A multi-channel micro-tube solid oxide electrolysis cell and a preparation method and application thereof

Abstract

This invention discloses a multi-channel microtubular solid oxide electrolytic cell, its preparation method, and its application. The electrolytic cell includes an anode layer, a cathode layer, and an electrolyte layer disposed between the cathode and cathode layers. A mass transfer selection layer is provided outside the electrolyte layer, and an interface optimization layer is provided outside the mass transfer selection layer. The anode layer has a multi-channel microtubular structure. First, a multi-channel microtubular anode support is prepared by extrusion, spinning, or other methods. An electrolyte layer is screen-printed on the outer surface of the anode support. Then, the anode electrolyte structure green body is co-sintered at high temperature to obtain a half-cell structure. Subsequently, a YSZ electron blocking layer is prepared on the electrolyte surface, and then cerium oxide-doped material is coated on the surface of the YSZ electron blocking layer. Finally, a cathode is coated and sintered to obtain a microtubular electrolytic cell with a complete structure. This invention can improve the mechanical strength, gas diffusion performance inside the tube, and electrolytic Faraday efficiency of the electrolytic cell.

Description

Technical Field

[0001] This invention relates to the field of solid oxide fuel electrolyzers, specifically to a multi-channel microtube solid oxide electrolyzer, its preparation method, and its application. Background Technology

[0002] Hydrogen, as a storable and transportable energy carrier, has attracted widespread attention in recent years. Due to its non-toxicity, high energy density, and wide availability, hydrogen is used in aerospace and other fields. As a secondary energy source, hydrogen is currently mainly produced through fossil fuel reforming and water electrolysis. Although traditional methods for producing hydrogen from fossil fuels are mature, they utilize non-renewable resources and offer no benefit to energy and environmental issues. Electrolysis of renewable resources for hydrogen production, however, has unique advantages: simple operation and high efficiency. Currently, there are two main technologies for hydrogen production via water electrolysis: alkaline water electrolysis, which can produce hydrogen at low temperatures but requires the addition of precious metals and has relatively low efficiency; and solid oxide electrolyzer (SOEC) water electrolysis, which includes oxygen-ion SOEC and proton-ion SOEC, both of which can convert and store electrical energy to produce hydrogen.

[0003] Faraday efficiency, as an effective parameter for evaluating the electrolysis efficiency of an electrolytic cell, is a crucial factor in assessing the application prospects of SOEC (Sodium Electrolytic Cell). Currently, oxygen-ion SOECs have higher Faraday efficiencies (70%-90%) than proton-type SOECs (40%-80%), making them more valuable for application. However, proton conduction is more advantageous than oxygen-ion conduction at medium and low temperatures. Therefore, proton-type SOECs can operate not only at high temperatures but also at medium and low temperatures with high efficiency and good stability. They consist of porous electrodes on both sides and a dense electrolyte layer in the middle. The proton-conducting electrolyte layer isolates the reactant gases while simultaneously facilitating proton transport. The electrode materials on both sides mainly utilize high-performance electrode materials found in oxygen-ion SOECs, such as NiO-BZCYYb anode materials. Due to the significant electronic conductivity of the proton-conducting electrolyte under electrolysis conditions, some current forms an internal short circuit within the electrolyte during electrolysis, ultimately leading to a generally low Faraday efficiency and a sharp decline in the effective utilization of electrical energy. Summary of the Invention

[0004] The purpose of this invention is to provide a multi-channel microtube solid oxide electrolytic cell, its preparation method and application, which has significantly higher mechanical strength, gas transport rate and electrolytic Faraday efficiency than flat plate and tubular electrolytic cells.

[0005] In one aspect of the invention, a multi-channel microtubular solid oxide electrolyzer is proposed. According to an embodiment of the invention, it includes a porous anode layer, a porous cathode layer, and a dense electrolyte layer disposed between the cathode layer and the cathode layer. A mass transfer selection layer is disposed outside the electrolyte layer, and an interface optimization layer is disposed outside the mass transfer selection layer.

