Solid oxide fuel cell

Solid oxide fuel cell technology field

[0001] The present invention relates to a solid oxide fuel cell (SOFC) including a metal support.

[0002] Background Art

[0003] US 2002/0048 699 relates to a solid oxide fuel cell including a ferritic stainless steel substrate. The ferritic stainless steel substrate includes a porous region and a non-porous region bounding the porous region. The ferritic stainless steel bipolar plate is located under one surface of the porous area of the substrate, and is hermetically connected to the non-porous area above the porous area of the substrate. The first electrode layer is located on the other surface of the porous region of the substrate, the electrolyte layer is located on the first electrode layer, and the second electrode layer is located on the electrolyte layer. Such solid oxide fuel cells are relatively inexpensive. But it is not robust (robust) ο

[0004] Summary of the Invention

[0005] The object of the present invention is to provide a solid oxide fuel cell that is relatively inexpensive and at the same time more robust than previously known solid oxide fuel cells.

[0006] A SOFC battery according to an aspect of the present invention includes:

[0007] Metal support material,

[0008] The active anode layer is composed of a good hydrocarbon cracking catalyst,

[0009] The electrolyte layer,

[0010] an active cathode layer, and

[0011] The transition layer to the cathode current collector is composed of a mixture of LSM and ferrite, or composed of single-phase LSM,

[0012] A device for preventing diffusion between the metal support and the active anode is provided,

[0013] Wherein, the diffusion between the metal support and the active anode is prevented by a graded metal support that terminates in a substantially pure electronic conductive oxide.

[0014] A SOFC battery according to another aspect of the present invention includes:

[0015] metal support material,

[0016] The active anode layer is composed of a good hydrocarbon cracking catalyst,

[0017] The electrolyte layer,

[0018] an active cathode layer, and

[0019] The transition layer to the cathode current collector is composed of a mixture of LSM and ferrite, or composed of single-phase LSM,

[0020] The transition layer to the cathode current collector is composed of a mixture of LSM and ferrite, or composed of single-phase LSM,

[0021] providing means for preventing diffusion between the metal support and the active anode,

[0022] Wherein, the diffusion between the metal support and the active anode is prevented by an anode layer, and the anode layer is composed of a porous material that is infiltrated after sintering.

[0023] The use of metal support instead of Ni-YSZ (Silver Oxide Stabilized Zirconium Oxide) anode support increases the mechanical strength of the support and ensures the redox stability of the support.

[0024] The problem when using a metal support is that during sintering (which is carried out at a relatively high temperature), the electrode material from the active anode layer and the metal support inter-diffusion, causing, for example, the detriment of the ferrite to austenite phase The support phase change.

[0025] According to the present invention, this can be avoided by forming the metal support to end in electrons

CN 1985397 Β

A graded cermet structure of conductive oxide (electron conducting oxide), or the active anode layer is formed as a porous layer, and the active anode material is infiltrated into it after sintering.

[0026] In a specific embodiment according to the present invention, the battery includes: a ferritic metal support composed of a graded, layered cermet structure terminated in a substantially pure electronically conductive oxide,

[0027] The active anode layer is composed of a good hydrocarbon catalyst, such as a mixture of doped oxidized lung and Ni-Fe alloy,

[0028] The electrolyte layer,

[0029] active cathode layer,

[0030] The transition layer, which is preferably composed of a mixture of LSMGa'SrrMnOj and ferrite, and ends in

[0031] The cathode current collector, which is preferably composed of a single-phase LSM.

[0032] The FeCr porous support has an oxide layer on all inner and outer surfaces, and the oxide layer can be formed by oxidizing the Fe-Cr alloy itself in a suitable atmosphere or by coating the alloy. The purpose of this coating is to prevent the deposition of carbon and tar. The composition of the coating can be based on, for example, Cr₂0₃, CeO₂,LaCrO₃, SrTi0₃o In any case, the base oxide should be appropriately doped.

[0033] The SOFC battery according to the present invention may be provided with a doped lung-oxidizing reaction barrier layer between the electrolyte layer and the active cathode layer, the reaction barrier layer having a thickness of 0.1~1 um. The barrier layer prevents the diffusion of cations from the cathode to the electrolyte. As a result, the service life can be increased.

