Electrolytic cell active layer material and its preparation method, and electrolytic cell and its preparation method

Abstract

This invention discloses an active layer material for an electrolytic cell and its preparation method, as well as an electrolytic cell and its preparation method, belonging to the technical field of solid-state electrolytic cells, and employing BaCe. 1‑x Zr x O3 material is coated on the surface of NiO to obtain a nanostructured active layer material NiO-BaCe. 1‑ x Zr x O3, and 0.2 x 0.5; the BaCe 1‑x Zr x O3 materials and active layer material NiO-BaCe 1‑x Zr x The mass ratio of O3 is 30~50 wt.%:1. The active layer material prepared by this invention can effectively inhibit the migration of Ni at high temperatures. At the same time, the active layer material undergoes a solid-state reaction with the cerium-based electrolyte at high temperatures, which can suppress the electronic conductivity of the cerium-based electrolyte. This invention significantly reduces the electronic conductivity of the electrolyte, improves the OCV of the battery, and has better electrochemical performance.

Description

Technical Field

[0001] This invention belongs to the technical field of solid-state electrolytic cells, specifically relating to the active layer material of electrolytic cells and its preparation method, as well as the electrolytic cell and its preparation method. Background Technology

[0002] Solid oxide electrolysis cells (SOECs), as highly efficient energy conversion devices, have become a research hotspot in the field of new energy technology due to their broad application prospects in areas such as hydrogen production and carbon dioxide resource utilization. The core performance of this type of electrolyzer depends on the density, interfacial bonding strength, and structural integrity of its multi-layered structure, including the support, active layer, electrolyte layer, and separator. The fabrication process directly determines the battery's energy conversion efficiency, lifespan, and potential for large-scale application.

[0003] In existing technologies, the preparation of all-solid-state high-temperature co-electrolytes generally employs a multi-layered stepwise sintering process. This involves first sintering the support, active layer, and electrolyte layer separately, followed by the preparation of the isolation layer and subsequent secondary or even multiple sintering processes. Some processes also require the independent sintering of the electrode layer. However, traditional processes have the following drawbacks:

[0004] (1) The battery sintering temperature is high, requiring temperatures above 1400℃ to ensure densification. High-temperature sintering significantly increases energy consumption during the production process.

[0005] (2) Multi-step sintering results in long battery preparation time, high cost of industrial production, and insufficient production capacity;

[0006] (3) High-temperature, long-term, multi-step sintering can easily lead to abnormal growth of material grains, and large grains will result in poor battery strength;

[0007] (4) The active layer of traditional batteries is composed of NiO and oxygen ion conductor ceramic materials. However, under high-temperature sintering, the bonding force between Ni and the ceramic phase is poor, which easily leads to Ni migration under high vapor conditions, ultimately increasing the ohmic resistance of the battery. In addition, the oxygen ion conductor materials have poor adsorption capacity for water vapor, resulting in insufficient electrochemical performance of the electrolytic cell. Summary of the Invention

[0008] The purpose of this invention is to provide an active layer material for an electrolytic cell and a method for preparing the same, as well as an electrolytic cell and a method for preparing the same, in order to solve any of the problems mentioned above.

[0009] This invention is mainly achieved through the following technical solutions:

[0010] The active layer material of the electrolytic cell is BaCe. 1-x Zr xO3 material is coated on the surface of NiO to obtain a nanostructured active layer material NiO-BaCe. 1-x Zr x O3, and 0.2 x 0.5; the BaCe 1-x Zr x O3 materials and active layer material NiO-BaCe 1- x Zr x The mass ratio of O3 is 30~50 wt.%:1. This invention is based on NiO coated with proton-conducting ceramic to prepare the active layer material NiO-BaCe. 1-x Zr x O3 can effectively inhibit the migration of Ni at high temperatures and also has strong water absorption properties, which can enhance the electrochemical performance against water vapor decomposition. All materials are nanostructured, ensuring the co-sintering of multilayer films in the battery at low temperatures.

[0011] This invention is mainly achieved through the following technical solutions:

[0012] A method for preparing an active layer material for an electrolytic cell as described above includes the following steps:

[0013] Step S1: Weigh out the metallic Ni salt and dissolve it in deionized water and anhydrous ethanol to obtain a solution A with a concentration of 0.1~5 mol / L; wherein the volume ratio of deionized water to anhydrous ethanol is 1:1~5.

[0014] Step S2: Add a complexing agent to solution A, stir and mix to obtain solution B, wherein the molar ratio of the complexing agent to nickel ions is 1~2:1;

[0015] Step S3: According to BaCe 1-x Zr x The stoichiometric ratio of O3 material is determined by adding a chloride or nitrate solution of Ba, Ce, and Zr to solution B to obtain solution C;

[0016] Step S4: Heat solution C at 100°C to evaporate water until a viscous gel is obtained; then, dry the gel at 300°C for 20 hours to obtain a dry gel precursor.

[0017] Step S5: Sinter the dry gel precursor at 600~800℃ for 2~10h to obtain the nanostructured active layer material NiO-BaCe. 1-x Zr x O3.

[0018] To better realize the present invention, in step S1, the volume ratio of deionized water to anhydrous ethanol is 1:3.

[0019] To better realize the present invention, in step S2, the complexing agent is any one or more of citric acid, ethylenediaminetetraacetic acid, and ethylene glycol, and the molar ratio of the complexing agent to the nickel ions is 1.5:1.

[0020] To better realize the present invention, in step S5, the sintering temperature of the dry gel precursor is 700°C and the sintering time is 5h.