[0006] In addition, a multi-channel microtube solid oxide electrolyzer according to the above embodiments of the present invention may also have the following additional technical features:

[0007] In some embodiments of the present invention, the porous anode layer comprises NiO and BaZr. x Ce y Y z Yb w O3, where x+y+z+w=1; the porous anode layer has a multi-channel microtube structure, the microtube diameter is 0.5-10mm, and the number of microtube channels is 2-10.

[0008] In some embodiments of the present invention, the dense electrolyte layer comprises BaZr. x Ce y Y z Yb w O3, where x+y+z+w=1; the porous cathode layer comprises La x Sr 1-x Co y Fe 1-y O3.

[0009] In some embodiments of the present invention, the mass transfer selectivity layer is yttrium-stabilized zirconium oxide, wherein the Y2O3 doping amount is 3wt%-13wt% and the thickness of the mass transfer selectivity layer is 0.1-0.5μm.

[0010] In some embodiments of the present invention, the interface optimization layer is composed of doped cerium oxide M. x Ce 1-x O2, where M is one of La, Gd, Sm or Pr, x is 0-0.4, and the thickness of the interface optimization layer is 0.1-10μm.

[0011] In another aspect, the present invention provides a method for preparing a multi-channel microtube solid oxide electrolytic cell. According to an embodiment of the present invention, the preparation method includes the following steps:

[0012] (1) The multi-channel anode support green body is sintered at 1000-1100℃ for 2-3 hours to obtain the multi-channel anode support, i.e. the anode layer;

[0013] (2) Electrolyte paste is screen-printed on the surface of the anode support and co-fired at 1400-1500℃ for 5-8 hours to obtain the phased electrolyte layer;

[0014] (3) A YSZ layer is further magnetron sputtered on the surface of the electrolyte layer as a mass transfer selective layer;

[0015] (4) Coat the surface of the mass transfer selection layer with a layer of cerium oxide doped slurry as an interface optimization layer;

[0016] (5) The battery structure after the above-mentioned coating interface optimization layer is sintered at 1350-1450℃ for 3-10h to obtain a multi-channel microtube half cell.

[0017] (6) The cathode material is coated on the surface of the half cell prepared above, and the multi-channel microtube solid oxide electrolytic cell is obtained after sintering at 1000-1100℃ for 2-3 hours.

[0018] In addition, the method for preparing a multi-channel microtube solid oxide electrolytic cell according to the above embodiments of the present invention may also have the following additional technical features:

[0019] In some embodiments of the present invention, in step (1), the multi-channel anode support green body is prepared by extrusion / phase inversion method, the anode layer material is extruded to a 10-20°C condensation bath and placed for 16-24h, and then transferred out and naturally dried for 24-48h to obtain the anode support green body; in step (2), 1wt%-4wt% of NiO electrolyte is added as a sintering aid.

[0020] In another aspect of the invention, the invention proposes to use the aforementioned multi-channel microtubular solid oxide electrolyzer for high-temperature water electrolysis to produce hydrogen.

[0021] In another aspect, the present invention proposes a multi-channel microtubular solid oxide electrolysis device. According to an embodiment of the present invention, the multi-channel microtubular solid oxide electrolysis cell of the device is sealed using conductive adhesive as a sealant. The two electrodes of the multi-channel microtubular solid oxide electrolysis cell are externally connected using silver wires as conductors. Both ends of the multi-channel microtubular solid oxide electrolysis cell are sealed with high-temperature resistant ceramic tubes. A hydrogen-transmitting ceramic tube, thinner than the high-temperature resistant ceramic tube, is fixed to the other end of the high-temperature resistant ceramic tube with a rubber stopper. The multi-channel microtubular solid oxide electrolysis cell is connected to a water-transmitting high-temperature resistant ceramic tube, and the electrolysis cell and the water-transmitting high-temperature resistant ceramic tube are sealed together by a sealing device.

[0022] In another aspect, the present invention proposes a method for producing hydrogen by electrolysis of water at a medium-high temperature of 500-800°C. According to an embodiment of the present invention, the aforementioned multi-channel microtubular solid oxide electrolysis device is used for high-temperature water electrolysis to produce hydrogen.

