A battery cell structure and stack of a hybrid solid oxide electrolytic cell stack

Abstract

This invention discloses a battery cell structure for a hybrid solid oxide electrolytic cell stack. The battery cell structure includes a hydrogen flow channel, an oxygen flow channel, and a water vapor reaction chamber. One side of the water vapor reaction chamber is separated from the hydrogen flow channel by a proton conductor electrolyte battery; the other side of the water vapor reaction chamber is separated from the oxygen flow channel by an oxygen ion conductor electrolyte battery. The water vapor reaction chamber is filled with a porous electronic conductor, which connects the positive electrode side of the proton conductor electrolyte battery to the negative electrode side of the oxygen ion conductor electrolyte battery. The proton conductor electrolyte battery converts the water vapor in the water vapor reaction chamber into protons and generates hydrogen gas in the hydrogen flow channel. The oxygen ion conductor electrolyte battery converts the water vapor in the water vapor reaction chamber into oxygen ions and generates oxygen gas in the oxygen flow channel.

Description

Technical Field

[0001] This invention relates to the field of solid oxide electrolyzers, and more specifically to a battery cell structure and stack of a hybrid solid oxide electrolyzer stack. Background Technology

[0002] With the increasing proportion of renewable energy, the demand for large-scale, long-cycle energy storage technologies has become extremely urgent. Among them, solid oxide electrolyzers have the highest electrolysis efficiency and are the next generation of competitive technologies. The oxygen obtained from electrolysis can be used for oxygen-enriched combustion, and hydrogen can be used as fuel for hydrogen fuel cell vehicles. It can also be used as a chemical raw material to produce fuels such as synthetic ammonia, methanol, and methane, which is of great significance to the realization of carbon emission reduction.

[0003] Traditional solid oxide electrolysis cells (SOECs) use either oxygen-ion conductors or proton-conducting electrolytes. Using an oxygen-ion conductor yields pure oxygen, but hydrogen is mixed with water vapor; using a proton conductor yields pure hydrogen, but oxygen is mixed with water vapor. Because the water vapor mixes with one of the electrolysis products (hydrogen or oxygen), the reactant gases must be removed from the stack and condensed after a certain point in the electrolysis process to obtain pure products. This process results in low steam utilization of the stack, impure products, complex system structure, and high manufacturing costs. Summary of the Invention

[0004] Purpose of the invention: The technical problem to be solved by the present invention is to provide a battery cell structure for a hybrid solid oxide electrolytic cell stack, which addresses the shortcomings of the prior art.

[0005] To address the aforementioned technical problems, this invention discloses a battery cell structure for a hybrid solid oxide electrolytic cell stack. This battery cell structure includes a hydrogen flow channel, an oxygen flow channel, and a water vapor reaction chamber. One side of the water vapor reaction chamber is separated from the hydrogen flow channel by a proton conductor electrolyte battery. The other side of the water vapor reaction chamber is separated from the oxygen flow channel by an oxygen ion conductor electrolyte battery. The water vapor reaction chamber is filled with a porous electronic conductor, which connects the positive electrode side of the proton conductor electrolyte battery to the negative electrode side of the oxygen ion conductor electrolyte battery. The proton conductor electrolyte battery converts the water vapor in the water vapor reaction chamber into protons and generates hydrogen gas in the hydrogen flow channel. The oxygen ion conductor electrolyte battery converts the water vapor in the water vapor reaction chamber into oxygen ions and generates oxygen gas in the oxygen flow channel.

[0006] In some embodiments, the water vapor reaction chamber includes an insulating support frame, a positive electrode side of a proton conductor electrolyte battery, and a negative electrode side of an oxygen ion conductor electrolyte battery.

[0007] In some embodiments, the battery cell structure further includes a conductive connection plate, the conductive connection comprising a first conductive connection surface and a second conductive connection surface. The first conductive connection surface is connected to the negative electrode side of the proton conductor electrolyte battery to form the hydrogen flow channel. The second conductive connection surface is connected to the positive electrode side of the oxygen ion conductor electrolyte battery to form the oxygen flow channel.

[0008] In some embodiments, the first conductive connection surface is sealed to the end face of the insulating support frame near the proton conductor electrolyte battery, and the second conductive connection surface is sealed to the end face of the insulating support frame near the oxygen ion conductor electrolyte battery.

[0009] The battery cell structure also includes a water vapor inlet channel, a hydrogen outlet channel, and an oxygen outlet channel, each penetrating through the first conductive connection surface, the insulating support frame, and the second conductive connection surface. The water vapor inlet channel is connected to the water vapor reaction chamber. The hydrogen outlet channel is connected to the hydrogen flow channel. The oxygen outlet channel is connected to the oxygen flow channel.

[0010] In some embodiments, the insulating support frame is rectangular, and the water vapor inlet channel, the hydrogen outlet channel, and the oxygen outlet channel are elongated. The hydrogen outlet channel and the oxygen outlet channel are respectively adjacent to the opposite narrow sides of the insulating support frame and extend along the direction of the narrow sides of the insulating support frame. The water vapor inlet channel is adjacent to one long side of the insulating support frame and extends along the direction of the long side of the insulating support frame.

[0011] In some embodiments, the proton conductor electrolyte of the proton conductor electrolyte battery is selected from BaZr. 1−x1−y1− z1 Ce x M1 y1 M2 z1 O 3−δ1 M1 and M2 respectively include those selected from Y 3+ Yb 3+ and Sc 3+ One of them, where the range of x1 is 0 < x1 < 1, the range of y1 is 0 ≤ y1 < 1, the range of z1 is 0 ≤ z1 < 1, and x1 + y1 + z1 < 1, and the range of δ1 is 0 < δ1 < 0.5.

[0012] The negative electrode of the proton conductor electrolyte battery is a metal-ceramic composed of the proton conductor electrolyte and Ni. The positive electrode of the proton conductor electrolyte battery is selected from PrBa, a perovskite-structured oxygen ion-proton-electron ternary hybrid conductor. 0.5 Sr 0.5 Co2O5–BaZr0.1 Ce 0.7 Y 0.2 O 3−δ9 The value of δ9 is in the range of 0 < δ9 < 0.5.

[0013] The oxygen ion conductor electrolyte of the oxygen ion conductor battery includes an oxygen ion conductor electrolyte selected from Y-stabilized zirconium oxide, Sc-stabilized zirconium oxide, Gd-doped cerium oxide (GDC), Sm-doped cerium oxide (SDC), and La. 1−x2 Sr x2 Ga 1−y2 Mg y2 O 3−δ2 One of them is that the range of x2 is 0 < x2 < 1, the range of y2 is 0 < y2 < 1, and x2 + y2 < 1, and the range of δ2 is 0 < δ2 < 0.5.