[0034] According to the present invention, the active cathode may be composed of the following compound, the compound is a material selected from the group consisting of blubber oxide and zinc oxide stabilized zirconium oxide (ScYSZ) or doped oxidized lung, and a material selected from LSM, manganese Saw dysprosium (LnSrMn) or oxidized diamond iron saw shop (LnSrFeCo), (Yj^Ca.) F_ei__yCo_y0₃, (Gdj^Sr.) _sF_ei__yCoy0₃ Or (Gdj^Ca.) _sF_ei__yCo_y0₃o This cathode material performs better than other cathode materials.

[0035] According to the present invention, the electrolyte layer may be composed of a co-doped aluminum oxide-based oxygen ion conductor. This electrolyte has higher oxygen ion conductivity than YSZ and better long-term stability than ScSZ. As an alternative, adulterated oxidized lung can be used.

[0036] According to the present invention, the SOFC battery may include: a ferritic stainless steel support; an active composite anode layer, which is composed of a good hydrocarbon cracking catalyst (such as Ni alloy) and a suitable ion conductor (such as doped oxidized lung Or ScYSZ); electrolyte layer; and active cathode layer and a transition layer to the cathode current collector, the transition layer is preferably composed of a mixture of LSM and ferrite, and the cathode current collector is preferably composed of single-phase LSM.

[0037] In a specific embodiment, the metal support may be composed of FeCrMx alloy. Mx is such as Ni, Ti, Ce, Mn, Mo,

Alloying elements of W, Co, La, Y or Al. The concentration remains below the level associated with the formation of austenite.

[0038] In another specific embodiment, the active anode may be composed of a porous layer of 8YSZ, co-doped zirconium oxide, or co-doped oxidized lung. 0~50% metal alloy can be added.

BRIEF DESCRIPTION OF THE DRAWINGS

[0040] The present invention is described below with reference to the drawings, in which:

[0041] FIG. 1 shows a robust medium temperature SOFC battery according to the present invention.

[0042] FIG. 2 shows the area specific resistance of a variety of cathode materials, including the cathode materials used in the SOFC battery according to the present invention.

[0043] FIG. 3 shows a SOFC cell with an anode permeable layer.

[0044] FIG. 4 shows an SOFC cell having an anode permeation layer and a barrier layer.

[0045] FIG. 5 shows a SOFC cell with a double-electrode permeable layer.

Detailed ways

[0046] FIG. 1 shows a solid oxide fuel cell SOFC according to the present invention. The battery includes: a metal support 1, which terminates in a substantially pure electronically conductive oxide; an active anode layer 2, which is composed of doped oxidized lung or ScYSZ.Ni-Fe alloy; an electrolyte layer 3, which is composed of a co-doped Zinc oxide or oxidized lung-based oxygen ion conductor; active cathode layer 5; and a mixture layer of LSM and ferrite layer, which serves as a cathode current collector 7 (or porous metal current collector) preferably composed of single-phase LSM or LnSrMnCo The transition layer 6.

[0047] The backbone of a complete solid oxide fuel cell composed of seven functional layers is the functionally graded porous cermet structure 1, which is composed of porous ferritic stainless steel and electronically conductive oxides such as (Sr^LaJsTirNbyCMLSTN), where OWxWO. 4,0.5WsWl, 0WyWl. Another example of this oxide is (La^S%) CrO₃ (LSC). Another example is Sr (La) Ti (Nb) 0₃ (LSTN) +FSS (for example, Fe22Cr). Generally, an electronically conductive oxide (η-type or ρ-type conductor) whose thermal expansion coefficient roughly matches that of metal can be used. The surface of the alloy (inside and outside) is coated with an electronic conductive oxide layer in order to prevent the cracking of hydrocarbons in the porous anode support 1. Since the cracking of hydrocarbons in the porous support may precipitate carbon and cause pore clogging, the cracking of hydrocarbons should only occur in the active anode.

