tubular, corrugated, flat tubular, or other shaped batteries). Similarly, the materials and manufacturing methods of the various structural layers in the membrane electrode structure can be freely selected and combined with the different division modes and the different cell types.
In addition, in the case of the tube-type fuel cell and the membrane electrode structure thereof, in the solution of the electrolyte support and the electrode division, the inner electrode is not divided, and the outer electrode is divided. Wherein the inner electrode and the outer electrode are defined by the relative positions of the tubular electrolyte layers of the tube-type fuel cell.
For example, when the membrane electrode structure is an anode (inner) -electrolyte layer (middle) -cathode (outer, divided by the network dividing structure) structure, the inner electrode is an anode and the outer electrode is a cathode.
When the membrane electrode structure is a cathode (inner) -electrolyte layer (middle) -anode (outer, divided by the network dividing structure) structure, the inner electrode is a cathode and the outer electrode is an anode.
The following describes the method for fabricating a membrane electrode structure according to the present invention in further detail with reference to the following examples.
Example 1
An example provides a flat-plate type fuel cell (electrolyte-supported, anode-split). The manufacturing method comprises the following steps:
step 101, preparing an electrolyte layer.
The electrolyte layer was made of La1-xSrxGa1-yMgyOz(LSGM). The electrolyte material is configured into slurry (organic solvent is dispersant), and is made into an electrolyte sheet by tape casting.
And 102, preparing a network segmentation structure.
The material for making the network partition structure is selected from alumina, and is configured into slurry (organic solvent is dispersant), and the slurry is brushed on the surface of the electrolyte layer by a screen printing mode, and the thickness is 30 micrometers.
And 103, preparing an anode.
The anode is made of nickel cermet, and is made of slurry prepared from an organic dispersant, and the slurry is coated on the side of the network division structure in the electrolyte layer + network division structure, so that the anode covers the network division structure.
And sintering the combination of the electrolyte layer, the network partition structure and the anode at 1000 ℃, and then cooling to room temperature.
And 105, preparing a cathode.
The cathode is of a microporous structure and adopts strontium-doped lanthanum manganite with a P-type semiconductor structure as a raw material. Preparing the cathode manufacturing raw materials into slurry by using an organic solvent, coating the slurry on the other side of the electrolyte layer, sintering the slurry for 1 hour at 960 ℃ in an air atmosphere, and cooling the slurry to room temperature along with a furnace.
Example 2
An example provides a fuel cell of the tube type (electrolyte support, anode split). The manufacturing method comprises the following steps:
step 101, preparing an electrolyte layer.
The electrolyte layer was made of La1-xSrxGa1-yMgyOz(LSGM). The electrolyte material is prepared into pug (organic solvent is dispersant), and the electrolyte tube is formed by extrusion molding。
And 102, preparing a network segmentation structure.
The material for making the network partition structure is selected from alumina, and is configured into slurry (organic solvent is dispersant), and the slurry is brushed on the outer surface of the electrolyte tube by a screen printing mode, and the thickness of the slurry is 15 micrometers.
The anode is of a microporous structure and adopts nickel ceramic as a raw material. The nickel ceramic powder is configured into a slurry with an organic solvent, and the surface of the network partition structure (anode-covered network partition structure) of the electrolyte layer + network partition structure prepared in step 102 is coated.
And 104, sintering.
And (3) sintering the electrolyte layer, the network segmentation structure and the anode prepared in the steps 101 to 103 at 1300 ℃ for 1 hour in an air atmosphere, and then cooling the mixture to room temperature along with the furnace.
Step 101, preparing a cathode (inner electrode).
The cathode is made of ABO3LSM (La) as an electrode of perovskite structure1-xSrxMo3E.g. La0.7Sr0.3Mo3) It can be prepared by solid phase synthesis or combustion or sol-gel method, in this example by dissolving lanthanum nitrate, strontium nitrate and manganese nitrate in water, adding glycine, heating and burning, and then baking at 1000 ℃.
LSM powder was dispersed in an organic dispersant (5 wt% ethyl cellulose and 95 wt% terpineol), ground in a mortar to obtain a slurry, formed on the inner surface of an electrolyte tube by dip coating, and then sintered at 1000 ℃.
While particular embodiments of the present invention have been illustrated and described, it would be obvious that various other changes and modifications can be made without departing from the spirit and scope of the invention. It is therefore intended to cover in the appended claims all such changes and modifications that are within the scope of this invention.
