Solid oxide battery
By designing multiple tapered protrusions on the electronic conductive particles of the fuel electrode of the solid oxide battery, the problem of low reaction efficiency of the electrode layer is solved, and the performance of the battery is significantly improved.
Patent Information
- Application Number
- CN202380063944.0
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Priority Date
- 2023-01-20
- Filing Date
- 2023-07-24
- Publication Date
- 2025-04-18
AI Technical Summary
The reaction efficiency of existing solid oxide batteries in the electrode layer is low, which affects the overall performance of the battery.
By designing a plurality of protrusions on the electronically conductive particles of the fuel electrode, the protrusions have a tapered shape away from the boundary of the main body, increasing the specific surface area of the electronically conductive particles, thereby improving the reaction efficiency of the fuel electrode.
The reaction efficiency of the electrode layer is improved, and the performance of solid oxide batteries in fuel cells or water electrolytic cells is improved, including increasing the voltage amplitude and hydrogen production amount.
Smart Images
Figure CN119856303A_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 batteries composed of air electrodes, fuel electrodes and solid electrolytes with ion conductivity, and in this case, the batteries may be referred to as solid oxide batteries. Solid oxide batteries 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 batteries have low overvoltage based on low activation polarization, and have high efficiency due to low irreversible losses. In addition, solid oxide batteries can be used as carbon-based fuels or hydrocarbon-based fuels and hydrogen, so there is a wide range of fuel selection. Due to the high reaction rate at the electrode, solid oxide batteries have the advantage of not requiring expensive precious metals as electrode catalysts.
[0003] As a method for improving the efficiency of solid oxide cells, attempts to improve the reaction efficiency in the electrode layer have continued in the art. Summary of the invention
[0004] Technical issues
[0005] An aspect of the present disclosure is to realize a solid oxide cell capable of improving reaction efficiency in an electrode layer, specifically, a fuel electrode.
[0006] Technical Solution
[0007] According to one aspect of the present disclosure, a novel structure of a solid oxide cell is proposed by way of example, and the solid oxide cell includes a fuel electrode, an air electrode, and an electrolyte disposed between the fuel electrode and the air electrode. The fuel electrode includes electronically conductive particles, and the electronically conductive particles include a main body and a plurality of protrusions disposed on a surface of the main body and having a shape that tapers from a boundary between the main body and the protrusions in a direction away from the main body.
[0008] The body may have a spherical shape.
[0009] When the diameter of the body is D and the height of the protrusion is H, H may be greater than or equal to 10% of D.
[0010] H may be greater than or equal to 10% of D and less than or equal to 50% of D.
[0011] The height of the protrusion may be 50 nm to 1 μm.
[0012] At least one of the plurality of protrusions may have a conical shape.
[0013] At least one of the plurality of protrusions may have a trumpet shape without an apex.
[0014] The protrusion may have an end portion in a flat shape or a curved shape.
[0015] In the electron conductive particle, at least two of the plurality of protrusions may have different heights.
[0016] At least two of the plurality of protrusions in the electron conductive particle may be spaced apart from each other.
[0017] The fuel electrode may include a plurality of the electron conductive particles, and at least two of the plurality of the electron conductive particles may form an aggregate with each other.
[0018] The electronically conductive particles may include Ni.
[0019] The fuel electrode may also include an ion conductor.
[0020] The ion conductor may include at least one of gadolinia doped ceria (GDC), samarium oxide doped ceria (SDC), ytterbium oxide doped ceria (YDC), scandia stabilized zirconia (SSZ), or ytterbium oxide ceria scandia stabilized zirconia (YbCSSZ).
[0021] The ion conductor may be in contact with an end portion of the protrusion.
[0022] The ion conductor may fill at least a portion of a space between adjacent protrusions of the plurality of protrusions.
