NiO / YSZ composite electrolyte membrane material impregnated in alkaline solution at high temperature, alkaline fuel cell and preparation method of alkaline fuel cell

Abstract

The invention discloses a high-temperature impregnated NiO / YSZ composite electrolyte membrane material in an alkaline solution, an alkaline fuel cell and a preparation method of the alkaline fuel cell, and a high-temperature impregnation method is adopted to impregnate the prepared NiO / YSZ membrane material in the alkaline solution to prepare the composite electrolyte membrane material. The method comprises the following steps: co-sintering a plurality of oxides which do not form a solid solution, then removing one component to prepare a porous membrane material, and impregnating an alkaline material in the porous membrane material, and belongs to the field of fuel cells. The NiO / YSZ composite material is prepared by adopting a tape casting method, powder is mixed with aqueous slurry of an adhesive and a dispersing agent, and the mixture is cast into a sheet shape in a mold. And calcining the sheet at about 1500 DEG C, and then repeatedly dipping in an alkaline solution at below 200 DEG C. The electrolyte membrane prepared by the method has the properties of higher ionic conductivity, good thermal stability and mechanical strength.

Description

Technical Field

[0001] The present invention relates to the technical field of high-temperature alkaline water electrolysis hydrogen production, and in particular to a NiO / YSZ composite electrolyte membrane material immersed in an alkaline solution at high temperature, an alkaline fuel cell and a preparation method thereof. Background Art

[0002] Although alkaline electrolysis of water is the most established and widely commercialized method for producing hydrogen through the water splitting process, it still faces challenges that limit its performance, efficiency and sustainability. New developments aim to overcome these shortcomings, increase current density, reduce electrolyte corrosivity, minimize gas permeation and improve dynamic response. Current density is the amount of electric current flowing through a unit area of ​​the electrode surface and is related to the hydrogen production rate, affecting the performance and efficiency of the alkaline electrolyzer. The current density of alkaline water electrolysis (AWE) is affected by various factors, including temperature, pressure, voltage, electrolyte concentration, catalyst efficiency and membrane properties. Typically, the current density values ​​of alkaline electrolyzers range from 100 to 500 mA / cm at temperatures of 60-80°C and voltages of 1.8-2.4 V. 2 However, increasing the temperature, pressure or voltage can achieve even higher current density values. High-temperature alkaline electrolysis of water vapor to produce hydrogen can effectively solve this shortcoming of low electrolysis efficiency.

[0003] H2O→H2+1 / 2O2

[0004] ΔH=ΔG+ΔQ

[0005]

[0006] The theoretical energy required for hydrogen production by electrolysis of water is shown in the above formula. It can be seen that in the temperature range of 0 to 1000 ° C, the ΔH required for water electrolysis (including the vaporization enthalpy ΔH vap ) basically fluctuates within the range of 283-292 kJ / mol and can be provided entirely by electrical energy or by both electrical energy and thermal energy. At the same time, the required electrical energy can be expressed by the Gibbs free energy ΔG, which is related to the theoretical decomposition voltage ΔE rev When steam is used instead of liquid water, the ΔH required for water electrolysis is reduced by 41 kJ / mol H2. When the temperature increases, the total energy ΔH remains unchanged, the proportion of ΔQ increases, and ΔG decreases accordingly. At the same time, the theoretical decomposition voltage of water ΔE rev It also decreases with decreasing ΔG, meaning that increasing temperature can reduce electrical energy consumption. This is why high-temperature alkaline electrolysis of water vapor can improve electrolysis efficiency. The following table compares existing electrolytic hydrogen production methods.

[0007]

[0008] Ceramics exhibit excellent chemical and thermal stability at high temperatures. They are not susceptible to decomposition or phase change, which is crucial for continuous water electrolysis hydrogen production systems operating under high-temperature conditions. Ceramics also exhibit excellent corrosion resistance in high-temperature alkaline environments. They are not easily corroded by alkaline substances in the electrolyte, thereby extending the life of the diaphragm. However, existing solid oxide electrolytic cells remain at a theoretical stage, and a low-cost, pollution-free, and simple preparation method is urgently needed to promote their widespread application. Summary of the Invention

[0009] In response to the technical problems raised above, a NiO / YSZ composite electrolyte membrane material immersed in an alkaline solution at high temperature, an alkaline fuel cell and a preparation method thereof are provided.