[0048] The use of the metal support 1 instead of the Ni-YSZ anode support increases the mechanical strength of the support and ensures the redox stability of the support. The porous ferritic stainless steel 1 is terminated with pure electronically conductive oxides, such as LSC or LSTN (Sr(La)Ti(Nb)03), in order to prevent the reaction between metals in the active anode 2, especially Ni or NiO, which Easily dissolves into ferritic stainless steel, causing a potentially harmful phase shift from ferrite to austenitic structure. Diffusion can also occur in the opposite direction, because elements from the metal support can diffuse into the anode.

[0049] The active anode layer 2 is a gradual structure of doped oxidized lung+ScYSZ+Ni-Fe alloy, which contains only a small percentage of nano-sized metal catalyst, which is a good hydrocarbon cracking catalyst. The thickness of this layer is 1 ~ 50 μ m_o

[0050] The active anode 2 is made of solid solutions of NiO and FeO' or their mixtures in ScYSZ and LSTN. This product guarantees a small percentage of the nano-particle Ni-Fe catalyst after reduction in the operation of the fuel cell. This achieves a high surface area of the catalyst, and since the catalyst particles are kept at a certain distance from each other, the aggregation of the catalyst is prevented. A small amount of nickel and iron with high surface area can realize the rapid kinetics of the conversion and cracking of hydrocarbons, as well as the efficient electrochemical conversion of hydrogen. Only by finely dispersing the catalyst, the formation of carbon nanotubes when hydrocarbons are used as fuel is avoided. When the active anode is reduced, a finely dispersed catalyst is formed. Since the anode contains only a small percentage of the catalyst, it will be redox stable (since only a small part of the anode shows redox activity). The redox cycle can finally revive the nanostructure of the Ni-Fe catalyst (revive)_oThe anode 2 contains a large amount of oxidized lung, which has the ability to catalyze the electrochemical oxidation of carbon, which can be formed as a result of the cracking process.

[0051] The electrolyte layer 3 is composed of co-doped zirconium oxide-based oxygen ion conductors (Y, Sc)Sz (armor oxide, blubber oxide stabilized zirconium oxide). This type of electrolyte has higher oxygen ion conductivity than YSZ and better long-term stability than ScSZ. Alternatively, adulterated oxidized lung can be used.

[0052] The active cathode 5 of a battery with an operating temperature of 550°C can be manufactured from the following compound, a material selected from ScYSZ that may be doped with Ce or doped oxidized lung (for example, oxidation rolling doping oxidation Lung, CGO), one material selected from (Y₁__xCa_x)Fe₁__yCo_y0₃, (Gd^S%) sFe-yCog, (GdMaJ sFe-yCoq. Another example is a gradient compound

(Y,Ca)FeCo0₃And doped with zirconium oxide or oxidized lung. Such a cathode 5 shows better performance than LSM and other cathode materials, see Figure 2. Replacement of Y and Ca at the A site, instead of the commonly used cations La and Sr, improves the performance and stability of the cathode. The improved stability is due to the avoidance of non-conductive complex salts (La) when Y and Ca are used instead of La and Sr.₂Zr₂O₇And the formation of SrZrOj. In order to obtain a sufficiently long service life, the reaction barrier layer 4 of the doped oxidized lung (preventing the diffusion of cations from the cathode to the ScYSZ electrolyte) may be necessary. For fuel cells operating in a temperature range above 700°C, LSM-YSZ or (Y, Sc)SZ composite cathodes can be used, and in this case, the oxidized lung barrier layer 4 is not required.

[0053] On the active cathode layer 5, a mixture of LSM and ferrite or LSM + (Y, Ca) FeCo.₃The graded layer 6 is formed as a single-phase LSM (La(Sr)MnO₃) Or LSFCo (LarSr'FerCo/U) transition of the cathode current collector 7, because this has the highest electronic conductivity. The function of the transition layer 6 is to prevent high local thermal stress due to the small difference in thermal expansion coefficient between LSM and ferrite. This layer can be eliminated when LSM/YSZ is used as a cathode.

[0054] FIG. 2 shows Arrhenius curves of various cathode properties given as area resistivity (ASR). It shows that GSFCo-ferrite is as good as a cathode containing a noble metal catalyst.

