Solid oxide battery
By introducing barrier portions with sheet and strip shapes into the fuel electrode of the solid oxide battery, the problem of deterioration of the characteristics of the solid oxide battery in a high temperature environment is solved, and the performance of the battery is significantly improved.
Patent Information
- Application Number
- CN202380065353.7
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Priority Date
- 2022-12-30
- Filing Date
- 2023-06-30
- Publication Date
- 2025-04-22
AI Technical Summary
When operating in high temperature environments, the characteristics of the solid oxide battery may deteriorate, especially the porous structure of the fuel electrodes decreases after prolonged operation.
A novel structure of a solid oxide cell is designed in which the fuel electrode comprises a porous metal body having pores and a barrier portion in these pores. The barrier portion has a sheet-like shape and a strip-like shape, and may include a conductor such as carbon or graphene, and an oxide of a protective film such as B and Al.
By providing a barrier portion in the fuel electrode, excessive coarseness of metal particles of the porous metal body can be prevented, thereby significantly reducing the problem of deterioration of solid oxide batteries in a high-temperature environment, and improving the performance of the batteries.
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Figure CN119866554A_ABST
Abstract
Description
Technical Field
[0001] The present disclosure relates to a solid oxide battery. Background Art
[0002] Solid oxide fuel cells (SOFC) and solid oxide electrolyzers (SOEC) include cells composed of air electrodes, fuel electrodes and solid electrolytes with oxygen ion conductivity, and in this case, the cells may be referred to as solid oxide cells. Solid oxide cells generate electrical energy by electrochemical reactions or electrolyze water to produce hydrogen by the reverse reaction of solid oxide fuel cells. Compared with other types of fuel cells or water electrolyzers (such as phosphoric acid fuel cells (PAFC), alkaline fuel cells (AFC), polymer electrolyte fuel cells (PEMFC), direct methanol fuel cells (DMFC), etc.), solid oxide cells have low overvoltage and low irreversible losses based on low activation polarization, and therefore have high efficiency. In addition, solid oxide cells can use carbon or hydrocarbon-based fuels as well as hydrogen, so there is a wide range of fuel options. Due to the high reaction rate at the electrode, it has the advantage of not requiring expensive precious metals as electrode catalysts.
[0003] When operating in a high temperature environment, the characteristics of a solid oxide cell may deteriorate. One of the causes of such degradation is that the reaction rate decreases when a fuel electrode having a porous structure is operated for a long time. Summary of the invention
[0004] Technical issues
[0005] An aspect of the present disclosure is to achieve a solid oxide cell that can significantly reduce degradation problems when operating in a high temperature environment.
[0006] Technical Solution
[0007] According to one aspect of the present disclosure, a new structure of a solid oxide cell is provided by way of example, wherein the solid oxide cell includes a fuel electrode, an air electrode, and an electrolyte arranged between the fuel electrode and the air electrode, wherein the fuel electrode includes a porous metal body having pores and a barrier portion arranged in the pores of the porous metal body, wherein the barrier portion has at least one of a sheet-like shape and a strip-like shape.
[0008] The barrier may include a conductor including carbon.
[0009] The conductor may include graphene.
[0010] The fuel electrode may include a plurality of barriers.
[0011] At least one of the plurality of blocking portions may not contact other blocking portions.
[0012] At least one of the plurality of barrier portions may be spaced apart from a surface of the pore in the porous metal body.
[0013] At least one of the plurality of barrier portions may be in contact with a surface of the pore in the porous metal body.
[0014] A portion of the plurality of barrier portions may be in a sheet shape, and at least a portion of the remaining barrier portions may be in a strip shape.
[0015] At least a portion of the plurality of barrier portions may be in the form of bent pieces.
[0016] The fuel electrode may also include an ion conductor.
[0017] The ion conductor may include a ceramic porous body disposed in the pores of the porous metal body.
[0018] The porous metal body may include Ni.
[0019] The barrier portion may include a protective film disposed on a surface of the barrier portion.
[0020] The protective film may include at least one of B and Al.