[0021] This invention is mainly achieved through the following technical solutions:

[0022] An electrolytic cell includes an active layer and an electrolyte layer arranged sequentially. The active layer is prepared based on the active layer material prepared by the above-described method for preparing electrolytic cell active layer material. The electrolyte layer is prepared based on an electrolyte, wherein the electrolyte is an SDC electrolyte.

[0023] This invention is mainly achieved through the following technical solutions:

[0024] A method for preparing an electrolytic cell as described above includes the following steps:

[0025] Step T1: Mix nickel oxide and pure phase ceramic powder, then add organic solvent, binder and dispersant, and roll mill to prepare slurry; degas the obtained slurry and cast it to obtain a film tape with a thickness of 100µm; the pure phase ceramic is 3YSZ, the organic solvent is anhydrous ethanol, and the binder is PVB;

[0026] Step T2: Stack several layers of film strips and hot press them together to prepare a support.

[0027] Step T3: Prepare slurries for the active layer and electrolyte layer based on the active layer material and electrolyte, respectively. Then, after degassing, print the slurries for the active layer and electrolyte layer onto the support and dry them.

[0028] Step T4: After isostatic pressing of several layers of the support body treated in step T3, high-temperature debinding and sintering are performed to obtain a half-cell of all-solid-state electrolytic cell.

[0029] Step T5: Print perovskite electrode paste on the half-cell of the all-solid-state electrolytic cell and sinter it to obtain the all-solid-state high-temperature co-electrolytic cell.

[0030] To better realize the present invention, further, in step T1, the ball-to-material ratio of the roller mill pulping is 1~10:1, preferably 5:1. The roller mill rotation speed is 100-1000 rad / min, preferably 500 rad / min. The roller milling time is 4-6 hours.

[0031] To better realize the present invention, further, in step T1, the pure phase ceramic is 3YSZ, 8YSZ, SSZ, or BaCe. 1-x Zr x The organic solvent is any one of O3; the binder is any one or more of PVB, PVA, or ethyl cellulose; and the pore-forming agent is any one or more of graphite, polymethyl methacrylate, or starch.

[0032] To better realize the present invention, further, in step T2, the thickness of the support is 350~1000µm; in step T3, the thickness of the active layer is 10~15µm; and in step T5, the thickness of the perovskite electrode is 10~30µm.

[0033] To better realize the present invention, further, in step T2, the pressure of the lamination hot pressing is 20 MPa; in step T4, the temperature of the isostatic pressing is 80°C; the sintering temperature is 1400°C, and the heating rate is 2°C / min; in step T5, the sintering temperature is 1100°C. Specifically, in step T2, the pressure of the lamination hot pressing is 3 MPa to 30 MPa; in step T4, the temperature of the isostatic pressing is 50-80°C; the pressure of the high-temperature debinding hot pressing is 40-100 MPa; the sintering temperature is 1100-1500°C, and the heating rate is 0.5-5°C / min, and the cooling rate is 1-5°C / min; in step T5, the sintering temperature is 900-1200°C.

[0034] The beneficial effects of this invention are as follows:

[0035] The active layer material NiO-BaCe prepared in this invention 1-x Zr x O3 can effectively prevent NiO from contacting water vapor, reducing the migration and sintering agglomeration of Ni at high temperatures, while BaCe... 1-x Zr x The high water absorption of O3 materials can enhance the vapor content on the surface of the active layer, thus promoting the electrochemical performance of the battery. Secondly, the active layer material NiO-BaCe in the active layer at high temperatures... 1-x Zr xO3 forms an interfacial diffusion region with the cerium-based electrolyte in the electrolyte layer; simultaneously, the active layer material NiO-BaCe 1-x Zr x O3 reacts with cerium-based electrolytes in a solid-state reaction at high temperatures, which can suppress the electronic conductivity of cerium-based electrolytes, reduce the electronic conductivity of cerium-based electrolytes, improve the OCV of the battery, and exhibit good electrochemical performance. Attached Figure Description

[0036] Figure 1 This is a flowchart of the preparation method of the active layer material of the electrolytic cell of the present invention;

[0037] Figure 2 This is a flowchart of the preparation method of an electrolytic cell;

[0038] Figure 3 SEM images of the active layer materials of the electrolytic cells prepared in Examples 1 to 4 and Comparative Example 1;

[0039] Figure 4 Electrochemical test diagrams of the electrolytic cells prepared in Examples 1 to 6 and Comparative Example 1;

[0040] Figure 5 The image shows the elemental analysis diagrams of the active layer materials of the electrolytic cells prepared in Examples 1 to 4 and Comparative Example 1.

[0041] in: Figure 3 (a) is a SEM image of the active layer material prepared in Example 1;

[0042] Figure 3 (b) is a SEM image of the active layer material prepared in Example 2;

[0043] Figure 3 (c) is a SEM image of the active layer material prepared in Example 3;

[0044] Figure 3 (d) is a SEM image of the active layer material prepared in Example 4;

[0045] Figure 3 (e) is a SEM image of the active layer material prepared in Comparative Example 1;

[0046] Figure 5 (a1), (a2), (a3), and (a4) are the elemental analysis diagrams of Ba, Ce, Zr, and Ni of the active layer material prepared in Example 1, respectively.

[0047] Figure 5 (b1), (b2), (b3), and (b4) are the elemental analysis diagrams of Ba, Ce, Zr, and Ni for the active layer material prepared in Example 2, respectively.