[0010] The technical means adopted in the present invention are as follows:

[0011] In a first aspect, the present invention discloses a method for preparing a NiO / YSZ composite electrolyte membrane material by high-temperature immersion in an alkaline solution, comprising the following steps: preparing a slurry, ball milling, degassing, casting, calcining, and drying. Specifically, the method comprises the following steps:

[0012] Zirconia powder or yttria-stabilized zirconia powder (YSZ), nickel oxide (NiO), a pore former, a dispersant, a binder, and water are prepared into a slurry;

[0013] After ball milling and drying the slurry to remove air, the slurry is cast into a NiO / YSZ film material in a mold;

[0014] The NiO / YSZ porous membrane material is prepared by sintering the cast NiO / YSZ membrane material at a high temperature;

[0015] Obtain an alkaline solution;

[0016] immersing the prepared porous membrane material in an alkaline solution at a preset high temperature;

[0017] The impregnation is repeated for a certain number of times, and vacuum drying is performed after the impregnation is completed to obtain a NiO / YSZ composite electrolyte membrane material.

[0018] Furthermore, the slurry is calculated by mass ratio, and the proportions of zirconium oxide powder or yttria-stabilized zirconium oxide powder, nickel oxide, pore-forming agent, dispersant, and binder are 34.9-38.8%, 11.6-19.4%, 14.1-17.4%, 1.7-2.4%, 4.7-5.8%, and the rest is water.

[0019] Furthermore, the specific steps of preparing the slurry are: preparing the slurry by mixing nickel oxide and zirconium oxide powder or yttria-stabilized zirconium oxide powder with a pore-forming agent in distilled water and a dispersant, stirring the mixture for a period of time, adding a binder to the slurry, and then stirring for another 9 to 12 hours.

[0020] Furthermore, the prepared slurry is cast into a NiO / YSZ film material in a mold by vacuuming the slurry, forming it on a casting machine, and then demolding it. The thickness of the ceramic sheet is 0.4-0.6 mm.

[0021] Furthermore, the preparation of NiO / YSZ porous membrane material is specifically as follows: high-temperature sintering is programmed temperature firing. When the NiO / YSZ film is programmed temperature fired, the heating rate from room temperature to 400±10℃ is 1~2℃ / min. After maintaining the temperature at 400±10℃ for 2±0.5h, the heating rate from 400±10℃ to 1300~1600℃ is 1~3℃ / min. The temperature is maintained at 1300~1600℃ for 4±0.5h, and finally the temperature is reduced to room temperature at 1~2℃ / min.

[0022] Furthermore, the sintered NiO / YSZ film is immersed in an alkaline solution at 150-200° C. for 4-6 hours.

[0023] Furthermore, the molar ratio of nickel oxide, yttria-stabilized zirconia, and alkaline material is used to calculate the content of the alkaline material in the composite material based on the actual weighed mass.

[0024] In a second aspect, the present invention claims protection for a NiO / YSZ composite electrolyte membrane immersed in an alkaline solution at a high temperature prepared based on the above method.

[0025] In a third aspect, the present invention also discloses a method for preparing an alkaline fuel cell, which comprises preparing a NiO / YSZ composite electrolyte membrane immersed in an alkaline solution at a high temperature based on the above method, laminating a Pt / C sheet with the immersed composite electrolyte membrane, and maintaining a constant temperature and pressure at 80±5°C and 15±1 MPa for 30±5 minutes to prepare an alkaline fuel cell.

[0026] In a fourth aspect, the present invention also claims protection for an alkaline fuel cell prepared based on the above method.

