A ceramic membrane electrolytic cell and a ceramic membrane electrolytic device

Abstract

The application discloses a ceramic membrane electrolytic cell and a ceramic membrane electrolytic device. It relates to the technical field of electrolytic cells. The ceramic membrane electrolytic cell comprises a single cell, a hole is formed in the single cell, and a reaction zone is arranged in the middle of the hole along the hole axis direction, and non-reaction zones are arranged close to both ends of the reaction zone; a positive electrode layer is arranged on the first surface of the single cell and corresponds to the position of the reaction zone; a first connecting piece comprises a first connecting piece body and a first heating element, and both are arranged on the side of the positive electrode layer; the first surface of the first connecting piece body forms a first gas flow channel, and the first surface of the first connecting piece body is in abutment with the positive electrode layer; the first heating element is connected with the first connecting piece body, the first heating element generates heat when electrified, and the reaction zone is heated; and a sealing piece is arranged in the non-reaction zone of the single cell, and the sealing piece has a second gas flow channel and is in sealed communication with the hole. The application reduces the sealing difficulty and gas leakage rate of the high-temperature operation electrolytic cell and improves the operation pressure of the ceramic membrane electrolytic cell.

Description

Technical Field

[0001] This disclosure relates to the field of electrolytic cell technology, and in particular to a ceramic membrane electrolytic cell and a ceramic membrane electrolysis device. Background Technology

[0002] Ceramic membrane electrolyzers, also known as solid oxide electrolysis cells (SOECs), can use solid oxides as electrolytes to electrolyze fuel gases (such as water vapor and / or carbon dioxide) under high temperature and applied voltage conditions, thereby realizing the conversion of electrical and thermal energy into chemical energy.

[0003] Currently, to meet the temperature requirements of ceramic membrane electrolyzers, the electrolyzer is placed inside a heating container (such as a furnace), and the temperature is raised through the heating container to meet the electrolysis temperature. Since the operating temperature of a ceramic membrane electrolyzer is between 600 and 850°C, this places extremely stringent requirements on its sealing materials and technology. Maintaining the sealing technology for long-term operation at high temperatures is extremely difficult, and maintaining the sealing stability of the internal sealing materials under long-term high-temperature operation is challenging. Therefore, when ceramic membrane electrolyzers are used for high-purity gas production (such as H2 or CO) or for precise adjustment of the syngas (H2 / CO) ratio, there is a risk of gas leakage and mixing through the sealing gaps on both sides of the electrodes (positive and negative electrodes). This sealing leakage leads to two problems: First, since the reaction rate and Nernst potential are directly related to the partial pressures of reactants and products, sealing leakage will change the local gas partial pressure at the electrodes, resulting in uneven potential and current density throughout the electrolyzer. Second, leaked fuel gas can come into contact with and burn with oxygen inside or outside the electrolyzer, or within the sealing material, potentially generating extremely high local temperatures. This can melt or damage the sealing material and adjacent metal connectors, and in severe cases, cause structural short circuits or overall failure of the electrolyzer. Third, gas cross-mixing is equivalent to forming a "parasitic" fuel cell inside the electrolyzer, spontaneously consuming products, reducing the system's electrolysis efficiency (manifested as a decrease in Faraday efficiency), and introducing an unstable heat source and chemical environment, accelerating the performance degradation of the electrolyzer.

[0004] Therefore, it is necessary to improve the current ceramic membrane electrolyzers to reduce the sealing difficulty of high-temperature operating electrolyzers, thereby reducing the risk of gas leakage. Summary of the Invention

[0005] This application provides a ceramic membrane electrolyzer and a ceramic membrane electrolysis device to at least solve one of the technical problems existing in the prior art.

[0006] In a first aspect, this application provides a ceramic membrane electrolyzer, comprising: At least one single cell, wherein a channel is formed inside the single cell, and a reaction zone is provided in the middle of the channel along the axial direction of the channel, and a non-reaction zone is provided at both ends of the reaction zone. A positive electrode layer is provided on the first surface of the single cell at the position corresponding to the reaction zone. At least one first connector, the first connector including a first connector body and a first heating element, both the first connector body and the first heating element being disposed on the positive electrode layer side of the single cell; the first connector body having a first gas flow channel formed on a first surface facing the positive electrode layer, the first surface of the first connector body abutting against the positive electrode layer to communicate the first gas flow channel with the positive electrode layer; the first heating element being connected to the first connector body, and when the first heating element is energized and generates heat, it can heat the reaction zone through the first connector body; A sealing element is disposed in the non-reactive region of the single cell, and the sealing element has a second gas flow channel that is sealed and connected to the orifice.

[0007] In one embodiment, the second surface of the single cell is provided with a negative electrode current collector layer at a position corresponding to the reaction region, the first surface of the single cell and the second surface of the single cell are disposed opposite to each other, and the negative electrode current collector layer is disposed opposite to the positive electrode layer; The negative electrode current collector layer is made of a conductive, dense, and airtight current collector material.

[0008] In one embodiment, the ceramic membrane electrolyzer further includes: The second connector includes a second connector body and a second heating element, both of which are located on the negative current collector side of the single battery. The second connector body abuts against the first surface of the negative electrode current collector layer; The second heating element is connected to the body of the second connector. When the second heating element is energized and generates heat, it heats the reaction zone through the body of the second connector and the negative electrode current collector.

[0009] In one embodiment, the single battery further includes a positive electrode current collector layer, which is disposed on the surface of the positive electrode layer facing the first connector body. The first surface of the first connector body abuts against the positive electrode current collector layer so that the first gas flow channel communicates with the positive electrode current collector layer.

[0010] In one possible embodiment, the single battery further includes: A negative electrode support layer, wherein the channel is formed inside the negative electrode support layer; a negative electrode layer is provided on the first surface of the negative electrode support layer, and a negative electrode current collector layer is provided on the second surface of the negative electrode support layer, wherein the first surface and the second surface of the negative electrode support layer are disposed opposite to each other; An electrolyte layer covers the negative electrode layer and the surface of the negative electrode support layer that is not covered by the negative electrode current collector and the negative electrode layer; the positive electrode layer is disposed on the first surface of the electrolyte layer, and the positive electrode layer is disposed opposite to the negative electrode current collector; the positive electrode current collector is disposed on the surface of the positive electrode layer facing away from the electrolyte layer.

[0011] In one embodiment, the material of the negative electrode current collector layer is selected from doped LaCrO3-based ceramics, La x Sr 1- x TiO 3-δ Composite materials with Ni-Fe alloys, wherein x = 0.2~0.8, δ is the oxygen vacancy content, ferritic stainless steel, a mixture of Ag and glass-ceramic sealing materials, and any one of chromium-based alloys.

[0012] In one embodiment, the doped LaCrO3-based ceramic is CeO2-doped La0.7Ca0.3CrO 3-δ ceramics; The La x Sr 1-x TiO 3-δ In the composite material with Ni-Fe alloy, based on 100wt% of the composite material, the La x Sr 1-x TiO 3-δ The mass percentage is 2~40wt%, and the mass percentage of the Ni-Fe alloy is 60~98wt%. In the mixture of Ag and glass-ceramic sealing material, the mass percentage of Ag is 50-99 wt%, and the remainder is glass-ceramic sealing material.

[0013] In one possible embodiment, when the material of the negative electrode current collector is CeO2-doped La0.7Ca0.3CrO 3-δ When ceramic, the negative electrode current collector layer is prepared by the following method: Preparation of La0.7Ca0.3CrO 3-δ Powder, negative electrode support layer green body; The La0.7Ca0.3CrO 3-δ The powder, CeO2, organic carrier, and dispersant are mixed and ball-milled to obtain a uniformly dispersed slurry; wherein the mass of the CeO2 is equal to that of the La0.7Ca0.3CrO2. 3-δ 2wt% of the powder mass; The slurry is coated on the second surface of the negative electrode support layer green body, and then sintered in a reducing atmosphere and / or an inert atmosphere at 1100~1400°C to obtain the negative electrode support layer, and the negative electrode current collector layer is formed on the second surface of the negative electrode support layer.

[0014] In one embodiment, based on a total organic carrier mass of 100 wt%, the organic carrier comprises 60-80 wt% organic solvent, 15-30 wt% binder, and 5-15 wt% plasticizer; The total mass of the dispersant and the organic carrier is equal to that of the La0.7Ca0.3CrO. 3-δ The powder mass ratio is 30~70:70~30.

[0015] In one embodiment, the glass-ceramic sealing material is composed of one of SiO2-Al2O3-Na2O-CaO, SiO2-Al2O3-Na2O-BaO, and SiO2-Al2O3-Na2O-BaO-YSZ.

[0016] In one possible embodiment, the first heating element is disposed inside the body of the first connector; The second heating element is disposed inside the body of the second connector; Both the first heating element and the second heating element are resistance wires.

[0017] In one possible implementation, the heating area of ​​the first heating element on the body of the first connector is greater than or equal to the area of ​​the positive electrode layer region of the single battery. The heating area of ​​the second heating element on the body of the second connector is greater than or equal to the area of ​​the negative electrode current collector region of the single battery.

[0018] In one embodiment, when multiple single batteries and multiple first connectors are provided, the multiple single batteries and multiple first connectors are alternately arranged along the stacking direction of the single batteries.

[0019] In one embodiment, the first connector body has a plurality of parallel first grooves on the first surface facing the positive electrode layer, and the plurality of first grooves form the first gas flow channel.

[0020] In one embodiment, the sealing element includes an air distribution module and a sealing module. The second gas flow channel is provided in the gas distribution module, and the sealing module has a mounting hole; The two ends of the single battery are respectively inserted into the mounting holes of the sealing module; the gas distribution module and the sealing module are sealed together so that the channel is sealed and connected to the second gas flow channel. The ceramic membrane electrolyzer also includes a first gas supply pipe, which is sealed and connected to the second gas flow channel of the gas distribution module.

[0021] In one embodiment, the center of the sealing module and the sealing connection area at one end of the single battery are at least 5 cm away from the edge of the reaction zone.

[0022] In one embodiment, the ceramic membrane electrolyzer further includes: The first current collector is disposed on the side of the first connector body facing away from the single battery and abuts against the first connector body; The second current collector is located on the side of the second connector body facing away from the single battery and abuts against the second connector body.

[0023] In one embodiment, the ceramic membrane electrolyzer further includes: The insulation component has a accommodating space, in which the reaction zone, the first current collector, the first connector, the second connector, and the second current collector are all housed. A gap for gas to flow out is provided between the single cell and the inner wall of the insulation component. Two first conductive elements are passed through the insulation element and are electrically connected to the first current collector and the second current collector, respectively. Two second conductive elements, one of which is electrically connected to the first end of the first heating element and the second heating element, and the other of which is electrically connected to the second end of the first heating element and the second heating element.

[0024] Secondly, this application provides a ceramic membrane electrolysis device, including a sealed container and a second gas supply pipe, and also includes a ceramic membrane electrolysis cell in any of the above-described possible embodiments; The sealed container is sealed to the outside of the ceramic membrane electrolyzer; the second gas supply pipe passes through the sealed container and is connected to the first gas flow channel.

