Self-heating electrolytic tank and electrolysis system

Abstract

The invention provides a self-heating electrolytic tank and an electrolysis system, and relates to the technical field of electrolysis, the self-heating electrolytic tank comprises an air electrode, a fuel electrode and a self-heating electrolyte; the self-heating electrolyte is composed of a single-phase mixed ion or electronic conductive material or is formed by compounding an ion conductive material and an electronic conductive material, the self-heating electrolyte conducts ions and electrons at the same time, the ions comprise oxygen ions, hydrogen ions or hydroxyl ions, and the electrons comprise oxygen ions, hydrogen ions or hydroxyl ions. The electrons generate Joule heat when flowing through the electrolyte to maintain an electroendothermic reaction. The self-heating electrolysis system comprises the self-heating electrolytic tank, and further comprises a heat exchanger I and a heat exchanger II. According to the invention, Joule heat generated when electrons flow through the electrolyte is utilized to maintain the electrolysis endothermic reaction, so that spontaneous heating in the electrolysis process is realized, an external heater is not needed, and efficient thermal circulation is realized, thereby improving the energy efficiency of the system and prolonging the service life of the electrolytic tank.

Description

Technical Field

[0001] The present invention relates to the field of electrolysis technology, and particularly to a self-heating electrolytic cell and an electrolysis system that achieve thermal balance through self-heating of an electrolyte. Background Art

[0002] Electrolysis technology has a wide range of applications in the fields of energy conversion and storage, such as hydrogen production, CO2 reduction, etc. During the operation of traditional electrolytic cells, especially when operating below the thermal neutral voltage, external heat is usually required to maintain the electrolysis reaction. This is because below the thermal neutral voltage, the electrolysis reaction is an endothermic process. In this case, the temperature of the gas entering the electrolytic cell is often higher than the temperature of the gas at the outlet of the electrolytic cell, which not only reduces the energy efficiency of the system but also may have an adverse impact on the long-term stability of the electrolytic cell.

[0003] Currently, most electrolysis systems rely on external heaters to provide the required heat. This method not only increases the complexity and cost of the system but also reduces the overall energy efficiency. In addition, external heating may cause temperature gradients inside the electrolytic cell, affecting the electrolysis performance and lifespan.

[0004] Therefore, developing an electrolytic cell system that can spontaneously generate heat during electrolysis without an external heater is of great significance for improving electrolysis efficiency, simplifying system design, and reducing operating costs. Such a self-heating electrolytic cell can not only improve the energy efficiency of the system but also potentially extend the service life of the electrolytic cell by optimizing the temperature distribution. Summary of the Invention

[0005] In view of this, the purpose of the present invention is to provide a self-heating electrolytic cell and an electrolysis system. By simultaneously conducting ions and electrons through the electrolyte and using the Joule heat generated by the flow of electrons through the electrolyte to maintain the endothermic electrolysis reaction, self-heating during the electrolysis process is achieved without an external heater, and efficient heat circulation is realized, thereby improving the energy efficiency of the system and extending the lifespan of the electrolytic cell.

[0006] To achieve the above purpose, the present invention provides the following technical solutions:

[0007] Based on the above purpose, in the first aspect, the present invention provides a self-heating electrolytic cell, including an air electrode, a fuel electrode, and a self-heating electrolyte; the self-heating electrolyte is composed of a single-phase mixed ion or electron conducting material, or is formed by compounding an ion conducting material and an electron conducting material. The self-heating electrolyte simultaneously conducts ions and electrons, and the ions include oxygen ions, hydrogen ions, or hydroxide ions. When electrons flow through the electrolyte, Joule heat is generated to maintain the endothermic electrolysis reaction.