[0023] Advantageous Effects of the Invention
[0024] In the case of the solid oxide cell according to the example, the reaction efficiency in the electrode layer can be improved. Therefore, when the solid oxide cell is used as a fuel cell or a water electrolyzer, the performance can be improved. BRIEF DESCRIPTION OF THE DRAWINGS
[0025] Figure 1 is an exploded perspective view schematically showing a solid oxide battery according to an embodiment;
[0026] Figure 2 yes Figure 1 A cross-sectional view of a region in a solid oxide cell;
[0027] Figure 3is a cross-sectional view of a region in a solid oxide battery according to a modification;
[0028] Figure 4 yes Figure 2 An enlarged view of region A of the fuel electrode is shown;
[0029] Figure 5 yes Figure 2 An enlarged view of region B of the air electrode is shown;
[0030] Figure 6 is a perspective view showing an example of electron conductive particles included in a fuel electrode;
[0031] Figure 7 is a cross-sectional view showing electron conductive particles and ion conductors included in a fuel electrode; and
[0032] Figure 8 is a perspective view showing another example of electron conductive particles included in the fuel electrode. DETAILED DESCRIPTION
[0033] Hereinafter, embodiments will be described with reference to specific embodiments and the accompanying drawings. However, the embodiments of the present disclosure may be modified in many different forms, and the scope of the present disclosure is not limited to the embodiments described below. In addition, embodiments of the present disclosure are provided to more completely describe the present disclosure to those skilled in the art. Therefore, in order to illustrate more clearly, the shapes and sizes of the elements in the drawings may be exaggerated, and the elements represented by the same reference numerals in the drawings are the same elements.
[0034] In order to clearly describe the present disclosure in the drawings, parts irrelevant to the description are omitted, and in order to clearly indicate various layers and regions, the thickness is enlarged and shown, and the same reference numerals are used to describe elements having the same function within the scope of the same concept. In addition, throughout the specification, unless otherwise specified, when a component is referred to as "comprising", it means that it may also include other components without excluding other components.
[0035] Figure 1 is an exploded perspective view schematically showing a solid oxide battery according to an embodiment. Figure 2 yes Figure 1 A cross-sectional view of a solid oxide battery. Figure 3 is a cross-sectional view of a solid oxide battery according to a modification. Figure 4 yes Figure 2 An enlarged view of region A of the fuel electrode is shown, and Figure 5 yes Figure 2 An enlarged view of region B of the air electrode is shown.
[0036] Reference Figures 1 to 5, the solid oxide cell 100 according to the embodiment includes a fuel electrode 110, an air electrode 120, and an electrolyte 130 disposed therebetween as main components. In this case, the fuel electrode 110 includes electronically conductive particles 111, and each of the electronically conductive particles 111 includes a main body 111a and a plurality of protrusions 111b, and the plurality of protrusions 111b are formed on the surface of the main body 111a and have a shape that tapers from the boundary between the main body and the protrusion in a direction away from the main body. As in the present embodiment, the electronically conductive particles 111 of the fuel electrode 110 include electronically conductive particles 111 having protrusions 111b as electronic conductors, so that the surface area of the electronic conductor can be improved, and thus the reaction area in the fuel electrode 110 can be increased. In addition, as the reaction efficiency in the fuel electrode 110 is improved, the performance of the fuel electrode 110 can be improved. For example, when the solid oxide cell 100 is a fuel cell, the amplitude of the generated voltage can be increased. When the solid oxide cell 100 is a water electrolysis cell, the amount of hydrogen generated per unit time can be increased. 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. When the solid oxide cell is used as a water electrolysis cell, a reaction opposite to that 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.
[0037] Specifically, when the solid oxide cell 100 is a fuel cell, for example, water generation due to hydrogen oxidation or an oxidation reaction of a carbon compound may occur in the fuel electrode 110, and an oxygen ion generation reaction due to oxygen decomposition may occur in the air electrode 120. 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, in the case of a fuel cell, a hydrogen decomposition (hydrogen ion generation) reaction may occur in the fuel electrode 110, and water generation due to the combination of oxygen ions and hydrogen ions may occur in the air electrode 120. 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.