[0048] Figure 5 In the figure, (c1), (c2), (c3) and (c4) are the elemental analysis diagrams of Ba, Ce, Zr and Ni of the active layer material prepared in Example 3, respectively;

[0049] Figure 5 In the figure, (d1), (d2), (d3) and (d4) are the elemental analysis diagrams of Ba, Ce, Zr and Ni of the active layer material prepared in Example 4, respectively;

[0050] Figure 5 In the figure, (e1), (e2) and (e3) are the elemental analysis diagrams of Sm, Ce and Ni of the active layer material prepared in Comparative Example 1, respectively. Detailed Implementation

[0051] Example 1:

[0052] A method for preparing an active layer material for an electrolytic cell, wherein the active layer material is NiO-BaCe. 0.7 Zr 0.3 O3, such as Figure 1 As shown, it includes the following steps:

[0053] (1) Weigh out the metal Ni salt and dissolve it to obtain solution A; taking 1 mol of NiO as an example, weigh out 290.81 g of Ni(NO3)2·6H2O and dissolve it in a solution of deionized water and anhydrous ethanol with a volume ratio of 1:3, and the metal ion concentration is 0.3 mol / L in solution A.

[0054] (2) Add a complexing agent to solution A and mix to obtain solution B; weigh 438.375 g of ethylenediaminetetraacetic acid, add it to solution A, and stir at 200 r / min for 10 h to obtain transparent solution B.

[0055] (3) Add a chloride or nitrate solution of Ba, Ce, and Zr to solution B to obtain solution C; weigh 26.1137 g of barium nitrate, 30.3954 g of cerium nitrate hexahydrate, and 10.177 g of zirconium nitrate, add them to deionized water to prepare a 0.1 mol / L mixed nitrate solution. Add the nitrate solution to the solution in step (2).

[0056] (4) After evaporating the water, dry at high temperature to obtain a dry gel precursor; heat the mixed solution obtained in step (3) at 100°C to evaporate the water to obtain a viscous gel substance, and dry the gel substance at 300°C for 20 hours to obtain a dry gel precursor.

[0057] (5) After sintering, a nanostructured active layer material is obtained; the dry gel obtained in step (4) is sintered at 700℃ for 5 h to obtain BaCe. 0.7 Zr0.3 O3-coated NiO active layer material. At this time, the NiO and BaCe in the active layer material... 0.7 Zr 0.3 The mass ratio of O3 is 7:3, meaning that BaCe in the active layer material... 0.7 Zr 0.3 O3 and active layer material NiO-BaCe 0.7 Zr 0.3 The mass ratio of O3 is 30 wt.% to 1.

[0058] Based on the active layer material prepared above, an all-solid-state high-temperature electrolytic cell is prepared, such as... Figure 2 As shown, it includes the following steps:

[0059] (1) Based on nickel oxide and pure phase ceramic powder, prepare film tape; weigh 100g of 50 nm nickel oxide powder and 100g of 50 nm 3YSZ powder and add them to 200g of anhydrous ethanol, add 4g of triethanolamine dispersant, add 10g of polyvinyl butyral and 10g of dibutyl phthalate, ball mill at 300r / min for 24h to obtain cast support slurry, degas the support slurry and cast it to obtain a support film tape with a thickness of 100µm.

[0060] (2) The membrane strips of several layers are stacked and hot-pressed to prepare a support; the four support membrane strips are stacked together and then pre-pressed at 20 MPa for 120 min to obtain the support.

[0061] (3) After degassing the slurry of the active layer and electrolyte layer, print it onto the support in sequence and dry it;

[0062] 31) Take 100g of NiO-BaCe 0.7 Zr 0.3 O3 and 100g of a terpineol solution containing 10wt.% polyvinyl butyral were mixed and ball-milled for 2h to obtain NiO-BaCe. 0.7 Zr 0.3 O3 active layer paste is used to screen print the active layer onto the surface of the support, which is done 4 times and then dried at 60°C.

[0063] 32) 100g of 50nm SDC was ball-milled with a terpineol solution containing 4wt.% polyvinyl butyral for 2h to obtain SDC electrolyte slurry. The electrolyte was screen-printed onto the surface of the support, printed twice, and dried at 60℃.

[0064] (4) After isostatic pressing, the treated support is subjected to high-temperature debinding and sintering to obtain a half-cell of all-solid-state electrolytic cell;

[0065] 41) The treated support was subjected to isostatic pressing at 400 MPa and 80°C for 100 min.

[0066] 42) The support body after pressure holding is debonded at 1000℃ and then sintered at 1400℃ for 5h to obtain a half cell. The heating and cooling rates are both 2℃ / min.

[0067] (5) Commercially available LSCF-SDC paste was screen-printed onto the surface of the half-cell to obtain the SDC surface, and then sintered at 1100℃ for 2 hours to obtain the full cell. The cell was tested at 700℃ in a 3% H2O and 97% H2 atmosphere, and the OCV was 0.95V. The corresponding current density of the electrolytic cell at 700℃ and 1.3V was 1.02 Acm. -2 .

[0068] Example 2:

[0069] A method for preparing an active layer material for an electrolytic cell, wherein the active layer material is NiO-BaCe. 0.6 Zr 0.4 O3, such as Figure 1 As shown, it includes the following steps:

[0070] (1) Weigh out the metal Ni salt and dissolve it to obtain solution A; taking 1 mol of NiO as an example, weigh out 290.81 g of Ni(NO3)2·6H2O and dissolve it in a solution of deionized water and anhydrous ethanol with a volume ratio of 1:3, and the metal ion concentration is 0.3 mol / L in solution A.

[0071] (2) Add a complexing agent to solution A and mix to obtain solution B; weigh 438.375 g of ethylenediaminetetraacetic acid, add it to solution A, and stir at 200 r / min for 10 h to obtain transparent solution B.