[0014] The negative electrode of the oxygen ion conductor electrolyte battery is a composite electrode composed of the oxygen ion conductor electrolyte and a perovskite-structured oxygen ion-electron hybrid conductor, wherein the perovskite-structured oxygen ion-electron hybrid conductor is selected from La 1−x3 Sr x3 Mn 1−y3 Cr y3 O 3−δ3 and La 1−x4 Sr x4 FeO 3−δ4 One type; or, the negative electrode of the oxygen ion conductor electrolyte battery is a composite electrode composed of the oxygen ion conductor electrolyte and Ni, wherein the value range of x3 is 0 < x3 < 1, the value range of y3 is 0 < y3 < 1, and x3 + y3 < 1, the value range of δ3 is 0 < δ3 < 0.5, the value range of x4 is 0 < x4 < 1, and the value range of δ4 is 0 < δ4 < 0.5.

[0015] The positive electrode of the oxygen ion conductor electrolyte battery is a composite electrode composed of the electrolyte of the oxygen ion conductor electrolyte battery and a perovskite-structured oxygen ion-electron hybrid conductor, wherein the perovskite-structured oxygen ion-electron hybrid conductor is selected from La 1−x5 Sr x5 Co 1−y5 Fe y5 O 3−δ5 and Ba 1−x6 Sr x6 Co 1−y6 Fe y6 O 3−δ6One type of x5 has a range of 0 < x5 < 1, a range of y5 has a range of 0 < y5 < 1, and x5 + y5 < 1, a range of δ5 has a range of 0 < δ5 < 0.5, a range of x6 has a range of 0 < x6 < 1, a range of y6 has a range of 0 < y6 < 1, and x6 + y6 < 1, and a range of δ6 has a range of 0 < δ6 < 0.5.

[0016] The porous electronic conductor 600 is selected from porous stainless steel, porous Ni felt, and La. 1−x7 Sr x7 Cr 1−y7 Mn y7 O 3−δ7 and La 1− x8 Sr x8 Cr 1−y8 Fe y8 O 3−δ8 One type of x7 has a range of 0 < x7 < 1, a range of y7 has a range of 0 < y7 < 1, and x7 + y7 < 1, a range of δ7 has a range of 0 < δ7 < 0.5, a range of x8 has a range of 0 < x8 < 1, a range of y8 has a range of 0 < y8 < 1, and x8 + y8 < 1, and a range of δ8 has a range of 0 < δ8 < 0.5.

[0017] In this application, δ1 to δ9 are all non-stoichiometric coefficients.

[0018] Preferably, the proton conductor electrolyte of the proton conductor electrolyte battery is BaZr. 0.1 Ce 0.7 Y 0.2 O 3−δ1 (Abbreviated as BZCY). The oxygen ion conductor electrolyte in the oxygen ion conductor electrolyte battery is (Y₂O₃). 0.08 (ZrO2) 0.92 The negative electrode of the oxygen ion conductor electrolyte battery is a composite electrode composed of the oxygen ion conductor electrolyte and Ni. The positive electrode of the oxygen ion conductor electrolyte battery is composed of the oxygen ion conductor electrolyte and a perovskite-structured oxygen ion-electron hybrid conductor La. 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3−δ5 The composite electrode consists of a value of δ5 in the range of 0 < δ5 < 0.5.

[0019] Preferably, the porous electronic conductor is made of porous Ni felt.

[0020] In some embodiments, the insulating support frame is made of ceramic with a coefficient of thermal expansion that matches that of the proton conductor electrolyte battery and the oxygen ion conductor electrolyte battery, respectively; or, the insulating support frame comprises a support frame body made of a metallic material and an insulating coating on the surface of the support frame body.

[0021] On the other hand, this application also provides a hybrid solid oxide electrolytic cell stack, which includes one or more battery cell structures provided in this application. The one or more battery cell structures are stacked sequentially. The water vapor inlet channels of each battery cell structure are sequentially connected to form a water vapor inlet channel. The hydrogen outlet channels of each battery cell structure are sequentially connected to form a hydrogen outlet channel. The oxygen outlet channels of each battery cell structure are sequentially connected to form an oxygen outlet channel.

[0022] Beneficial effects:

[0023] (1) The battery cell structure provided by the present invention uses a proton conductor electrolyte battery and an oxygen ion conductor electrolyte battery in a paired and mixed manner. A porous electronic conductor connects the positive electrode side of the proton conductor electrolyte battery and the negative electrode side of the oxygen ion conductor electrolyte battery to form a continuous current. By introducing water vapor into the water vapor reaction chamber as the reaction gas and applying a corresponding voltage to the battery cell structure, the proton conductor electrolyte battery and the oxygen ion conductor electrolyte battery can react together. Pure hydrogen is produced on the negative electrode side of the proton conductor electrolyte battery, and pure oxygen is produced on the positive electrode side of the oxygen ion conductor electrolyte battery. Through the above process, the battery cell structure can obtain the corresponding electrolysis products through the hydrogen flow channel and the oxygen flow channel, respectively. Compared with the electrolysis products mixed with water vapor in the single-type solid oxide electrolyte battery of the prior art, the electrolysis products of this application are pure and do not require condensation separation, saving the equipment cost and energy consumption of subsequent product gas drying and purification, which helps to reduce manufacturing costs and simplify the system.

[0024] (2) The electrolysis reaction products hydrogen and oxygen are not mixed with the reaction gas water vapor, that is, the reaction gas water vapor is not diluted by the product gas, so there is no need to discharge the stack. Theoretically, 100% conversion rate can be achieved for the reaction gas.

[0025] (3) The hybrid solid oxide electrolytic cell stack provided in this application includes several battery cell structures provided in this application stacked sequentially. The water vapor inlet channels are formed by sequentially connecting the water vapor inlet slots of each battery cell structure. In this application, water vapor enters the porous electronic conductor of the water vapor reaction chamber of each battery cell structure through the water vapor inlet channels. The heat from the water vapor is transferred to both the proton conduction battery cell and the oxygen ion conduction battery cell. The water vapor has a short transmission path and low heat loss. Combined with a pressure vessel, pressurizing the reactants is conducive to the forward reaction, that is, it makes the water vapor move in the direction of electrolysis, thereby helping to improve the electrolysis efficiency.

[0026] (4) In this application, because the water vapor reaction chamber contains only water vapor, both the proton conductor electrolyte battery and the oxygen ion conductor electrolyte battery of each battery cell structure operate in a mild (non-strong redox) environment. Unlike the prior art, electrolyte materials that are difficult to use in traditional solid oxide electrolyzers and cannot be stable in a strong redox atmosphere, such as GDC, can be selected. Therefore, compared with the prior art, the range of electrolyte materials that can be selected for the battery cell structure of this application is broadened.