[0008] As a further solution of the present invention, the self-heating electrolyte includes:

[0009] Oxygen ion conductor oxide materials, including one or more of ZrO2, CeO2, Bi2O3, and LaGaO3 doped with alkali metal elements, alkaline earth metal elements, rare earth elements, and transition metal elements;

[0010] Proton conductor oxide materials, including one or more of alkali metal oxides such as BaO, SrO, CaO, and MgO, perovskite zirconates doped with alkali metal elements, perovskite cerates doped with alkali metal elements, perovskite titanates, and perovskite ferrites;

[0011] Electronic conductive oxide materials, including cerium oxide doped with rare earth elements and transition metal elements, and one or more of perovskite titanates, chromates, ferrites, manganates, nickelates, and vanadates doped with alkali metal elements, transition metal elements, and rare earth elements.

[0012] As a further aspect of the present invention, the electronic conductive material accounts for 0% - 60% of the total volume of the electrolyte material by volume, and the resistivity when current flows through the electrolyte is 1 - 120 Ωm.

[0013] As a further aspect of the present invention, the self-heating electrolytic cell operates below the thermal neutral voltage, and the electrolysis operating voltage range is: 80% * thermal neutral voltage to the thermal neutral voltage.

[0014] As a further aspect of the present invention, the material of the air electrode is one or more of perovskite-type oxides, spinel-type oxides, and mixtures of perovskite-type oxides and spinel-type oxides.

[0015] As a further aspect of the present invention, the fuel electrode material includes:

[0016] A mixture of transition metals including Ni, Fe, Co, and Cu and an oxygen ion conductor including ZrO2, CeO2, and LaGaO 3的 ;

[0017] A mixture of noble metals Ru, Pt, Pd, Au, Rh, and Ir and an oxygen ion conductor including ZrO2, CeO2, and LaGaO3;

[0018] A mixture of Ni, Fe, Co, Cu and Ru, Pt, Pd, Au, Rh, Ir and an oxygen ion conductor of ZrO2, CeO2 and LaGaO3;

[0019] A mixture of the above mixtures and a conductive oxide, where the conductive oxide includes one or more of cerium oxide doped with rare earth elements and transition metal elements, and perovskite titanates, chromates, ferrites, manganates, nickelates, and vanadates doped with alkali metal elements, transition metal elements, and rare earth elements.

[0020] As a further aspect of the present invention, when the ratio of oxygen element to carbon element O / C in the high-temperature fuel entering the electrolytic cell is in the range of 0.5 - 3.0, no carbon deposition occurs on the surface of the electrode material of the fuel electrode.

[0021] As a further aspect of the present invention, when the electrolyte material is an oxygen ion conductor material, the fuel electrode material includes: cerium oxide doped with rare earth elements and transition metal elements, one or more of perovskite titanates, chromates, ferrites, manganates, nickelates, vanadates doped with alkali metal elements, transition metal elements, and rare earth elements, and a mixture of oxides with oxygen ion conduction characteristics of doped ZrO2, doped CeO2, and doped LaGaO3.

[0022] As a further aspect of the present invention, the fuel electrode material further includes metals such as Ni, Fe, Co, Cu, Ru, Pt, Pd, Au, Rh, Ir and alloys containing these metals in a mass ratio of 0% - 20%.

[0023] As a further aspect of the present invention, when the electrolyte material is a proton conductor material, the fuel electrode material includes a mixture of a proton conductor oxide material and an electron conductive oxide material, where:

[0024] The proton conductor oxide material is one or more of a mixture of alkali metal oxides containing BaO, SrO, CaO, MgO, perovskite zirconate oxides doped with alkali metal elements, perovskite cerates doped with alkali metal elements, perovskite titanates, and perovskite ferrites;

[0025] The electron conductive oxide material is one or more of cerium oxide doped with rare earth elements and transition metal elements, perovskite titanates, chromates, ferrites, manganates, nickelates, vanadates doped with alkali metal elements, transition metal elements, and rare earth elements.

[0026] As a further aspect of the present invention, the fuel electrode is a metal-oxide composite, the mass ratio of the metal is ≤20%, and no carbon deposition occurs when the O / C ratio is 0.5 - 3.0.

[0027] As a further aspect of the present invention, the fuel electrode material further includes metals such as Ni, Fe, Co, Cu, Ru, Pt, Pd, Au, Rh, Ir and alloys containing these metals in a mass ratio of 0% - 20%.