[0023] Compared with the prior art, the beneficial effects of the present invention are:

[0024] 1) This invention uses a multi-channel anode support with different microtube diameters and different numbers of microtubes. The anode has micron-level internal pores and millimeter-level microtube channels, which can effectively improve the gas transport rate, quickly transport the H2 product from the anode, and avoid product accumulation. At the same time, compared with tubular SOEC, multi-channel microtube SOEC has more support structures and higher mechanical strength.

[0025] 2) The present invention adds a YSZ mass transfer selectivity layer on the surface of the electrolyte layer, which has negligible electronic conductivity. Therefore, it can avoid the conduction of electrons generated by the electrode reaction inside the battery, thereby reducing electron loss and greatly improving the electrolytic Faraday efficiency.

[0026] 3) Use doped cerium oxide M x Ce 1-x O2, as an interface optimization layer, has an adjustable coefficient of thermal expansion and excellent interface matching performance. It plays a role in interface matching and optimizing interface impedance between the mass transfer selective layer and the cathode, which can effectively improve the electrochemical performance of the electrolytic cell.

[0027] 4) This invention has a unique structure, high strength, high electrolytic Faraday efficiency, and good stability, making it suitable for industrial applications. Attached Figure Description

[0028] Figure 1 This is a schematic diagram of the two-dimensional structure of the four-channel microtube solid oxide fuel electrolyzer in Embodiment 1 of the present invention (the electrolyzer structure is NiO-BZCYYb|BZCYYb|YSZ|GDC|LSCF), wherein the left figure is the main view and the right figure is the side view;

[0029] Figure 2 This is a schematic diagram of the three-dimensional structure and water electrolysis principle of the four-channel microtubular solid oxide fuel electrolyzer in Embodiment 1 of the present invention;

[0030] Figure 3 This is a graph showing the change in current density over a long period of time in the four-channel microtube solid oxide fuel electrolyzer of Embodiment 1 of the present invention (the test conditions were 700℃ and 1.5V applied voltage, with 10% H2O / H2 introduced as a water source on the cathode side).

[0031] Figure 4 This is a schematic diagram of the three-dimensional structure of the eight-channel microtubular solid oxide fuel electrolyzer in Embodiment 2 of the present invention (the electrolyzer structure is NiO-BZCYYb|BZCYYb|YSZ|GDC|LSCF);

[0032] Figure 5 This is a schematic diagram of the three-dimensional structure of the four-channel microtubular solid oxide fuel electrolyzer in Embodiment 3 of the present invention (the electrolyzer structure is NiO-BZCYYb|BZCYYb|YSZ|LSCF);

[0033] Figure 6 This is a schematic diagram of the three-dimensional structure of the four-channel microtubular solid oxide fuel electrolyzer in Embodiment 4 of the present invention (the electrolyzer structure is NiO-BZCYYb|BZCYYb|GDC|LSCF);

[0034] Figure 7 This is a schematic diagram of the three-dimensional structure of the four-channel microtubular solid oxide fuel electrolyzer in Embodiment 5 of the present invention (the electrolyzer structure is NiO-BZCYYb|BZCYYb|LSCF);

[0035] Figure 8 This is a schematic diagram of a multi-channel microtube solid oxide fuel electrolysis device in Embodiment 6 of the present invention. In the figure, 1 is a multi-channel microtube solid oxide electrolysis cell, 2 is a high-temperature resistant ceramic tube, 3 is a rubber stopper, 4 is a high-temperature resistant ceramic tube for transmitting hydrogen, 5 is a high-temperature resistant ceramic tube for transmitting water, 6 is a high-temperature resistant ceramic tube for sealing device, 7 is a furnace body temperature zone, and 8 is a wire.