[0055] As an alternative, the SOFC can be manufactured with a porous electrode permeable layer to ignore the diffusion between the metal support and the active anode, see FIG. 3, layers 11-13.

[0056] Layer 11: Metal support (200~2000 μm), FeCrMx alloy, with 0~50Vol% oxide (such as doped zirconium oxide, doped oxide lung or other oxides, such as Al₂0₃»Ti0₂, MgO, CaO, Cr₂0₃Or a combination thereof, but not limited to this material). The addition of oxides has the following functions: 1) enhance the chemical bonding between the anode layer and the metal support; 2) adjust the thermal expansion coefficient; and 3) control the sintering ability and grain growth.

[0057] Layer 12: A porous layer (20-100 μm) for anode penetration, Sc-Y-Ga-Ce doped with zirconium oxide/Sm-Gd-Y or any Ln element or CaO doped with oxidized lung, added With or without adding metal alloys (FeCrMx). In the case of adding a metal support material, the layer will have oxygen ion conductivity (doped zirconium oxide/oxidized lung) as well as electronic conductivity (metal). In the case of doped oxidized lungs, the layer will also have some electrocatalytic effect. After sintering, the anode is completed by infiltration of electrocatalytic components (Ni, with or without doped oxidized lung or any other electrocatalyst).

[0058] Layer 13: Standard electrolyte (~10 μm) similar to the ion conductive material of layer 12 or LaGa()3-based electrolyte.

[0059] Layer 14: Full battery; with two different options, as listed in Figures 3 and 5 below.

[0060] Figure 3: Ordinary cathodic spraying or screen printing.

[0061] FIG. 5: Permeation of the second porous layer 14 with the cathode.

[0062] The following advantages are obtained through application penetration:

[0063] 1. Simple, no anode/metal supporting barrier layer is required.

[0064] 2. Inexpensive treatment: only one sintering is required in the case of a double permeable layer.

[0065] 3. Sintering is performed in the absence of Ni, so grain growth during sintering (coarsening) is not a problem.

[0066] 4. Infiltration provides the possibility of obtaining electrodes with a high surface area.

5. Because the operating temperature is lower than the sintering temperature, the chemical reaction between the electrode material and another battery material is prevented/weakened.

[0068] 6. The composite structure of the permeable layer ensures a good mechanical bond between the electrolyte and the metal support, and good conductivity across the interface.

[0069] Examples are given below.

CN 1985397 Β

Example 1

[0071] The first step is to tape cast a ferritic stainless steel slurry with a composition of Fe-22% Cr to a thickness of 1 mm.

[0072] The second step is to cast the upper part of Fe-Cr ferritic steel by 80wt% (Sr₀.₈La₀.₂) ₀.₉₅Ti₀.₉Nb₀. jOg

A composite composed of 20wt% Fe-22% Cr slurry, with a thickness of 5-50 μm_o

[0073] The third step is to spray (SroJa.. 2) 0.95^0.9^0/3° with a thickness of 5-50um

[0074] The fourth step is to spray the active anode slurry with a thickness of 10 μ mo. The composition of the slurry is 50wt% Yo.o₄Sc_o.₁₆Zr_o.₈O₂ And 50wt% Sro.^Nio.ogFeo.JiOgo

[0075] The fifth step is that the spray composition is Y₀.₀₄Sc₀.₁₆Zr_o.₈O₂Electrolyte with a thickness of 5 μm_o

[0076] The sixth step is to co-sinter the obtained half-cell at 1300°C in a reducing atmosphere of 9% + 91% Ar.

[0077] The seventh step is to spray a barrier layer composed of Ceo.9Gdo.Q95, with a thickness of 0.2 μm, and then sintered at 700°C.

[0078] The eighth step is to coat Fe-Cr alloy.

[0079] The ninth step is to spray 50wt% (Gd₀.₆Sr₀.₄) ₀.₉₉Co₀.₂Fe₀.₈0₃ And 50wt% Y_{0 04}Sc₀.₁₆Zr_o.₈O₂ The formed cathode has a thickness of 20 μ mo

[0080] The tenth step is to spray 50wt% (La_{0 85}Sr₀.₁₅) ₀.9₅Μ^ηθ3 and 50wt% (Gd₀.₈Sr₀.₄) q. 9₉Co₀.₂Fe₀.₈0₃, The thickness is 1 ~ 30 um.