[0027] (5) In traditional solid oxide batteries, the electrolyte material is exposed to an oxidizing or reducing atmosphere, which easily leads to electronic conductivity. The presence of electronic conductivity reduces the Faradaic efficiency of traditional solid oxide batteries. In contrast, the proton conductor electrolyte battery and oxygen ion conductor electrolyte battery of each cell structure in this application operate in a mild (non-strong redox) environment, shielding the electronic conductivity of oxygen ion conductor GDC in a reducing atmosphere and the positive hole conductivity of proton conductor BZCY in an air atmosphere. Therefore, the electrolyte of this application only has ionic conductivity, which improves the Faradaic efficiency of each cell structure of this application, thereby improving the Faradaic efficiency of the stack. Attached Figure Description

[0028] The present invention will be further described in detail below with reference to the accompanying drawings and specific embodiments, and the advantages of the present invention in the above and / or other aspects will become clearer.

[0029] Figure 1 A longitudinal sectional view of a battery cell structure of a hybrid solid oxide electrolytic cell stack is provided as an embodiment of this application;

[0030] Figure 2 for Figure 1 A cross-sectional view along line A of a hybrid solid oxide electrolytic cell stack cell structure is shown.

[0031] Figure 3 for Figure 1The diagram shows an exploded three-dimensional structure of a battery cell in a hybrid solid oxide electrolytic cell stack. Figure 1 ;

[0032] Figure 4 for Figure 1 The diagram shows an exploded three-dimensional structure of a battery cell in a hybrid solid oxide electrolytic cell stack. Figure 2 ;

[0033] Figure 5 An exploded three-dimensional structural diagram of a hybrid solid oxide electrolytic cell stack is provided as an embodiment of this application.

[0034] Figure 6 for Figure 5 The diagram shows a cross-sectional view of a hybrid solid oxide electrolytic cell stack. Detailed Implementation

[0035] The reference numerals in the accompanying drawings of this application are as follows:

[0036] The battery cell structure includes: a hydrogen flow channel 100, an oxygen flow channel 200, a water vapor reaction chamber 300, a proton conductor electrolyte battery 400, a positive electrode side 410 of the proton conductor electrolyte battery 400, a negative electrode side 420 of the proton conductor electrolyte battery 400; an oxygen ion conductor electrolyte battery 500, a negative electrode side 510 of the oxygen ion conductor electrolyte battery 500, a positive electrode side 520 of the oxygen ion conductor electrolyte battery 500, a porous electronic conductor 600, an insulating support frame 700, an end face 710, an end face 720, a first mounting step 730, a second mounting step 740, a gas guide channel 750, a conductive connecting plate 800, a first conductive connecting surface 810, a second conductive connecting surface 820, a water vapor inlet channel 910, a hydrogen outlet channel 920, and an oxygen outlet channel 930.

[0037] The technical solution of this application will now be described in detail with reference to the accompanying drawings.

[0038] like Figures 1 to 4 As shown, this application provides a battery cell structure for a hybrid solid oxide electrolytic cell stack. Figure 1 and Figure 2As shown, the battery cell structure 000 includes a hydrogen flow channel 100, an oxygen flow channel 200, and a water vapor reaction chamber 300. One side of the water vapor reaction chamber 300 is separated from the hydrogen flow channel 100 by a proton conductor electrolyte battery 400. The other side of the water vapor reaction chamber 300 is separated from the oxygen flow channel 200 by an oxygen ion conductor electrolyte battery 500. The water vapor reaction chamber 300 is filled with a porous electronic conductor 600, which connects the positive electrode side 410 of the proton conductor electrolyte battery 400 to the negative electrode side 510 of the oxygen ion conductor electrolyte battery 500. The proton conductor electrolyte battery 400 is used to convert the water vapor in the water vapor reaction chamber 300 and generate hydrogen in the hydrogen flow channel 100. The oxygen ion conductor electrolyte battery 500 is used to convert the water vapor in the water vapor reaction chamber 300 and generate oxygen in the oxygen flow channel 200.

[0039] The battery cell structure 000 provided by this invention uses a proton conductor electrolyte battery 400 and an oxygen ion conductor electrolyte battery 500 in a paired and mixed manner. A porous electronic conductor 600 connects the positive electrode side of the proton conductor electrolyte battery and the negative electrode side of the oxygen ion conductor electrolyte battery to form a continuous current. By introducing water vapor into the water vapor reaction chamber 300 as a reaction gas and applying a corresponding voltage to the battery cell structure 000, the proton conductor electrolyte battery 400 and the oxygen ion conductor electrolyte battery 500 can react together, producing pure hydrogen on the negative electrode side of the proton conductor electrolyte battery 400 and pure oxygen on the positive electrode side of the oxygen ion conductor electrolyte battery 500. The voltage applied to the battery cell structure is the sum of the voltages of the proton conductor electrolyte battery 400 and the oxygen ion conductor electrolyte battery 500 within the battery cell structure.

[0040] Through the above process, the battery cell structure 000 can obtain corresponding electrolysis products through the hydrogen flow channel 100 and the oxygen flow channel 200 respectively. Compared with the electrolysis products mixed with water vapor in the single type of solid oxide electrolyte battery in the prior art, the electrolysis products of this application are pure and do not require condensation separation, which saves the equipment cost and energy consumption for subsequent product gas drying and purification, and helps to reduce manufacturing costs and simplify the system.

[0041] Specifically, the process by which the proton conductor electrolyte battery 400 and the oxygen ion conductor electrolyte battery 500 can react together includes two modes: the first reaction mode and the second reaction mode.

[0042] In the first reaction mode, the reactions at each electrode are as follows:

[0043] The negative electrode side of the proton conductor electrolyte battery 400 is 420:2H + +2e - =H2;

[0044] The positive electrode side of the proton conductor electrolyte battery 400 is 410: H2O = 2H + +2e - +0.5O2;

[0045] The negative electrode side of the oxygen ion conductor electrolyte battery 500 is 510: H2O + 2e - =O 2- +H2;

[0046] The positive electrode side of the oxygen ion conductor electrolyte battery 500 is 520: O 2- =2e - +0.5O2;

[0047] Simultaneously, the porous electronic conductor 600 filling the water vapor reaction chamber 300 catalytically combusts the oxygen generated on the positive electrode side 410 of the proton conductor electrolyte battery 400 and the hydrogen generated on the negative electrode side 510 of the oxygen ion conductor electrolyte battery 500, recombining them into water vapor. The heat released by the aforementioned catalytic combustion reaction is utilized as part of the thermal energy required for the electrode reaction of the battery cell structure 000, thereby achieving energy loss reduction.

[0048] Because hydrogen diffuses faster than oxygen, or because oxygen production within the water vapor reaction chamber 300 is suppressed, hydrogen becomes the mass transfer species within the water vapor reaction chamber 300. At this time, a second reaction mode occurs within the battery cell structure, and the reactions at each electrode are as follows:

[0049] The negative electrode side of the proton conductor electrolyte battery 400 is 420:2H + +2e - =H2;

[0050] The positive electrode side of the proton conductor electrolyte battery 400 has the following composition: H2 = 2H2O + +2e - ;

[0051] The negative electrode side of the oxygen ion conductor electrolyte battery 500 is 510: H2O + 2e - =O 2- +H2;

[0052] The positive electrode side of the oxygen ion conductor electrolyte battery 500 is 520: O 2- =2e - +0.5O2;

[0053] In the second reaction mode, the oxygen ion conductor electrolyte battery 500 performs normal electrolysis, while the proton conductor electrolyte battery 400 acts as an electrochemical hydrogen pump to aid in hydrogen purification. Since no oxygen is generated in the water vapor reaction chamber 300, there is no need for hydrogen and oxygen to recombine.