[0036] Figure 9 The hydrogen production rate of different multi-channel microtube solid oxide fuel electrolyzers in Example 6 of this invention is shown. The test conditions are 700℃ and 1.5V external voltage, and 10% H2O / H2 is introduced into the cathode side as a water source. The horizontal axis 1-5 correspond to the hydrogen production rate of Examples 1-5 respectively.

[0037] Figure 10 This is a comparison chart of the Faradaic efficiencies of different multi-channel microtube solid oxide fuel electrolyzers in Example 6 of the present invention. The test conditions were all at 700℃ and 1.5V applied voltage, with 10% H2O / H2 introduced as the water source on the cathode side. Among them, 1-1, 1-2, and 1-3 are the Faradaic efficiencies of the electrolyzer assembled in Example 1, 2-1 and 2-2 are the Faradaic efficiencies of the electrolyzer assembled in Example 2, 3-1, 3-2, and 3-3 are the Faradaic efficiencies of the electrolyzer assembled in Example 3, 4 is the average Faradaic efficiency of the electrolyzer assembled in Example 4, and 5 is the average Faradaic efficiency of the electrolyzer assembled in Example 5. Detailed Implementation

[0038] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0039] Example 1

[0040] A method for preparing a multi-channel microtube solid oxide electrolytic cell includes the following steps:

[0041] (1) Using a 4-hole nozzle, BaZr was extruded / phase-inversioned via extrusion / phase-inversion method. 0.1 Ce 0.7 Y 0.1 Yb 0.1 An anode slurry with an O3 to NiO mass ratio of 4:6 was extruded into a 20°C condenser bath and placed for 24 hours. It was then transferred out and naturally dried for 24 hours to obtain a four-channel anode support green body with a green body diameter of 3 mm and a microtube diameter of 0.8 mm.

[0042] (2) A 30 μm thick layer of BaZr with 1 wt% NiO added was screen-printed on the surface of the anode support green body. 0.1 Ce 0.7 Y 0.1 Yb 0.1 O3 electrolyte slurry was co-fired at 1450℃ for 5 hours to obtain a phased anode electrolyte structure;

[0043] (3) For the completed anodic electrolytic cell structure, a 0.2 μm thick 8YSZ layer is further magnetron sputtered on its surface as a mass transfer selective layer;

[0044] (4) Coat the surface of the battery structure after the above-mentioned mass transfer selective layer with a 5μm thick Gd layer. 0.1 Ce 0.9 O2 slurry is used as an interface optimization layer;

[0045] (5) The battery structure after coating the interface optimization layer was sintered at 1400℃ for 5h to obtain a multi-channel microtube half cell.

[0046] (6) Coat the surface of the half-cell prepared above with a La layer with a thickness of 30 μm. 0.6 Sr 0.4 Co 0.2 Fe 0.8 O3 cathode paste was used to prepare a complete electrolytic cell after sintering at 1000℃ for 2 hours;

[0047] (7) The above-mentioned complete four-channel tubular solid oxide fuel electrolyzer structure is sealed to obtain the four-channel microtubular solid oxide electrolyzer used for high-temperature water electrolysis to produce hydrogen.

[0048] Figure 1 This is a schematic diagram of the two-dimensional structure of the four-channel microtube solid oxide fuel electrolyzer in Embodiment 1 of the present invention, which includes a complete four-channel porous anode layer, a dense electrolyte layer, a dense YSZ mass transfer selection layer, a cerium oxide doped interface optimization layer, and a porous cathode layer, comprising a five-layer structure. Figure 2 This is a schematic diagram of the three-dimensional structure and water electrolysis principle of the four-channel microtube solid oxide electrolytic cell in Embodiment 1 of the present invention. Under an applied voltage, water in the cathode of the electrolytic cell loses electrons to generate oxygen, electrons, and H2O. + H + Electrons reach the anode through the interface optimization layer, mass transfer selectivity layer, and dense electrolyte. Electrons are blocked by the mass transfer selectivity layer and can only be transported to the anode via the external circuit, where they interact with H+. + The hydrogen gas produced by the reaction is discharged and collected through the pores of the anode support; Figure 3 This is a graph showing the change in current density during continuous electrolysis for 10 hours in the four-channel microtube solid oxide fuel electrolyzer of Embodiment 1 of the present invention. Under the test conditions, the current density was kept constant at the temperature during the Faraday efficiency test, indicating good electrolysis stability.