[0025] Compared with the prior art, the technical effects of this application are at least as follows: 1) In this application, by setting a single cell, a first connector, and a seal, along the axial direction of the single cell's channel, the single cell includes a reaction zone in the middle and non-reaction zones at both ends. The first surface of the single cell has a positive electrode layer at the position corresponding to the reaction zone, and a first connector is set on the positive electrode layer side. The first heating element of the first connector can be energized and heated to heat the reaction zone of the single cell that abuts against the body of the first connector. This concentrates the high-temperature electrolytic reaction of the single cell in the reaction zone, while the non-reaction zone, since it does not have a heating element and is located far from the reaction zone, is a low-temperature region at both ends of the single cell. The non-reaction zones at both ends of the single cell are connected to the seal, and the raw material gas is introduced and the reduction product gas is output through the second gas flow channel of the seal. Thus, the sealing positions for the raw material gas introduced into the single cell and the reduction product gas output from the single cell are both set in the low-temperature regions at both ends of the single cell, avoiding the problem of high-temperature sealing failure, reducing the sealing difficulty and gas leakage rate of the high-temperature operating electrolytic cell, and enabling the long-term operation of the electrolytic cell under high temperature and high pressure environment.

[0026] 2) In this application, the second surface of the single cell has a negative electrode current collector layer at the location corresponding to the reaction zone. This negative electrode current collector layer is made of a conductive and dense, leak-proof current collector material, which can form a dense, conductive passivation layer on the second surface of the single cell, protecting the interior from oxidation. Furthermore, because the negative electrode current collector layer itself is dense and leak-proof, it can operate in high-temperature environments without the need for additional sealing materials, achieving high-temperature operation without sealing while also preventing reduction product gases (such as CO and H2) from escaping through the negative electrode current collector layer. Therefore, the ceramic membrane electrolyzer of this application only needs to use sealing materials in the low-temperature regions at both ends of the single cell to achieve sealed gas inlet / outlet with the sealing element. The low-temperature region has a lower impact on the long-term stability of the sealing material, thus avoiding high-temperature sealing failure. This reduces the sealing difficulty and gas leakage rate of the high-temperature operating electrolyzer, while also preventing gas leakage on the negative electrode side and increasing the operating pressure of the ceramic membrane electrolyzer.

[0027] 3) In this application, compared to existing traditional ceramic membrane electrolyzers and devices that can only produce syngas at atmospheric pressure, further pressurization of the syngas or the synthesis device is required when synthesizing fuels such as methane, which undoubtedly increases the synthesis cost. However, the ceramic membrane electrolyzer and device of this application, due to their superior sealing performance, can directly electrolyze and generate high-pressure syngas. This high-pressure syngas can then be directly coupled to fuel synthesis devices such as methane, further reducing the energy consumption for synthesizing methane and other fuels, thus lowering economic costs.

[0028] 4) In this application, the heating area of ​​the first heating element over the first connector body is greater than or equal to the positive electrode layer area of ​​the single cell. In this application, the heating area of ​​the first connector body covers the positive electrode layer area of ​​the single cell, avoiding localized overheating or underheating, ensuring a uniform temperature field in the single cell's reaction zone, and improving electrolysis efficiency and stability. Furthermore, the heat from the first heating element directly acts on the reaction zone, resulting in concentrated energy, high thermal efficiency, and reduced heat loss. In this application, the heating area of ​​the second heating element over the second connector body covers the entire negative electrode current collector layer of the single cell, avoiding localized overheating or underheating, ensuring a uniform temperature field in the single cell, and improving electrolysis efficiency and stability. Furthermore, the heat from the second heating element directly acts on the reaction zone of the single cell, resulting in concentrated energy, high thermal efficiency, and reduced heat loss.

[0029] 5) This application places the first heating element inside the first connector body and the second heating element inside the second connector body. Heat can be transferred to the single cell in contact with the connector body through the two heating elements, realizing short-distance heat conduction path transfer, shortening the heat transfer path of the ceramic membrane electrolyzer, and avoiding heat loss and heat conduction delay caused by external heating. The first and second heating elements achieve precise heating only for the reaction zone in contact, without the need to heat the external environment or redundant structures of the ceramic membrane electrolyzer, reducing ineffective heating areas. 6) In this application, both the first heating element and the second heating element are resistance wires. By setting the resistance wires as internal heating elements, on the one hand, the overall weight of the ceramic membrane electrolyzer is reduced, achieving a lightweight structure; on the other hand, the heat transfer path for heating the core components of the ceramic membrane electrolyzer is reduced, thus achieving low energy consumption of the ceramic membrane electrolyzer.

[0030] 7) When the ceramic membrane electrolysis device of this application is introduced with gas exceeding 1MPa, the seal of the ceramic membrane electrolysis device is not damaged after the operation is completed. This shows that by separating the high-temperature reaction zone and the non-reaction zone, and setting the sealing position between the two ends of the single cell and the sealing element in the non-reaction zone, which is in a low-temperature region, the high-temperature sealing failure problem of existing sealing materials can be effectively avoided. Moreover, the airtightness of the raw material gas intake and the reduction product gas output is achieved, which greatly extends the service life of the ceramic membrane electrolysis device.

[0031] 8) The reduction product gas output from the negative electrode layer side of the ceramic membrane electrolysis device of this application can be directly coupled with the high-pressure methanation reaction, thereby improving system efficiency, realizing the system integration of the ceramic membrane electrolysis device and the methanation synthesis device, reducing weight, and reducing costs and increasing efficiency.

[0032] It should be understood that the description in this section is not intended to identify key or essential features of the embodiments of this disclosure, nor is it intended to limit the scope of this disclosure. Other features of this disclosure will become readily apparent from the following description. Attached Figure Description

[0033] The above and other objects, features, and advantages of this disclosure will become readily apparent from the following detailed description of exemplary embodiments, taken in conjunction with the accompanying drawings. Several embodiments of this disclosure are illustrated in the drawings by way of example and not limitation, in which: In the accompanying drawings, the same or corresponding reference numerals indicate the same or corresponding parts.

[0034] Figure 1 A schematic diagram of the structure of a ceramic membrane electrolyzer according to an embodiment of the present disclosure is shown; Figure 2 A disassembly diagram of the ceramic membrane electrolyzer according to an embodiment of the present disclosure is shown. Figure 1 ; Figure 3 A disassembly diagram of the ceramic membrane electrolyzer according to an embodiment of the present disclosure is shown. Figure 2 ; Figure 4 A disassembly diagram of the ceramic membrane electrolyzer according to an embodiment of the present disclosure is shown. Figure 3 ; Figure 5 A disassembly diagram of the ceramic membrane electrolyzer according to an embodiment of the present disclosure is shown. Figure 4 ; Figure 6 A schematic diagram of the structure of a single battery connected to a first connector, a second connector, and a seal, according to an embodiment of the present disclosure, is shown. Figure 7 It shows Figure 6 Disassembly Figure 1 ; Figure 8 It shows Figure 6 Disassembly Figure 2 ; Figure 9 A schematic diagram of the structure of a single cell according to an embodiment of this disclosure is shown. Figure 1 ; Figure 10 A schematic diagram of the structure of a single cell according to an embodiment of this disclosure is shown. Figure 2 ; Figure 11 This diagram illustrates the structure of a single battery in contact with the first connector and the second connector according to an embodiment of the present disclosure. Figure 12 A schematic diagram of the structure of the air distribution module according to an embodiment of this disclosure is shown. Figure 1 ; Figure 13 A schematic diagram of the structure of the air distribution module according to an embodiment of this disclosure is shown. Figure 2 ; Figure 14 A schematic diagram of an electrolytic stack, comprising alternating stacks of multiple single cells and a first connector, is shown according to an embodiment of this disclosure. Figure 15 It shows Figure 14 Disassembly diagram Figure 1 ; Figure 16 It shows Figure 14 Disassembly diagram Figure 2 ; Figure 17 It shows Figure 14 Disassembly diagram Figure 3 ; Figure 18 It shows Figure 14 A schematic diagram of the structure of the first type of air distribution module; Figure 19 It shows Figure 14 Schematic diagram of the structure of the second type of air distribution module Figure 1 ; Figure 20 It shows Figure 14 Schematic diagram of the structure of the second type of air distribution module Figure 2 ; Figure 21 A schematic diagram of the structure of the sealing module of this disclosure connected to a single battery is shown; Figure 22 A schematic diagram of the layer structure of the first single cell of this disclosure is shown; Figure 23 A schematic diagram of the layer structure of the second type of single cell of this disclosure is shown; Figure 24 A schematic diagram of the layer structure of the third type of single cell of this disclosure is shown; Figure 25 A schematic diagram of the airtightness test structure of this disclosure is shown; Figure 26 A schematic diagram of the structure of a ceramic membrane electrolysis apparatus according to an embodiment of the present disclosure is shown; Figure 27 A disassembly diagram of a ceramic membrane electrolysis apparatus according to an embodiment of the present disclosure is shown.

[0035] Reference numerals: 1-Single cell, 11-Reaction region, 12-Non-Reaction region, 13-First surface of single cell, 111-Positive electrode layer, 112-Pore, 113-Positive electrode current collector layer, 114-Electrolyte layer, 115-Negative electrode layer, 116-Negative electrode support layer, 117-Negative electrode current collector layer, 118-Barrier layer; 2-First connector, 21-First connector body, 22-First heating element, 211-First gas flow channel, 2111-First groove; 3-Seal, 31-Gas distribution module, 32-Sealing module, 33-Fastener, 311-Second gas flow channel, 312-First gas supply pipe, 321-Mounting hole, 322-Sealing ring, 323-First connecting hole, 3111-Second groove, 3112-First through groove, 3113-Third groove, 3114-Second through groove, 3115-Fourth groove, 3116-Third through groove, 3211-First through hole, 3212-Slot; 4-Second connector, 41-Second connector body, 42-Second heating element; 5-First collector, 6-Second collector; 7-Insulation component, 71-First conductive component, 72-Second conductive component, 73-Gap, 74-First insulation component, 75-Second insulation component; 8-Sealed container, 81-Second gas supply pipe, 82-Second connecting hole. Detailed Implementation

[0036] To make the objectives, features, and advantages of this disclosure more apparent and understandable, the technical solutions in the embodiments of this disclosure 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 this disclosure, and not all of them. All other embodiments obtained by those skilled in the art based on the embodiments of this disclosure without creative effort are within the scope of protection of this disclosure.

[0037] Firstly, such as Figure 1-11 As shown, this application provides a ceramic membrane electrolyzer, comprising: At least one single cell 1, the single cell 1 having a channel 112 inside for the transmission of raw material gas and reduction product gas; along the axial direction of the channel 112 of the single cell 1, a reaction zone 11 located in the middle of the channel 112 and a non-reaction zone 12 adjacent to both ends of the reaction zone are respectively provided; the first surface 13 of the single cell has a positive electrode layer 111 at the position corresponding to the reaction zone 11. At least one first connector 2, the first connector 2 includes a first connector body 21 and a first heating element 22, and both the first connector body 21 and the first heating element 22 are disposed on the positive electrode layer side of the single battery 1. The first connector body 21 has a first gas flow channel 211 formed on a first surface facing the positive electrode layer 111, and the first surface of the first connector body 21 abuts against the positive electrode layer 111 so that the first gas flow channel 211 communicates with the positive electrode layer 111. The first heating element 22 is connected to the first connector body 21. When the first heating element 22 is energized and heats up, it can heat the reaction zone 11 of the single battery through the first connector body 21. The sealing element 3 is respectively disposed in the non-reaction zone 12 at both ends of the single cell 1. The sealing element 3 has a second gas flow channel 311, which is sealed and connected to the channel 112 of the single cell 1.

[0038] In this application, the single cell 1 serves as the core working component of the ceramic membrane electrolyzer. The single cell 1 mainly comprises a positive electrode layer 111 (i.e., the anode layer), an electrolyte layer, and a negative electrode layer (i.e., the cathode layer). The single cell 1 provides an electrochemical reaction site for the feed gas. For example, using water vapor and / or carbon dioxide as the feed gas, the electrochemical reduction reaction of the feed gas occurs in the three-phase interface region on the negative electrode layer side of the single cell, generating reduction product gases H2 and CO, while simultaneously producing O2. 2- The positive electrode layer migrates through the electrolyte layer, undergoes an oxidation reaction in the positive electrode layer, and produces oxidation product gas O2, which overflows from the positive electrode layer side of the single cell.