[0028] In a second aspect, the present invention provides a self-heating electrolysis system, which includes the above self-heating electrolytic cell, and further includes:

[0029] Heat exchanger I: used to exchange heat between the hot air discharged from the electrolytic cell and the fresh air entering the system, and preheat the inlet air with the hot air at the outlet of the electrolytic cell;

[0030] Heat exchanger II: used to exchange heat between the electrolysis products discharged from the electrolytic cell and the fresh water vapor entering the system, and use the electrolysis products to preheat the inlet water vapor;

[0031] Control the heating power of the electrolytic cell by adjusting the electrolysis current and gas flow rate, so that the outlet temperature ≥ the inlet temperature.

[0032] As a further aspect of the present invention, the electrolysis working voltage of the autothermal electrolysis system is 80% - 100% of the thermal neutral voltage.

[0033] As a further aspect of the present invention, at the initial stage of startup of the autothermal electrolysis system, the electrolytic cell is used as an electric heater to preheat the entire system. Cold air enters the electrolytic cell after passing through the cold heat exchanger. After the electrolytic cell heats the air, the hot air preheats the cold heat exchanger until the heat exchanger is preheated to the set temperature. At this time, the operating voltage of the electrolytic cell can be higher than the electrolysis thermal neutral voltage. When the autothermal electrolysis system is operating in a steady state, gradually reduce the electrolysis voltage below the thermal neutral voltage, and control the change of the inlet and outlet temperatures of the electrolytic cell by controlling the magnitude of the electrolysis current and the magnitude of the gas flow rate entering the electrolytic cell to make the outlet temperature ≥ the inlet temperature.

[0034] As a further aspect of the present invention, when the autothermal electrolytic cell in the autothermal electrolysis system is electrolyzing, it includes the following steps:

[0035] a) Introduce an oxygen-containing gas into the air electrode of the electrolytic cell;

[0036] b) Introduce water vapor or a carbon-containing fuel into the fuel electrode of the electrolytic cell;

[0037] c) Apply a voltage between the air electrode and the fuel electrode of the electrolytic cell to enable electrons and ions to pass through the electrolyte simultaneously, generate self-heating and maintain the electrolysis reaction;

[0038] d) Collect the electrolysis products.

[0039] Compared with the prior art, an autothermal electrolytic cell and an electrolysis system proposed by the present invention have the following beneficial effects:

[0040] The self-heating electrolytic cell of the present invention uses self-heating of the electrolyte to replace external heating, eliminating the need for an external heater, improving the energy efficiency of the system, reducing the system complexity and energy consumption; the inlet temperature of the electrolytic cell is lower than the outlet temperature, reducing the risk of carbon deposition on the electrodes, extending the lifespan, and being beneficial to improving the long-term durability of the electrolytic cell; by adjusting the addition ratio of the electron-conducting material inside the electrolyte to regulate the self-heating power, the system startup and steady-state operation strategies are flexible, and the electrolysis voltage and gas flow can be adjusted as needed; the present invention is compatible with oxygen ion or proton conductor systems, with flexible material selection, and the electrolysis voltage and gas flow can be adjusted as needed, extending the service life of the electrolytic cell and reducing energy consumption.

[0041] These aspects or other aspects of the present application will be more clearly understood in the following description of the embodiments. It should be understood that the above general description and the following detailed description are only exemplary and explanatory, and do not limit the present application. BRIEF DESCRIPTION OF THE DRAWINGS

[0042] In order to more clearly illustrate the technical solutions in the embodiments of the present invention or in the related art, the following briefly introduces the drawings required for use in the description of the exemplary embodiments or the related art. The drawings are used to provide a further understanding of the present invention and constitute a part of the specification. Together with the embodiments of the present invention, they are used to explain the present invention and do not constitute a limitation to the present invention. In the drawings:

[0043] Figure 1 It is a schematic diagram of the electrolysis process of a self-heating electrolytic cell according to an embodiment of the present invention.