[0049] Example 2

[0050] The difference between this embodiment and Embodiment 1 is that an 8-hole nozzle is used.

[0051] A method for preparing a multi-channel microtube solid oxide electrolytic cell includes the following steps:

[0052] (1) Using an 8-hole nozzle, BaZr was extruded / phase-inversioned via an extrusion / phase-inversion method. 0.1 Ce 0.7 Y 0.1 Yb 0.1 An anode slurry with an O3 to NiO mass ratio of 4:6 was extruded into a 20°C condenser bath and placed for 24 hours. It was then transferred out and naturally dried for 24 hours to obtain a four-channel anode support green body with a green body diameter of 3 mm and a microtube diameter of 0.8 mm.

[0053] (2) A 30 μm thick layer of BaZr with 1 wt% NiO added was screen-printed on the surface of the anode support green body. 0.1 Ce 0.7 Y 0.1 Yb 0.1 O3 electrolyte slurry was co-fired at 1450℃ for 5 hours to obtain a phased anode electrolyte structure;

[0054] (3) For the completed anodic electrolytic cell structure, a 0.2 μm thick 8YSZ layer is further magnetron sputtered on its surface as a mass transfer selective layer;

[0055] (4) Coat the surface of the battery structure after the above-mentioned mass transfer selective layer with a 5μm thick Gd layer. 0.1 Ce 0.9 O2 slurry is used as an interface optimization layer;

[0056] (5) The battery structure after coating the interface optimization layer was sintered at 1400℃ for 5h to obtain a multi-channel microtube half cell.

[0057] (6) Coat the surface of the half-cell prepared above with a La layer with a thickness of 30 μm. 0.6 Sr 0.4 Co 0.2 Fe 0.8 O3 cathode paste was used to prepare a complete electrolytic cell after sintering at 1000℃ for 2 hours;

[0058] (7) The above-mentioned complete eight-channel tubular solid oxide fuel electrolyzer structure is sealed to obtain the eight-channel microtubular solid oxide electrolyzer used for high-temperature water electrolysis to produce hydrogen.

[0059] Figure 4 This is a schematic diagram of the three-dimensional structure of the eight-channel microtubular solid oxide fuel electrolyzer in Embodiment 2 of the present invention, which includes a complete five-layer structure: an eight-channel porous anode layer, a dense electrolyte layer, a dense YSZ mass transfer selection layer, a cerium oxide doped interface optimization layer, and a porous cathode layer.

[0060] Example 3

[0061] The difference between this embodiment and Embodiment 1 is that no cerium oxide doped interface optimization layer is added.

[0062] A method for preparing a multi-channel microtube solid oxide electrolytic cell includes the following steps:

[0063] (1) Using a 4-hole nozzle, BaZr was extruded / phase-inversioned via extrusion / phase-inversion method. 0.1 Ce 0.7 Y 0.1 Yb 0.1 An anode slurry with an O3 to NiO mass ratio of 4:6 was extruded into a 20°C condenser bath and placed for 24 hours. It was then transferred out and naturally dried for 24 hours to obtain a four-channel anode support green body with a green body diameter of 3 mm and a microtube diameter of 0.8 mm.

[0064] (2) A 30 μm thick layer of BaZr with 1 wt% NiO added was screen-printed on the surface of the anode support green body. 0.1 Ce 0.7 Y 0.1 Yb 0.1 O3 electrolyte slurry was co-fired at 1450℃ for 5 hours to obtain a phased anode electrolyte structure;

[0065] (3) For the completed anodic electrolytic cell structure, a 0.2 μm thick 8YSZ layer is further magnetron sputtered on its surface as a mass transfer selective layer;

[0066] (4) Coat the surface of the above-mentioned half-cell with a mass transfer selectivity layer with a La layer of 30 μm thickness. 0.6 Sr 0.4 Co0.2 Fe 0.8 O3 cathode paste was used to prepare a complete electrolytic cell after sintering at 1000℃ for 2 hours;

[0067] (5) The above-mentioned complete four-channel tubular solid oxide fuel electrolyzer structure is sealed to obtain the four-channel microtubular solid oxide electrolyzer used for high-temperature water electrolysis to produce hydrogen.