[0039] The chemical reaction equation is as follows: Reduction reaction: Electrolysis of carbon dioxide: CO2 + 2e- → CO + O 2- Electrolysis of water: H₂O + 2e⁻ → H₂ + O₂ 2- Co-electrolysis of water and carbon dioxide: H₂O + CO₂ + 4e⁻ → H₂ + CO + 2O 2- Oxygen negative ions (O 2- It migrates from the negative electrode layer through the electrolyte layer (such as YSZ: yttrium oxide stabilized zirconium oxide) to the positive electrode layer, where it undergoes an oxidation reaction to generate oxygen: 2O 2 →O2+4e- In this application, such as Figure 9 As shown, the area of ​​the positive electrode layer 111 of the single cell 1 is reduced to a smaller area than the area of ​​the first surface 13 of the single cell, and is located in the middle. Since the positive electrode layer and the negative electrode layer of the single cell 1 are arranged correspondingly, the reaction regions (including electrochemical reduction reaction regions and electrochemical oxidation reaction regions) corresponding to the positive electrode layer are also reduced accordingly; thus, the area where the electrochemical reaction actually occurs in the single cell is concentrated in the corresponding areas of the positive electrode layer and the negative electrode layer. Therefore, in this application, the reaction region 11 of the single cell refers to the area where the raw material gas undergoes electrochemical oxidation / reduction, and the non-reaction region 12 refers to the input area of ​​the raw material gas and the output area of ​​the reduction product gas (such as CO, H2). Thus, along the axial direction of the channel 112 of the single cell 1, the single cell is divided into three regions: the reaction region 11 located in the middle (that is, the reaction region located in the middle of the channel), and the non-reaction region 12 adjacent to both ends of the reaction region. The two ends of the reaction region 11 and the non-reaction region 12 are arranged adjacent to each other; the channels of the reaction region 11 and the non-reaction region 12 are connected.

[0040] In this application, "middle" refers to any region between the two ends of a single cell, not just the central region of the single cell. Preferably, the reaction region 11 of the single cell in this application can be located in the central region of the single cell.

[0041] In this application, by setting a single battery 1, a first connector 2 and a sealing member 3, along the axial direction of the channel 112 of the single battery, the single battery 1 is configured to include a reaction zone 11 located in the middle of the channel and a non-reaction zone 12 adjacent to both ends of the reaction zone. The first surface 13 of the single battery is provided with a positive electrode layer 111 at the position corresponding to the reaction zone 11, and the first connector 2 is provided on the side of the positive electrode layer 111. The first heating element 22 of the first connector can be energized and heated to heat the reaction zone 11 of the single battery that is in contact with the body 21 of the first connector. As a result, the high-temperature electrolysis reaction of the single battery is concentrated in the reaction zone 11, while the non-reaction zone 12 is a low-temperature region because no heating element is provided. The non-reaction zones 12 at both ends of the single cell are connected to the sealing element 3. The raw material gas is introduced and the reduction product gas is output through the second gas flow channel 311 of the sealing element 3. Thus, the sealing positions for the raw material gas introduced into the single cell and the reduction product gas output from the single cell are both set in the low-temperature regions at both ends of the single cell. This avoids the problem of high-temperature sealing failure of existing sealing materials, reduces the sealing difficulty and gas leakage rate of high-temperature ceramic membrane electrolyzers, and enables the long-term operation of ceramic membrane electrolyzers under high temperature and high pressure environments.

[0042] For example, such as Figure 9 As shown, along the length direction of single cell 1, i.e. Figure 9 As shown in the diagram (L represents length), a channel 112 is formed inside the single battery 1, with the axis of the channel 112 aligned with the length direction of the single battery 1. Alternatively, the channel 112 can be formed along the width direction of the single battery 1, again with the axis of the channel 112 aligned with the width direction of the single battery 1. Preferably, the channel 112 is formed along the length direction of the single battery 1.

[0043] In this application, such as Figure 4-5As shown, the first connector body 21 has a first gas flow channel 211 formed on the first surface facing the positive electrode layer of the single cell. The second surface of the first connector body 21 facing away from the positive electrode layer of the single cell is a planar structure. The first and second surfaces of the first connector body are arranged opposite to each other along the thickness direction of the first connector body. The first surface of the first connector body 21 contacts and abuts against the positive electrode layer 111 so that the first gas flow channel 211 is connected to the positive electrode layer 111. This allows the oxidation product gas (such as O2) generated by the oxidation reaction in the positive electrode layer 111 to diffuse from the positive electrode layer 111 into the first gas flow channel 211 and be smoothly discharged from the first gas flow channel 211. Meanwhile, the reduction product gas is discharged from the second gas flow channel 311 of the seal, thus avoiding cross contact between the oxidation product gas and the reduction product gas inside the electrolytic cell. The contact portion between the first gas flow channel 211 and the positive electrode layer 111 is used for electron conduction.

[0044] For example, such as Figure 5 As shown, the first gas flow channel 211 is an array of grooves formed on the first surface of the first connector body 21 facing the positive electrode layer 111. Specifically, multiple first grooves 2111 arranged side by side are formed on the first surface of the first connector body 21 facing the positive electrode layer 111 of the single cell. These first grooves 2111 form an array of grooves, which is the first gas flow channel 211. The opening end face of the first gas flow channel 211 is in contact with the positive electrode layer 111, thereby allowing the oxidation product gas (such as O2) generated by the oxidation reaction in the positive electrode layer of the single cell to flow out from the first gas flow channel 211.

[0045] For example, there are two seals 3, which are respectively located in the non-reaction zones 12 at both ends of the single cell. The second gas flow channels 311 of the two seals 3 are sealed and connected to the channel 112 of the single cell. The second gas flow channel 311 of one seal 3 is used to introduce raw material gas and introduce the raw material gas into the channel 112 of the single cell. An electrochemical oxidation-reduction reaction occurs in the reaction zone 11 of the single cell. The reduction product gas (such as H2 and / or CO) is discharged through the channel 112 from the second gas flow channel 311 of the other seal 3. The oxidation product gas (such as O2) is discharged through the first gas flow channel 211.

[0046] For example, the structure of the first heating element 22 can be filamentous or planar. The filamentous or planar structure can be designed into complex shapes such as serpentine or circular. The first heating element 22 can be combined in parallel or series to flexibly adjust the heating power and temperature distribution, adapting to the needs of single batteries of different sizes and types.

[0047] For example, the heating area of ​​the first heating element 22 on the first connector body 21 is greater than or equal to the area of ​​the positive electrode layer 111 of the single cell 1. In this application, the heating area of ​​the first connector body 21 covers the area of ​​the positive electrode layer 111 of the single cell 1, avoiding local overheating or local low temperature, making the temperature field of the single cell reaction zone 11 uniform, and improving electrolysis efficiency and stability. Moreover, the heat from the first heating element 22 on the first connector body 21 acts directly on the reaction zone 11, resulting in concentrated energy, high thermal efficiency, and reduced heat loss.

[0048] Preferably, such as Figure 4 As shown, the positive electrode layer 111 of the single battery 1 is square in shape, with a length and width of at least 1 cm. The shape of the first connector body 21 corresponds to the shape of the positive electrode layer 111, and is also square. The length and width of the first connector body 21 are slightly larger than the length and width of the positive electrode layer 111 of the single battery 1, so that the heating area of ​​the first heating element 22 on the first connector body 21 is slightly larger than the area of ​​the positive electrode layer 111 of the single battery, thereby achieving comprehensive heating of the reaction zone 11 of the single battery. In addition, the shape of the positive electrode layer 111 of the single battery 1 can also be rectangular or circular, and correspondingly, the shape of the first connector body 21 is rectangular or circular.

[0049] In some possible implementations, such as Figure 10 As shown, the second surface of the single cell 1 has a negative electrode current collector layer 117 at a position corresponding to the reaction zone 11, and the first surface and the second surface of the single cell 1 are arranged opposite to each other, with the negative electrode current collector layer 117 arranged opposite to the positive electrode layer 111; the material of the negative electrode current collector layer 117 is a conductive and dense current collector material. In this application, the second surface and the first surface of the single cell are arranged opposite to each other. When the material of the negative electrode current collector layer 117 is a conductive and dense current collector material, it can prevent the reduction product gas generated in the reaction zone 11 from overflowing from the negative electrode layer side of the single cell, so that the reduction product gas can only be discharged from the second gas flow channel 311 of the pore 112 and the sealing member 3, avoiding cross-mixing and reaction with the oxidation product gas discharged from the first gas flow channel 211, and maintaining the electrolysis efficiency of the ceramic membrane electrolyzer.

[0050] Furthermore, such as Figure 2-6 As shown, the ceramic membrane electrolyzer also includes: The second connector 4 includes a second connector body 41 and a second heating element 42, both of which are located on the negative electrode current collector layer 117 side of the single battery 1. The second connector body 41 abuts against the first surface of the negative current collector layer 117 of the single battery 1; The second heating element 42 is connected to the second connector body 41. When the second heating element 42 is powered on and generates heat, it can heat the reaction zone 11 of the single cell 1 through the second connector body 41 and the negative electrode current collector layer.

[0051] In this application, by adding a second connector 4, which cooperates with the first connector 2, the reaction zone 11 of the single cell 1 can be sandwiched between them, allowing the first and second surfaces of the single cell located in the reaction zone to heat up simultaneously and stably, avoiding temperature differences between the two surfaces of the single cell. The second surface of the single cell located in the reaction zone has a negative electrode current collector layer 117 (i.e., the second surface of the single cell has a negative electrode current collector layer 117 at the position corresponding to the reaction zone 11). This negative electrode current collector layer 117 is made of a conductive and dense, airtight current collector material, which can form a dense, conductive passivation layer on the second surface of the single cell, protecting the interior from oxidation. Furthermore, since the negative electrode current collector layer itself is dense and airtight, it can operate in high-temperature environments without the need for additional sealing materials, achieving high-temperature, unsealed operation while also preventing reduction product gases (such as CO and H2) from escaping through the negative electrode current collector layer. Therefore, the ceramic membrane electrolyzer of this application only needs to use sealing materials in the low-temperature regions at both ends of a single cell to achieve air inlet / outlet sealing with the sealing element 3. The low-temperature region has a low impact on the long-term stability of the sealing material, thereby avoiding the problem of high-temperature sealing failure of the sealing material. This reduces the sealing difficulty and gas leakage rate of the ceramic membrane electrolyzer operating at high temperatures, while avoiding gas leakage on the negative electrode layer side and increasing the operating pressure of the ceramic membrane electrolyzer.

[0052] For example, preferably, such as Figure 4 As shown, the first heating element 22 is disposed inside the first connector body 21, and the second heating element 42 is disposed inside the second connector body 41. In this application, both the first heating element 22 and the second heating element 42 can generate heat through electrical energy to heat the reaction zone of the single cell in contact with the first connector body 21 and the second connector body 41. Unlike traditional ceramic membrane electrolyzers that rely on external heating furnaces for heating, this application places the first heating element 22 inside the first connector body 21 and the second heating element 42 inside the second connector body 41. Heat can be transferred to the reaction zone of the single cell in contact with the connector body through the two heating elements, achieving short-distance heat conduction path transfer, shortening the heat transfer path of the ceramic membrane electrolyzer, and avoiding heat loss and heat conduction delay caused by external heating. The first heating element 22 and the second heating element 42 achieve precise heating only for the contacting reaction zone 11, without the need to heat the external environment or redundant structures of the ceramic membrane electrolyzer, reducing ineffective heating areas. For example, such as Figure 4-5As shown, both the first and second sides of the second connector body 41 are planar structures and are arranged opposite to each other. Since the first side of the second connector body 41 abuts against the first surface of the negative current collector layer, making the first side of the second connector body 41 planar allows for better contact with the negative current collector layer 117 of the single cell, achieving high-efficiency conductivity. Making the second side of the second connector body 41 planar also allows for better contact and conductivity with the second current collector 6.