[0027] Compared with the prior art, the present invention has the following advantages:

[0028] 1. The tape casting process is simple, low-cost, and pollution-free. By changing the content of the pore-forming agent in the slurry, the porosity of the material can be adjusted, and the doping amount of the alkaline solution can be further increased.

[0029] 2. The present invention provides a method for preparing a high-temperature alkaline water electrolysis hydrogen production composite electrolyte membrane with low production cost, simple process and strong operability. BRIEF DESCRIPTION OF THE DRAWINGS

[0030] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the following briefly introduces the drawings required for use in the embodiments or the description of the prior art. Obviously, the drawings described below are some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying any creative labor.

[0031] Figure 1 It shows the IV curve of the YSZ film of Example 4 of the present invention in alkaline electrolysis at 150°C.

[0032] Figure 2 The figure shows the stability curve of the YSZ film of Example 4 of the present invention at different current densities in alkaline electrolysis at 150°C. DETAILED DESCRIPTION

[0033] It should be noted that, in the absence of conflict, the embodiments and features of the embodiments of the present invention can be combined with each other. The present invention will be described in detail below with reference to the accompanying drawings and in combination with the embodiments.

[0034] In order to make the purpose, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the drawings in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. The following description of at least one exemplary embodiment is actually only illustrative and is in no way intended to limit the present invention and its application or use. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of the present invention.

[0035] It should be noted that the terms used herein are only for describing specific embodiments and are not intended to limit the exemplary embodiments according to the present invention. As used herein, unless the context clearly indicates otherwise, the singular form is intended to include the plural form. In addition, it should be understood that when the terms "comprise" and / or "include" are used in this specification, they indicate the presence of features, steps, operations, devices, components and / or combinations thereof.

[0036] Unless otherwise specified, the relative arrangement of the parts and steps, numerical expressions and numerical values ​​set forth in these embodiments do not limit the scope of the present invention. At the same time, it should be clear that, for ease of description, the sizes of the various parts shown in the accompanying drawings are not drawn according to actual proportional relationships. The technology, methods and equipment known to those of ordinary skill in the relevant art may not be discussed in detail, but in appropriate cases, the technology, methods and equipment should be considered as a part of the specification. In all examples shown and discussed here, any specific value should be interpreted as being merely exemplary, rather than as a limitation. Therefore, other examples of the exemplary embodiments can have different values. It should be noted that similar numbers and letters represent similar items in the following drawings, and therefore, once an item is defined in an accompanying drawing, it does not need to be further discussed in subsequent drawings.

[0037] In the description of the present invention, it should be understood that the directions or positional relationships indicated by directional words such as "front, back, up, down, left, right", "horizontal, vertical, vertical, horizontal" and "top, bottom" are usually based on the directions or positional relationships shown in the accompanying drawings. They are only for the convenience of describing the present invention and simplifying the description. Unless otherwise specified, these directional words do not indicate or imply that the device or element referred to must have a specific direction or be constructed and operated in a specific direction. Therefore, they cannot be understood as limiting the scope of protection of the present invention: the directional words "inside and outside" refer to the inside and outside relative to the outline of each component itself.

[0038] For ease of description, spatially relative terms such as "above", "above", "on the upper surface of", "above", etc. may be used herein to describe the spatial positional relationship of a device or feature to other devices or features as shown in the figures. It should be understood that spatially relative terms are intended to include different orientations of the device in use or operation in addition to the orientation described in the figures. For example, if the device in the drawings is inverted, the device described as "above other devices or structures" or "above other devices or structures" will be positioned as "below other devices or structures" or "below their position devices or structures". Thus, the exemplary term "above" can include both "above" and "below". The device can also be positioned in other different ways (rotated 90 degrees or in other orientations), and the spatially relative descriptions used here are interpreted accordingly.

[0039] In addition, it should be noted that the use of terms such as "first" and "second" to limit components is only for the convenience of distinguishing the corresponding components. Unless otherwise stated, the above terms have no special meaning and therefore cannot be understood as limiting the scope of protection of the present invention.