[0068] Figure 5 This is a schematic diagram of the three-dimensional structure of the four-channel microtubular solid oxide fuel electrolyzer in Embodiment 3 of the present invention, which includes only four layers: a four-channel porous anode layer, a dense electrolyte layer, a dense YSZ mass transfer selective layer, and a porous cathode layer.

[0069] Example 4

[0070] The difference between this embodiment and Embodiment 1 is that the YSZ mass transfer selection layer is not added.

[0071] A method for preparing a multi-channel microtube solid oxide electrolytic cell includes the following steps:

[0072] (1) Using a 4-hole nozzle, BaZr was extruded / phase-inversioned via extrusion / phase-inversion method. 0.1 Ce 0.7 Y 0.1 Yb 0.1 An anode slurry with an O3 to NiO mass ratio of 4:6 was extruded into a 20°C condenser bath and placed for 24 hours. It was then transferred out and naturally dried for 24 hours to obtain a four-channel anode support green body with a green body diameter of 3 mm and a microtube diameter of 0.8 mm.

[0073] (2) A 30 μm thick layer of BaZr with 1 wt% NiO added was screen-printed on the surface of the anode support green body. 0.1 Ce 0.7 Y 0.1 Yb 0.1 O3 electrolyte slurry was co-fired at 1450℃ for 5 hours to obtain a phased anode electrolyte structure;

[0074] (3) Coating the electrolyte surface with a 5 μm thick layer of Gd 0.1 Ce 0.9 O2 slurry was used as an interface optimization layer and sintered at 1400℃ for 5 hours to obtain a multi-channel microtubular half cell.

[0075] (4) Coat the surface of the half-cell prepared above with a La layer with a thickness of 30 μm. 0.6 Sr 0.4 Co 0.2 Fe 0.8 O3 cathode paste was used to prepare a complete electrolytic cell after sintering at 1000℃ for 2 hours;

[0076] (5) The above-mentioned complete four-channel tubular solid oxide fuel electrolyzer structure is sealed to obtain the four-channel microtubular solid oxide electrolyzer used for high-temperature water electrolysis to produce hydrogen.

[0077] Figure 6 This is a schematic diagram of the three-dimensional structure of the four-channel microtube solid oxide fuel electrolyzer in Embodiment 4 of the present invention, which includes only four layers: a four-channel porous anode layer, a dense electrolyte layer, a cerium oxide doped interface optimization layer, and a porous cathode layer.

[0078] Example 5

[0079] The difference between this embodiment and Embodiment 1 is that the YSZ mass transfer selection layer and the doped cerium oxide interface optimization layer are not added.

[0080] A method for preparing a multi-channel microtube solid oxide electrolytic cell includes the following steps:

[0081] (1) Using a 4-hole nozzle, BaZr was extruded / phase-inversioned via extrusion / phase-inversion method. 0.1 Ce 0.7 Y 0.1 Yb 0.1 An anode slurry with an O3 to NiO mass ratio of 4:6 was extruded into a 20°C condenser bath and placed for 24 hours. It was then transferred out and naturally dried for 24 hours to obtain a four-channel anode support green body with a green body diameter of 3 mm and a microtube diameter of 0.8 mm.

[0082] (2) A 30 μm thick layer of BaZr with 1 wt% NiO added was screen-printed on the surface of the anode support green body. 0.1 Ce 0.7 Y 0.1 Yb 0.1 O3 electrolyte slurry was co-fired at 1450℃ for 5 hours to obtain a phased anode electrolyte structure;

[0083] (3) Coating the electrolyte surface with a 30 μm thick layer of La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O3 cathode paste was used to prepare a complete electrolytic cell after sintering at 1000℃ for 2 hours;

[0084] (4) The above-mentioned complete four-channel tubular solid oxide fuel electrolyzer structure is sealed to obtain the four-channel microtubular solid oxide electrolyzer used for high-temperature water electrolysis to produce hydrogen.