[0072] (3) Add a chloride or nitrate solution of Ba, Ce, and Zr to solution B to obtain solution C; according to BaCe 0.6 Zr 0.4 Weigh out barium nitrate, cerium nitrate hexahydrate, and zirconium nitrate, and add them to deionized water to prepare a 0.1 mol / L mixed nitrate solution. Add the nitrate solution to the solution in step (2).

[0073] (4) After evaporating the water, dry at high temperature to obtain a dry gel precursor; heat the mixed solution obtained in step (3) at 100°C to evaporate the water to obtain a viscous gel substance, and dry the gel substance at 300°C for 20 hours to obtain a dry gel precursor.

[0074] (5) After sintering, a nanostructured active layer material is obtained; the dry gel obtained in step (4) is sintered at 700℃ for 5 h to obtain BaCe. 0.6 Zr 0.4 O3-coated NiO active layer material. At this time, the NiO and BaCe in the active layer material... 0.6 Zr 0.4 The mass ratio of O3 is 7:3, meaning that BaCe in the active layer material... 0.6 Zr 0.4 O3 and active layer material NiO-BaCe 0.6 Zr 0.4 The mass ratio of O3 is 30 wt.% to 1.

[0075] Based on the active layer material prepared above, an all-solid-state high-temperature electrolytic cell is prepared, such as... Figure 2 As shown, it includes the following steps:

[0076] (1) Based on nickel oxide and pure phase ceramic powder, prepare film tape; weigh 100g of 50 nm nickel oxide powder and 100g of 50 nm 3YSZ powder and add them to 200g of anhydrous ethanol, add 4g of triethanolamine dispersant, add 10g of polyvinyl butyral and 10g of dibutyl phthalate, ball mill at 300r / min for 24h to obtain cast support slurry, degas the support slurry and cast it to obtain a support film tape with a thickness of 100µm.

[0077] (2) The membrane strips of several layers are stacked and hot-pressed to prepare a support; the four support membrane strips are stacked together and then pre-pressed at 20 MPa for 120 min to obtain the support.

[0078] (3) After degassing the slurry of the active layer and electrolyte layer, print it onto the support in sequence and dry it;

[0079] 31) Take 100g of NiO-BaCe 0.6 Zr 0.4 O3 and 100g of a terpineol solution containing 10wt.% polyvinyl butyral were mixed and ball-milled for 2h to obtain NiO-BaCe. 0.6 Zr 0.4 O3 active layer paste is used to screen print the active layer onto the surface of the support, which is done 4 times and then dried at 60°C.

[0080] 32) 100g of 50nm SDC was ball-milled with a terpineol solution containing 4wt.% polyvinyl butyral for 2h to obtain SDC electrolyte slurry. The electrolyte was screen-printed onto the surface of the support, printed twice, and dried at 60℃.

[0081] (4) After isostatic pressing, the treated support is subjected to high-temperature debinding and sintering to obtain a half-cell of all-solid-state electrolytic cell;

[0082] 41) The treated support was subjected to isostatic pressing at 400 MPa and 80°C for 100 min.

[0083] 42) The support body after pressure holding is debonded at 1000℃ and then sintered at 1400℃ for 5h to obtain a half cell. The heating and cooling rates are both 2℃ / min.

[0084] (5) Commercially available LSCF-SDC paste was screen-printed onto the surface of the half-cell to obtain the SDC, and then sintered at 1100℃ for 2 hours to obtain the full cell. The cell's OCV was measured at 700℃ in an atmosphere of 3% H2O and 97% H2, with a corresponding current density of 0.93 Acm at 1.3V. -2 .

[0085] Example 3:

[0086] A method for preparing an active layer material for an electrolytic cell, wherein the active layer material is NiO-BaCe. 0.5 Zr 0.5 O3, such as Figure 1 As shown, it includes the following steps:

[0087] (1) Weigh out the metal Ni salt and dissolve it to obtain solution A; taking 1 mol of NiO as an example, weigh out 290.81 g of Ni(NO3)2·6H2O and dissolve it in a solution of deionized water and anhydrous ethanol with a volume ratio of 1:3, and the metal ion concentration is 0.3 mol / L in solution A.

[0088] (2) Add a complexing agent to solution A and mix to obtain solution B; weigh 438.375 g of ethylenediaminetetraacetic acid, add it to solution A, and stir at 200 r / min for 10 h to obtain transparent solution B.

[0089] (3) Add a chloride or nitrate solution of Ba, Ce, and Zr to solution B to obtain solution C; according to BaCe 0.5 Zr 0.5 Weigh out barium nitrate, cerium nitrate hexahydrate, and zirconium nitrate, and add them to deionized water to prepare a 0.1 mol / L mixed nitrate solution. Add the nitrate solution to the solution in step (2).

[0090] (4) After evaporating the water, dry at high temperature to obtain a dry gel precursor; heat the mixed solution obtained in step (3) at 100°C to evaporate the water to obtain a viscous gel substance, and dry the gel substance at 300°C for 20 hours to obtain a dry gel precursor.

[0091] (5) After sintering, a nanostructured active layer material is obtained; the dry gel obtained in step (4) is sintered at 700℃ for 5 h to obtain BaCe. 0.5 Zr 0.5 O3-coated NiO active layer material. At this time, the NiO and BaCe in the active layer material... 0.5 Zr 0.5 The mass ratio of O3 is 7:3, meaning that BaCe in the active layer material... 0.5 Zr 0.5 O3 and active layer material NiO-BaCe 0.5 Zr 0.5 The mass ratio of O3 is 30 wt.% to 1.