[0053] For example, the structure of the second heating element 42 can be filamentous or planar. The filamentous or planar structure can be designed into complex shapes such as serpentine or circular. The second heating element 42 can be combined in parallel or series to flexibly adjust the heating power and temperature distribution, adapting to the needs of single batteries of different sizes and types.

[0054] In some possible implementations, such as Figure 23 As shown, the single cell 1 also includes a positive electrode current collector layer 113. The positive electrode current collector layer 113 is disposed on the surface of the positive electrode layer 111 facing the first connector body 21. The first surface of the first connector body 21 abuts against the positive electrode current collector layer 113 so that the first gas flow channel 211 is connected to the positive electrode current collector layer 113.

[0055] like Figure 23 As shown, the surface of the positive electrode layer 111 of the single battery 1 faces the first connector body 21, and a positive electrode current collector layer 113 is provided on the surface of the positive electrode layer 111. The positive electrode current collector layer 113 is in contact with the opening end face of the first gas flow channel 211, which allows the oxidation product gas to diffuse from the positive electrode layer 111 and the positive electrode current collector layer 113 into the first gas flow channel 211 and be smoothly discharged from the first gas flow channel 211. The positive electrode current collector layer 113 is disposed between the positive electrode layer 111 and the first gas flow channel 211 for current collection.

[0056] For example, in this application, single cell 1 is a negative electrode supported single cell (i.e., a cathode supported single cell).

[0057] For example, such as Figure 22 As shown, the single battery 1 includes a positive electrode layer 111, an electrolyte layer 114, a negative electrode layer 115, a negative electrode support layer 116, and a negative electrode current collector layer 117 stacked sequentially from top to bottom. Specifically, the negative electrode support layer 116 has a channel 112 inside, the negative electrode layer 115 is provided on the first surface of the negative electrode support layer 116, the negative electrode current collector layer 117 is provided on the second surface of the negative electrode support layer 116, and the first surface and the second surface of the negative electrode support layer are arranged opposite to each other, and the negative electrode current collector layer 117 is arranged opposite to the negative electrode layer 115. The electrolyte layer 114 covers the surface of the negative electrode layer 115 and the surface of the negative electrode support layer 116 that is not covered by the negative electrode current collector layer 117 and the negative electrode layer 115; the first surface of the electrolyte layer 114 is provided with a positive electrode layer 111, and the positive electrode layer 111 is disposed opposite to the negative electrode current collector layer 117.

[0058] For example, in this application, the area of ​​the region where the negative electrode layer 115 is located is greater than or equal to the area of ​​the region where the positive electrode layer 111 is located. Furthermore, the negative electrode layer 115 may even cover the first surface of the negative electrode support layer 116. Therefore, when the area of ​​the region where the negative electrode layer 115 is located is smaller than the area of ​​the region where the first surface of the negative electrode support layer 116 is located (i.e., the negative electrode layer does not completely cover the first surface of the negative electrode support layer 116), but is greater than or equal to the area of ​​the region where the positive electrode layer 111 is located, the electrolyte layer 114 covers the surface of the negative electrode layer 115 and the surface of the negative electrode support layer 116 that is not covered by the negative electrode current collector layer 117 and the negative electrode layer 115.

[0059] When the area of ​​the region where the negative electrode layer 115 is located is equal to the area of ​​the region where the first surface of the negative electrode support layer 116 is located (i.e., the negative electrode layer 115 completely covers the first surface of the negative electrode support layer 116), the electrolyte layer 114 covers the surface of the negative electrode layer 115 and the surface of the negative electrode support layer 116 that is not covered by the negative electrode current collector layer 117 and the negative electrode layer 115.

[0060] In this application, when the area of ​​the negative electrode layer 115 is larger than the area of ​​the positive electrode layer 111, or even covers the first surface of the negative electrode support layer 116, since the first heating element on the first connector and the second heating element on the second connector only heat the reaction zone 11 of the single cell and the non-reaction zone 12 is not heated, the electrochemical reduction reaction of the raw material gas on the negative electrode layer side is still concentrated in the reaction zone 11.

[0061] Furthermore, such as Figure 23 As shown, the single cell also includes a positive current collector layer 113. Specifically, a channel 112 is opened inside the negative electrode support layer 116, a negative electrode layer 115 is provided on the first surface of the negative electrode support layer 116, a negative current collector layer 117 is provided on the second surface of the negative electrode support layer 116, and the negative current collector layer 117 is arranged opposite to the negative electrode layer 115. The electrolyte layer 114 covers the surface of the negative electrode layer 115 and the surface of the negative electrode support layer 116 that is not covered by the negative electrode current collector 117 and the negative electrode layer 115; the first surface of the electrolyte layer 114 is provided with a positive electrode layer 111, and the positive electrode layer 111 is disposed opposite to the negative electrode current collector 117; the surface of the positive electrode layer 111 facing away from the electrolyte layer 114 is provided with the positive electrode current collector 113.

[0062] Of course, preferably, such as Figure 24As shown, a barrier layer 118 is provided between the positive electrode layer 111 and the electrolyte layer 114.

[0063] In this application, the single cell 1 includes at least a positive electrode layer 111, an electrolyte layer 114, a negative electrode layer 115, a negative electrode support layer 116, and a negative electrode current collector layer 117, which can provide an electrochemical reaction site for the feed gas. Based on this, additional layer structures can be added, such as a barrier layer 118, a positive electrode current collector layer 113, or other layer structures.

[0064] In this application, the various layers of the single cell 1 suitable for electrolysis, including the positive electrode current collector layer 113, the positive electrode layer 111, the barrier layer 118, the electrolyte layer 114, the negative electrode layer 115, and the negative electrode support layer 116, can be prepared using existing known technologies and are not specifically limited herein. Exemplarily, the material of the positive electrode layer 111 can be one of LSCF (lanthanum strontium cobalt ferrite), LSCF-GDC, LSC (lanthanum strontium cobalt ferrite), LSC-GDC, LSM (lanthanum strontium manganate), and LSM-GDC; wherein GDC is gadolinium oxide-doped cerium dioxide. Exemplarily, the chemical formula of the LSCF is La. 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3-δ GDC has the chemical formula Gd 0.1 Ce 0.9 O 3-δ Where δ represents oxygen vacancies; the chemical formula of the LSM material is La0.8Sr0.2MnO. 3-δ For example, the electrolyte layer 114 is made of YSZ (yttrium-stabilized zirconium oxide), the negative electrode layer 115 is made of NiO-8YSZ, and the negative electrode support layer 116 is made of NiO-3YSZ.

[0065] In some possible implementations, the negative electrode current collector 117 material of this application is a conductive and dense current collector material that does not leak air.

[0066] For example, the current collector material of the negative electrode current collector layer 117 is selected from doped LaCrO3-based ceramics and La x Sr 1-x TiO 3-δ Composite materials with Ni-Fe alloys, where x = 0.2~0.8, δ is the oxygen vacancy content, and La is calculated based on 100wt% of the composite material mass. x Sr 1-x TiO 3-δ The composition is 2-40 wt% by weight, Ni-Fe alloy with a mass percentage of 60-98 wt%, ferritic stainless steel, a mixture of Ag and glass-ceramic sealing materials, and any one of chromium-based alloys.

[0067] For example, this doped LaCrO3-based ceramic is CeO2-doped La0.7Ca0.3CrO 3-δ Ceramics. The ferritic stainless steel used is Crofer-22 APU ferritic stainless steel. The chromium-based alloy is Cr5Fe1Y2O3 alloy.

[0068] For example, in a mixture of Ag and glass-ceramic sealing material, the mass percentage of Ag is 50% to 99 wt%, with the remainder being glass-ceramic sealing material. Exemplarily, the mass percentage of Ag is 50 wt%, 55 wt%, 60 wt%, 65 wt%, 70 wt%, 75 wt%, 80 wt%, 85 wt%, 90 wt%, 95 wt%, 99 wt%, or any value between adjacent values.

[0069] Furthermore, when the current collector material of the negative electrode current collector layer is CeO2-doped La0.7Ca0.3CrO 3-δ When ceramicizing, the negative electrode current collector layer is prepared by the following method: Step 1), Preparation of La0.7Ca0.3CrO 3-δ Powder and preparation of negative electrode support layer green blank; Step 2), La0.7Ca0.3CrO 3-δ The powder, CeO2, appropriate amount of organic carrier, and dispersant are mixed and ball-milled to obtain a stable and uniformly dispersed slurry; wherein, the mass of CeO2 is equal to that of the La0.7Ca0.3CrO2. 3-δ 2wt% of the powder mass; Step 3) The slurry is coated on the second surface of the negative electrode support layer 116 green blank, and then sintered in a reducing atmosphere and / or an inert atmosphere at 1100~1400°C to obtain the negative electrode support layer 116, and a negative electrode current collector layer 117 is formed on the second surface of the negative electrode support layer 116.

[0070] In this application, to further address the densification difficulty, a second-phase sintering aid must be introduced. La0.7Ca0.3CrO3- is selected. δ (LCC for short). Ca doping at the A site (replacing part of La) can improve the material's conductivity and stability. The key additive is the introduction of 2wt% CeO2 into LCC. The mechanism of action is that CeO2, as a highly efficient sintering aid, can significantly promote the densification process of LCC under a reducing atmosphere. Specifically, sintering in a reducing atmosphere at 1100~1400℃ yields a high-density negative electrode current collector layer with a density >95.4%, effectively blocking gas permeation paths and meeting the requirement of no gas leakage. When the negative electrode current collector 117 is doped with CeO2-doped La0.7Ca0.3CrO 3-δWhen the ceramic is prepared, the conductivity of the negative electrode current collector can reach 52.7 S·cm in the mid-temperature region at 850℃. - ¹ This is far higher than the conductivity of the negative electrode current collector layer prepared with undoped LCC (approximately 2.5 times higher), meeting the current collection requirements.

[0071] For example, in step 1), La0.7Ca0.3CrO 3-δ The powder is a highly reactive powder that can be synthesized using wet chemical methods such as self-ignition or sol-gel processes to obtain LCC powder with uniform chemical composition, fine particles, and extremely high sintering activity. This is the basis for subsequent densification at relatively low temperatures (<1400℃). Among these, the self-ignition process or sol-gel process and other wet chemical methods are existing well-known technologies and will not be elaborated here.

[0072] For example, in step 2), the amount of organic carrier is not particularly limited, as long as it can be mixed with LCC powder, CeO2 and dispersant and ball-milled to form a uniformly dispersed slurry.

[0073] For example, in step 2), based on a total organic carrier mass of 100 wt%, the organic carrier includes 60-80 wt% organic solvent, 15-30 wt% binder and 5-15 wt% plasticizer.

[0074] For example, in step 2), the total mass of the dispersant and the organic carrier is related to the mass of La0.7Ca0.3CrO. 3-δ The mass ratio of the powder (LCC powder) is 30-70:70-30. Exemplarily, the total mass ratio of the dispersant and organic carrier to the LCC powder is 30:70, 40:60, 50:50, 60:40, or 70:30. Preferably, the total mass ratio of the dispersant and organic carrier to the LCC powder is 40:60.