[0040] In a first aspect, the present invention discloses a method for preparing a NiO / YSZ composite electrolyte membrane material by high-temperature immersion in an alkaline solution, comprising the following steps: preparing a slurry, ball milling, degassing, casting, calcining, and drying. Specifically, the method comprises the following steps:

[0041] Zirconia powder or yttria-stabilized zirconia powder (YSZ), nickel oxide (NiO), a pore-forming agent, a dispersant, a binder, and water are prepared into a slurry. Graphite or starch materials can be used as the pore-forming agent; ammonium polyacrylate, sodium polyacrylate, or ammonium citrate can be used as the dispersant; and polyvinyl alcohol or polyacrylic acid can be used as the binder.

[0042] After ball milling and drying the slurry to remove air, the slurry is cast into a NiO / YSZ film material in a mold;

[0043] The NiO / YSZ porous membrane material is prepared by sintering the cast NiO / YSZ membrane material at a high temperature;

[0044] Obtain an alkaline solution;

[0045] immersing the prepared porous membrane material in an alkaline solution at a preset high temperature;

[0046] The impregnation is repeated for a certain number of times, and vacuum drying is performed after the impregnation is completed to obtain a NiO / YSZ composite electrolyte membrane material.

[0047] Furthermore, the slurry is calculated by mass ratio, and the proportions of zirconium oxide powder or yttria-stabilized zirconium oxide powder, nickel oxide, pore-forming agent, dispersant, and binder are 34.9-38.8%, 11.6-19.4%, 14.1-17.4%, 1.7-2.4%, 4.7-5.8%, and the rest is water.

[0048] As a specific embodiment, the mass range of yttria-stabilized zirconia, nickel oxide, dispersant, binder, graphite or starch used to prepare NiO / YSZ film material is 30-40g, 10-20g, 10.5-14.5g, 1.5-2.5g, 4-6g.

[0049] Furthermore, the slurry is prepared by mixing nickel oxide and zirconium oxide powder or yttria-stabilized zirconium oxide powder with a pore-forming agent in distilled water and a dispersant to prepare a slurry, stirring the mixture for a period of time, adding a binder to the slurry, and stirring for another 9 to 12 hours. In this embodiment, the standing time is 24 ± 12 hours.

[0050] Furthermore, the prepared slurry is cast into a NiO / YSZ film material in a mold by vacuuming the slurry, forming it on a casting machine, and then demolding it. The thickness of the ceramic sheet is 0.4-0.6 mm.

[0051] Furthermore, the preparation of NiO / YSZ porous membrane material is specifically as follows: high-temperature sintering is programmed temperature firing. When the NiO / YSZ film is programmed temperature fired, the heating rate from room temperature to 400±10℃ is 1~2℃ / min. After maintaining the temperature at 400±10℃ for 2±0.5h, the heating rate from 400±10℃ to 1300~1600℃ is 1~3℃ / min. The temperature is maintained at 1300~1600℃ for 4±0.5h, and finally the temperature is reduced to room temperature at 1~2℃ / min.

[0052] Furthermore, the sintered NiO / YSZ film is immersed in an alkaline solution at 150-200° C. for 4-6 hours.

[0053] Furthermore, the molar ratio of nickel oxide, yttria-stabilized zirconia, and alkaline material is used to calculate the content of the alkaline material in the composite material based on the actual weighed mass.

[0054] In the process of preparing the alkaline solution, KOH and deionized water are reacted in a certain molar ratio to prepare the alkaline solution. The alkaline solution can be KOH or NaOH. The mass of the alkaline solution is 40-50g corresponding to the mass of the above slurry.

[0055] In a second aspect, the present invention claims protection for a NiO / YSZ composite electrolyte membrane immersed in an alkaline solution at a high temperature prepared based on the above method.

[0056] In a third aspect, the present invention also discloses a method for preparing an alkaline fuel cell, which comprises preparing a NiO / YSZ composite electrolyte membrane immersed in an alkaline solution at a high temperature based on the above method, laminating a Pt / C sheet with the immersed composite electrolyte membrane, and maintaining a constant temperature and pressure at 80±5°C and 15±1 MPa for 30±5 minutes to prepare an alkaline fuel cell.