[0054] In some embodiments, such as Figure 1 and Figure 2 As shown, the water vapor reaction chamber 300 includes an insulating support frame 700, a positive electrode side 410 of a proton conductor electrolyte battery 400, and a negative electrode side 510 of an oxygen ion conductor electrolyte battery 500.

[0055] Specifically, such as Figure 3 and Figure 4 As shown, the top end face of the insulating support frame 700 is provided with a first mounting step 730 that is recessed inward and adapted to the proton conductor electrolyte battery 400. The proton conductor electrolyte battery 400 is mounted in the first mounting step 730. The bottom end face of the insulating support frame 700 is provided with a second mounting step 740 that is recessed inward and adapted to the oxygen ion conductor electrolyte battery 500. The oxygen ion conductor electrolyte battery 500 is mounted in the second mounting step 740. The positive electrode side 410 of the proton conductor electrolyte battery 400, the negative electrode side 510 of the oxygen ion conductor electrolyte battery 500, and the inner wall of the insulating support frame 700 enclose a relatively sealed water vapor reaction chamber 300.

[0056] In some embodiments, such as Figure 1 and Figure 2 As shown, the battery cell structure 000 also includes a conductive connecting plate 800, which includes a first conductive connecting surface 810 and a second conductive connecting surface 820. The first conductive connecting surface 810 is connected to the negative electrode side 420 of the proton conductor electrolyte battery 400 to form a hydrogen flow channel 100. The second conductive connecting surface 820 is connected to the positive electrode side 520 of the oxygen ion conductor electrolyte battery 500 to form an oxygen flow channel 200.

[0057] The conductive connection plate 800 can be a fully connected plate or a half-connected plate, depending on the position of the battery cell structure 000 in the stack. In a stacked electrolytic cell stack, the conductive connection surface 800 between a proton conductor electrolyte battery 400 connected in series with an oxygen ion conductor electrolyte battery 500 of an adjacent battery cell structure 000 can be a fully connected plate; the conductive connection surface 800 between a short plate connected in series with an adjacent battery cell structure 000 can be a half-connected plate. The conductive connection plate 800 must be sufficiently dense to isolate oxygen and hydrogen, and also needs to have a corresponding flow channel structure and resistance to oxidation and hydrogen corrosion. The connection plate structure and coating used in conventional SOEC can be referenced in the conductive connection plate 800 of this application.

[0058] In some embodiments, such as Figure 1 and Figure 2As shown, the first conductive connection surface 810 faces the negative electrode side 420 of the proton conductor electrolyte battery 400, and the second conductive connection surface 820 faces the positive electrode side 520 of the oxygen ion conductor electrolyte battery 500. Both the first and second conductive connection surfaces 810 and 820 have inwardly recessed flow channels formed therein. These flow channels are arranged parallel to each other, and adjacent flow channels are separated by raised ribs. The raised ribs on the first conductive connection surface 810 are used to connect to the negative electrode side 420 of the proton conductor electrolyte battery 400, and the raised ribs on the second conductive connection surface 820 are used to conform to the positive electrode side 520 of the oxygen ion conductor electrolyte battery 500, in order to achieve current collection.

[0059] In some embodiments, such as Figure 1 and Figure 2 As shown, the first conductive connection surface 810 is sealed to the end face 710 of the insulating support frame 700 near the proton conductor electrolyte battery 400, and the second conductive connection surface 820 is sealed to the end face 720 of the insulating support frame 700 near the oxygen ion conductor electrolyte battery 500, so as to form a relatively sealed hydrogen flow channel 100 and oxygen flow channel 200, while making the hydrogen flow channel 100 of each battery cell structure 000 independent from the oxygen flow channel 200 of the adjacent cell.

[0060] The battery cell structure 000 also includes a water vapor inlet channel 910, a hydrogen outlet channel 920, and an oxygen outlet channel 930, each penetrating through the first conductive connection surface 810, the insulating support frame 700, and the second conductive connection surface 820. The water vapor inlet channel 910 is connected to the water vapor reaction chamber 300. The hydrogen outlet channel 920 is connected to the hydrogen flow channel 100. The oxygen outlet channel 930 is connected to the oxygen flow channel 200.

[0061] Water vapor, acting as the reactant gas, flows into the water vapor reaction chamber 300 from the water vapor inlet channel 910. The proton conductor electrolyte battery 400 converts the water vapor in the water vapor reaction chamber 300 and generates hydrogen gas in the hydrogen flow channel 100. The generated hydrogen gas flows out from the hydrogen gas outlet channel 920. The oxygen ion conductor electrolyte battery 500 converts the water vapor in the water vapor reaction chamber 300 and generates oxygen gas in the oxygen flow channel 200. The generated oxygen gas flows out from the oxygen outlet channel 930.

[0062] In some embodiments, such as Figure 3 and Figure 4As shown, the insulating support frame 700 is rectangular, and the water vapor inlet channel 910, hydrogen outlet channel 920, and oxygen outlet channel 930 are elongated. The hydrogen outlet channel 920 and the oxygen outlet channel 930 are adjacent to the opposite narrow sides of the insulating support frame 700 and extend along the direction of the narrow sides of the insulating support frame 700. The water vapor inlet channel 910 is adjacent to one long side of the insulating support frame 700 and extends along the direction of the long side of the insulating support frame 700.

[0063] Specifically, such as Figure 3 and Figure 4 As shown, the oxygen outlet channel 930 and the water vapor reaction chamber 300 are connected by several gas guiding channels 750. Figure 2 As shown, the gas guide channel 750 is opened on the inner wall of the oxygen outlet channel 930 near the water vapor reaction chamber 300 and extends to the inner wall of the water vapor reaction chamber 300.

[0064] In some embodiments, the proton conductor electrolyte of the proton conductor electrolyte battery 400 is selected from BaZr. 1−x1−y1−z1 Ce x M1 y1 M2 z1 O 3−δ1 M1 and M2 respectively include those selected from Y 3+ Yb 3+ and Sc 3+ One of them, where the range of x1 is 0 < x1 < 1, the range of y1 is 0 ≤ y1 < 1, the range of z1 is 0 ≤ z1 < 1, and x1 + y1 + z1 < 1, and the range of δ1 is 0 < δ1 < 0.5.

[0065] The negative electrode of the proton conductor electrolyte battery 400 is a metal-ceramic composed of the proton conductor electrolyte and Ni. The positive electrode of the proton conductor electrolyte battery 400 is selected from PrBa, a perovskite-structured oxygen ion-proton-electron ternary hybrid conductor. 0.5 Sr 0.5 Co2O5–BaZr 0.1 Ce 0.7 Y 0.2 O 3−δ9 The value of δ9 is in the range of 0 < δ9 < 0.5.

