A solid oxide electrolytic cell sheet anode material and its preparation method and application

Abstract

The present invention discloses a solid oxide electrolytic cell sheet anode material and its preparation method and application. The solid oxide electrolytic cell sheet anode material comprises LSCF particles and LNO particles deposited and grown on the surface of the LSCF particles, referred to as LSCF-LNO material. The chemical formula of LSCF is La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O3, the chemical formula of LNO is La2NiO4, and the mass of LNO on the LSCF-LNO material is 10%-50% of the mass of LSCF. This invention leverages the excellent electronic conductivity of LSCF and the excellent oxygen ion transport properties of LNO. Through a two-step synthesis method, LNO particles are formed on the surface of LSCF, enhancing the material's oxygen surface exchange and transport capacity, increasing the three-phase interface and oxygen ion transport channels, and ultimately improving the electrochemical performance of high-temperature solid oxide electrolyzers.

Description

Technical Field

[0001] The present invention relates to the technical field of energy and electrolytic cells, and in particular to a solid oxide electrolytic cell sheet anode material, a preparation method and application thereof. Background Art

[0002] The high-temperature solid oxide electrolyzer (SOEC) is a highly efficient, rapid, and flexible device for producing hydrogen by electrolyzing water vapor. It is more efficient than currently mainstream methods for producing hydrogen by electrolysis, such as alkaline electrolysis (ALK) and proton exchange membrane electrolysis (PEM). However, the long-term, large-scale application of SOEC technology currently faces challenges in electrode performance.

[0003] Although solid oxide electrolyzer technology has significant advantages in electrolytic conversion, its anode material development still faces bottlenecks. Among them, the oxygen evolution reaction (OER) is a key factor determining electrode performance. The slow kinetics of OER on the anode material severely limits the electrochemical performance of SOEC. Bulk diffusion and surface diffusion in the oxygen evolution reaction step on the anode are generally considered to be rate-limiting steps. Therefore, the anode material requirements of solid oxide electrolyzer (SOEC) should meet the requirements of excellent catalytic activity in the oxygen evolution reaction (OER).

[0004] There are two types of anode materials that have been widely studied. The first type is electronic conductor materials such as La 1-x Sr x Due to the extremely low ionic conductivity of MnO3, the electrochemical reaction area of ​​the anode is severely limited, making it difficult to improve the electrochemical performance of the electrolytic cell. The second type of electronic and ion dual conductive materials such as La 1-x Sr x Co 1-y Fe y Although O3, La2NiO4, etc. have more electrochemical reaction areas than the first type, they still have problems such as low oxygen ion transport, oxygen surface exchange rate and oxygen diffusion coefficient, or insufficient electronic conductivity, which limit the improvement of electrochemical performance.

[0005] In recent years, although some related research has solved the above problems by developing composite anodes, such as the patent CN106876720A proposed that the traditional perovskite anode material La 1-x Sr x MnO 3+δ Bismuth oxide is added to form a bismuth oxide-perovskite composite material to improve the electron-ion mixed conductivity, electrocatalytic activity, etc. However, the perovskite anode material La 1- x Sr x MnO 3+δAs an electronic conductor, it cannot conduct ions, which limits the further expansion of the reaction area inside the material. The preparation method of this patent is prone to by-products when synthesizing composite materials through the co-synthesis method, making it difficult to generate the target composite material. Chinese patent CN112647089A proposes to prepare a ternary composite anode by regulating the formula and foaming conditions to achieve precise control of the electrode pore size and pore density, and avoid the mutual reaction between materials caused by high-temperature roasting, thereby improving the anode activity. However, the patent focuses on how to improve the gas mass transfer in the anode. There are problems such as complex process and high cost in the preparation of materials, which limits its large-scale application.