[0081] The first step is screen printing by (La_{0 85}Sr₀.₁₅)o.9₅MnO₃The formed current collector has a thickness of 50 μm.

[0082] The cathode and the cathode current collector are sintered in situ in the stack.

[0083] The resulting solid oxide fuel cell is robust and flexible because both hydrocarbons and hydrogen can be converted at the anode. The fuel cell converts hydrocarbons through cracking, and then electrochemically oxidizes the cracked products. Either air or pure oxygen can be used as the oxidant.

Embodiment 2

[0085] The first step is to cast a ferritic stainless steel slurry with a composition of Fe-22% Cr to a thickness of 1 mm. [0086] The second step is to cast the upper part of Fe-Cr ferritic steel by 80wt% (Sr₀.₈La₀.₂) ₀.₉₅Ti₀.₉Nb₀. jOg 20wt% Fe-22% Cr slurry composition, the thickness is 5~50 μ m_o

[0087] The third step is to spray with a thickness of 5~30um

[0088] The fourth step is to spray the active anode slurry with a thickness of 10 μ mo. The composition of the slurry is 50wt% Yo.o₄Sc_o.₁₆Zr_o.₈O₂_₅ And 50wt% Sro.84Nio.o5Feo.JiO3.

[0089] The fifth step is that the spray composition is Y₀.₀₄Sc₀.₁₆Zr_o.₈O₂_₅The electrolyte has a thickness of 5 μm.

[0090] The sixth step is to co-sinter the obtained half-cell at 1300°C in a reducing atmosphere of 9% + 91% Ar.

[0091] The seventh step is to spray a barrier layer composed of Ceo.9Gdo.Q95 with a thickness of 0.2 μm, and then sinter at 700°C.

[0092] The eighth step is to coat Fe-Cr alloy.

[0093] The ninth step is to spray 50wt% (Gd₀.₆Sr₀.₄) ₀.₉₉Co₀.₂Fe₀.₈0₃__δ And 50wt% of CG010 constitute the cathode, the thickness is 20 μ mo

[0094] The tenth step is to spray 50wt% (La_{0 85}Sr₀.₁₅) ₀.9₅Μ^ηθ3 and 50wt% (Gd₀.₆Sr₀.₄) q. 9₉Co₀.₂Fe₀.₈0₃, The thickness is 1 ~ 30 um.

[0095] The first step is screen printing by (La_{0 85}Sr₀.₁₅)o.9₅MnO₃The formed current collector has a thickness of 50 μm. The cathode is sintered on-site in the stack.

[0096] The resulting solid oxide fuel cell is robust and flexible because both hydrocarbons and hydrogen can

CN 1985397 Β

Enough to switch at the anode. The fuel cell converts hydrocarbons through cracking, and then electrochemically oxidizes the cracked products. Either air or pure oxygen can be used as the oxidant.

Example 3

[0098] The first step is to cast a ferritic stainless steel slurry with a composition of Fe-22% Cr to a thickness of 1 mm.

[0099] The second step is to cast the upper part of Fe-Cr ferritic steel by 80wt% (Sr₀.₈La₀.₂) ₀.₉₅Ti₀.₉Nb₀. jOg and

A composite composed of 20wt% Fe-22% Cr slurry, with a thickness of 5-50 μm_o

[0100] The third step is to spray the thickness of 1 ~ 30um (Sro.^ao.^o.ggTio.gNbO.Ao

[0101] The fourth step is to spray the active anode slurry with a thickness of 10 μ mo. The composition of the slurry is 50 wt%

Yo.o₄Sc_o.₁₆Zr_o.₈O₂_₅ And 50wt% Sro.84Nio.o5Feo.JiO3.

[0102] The fifth step is to spray the composition as Y₀.₀₄Sc₀.₁₆Zr_o.₈O₂_₅The electrolyte has a thickness of 5 μm.