[0044] Figure 2 It is a schematic diagram of the distribution of internal ion conductors and electron conductors of a self-heating electrolyte in a self-heating electrolytic cell according to an embodiment of the present invention.

[0045] Figure 3 It is a schematic diagram of the structural principle of a self-heating electrolysis system according to an embodiment of the present invention. DETAILED DESCRIPTION OF THE EMBODIMENTS

[0046] Next, in combination with the drawings and the specific embodiments, the present application will be further described. It should be noted that, on the premise of no conflict, the following-described embodiments or technical features can be arbitrarily combined to form new embodiments.

[0047] To make the purpose, technical solutions, and advantages of the present invention clearer, the following further details the embodiments of the present invention in combination with specific embodiments and with reference to the drawings. It should be understood that the specific embodiments described herein are only used to explain the present application and are not used to limit the present application.

[0048] It should be noted that in the embodiments of the present invention, all expressions using "first" and "second" are for distinguishing two non-identical entities or non-identical parameters with the same name. It can be seen that "first" and "second" are only for the convenience of expression and should not be construed as a limitation on the embodiments of the present invention. In addition, the terms "comprising" and "having" and any variations thereof are intended to cover non-exclusive inclusion. For example, a process, method, system, product or device that includes a series of steps or units inherently includes other steps or units.

[0049] Next, the technical solutions in the embodiments of the present application will be clearly and completely described with reference to the accompanying drawings in the embodiments of the present application. Obviously, the described embodiments are part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present application.

[0050] The flowcharts shown in the accompanying drawings are only illustrative examples, and do not necessarily include all contents and operations / steps, nor do they necessarily need to be executed in the described order. For example, some operations / steps can also be decomposed, combined or partially merged, so the actual execution order may change according to the actual situation.

[0051] Next, some embodiments of the present application will be described in detail with reference to the accompanying drawings. Without conflict, the following embodiments and the features in the embodiments can be combined with each other.

[0052] See Figures 1 to 2 As shown, an embodiment of the present invention provides a self-heating electrolytic cell, including an air electrode, a fuel electrode and a self-heating electrolyte; the self-heating electrolyte is composed of a single-phase mixed ionic or electronic conducting material, or is composed of a composite of an ionic conducting material and an electronic conducting material. The self-heating electrolyte conducts ions and electrons simultaneously. The ions include oxygen ions, hydrogen ions or hydroxide ions. When electrons flow through the electrolyte, Joule heat is generated to maintain the endothermic electrolysis reaction. Among them, during the electrolysis process, electrons and ions pass through the electrolyte simultaneously, and the moving directions are the same or opposite. When electrons pass through the electrolyte, due to the existence of the internal resistance of the electrolyte, heat is generated during the electrolysis process, and this heat is provided to the electrolytic cell to maintain the endothermic electrolysis reaction.

[0053] In this embodiment, the self-heating electrolyte includes:

[0054] An oxygen ion conductor oxide material, an oxygen ion conductor material including one or more of ZrO2, CeO2, Bi2O3, LaGaO3 doped with alkali metal elements, alkaline earth metal elements, rare earth elements, and transition metal elements;

[0055] Proton-conducting oxide materials, including one or more of alkali metal oxides such as BaO, SrO, CaO, and MgO, perovskite zirconate oxides doped with alkali metal elements and calcium, perovskite cerates doped with alkali metal elements, perovskite titanates, and perovskite ferrites;

[0056] Electron-conducting oxide materials, including cerium oxide doped with rare earth elements and transition metal elements, and one or more of perovskite titanates, chromates, ferrites, manganates, nickelates, and vanadates doped with alkali metal elements, transition metal elements, and rare earth elements.

[0057] In this embodiment, the electron-conducting material accounts for 0% to 60% of the total volume of the electrolyte material by volume, and the resistivity when current flows through the electrolyte is 1 - 120 Ωm. Among them, the self-heating electrolytic cell operates below the thermal neutral voltage, and the electrolysis operating voltage range is: 80% of the thermal neutral voltage to this thermal neutral voltage.