[0075] For example, the organic solvent includes, but is not limited to, terpineol, butyl carbitol, and dibutyl phthalate. The role of the organic solvent is to dissolve other organic substances and adjust viscosity.

[0076] Binders include, but are not limited to, ethyl cellulose and polyvinyl butyral (PVB).

[0077] Plasticizers include, but are not limited to, diethyl phthalate (DEP) and polyethylene glycol (PEG). The role of plasticizers is to increase the flexibility of the negative electrode current collector 117 and prevent cracking.

[0078] Dispersants include, but are not limited to, glyceryl oleate. Dispersants are used to improve the dispersibility of powders in solvents and prevent agglomeration.

[0079] For example, in step 3), the coating is prepared using screen printing, slurry impregnation coating, or spraying to create a wet film for the negative electrode current collector. The key is to utilize the capillary adsorption force of the negative electrode support layer to fix the wet film. Then, the green negative electrode support layer with the wet film (i.e., the unsintered negative electrode support layer 116) is co-sintered at 1100–1400°C in a reducing atmosphere and / or an inert atmosphere. During this process, the LCC layer with added CeO2 gradually densifies, and the green negative electrode support layer is also sintered into a porous support with a certain strength. This double-layer co-firing process ensures a good bond between the negative electrode current collector 117 and the negative electrode support layer 116, avoiding delamination.

[0080] The reducing atmosphere includes, but is not limited to, H2, and the inert atmosphere includes, but is not limited to, Ar. The reducing atmosphere and / or inert atmosphere can ensure that the material is not oxidized during sintering.

[0081] In this application, La0.7Ca0.3CrO doped with CeO2 will be used. 3-δ The airtightness of the ceramic-based negative electrode current collector was tested: such as Figure 25 As shown, two stainless steel chambers with gas tubes are bonded together through the negative electrode current collector (i.e., forming sample 95), and a temperature-controlled furnace is installed outside the stainless steel chambers. Figure 25 (Not shown in the diagram) Used to provide temperature, gas source 91 is connected to the gas pipe of the stainless steel cavity via pressure reducing valve 92, pressure regulating valve 93, and flow meter 94, providing gas pressure to the stainless steel cavity to achieve the airtightness test of the negative electrode current collector. Gas source 91 is a nitrogen gas source. The temperature-controlled furnace is heated to the operating temperature of 750℃ and pressure is applied, nitrogen is introduced to maintain the pressure at 1MPa, and the gas leakage is detected to be <10 sccm / cm. This indicates that the CeO2-doped La0.7Ca0.3CrO 3-δ The negative electrode current collector 117 prepared by ceramic has good airtightness. Therefore, when applied to the single cell of this application, it can effectively prevent gas from leaking from the negative electrode current collector 117.

[0082] Furthermore, the current collection material of the negative electrode current collection layer can be a mixture of Ag and glass-ceramic sealing material, wherein the mass percentage of Ag in the mixture is 50~99wt%, and the remainder is glass-ceramic sealing material.

[0083] For example, the particle size of Ag is 0.5~3μm, preferably about 1μm.

[0084] For example, glass-ceramic sealing materials may have one of the following compositions: SiO2-Al2O3-Na2O-CaO, SiO2-Al2O3-Na2O-BaO, or SiO2-Al2O3-Na2O-BaO-YSZ. These glass-ceramic sealing materials, when mixed with Ag, can form current collectors with a thermal expansion coefficient of 9~17×10⁻⁶.-6 ℃ -1 Ag powder and glass-ceramic sealing material powder are mixed with organic solvents (including but not limited to terpineol, ethyl cellulose, epoxy resin, and phenolic resin), and then ball-milled with φ10mm and φ5mm ceramic beads for 12 hours to obtain a gel-like liquid. This liquid is easy to screen print onto the second surface of the negative electrode support layer of a single cell. It needs to be coated with 3-4 layers, with a thickness of about 200μm.

[0085] For example, taking a glass-ceramic sealing material with the composition SiO2-Al2O3-Na2O-BaO as an example, the preparation of SiO2-Al2O3-Na2O-BaO is as follows: take the raw material powders corresponding to SiO2, Al2O3, Na2O and BaO respectively, weigh them in a ratio of 70%:10%:15%:5%, put them into a ball mill and ball mill for 4 hours to mix them evenly; put them into a crucible and heat them at 1400 degrees Celsius to completely melt them; quickly pour them into pure water for cold extraction to obtain solid block glass; crush and grind them to obtain glass powder, and then pass them through a 300-mesh sieve to obtain SiO2-Al2O3-Na2O-BaO powder with a particle size of 60μm.

[0086] Furthermore, when the current collection material of the negative electrode current collector layer is selected as La... x Sr 1-x TiO 3-δ When composites are made with Ni-Fe alloys, where x = 0.2~0.8, δ is the oxygen vacancy content, with a value of 0~0.2, and La is calculated based on a composite material mass of 100wt%. x Sr 1- x TiO 3-δ The mass percentage is 2~40wt%, and the mass percentage of Ni-Fe alloy is 60~98wt%. This ratio can be achieved through LST (i.e., La). x Sr 1-x TiO 3-δ The "pinning effect" of the particles (abbreviated as NiFe) effectively inhibits the coarsening of NiFe particles while maintaining high electrical conductivity (>100 S·cm). - ¹).

[0087] For example, when the current collection material of the negative electrode current collection layer is La 0.2 Sr 0.8 TiO 3-δ When used in composite materials with Ni-Fe alloys, the negative electrode current collector layer is prepared by the following method, including: Step (A): La was prepared using the sol-gel method. 0.2 Sr 0.8 TiO 3-δ : According to the molar ratio of metal cations n(La):n(Sr):n(Ti)=0.2:0.8:(3) δ) (where δ is the oxygen vacancy content, usually taken as 0~0.2) Weigh out the corresponding masses of lanthanum nitrate hexahydrate (La(NO3)3·6H2O), strontium nitrate (Sr(NO3)2), and tetrabutyl titanate (C) respectively. 16 H 36 O4Ti). Using N,N-dimethylformamide (DMF) as solvent and polyvinylpyrrolidone (PVP) as complexing agent and viscosity modifier, La was formulated. 0.2 Sr 0.8 TiO 3-δ Precursor solution. Specifically, PVP was first dissolved in DMF, followed by the addition of metal nitrates (including La(NO3)3·6H2O) and Sr(NO3)2. The solution was stirred in a 55 °C water bath until completely dissolved, yielding a solution. After cooling, concentrated nitric acid was slowly added dropwise to prevent the hydrolysis of tetrabutyl titanate. After stirring until homogeneous, tetrabutyl titanate was added dropwise, and stirring continued until a homogeneous and transparent precursor solution was formed. The mass ratio of the components in the precursor solution system was m(PVP):m(metal ions):m(DMF):m(concentrated nitric acid) = 1:2:18:0.27. After drying at 80-120 °C, a dry gel was obtained. This gel was then calcined at 1000 °C and held for 3 h at a heating rate of 1 °C / min to remove organic matter and form a perovskite phase, thus preparing La. 0.2 Sr 0.8 TiO 3-δ Material.

[0088] Step (B): The molar ratio of Ni to Fe in the Ni-Fe alloy powder is 1:1, according to the formula: Ni-Fe alloy powder: La 0.2 Sr 0.8 TiO 3-δ Weigh out Ni-Fe alloy powder and La in a mass ratio of 90:10 to 98:2 respectively. 0.2 Sr 0.8 TiO 3-δ Materials. Using anhydrous ethanol or acetone as the medium, wet ball milling was performed at 300-400 rpm for 4-12 hours to obtain a slurry. Ball milling can effectively refine La. 0.2 Sr 0.8 TiO 3-δ Particles, and achieve Ni-Fe, La 0.2 Sr 0.8 TiO 3-δ The two phases are mixed uniformly.

[0089] Step (C): The ball-milled slurry is dried, sieved (e.g., 200 mesh), mixed with an organic carrier and dispersant, and then ball-milled using a three-roll mill to obtain a current collector slurry with a thickness of 0.1~5μm. This current collector slurry is then screen-printed onto the second surface of the unsintered negative electrode support layer 116 (i.e., the negative electrode support layer green body), with a thickness of 5~100μm. It is then sintered at 1200~1500℃ in a reducing atmosphere and / or an inert atmosphere to obtain the negative electrode support layer, and the negative electrode current collector 117 is formed on the second surface of the negative electrode support layer. The density of the negative electrode current collector 117 obtained after sintering exceeds 98%.

[0090] In step (C), the organic carrier comprises 60-80 wt% organic solvent, 15-30 wt% binder and 5-15 wt% plasticizer, based on a total organic carrier mass of 100 wt%.

[0091] For example, in step (C), based on a total mass of 100wt% of the slurry in the flow collector layer, the La 0.2 Sr 0.8 TiO 3-δ The total mass percentage of the material and Ni-Fe alloy powder is 30-70 wt%. For example, this La... 0.2 Sr 0.8 TiO 3-δ The total mass percentage of the material and Ni-Fe alloy powder is 30wt%, 40wt%, 50wt%, 60wt%, 70wt%, or any value between adjacent values. Preferably, the La... 0.2 Sr 0.8 TiO 3-δ The total mass percentage of the material and Ni-Fe alloy powder is 60 wt%.

[0092] For example, the organic solvent includes, but is not limited to, terpineol, butyl carbitol, and dibutyl phthalate. The role of the organic solvent is to dissolve other organic substances and adjust viscosity.

[0093] Binders include, but are not limited to, ethyl cellulose and polyvinyl butyral (PVB).

[0094] Plasticizers include, but are not limited to, diethyl phthalate (DEP) and polyethylene glycol (PEG). The role of plasticizers is to increase the flexibility of the negative electrode current collector and prevent cracking.

[0095] Dispersants include, but are not limited to, glyceryl oleate. Dispersants are used to improve the dispersibility of powders in solvents and prevent agglomeration.

[0096] In some possible implementations, both the first heating element 22 and the second heating element 42 are resistance wires. In this application, by setting the resistance wires in the form of internal heating, on the one hand, the overall weight of the ceramic membrane electrolyzer is reduced, achieving a lightweight structure; on the other hand, the heat transfer path for heating the core components of the ceramic membrane electrolyzer is reduced, thus achieving low energy consumption of the ceramic membrane electrolyzer.

[0097] For example, the material of this resistance wire is Cr. 20 Ni 80 High resistance heating alloy, average temperature coefficient of resistance (unit: °C) -1 The approximate value is: α = (8 ~ 9) × 10 -5 / ℃, prepare the lead-out part with 3-4 layers of folding before leading out, minimize the resistance at the lead-out head and increase the strength to avoid the resistance wire breaking during long-term heating.

[0098] For example, the average temperature coefficient of resistance of this resistance wire is α = (8 ~ 9) × 10 -5 At / ℃, the resistance changes little with temperature, resulting in small resistance fluctuations and stable output during the heating process of the resistance wire.

[0099] For example, such as Figure 5 As shown, the heating area of ​​the second heating element 42 on the second connector body 41 is greater than or equal to the area of ​​the negative electrode current collector layer 117 of the single battery 1.

[0100] In this application, the heating area of ​​the second heating element 42 on the second connector body 41 covers the entire negative electrode current collector layer of the single cell 1, avoiding local overheating or local underheating, making the temperature field of the single cell uniform, and improving electrolysis efficiency and stability. Moreover, the heat from the second heating element on the second connector body acts directly on the reaction zone of the single cell, resulting in concentrated energy, high thermal efficiency, and reduced heat loss.