[0103] The sixth step is spraying by Ce_o.₉Gd_oThe barrier layer composed of .iOi.95 with a thickness of 0.5 μ m_o

[0104] The seventh step is to co-sinter the obtained half-cell at 1350°C in a reducing atmosphere of 9% + 91% Ar.

[0105] The eighth step is to coat Fe-Cr alloy.

[0106] The ninth step is to spray 50wt% (Gd₀.₆Ca₀.₄)₀.₉₉Co₀.₂Fe₀.₈0₃ A cathode composed of 50wt% CG010 with a thickness of 20 μm_o

[0107] The tenth step is to spray 50wt% (La_{0 85}Sr₀.₁₅) ₀.9₅Μ^ηθ3 and 50wt% (Gd₀.₆Sr₀.₄) q. 9₉Co₀.₂Fe₀.₈0₃, The thickness is 1 ~ 30 um.

[0108] The first step is screen printing by (La_{0 85}Sr₀.₁₅)o.9₅MnO₃The formed current collector has a thickness of 50 μm. The cathode is sintered on-site in the stack.

[0109] The resulting solid oxide fuel cell is robust and flexible because both hydrocarbons and hydrogen can be converted at the anode. The fuel cell converts hydrocarbons through cracking, and then electrochemically oxidizes the cracked products. Either air or pure oxygen can be used as the oxidant.

Example 4

[0111] The first step is to cast a ferritic stainless steel slurry with a composition of Fe-22% Cr to a thickness of 1 mm.

[0112] The second step is to cast on the upper part of Fe-Cr ferritic steel by 80wt% (Sr_{0 8}La_{0 2}) ₀.₉₅Ti_{0 9}Nb₀. Q and

A composite composed of 20wt% Fe-22% Cr slurry, with a thickness of 5-50 μm_o

[0113] The third step is to spray (SroJa..2) 0.95^0.9^0/3° with a thickness of 1-30um

[0114] The fourth step is to spray active anode slurry with a thickness of 10 μ mo. The composition of the slurry is 50 wt%

Yo.o₄Sc_o.₁₆Zr_o.₈O₂_₅ And 50wt% Sro.84Nio.o5Feo.JiO3.

[0H5] The fifth step is to spray the composition as Y_o.o4Sc_o. i₆Zr_o.8O₂_₅Electrolyte with a thickness of 5 μm_o

[0116] The sixth step is to co-sinter the obtained half-cell at 1350°C in a reducing atmosphere of 9% + 91% Ar.

[0117] The seventh step is to spray a cathode composed of 50wt% LSM and 50wt% Y().04SC0. Significant%8.2_$, with a thickness of μm_o

[0118] The eighth step is screen printing by (La_o.₈₅Sr_o.₁₅)_o.₉₅MnO₃The formed current collector has a thickness of 50 μm_oThe cathode is sintered in situ in the stack.

[0119] The resulting solid oxide fuel cell is robust and flexible because both hydrocarbons and hydrogen can be converted at the anode. The fuel cell converts hydrocarbons through cracking, and then electrochemically oxidizes the cracked products. Either air or pure oxygen can be used as the oxidant.

Example 5

CN 1985397 Β

[0121] The first step is to cast a ferritic stainless steel slurry with a composition of Fe-22% Cr to a thickness of 1 mm. [0122] The second step is to cast the upper part of Fe-Cr ferritic steel by 80wt% (Sr₀.₈La₀.₂） ₀.₉₅Ti₀.₉Nb₀. jOg 20wt% Fe-22% Cr slurry composition, the thickness is 5~50 μ m_o

[0123] The third step is to spray the thickness of 1 ~ 30um (SroJa.. 2) 0.95^0.9^0/3°

[0124] The fourth step is to spray the active anode slurry with a thickness of 10 μ mo. The composition of the slurry is 50wt% Yo.o₄Sc_o.₁₆Zr_o.₈O₂_₅ And 50wt% Sro.84Nio.o5Feo.JiO3.

[0125] The fifth step is to spray the composition as Y₀.₀₄Sc₀.₁₆Zr_o.₈O₂_₅The electrolyte has a thickness of 5 μm.