[0092] Based on the active layer material prepared above, an all-solid-state high-temperature electrolytic cell is prepared, such as... Figure 2 As shown, it includes the following steps:

[0093] (1) Based on nickel oxide and pure phase ceramic powder, prepare film tape; weigh 100g of 50 nm nickel oxide powder and 100g of 50 nm 3YSZ powder and add them to 200g of anhydrous ethanol, add 4g of triethanolamine dispersant, add 10g of polyvinyl butyral and 10g of dibutyl phthalate, ball mill at 300r / min for 24h to obtain cast support slurry, degas the support slurry and cast it to obtain a support film tape with a thickness of 100µm.

[0094] (2) The membrane strips of several layers are stacked and hot-pressed to prepare a support; the four support membrane strips are stacked together and then pre-pressed at 20 MPa for 120 min to obtain the support.

[0095] (3) After degassing the slurry of the active layer and electrolyte layer, print it onto the support in sequence and dry it;

[0096] 31) Take 100g of NiO-BaCe 0.5 Zr 0.5 O3 and 100g of a terpineol solution containing 10wt.% polyvinyl butyral were mixed and ball-milled for 2h to obtain NiO-BaCe. 0.5 Zr 0.5 O3 active layer paste is used to screen print the active layer onto the surface of the support, which is done 4 times and then dried at 60°C.

[0097] 32) 100g of 50nm SDC was ball-milled with a terpineol solution containing 4wt.% polyvinyl butyral for 2h to obtain SDC electrolyte slurry. The electrolyte was screen-printed onto the surface of the support, printed twice, and dried at 60℃.

[0098] (4) After isostatic pressing, the treated support is subjected to high-temperature debinding and sintering to obtain a half-cell of all-solid-state electrolytic cell;

[0099] 41) The treated support was subjected to isostatic pressing at 400 MPa and 80°C for 100 min.

[0100] 42) The support body after pressure holding is debonded at 1000℃ and then sintered at 1400℃ for 5h to obtain a half cell. The heating and cooling rates are both 2℃ / min.

[0101] (5) Commercially available LSCF-SDC paste was screen-printed onto the surface of the half-cell to obtain the SDC, and then sintered at 1100℃ for 2 hours to obtain the full cell. The cell's OCV was measured to be 0.92 in an atmosphere of 3% H2O and 97% H2 at 700℃, corresponding to a current density of 0.83 Acm at 1.3V. -2 .

[0102] Example 4:

[0103] A method for preparing an active layer material for an electrolytic cell, wherein the active layer material is NiO-BaCe. 0.8 Zr 0.2 O3, such as Figure 1 As shown, it includes the following steps:

[0104] (1) Weigh out the metal Ni salt and dissolve it to obtain solution A; taking 1 mol of NiO as an example, weigh out 290.81 g of Ni(NO3)2·6H2O and dissolve it in a solution of deionized water and anhydrous ethanol with a volume ratio of 1:3, and the metal ion concentration is 0.3 mol / L in solution A.

[0105] (2) Add a complexing agent to solution A and mix to obtain solution B; weigh 438.375 g of ethylenediaminetetraacetic acid, add it to solution A, and stir at 200 r / min for 10 h to obtain transparent solution B.

[0106] (3) Add a chloride or nitrate solution of Ba, Ce, and Zr to solution B to obtain solution C; according to BaCe 0.8 Zr 0.2 O3, corresponding to the weighing of barium nitrate, cerium nitrate hexahydrate, and zirconium nitrate, is added to deionized water to prepare a 0.1 mol / L mixed nitrate solution. The nitrate solution is then added to the solution in step (2).

[0107] (4) After evaporating the water, dry at high temperature to obtain a dry gel precursor; heat the mixed solution obtained in step (3) at 100°C to evaporate the water to obtain a viscous gel substance, and dry the gel substance at 300°C for 20 hours to obtain a dry gel precursor.

[0108] (5) After sintering, a nanostructured active layer material is obtained; the dry gel obtained in step (4) is sintered at 700℃ for 5 h to obtain BaCe. 0.8 Zr 0.2 O3-coated NiO active layer material. At this time, the NiO and BaCe in the active layer material... 0.8 Zr 0.2 The mass ratio of O3 is 7:3, which means that BaCe in the active layer material... 0.8 Zr 0.2 O3 and active layer material NiO-BaCe 0.8 Zr 0.2 The mass ratio of O3 is 30 wt.% to 1.

[0109] Based on the active layer material prepared above, an all-solid-state high-temperature electrolytic cell is prepared, such as... Figure 2 As shown, it includes the following steps:

[0110] (1) Based on nickel oxide and pure phase ceramic powder, prepare film tape; weigh 100g of 50 nm nickel oxide powder and 100g of 50 nm 3YSZ powder and add them to 200g of anhydrous ethanol, add 4g of triethanolamine dispersant, add 10g of polyvinyl butyral and 10g of dibutyl phthalate, ball mill at 300r / min for 24h to obtain cast support slurry, degas the support slurry and cast it to obtain a support film tape with a thickness of 100µm.

[0111] (2) The membrane strips of several layers are stacked and hot-pressed to prepare a support; the four support membrane strips are stacked together and then pre-pressed at 20 MPa for 120 min to obtain the support.

[0112] (3) After degassing the slurry of the active layer and electrolyte layer, print it onto the support in sequence and dry it;

[0113] 31) Take 100g of NiO-BaCe 0.8 Zr 0.2 O3 and 100g of a terpineol solution containing 10wt.% polyvinyl butyral were mixed and ball-milled for 2h to obtain NiO-BaCe. 0.8 Zr 0.2 O3 active layer paste is used to screen print the active layer onto the surface of the support, which is done 4 times and then dried at 60°C.