[0066] The oxygen ion conductor electrolyte of the oxygen ion conductor battery 500 includes an oxygen ion conductor electrolyte selected from Y-stabilized zirconium oxide, Sc-stabilized zirconium oxide, Gd-doped cerium oxide, Sm-doped cerium oxide, and La. 1−x2 Sr x2 Ga 1−y2 Mg y2 O 3−δ2One of them is that the range of x2 is 0 < x2 < 1, the range of y2 is 0 < y2 < 1, and x2 + y2 < 1, and the range of δ2 is 0 < δ2 < 0.5.

[0067] The negative electrode of the oxygen ion conductor electrolyte battery 500 is a composite electrode composed of the oxygen ion conductor electrolyte and a perovskite-structured oxygen ion-electron hybrid conductor, wherein the perovskite-structured oxygen ion-electron hybrid conductor is selected from La 1−x3 Sr x3 Mn 1−y3 Cr y3 O 3−δ3 and La 1−x4 Sr x4 FeO 3−δ4 One type; or, the negative electrode of the oxygen ion conductor electrolyte battery 500 is a composite electrode composed of the oxygen ion conductor electrolyte and Ni, wherein the value range of x3 is 0 < x3 < 1, the value range of y3 is 0 < y3 < 1, and x3 + y3 < 1, the value range of δ3 is 0 < δ3 < 0.5, the value range of x4 is 0 < x4 < 1, and the value range of δ4 is 0 < δ4 < 0.5.

[0068] The positive electrode of the oxygen ion conductor electrolyte battery 500 is a composite electrode composed of the electrolyte of the oxygen ion conductor electrolyte battery 500 and a perovskite-structured oxygen ion-electron hybrid conductor, wherein the perovskite-structured oxygen ion-electron hybrid conductor is selected from La 1−x5 Sr x5 Co 1−y5 Fe y5 O 3−δ5 and Ba 1−x6 Sr x6 Co 1−y6 Fe y6 O 3−δ6 One type of x5 has a range of 0 < x5 < 1, a range of y5 has a range of 0 < y5 < 1, and x5 + y5 < 1, a range of δ5 has a range of 0 < δ5 < 0.5, a range of x6 has a range of 0 < x6 < 1, a range of y6 has a range of 0 < y6 < 1, and x6 + y6 < 1, and a range of δ6 has a range of 0 < δ6 < 0.5.

[0069] The porous electronic conductor 600 is selected from porous stainless steel, porous Ni felt, and La. 1−x7 Sr x7 Cr 1−y7 Mn y7 O 3−δ7 and La 1− x8 Sr x8 Cr 1−y8 Fe y8 O3−δ8 One type of x7 has a range of 0 < x7 < 1, a range of y7 has a range of 0 < y7 < 1, and x7 + y7 < 1, a range of δ7 has a range of 0 < δ7 < 0.5, a range of x8 has a range of 0 < x8 < 1, a range of y8 has a range of 0 < y8 < 1, and x8 + y8 < 1, and a range of δ8 has a range of 0 < δ8 < 0.5.

[0070] In this application, δ1 to δ9 are all non-stoichiometric coefficients.

[0071] Preferably, the proton conductor electrolyte of the proton conductor electrolyte battery 400 is BaZr. 0.1 Ce 0.7 Y 0.2 O 3−δ1 The value of δ1 ranges from 0 to 0.5. The oxygen ion conductor electrolyte in the oxygen ion conductor electrolyte battery 500 is (Y₂O₃). 0.08 (ZrO2) 0.92 The negative electrode of the oxygen ion conductor electrolyte battery 500 is a composite electrode composed of the oxygen ion conductor electrolyte and Ni. The positive electrode of the oxygen ion conductor electrolyte battery 500 is composed of the oxygen ion conductor electrolyte and a perovskite-structured oxygen ion-electron hybrid conductor La. 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3−δ5 The composite electrode consists of a value of δ5 in the range of 0 < δ5 < 0.5.

[0072] Preferably, the porous electronic conductor 600 is made of porous Ni felt, which has the advantages of good ductility, high porosity, good electronic conductivity, and simple preparation process.

[0073] In some embodiments, the insulating support frame 700 is made of ceramic with a coefficient of thermal expansion that matches that of the proton conductor electrolyte battery 400 and the oxygen ion conductor electrolyte battery 500, respectively; or, the insulating support frame 700 includes a support frame body made of a metallic material and an insulating coating on the surface of the support frame body.

[0074] like Figure 5 and Figure 6 As shown, this application also provides a hybrid solid oxide electrolytic cell stack, which includes one or more battery cell structures provided in this application. The one or more battery cell structures are stacked sequentially. The water vapor inlet channels 910 of each battery cell structure are sequentially connected to form a water vapor inlet channel. The hydrogen outlet channels 920 of each battery cell structure are sequentially connected to form a hydrogen outlet channel. The oxygen outlet channels 930 of each battery cell structure are sequentially connected to form an oxygen outlet channel.

[0075] Example 1

[0076] In this embodiment, the electrolyte of the proton conductor electrolyte battery 400 is BaZr. 0.6 Ce 0.3 Y 0.1 O 3−δ1 The proton conductor electrolyte battery 400 is an electrolyte-supported battery. The negative electrode material of the proton conductor electrolyte battery 400, 420, is Ni–BaZr. 0.1 Ce 0.7 Y 0.2 O 3−δ1 The positive electrode material of the 400 proton conductor electrolyte battery is PrBa, a perovskite-structured oxygen-proton-electron ternary hybrid conductor. 0.5 Sr 0.5 Co2O5–BaZr 0.1 Ce 0.7 Y 0.2 O 3−δ9 .

[0077] In this embodiment, press PrBa 0.5 Sr 0.5 The stoichiometric proportions of Pr(NO3)3·6H2O, Ba(NO3)2, Sr(NO3)2, and Co(NO3)2·6H2O for the Co2O5 molecule were weighed, and ethylenediaminetetraacetic acid (EDTA) and citric acid were added as chelating and complexing agents, respectively, to synthesize PrBa 0.5 Sr 0.5 Co2O 5+δ Ammonium hydroxide (Sigma-Aldrich, ammonia content 28.0%~30.0%) was added to promote the dissolution of EDTA in deionized water to obtain a solution. The solution was then slowly evaporated in a furnace, and the resulting brown gel was dried at 300°C. The dried ash was then placed in a muffle furnace and treated in air at 1100°C for 6 hours to remove residual organic matter, thereby obtaining the desired PrBa. 0.5 Sr 0.5 Co2O5. For specific preparation methods, please refer to the paper "Layered perovskite PrBa" by Fei Zhao et al. published in the Journal of Power Sources. 0.5 S r0.5 Co2O 5+δ ashigh performance cathode for solid oxide fuel cells using oxide proton-conducting electrolyte.