[0126] The sixth step is to co-sinter the obtained half-cell at 1350°C in a reducing atmosphere of 9% + 91% Ar.

[0127] The seventh step is to spray a cathode composed of 50wt% LSM and 50wt% Y().04SC0. Significant%8.2_$, with a thickness of μm_o

[0128] The eighth step is to screen-print a current collector composed of (La. 85S% © ο. 95Mn () 3 with a thickness of 50 μm.

[0129] The cathode is sintered in situ in the stack.

[0130] The resulting solid oxide fuel cell is robust and flexible because both hydrocarbons and hydrogen can be converted at the anode. The fuel cell converts hydrocarbons through cracking, and then electrochemically oxidizes the cracked products. Either air or pure oxygen can be used as the oxidant.

Example 6

[0132] A support sheet with a thickness in the range of 200-2000 μm is manufactured by casting a Fe22Cr alloy (+small amount of components, such as Mn) powder suspension, see FIG. 3. After drying the support 11, deposit the layer for anode penetration (layer 12, 50um) and the final electrolyte layer (layer 13, 10 μm) by spraying. The composition of both layers is Zr₀.₇₈Sc₀.₂₀Y₀.₀₂0₂__{5 ο}The suspension for spraying is manufactured so that the permeable layer 12 has a porosity of at least 40%, an average pore size of 3um, and the electrolyte is dense after sintering. The sample is then stamped to the desired size and sintered under controlled reduction conditions for the so-called half-cell. The Ni-, Ce-, Gd-nitrate solution penetrates into the porous dislocation oxide layer 12 by vacuum immersion. The resulting anode has a volume concentration of 40% Ni and 60% (GdoJeoJOzY. After drying and cleaning the electrolyte surface, it is deposited by spraying method (Gd₀.₆Sr₀.₄） ₀.₉₉ (Co₀.₂Fe₀.₈） 0₃__δ Cathode (layer 14,40 pm).

Example 7

[0134] A support sheet with a thickness in the range of 200-2000 μm is manufactured by casting a Fe22Cr alloy (with a small amount of additional components) powder suspension, see FIG. 3. After drying the support 11, screen printing includes Zr with a volume ratio of 1:1₀. ₇₈Sc₀.₂₀Y₀.₀₂0₂_₅Ink with a mixture of FeCr alloy to deposit a layer for anodic penetration (layer 12,50 μm) _oThe addition of metal to the infiltration layer ensures a good bond between the metal support and the infiltration layer. Finally, the electrolyte layer (layer 13, 10 ~ 15 μm) was deposited by spraying. The battery was completed as described in Example 6.

Example 8

[0136] A support sheet with a thickness in the range of 200-2000 μm is manufactured by casting a powder suspension of Fe22Cr alloy (with a small amount of components) mixed with 2-10 Vol% ZroyYo.c ^r, see FIG. 3. The battery was completed as described in Example 7.

Example 9

[0138] A support sheet with a thickness in the range of 200-2000 μm is manufactured by casting a Fe22Cr alloy (with a small amount of additional components) powder suspension, see FIG. 3. The graded permeable layer is made from one or more flakes including electrolyte material and metal alloy (FeCrMj mixture). Flake with a thickness of 30~70 μm is produced by casting a powder suspension, which has varying particle sizes and the resulting pores Size. Through calendering and pressing, laminated metal support sheet and 1~

4 permeable layers to make the battery structure. The resulting permeable layer has a gradual change in composition, with pore size and particle size varying in the range of 5-10 μm, and the relative metal support is reduced to ~1 μm at the electrolyte interface. The battery is completed as described in Example 6.

Example 10

[0140] As in Example 9, but adding a pore former to control the final porosity of the permeable layer and the metal support.

Example 11

[0142] As in Example 10, but adding a sintering additive (15) to control the shrinkage of the layer. Examples include (but are not limited to) A12()3, MgO, CaO, Sr0, Co0_x, MnO_x, B₂0₃, CuO_x, ZnO₂, V0_x, Cr₂O₃, FeO_x, NiO, Mo0_x, W0₃, Ga₂0₃Or a combination thereof.