[0038] Figure 2 An embodiment in which the electrolyte 130 supports the solid oxide cell 100 is shown. In this case, among the fuel electrode 110, the air electrode 120, and the electrolyte 130, the width of the electrolyte 130 may be the widest. In contrast, Figure 3An embodiment is shown in which the fuel electrode 110 supports the air electrode 120 and the electrolyte 130. In this case, among the fuel electrode 110, the air electrode 120, and the electrolyte 130, the fuel electrode 110 may be the thickest.
[0039] like Figure 4 As shown, the fuel electrode 110 includes electronically conductive particles 111 as electronic conductors, and may also include ionic conductors 112. In this case, the electronically conductive particles 111 and the ionic conductors 112 may be sintered bodies. Therefore, the fuel electrode 110 may have a porous structure including pores H1, and gases, fluids, etc. may flow in and out through the pores H1. In this case, the electronically conductive particles 111 of the fuel electrode 110 may act as electrical conductors or play a catalytic role, etc., and may include metal particles. In some embodiments, the electronically conductive particles 111 may include Ni.
[0040] Reference Figure 5 , the air electrode 120 may include an electronic conductor 121 and an ion conductor 122, and the electronic conductor 121 and the ion conductor 122 may be sintered bodies. In the air electrode 120, the electronic conductor 121 includes a lanthanum strontium manganese (LSM)-based material, a lanthanum strontium cobalt (LSC)-based material, a lanthanum strontium cobalt manganese (LSCM)-based material, a lanthanum strontium cobalt ferrite (LSCF)-based material, a lanthanum strontium ferrite (LSF)-based material, a barium strontium cobalt iron (BSCF)-based material, or a samarium strontium cobalt (SSC)-based material. The ion conductor 122 may include materials such as yttria stabilized zirconia (YSZ), cerium dioxide (CeO2), bismuth oxide (Bi2O3), lanthanum gallate (LaGaO3), etc. In addition, the air electrode 120 may be a porous body including pores H2, and a gas or fluid, etc. may flow in and out through the pores H2.
[0041] The electrolyte 130 is disposed between the fuel electrode 110 and the air electrode 120, and ions may move toward the fuel electrode 110 or the air electrode 120. In some embodiments, materials constituting the ion conductor 112 of the fuel electrode 110 and the ion conductor 122 of the air electrode 120 may be included in the electrolyte 130. As a representative example, the electrolyte 130 may include stabilized zirconia. Specifically, the electrolyte 130 may include scandia stabilized zirconia (SSZ), yttria stabilized zirconia (YSZ), scandia ceria stabilized zirconia (SCSZ), scandia ceria yttria stabilized zirconia (SCYSZ), or scandia ceria ytterbium stabilized zirconia (SCYbSZ), and the like.
[0042] Will refer to Figure 4 as well as Figures 6 to 8The configuration of the fuel electrode 110 is described in more detail. As described above, the fuel electrode 110 may include a plurality of electronically conductive particles 111. In this case, each of the electronically conductive particles 111 includes a main body 111a and a plurality of protrusions 111b, the plurality of protrusions 111b are formed on the surface of the main body 111a and have a shape that tapers from a boundary between the main body and the protrusion in a direction away from the main body, and the protrusions 111b may be in the shape of a trumpet. The surface of the electronically conductive particle 111 may be used as a region where a reaction occurs within the fuel electrode 110. By including a plurality of trumpet structures formed on the surface of the electronically conductive particle 111, the specific surface area of the electronically conductive particle 111 may be increased, and thus the reactivity within the fuel electrode 110 may be improved. A powder having protrusions on its surface may be used as a raw material for manufacturing the electronically conductive particle 111, so that the electronically conductive particle 111 has the above-mentioned surface structure. According to the experiments of the inventors, it was confirmed that after sintering the powder having protrusions, the shape of the protrusions of the powder is maintained in at least some areas. After sintering, as Figure 4 As shown, at least two of the plurality of electron conductive particles 111 may form an aggregate with each other. In some embodiments, a Ni-based powder such as NiO powder may be used as a powder for manufacturing electron conductive particles 111.