[0058] In this embodiment, the material of the air electrode is one or more of perovskite-type oxides, spinel-type oxides, and mixtures of perovskite-type oxides and spinel-type oxides.

[0059] In this embodiment, the fuel electrode material includes:

[0060] A mixture of transition metals containing Ni, Fe, Co, Cu and an oxygen ion conductor containing ZrO2, CeO2 and LaGaO 3的 An oxygen ion conductor mixture;

[0061] A mixture of noble metals Ru, Pt, Pd, Au, Rh, Ir and an oxygen ion conductor containing ZrO2, CeO2 and LaGaO3;

[0062] A mixture of Ni, Fe, Co, Cu and Ru, Pt, Pd, Au, Rh, Ir and an oxygen ion conductor of ZrO2, CeO2 and LaGaO3;

[0063] A mixture of the above mixtures and a conducting oxide, where the conducting oxide includes one or more of cerium oxide doped with rare earth elements and transition metal elements, and perovskite titanates, chromates, ferrites, manganates, nickelates, and vanadates doped with alkali metal elements, transition metal elements, and rare earth elements.

[0064] The material of the fuel electrode satisfies that no carbon deposition occurs on the surface of the electrode material when the ratio of oxygen element to carbon element O / C in the high-temperature fuel entering the electrolytic cell is in the range of 0.5 - 3.0.

[0065] When the electrolyte material is an oxygen ion conductor material, the fuel electrode material includes: cerium oxide doped with rare earth elements and transition metal elements, one or more of perovskite titanates, chromates, ferrites, manganates, nickelates, vanadates doped with alkali metal elements, transition metal elements, and rare earth elements, and a mixture of oxides with oxygen ion conduction characteristics of doped ZrO2, doped CeO2, and doped LaGaO3.

[0066] The fuel electrode material further includes metals such as Ni, Fe, Co, Cu, Ru, Pt, Pd, Au, Rh, Ir and alloys containing the metal in a mass ratio of 0% to 20%.

[0067] In this embodiment, when the electrolyte material is a proton conductor material, the fuel electrode material includes a mixture of a proton conductor oxide material and an electron conductive oxide material, where:

[0068] The proton conductor oxide material is one or more of a mixture of alkali metal oxides containing BaO, SrO, CaO, MgO, perovskite zirconate oxides doped with alkali metal elements and calcium, perovskite cerates doped with alkali metal elements, perovskite titanates, and perovskite ferrites;

[0069] The electron conductive oxide material is one or more of cerium oxide doped with rare earth elements and transition metal elements, perovskite titanates, chromates, ferrites, manganates, nickelates, vanadates doped with alkali metal elements, transition metal elements, and rare earth elements.

[0070] Among them, the fuel electrode is a metal-oxide composite, the mass fraction of the metal is ≤20%, and there is no carbon deposition when the O / C ratio is 0.5 - 3.0.

[0071] The fuel electrode material further includes metals such as Ni, Fe, Co, Cu, Ru, Pt, Pd, Au, Rh, Ir and alloys containing the metal in a mass ratio of 0% to 20%.

[0072] See Figures 1 to 3 As shown, the embodiment of the present invention further provides a self-heating electrolysis system, including the above self-heating electrolytic cell, and further including:

[0073] Heat exchanger I: used for heat exchange between the hot air discharged from the electrolytic cell and the fresh air entering the system, and preheating the inlet air with the hot air at the outlet of the electrolytic cell;

[0074] Heat exchanger II: used for heat exchange between the electrolysis products discharged from the electrolytic cell and the fresh water vapor entering the system, and preheating the inlet water vapor with the electrolysis products;

[0075] By adjusting the electrolysis current and gas flow rate, the heating power of the electrolytic cell is controlled so that the outlet temperature ≥ the inlet temperature.

[0076] Among them, the electrolysis working voltage of the autothermal electrolysis system is 80% - 100% of the thermal neutral voltage.