Example 12

[0144] The half-cell as described in the previous embodiment was manufactured. The cathode/electrolyte barrier layer 14 (FIG. 4) (0.5 μm) was deposited on the surface of the electrolyte by spin-coating a Gd-Ce nitrate solution. After sintering the barrier layer at 700°C, the

0₂__δThe anode penetrates into layer 12 as described in Example 6. After drying and cleaning the electrolyte surface, it is deposited by screen printing (La_{0 6}Sr₀. J ο. 99 (Co_{0 2}Fe_{0 8}） 0₃__δ Cathode (layer 15,40pm).

Example 13

[0146] A support sheet with a thickness of about 800 um was manufactured by rolling Fe22Cr alloy slurry, layer 11 in FIG. 3. After drying the support, the layer for anode penetration (layer 12) and the electrolyte layer are deposited by screen printing. The composition of the two layers is (SnviCeaJO^s. The ink used for screen printing is manufactured so that the permeable layer has a porosity of >50%, the average pore size is 1~2 um, and the electrolyte is dense. Then the sample is stamped To the desired size and sinter the so-called half-cell under controlled reducing conditions.

[0147] A solution of Ni nitrate was prepared and penetrated into the porous (SmaiCecJO-layer (layer ) by dipping. After drying and cleaning the electrolyte surface, it was deposited by spraying method (La₀.₆Sr₀.₄）₀.₉₉ (Co₀.₂Fe₀.₈） 0₃__δCathode (layer 14).

Example 14

[0149] Containing 5vol% (Gd₀ jCeo ₉） 0₂__δThe Fe22Cr alloy powder suspension is used to make a support sheet with a thickness of about 500 μm to enhance the combination with the permeable layer, see Figure 3. The layer for anode penetration (30 μm) and the final electrolyte layer (10 μm) are deposited by spraying. The composition of these two layers is (Gdo.jCeo.g) 0₂__δοAfter sintering, the nitrates of Ni, Gd and Ce are penetrated into the porous oxidized lung layer by vacuum immersion. After drying and cleaning the electrolyte surface, the LSCF cathode was deposited by screen printing.

Example 15

[0151] The support was manufactured as described in Example 8. The layer for anodic penetration (30 μm) and (Gd₀ jCeo ₉）0₂__δElectrolyte layer (10 μm), the layer used for anode infiltration includes Fe-Cr alloy powder and (Gdo.iCeo.g) 0₂__δ, The volume ratio is 1: Ιο complete the battery as described in Example 6.

Example 16

[0153] The support was manufactured as described in Example 6 (layer 11 in FIG. 3). After drying the support, deposit the layer for electrode penetration by spraying method (layer 12, 70 μm)> Zr_{0 78}Sc_{0 20}Y_{0 02}0₂_ _δElectrolyte layer (layer 13, 10 pm), and finally another layer for electrode penetration (layer 14, 30 pm) ο The composition of both penetration layers is Zr₀.₇₈Sc₀.₂₀Y₀.₀₂0₂-₅With 40vol% FeCr powder, it has an approximate porosity of ~60% porosity.

[0154] The sample is then stamped to the desired size, and the sample is sintered under controlled reducing conditions. The shielding layer 14, and the Ni-, Ce-, Gd-nitrate solution is penetrated into the porous layer 12 by vacuum immersion. The resulting anode will have a volumetric concentration

CN 1985397 Β

Ni with a degree of 40% and 60% (GdoJeo.JCU. After drying, remove the mask on layer 14, mask layer 12 and infiltrate the active cathode material by vacuum immersion in a nitrate solution (the resulting cathode composition) :

[0155] (Gd_{0 6}Sr₀.₄) Ο. 99 (Co_{0 2}Fe₀.₈） 0₃_ _δ °

Example 17

[0157] The battery structure was manufactured as described in Example 6. Penetrate nano-sized NiO and (Gdo.iCeo.g) through pressure 0₂__δThe suspension is used to make the anode layer.

Example 18

[0159] As in Example 7, but characterized by the use of a sintering additive (selected from (but not limited to) one or more of the list given in Example 12), which enables oxidation at a temperature lower than 1100°C Various components are sintered appropriately under the conditions.

CN 1985397 Β