[0101] In some possible implementations, such as Figure 2 , Figure 7-8 , Figure 12-13 As shown, the sealing element 3 includes an air distribution module 31 and a sealing module 32. The second gas flow channel 311 is opened in the air distribution module 31, and the sealing module 32 is provided with a mounting hole 321. The two ends of the single battery 1 are respectively inserted into the mounting holes 321 of the sealing module 32 and the single battery 1 is sealed to the mounting holes 321. The gas distribution module 31 and the sealing module 32 are sealed to the gas flow channel 311. The ceramic membrane electrolyzer also includes a first gas supply pipe 312, which is sealed and connected to the second gas flow channel 311 of the gas distribution module 31.

[0102] For example, there are two first gas supply pipes 312, which are respectively located at both ends of the single cell. Each first gas supply pipe 312 is sealed and connected to the second gas flow channel 311 of the gas distribution module 31 of a sealing element 3. One end of the first gas supply pipe 312 is also used to seal and connect with an external gas pipe to transport raw material gas into the second gas flow channel 311, and then into the channel of the single cell for electrochemical reaction. The other end of the first gas supply pipe 312 is used to output the reduction product gas discharged from the channel and the second gas flow channel. For example, such as Figure 7-8 As shown, in this application, the sealing module 32 has a mounting hole 321, which is an irregularly shaped structure. Specifically, the mounting hole 321 can be implemented in the following way: along the thickness direction of the sealing module 32, such as... Figure 8 In the direction T, where T represents the thickness, a through hole 3211 is formed in the sealing module 32. This through hole 3211 is adapted to the shape of the single battery. A slot 3212 is formed on one side of the sealing module 32. The slot 3212 is located outside the opening end of the first through hole 3211 and communicates with the first through hole 3211. Thus, the first through hole 3211 and the slot 3212 form the mounting hole 321. A matching sealing ring 322 is placed in the slot 3212 so that one end of the single battery is sealed through the mounting hole 321, achieving a sealed connection between one end of the single battery and the sealing module 32. Furthermore, a heat-resistant sealant can be applied between one end of the single battery and the mounting hole to further strengthen the sealing connection between them. The thickness directions of the sealing element 3, the sealing module 32, and the air distribution module 31 are all aligned in the same direction. Furthermore, the thickness direction of the seal 3 is aligned with the length direction of the single cell 1 and the axial direction of the channel 112.

[0103] For example, such as Figure 7-8 , Figure 12-13 As shown, a second gas flow channel 311 is formed on the gas distribution module 31 along its thickness direction. The second gas flow channel 311 is also an irregularly shaped structure. Specifically, the second gas flow channel 311 can be implemented as follows: a second groove 3111 is formed on the first side of the gas distribution module 31 along its thickness direction, and a first through groove 3112 is formed on the second side at a position corresponding to the second groove. The first side and the second side of the gas distribution module are arranged opposite each other along the thickness direction of the gas distribution module. The second groove 3111 and the first through groove 3112 are connected, thereby forming the second gas flow channel 311.

[0104] The second groove 3111 is shaped to match the shape of a single battery, and is generally elongated. The first through groove 3112 is used to seal and connect to the first gas supply pipe 312, which further seals and connects to an external pipe. Preferably, the first through groove 3112 is circular to facilitate connection to the first gas supply pipe 312, thereby facilitating the connection of the first gas supply pipe 312 to an external circular pipe, and the diameter of the first through groove 3112 is smaller than the length of the second groove 3111. Of course, the first through groove 3112 can also be other shapes, such as elliptical, as long as it can achieve a sealed connection with the first gas supply pipe 312 and the external pipe. Preferably, the first through groove 3112 can be integrated with the first gas supply pipe 312.

[0105] Since the shape of the second groove 3111 is adapted to the single cell, the second gas flow channel 311 can communicate with the channels of the single cell. Furthermore, in order to avoid gas leakage during gas delivery, the size of the second groove 3111 can be slightly smaller than the cross-sectional size of the end of the single cell, as long as the second groove 3111 can cover all the channels of the single cell.

[0106] The sealing ring is a rubber sealing ring, custom-fitted to the dimensions of a single cell, with its thickness matching the slot 3212 on the sealing module. The rubber sealing ring has an operating temperature above 50°C and is made of rubber or fluororubber, etc., to meet high-pressure resistance requirements. For example, the sealing ring thickness is 2~6mm.

[0107] For example, such as Figure 7-8 As shown, a sealing element 3 includes two sealing modules 32 and one gas distribution module 31. The two sealing modules 32 are arranged side by side, and are respectively designated as the first sealing module and the second sealing module. A sealing ring 322 is provided in the slot 3212 of the first sealing module and the slot 3212 of the second sealing module. The gas distribution module, the second sealing module and the first sealing module are respectively provided with a first connecting hole 323 at corresponding positions. The first connecting hole 323 is located away from the second gas flow channel 311 and the mounting hole 321.

[0108] The assembly process between the sealing module 32, the air distribution module 31, and the single battery 1 of the sealing component 3 is as follows: One end of the single battery 1 is sequentially passed through the mounting hole 321 of the first sealing module, the sealing ring 322, and the mounting hole 321 and sealing ring 322 of the second sealing module. At this time, one end of the single battery is located within the slot 3212 of the second sealing module, and the sealing ring 322 is fitted onto one end of the single battery. Figure 7As shown; then, the first side of the gas distribution module 31 is tightly attached to the side of the second sealing module, and fasteners 33 are sequentially inserted into the first connecting holes 323 reserved at corresponding positions in the first sealing module, the second sealing module, and the gas distribution module, so that the three can be tightly connected by fasteners; thereby, the second sealing module is clamped between the gas distribution module and the first sealing module, and the sealing ring 322 on the second sealing module seals and presses against the outer circumferential direction of the opening end of the second groove 3111 of the gas distribution module, while the sealing ring 322 on the first sealing module also seals and presses against the outer circumferential direction of the opening end of the first through hole 3211 of the second sealing module. Thus, the sealing module and the gas distribution module are fastened by fasteners, forming a clamping pressure on the sealing module and the gas distribution module, preventing gas entering the single battery from the gas distribution module from leaking along the axial and longitudinal direction of the seal. The other end of the single battery is also assembled with the seal in the same manner as described above.

[0109] For example, fasteners 33 include, but are not limited to, bolts, screws, pins, and fastening threaded rods. The sealing ring 322 prevents gas leakage.

[0110] Of course, besides using the above-described method to achieve a leak-proof seal between the sealing module 32 and the gas distribution module 31 of the sealing element 3, the sealing connection between the sealing module 32 and the gas distribution module 31 of the sealing element 3 can also be achieved using existing known technologies, as long as a sealing connection can be achieved so that the channel of the single cell is sealed and connected to the second gas flow channel 311 of the gas distribution module. For example, after one end of the single cell passes through the mounting hole 321 of the sealing module 32, a sealing material (such as a high-temperature resistant sealant) can be used to seal the contact surfaces between the sealing module and the gas distribution module, and between the sealing modules. Alternatively, for example, the contact surfaces between the sealing module and the gas distribution module, and between the sealing modules, can be directly welded. A sealing material (such as a high-temperature resistant sealant) can also be used to further strengthen the seal between one end of the single cell and the mounting hole. Alternatively, as an example, in addition to setting the sealing module 32 and the gas distribution module 31 as separate components as described above, the sealing component 3 can also be an integrally formed structure composed of the sealing module 32 and the gas distribution module 31. The sealing module and the gas distribution module are integrally formed using a mold, and a second gas flow channel 311 is formed inside the gas distribution module 31. An installation hole 321 connected to the second gas flow channel 311 is formed inside the sealing module 32. One end of the single battery is passed through the installation hole 321 and the single battery is sealed with a sealing material, so that the channel 112 of the single battery is connected to the second gas flow channel 311. Thus, when the raw material gas enters the second gas flow channel 311 from one of the first gas delivery pipes 312, it can only enter the channel 112 of the single battery.

[0111] Furthermore, after the two ends of the single battery 1 are assembled with the sealing element 3 respectively, the sealing elements 3 at both ends can be further connected by a connector (such as a screw) to ensure the balance between the assembled single battery and the sealing elements 3 at both ends.

[0112] In one possible implementation, such as Figure 14-17 As shown, when multiple single batteries 1 and multiple first connectors 2 are provided, the multiple single batteries 1 and multiple first connectors 2 are alternately stacked along the stacking direction of the single batteries. The stacked structure is compact and regular, which facilitates mass assembly, standardized production and subsequent maintenance and replacement, and the overall structural strength and stability are stronger. Among them, the first connector 2 includes a first connector body 21 and a first heating element 22. The first connector body 21 has a first gas flow channel 211 formed on the first surface facing the positive electrode layer. The first surface of the first connector body abuts against the positive electrode layer so that the first gas flow channel 211 is connected to the positive electrode layer 111.

[0113] For example, in this application, "multiple" refers to two or more.

[0114] For example, in this application, multiple single cells 1 and multiple first connectors 2 are alternately stacked along the stacking direction of the single cells. Specifically, as shown... Figure 14-17 As shown, taking the stacking direction as the vertical direction as an example ( Figure 14 (shown in the Z direction), the first connector 2 includes a first connector body 21 and a first heating element 22. The first surface of the first connector body 21 facing the positive electrode layer of the single cell has a first gas flow channel 211. The second surface of the first connector body 21 is a planar structure and is disposed opposite to the first surface. Thus, when multiple single cells 1 and multiple first connectors 2 are stacked alternately along the stacking direction of the single cells, the end face of the opening of the first gas flow channel 211 on the first surface of the first connector body 21 contacts the positive electrode layer 111 of the single cell, and the second surface of the first connector body 21 contacts the negative electrode current collector layer 117 of the adjacent single cell above it. The negative electrode current collector layer 117 is located on the second surface of the single cell and is disposed opposite to the positive electrode layer 111.

[0115] Among them, the negative electrode current collector layer 117 of the bottommost single battery contacts and abuts against the first side of the second connector body 41.

[0116] In this application, the first connector 2 simultaneously performs multiple functions such as conducting electricity, separating gas, and supporting in the stack, thereby realizing heating inside the ceramic membrane electrolyzer, reducing the overall volume of the ceramic membrane electrolyzer, reducing heating energy consumption, and saving costs.

[0117] For example, compared to when there is only one single cell, the seal 3 needs to be adapted to accommodate multiple stacked single cells 1. The seal 3 includes a sealing module 32 and an air distribution module 31. The sealing module 32 is configured as described above, i.e., as... Figure 16-17 As shown, a plurality of mounting holes 321, equal in number to the number of individual batteries, are provided on the sealing module 32 along the stacking direction, with the mounting holes 321 spaced apart. The arrangement of each mounting hole 321 and the arrangement of the sealing ring 322 can refer to the arrangement described above. For example, the sealing module 32 may have a mounting hole 321 with an irregular shape. Specifically, a through hole 3211 is formed along the thickness direction of the sealing module 32, adapting to the shape of the individual battery. A slot 3212 is formed on one side of the sealing module 32, located outside the opening end of the through hole 3211 and communicating with it. Thus, the first through hole 3211 and the slot 3212 constitute the mounting hole 321. The slot 3212 is used to place a matching sealing ring 322, allowing the individual battery to be sealed and inserted into the mounting hole 321.

[0118] Along the thickness direction of the gas distribution module 31, a second gas flow channel 311 is formed on the gas distribution module 31. The second gas flow channel 311 is also an irregularly shaped structure. Specifically, the second gas flow channel 311 can be implemented in the following way: Figure 17-18 As shown, along the thickness direction of the gas distribution module 31, a third groove 3113 is provided on the first side of the gas distribution module 31, and a second through groove 3114 is provided on the second side at a position corresponding to the third groove. The first side and the second side of the gas distribution module are arranged opposite to each other along the thickness direction of the gas distribution module. The third groove 3113 and the second through groove 3114 are connected, so that the third groove 3113 and the second through groove 3114 form the second gas flow channel 311.