[0077] In the initial stage of starting up the autothermal electrolysis system, the electrolytic cell acts as an electric heater to preheat the whole system. Cold air enters the electrolytic cell after passing through the cold heat exchanger. After the electrolytic cell heats the air, the hot air preheats the cold heat exchanger until the heat exchanger is preheated to the set temperature. At this time, the operating voltage of the electrolytic cell can be higher than the electrolytic thermal neutral voltage. When the autothermal electrolysis system operates in a steady state, the electrolysis voltage is gradually reduced below the thermal neutral voltage. By controlling the magnitude of the electrolysis current and the magnitude of the gas flow rate entering the electrolytic cell, the change in the inlet and outlet temperatures of the electrolytic cell is controlled so that the outlet temperature ≥ the inlet temperature.

[0078] In this embodiment, when the autothermal electrolytic cell in the autothermal electrolysis system performs electrolysis, it includes the following steps:

[0079] a) Introduce an oxygen-containing gas into the air electrode of the electrolytic cell;

[0080] b) Introduce water vapor or a carbon-containing fuel into the fuel electrode of the electrolytic cell;

[0081] c) Apply a voltage between the air electrode and the fuel electrode of the electrolytic cell to enable electrons and ions to pass through the electrolyte simultaneously, generating self-heating and maintaining the electrolysis reaction;

[0082] d) Collect the electrolysis products.

[0083] The autothermal electrolytic cell of the present invention replaces external heating with self-heating through the electrolyte, eliminates the need for an external heater, improves the energy efficiency of the system, reduces the system complexity and energy consumption; the inlet temperature of the electrolytic cell is lower than the outlet temperature, reducing the risk of carbon deposition on the electrodes and extending the service life, which is beneficial to improving the long-term durability of the electrolytic cell; by regulating the addition ratio of the electron-conducting material inside the electrolyte to adjust the self-heating power, the system startup and steady-state operation strategies are flexible, and the electrolysis voltage and gas flow rate can be adjusted as needed; the present invention is compatible with oxygen ion or proton conductor systems, the material selection is flexible, the electrolysis voltage and gas flow rate can be adjusted as needed, extending the service life of the electrolytic cell and reducing energy consumption.

[0084] The above are the exemplary embodiments disclosed by the present invention. However, it should be noted that various changes and modifications can be made without departing from the scope of the embodiments disclosed by the present invention defined by the claims. The functions, steps, and / or actions of the method claims according to the disclosed embodiments herein do not need to be executed in any specific order. In addition, although the elements disclosed in the embodiments of the present invention can be described or claimed in an individual form, they can also be understood as multiple unless explicitly limited to the singular.

[0085] It should be understood that, as used herein, unless the context clearly supports the exception, the singular form "a" is intended to also include the plural form. It should also be understood that the "and / or" used herein refers to any and all possible combinations of one or more of the associated listed items. The serial numbers of the disclosed embodiments of the present invention above are only for description and do not represent the superiority or inferiority of the embodiments.

[0086] Those of ordinary skill in the art should understand that: the discussion of any of the above embodiments is only exemplary and is not intended to imply that the scope (including the claims) of the disclosed embodiments of the present invention is limited to these examples; under the concept of the embodiments of the present invention, the technical features in the above embodiments or different embodiments can also be combined, and there are many other variations in different aspects of the embodiments of the present invention as above, which are not provided in detail for the sake of brevity. Therefore, any omission, modification, equivalent replacement, improvement, etc. made within the spirit and principle of the embodiments of the present invention shall be included in the protection scope of the embodiments of the present invention.

Claims

1. A self-heating electrolytic cell, characterized in that, It includes an air electrode, a fuel electrode, and a self-heating electrolyte; the self-heating electrolyte is composed of a single-phase mixed ion or electron conduction material, or is composed of a composite of an ion conduction material and an electron conduction material. The self-heating electrolyte conducts both ions and electrons simultaneously. The ions include oxygen ions, hydrogen ions, or hydroxide ions. When electrons flow through the electrolyte, Joule heat is generated to maintain the endothermic electrolysis reaction.