[0114] 32) 100g of 50nm SDC was ball-milled with a terpineol solution containing 4wt.% polyvinyl butyral for 2h to obtain SDC electrolyte slurry. The electrolyte was screen-printed onto the surface of the support, printed twice, and dried at 60℃.

[0115] (4) After isostatic pressing, the treated support is subjected to high-temperature debinding and sintering to obtain a half-cell of all-solid-state electrolytic cell;

[0116] 41) The treated support was subjected to isostatic pressing at 400 MPa and 80°C for 100 min.

[0117] 42) The support body after pressure holding is debonded at 1000℃ and then sintered at 1400℃ for 5h to obtain a half cell. The heating and cooling rates are both 2℃ / min.

[0118] (5) Commercially available LSCF-SDC paste was screen-printed onto the surface of the half-cell to obtain the SDC, and then sintered at 1100℃ for 2 hours to obtain the full cell. The cell's OCV was measured to be 0.92 in an atmosphere of 3% H2O and 97% H2 at 700℃, corresponding to a current density of 0.88 Acm at 1.3V. -2 .

[0119] Example 5:

[0120] A method for preparing an active layer material for an electrolytic cell, wherein the active layer material is NiO-BaCe. 0.5 Zr 0.5 O3, such as Figure 1 As shown, it includes the following steps:

[0121] (1) Weigh out the metal Ni salt and dissolve it to obtain solution A; taking 1 mol of NiO as an example, weigh out 290.81 g of Ni(NO3)2·6H2O and dissolve it in a solution of deionized water and anhydrous ethanol with a volume ratio of 1:3, and the metal ion concentration is 0.3 mol / L in solution A.

[0122] (2) Add a complexing agent to solution A and mix to obtain solution B; weigh 438.375 g of ethylenediaminetetraacetic acid, add it to solution A, and stir at 200 r / min for 10 h to obtain transparent solution B.

[0123] (3) Add a chloride or nitrate solution of Ba, Ce, and Zr to solution B to obtain solution C; according to BaCe 0.5 Zr 0.5 Weigh out barium nitrate, cerium nitrate hexahydrate, and zirconium nitrate, and add them to deionized water to prepare a 0.1 mol / L mixed nitrate solution. Add the nitrate solution to the solution in step (2).

[0124] (4) After evaporating the water, dry at high temperature to obtain a dry gel precursor; heat the mixed solution obtained in step (3) at 100°C to evaporate the water to obtain a viscous gel substance, and dry the gel substance at 300°C for 20 hours to obtain a dry gel precursor.

[0125] (5) After sintering, a nanostructured active layer material is obtained; the dry gel obtained in step (4) is sintered at 700℃ for 5 h to obtain BaCe. 0.5 Zr 0.5 O3-coated NiO active layer material. At this time, the NiO and BaCe in the active layer material... 0.5 Zr 0.5 The mass ratio of O3 is 6:4, which means that BaCe in the active layer material... 0.5 Zr 0.5 O3 and active layer material NiO-BaCe 0.5 Zr 0.5 The mass ratio of O3 is 40 wt.% to 1.

[0126] Based on the active layer material prepared above, an all-solid-state high-temperature electrolytic cell is prepared, such as... Figure 2 As shown, it includes the following steps:

[0127] (1) Based on nickel oxide and pure phase ceramic powder, prepare film tape; weigh 100g of 50 nm nickel oxide powder and 100g of 50 nm 3YSZ powder and add them to 200g of anhydrous ethanol, add 4g of triethanolamine dispersant, add 10g of polyvinyl butyral and 10g of dibutyl phthalate, ball mill at 300r / min for 24h to obtain cast support slurry, degas the support slurry and cast it to obtain a support film tape with a thickness of 100µm.

[0128] (2) The membrane strips of several layers are stacked and hot-pressed to prepare a support; the four support membrane strips are stacked together and then pre-pressed at 20 MPa for 120 min to obtain the support.

[0129] (3) After degassing the slurry of the active layer and electrolyte layer, print it onto the support in sequence and dry it;

[0130] 31) Take 100g of NiO-BaCe 0.5 Zr 0.5 O3 and 100g of a terpineol solution containing 10wt.% polyvinyl butyral were mixed and ball-milled for 2h to obtain NiO-BaCe. 0.5 Zr 0.5 O3 active layer paste is used to screen print the active layer onto the surface of the support, which is done 4 times and then dried at 60°C.

[0131] 32) 100g of 50nm SDC was ball-milled with a terpineol solution containing 4wt.% polyvinyl butyral for 2h to obtain SDC electrolyte slurry. The electrolyte was screen-printed onto the surface of the support, printed twice, and dried at 60℃.

[0132] (4) After isostatic pressing, the treated support is subjected to high-temperature debinding and sintering to obtain a half-cell of all-solid-state electrolytic cell;

[0133] 41) The treated support was subjected to isostatic pressing at 400 MPa and 80°C for 100 min.

[0134] 42) The support body after pressure holding is debonded at 1000℃ and then sintered at 1400℃ for 5h to obtain a half cell. The heating and cooling rates are both 2℃ / min.

[0135] (5) Commercially available LSCF-SDC paste was screen-printed onto the surface of the half-cell to obtain the SDC, and then sintered at 1100℃ for 2 hours to obtain the full cell. The cell's OCV was 0.95 in an atmosphere of 3% H2O and 97% H2 at 700℃. The corresponding current density of the electrolytic cell at 700℃ and 1.3V was 0.75 Acm. -2 .