[0006] In response to the above problems, the present invention aims to develop a LSCF-LNO surface-modified composite anode material prepared by a two-step synthesis method, which fully utilizes the excellent electronic conductivity of LSCF and the excellent oxygen ion transport performance of LNO, and forms LNO particles on the surface of LSCF as the main body through a two-step synthesis method to enhance the oxygen surface exchange and transport capacity of the material and increase the reaction three-phase interface and oxygen ion transport channel, so as to improve the electrochemical performance of the high-temperature solid oxide electrolysis cell. Summary of the Invention

[0007] The electrolytic cell sheet prepared by the present invention is a cathode-supported solid oxide electrolytic cell sheet. The surface-modified composite anode invented has the characteristics of good uniformity and interface connectivity, high ionic and electronic conductivity, and larger three-phase interface reaction sites. It has good electrochemical performance for high-temperature electrolysis of water and provides a simple and direct modification approach for anode development.

[0008] The electrode catalyst of the surface-modified composite anode of the SOEC described in the present invention is LSCF-LNO composite particles. This material has a composite structure of a simple perovskite phase and a "Ruddlesden-Popper" layered perovskite phase. LNO is synthesized on the surface of the LSCF particles to obtain a large number of reaction sites, thereby promoting the oxygen surface exchange kinetics to improve the electrochemical performance of the electrolytic cell. The high electrical conductivity of LSCF itself is combined with the high oxygen surface exchange energy and high ionic conductivity of LNO. LNO modification is synthesized on the surface of the LSCF particles through a two-step synthesis method to ultimately achieve higher conductivity and faster oxygen exchange kinetics and oxygen surface diffusion process, providing a continuous network structure for the transmission of electrons and ions and increasing the three-phase interface area, thereby improving the current density of water electrolysis.

[0009] The present invention adopts a two-step synthesis method to prepare an LSCF-LNO surface-modified composite active catalyst, then uses a screen printing method to evenly apply and print the LSCF-LNO catalyst slurry on the surface of a GDC isolation layer to prepare an LSCF-LNO surface-modified composite anode active catalytic layer, and then obtains a surface-modified composite anode for a high-temperature solid oxide electrolytic cell sheet after high-temperature sintering.

[0010] The technical solution adopted in the present invention is as follows:

[0011] A solid oxide electrolytic cell sheet anode material, comprising LSCF particles and LNO particles deposited and grown on the surface of the LSCF particles, referred to as LSCF-LNO material; the chemical formula of LSCF is La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O3, the chemical formula of LNO is La2NiO4, and the mass of LNO on the LSCF-LNO material is 10%-50% of the mass of LSCF.

[0012] Furthermore, the mass of LNO on the LSCF-LNO material is 30%-50% of the mass of LSCF.

[0013] The method for preparing a solid oxide electrolytic cell sheet anode material comprises the following steps:

[0014] (1) According to the chemical formula of LSCF, weigh the nitrates of each metal into a beaker, add deionized water and stir to dissolve, obtaining an LSCF nitrate solution, add citric acid, and adjust the pH of the mixture to 6-7 with ammonia water. Then, heat and stir in an oil bath to form a gel precursor, which is then dried, ground, and calcined at high temperature to obtain an LSCF catalyst powder.

[0015] (2) Add LSCF catalyst powder into a beaker, and add nitrates of various metals according to the chemical formula of LNO. Add deionized water and stir to fully disperse the mixture to dissolve the nitrates of various metals. Then add citric acid and adjust the pH of the mixture to 6-7 with ammonia water. Then, place the mixture in an oil bath and heat and stir to form a gel precursor. After drying, grinding, and high-temperature calcination, the LSCF-LNO surface-modified composite catalyst powder is obtained. The preparation is complete.

[0016] Furthermore, in step (1) or step (2), the ratio of the molar amount of citric acid added to the total molar amount of metal ions in the solution is 2-4:1.

[0017] Furthermore, in step (1) or step (2), the temperature of the oil bath is heated to 70-85°C.

[0018] Furthermore, in step (1) or step (2), the drying temperature is 100-250° C., the high-temperature calcination temperature is 900-1100° C., and the calcination time is 2-8 hours.