2. The self-heating electrolytic cell according to claim 1, wherein, The self-heating electrolyte includes: Oxygen ion conductor oxide materials, including one or more of ZrO2, CeO2, Bi2O3, LaGaO3 doped with alkali metal elements, alkaline earth metal elements, rare earth elements, and transition metal elements; Proton conductor oxide materials, including one or more of a mixture of one or more alkali metal oxides such as BaO, SrO, CaO, MgO, perovskite zirconate oxides doped with alkali metal elements in calcium, perovskite cerates doped with alkali metal elements, perovskite titanates, and perovskite ferrites; Electron-conducting oxide materials, including cerium oxide doped with rare earth elements and transition metal elements, and one or more of perovskite titanates, chromates, ferrites, manganates, nickelates, and vanadates doped with alkali metal elements, transition metal elements, and rare earth elements.

3. The self-heating electrolytic cell according to claim 2, wherein, The electron-conducting material accounts for 0% to 60% of the total volume of the electrolyte material by volume, and the resistivity when current flows through the electrolyte is 1 - 120 Ωm.

4. The self-heating electrolytic cell according to claim 3, wherein The self-heating electrolytic cell operates below the thermal neutral voltage, and the electrolysis operating voltage range is: 80% of the thermal neutral voltage to this thermal neutral voltage.

5. The self-heating electrolytic cell according to claim 1, characterized in that, The material of the air electrode is one or more of perovskite-type oxides, spinel-type oxides, and a mixture of perovskite-type oxides and spinel-type oxides.

6. The self-heating electrolytic cell according to claim 5, characterized in that, The fuel electrode materials include: A mixture of transition metals including Ni, Fe, Co, Cu and an oxygen ion conductor including ZrO2, CeO2 and LaGaO 3的 ; A mixture of noble metals Ru, Pt, Pd, Au, Rh, Ir and an oxygen ion conductor containing ZrO2, CeO2, and LaGaO3; A mixture of Ni, Fe, Co, Cu and a mixture of noble metals Ru, Pt, Pd, Au, Rh, Ir and an oxygen ion conductor containing ZrO2, CeO2, and LaGaO3; A mixture of the above mixture and a conducting oxide, where the conducting oxide includes one or more of cerium oxide doped with rare earth elements and transition metal elements, and perovskite titanates, chromates, ferrites, manganates, nickelates, and vanadates doped with alkali metal elements, transition metal elements, and rare earth elements.

7. The self-heating electrolytic cell according to claim 6, wherein, The material of the fuel electrode satisfies that no carbon deposition occurs on the surface of the electrode material when the ratio of oxygen element to carbon element O / C in the high-temperature fuel entering the electrolytic cell is in the range of 0.5 - 3.

0.

8. The self-heating electrolytic cell according to claim 1, characterized in that, When the electrolyte material is an oxygen ion conductor material, the fuel electrode materials include: one or more of cerium oxide doped with rare earth elements and transition metal elements, perovskite titanates, chromates, ferrites, manganates, nickelates, and vanadates doped with alkali metal elements, transition metal elements, and rare earth elements, and a mixture with oxides having oxygen ion conduction characteristics of doped ZrO2, doped CeO2, and doped LaGaO3.

9. The self-heating electrolytic cell according to claim 8, wherein, The fuel electrode material further includes metals of Ni, Fe, Co, Cu, Ru, Pt, Pd, Au, Rh, Ir and alloys containing the metals in a mass ratio of 0% to 20%.

10. A self-heating electrolysis system, characterized in that, Comprising the autothermal electrolytic cell according to any one of claims 1-9, further comprising: Heat exchanger I: used for heat-exchanging the hot air discharged from the electrolytic cell with the fresh air entering the system, and preheating the inlet air by using the hot air at the outlet of the electrolytic cell; Heat exchanger II: used for heat-exchanging the electrolytic products discharged from the electrolytic cell with the fresh water vapor entering the system, and preheating the inlet water vapor by using the electrolytic products; By adjusting the electrolysis current and gas flow rate, the heating power of the electrolytic cell is controlled so that the outlet temperature ≥ the inlet temperature.

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