[0136] Example 6:

[0137] A method for preparing an active layer material for an electrolytic cell, wherein the active layer material is NiO-BaCe. 0.5 Zr 0.5 O3, such as Figure 1 As shown, it includes the following steps:

[0138] (1) Weigh out the metal Ni salt and dissolve it to obtain solution A; taking 1 mol of NiO as an example, weigh out 290.81 g of Ni(NO3)2·6H2O and dissolve it in a solution of deionized water and anhydrous ethanol with a volume ratio of 1:3, and the metal ion concentration is 0.3 mol / L in solution A.

[0139] (2) Add a complexing agent to solution A and mix to obtain solution B; weigh 438.375 g of ethylenediaminetetraacetic acid, add it to solution A, and stir at 200 r / min for 10 h to obtain transparent solution B.

[0140] (3) Add a chloride or nitrate solution of Ba, Ce, and Zr to solution B to obtain solution C; according to BaCe 0.5 Zr 0.5 Weigh out barium nitrate, cerium nitrate hexahydrate, and zirconium nitrate, and add them to deionized water to prepare a 0.1 mol / L mixed nitrate solution. Add the nitrate solution to the solution in step (2).

[0141] (4) After evaporating the water, dry at high temperature to obtain a dry gel precursor; heat the mixed solution obtained in step (3) at 100°C to evaporate the water to obtain a viscous gel substance, and dry the gel substance at 300°C for 20 hours to obtain a dry gel precursor.

[0142] (5) After sintering, a nanostructured active layer material is obtained; the dry gel obtained in step (4) is sintered at 700℃ for 5 h to obtain BaCe. 0.5 Zr 0.5 O3-coated NiO active layer material. At this time, the NiO and BaCe in the active layer material... 0.5 Zr 0.5 The mass ratio of O3 is 5:5, meaning that BaCe in the active layer material... 0.5 Zr 0.5 O3 and active layer material NiO-BaCe 0.5 Zr 0.5 The mass ratio of O3 is 50 wt.% to 1.

[0143] Based on the active layer material prepared above, an all-solid-state high-temperature electrolytic cell is prepared, such as... Figure 2 As shown, it includes the following steps:

[0144] (1) Based on nickel oxide and pure phase ceramic powder, prepare film tape; weigh 100g of 50 nm nickel oxide powder and 100g of 50 nm 3YSZ powder and add them to 200g of anhydrous ethanol, add 4g of triethanolamine dispersant, add 10g of polyvinyl butyral and 10g of dibutyl phthalate, ball mill at 300r / min for 24h to obtain cast support slurry, degas the support slurry and cast it to obtain a support film tape with a thickness of 100µm.

[0145] (2) The membrane strips of several layers are stacked and hot-pressed to prepare a support; the four support membrane strips are stacked together and then pre-pressed at 20 MPa for 120 min to obtain the support.

[0146] (3) After degassing the slurry of the active layer and electrolyte layer, print it onto the support in sequence and dry it;

[0147] 31) Take 100g of NiO-BaCe 0.5 Zr 0.5 O3 and 100g of a terpineol solution containing 10wt.% polyvinyl butyral were mixed and ball-milled for 2h to obtain NiO-BaCe. 0.5 Zr 0.5 O3 active layer paste is used to screen print the active layer onto the surface of the support, which is done 4 times and then dried at 60°C.

[0148] 32) 100g of 50nm SDC was ball-milled with a terpineol solution containing 4wt.% polyvinyl butyral for 2h to obtain SDC electrolyte slurry. The electrolyte was screen-printed onto the surface of the support, printed twice, and dried at 60℃.

[0149] (4) After isostatic pressing, the treated support is subjected to high-temperature debinding and sintering to obtain a half-cell of all-solid-state electrolytic cell;

[0150] 41) The treated support was subjected to isostatic pressing at 400 MPa and 80°C for 100 min.

[0151] 42) The support body after pressure holding is debonded at 1000℃ and then sintered at 1400℃ for 5h to obtain a half cell. The heating and cooling rates are both 2℃ / min.

[0152] (5) Commercially available LSCF-SDC paste was screen-printed onto the surface of the half-cell to obtain the SDC, and then sintered at 1100℃ for 2 hours to obtain the full cell. The cell's OCV was measured to be 0.94 in an atmosphere of 3% H2O and 97% H2 at 700℃, corresponding to a current density of 0.69 Acm at 1.3V. -2 .

[0153] Comparative Example 1:

[0154] A method for preparing an active layer material for an electrolytic cell, wherein the active layer material is NiO-SDC, such as... Figure 1 As shown, it includes the following steps:

[0155] (1) Weigh out the metal Ni salt and dissolve it to obtain solution A; taking 1 mol of NiO as an example, weigh out 290.81 g of Ni(NO3)2·6H2O and dissolve it in a solution of deionized water and anhydrous ethanol with a volume ratio of 1:3, and the metal ion concentration is 0.3 mol / L in solution A.

[0156] (2) Add a complexing agent to solution A and mix to obtain solution B; weigh 438.375 g of ethylenediaminetetraacetic acid, add it to solution A, and stir at 200 r / min for 10 h to obtain transparent solution B.

[0157] (3) Add SDC to solution B to obtain solution C;

[0158] (4) After evaporating the water, dry at high temperature to obtain a dry gel precursor; heat the mixed solution obtained in step (3) at 100°C to evaporate the water to obtain a viscous gel substance, and dry the gel substance at 300°C for 20 hours to obtain a dry gel precursor.

[0159] (5) After sintering, a nanostructured active layer material is obtained; the dry gel obtained in step (4) is sintered at 700℃ for 5h to obtain an active layer material of NiO coated with SDC. At this time, the mass ratio of NiO to SDC in the active layer material is 6:4.