[0078] Similarly, the material BaZr in this embodiment 0.1 Ce 0.7 Y 0.2 O 3−δ1 Using Ba(NO3)2, Ce(NO3)3·6H2O, Y(NO3)3·6H2O and ZrO(NO3)2·2H2O as raw materials, according to the chemical formula Ni–BaZr 0.1 Ce 0.7 Y 0.2 O 3−δ1 The raw materials are added in a stoichiometric ratio, using the same PrBa method as in this embodiment. 0.5 Sr 0.5 It was synthesized using the same method as Co2O5.

[0079] Ni–BaZr in this embodiment 0.1 Ce 0.7 Y 0.2 O 3−δ1 BaZr is synthesized directly from Ni powder. 0.1 Ce 0.7 Y 0.2 O 3−δ1 Obtained through physical mixing.

[0080] The material BaZr in this embodiment 0.6 Ce 0.3 Y 0.1 O 3−δ1 Using Ba(NO3)2, Ce(NO3)3·6H2O, Y(NO3)3·6H2O and ZrO(NO3)2·2H2O as raw materials, according to the chemical formula BaZr 0.6 Ce 0.3 Y 0.1 O 3−δ1 The raw materials are added in a stoichiometric ratio, using the same PrBa method as in this embodiment. 0.5 Sr 0.5 It was synthesized using the same method as Co2O5.

[0081] In this embodiment, the proton conductor electrolyte battery 400 uses BaZr. 0.6 Ce 0.3 Y 0.1 O 3−δ1 A 300 μm thick preform was prepared by tape casting and hot pressing, and then calcined at 1450 °C for 10 h to become an electrolyte sheet. Then, Ni–BaZr electrode material was applied to the negative electrode side. 0.1 Ce 0.7 Y 0.2 O 3−δ1 and positive electrode material PrBa 0.5 Sr0.5 Co2O5–BaZr 0.1 Ce 0.7 Y 0.2 O 3−δ9 The electrolyte is prepared on both sides by screen printing, with a thickness of 20~30μm on each side, thus obtaining the electrolyte-supported proton conductor electrolyte battery in this embodiment.

[0082] In this embodiment, the oxygen ion conductor electrolyte of the oxygen ion conductor electrolyte battery 500 is selected as (Y2O3). 0.08 (ZrO2) 0.92 The electrolyte support membrane, the negative electrode material 510 of the oxygen ion conductor electrolyte battery 500 is selected from a composite electrode composed of the oxygen ion conductor electrolyte of this embodiment and metallic Ni, and the positive electrode material 520 of the oxygen ion conductor electrolyte battery 500 is selected from the oxygen ion conductor electrolyte of this embodiment and a perovskite-structured oxygen ion-electron hybrid conductor La. 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3−δ5 A composite electrode is formed by combining these components. Specifically, in this embodiment, the oxygen ion conductor electrolyte and La... 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3−δ5 The space between (Ce) 0.9 Gd 0.1 )O 1.95 Barrier layer, in (Ce 0.9 Gd 0.1 )O 1.95 La screen printing on barrier layer 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3−δ5 The (Ce) 0.9 Gd 0.1 )O 1.95 The barrier layer is located between the oxygen ion conductor electrolyte and La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3−δ5 Between them, used to isolate La, which has poor chemical compatibility. 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3−δ5 and (Y2O3) 0.08 (ZrO2) 0.92This inhibits the reaction between the two to form an insulating phase that affects performance output. The oxygen-ion conductor electrolyte battery 500 in this embodiment uses a commercial battery manufactured by Ningbo Sofor Energy Technology Co., Ltd. The two batteries are designed according to... Figure 2 The structure shown constitutes a battery cell structure. The porous electronic conductor 600 used in this embodiment is a porous Ni felt. Operating at a thermal neutral voltage of 2.6V and a working temperature of 750℃, the electrolytic current density of the battery cell structure in this embodiment reaches 0.3A / cm². 2 This verifies the feasibility of the present invention.

[0083] Example 2

[0084] In this embodiment, the proton conductor electrolyte of the proton conductor electrolyte battery 400 is BaZr. 0.6 Ce 0.3 Y 0.1 O 3−δ1 The proton conductor electrolyte battery 400 in this embodiment is Ni–BaZr. 0.1 Ce 0.7 Y 0.2 O 3−δ1 The negative electrode-supported battery design allows the electrolyte thickness to be reduced to 20 micrometers. The negative electrode 420 of the proton-conducting electrolyte battery 400 uses a proton-conducting electrolyte BaZr. 0.1 Ce 0.7 Y 0.2 O 3−δ1 The composite electrode, formed by combining with metallic Ni, is used as the positive electrode material (410) of the proton conductor electrolyte battery 400. This material is a perovskite-structured oxygen-proton-electron ternary hybrid conductor, PrBa. 0.5 Sr 0.5 Co2O5–BaZr 0.1 Ce 0.7 Y 0.2 O 3−δ9 .

[0085] The proton conductor electrolyte battery 400 of this embodiment adopts the conventional preparation method reported by Huang Zuzhi et al. in the paper Large–area anode–supported protonic ceramic fuel cells combining with multilayer–tape casting and hot–pressing lamination technology in Journal of the European Ceramic Society 43 (2023) 428~437.

[0086] In this embodiment, the oxygen ion conductor electrolyte battery 500 uses a commercially available battery manufactured by Ningbo Sofor Energy Technology Co., Ltd. The oxygen ion conductor electrolyte of the oxygen ion conductor electrolyte battery 500 is selected as (Y₂O₃). 0.08 (ZrO2) 0.92 Electrolyte. In this embodiment, the oxygen ion conductor electrolyte battery 500 is Ni–(Y₂O₃). 0.08 (ZrO2) 0.92 In the negative electrode-supported battery, the thickness of the oxygen ion conductor electrolyte is reduced to 20 micrometers. The negative electrode material (510) of the oxygen ion conductor electrolyte battery 500 is Ni–(Y₂O₃). 0.08 (ZrO2) 0.92 The positive electrode material 520 of the oxygen ion conductor electrolyte battery 500 is the same as the positive electrode material 520 of the oxygen ion conductor electrolyte battery 500 in Embodiment 1 of this application. And according to... Figure 2 The structure shown constitutes a battery cell structure, wherein the porous electronic conductor 600 used in this embodiment is a porous Ni felt. Operating at a thermally neutral voltage of 2.6V and an operating temperature of 650℃, the electrolytic current density of the battery cell structure in this embodiment reaches 1.0 A / cm². 2 The electrolytic performance of the battery cell structure in Example 2 is better than that of the battery cell structure in Example 1.