[0019] A method for preparing a solid oxide electrolytic cell sheet comprises the following steps:

[0020] Step 1: Weigh the LSCF-LNO material powder of the present invention and perform wet grinding in a planetary ball mill to obtain micro-nanoscale LSCF-LNO powder;

[0021] Step 2: The LSCF-LNO powder, organic solvent, and dispersant after ball milling in step 1 are mixed uniformly in a ball mill to obtain a LSCF-LNO catalyst slurry;

[0022] Step 3: The LSCF-LNO slurry obtained in step 2 is evenly coated on the surface of the CGO layer of the cathode supporting half electrolytic cell sheet by screen printing, and then calcined at high temperature in an air atmosphere to obtain an electrolytic cell sheet with a LSCF-LNO surface-modified composite anode.

[0023] Furthermore, in step 1, the ball milling medium in the planetary ball mill is zirconia balls, the mass ratio of LSCF-LNO material powder to zirconia balls is 1:40-60, an appropriate amount of ethanol is added as a solvent during ball milling, the ball milling time is 48 hours, the ball mill speed is 200-400 r / min, and after ball milling, the mixture is dried to evaporate the solvent to obtain the micro-nanoscale LSCF-LNO powder.

[0024] Furthermore, in step 2, the LSCF-LNO powder is 45-55% by weight, the dispersant is 0.2-0.8%, and the balance is an organic solvent. The dispersant is an acrylic resin, and the organic solvent is terpineol and ethyl cellulose in a mass ratio of 10-20:1. The ball mill speed is 200-400 r / min, and the ball milling time is 12 h.

[0025] Furthermore, in step 3, the high temperature calcination temperature is 1000-1200° C., and the calcination time is 1-3 hours.

[0026] The solid oxide electrolytic cell sheet anode described in the present invention is a LSCF-LNO surface-modified composite electrode, which can provide sufficient reaction sites and gas diffusion channels for the electrolysis reaction, thereby improving the electrochemical reaction performance of the electrolytic cell and has strong interfacial bonding force.

[0027] The surface-modified composite anode material of the solid oxide electrolytic cell sheet LSCF-LNO of the present invention has a large number of oxygen ion transport networks and three-phase interfaces, which promote oxygen surface exchange kinetics to improve the electrochemical performance of the electrolytic cell.

[0028] In general, the above technical solutions conceived by the present invention can achieve the following beneficial effects compared with the prior art:

[0029] 1) The present invention prepares La by a two-step synthesis method 0.6 Sr 0.4 Co 0.2 Fe0.8 The O3-La2NiO4 surface-modified composite material grows LNO particles on the surface of LSCF particles. Compared with the composite material formed by simple impregnation, the surface bonding force between the materials is strengthened, and this preparation method makes the composite between the materials more uniform.

[0030] 2) La prepared by the present invention 0.6 Sr 0.4 Co 0.2 Fe 0.8 Compared with the single LSCF or LNO anode solid electrolytic cell sheet, the O3-x%La2NiO4 surface-modified composite material exhibits higher conductivity, faster oxygen exchange kinetics and bulk diffusion process, good electrocatalytic performance, and stable structure at high electrolysis voltage. It can be used as an anode material for high-temperature solid oxide electrolytic cells.

[0031] 3) Using the anode material La of the present invention 0.6 Sr 0.4 Co 0.2 Fe 0.8 The electrolytic cell sheet assembled with O3-La2NiO4 as the electrode, YSZ as the electrolyte, CGO as the separator, and Ni-YSZ as the composite cathode material has excellent electrolytic performance and provides a simple and direct method for improving the anode. BRIEF DESCRIPTION OF THE DRAWINGS

[0032] Figure 1 The LSCF of Example 1 with LNO: 10% material, the LSCF of Example 2 with LNO: 30% material, the LSCF of Example 3 with LNO: 50% material, the La 0.6 Sr 0.4 Co 0.2 Fe 0.8 Comparison of X-ray diffraction spectra of O3 material and La2NiO4 material of comparative example 2;

[0033] Figure 2 Comparative results of the relationship between voltage and current density during water electrolysis for the electrolytic cell sheets prepared in Examples 1-3 of the present invention and Comparative Examples 1-2;

[0034] Figure 3 This is an SEM image of the LSCF-attached LNO:50% material according to Example 3 of the present invention. DETAILED DESCRIPTION