[0021] According to one aspect of the present disclosure, a solid oxide cell includes a fuel electrode, an air electrode, and an electrolyte arranged between the fuel electrode and the air electrode, the fuel electrode includes a porous metal body having pores and a barrier portion arranged in the pores of the porous metal body, wherein the barrier portion includes a protective film arranged on the surface of the barrier portion.
[0022] The barrier may include a conductor including carbon.
[0023] The conductor may include graphene.
[0024] The barrier may be spaced apart from surfaces of the pores in the porous metal body.
[0025] The fuel electrode may also include an ion conductor.
[0026] The ion conductor may include a ceramic porous body disposed in the pores of the porous metal body.
[0027] The protective film may include at least one of B and Al.
[0028] Advantageous Effects of the Invention
[0029] In the case of the solid oxide cell according to the embodiment, even when operating in a high temperature environment, the degradation of characteristics can be significantly reduced. Therefore, when the solid oxide cell is used as a fuel cell or a water electrolysis cell, the performance can be improved. BRIEF DESCRIPTION OF THE DRAWINGS
[0030] Figure 1 is an exploded perspective view schematically showing a solid oxide battery according to an embodiment;
[0031] Figure 2 and Figure 3 is a cross-sectional view of a region of a solid oxide cell;
[0032] Figure 4 is a magnified view of a region of the fuel electrode;
[0033] Figure 5 shows the shape of a barrier included in a fuel electrode;
[0034] Figure 6 shows the form in which metal particles constituting the fuel electrode are sintered;
[0035] Figure 7 An example of raw material powder for obtaining a fuel electrode is shown;
[0036] Figure 8 shows the shape of a barrier included in a fuel electrode in a solid oxide cell according to a modified embodiment; and
[0037] Fig. 9 is an enlarged view of a region of a fuel electrode in a solid oxide cell according to a modified embodiment. DETAILED DESCRIPTION
[0038] Hereinafter, the example embodiments of the present disclosure will be described with reference to specific example embodiments and the accompanying drawings. However, the example embodiments of the present disclosure may be illustrated in many different forms and should not be construed as being limited to the specific embodiments set forth herein. The example embodiments disclosed herein are provided to better explain the present disclosure to those skilled in the art. In the accompanying drawings, for the sake of clarity, the shapes and sizes of the elements may be exaggerated, and the same reference numerals will always be used to represent the same or similar elements.
[0039] In order to clearly explain the present disclosure in the drawings, contents irrelevant to the description are omitted, the thickness of each component is exaggerated to clearly indicate multiple layers and multiple regions, and components having the same functions within the scope of the same concept are described using the same reference numerals. Throughout the specification, unless otherwise specified, when a part "includes" or "contains" a component, this indicates that other components are not excluded and other components may be further included.
[0040] Figure 1 is an exploded perspective view schematically showing a solid oxide battery according to an embodiment. Figure 2 and Figure 3 is a cross-sectional view of a region of a solid oxide cell. Figure 4 is an enlarged view of an area of the fuel electrode.
[0041] Reference Figures 1 to 4 According to the embodiment, the solid oxide cell 100 includes a fuel electrode 110, an air electrode 120, and an electrolyte 130 disposed between the fuel electrode 110 and the air electrode 120 as main components. The fuel electrode 110 includes a porous metal body 111 having pores H and a barrier 112, and the barrier 112 has at least one of a sheet shape and a flake shape. By providing the barrier 112 in the fuel electrode 110, the metal particles constituting the porous metal body 111 can be prevented from being excessively coarsened, and thus, the degradation problem of the solid oxide cell 100 during high temperature operation can be reduced. Hereinafter, the components of the solid oxide cell 100 will be described in detail, and the case where the solid oxide cell 100 is used as a fuel cell will be mainly described. However, the solid oxide cell 100 can also be used as a water electrolysis cell, and in this case, a reaction opposite to the reaction in the case of a fuel cell will occur in the fuel electrode 110 and the air electrode 120 of the solid oxide cell 100.