[0043] like Figure 6 As shown, the main body 111a of the electronic conductive particles 111 may have a spherical shape. However, the main body 111a may also have a shape other than a spherical shape, such as a polyhedral structure such as a hexahedron, an octahedron or a dodecahedron. In some embodiments, the main body 111a of the electronic conductive particles 111 may have an amorphous structure. The diameter (D) of the main body 111a may be measured on a cross section passing through the center of the main body 111a. If the cross section is not a circle, the diameter can be obtained by converting it to the diameter of an equivalent circle. In addition, the horn shape of the protrusion 111b may be defined as a shape in which the diameter of the protrusion 111b or the area of the cross section parallel to the bottom surface decreases in a direction away from the area adjacent to the main body 111a. If the bottom surface of the protrusion 111b is not circular, the diameter may refer to a diameter equivalent to an equivalent circle diameter. In some embodiments, at least one of the plurality of protrusions 111b may have a conical shape. Figure 6 It is shown that all of the protrusions 111 b have a conical shape, but some of the protrusions 111 b may have other shapes such as a pyramid shape, a cone shape, a trumpet-like shape, or the like.
[0044] In some embodiments, the height of the protrusion 111b may be preferably maintained at a predetermined level relative to the size of the main body 111a, so that the specific surface area of the electronic conductive particles 111 can be fully ensured. For example, if the protrusion 111b is not formed to a sufficient height, the effect of improving the specific surface area may not be obvious. In view of this, when D is the diameter of the main body 111a and H is the height of the protrusion 111b, H may be greater than or equal to 10% of D. In some embodiments, H may be greater than or equal to 10% of D and less than or equal to 50% of D. In some embodiments, H may be greater than or equal to 20% of D and less than or equal to 40% of D. In some embodiments, H may be greater than or equal to 30% of D and less than or equal to 40% of D. In some embodiments, the height (H) of at least one of the protrusions 111b may be 50nm to 1μm. In some embodiments, the height (H) of at least one of the protrusions 111b may be at least 100nm, at least 500nm or at least 800nm. In addition, as described above, in addition to the conical shape, the protrusion 111b of the electronic conductive particles 111 may also be formed in a pyramidal shape or a similar trumpet shape. In some embodiments, the size of the protrusion 111b may be different. In some embodiments, at least two of the plurality of protrusions 111b of the electron conductive particle 111 may have heights H different from each other. If the plurality of protrusions 111b have a trumpet structure, the trumpet structure may have a vertex. In some embodiments, the end of at least one of the plurality of protrusions 111b may have a vertex shape. In some embodiments, as an example of a trumpet-like structure without a vertex, or as in Figure 8 In a modified example, an end portion of at least one of the plurality of protrusions 111b may have a flat surface on the top or a curved shape.
[0045] As described above, the fuel electrode 110 may further include an ion conductor 112. In some embodiments, the ion conductor 112 may include at least one of gadolinia doped ceria (GDC), samarium oxide doped ceria (SDC), ytterbium oxide doped ceria (YDC), scandia stabilized zirconia (SSZ), or ytterbium oxide ceria scandia stabilized zirconia (YbCSSZ). Figure 7 As shown, the contact area between the ion conductor 112 and the electronically conductive particles 111 can be increased by the protrusions 111b of the electronically conductive particles 111. Since the contact area between the electronically conductive particles 111 and the ion conductor 112 is increased in this manner, the reaction efficiency within the fuel electrode 110 can be significantly improved. In this case, the ion conductor 112 can contact the end P of the protrusion 111b. In some embodiments, the ion conductor 112 can fill at least a portion of the space S between adjacent protrusions 111b among the plurality of protrusions 111b.