[0087] Example 3

[0088] In this embodiment, the electrolyte of the proton conductor electrolyte battery 400 is BaZr. 0.6 Ce 0.3 Y 0.1 O 3−δ1 The proton conductor electrolyte battery 400 in this embodiment is Ni–BaZr. 0.1 Ce 0.7 Y 0.2 O 3−δ1 The negative electrode-supported battery design reduces the electrolyte thickness to 20 micrometers. The negative electrode material of the proton conductor electrolyte battery 400 is Ni–BaZr. 0.1 Ce 0.7 Y 0.2 O 3−δ1 The positive electrode material of the proton conductor electrolyte battery 400 is PrBa. 0.5 Sr 0.5 Co2O5–BaZr 0.1 Ce 0.7 Y 0.2 O 3−δ9The preparation method of the proton conductor electrolyte battery 400 in this embodiment is also the conventional preparation method reported by Huang Zuzhi et al. in the paper Large-area anode-supported protonic ceramic fuel cells combining with multilayer-tape casting and hot-pressing lamination technology in Journal of the European Ceramic Society 43 (2023) 428–437.

[0089] In this embodiment, the electrolyte selected for the oxygen ion conductor electrolyte battery 500 is La. 0.9 Sr 0.1 Ga 0.8 Mg 0.2 O 3−δ2 Electrolytes. The La 0.9 Sr 0.1 Ga 0.8 Mg 0.2 O 3−δ2 The electrolyte has a three-layer structure, including porous La layers stacked sequentially. 0.9 Sr 0.1 Ga 0.8 Mg 0.2 O 3−δ2 Dense La 0.9 Sr 0.1 Ga 0.8 Mg 0.2 O 3−δ2 and porous La 0.9 Sr 0.1 Ga 0.8 Mg 0.2 O 3−δ2 , the La 0.9 Sr 0.1 Ga 0.8 Mg 0.2 O 3−δ2 Porous La on one side of the electrolyte 0.9 Sr 0.1 Ga 0.8 Mg 0.2 O 3−δ2 To obtain the negative electrode by impregnating Ni nanoparticles, the La 0.9 Sr 0.1 Ga 0.8 Mg 0.2 O 3−δ2 Porous La on one side of the electrolyte 0.9 Sr 0.1 Ga 0.8 Mg0.2 O 3−δ2 Impregnation La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3−δ5 Nanoparticles are used to obtain the positive electrode, and the electrolyte thickness is reduced to 50 micrometers. The fabrication method of the oxygen-ion conductor electrolyte battery 500 in this embodiment is described in the paper "Enhanced performance of solid oxide fuel cell fabricated by a replica technique combined with infiltrating process" by Da Han et al. published in the International Journal of Hydrogen Energy. Both batteries are manufactured according to... Figure 2 The structure shown constitutes a battery cell structure, wherein the porous electronic conductor 600 is made of porous Ni felt. Operating at a thermal neutral voltage of 2.6V and an operating temperature of 650°C, the electrolytic current density of the battery cell structure in this embodiment reaches 0.8A / cm². 2 .

[0090] The battery cell structure of Example 1 is an electrolyte support structure, the battery cell structure of Example 2 is a negative electrode support structure, and the battery cell structure of Example 3 adopts a porous skeleton impregnation method, demonstrating the diversity of battery structure forms of the present invention.

[0091] In their paper published in the *Journal of Ceramics*, Zhang Xuebai et al. pointed out that, under the same conditions, the electrolysis current density of traditional single-structure oxygen ion conductor batteries and proton conductor batteries is approximately 0.5 A / cm². 2 and 0.4A / cm 2 In comparison, the electrolytic current density of the battery cell structures in Embodiments 2 and 3 of this application is comparable to that of the prior art. However, compared to the mixing of electrolytic products with water vapor in the single-type solid oxide electrolyte battery of the prior art, the electrolytic products of this application are pure and do not require condensation separation. This saves on the equipment costs and energy consumption for subsequent product gas drying and purification, and helps to reduce manufacturing costs and simplify the system.

[0092] This invention provides a battery cell structure and stack concept and method for a hybrid solid oxide electrolytic cell stack. Many methods and approaches exist for implementing this technical solution; the above description is merely a preferred embodiment of the invention. It should be noted that those skilled in the art can make various improvements and modifications without departing from the principles of this invention, and these improvements and modifications should also be considered within the scope of protection of this invention. All components not explicitly stated in this embodiment can be implemented using existing technologies.

Claims

1. A cell unit structure of a hybrid solid oxide electrolysis stack, characterized by, The battery cell structure (000) comprises a hydrogen flow channel (100), an oxygen flow channel (200), and a water vapor reaction cavity (300); one side of the water vapor reaction cavity (300) is separated from the hydrogen flow channel (100) by a proton conductor electrolyte cell (400); the other side of the water vapor reaction cavity (300) is separated from the oxygen flow channel (200) by an oxygen ion conductor electrolyte cell (500); the water vapor reaction cavity (300) is filled with a porous electronic conductor (600), which connects the positive side (410) of the proton conductor electrolyte cell (400) and the negative side (510) of the oxygen ion conductor electrolyte cell (500) to form a continuous current; the proton conductor electrolyte cell (400) is used to convert the water vapor in the water vapor reaction cavity (300) into protons and generate hydrogen gas in the hydrogen flow channel (100); the oxygen ion conductor electrolyte cell (500) is used to convert the water vapor in the water vapor reaction cavity (300) into oxygen ions and generate oxygen gas in the oxygen flow channel (200); By introducing water vapor into the water vapor reaction cavity (300) as a reaction gas, and applying a corresponding voltage to the battery cell structure (000), the proton conductor electrolyte cell (400) and the oxygen ion conductor electrolyte cell (500) can jointly react to complete the production of pure hydrogen gas at the negative side of the proton conductor electrolyte cell (400), and at the same time complete the production of pure oxygen gas at the positive side of the oxygen ion conductor electrolyte cell (500); the voltage applied to the battery cell structure is the sum of the voltages of the proton conductor electrolyte cell (400) and the oxygen ion conductor electrolyte cell (500) in the battery cell structure.

2. A cell structure for a hybrid solid oxide electrolysis stack according to claim 1, characterized in that The water vapor reaction cavity (300) comprises an insulating support frame (700), a positive side (410) of the proton conductor electrolyte cell (400), and a negative side (510) of the oxygen ion conductor electrolyte cell (500).

3. A cell structure for a hybrid solid oxide electrolysis stack according to claim 2, characterised in that, It also includes a conductive connecting plate (800) comprising a first conductive connecting surface (810) and a second conductive connecting surface (820), the first conductive connecting surface (810) is connected with the negative side (420) of the proton conductor electrolyte cell (400) to form the hydrogen flow channel (100); the second conductive connecting surface (820) is connected with the positive side (520) of the oxygen ion conductor electrolyte cell (500) to form the oxygen flow channel (200).