[0042] In detail, when the solid oxide cell 100 is a fuel cell, for example, in the fuel electrode 110, water generation due to oxidation of hydrogen or oxidation reaction of carbon compounds may occur, and in the air electrode 120, oxygen ion generation due to decomposition of oxygen may occur. When the solid oxide cell 100 is a water electrolysis cell, the opposite reaction may occur. For example, hydrogen may be generated in the fuel electrode 110 according to a reduction reaction of water, and oxygen may be generated in the air electrode 120. As another example, when the solid oxide cell 100 is a fuel cell, a hydrogen decomposition (hydrogen ion generation) reaction may occur in the fuel electrode 110, and oxygen ions and hydrogen ions are combined in the air electrode 120 to generate water, and in the case of a water electrolysis cell, water decomposition (generation of hydrogen ions and oxygen ions) occurs in the fuel electrode 110, and oxygen may be generated in the air electrode 120. In the electrolyte 130, ions may move to the fuel electrode 110 or the air electrode 120.
[0043] on the other hand, Figure 2 The embodiment corresponds to the solid oxide cell 100 supported by the electrolyte 130, and in this case, the width of the electrolyte 130 may be the widest. Figure 3In the embodiment, the fuel electrode 110 support type may be implemented, and in this case, the fuel electrode 110 may be the thickest.
[0044] Reference Figure 4 The fuel electrode 110 includes a porous metal body 111, and holes H are formed in the porous metal body 111. In addition, in the fuel electrode 110, the barrier 112 is provided in the hole H of the porous metal body 111, and as shown in FIG. Figure 5 As shown, the barrier portion 112 has a sheet shape (see Figure 5 (a)) and strips (see Figure 5 (b)). The porous metal body 111 can be used as a conductor in the fuel electrode 110, and can also be used as a catalyst for the reaction in the fuel electrode 110. The porous metal body 111 may include Ni, and can be obtained, for example, by sintering Ni-containing particles in a reducing atmosphere. In this case, the Ni-containing particles can be Ni oxide particles. In the process of sintering the metal particles, the porous metal body 111 can be obtained, and for this purpose, a pore-forming agent can be added to the mixture before sintering.
[0045] The barrier 112 can prevent the metal particles constituting the porous metal body 111 from becoming too large during the operation of the fuel electrode 110. For example, when the solid oxide cell 100 is operated, the size of the porous metal body 111 of the fuel electrode 110 may increase due to the movement of materials (such as Ni) on the surface of the porous metal body 111. In this case, as the distance between the reaction areas of the fuel material is shortened, the reaction rate may decrease. The barrier 112 may be present in the pores H of the porous metal body 111 to reduce the possibility of such coarsening, and thus, the degradation of the solid oxide cell 100 can be reduced. The material constituting the barrier 112 can be selected in consideration of the material transfer blocking function and conductivity, and in the present embodiment, a conductor of a carbon material is used. As a more detailed example, the conductor may include graphene, and since graphene has a relatively high conductivity while effectively preventing the coarsening of metal particles even at a thin thickness, graphene can help improve the characteristics of the fuel electrode 110 using graphene.
[0046] For example, the air electrode 120 may include a conductive material, such as a conductive perovskite material, such as lanthanum strontium manganite (LSM). For example, lanthanum strontium cobalt (LSC), lanthanum strontium cobalt manganese (LSCM), lanthanum strontium cobalt ferrite (LSCF), lanthanum strontium ferrite (LSF), La 0.85 Sr 0.15 Cr 0.9 Ni 0.1O3 (LSCN) or other conductive perovskites or metals such as Pt. In some embodiments, the air electrode 120 may include a mixture of a conductive material and an ion conductive ceramic material. For example, the air electrode 120 may include about 10 wt % to about 90 wt % of a conductive material (e.g., LSM, etc.) and about 10 wt % to about 90 wt % of an ion conductive material. In this case, the ion conductive material may further include a zirconium oxide-based (e.g., YSZ) material and / or a ceria-based material.