[0035] In order to make the purpose, technical solutions and advantages of the present invention more clearly understood, the present invention is further described in detail below with reference to the embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not intended to limit the present invention. In addition, the technical features involved in the various embodiments of the present invention described below can be combined with each other as long as they do not conflict with each other:

[0036] The cathode-supported half-electrolytic cell sheet in this embodiment includes a cathode layer made of Ni-YSZ, an electrolyte layer made of YSZ, and a separator layer made of CGO, arranged in that order. This half-electrolytic cell sheet is a combination of Ni-YSZ / YSZ / CGO and was purchased from Zhejiang Hydrogen Technology Co., Ltd. The thickness of the Ni-YSZ cathode layer is 400 microns, the thickness of the YSZ electrolyte layer is 5 microns, and the thickness of the CGO separator layer is 3 microns.

[0037] Example 1: Preparation of a solid oxide electrolytic cell sheet

[0038] (1) According to the chemical formula of LSCF La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O3 prepares nitrate solution, accurately weighs La(NO3)3, Sr(NO3)2, Fe(NO3)3 and Co(NO3)2 into a beaker according to the ratio of metal ions in the chemical formula, adds an appropriate amount of deionized water sufficient to dissolve the above nitrates, and stirs to dissolve to obtain LSCF nitrate solution.

[0039] (2) Add citric acid to the LSCF nitrate solution, with the ratio of the molar amount of citric acid added to the total molar number of metal ions in the solution being 3:1. Adjust the pH of the solution obtained above to 6-7 with aqueous ammonia to prepare a mixed solution.

[0040] (3) The mixed solution obtained in step (2) is placed in an 80°C oil bath and stirred to evaporate the water until a gel precursor is formed. The gel precursor is placed in a thermostat and completely dried at 200°C to form a solid precursor powder. The generated solid precursor powder is preliminarily ground, and the ground precursor powder is placed in a heating furnace and calcined at 1000°C for 5 hours to generate LSCF catalyst powder.

[0041] (4) Weigh a certain amount of LSCF catalyst powder into a beaker, calculate the amount of La2NiO4 generated based on the mass of La2NiO4 being 10% of the mass of the LSCF catalyst, and then accurately weigh La(NO3)3 and Ni(NO3)2 into the beaker based on the calculated amount of La2NiO4 and the ratio of metal ions in the chemical formula La2NiO4. Add an appropriate amount of deionized water sufficient to dissolve the above nitrates, and stir to dissolve the nitrates to obtain a mixed solution.

[0042] (5) Add citric acid to the mixed solution of step (4), wherein the ratio of the molar amount of citric acid added to the total molar number of free metal ions in the mixed solution is 3:1. Adjust the pH value of the solution obtained above to 6-7 with aqueous ammonia to prepare a mixed solution.

[0043] (6) The mixed solution obtained in step (5) was placed in an 80°C oil bath and stirred to evaporate the water until a gel precursor was formed. The gel precursor was placed in a constant temperature oven and completely dried at 200°C to form a solid precursor powder. The generated solid precursor powder was preliminarily ground, and the ground precursor powder was placed in a heating furnace and calcined at 1000°C for 5 hours to generate LSCF-LNO surface-modified composite catalyst powder, which was labeled as LSCF-attached LNO: 10% material.

[0044] (7) The LSCF-LNO powder obtained in step (6) (i.e., LSCF with LNO: 10%) was weighed and wet-ground in a planetary ball mill. Zirconia balls were added, wherein the mass ratio of powder to zirconia balls was 1:50, and the diameter of the zirconia balls was 6 mm. An appropriate amount of ethanol was added to the milling jar as a solvent to cover the zirconia balls and powder. The ball mill speed was 300 r / min, and the milling time was 48 h. The ball-milled mixture was removed and placed in a drying oven at 60°C to evaporate the ethanol, resulting in a ball-milled LSCF-LNO powder with a uniform particle size of approximately 500 nm.

[0045] (8) 50 wt% of the ball-milled LSCF-LNO powder was mixed uniformly with 49.5 wt% of an organic solvent and 0.5 wt% of a dispersant in a ball mill. The organic solvent consisted of terpineol and ethyl cellulose in a mass ratio of 93:6, and the dispersant was an acrylic resin. The ball mill was rotated at 300 rpm for 12 h to obtain a uniform LSCF-LNO catalyst slurry.