[0057] In a fourth aspect, the present invention also claims protection for an alkaline fuel cell prepared based on the above method.

[0058] Example 1

[0059] This embodiment relates to a method for preparing a NiO / YSZ composite electrolyte membrane material immersed in an alkaline solution at high temperature. In the composite electrolyte membrane, the mass percentage of zirconium oxide, nickel oxide, and alkaline solution is 5:3:3. The method specifically includes the following steps:

[0060] Step 1: nickel oxide, zirconium oxide, pore former, dispersant and water are prepared into a slurry; in this embodiment, 30g of zirconium oxide powder, 18g of nickel oxide, 10.5g of dispersant, 5g of graphite pore former and 30g of water are used as the dispersant; ammonium polyacrylate is used as the dispersant;

[0061] Step 2: After ball milling the mixed slurry for 24 hours, 1.5 g of a binder was added, stirred, and ball milled for 9 hours; polyvinyl alcohol was used as the binder;

[0062] Step 3: After drying and degassing, the slurry was formed on a tape casting machine and then demolded to form a NiO / YSZ film with a thickness of 0.42 mm;

[0063] Step 4: sintering the NiO / YSZ film at a high temperature, wherein the high temperature sintering is a programmed temperature firing. When the NiO / YSZ film is programmed temperature fired, the heating rate from room temperature to 400°C is 2°C / min, after being kept constant at 400°C for 2 hours, the heating rate from 400°C to 1400°C is 2°C / min, and the temperature is kept constant at 1400°C for 4 hours, and finally the temperature is cooled to room temperature at 2°C / min to prepare a NiO / YSZ porous film;

[0064] Step 5: Heat 40 g of the prepared alkaline solution to 200° C.; in this embodiment, the alkaline solution is KOH.

[0065] Step 6: Vacuum the NiO / YSZ porous film to remove the air in its pores, place it in a heated alkaline solution, and immerse it at a constant temperature for 4 hours. Repeat the above process 8 to 10 times. After drying at room temperature, weigh 0.116 g.

[0066] Step 7: Take out the immersed composite electrolyte film material and heat-treat it in water vapor at 150° C., dry it at room temperature, and weigh it to 0.145 g.

[0067] Example 2

[0068] This embodiment relates to a method for preparing a NiO / YSZ composite electrolyte membrane material immersed in an alkaline solution at high temperature. In the composite electrolyte membrane, the total mass percentage of yttria-stabilized zirconium oxide, nickel oxide, and alkaline material is 6:3:1. The method specifically includes the following steps:

[0069] Step 1: Yttria-stabilized zirconium oxide, nickel oxide, a pore-forming agent, a dispersant, and water are prepared into a slurry; in this embodiment, 32g of zirconium oxide powder, 16g of nickel oxide, 11g of dispersant, 6g of starch pore-forming agent, and 33g of water are used as the pore-forming agent: sodium polyacrylate is used as the dispersant;

[0070] Step 2: After ball milling the mixed slurry for 12 hours, 2 g of binder was added, stirred, and ball milled for 12 hours; polyacrylic acid was used as the binder;

[0071] Step 3: After drying and degassing, the slurry is formed on a casting machine and demolded to form a NiO / YSZ film with a thickness of 0.6 mm;

[0072] Step 4: sintering the NiO / YSZ film at a high temperature, wherein the high temperature sintering is a programmed temperature firing. When the NiO / YSZ film is programmed temperature fired, the heating rate from room temperature to 405°C is 2°C / min, after being kept constant at 405°C for 2.5 hours, the heating rate from 405°C to 1500°C is 3°C / min, and the temperature is kept constant at 1500°C for 4.5 hours. Finally, the temperature is cooled to room temperature at a rate of 1°C / min to prepare a NiO / YSZ porous film.

[0073] Step 5: Heat 45 g of the prepared alkaline solution to 200° C.; in this embodiment, the alkaline solution is NaOH.