[0119] The second through groove 3114 is used to seal and connect the first gas supply pipe 312, which in turn seals and connects to an external pipe. Preferably, the second through groove 3114 is circular to facilitate sealing and connecting the first gas supply pipe, and thus to facilitate the first gas supply pipe connecting to an external circular pipe. Of course, the second through groove 3114 can also be other shapes, such as elliptical, as long as it can achieve a sealed connection with the first gas supply pipe 312 and the external pipe.

[0120] like Figure 17 As shown, the shape of the third groove 3113 can simultaneously match the stacking of multiple single cells, so that after the raw material gas enters the third groove 3113 from the external pipe, the first gas supply pipe 312, and the second through groove 3114, it can simultaneously enter the channels 112 of multiple single cells 1.

[0121] One end of each of the multiple individual cells is respectively sealed through the multiple mounting holes 321 of the sealing module 32, and the end of each individual cell is located in the slot 3212 of the mounting hole 321. A sealing ring 322 is fitted onto the end of each individual cell to achieve a sealed connection between the individual cell and the mounting hole. The sealing ring 322 is located within the slot 3212. The gas distribution module 31 is located outside the sealing module 32, and after the gas distribution module and the sealing module are fastened together with fasteners, the sealing ring is sandwiched between them. The sealing ring in the sealing module can achieve a sealed connection between the gas distribution module and the sealing module, so that the second gas flow channel 311 is sealed and connected to the channel 112 of the individual cell. Furthermore, in order to enhance the sealing effect, a heat-resistant sealant can be coated on the first side of the gas distribution module and on the outer periphery of the third groove 3113. The first side of the gas distribution module is sealed to the side of the sealing module through the heat-resistant sealant to further enhance the sealed connection between the sealing module and the gas distribution module.

[0122] For example, when multiple single batteries 1 are provided and stacked along the stacking direction, the second gas flow channel 311 of the gas distribution module 31 can also refer to Figure 12-13 Configure settings: like Figures 19-20 As shown, a second gas flow channel 311 is formed on the gas distribution module 31 along its thickness direction. The second gas flow channel 311 is also an irregularly shaped structure. Specifically, the second gas flow channel 311 is implemented in the following way: a plurality of fourth grooves 3115 are formed on the first side of the gas distribution module 31. The number of fourth grooves 3115 is equal to the number of single batteries, and the plurality of fourth grooves 3115 are spaced apart along the stacking direction of the single batteries.

[0123] A third through groove 3116 is provided on the second side of the gas distribution module 31. The first side and the second side of the gas distribution module are arranged opposite to each other along the thickness direction of the gas distribution module. The third through groove 3116 is connected to a plurality of fourth grooves 3115, so that the plurality of fourth grooves 3115 and the third through groove 3116 form the second gas flow channel 311.

[0124] Each fourth groove 3115 is shaped to fit the shape of the single cell, and is generally elongated. Furthermore, in order to avoid gas leakage during gas delivery, the size of the fourth groove 3115 can be slightly smaller than the cross-sectional size of the end of the single cell, as long as the fourth groove 3115 can cover all the channels of the single cell.

[0125] The third through groove 3116 is used to seal and connect the first gas supply pipe 312, thereby connecting the first gas supply pipe 312 to an external pipe; preferably, the third through groove 3116 is circular in shape to facilitate connection to the first gas supply pipe 312. Of course, the third through groove 3116 can also be other shapes, such as elliptical, as long as it can achieve a sealed connection with the external pipe and the first gas supply pipe 312.

[0126] One end of the single battery 1 is passed through the mounting hole 321 and sealing ring 322 of the sealing module. At this time, one end of the single battery is located in the slot 3212 of the mounting hole 321 of the sealing module, and the sealing ring 322 is fitted onto one end of the single battery. Then, the first side of the gas distribution module 31 is pressed tightly against the side of the sealing module, and fasteners are sequentially inserted into the first connection holes reserved at corresponding positions on the gas distribution module and the sealing module, so that the three can be fastened together by the fasteners. This causes the sealing ring 322 on the sealing module to press against the outer circumferential direction of the opening end of the fourth groove 3115 of the gas distribution module. Thus, the sealing module and the gas distribution module are fastened together by the fasteners, forming a clamping pressure on the sealing module and the gas distribution module, preventing gas from entering the single battery from the gas distribution module from leaking along the axial and longitudinal direction of the seal. The other end of the single battery is also assembled with the seal in the same way as described above.

[0127] Preferably, to further improve airtightness, each seal may have two sealing modules. After the two sealing modules are fastened to the air distribution module with fasteners, there is a sealed connection between the two adjacent sealing modules and between the sealing module and the air distribution module. More preferably, the seal may be further strengthened by applying a heat-resistant sealant to the contact surfaces between the two sealing modules and between the sealing module and the air distribution module.

[0128] For example, such as Figure 21 As shown, the center of the sealing connection area between the sealing module 32 and one end of the single battery 1 is at least 5 cm away from the edge of the reaction zone 11. In this application, whether the sealing connection between the sealing module 32 and one end of the single battery 1 is achieved using a sealing ring 322 or the sealing connection between the sealing module and the gas distribution module, the sealing is concentrated on their contact surface. Therefore, the sealing material involved between the sealing element and the single battery is mainly concentrated on the sealing module. Thus, in this application, the distance L between the center of the sealing connection area between one end of the single battery 1 and the sealing module 32 and the edge of the reaction zone 11 is set to at least 5 cm to ensure that the sealing elements at both ends of the single battery remain at a low temperature, thereby preventing the sealing material used to seal the sealing elements and the two ends of the single battery from being affected by the high temperature operation of the reaction zone 11. In some possible implementations, such as Figure 2-5 As shown, the ceramic membrane electrolyzer also includes: The first current collector 5 is located on the side of the first connector body 21 facing away from the single battery 1 and abuts against the first connector body 21. The second current collector 6 is located on the side of the second connector body 41 facing away from the single battery and abuts against the second connector body 41; the first current collector 5 and the second current collector 6 are locked together by fasteners.

[0129] The first current collector 5 and the second current collector 6 are locked together by fasteners, forming a locking force along the stacking direction on the first connector body 21, the second connector body 41 and the single cell 1, so as to achieve better conductivity.

[0130] For example, the fastener includes, but is not limited to, bolts, screws, etc. To prevent the first current collector 5 from conducting electricity with the second current collector 6 through the fastener, insulating materials are provided between the fastener and the first current collector 5, and between the fastener and the second current collector 6. These insulating materials include, but are not limited to, mica gaskets.

[0131] Furthermore, such as Figure 1-5 As shown, the ceramic membrane electrolyzer also includes: The insulation component 7 has a accommodating space in which the reaction zone 11 of the single cell, the first current collector 5, the first connector 2, the second connector 4 and the second current collector 6 are all housed; and a gap 73 for gas to flow out is left between the inner wall of the insulation component and the single cell 1. Two first conductive elements 71 are provided, which are installed on the heat insulation element 7 and are electrically connected to the first current collector 5 and the second current collector 6 respectively. Two second conductive elements 72 are provided. One second conductive element 72 is electrically connected to the first end of the first heating element 22 and the second heating element 42, and the other second conductive element 72 is electrically connected to the second end of the first heating element 22 and the second heating element 42.

[0132] For example, there are two first conductive elements 71. One first conductive element 71 is electrically connected to the first current collector 5, and the other first conductive element 71 is electrically connected to the second current collector 6. The two first conductive elements 71 are respectively connected to the positive and negative terminals of the power supply to realize the conduction of the circuit.

[0133] Both ends of the first heating element 22 and the second heating element 42 are exposed on the insulation component 7. The two second conductive components 72 are respectively connected to the positive and negative terminals of the power supply to energize and heat the first heating element and the second heating element.

[0134] For example, the insulation component 7 is made of high-temperature resistant insulation material, and it covers the outside of the single cell's reaction zone 11, the first current collector 5, the first connector 2, the second connector 4, and the second current collector 6. Preferably, as shown... Figure 1As shown, the insulation component 7 also covers a portion of the non-reaction zone 12 adjacent to the reaction zone. Gaps 73 are provided between the inner wall of the insulation component 7 and the single cell in the non-reaction zone, and between the inner wall of the insulation component 7 and the first conductive component 71, to allow the oxidation product gas flowing out from the first gas flow channel to exit through these gaps 73. The insulation component 7 effectively maintains a high-temperature environment in the reaction zone 11 during operation, preventing heat loss. Furthermore, a gap is also provided between the inner wall of the insulation component 7 and the first conductive component 71.

[0135] For example, such as Figure 3-4 As shown, the insulation component 7 is a separate component, consisting of a first insulation component 74 and a second insulation component 75 connected together, so that the interior of the insulation component 7 forms an accommodating space for accommodating the reaction zone 11 of the single battery, the first current collector 5, the first connector 2, the second connector 4 and the second current collector 6. Making the insulation component 7 a separate component facilitates its manufacture.

[0136] Secondly, such as Figure 26 As shown, this application also provides a ceramic membrane electrolysis device, including the ceramic membrane electrolysis cell in any of the above-described possible embodiments; the ceramic membrane electrolysis device further includes: a sealed container 8, which is sealed to the outside of the ceramic membrane electrolysis cell; The second gas delivery pipe 81 is sealed and installed on the sealed container 8, and is connected to the first gas flow channel 211.

[0137] For example, since a first gas supply pipe 312 is connected to the seal 3 of the ceramic membrane electrolyzer, this first gas supply pipe 312 can pass through the sealed container 8 in a sealed manner to achieve communication with external pipelines. Figure 27 As shown, a second connection hole 82 is provided on the sealed container 8, and the first gas supply pipe 312 is sealed through the second connection hole 82, for example, by using a sealing material such as sealant; or after the first gas supply pipe 312 passes through the second connection hole 82, the first gas supply pipe 312 is welded to the sealed container 8 to achieve a seal.

[0138] The sealed container 8 has an internal cavity to accommodate the ceramic membrane electrolyzer. Two first conductive elements 71 pass through the sealed container 8 in a sealed manner and are electrically connected to a first current collector and a second current collector. Two second conductive elements 72 pass through the sealed container 8 in a sealed manner and are electrically connected to a first heating element and a second heating element.

[0139] Taking the electrolysis of water and carbon dioxide in a ceramic membrane electrolyzer as an example, water and carbon dioxide, as raw materials, enter the second gas flow channel 311 of the seal 3 connected to one end of the single cell through one of the first gas supply pipes 312, and then enter the channel 112 of the single cell 1. An electrochemical reaction occurs in the reaction zone 11. The resulting reduction product gas H2 / CO is output through the channel 112 from the second gas flow channel 311 of the seal 3 connected to the other end of the single cell and the other first gas supply pipe 312. The resulting oxidation product gas O2 is discharged from the first gas flow channel 211 of the first connector 2 and the gap 73 of the heat insulation member 7 into the sealed container 8, and then flows out from the second gas supply pipe 81.

[0140] The ceramic membrane electrolyzer of this application can be applied to ceramic membrane electrolysis devices to achieve sealed input of raw material gas, sealed output of reduction product gas and sealed output of oxidation product gas. On the one hand, it can avoid the problem of high temperature failure of sealing material, on the other hand, it can avoid gas cross-contamination and reaction, and also shorten the heat conduction path and reduce energy loss.