[0046] (9) The LSCF-LNO slurry of step (8) was evenly coated on the surface of the CGO layer of the cathode support semi-electrolytic cell sheet by screen printing to obtain an electrolytic cell sheet with a LSCF-LNO heterostructure composite anode, which was composed of a cathode layer material Ni-YSZ, an electrolyte layer material YSZ, an isolation layer material CGO, and an anode layer material LSCF-LNO arranged in sequence.

[0047] (10) The electrolytic cell sheet of the LSCF-LNO heterostructure composite anode of step (9) was sintered at a temperature of 1100° C. in an air atmosphere for 2 h to obtain a complete LSCF-LNO heterostructure composite anode electrolytic cell sheet, and the thickness of the anode layer material LSCF-LNO was about 10 μm.

[0048] The electrolytic cell obtained in Example 1 of the present invention was operated at 800°C under the following experimental conditions: the cathode inlet gas flow rates were 75 ml / min H2, 75 ml / min N2, and 280 ml / min H2O, respectively, and the anode inlet gas flow rate was 200 ml / min air. Under these experimental conditions, an open circuit voltage of 0.88 V was obtained. Electrolytic performance was tested using an electrochemical workstation. When the voltage reached 1.3 V, the current density reached 9963 A / m 2 , the hydrogen production rate was 3.46 mL / min.

[0049] Example 2: Preparation of a solid oxide electrolytic cell sheet

[0050] The preparation steps of the electrolytic cell sheet of Example 2 repeat steps (1) to (10) of Example 1, with the only difference being that "in step (4), a certain amount of LSCF catalyst powder is weighed into a beaker, and the amount of La2NiO4 generated is calculated based on the mass of La2NiO4 being 30% of the mass of the LSCF catalyst, and then La(NO3)3 and Ni(NO3)2 are accurately weighed into a beaker according to the calculated amount of La2NiO4 and the ratio of metal ions in the chemical formula La2NiO4, and an appropriate amount of deionized water sufficient to dissolve the above-mentioned nitrate is added, and the nitrate is dissolved by stirring to obtain a mixed solution", and the other conditions remain unchanged, and finally a complete LSCF-LNO heterostructure composite anode electrolytic cell sheet is obtained.

[0051] The LSCF-LNO surface-modified composite catalyst powder prepared in step (6) of Example 2 is labeled as LSCF-attached LNO: 30% material.

[0052] The electrolytic cell obtained in Example 2 of the present invention was operated at 800°C under the following experimental conditions: the cathode inlet gas flow rates were 75 ml / min H2, 75 ml / min N2, and 280 ml / min H2O, respectively, and the anode inlet gas flow rate was 200 ml / min air. Under these experimental conditions, an open circuit voltage of 0.88 V was obtained. Electrolytic performance was tested using an electrochemical workstation. When the voltage reached 1.3 V, the current density reached 10,887 A / m 2 , the hydrogen production rate was 3.78 mL / min.

[0053] Example 3: Preparation of a solid oxide electrolytic cell sheet

[0054] The preparation steps of the electrolytic cell sheet in Example 3 are repeated as follows: Steps (1) to (10) of Example 1, with the only difference being that "in step (4), a certain amount of LSCF catalyst powder is weighed into a beaker, and the amount of La2NiO4 generated is calculated based on the mass of La2NiO4 being 50% of the mass of the LSCF catalyst, and then La(NO3)3 and Ni(NO3)2 are accurately weighed into a beaker according to the ratio of metal ions in the chemical formula La2NiO4 based on the calculated amount of La2NiO4 generated, and an appropriate amount of deionized water sufficient to dissolve the above-mentioned nitrate is added, and the nitrate is dissolved by stirring to obtain a mixed solution". The other conditions remain unchanged, and a complete LSCF-LNO heterostructure composite anode electrolytic cell sheet is finally obtained.

[0055] The LSCF-LNO surface-modified composite catalyst powder prepared in step (6) of Example 3 is labeled as LSCF-attached LNO: 50% material.