[0074] Step 6: Vacuum the NiO / YSZ porous film to remove the air in its pores, place it in a heated alkaline solution, and immerse it at a constant temperature for 4 hours. Repeat the above process 8 to 10 times. After drying at room temperature, weigh 0.12 g.

[0075] Step 7: Take out the immersed composite electrolyte film material and heat-treat it in water vapor at about 150° C., and then dry it at room temperature and weigh it to 0.133 g.

[0076] Example 3

[0077] This embodiment relates to a method for preparing a NiO / YSZ composite electrolyte membrane material immersed in an alkaline solution at high temperature. In the composite electrolyte membrane, the total mass percentage of yttria-stabilized zirconium oxide, nickel oxide, and alkaline solution is 6:2:2. The method specifically includes the following steps:

[0078] Step 1: Prepare a slurry of nickel oxide, yttria-stabilized zirconium oxide, a pore former, a dispersant, and water. In this embodiment, 30 g of zirconium oxide powder, 10 g of nickel oxide, 10.5 g of dispersant, 5 g of graphite pore former, and 23 g of water: ammonium citrate is used as the dispersant.

[0079] Step 2: After ball milling the mixed slurry for 12 hours, 1.5 g of a binder was added, stirred, and ball milled for 9 hours; polyacrylic acid was used as the binder;

[0080] Step 3: After drying and degassing, the slurry is formed on a casting machine and demolded to form a NiO / YSZ film with a thickness of 0.5 mm;

[0081] Step 4: sintering the NiO / YSZ film at a high temperature. The high temperature sintering is a programmed temperature firing. When the NiO / YSZ film is programmed temperature fired, the heating rate from room temperature to 400°C is 1°C / min. After being kept constant at 400°C for 2 hours, the heating rate from 400°C to 1600°C is 2°C / min. After being kept constant at 1600°C for 4 hours, the temperature is finally cooled to room temperature at 2°C / min to prepare a NiO / YSZ porous film.

[0082] Step 5: Heat 50 g of the prepared alkaline solution to 150° C.; in this embodiment, the alkaline solution is KOH.

[0083] Step 6: Vacuum the NiO / YSZ porous film to remove the air in its pores, place it in a heated alkaline solution, and immerse it at a constant temperature for 6 hours. Repeat the above process 8 to 10 times. After drying at room temperature, weigh 0.118 g.

[0084] Step 7: Take out the immersed composite electrolyte film material and heat-treat it in water vapor at 150° C., and then dry it at room temperature and weigh it to 0.147 g.

[0085] Example 4

[0086] This example relates to a method for preparing an alkaline fuel cell. 70.58 g of KOH powder was weighed using weighing paper. 29.42 g of deionized water was prepared, followed by a 60% KOH solution. The heating table was set to 150°C and heated continuously to maintain a liquid state. The prepared NIO / YSZ porous film was removed and soaked in the prepared KOH solution for 6 hours. The Pt / C sheet and the soaked composite electrolyte film were then laminated. The alkaline fuel cell was prepared by maintaining a constant temperature and pressure at 80°C and 15 MPa for 30 minutes.

[0087] Example 5

[0088] Weigh 70.58g of KOH powder using weighing paper, prepare 29.42g of deionized water, and prepare a 60% KOH solution. Allow the solution to cool until it solidifies, then grind it into a powder. Sprinkle the ground powder particles onto the prepared NIO / YSZ porous film, then laminate the Pt / C sheet and composite electrolyte film. Maintain constant temperature and pressure at 85°C and 15.5 MPa for 25 minutes to prepare an alkaline fuel cell.

[0089] The alkaline fuel cells prepared in Examples 4 and 5 were used to electrolyze water, and the IV curves were obtained by testing and analyzing using an electrochemical station. Figure 1 and Figure 2 Compared with traditional alkaline electrolysis, the performance has been greatly improved, and it can also improve utilization and reduce energy loss.