[0085] Figure 7This is a schematic diagram of the three-dimensional structure of the four-channel microtubular solid oxide fuel electrolyzer in Embodiment 5 of the present invention, which includes only three basic layers: a four-channel porous anode layer, a dense electrolyte layer, and a porous cathode layer.

[0086] Example 6

[0087] A multi-channel microtube solid oxide electrolysis device, such as Figure 8 As shown, the multi-channel microtube solid oxide electrolyzer 1 prepared in Examples 1-5 uses conductive adhesive as a sealant. The multi-channel microtube solid oxide electrolyzer 1 is placed in the furnace temperature zone 7. First, the two poles of the multi-channel microtube solid oxide electrolyzer 1 are connected externally with silver wires as conductors 8. Then, both ends of the multi-channel microtube solid oxide electrolyzer 1 are sealed with high-temperature resistant ceramic tubes 2. At the other end of the high-temperature resistant ceramic tube 2, a thin high-temperature resistant ceramic tube 4 for transporting hydrogen is fixed with a rubber stopper 3 to export hydrogen products. Then, the aforementioned multi-channel microtube solid oxide electrolyzer 1 and the high-temperature resistant ceramic tube 5 for transporting water are sealed and packaged using a sealing device high-temperature resistant ceramic tube 6.

[0088] Figure 9 The hydrogen production rate of the electrolysis device prepared by the multi-channel microtube solid oxide fuel electrolysis cell in Examples 1-5 of this invention is shown. Under the same electrolysis conditions, the hydrogen production rate of Examples 1-3 is high, that is, the electron utilization rate is high, indicating that the YSZ mass transfer selective layer is very effective in blocking the internal conduction of electrons. The hydrogen production rate of Example 2 is higher than that of Example 1, indicating that the large number of microtubes and the fast H2 transport rate are beneficial to improving the electrolysis performance. The hydrogen production rate of Example 1 is higher than that of Example 3 and the hydrogen production rate of Example 4 is higher than that of Example 5, which both indicate that the interface optimization layer is beneficial to improving the electrolysis performance. Figure 10 This is a comparison chart of the Faraday efficiencies of the electrolysis devices prepared by the multi-channel microtubular solid oxide fuel electrolyzers in Examples 1-5 of this invention. The test conditions were all at 700℃ and an applied voltage of 1.5V, with 10% H2O / H2 introduced as the water source on the cathode side. Multiple tests were conducted on the electrolyzer with the YSZ mass transfer selectivity layer. The Faraday efficiency of the four-channel microtubular solid oxide fuel electrolyzer (Example 1) with the mass transfer selectivity layer and the interface optimization layer can reach 97%. The Faraday efficiency of the eight-channel microtubular solid oxide fuel electrolyzer (Example 2) with the mass transfer selectivity layer and the interface optimization layer can reach 98.5%. The Faraday efficiency of the four-channel microtubular solid oxide fuel electrolyzer (Example 3) with the mass transfer selectivity layer is close to 90%. The Faraday efficiency of the four-channel microtubular solid oxide fuel electrolyzer (Example 4) with only the interface optimization layer is only 75%. The Faraday efficiency of the four-channel microtubular solid oxide fuel electrolyzer (Example 5) with only the basic structure of the electrolyzer is less than 70%.

[0089] The above description is merely an example and illustration of the structure of the present invention. Those skilled in the art can make various modifications or additions to the specific embodiments described or use similar methods to replace them, as long as they do not deviate from the structure of the present invention or exceed the scope defined in the claims, they should all fall within the protection scope of the present invention.