[0056] The electrolytic cell obtained in Example 3 of the present invention was operated at 800°C under the following experimental conditions: the cathode inlet gas flow rates were 75 ml / min H2, 75 ml / min N2, and 280 ml / min H2O, respectively, and the anode inlet gas flow rate was 200 ml / min air. Under these experimental conditions, an open circuit voltage of 0.88 V was obtained. Electrolytic performance was tested using an electrochemical workstation. When the voltage reached 1.3 V, the current density reached 12110 A / m 2 , the hydrogen production rate was 4.2 mL / min.

[0057] In addition, the electrolytic cell obtained in Example 3 of the present invention was operated at 800°C, with a fixed total cathode gas flow rate of 430 ml / min and an anode atmosphere of 200 ml / min of air. By varying the volume ratios of the different cathode gas components, the open circuit voltage and current density at 1.3 V were obtained, as shown in Table 1.

[0058] Table 1 Current density results with varying reaction gas volume ratio

[0059] .

[0060] The purpose of examining the data in Table 1 is to supplement the data results under different working conditions. The conclusion that can be drawn is that the higher the water concentration, the lower the open circuit voltage and the higher the working current density at 1.3 V.

[0061] Comparative Example 1: Preparation of a solid oxide electrolytic cell sheet

[0062] La 0.6 Sr 0.4 Co 0.2 Fe 0.8The preparation of O3 material is carried out by repeating steps (1) to (3) of Example 1.

[0063] Comparative Example 1 La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O3 was used as the anode material to prepare the electrolytic cell sheet. The preparation steps were similar to those in step (7) to step (10) of Example 1, except that "LSCF attached LNO: 10% material" was replaced by "La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O3 material".

[0064] Comparative Example 2: Preparation of a solid oxide electrolytic cell sheet

[0065] Step 1: Accurately weigh La(NO3)3 and Ni(NO3)2 in a beaker according to the ratio of metal ions in the chemical formula La2NiO4. Add an appropriate amount of deionized water sufficient to dissolve the above nitrates and stir to dissolve the nitrates to obtain a mixed solution.

[0066] Step 2: Add citric acid to the mixed solution prepared in step 1, with the ratio of the molar amount of citric acid added to the total molar number of free metal ions in the mixed solution being 3:1. Adjust the pH of the solution obtained above to 6-7 with aqueous ammonia to prepare a mixed solution.

[0067] Step 3: Place the mixed solution obtained in Step 2 in an 80°C oil bath and stir to evaporate the water until a gel-like precursor is formed. The gel-like precursor is placed in a thermostat and completely dried at 200°C to form a solid precursor powder. The resulting solid precursor powder is preliminarily ground and then calcined in a furnace at 1000°C for 5 hours to obtain the La2NiO4 material.

[0068] The La2NiO4 of Comparative Example 2 was used as the anode material to prepare the electrolytic cell sheet. The preparation steps were similar to steps (7) to (10) of Example 1, except that the "LSCF attached LNO: 10% material" was replaced by "La2NiO4 material".

[0069] LSCF of Example 1 with LNO: 10% material, LSCF of Example 2 with LNO: 30% material, LSCF of Example 3 with LNO: 50% material, La 0.6 Sr 0.4 Co 0.2 Fe 0.8 The X-ray diffraction spectra of the O3 material and the La2NiO4 material of comparative example 2 are compared as shown in FIG. Figure 1 ,from Figure 1 It can be seen that Examples 1-3 all synthesized the corresponding target material phases.

[0070] The electrolytic cell sheets prepared in Examples 1-3 of the present invention and Comparative Examples 1-2 were operated at 800°C, with the cathode inlet gas flow rates of H2: 75 ml / min, N2: 75 ml / min, and H2O: 280 ml / min, respectively, and the anode inlet gas flow rate of air was 200 ml / min. The comparative results of the relationship between the voltage and current density of water electrolysis under the experimental conditions are shown in FIG. Figure 2 .according to Figure 2 The performance of electrolyzed water was judged, and the results showed that the performance of the electrolytic cell sheet obtained in Example 3 was better.