[0141] The ceramic membrane electrolysis device of this application was subjected to an airtightness test: (Refer to...) Figure 25 The ceramic membrane electrolysis device is placed in a temperature-controlled furnace, which is then heated to the operating temperature (600~850℃), and the second gas supply pipe 81 is sealed. Then, the gas source 91 is opened, and the gas (e.g., N2) from the gas source 91 enters the single-cell channel of the ceramic membrane electrolysis device through one of the first gas supply pipes 312. The other first gas supply pipe 312 is connected to a pressure gauge 96. When the pressure displayed on the pressure gauge 96 increases to 0.1 MPa, the gas source is shut off. The pressure stabilizes within 30 seconds, indicating that the entire ceramic membrane electrolysis device is leak-free. This further demonstrates that both the sealing element and the two ends of the single cell achieve a sealed connection, and the negative electrode current collector layer 117 prepared using the current collector material is also dense and leak-proof.

[0142] Furthermore, when the ceramic membrane electrolysis device of this application was purged with gas exceeding 1 MPa, the seal of the ceramic membrane electrolysis device remained intact after operation. This indicates that by separating the high-temperature reaction zone 11 and the non-reaction zone 12, and setting the sealing positions of the two ends of the single cell and the sealing element in the non-reaction zone, which is located in a low-temperature region, the problem of high-temperature sealing failure of existing sealing materials can be effectively avoided. Moreover, the airtightness of the raw material gas intake and the reduction product gas output is achieved, which greatly extends the service life of the ceramic membrane electrolysis device.

[0143] Taking the electrolysis of CO2 and water vapor by a ceramic membrane electrolysis device to produce syngas (H2 / CO) as an example, syngas (H2 / CO) is generated during the electrolysis of CO2 and water vapor. However, H2 / CO requires high pressure to synthesize fuels such as methane. Currently, existing traditional ceramic membrane electrolysis cells and devices can only produce syngas at atmospheric pressure. If further synthesis of fuels such as methane is required, the atmospheric pressure syngas or the synthesis device itself needs to be pressurized, which undoubtedly increases the synthesis cost. However, using the ceramic membrane electrolysis cell and device of this application, due to its better sealing performance, high-pressure syngas can be directly generated through electrolysis. This high-pressure syngas can be directly coupled into the methane and other fuel synthesis device, further reducing the energy consumption for synthesizing methane and other fuels and lowering economic costs.

[0144] Therefore, the reduction product gas output from the negative electrode layer side of the ceramic membrane electrolysis device of this application can be directly coupled with the high-pressure methanation reaction, thereby improving system efficiency, realizing the system integration of the ceramic membrane electrolysis device and the methanation synthesis device, reducing weight, and increasing efficiency.

[0145] It should be understood that the various forms of processes shown above can be used to rearrange, add, or delete steps. For example, the steps described in this disclosure can be executed in parallel, sequentially, or in different orders, as long as the desired result of the technical solution of this disclosure can be achieved, and this is not limited herein.

[0146] Furthermore, the terms "first" and "second" are used for descriptive purposes only and should not be construed as indicating or implying relative importance or implicitly specifying the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include at least one of that feature. In the description of this disclosure, "a plurality of" means two or more, unless otherwise explicitly specified.

[0147] The above description is merely a specific embodiment of this disclosure, but the scope of protection of this disclosure is not limited thereto. Any variations or substitutions that can be easily conceived by those skilled in the art within the scope of the technology disclosed in this disclosure should be included within the scope of protection of this disclosure. Therefore, the scope of protection of this disclosure should be determined by the scope of the claims.

Claims

1. A ceramic membrane electrolyzer, characterized in that, include: At least one single cell, wherein a channel is formed inside the single cell, and a reaction zone is provided in the middle of the channel along the axial direction of the channel, and a non-reaction zone is provided at both ends of the reaction zone. A positive electrode layer is provided on the first surface of the single cell at the position corresponding to the reaction zone. At least one first connector, the first connector including a first connector body and a first heating element, both the first connector body and the first heating element being disposed on the positive electrode layer side of the single cell; the first connector body having a first gas flow channel formed on a first surface facing the positive electrode layer, the first surface of the first connector body abutting against the positive electrode layer to communicate the first gas flow channel with the positive electrode layer; the first heating element being connected to the first connector body, and when the first heating element is energized and generates heat, it can heat the reaction zone through the first connector body; A sealing element is disposed in the non-reactive region of the single cell, and the sealing element has a second gas flow channel that is sealed and connected to the orifice.

2. The ceramic membrane electrolyzer according to claim 1, characterized in that, The second surface of the single cell has a negative electrode current collector layer at a position corresponding to the reaction region. The first surface and the second surface of the single cell are arranged opposite to each other, and the negative electrode current collector layer is arranged opposite to the positive electrode layer. The negative electrode current collector layer is made of a conductive, dense, and airtight current collector material.

3. The ceramic membrane electrolyzer according to claim 2, characterized in that, The ceramic membrane electrolyzer further includes: The second connector includes a second connector body and a second heating element, both of which are located on the negative current collector side of the single battery. The second connector body abuts against the first surface of the negative electrode current collector layer; The second heating element is connected to the body of the second connector. When the second heating element is energized and generates heat, it heats the reaction zone through the body of the second connector and the negative electrode current collector.

4. The ceramic membrane electrolyzer according to claim 2, characterized in that, The single battery also includes a positive electrode current collector layer, which is disposed on the surface of the positive electrode layer facing the first connector body. The first surface of the first connector body abuts against the positive electrode current collector layer so that the first gas flow channel is connected to the positive electrode current collector layer.

5. The ceramic membrane electrolyzer according to claim 4, characterized in that, The single battery also includes: A negative electrode support layer, wherein the channel is formed inside the negative electrode support layer; a negative electrode layer is provided on the first surface of the negative electrode support layer, and a negative electrode current collector layer is provided on the second surface of the negative electrode support layer, wherein the first surface and the second surface of the negative electrode support layer are disposed opposite to each other; An electrolyte layer covers the negative electrode layer and the surface of the negative electrode support layer that is not covered by the negative electrode current collector and the negative electrode layer; the positive electrode layer is disposed on the first surface of the electrolyte layer, and the positive electrode layer is disposed opposite to the negative electrode current collector; the positive electrode current collector is disposed on the surface of the positive electrode layer facing away from the electrolyte layer.

6. The ceramic membrane electrolyzer according to claim 5, characterized in that, The negative electrode current collector layer is made of doped LaCrO3-based ceramics and La... x Sr 1-x TiO 3-δ Composite materials with Ni-Fe alloys, wherein x = 0.2~0.8, δ is the oxygen vacancy content, ferritic stainless steel, a mixture of Ag and glass-ceramic sealing materials, and any one of chromium-based alloys.

7. The ceramic membrane electrolyzer according to claim 6, characterized in that, The doped LaCrO3-based ceramic is CeO2-doped La0.7Ca0.3CrO 3-δ ceramics; The La x Sr 1-x TiO 3-δ In the composite material with Ni-Fe alloy, based on 100wt% of the composite material, the La x Sr 1-x TiO 3-δ The mass percentage is 2~40wt%, and the mass percentage of the Ni-Fe alloy is 60~98wt%. In the mixture of Ag and glass-ceramic sealing material, the mass percentage of Ag is 50-99 wt%, and the remainder is glass-ceramic sealing material.

8. The ceramic membrane electrolyzer according to claim 7, characterized in that, When the material of the negative electrode current collector is CeO2-doped La0.7Ca0.3CrO 3-δ When ceramic, the negative electrode current collector layer is prepared by the following method: Preparation of La0.7Ca0.3CrO 3-δ Powder, negative electrode support layer green body; The La0.7Ca0.3CrO 3-δ The powder, CeO2, organic carrier, and dispersant are mixed and ball-milled to obtain a uniformly dispersed slurry; wherein the mass of the CeO2 is equal to that of the La0.7Ca0.3CrO2. 3-δ 2wt% of the powder mass; The slurry is coated on the second surface of the negative electrode support layer green body, and then sintered in a reducing atmosphere and / or an inert atmosphere at 1100~1400°C to obtain the negative electrode support layer, and the negative electrode current collector layer is formed on the second surface of the negative electrode support layer.

9. The ceramic membrane electrolyzer according to claim 8, characterized in that, Based on a total organic carrier mass of 100 wt%, the organic carrier comprises 60-80 wt% organic solvent, 15-30 wt% binder, and 5-15 wt% plasticizer; The total mass of the dispersant and the organic carrier is equal to that of the La0.7Ca0.3CrO. 3-δ The powder mass ratio is 30~70:70~30.

10. The ceramic membrane electrolyzer according to claim 7, characterized in that, The glass-ceramic sealing material is composed of one of SiO2-Al2O3-Na2O-CaO, SiO2-Al2O3-Na2O-BaO, or SiO2-Al2O3-Na2O-BaO-YSZ.

11. The ceramic membrane electrolyzer according to claim 3, characterized in that, The first heating element is disposed inside the body of the first connector; The second heating element is disposed inside the body of the second connector; Both the first heating element and the second heating element are resistance wires.

12. The ceramic membrane electrolyzer according to claim 3, characterized in that, The heating area of ​​the first heating element on the body of the first connector is greater than or equal to the area of ​​the positive electrode layer of the single battery. The heating area of ​​the second heating element on the body of the second connector is greater than or equal to the area of ​​the negative electrode current collector region of the single battery.

13. The ceramic membrane electrolyzer according to claim 1, characterized in that, When multiple single batteries and multiple first connectors are provided, the multiple single batteries and multiple first connectors are alternately arranged along the stacking direction of the single batteries.

14. The ceramic membrane electrolyzer according to claim 1, characterized in that, The first connector body has a plurality of parallel first grooves on the first surface facing the positive electrode layer, and the plurality of first grooves form the first gas flow channel.

15. The ceramic membrane electrolyzer according to claim 1, characterized in that, The sealing element includes an air distribution module and a sealing module. The second gas flow channel is provided in the gas distribution module, and the sealing module has a mounting hole; The two ends of the single battery are respectively inserted into the mounting holes of the sealing module; the gas distribution module and the sealing module are sealed together so that the channel is sealed and connected to the second gas flow channel. The ceramic membrane electrolyzer also includes a first gas supply pipe, which is sealed and connected to the second gas flow channel of the gas distribution module.

16. The ceramic membrane electrolyzer according to claim 15, characterized in that, The center of the sealing module and the sealing connection area at one end of the single battery are at least 5 cm away from the edge of the reaction zone.

17. The ceramic membrane electrolyzer according to claim 3, characterized in that, The ceramic membrane electrolyzer further includes: The first current collector is disposed on the side of the first connector body facing away from the single battery and abuts against the first connector body; The second current collector is located on the side of the second connector body facing away from the single battery and abuts against the second connector body.

18. The ceramic membrane electrolyzer according to claim 17, characterized in that, The ceramic membrane electrolyzer further includes: The insulation component has a accommodating space, in which the reaction zone, the first current collector, the first connector, the second connector, and the second current collector are all housed. A gap for gas to flow out is provided between the single cell and the inner wall of the insulation component. Two first conductive elements are passed through the insulation element and are electrically connected to the first current collector and the second current collector, respectively. Two second conductive elements, one of which is electrically connected to the first end of the first heating element and the second heating element, and the other of which is electrically connected to the second end of the first heating element and the second heating element.

19. A ceramic membrane electrolysis device, characterized in that, It includes a sealed container and a second gas delivery pipe, and also includes a ceramic membrane electrolyzer according to any one of claims 1-18; The sealed container is sealed to the outside of the ceramic membrane electrolyzer; the second gas supply pipe passes through the sealed container and is connected to the first gas flow channel.

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