[0046] If the ion conductor 112 contacts the end P of the protrusion 111b or the space S between the protrusions 111b is filled with the ion conductor 112, the contact area between the electronic conductive particles 111 and the ion conductor 112 can be effectively increased. In this case, at least two of the multiple protrusions 111b of the electronic conductive particles 111 can be spaced apart from each other. Compared to the case where a simple irregular shape (e.g., a form in which all irregular parts are connected to each other) is formed on the surface of the body 111a, as in the present embodiment, the protrusion 111b has a trumpet shape, a pyramid shape, a cone shape or a trumpet-like shape, and the interface between the electronic conductive particles 111 and the ion conductor 112 can be increased. In addition, when at least two protrusions 111b spaced apart from each other are provided, the contact area between the electronic conductive particles 111 and the ion conductor 112 can be further increased due to the guarantee of the space S between the protrusions 111b.
[0047] As described above, in the case of the solid oxide cell according to the example, the reaction efficiency in the electrode layer can be improved. Therefore, when the solid oxide cell is used as a fuel cell or a water electrolysis cell, the performance can be improved.
[0048] 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: Fuel electrode; Air electrode; as well as an electrolyte disposed between the fuel electrode and the air electrode, The fuel electrode includes electronically conductive particles, and the electronically conductive particles include a body and a plurality of protrusions extending from a surface of the body and having a shape tapering from a boundary between the body and the protrusions in a direction away from the body.
2. The solid oxide battery according to claim 1, wherein: The body is spherical.
3. The solid oxide battery according to claim 2, wherein: When the diameter of the body is D and the height of at least one of the plurality of protrusions is H, H is greater than or equal to 10% of D.
4. The solid oxide battery according to claim 3, wherein: H is greater than or equal to 10% of D and less than or equal to 50% of D.
5. The solid oxide battery according to claim 1, wherein: A height of at least one of the plurality of protrusions is 50 nm to 1 μm.
6. The solid oxide battery according to claim 1, wherein: At least one of the plurality of protrusions has a conical shape.
7. The solid oxide battery according to claim 1, wherein: At least one of the plurality of protrusions has no apex.
8. The solid oxide battery according to claim 7, wherein: The at least one of the plurality of protrusions has a top portion in a flat shape or a curved shape.
9. The solid oxide battery according to claim 1, wherein: In the electron conductive particle, at least two of the plurality of protrusions have different heights.
10. The solid oxide battery according to claim 1, wherein: At least two of the plurality of protrusions in the electron conductive particle are spaced apart from each other.
11. The solid oxide battery according to claim 1, wherein: The fuel electrode comprises a plurality of the electron conductive particles, At least two of the plurality of electron conductive particles form aggregates with each other.
12. The solid oxide battery according to claim 1, wherein: The electronically conductive particles include Ni.
13. The solid oxide battery according to claim 1, wherein: The fuel electrode also includes an ion conductor.
14. The solid oxide battery according to claim 13, wherein: The ion conductor includes at least one of gadolinia doped ceria (GDC), samarium oxide doped ceria (SDC), ytterbium oxide doped ceria (YDC), scandia stabilized zirconia (SSZ), or ytterbium oxide ceria scandia stabilized zirconia (YbCSSZ).
15. The solid oxide battery according to claim 13, wherein: The ion conductor is in contact with an end portion of the protrusion.
16. The solid oxide battery according to claim 13, wherein: The ion conductor fills at least a portion of a space between adjacent protrusions of the plurality of protrusions.
17. An electron conductor, comprising an electron conductive particle, the electron conductive particle comprising a body and a plurality of protrusions extending from a surface of the body, in, At least one of the plurality of protrusions has a shape that tapers from a boundary between the body and the protrusion in a direction away from the body.
18. The solid oxide battery according to claim 17, wherein: When the diameter of the body is D and the height of at least one of the plurality of protrusions is H, H is greater than or equal to 10% of D.
19. The solid oxide battery according to claim 18, wherein: H is greater than or equal to 10% of D and less than or equal to 50% of D.
20. The solid oxide battery according to claim 17, wherein: A height of at least one of the plurality of protrusions is 50 nm to 1 μm.