[0090] The present invention does not emit any harmful substances during the process of producing hydrogen by electrolysis of water. It only produces water, hydrogen, and oxygen. It is a very environmentally friendly way to produce hydrogen. The electrolysis voltage of the present invention using YSZ membrane to produce hydrogen by high-temperature and high-concentration alkaline water electrolysis is 1.1V-1.3V, while the electrolysis voltage of traditional alkaline water electrolysis hydrogen production devices is 1.7V-2.4V. The energy consumption is lower than that of traditional alkaline water electrolysis hydrogen production devices, greatly reducing energy consumption. Improve electrolysis efficiency

[0091] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit it. Although the present invention has been described in detail with reference to the above embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the above embodiments, or replace some or all of the technical features therein with equivalents. However, these modifications or replacements do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. A method for preparing a NiO / YSZ composite electrolyte membrane material by high-temperature immersion in an alkaline solution, characterized in that: The process comprises the following steps: preparing slurry, ball milling, degassing, casting, calcining, and drying, specifically comprising the following steps: Prepare slurry by mixing zirconium oxide powder or yttria-stabilized zirconium oxide powder, nickel oxide, a pore-forming agent, a dispersant, a binder and water; After ball milling and drying the slurry to remove air, the slurry is cast into a NiO / YSZ film material in a mold; The NiO / YSZ porous membrane material is prepared by sintering the cast NiO / YSZ membrane material at a high temperature; Obtain an alkaline solution; immersing the prepared porous membrane material in an alkaline solution at a preset high temperature; The impregnation is repeated for a certain number of times, and vacuum drying is performed after the impregnation is completed to obtain a NiO / YSZ composite electrolyte membrane material.

2. The preparation method according to claim 1, characterized in that Calculated by mass ratio, the slurry contains zirconia powder or yttria-stabilized zirconia powder, nickel oxide, pore-forming agent, dispersant, and binder in proportions of 34.9-38.8%, 11.6-19.4%, 14.1-17.4%, 1.7-2.4%, 4.7-5.8%, and the rest is water.

3. The preparation method according to claim 1, characterized in that The specific steps of preparing the slurry are: preparing the slurry by mixing nickel oxide and zirconium oxide powder or yttria-stabilized zirconium oxide powder with a pore-forming agent in distilled water and a dispersant, stirring the mixture for a period of time, adding the binder to the slurry, and then stirring for another 9 to 12 hours.

4. The preparation method according to claim 1, characterized in that The prepared slurry is cast into a NiO / YSZ film material in a mold by vacuuming the slurry, forming it on a casting machine, and then demolding it. The thickness of the ceramic sheet is 0.4-0.6 mm.

5. The preparation method according to claim 1, characterized in that The specific preparation process of NiO / YSZ porous membrane material is as follows: high-temperature sintering is programmed temperature firing. When programmed temperature firing of NiO / YSZ film, the heating rate from room temperature to 400±10℃ is 1~2℃ / min. After maintaining the temperature at 400±10℃ for 2±0.5h, the heating rate from 400±10℃ to 1300~1600℃ is 1~3℃ / min. The temperature is maintained at 1300~1600℃ for 4±0.5h, and finally the temperature is reduced to room temperature at 1~2℃ / min.

6. The preparation method according to claim 1, characterized in that The sintered NiO / YSZ film is immersed in an alkaline solution at 150-200° C. for 4-6 hours.

7. The preparation method according to claim 1, characterized in that The molar ratio of nickel oxide, yttria-stabilized zirconia, and alkaline material is used to calculate the content of the alkaline material in the composite material based on the actual weighed mass.

8. A NiO / YSZ composite electrolyte membrane immersed in an alkaline solution at high temperature, prepared by the method according to any one of claims 1 to 7.

9. A method for preparing an alkaline fuel cell, characterized in that: A NiO / YSZ composite electrolyte membrane prepared by the method of any one of claims 1 to 7 is immersed in an alkaline solution at high temperature, and a Pt / C sheet is stacked with the impregnated composite electrolyte membrane, and constant temperature and pressure are maintained at 80±5°C and 15±1 MPa for 30±5 minutes to prepare an alkaline fuel cell.

10. An alkaline fuel cell prepared according to claim 9.

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