[0047] The electrolyte 130 is provided between the fuel electrode 110 and the air electrode 120. As an example of a material constituting the electrolyte 130, the electrolyte 130 may include stabilized zirconia. In detail, the electrolyte 130 may include scandia stabilized zirconia (SSZ), yttria stabilized zirconia (YSZ), scandia ceria stabilized zirconia (SCSZ), scandia ceria yttria stabilized zirconia (SCYSZ), scandia ceria ytterbium stabilized zirconia (SCYbSZ), etc.
[0048] When describing the construction of the fuel electrode 110 in more detail, reference will be made to Figure 6 A process of forming the porous metal body 111 and the barrier portion 112 is described. Figure 6 The metal particles constituting the fuel electrode are sintered. First, a raw material powder 113 ( Figure 6 ). The raw material powder 113 includes a metal component constituting the porous metal body 111, for example, Ni, and may include Ni oxide as described above. The coating layer 114 is a region where the barrier portion 112 is formed after sintering, and a material including graphene or the like may be formed on the surface of the raw material powder 113 before sintering. In this case, as a process for forming the coating layer 114, an appropriate deposition process known in the art, such as thermal or chemical vapor deposition, may be used. After sintering, the raw material powder 113 constitutes the porous metal body 111, and the sintering process may be performed in a reducing atmosphere. For example, in a sintering process in a reducing atmosphere, the raw material powder 113 containing Ni oxide may be changed into a porous metal body 111, which is a sintered body of Ni particles. In this process, the size of the raw material powder 113 may be reduced by shrinking, and the barrier portion 112 may be broken and separated into a plurality of pieces. For example, as shown in the figure, the fuel electrode 110 may include a plurality of barrier portions 112. Also in this case, unlike the porous metal body 111 , the barrier portion 112 may maintain the overall shape of the coating layer 114 , as shown in the figure.
[0049] As such, when the coating layer 114 remains as the barrier 112 after sintering, coarsening of the porous metal body 111 that may occur during operation of the solid oxide cell 100 may be prevented. Figure 51 shows an example of the barrier 112 existing in the pores H of the porous metal body 111 in the fuel electrode 110. As described above, the broken barrier 112 may have a flake shape, and in more detail, may have a shape such as Figure 5 The curved sheet shown in (a) may also have Figure 5 (b) The stripe shape shown in FIG. 1. For example, some of the plurality of barrier portions 112 may have a sheet shape, and at least some of the other barrier portions may have a stripe shape.
[0050] On the other hand, despite Figure 6 1 shows a form in which the entire surface of the raw material powder 113 is covered with the coating layer 114, but Figure 7 As shown, it is also possible to use a raw material powder 113 having a coating layer 114 formed only on a portion of the surface. Figure 6 If the coating layer 114 in the raw material powder 113 is not broken after sintering, the catalytic function of the porous metal body 111 may be deteriorated. Figure 7 As shown, by using the raw material powder 113 having the surface exposed portion, a decrease in reactivity due to a decrease in the catalytic function of the porous metal body 111 can be prevented.
[0051] As another variation example, Figure 8 As shown in , the barrier 112 may further include a protective film 115 formed on the surface thereof. The protective film 115 may play a role in protecting the barrier 112, preventing oxidation, etc., and may include, for example, at least one of B and Al. In this case, the protective film 115 may be formed using a metal of B or Al or an oxide of B or Al.
[0052] The presence of the barrier 112 and the protective film 115 and the shape of the barrier can be determined by electron microscopy and / or energy dispersive spectroscopy. Even if not described in the present disclosure, other methods and / or tools understood by those of ordinary skill in the art may be used.
[0053] Refer again Figure 4 , a more detailed arrangement method of the barrier portion 112 will be described. In the case where the barrier portion 112 is formed using the coating layer 114 as described above, various types of barrier portions 112 may be obtained according to the shape of the coating layer 114, sintering conditions, and the like. First, at least one of the plurality of barrier portions 112 may not contact another barrier portion 112. In this case, another barrier portion of the plurality of barrier portions 112 may contact yet another barrier portion 112. In addition, at least one of the plurality of barrier portions 112 may be spaced apart from the surface where the pores H are formed in the porous metal body 111. However, at least one of the plurality of barrier portions 112 may contact the surface where the pores H are formed in the porous metal body 111.