Claims (9)
1. A membrane electrode structure manufacturing method is applied to manufacturing of a fuel cell and is characterized in that the membrane electrode structure comprises a first electrode, an electrolyte layer and a second electrode which are sequentially stacked, the electrolyte layer is formed by extending from a first surface to a second surface, the first electrode is positioned on the first surface side of the electrolyte layer, the second electrode is positioned on the second surface side of the electrolyte layer, network partition structures are distributed in the first electrode and/or the second electrode, and the thermal expansion coefficient of the network partition structures is smaller than or equal to that of the electrolyte layer;
the manufacturing method comprises the following steps:
providing an intermediate body including an electrolyte layer and a network partition structure formed on a first surface and/or a second surface of the electrolyte layer, the network partition structure partitioning the first surface and/or the second surface of the electrolyte layer into a void region and a coverage region;
forming the first electrode made of a first electrode material on a first surface side of the intermediate body, and forming the second electrode made of a second electrode material on a second surface side of the intermediate body;
the first electrode material and/or the second electrode material covers the void region and/or the coverage region.
2. The method of fabricating a membrane electrode structure according to claim 1, wherein the method of fabricating the intermediate body comprises:
and manufacturing a network partition structure on the first surface and/or the second surface by taking the electrolyte layer as a support.
3. The method of manufacturing a membrane electrode structure according to claim 2, wherein the method of manufacturing the electrolyte layer includes:
molding the manufacturing material of the electrolyte layer into a desired shape in a fluid state and solidifying;
alternatively, the material of which the electrolyte layer is made is molded into a desired shape in a solid state, and optionally hardened.
4. The method of manufacturing a membrane electrode structure according to claim 3, wherein the method of molding and solidifying the manufacturing material of the electrolyte layer in a fluid state into a desired shape includes: tape casting or extrusion molding.
5. A method of fabricating a membrane electrode assembly according to any one of claims 2 to 4, wherein the method of fabricating a network partition structure on the first surface and/or the second surface using the electrolyte layer as a support comprises:
transferring the material for fabricating the network partition structure to the support body in a fluid, and curing the material for fabricating the network partition structure.
6. The method of manufacturing a membrane electrode structure according to claim 5, wherein the method of transferring the manufacturing material of the network partition structure to the support as a fluid comprises: ceramic ink jet or screen printing.
7. The method of manufacturing a membrane electrode structure according to claim 1, wherein the method of manufacturing the first electrode made of a first electrode material on the first surface side of the intermediate body includes: transferring a first electrode material in a fluid state to a first surface side of the intermediate body, and curing the first electrode material.
8. The method of producing a membrane electrode structure according to claim 1 or 7, wherein the method of producing the second electrode made of a second electrode material on the second surface side of the intermediate body includes: transferring a second electrode material to a second surface side of the intermediate body in a fluid state, and curing the second electrode material.
9. The method of manufacturing a membrane electrode structure according to claim 8, wherein the method of transferring the first electrode material in a fluid state to the first surface side of the intermediate body includes: coating;
the method of transferring the second electrode material to the second surface side of the intermediate body in a fluid state includes: and (4) coating.
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| CN1489799A (en) * | 2000-11-27 | 2004-04-14 | �ղ��Զ�����ʽ���� | Single cell for fuel cell and solid oxide fuel cell |
| CN1636296A (en) * | 2000-11-28 | 2005-07-06 | 日产自动车株式会社 | Solid oxide fuel cell stack and method of manufacturing the same |
| CN1667860A (en) * | 2005-04-07 | 2005-09-14 | 天津大学 | Structure and preparation method of fuel cell |
| CN103050724A (en) * | 2013-01-25 | 2013-04-17 | 珠海市香之君电子有限公司 | Single-cell structure of fuel cell and preparation method thereof |
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2019
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1489799A (en) * | 2000-11-27 | 2004-04-14 | �ղ��Զ�����ʽ���� | Single cell for fuel cell and solid oxide fuel cell |
| CN1636296A (en) * | 2000-11-28 | 2005-07-06 | 日产自动车株式会社 | Solid oxide fuel cell stack and method of manufacturing the same |
| CN1667860A (en) * | 2005-04-07 | 2005-09-14 | 天津大学 | Structure and preparation method of fuel cell |
| CN103050724A (en) * | 2013-01-25 | 2013-04-17 | 珠海市香之君电子有限公司 | Single-cell structure of fuel cell and preparation method thereof |
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