[0071] The SEM image of the LSCF attached LNO: 50% material of Example 3 is as follows Figure 3 As shown, the morphology and structure of LSCF-LNO materials are identified according to Figure 3 It can be seen that LNO particles were successfully synthesized on the surface of LSCF particles.

Claims

1. A solid oxide electrolytic cell sheet anode material, characterized in that: It includes LSCF particles and LNO particles deposited and grown on the surface of LSCF particles, referred to as LSCF-LNO material; the chemical formula of LSCF is La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O3, the chemical formula of LNO is La2NiO4, and the mass of LNO on the LSCF-LNO material is 10%-50% of the mass of LSCF.

2. The solid oxide electrolytic cell sheet anode material according to claim 1, wherein: The mass of LNO on the LSCF-LNO material is 30%-50% of the mass of LSCF.

3. The method for preparing a solid oxide electrolytic cell sheet anode material according to claim 1 or 2, wherein: The following steps are involved: (1) According to the chemical formula of LSCF described in claim 1, weigh the nitrates of each metal, add deionized water and stir to dissolve, to obtain an LSCF nitrate solution, add citric acid, adjust the pH of the mixture to 6-7, then heat and stir to form a gel precursor, and sequentially dry, grind, and calcine at high temperature to obtain an LSCF catalyst powder; (2) Add LSCF catalyst powder into a beaker, and add nitrates of various metals according to the chemical formula of LNO as described in claim 1, add deionized water and stir to fully disperse, so that the nitrates of various metals are dissolved, then add citric acid and adjust the pH of the mixture to 6-7, then heat and stir to form a gel precursor, and then dry, grind, and calcined at high temperature in sequence to obtain LSCF-LNO surface modified composite catalyst powder.

4. The method for preparing a solid oxide electrolytic cell sheet anode material according to claim 3, wherein: In step (1) or step (2), the ratio of the molar amount of citric acid added to the total molar amount of metal ions in the solution is 2-4:

1.

5. The method for preparing anode material for solid oxide electrolytic cell according to claim 3, wherein: In step (1) or step (2), the heating temperature is 70-85°C.

6. The method for preparing anode material for solid oxide electrolytic cell according to claim 3, wherein: In step (1) or step (2), the drying temperature is 100-250° C., the high-temperature calcination temperature is 900-1100° C., and the calcination time is 2-8 hours.

7. A method for preparing a solid oxide electrolytic cell sheet, characterized in that: The steps include: Step 1: Weigh the LSCF-LNO material according to claim 1 and perform wet grinding in a planetary ball mill to obtain micro-nanoscale LSCF-LNO powder; Step 2: The LSCF-LNO powder, organic solvent, and dispersant after ball milling in step 1 are mixed uniformly in a ball mill to obtain a LSCF-LNO catalyst slurry; Step 3: The LSCF-LNO slurry obtained in step 2 is evenly coated on the surface of the CGO layer of the cathode supporting half electrolytic cell sheet by screen printing, and then calcined at high temperature in an air atmosphere to obtain an electrolytic cell sheet with a LSCF-LNO surface-modified composite anode.

8. The method for preparing a solid oxide electrolytic cell sheet according to claim 7, wherein: In step 1, the ball milling medium in the planetary ball mill is zirconia balls, the mass ratio of LSCF-LNO material powder to zirconia balls is 1:40-60, an appropriate amount of ethanol is added as a solvent during ball milling, the ball milling time is 48 hours, the ball mill speed is 200-400 r / min, and after ball milling, the mixture is dried to evaporate the solvent to obtain the micro-nanoscale LSCF-LNO powder.

9. The method for preparing a solid oxide electrolytic cell sheet according to claim 7, wherein: In step 2, the LSCF-LNO powder is 45-55% by weight, the dispersant is 0.2-0.8%, and the balance is an organic solvent. The dispersant is an acrylic resin, and the organic solvent is terpineol and ethyl cellulose in a mass ratio of 10-20:

1. The ball mill speed is 200-400 r / min, and the ball milling time is 12 h.

10. The method for preparing a solid oxide electrolytic cell sheet according to claim 7, wherein: In step 3, the high temperature calcination temperature is 1000-1200° C., and the calcination time is 1-3 hours.

Images