[0054] In the above embodiment, the structure in which the fuel electrode 110 includes the porous metal body 111 and the barrier portion 112 is shown, but Fig. 9 As in the embodiment of the present invention, the fuel electrode 110 may further include an ion conductor 116. In this case, the ion conductor 116 may be a ceramic porous body structure disposed in the pores H of the porous metal body 111. In the case of the ceramic constituting the ion conductor 116, for example, it may include gadolinium oxide-doped ceria (GDC), samarium oxide-doped ceria (SDC), ytterbium oxide-doped ceria (YDC), scandia stabilized zirconia (SSZ), ytterbium oxide ceria scandia stabilized zirconia (YbCSSZ), and the like.
[0055] As described above, in the case of the solid oxide cell according to the embodiment, even when operating in a high temperature environment, the degradation of characteristics can be significantly reduced. Therefore, when the solid oxide cell is used as a fuel cell or a water electrolysis cell, the performance can be improved.
[0056] While example embodiments have been shown and described above, it will be readily apparent to those skilled in the art that modifications and variations may be made without departing from the scope of the present disclosure as defined by the appended claims.
Claims
1. A solid oxide battery comprising: A fuel electrode, comprising: a porous metal body having pores; and a barrier portion disposed in the pores of the porous metal body, wherein the barrier portion has at least one of a sheet shape and a strip shape; air electrode; and An electrolyte is provided between the fuel electrode and the air electrode.
2. The solid oxide battery according to claim 1, wherein: The barrier portion includes a conductor including carbon.
3. The solid oxide battery according to claim 2, wherein: The conductor includes graphene.
4. The solid oxide battery according to claim 1, wherein: The fuel electrode includes a plurality of barriers.
5. The solid oxide battery according to claim 4, wherein: At least one of the plurality of blocking portions does not contact other blocking portions.
6. The solid oxide battery according to claim 4, wherein: At least one of the plurality of barriers is spaced apart from a surface of the pore in the porous metal body.
7. The solid oxide battery according to claim 4, wherein: At least one of the plurality of barrier portions is in contact with a surface of the pore in the porous metal body.
8. The solid oxide battery according to claim 4, wherein: A portion of the plurality of barrier portions is in a sheet shape, and at least a portion of the remaining barrier portions is in a strip shape.
9. The solid oxide battery according to claim 4, wherein: At least a portion of the plurality of blocking portions is in the form of bent pieces.
10. The solid oxide battery according to claim 1, wherein: The fuel electrode also includes an ion conductor.
11. The solid oxide battery according to claim 10, wherein: The ion conductor includes a ceramic porous body disposed in the pores of the porous metal body.
12. The solid oxide battery according to claim 1, wherein: The porous metal body contains Ni.
13. The solid oxide battery according to claim 1, wherein: The barrier portion includes a protective film disposed on a surface of the barrier portion.
14. The solid oxide battery according to claim 13, wherein: The protective film includes at least one of B and Al.
15. A solid oxide battery comprising: A fuel electrode, comprising: a porous metal body having pores; and a barrier portion disposed in the pores of the porous metal body, wherein the barrier portion comprises a protective film disposed on a surface of the barrier portion; air electrode; and An electrolyte is provided between the fuel electrode and the air electrode.
16. The solid oxide battery according to claim 15, wherein: The barrier portion includes a conductor including carbon.
17. The solid oxide battery according to claim 16, wherein: The conductor includes graphene.
18. The solid oxide battery according to claim 15, wherein: The barrier is spaced apart from surfaces of the pores in the porous metal body.
19. The solid oxide battery according to claim 15, wherein: The fuel electrode also includes an ion conductor.
20. The solid oxide battery according to claim 19, wherein: The ion conductor includes a ceramic porous body disposed in the pores of the porous metal body.
21. The solid oxide battery according to claim 15, wherein: The protective film includes at least one of B and Al.