4. A cell structure for a hybrid solid oxide electrolysis stack according to claim 3, wherein The first conductive connecting surface (810) is sealingly connected with the end surface (710) of the proton conductor electrolyte cell (400) of the insulating support frame (700), and the second conductive connecting surface (820) is sealingly connected with the end surface (720) of the oxygen ion conductor electrolyte cell (500) of the insulating support frame (700); further comprising a water vapor inlet passage (910), a hydrogen gas outlet passage (920) and an oxygen gas outlet passage (930) which respectively pass through the first conductive connecting surface (810), the insulating support frame (700) and the second conductive connecting surface (820), the water vapor inlet passage (910) is communicated with the water vapor reaction cavity (300); the hydrogen gas outlet passage (920) is communicated with the hydrogen gas flow channel (100); and the oxygen gas outlet passage (930) is communicated with the oxygen gas flow channel (200).

5. A cell structure for a hybrid solid oxide electrolysis stack according to claim 4, wherein The insulating support frame (700) is rectangular, the water vapor inlet passage (910), the hydrogen gas outlet passage (920) and the oxygen gas outlet passage (930) are long strips, the hydrogen gas outlet passage (920) and the oxygen gas outlet passage (930) are respectively adjacent to the two opposite narrow sides of the insulating support frame (700) and extend along the direction of the narrow sides of the insulating support frame (700); and the water vapor inlet passage (910) is adjacent to one long side of the insulating support frame (700) and extends along the direction of the long side of the insulating support frame (700).

6. The cell unit structure of the hybrid solid oxide electrolysis stack according to claim 1, wherein The proton-conductor electrolyte cell (400) has a proton-conductor electrolyte selected from BaZr 1−x1−y1−z1 Ce x M1 y1 M2 z1 O 3−δ1 wherein M1 and M2 each include one selected from Y 3+ , Yb 3+ and Sc 3+ , x1 has a value in a range of 0 < x1 < 1, y1 has a value in a range of 0 ≤ y1 < 1, z1 has a value in a range of 0 ≤ z1 < 1, and x1 + y1 + z1 < 1, and δ1 has a value in a range of 0 < δ1 < 0.

5. The negative electrode of the proton-conductor electrolyte cell (400) is a cermet composed of the proton-conductor electrolyte combined with Ni; the positive electrode of the proton-conductor electrolyte cell (400) is selected from the group of oxygen-ion-proton-electron ternary mixed conductors of perovskite structure PrBa 0.5 Sr 0.5 Co2O5–BaZr 0.1 Ce 0.7 Y 0.2 O 3−δ9 , the value of δ9 is in the range of 0 < δ9 < 0.5; The oxygen-ion conductor electrolyte of the oxygen-ion conductor electrolyte cell (500) comprises one selected from the group consisting of Y-stabilized zirconia, Sc-stabilized zirconia, Gd-doped ceria, Sm-doped ceria, and La 1−x2 Sr x2 Ga 1−y2 Mg y2 O 3−δ2 , x2 is in the range of 0 < x2 < 1, y2 is in the range of 0 < y2 < 1, and x2 + y2 < 1, and δ2 is in the range of 0 < δ2 < 0.5; The negative electrode of the oxygen-ion conductor electrolyte battery (500) is a composite electrode composed of the oxygen-ion conductor electrolyte and a perovskite-structured oxygen-ion-electron mixed conductor selected from La 1−x3 Sr x3 Mn 1−y3 Cr y3 O 3−δ3 and La 1−x4 Sr x4 FeO 3−δ4 ; or, the negative electrode of the oxygen-ion conductor electrolyte battery (500) is a composite electrode composed of the oxygen-ion conductor electrolyte and Ni, x3 is in the range of 0 < x3 < 1, y3 is in the range of 0 < y3 < 1, and x3 + y3 < 1, δ3 is in the range of 0 < δ3 < 0.5, x4 is in the range of 0 < x4 < 1, and δ4 is in the range of 0 < δ4 < 0.

5. The positive electrode of the oxygen-ion conductor electrolyte cell (500) is a composite electrode consisting of the electrolyte of the oxygen-ion conductor electrolyte cell (500) and a perovskite-structured oxygen-ion-electron mixed conductor selected from the group consisting of La 1−x5 Sr x5 Co 1−y5 Fe y5 O 3−δ5 and Ba 1−x6 Sr x6 Co 1−y6 Fe y6 O 3−δ6 , x5 is in the range of 0 < x5 < 1, y5 is in the range of 0 < y5 < 1, and x5 + y5 < 1, δ5 is in the range of 0 < δ5 < 0.5, x6 is in the range of 0 < x6 < 1, y6 is in the range of 0 < y6 < 1, and x6 + y6 < 1, δ6 is in the range of 0 < δ6 < 0.5; The porous electronic conductor (600) is selected from the group consisting of porous stainless steel, porous Ni felt, La 1−x7 Sr x7 Cr 1−y7 Mn y7 O 3−δ7 and La 1− x8 Sr x8 Cr 1−y8 Fe y8 O 3−δ8 one of x7 is in the range of 0 < x7 < 1, y7 is in the range of 0 < y7 < 1, and x7 + y7 < 1, and δ7 is in the range of 0 < δ7 < 0.5, x8 is in the range of 0 < x8 < 1, y8 is in the range of 0 < y8 < 1, and x8 + y8 < 1, and δ8 is in the range of 0 < δ8 < 0.

5.

7. The cell unit structure of the hybrid solid oxide electrolysis stack according to claim 6, wherein The proton conductor electrolyte of the proton conductor electrolyte cell (400) is BaZr 0.6 Ce 0.3 Y 0.1 O 3−δ1 , and δ1 is in the range of 0 < δ1 < 0.5; the oxygen ion conductor electrolyte of the oxygen ion conductor electrolyte cell (500) is (Y2O3) 0.08 (ZrO2) 0.92 ; the negative electrode of the oxygen ion conductor electrolyte cell (500) is a composite electrode composed of the oxygen ion conductor electrolyte and Ni; the positive electrode of the oxygen ion conductor electrolyte cell (500) is a composite electrode composed of the oxygen ion conductor electrolyte and a perovskite structure oxygen ion-electron mixed conductor La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3−δ5 , and δ5 is in the range of 0 < δ5 < 0.

5.

8. A cell structure for a hybrid solid oxide electrolysis stack according to claim 7, characterized in that The porous electronic conductor (600) is selected from porous Ni felt.

9. A cell structure for a hybrid solid oxide electrolysis stack according to claim 2, wherein, The material of the insulating support frame (700) is ceramic with a thermal expansion coefficient matching the proton conductor electrolyte cell (400) and the oxygen ion conductor electrolyte cell (500); or the insulating support frame (700) comprises a support frame body made of metal material and an insulating coating layer covering the surface of the support frame body.

10. A hybrid solid oxide electrolysis stack, characterized in that, The cell unit structure comprises one or more cell unit structures as claimed in claim 4; the one or more cell unit structures are sequentially stacked; the water vapor inlet passages (910) of the cell unit structures are sequentially communicated to form a water vapor inlet passage; the hydrogen gas outlet passages (920) of the cell unit structures are sequentially communicated to form a hydrogen gas outlet passage; and the oxygen gas outlet passages (930) of the cell unit structures are sequentially communicated to form an oxygen gas outlet passage.

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