Claims

1. A multi-channel microtube solid oxide electrolytic cell, characterized in that: It includes a porous anode layer, a porous cathode layer, and a dense electrolyte layer disposed between the cathode layer and the cathode layer. A mass transfer selection layer is disposed outside the electrolyte layer, and an interface optimization layer is disposed outside the mass transfer selection layer. The porous anode layer comprises NiO and BaZr. x Ce y Y z Yb w O3, where x+y+z+w=1; the dense electrolyte layer comprises BaZr. x Ce y Y z Yb w O3, where x+y+z+w=1; the porous cathode layer comprises La x Sr 1- x Co y Fe 1-y O3; the mass transfer selection layer is yttrium oxide-stabilized zirconium oxide, wherein the Y2O3 doping content is 3wt%-13wt%; the interface optimization layer is composed of cerium oxide-doped M. x Ce 1-x O2, where M is one of La, Gd, Sm or Pr, and x is 0-0.

4.

2. The multi-channel microtube solid oxide electrolytic cell according to claim 1, characterized in that: The porous anode layer has a multi-channel microtube structure with a microtube diameter of 0.5-10 mm and a number of 2-10 microtube channels.

3. The multi-channel microtube solid oxide electrolytic cell according to claim 1, characterized in that: The thickness of the mass transfer selective layer is 0.1-0.5 μm.

4. The multi-channel microtube solid oxide electrolytic cell according to claim 1, characterized in that: The thickness of the interface optimization layer is 0.1-10 μm.

5. A method for preparing a multi-channel microtube solid oxide electrolytic cell according to any one of claims 1-4, characterized in that, Includes the following steps: (1) The multi-channel anode support green body is sintered at 1000-1100℃ for 2-3 hours to obtain the multi-channel anode support, i.e. the anode layer; (2) Electrolyte paste is screen-printed on the surface of the anode support and co-fired at 1400-1500℃ for 5-8 hours to obtain the phased electrolyte layer; (3) A YSZ layer is further magnetron sputtered on the surface of the electrolyte layer as a mass transfer selective layer; (4) Coat the surface of the mass transfer selectivity layer with a layer of cerium oxide-doped slurry as an interface optimization layer; (5) The battery structure after the above-mentioned coating interface optimization layer is sintered at 1350-1450℃ for 3-10h to obtain a multi-channel microtube half cell. (6) The cathode material is coated on the surface of the half cell prepared above, and the multi-channel microtube solid oxide electrolytic cell is obtained after sintering at 1000-1100℃ for 2-3 hours.

6. The method for preparing a multi-channel microtube solid oxide electrolytic cell according to claim 5, characterized in that: In step (1), the multi-channel anode support green body is prepared by extrusion / phase transformation method. The material of the anode layer is extruded into a condensation bath at 10-20℃ and placed for 16-24h, and then transferred out and naturally dried for 24-48h to obtain the anode support green body. In step (2), 1wt%-4wt% of NiO electrolyte is also added as a sintering aid.

7. The multi-channel microtubular solid oxide electrolyzer according to any one of claims 1-4 is used for high-temperature water electrolysis to produce hydrogen.

8. A multi-channel microtube solid oxide electrolysis device, characterized in that: The multi-channel microtubular solid oxide electrolyzer, as described in any one of claims 1-4, is sealed using conductive adhesive as a sealant. The electrodes of the multi-channel microtubular solid oxide electrolyzer are externally connected using silver wires as conductors. Both ends of the multi-channel microtubular solid oxide electrolyzer are sealed with high-temperature resistant ceramic tubes. A hydrogen-transmitting ceramic tube is fixed to the other end of the high-temperature resistant ceramic tube with a rubber stopper. The hydrogen-transmitting ceramic tube is thinner than the high-temperature resistant ceramic tube. The multi-channel microtubular solid oxide electrolyzer is connected to a water-transmitting high-temperature resistant ceramic tube. The electrolyzer and the water-transmitting high-temperature resistant ceramic tube are sealed together using a sealing device.

9. A method for producing hydrogen by high-temperature electrolysis of water, characterized in that: High-temperature water electrolysis for hydrogen production is performed using the multi-channel microtube solid oxide electrolysis device described in claim 8.

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