[0160] Based on the active layer material prepared above, an all-solid-state high-temperature electrolytic cell is prepared, such as... Figure 2 As shown, it includes the following steps:

[0161] (1) Based on nickel oxide and pure phase ceramic powder, prepare film tape; weigh 100g of 50 nm nickel oxide powder and 100g of 50 nm 3YSZ powder and add them to 200g of anhydrous ethanol, add 4g of triethanolamine dispersant, add 10g of polyvinyl butyral and 10g of dibutyl phthalate, ball mill at 300r / min for 24h to obtain cast support slurry, degas the support slurry and cast it to obtain a support film tape with a thickness of 100µm.

[0162] (2) The membrane strips of several layers are stacked and hot-pressed to prepare a support; the four support membrane strips are stacked together and then pre-pressed at 20 MPa for 120 min to obtain the support.

[0163] (3) After degassing the slurry of the active layer and electrolyte layer, print it onto the support in sequence and dry it;

[0164] 31) Mix 100g of NiO-SDC and 100g of terpineol solution containing 10wt.% polyvinyl butyral and ball mill for 2h to obtain NiO-SDC active layer slurry. Screen print the active layer onto the surface of the support, print 4 times, and dry at 60℃.

[0165] 32) 100g of 50nm SDC was ball-milled with a terpineol solution containing 4wt.% polyvinyl butyral for 2h to obtain SDC electrolyte slurry. The electrolyte was screen-printed onto the surface of the support, printed twice, and dried at 60℃.

[0166] (4) After isostatic pressing, the treated support is subjected to high-temperature debinding and sintering to obtain a half-cell of all-solid-state electrolytic cell;

[0167] 41) The treated support was subjected to isostatic pressing at 400 MPa and 80°C for 100 min.

[0168] 42) The support body after pressure holding is debonded at 1000℃ and then sintered at 1400℃ for 5h to obtain a half cell. The heating and cooling rates are both 2℃ / min.

[0169] (5) Commercially available LSCF-SDC paste was screen-printed onto the surface of the half-cell to obtain the SDC, and then sintered at 1100℃ for 2 hours to obtain the full cell. The cell's OCV was tested at 700℃ in an atmosphere of 3% H2O and 97% H2, and the corresponding current density of the electrolytic cell at 700℃ and 1.3V was 0.58 Acm. -2 .

[0170] like Figure 3 (a) ~ Figure 3 As shown in (d), the active layer materials prepared in Examples 1 to 4 have a compact structure and many nanoparticles on their surface. These nanoparticles are coated on the Ni surface, such as... Figure 5 (a1) ~ Figure 5 As shown in (d4), the active layer materials prepared in Examples 1 to 4 have a uniform distribution of Ba, Ce, Zr and Ni elements, which can increase the three-phase interface of the electrode and improve the activity of the electrode.

[0171] like Figure 3 As shown in (e), the active layer material prepared in Comparative Example 1 has a sheet-like structure, and the bonding force between Ni and the ceramic phase is poor. Figure 5 As shown in (e1), (e2) and (e3), the active layer material prepared in Comparative Example 1 has a uniform distribution of Sm, Ce and Ni elements.

[0172] As shown in Table 1, Examples 1-6 exhibit good electrochemical performance, such as... Figure 4 As shown, the electrolytic cell prepared in Example 1 can achieve a maximum current density of 1.02 A cm⁻¹ at 700°C and 1.3V. -2 The corresponding battery has an OCV of 0.95V at 700℃, while the battery in Comparative Example 1, which contains a NiO / SDC active layer, has an OCV of only 0.72V, and the corresponding electrolytic cell current density is only 0.58A cm⁻¹. -2 This is mainly due to the electronic conductivity of SDC. Examples 1-6 confirm that when the active layer NiO-BaCe is introduced... 1-x Zr x After O3 treatment, the OCV of the electrolytic cell was above 0.9V, indicating that an electron-blocking intermediate phase was generated in situ within the battery, and that an active layer NiO-BaCe was introduced. 1-x Zr x The current density of the electrolytic cell after O3 at 1.3V is higher than that of Comparative Example 1. This invention uses the proton-conducting ceramic BaCe. 1-x Zr x O3-coated NiO serves as the active layer, significantly improving the performance of existing electrolytic cells and demonstrating good practicality.

[0173] Table 1

[0174]

[0175] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention in any way. Any simple modifications or equivalent changes made to the above embodiments based on the technical essence of the present invention shall fall within the protection scope of the present invention.

Claims

1. An active layer material for an electrolytic cell, characterized in that, BaCe 1-x Zr x O3 material is coated on the surface of NiO to obtain a nanostructured active layer material NiO-BaCe. 1-x Zr x O3, and 0.2 x 0.5; the BaCe 1-x Zr x O3 materials and active layer material NiO-BaCe 1-x Zr x The mass ratio of O3 is 30~50 wt.%:

1.

2. A method for preparing the active layer material of an electrolytic cell as described in claim 1, characterized in that, Includes the following steps: Step S1: Weigh out the metallic Ni salt and dissolve it in deionized water and anhydrous ethanol to obtain a solution A with a concentration of 0.1~5 mol / L; wherein the volume ratio of deionized water to anhydrous ethanol is 1:1~5. Step S2: Add a complexing agent to solution A, stir and mix to obtain solution B, wherein the molar ratio of the complexing agent to nickel ions is 1~2:1; Step S3: According to BaCe 1-x Zr x The stoichiometric ratio of O3 material is determined by adding a chloride or nitrate solution of Ba, Ce, and Zr to solution B to obtain solution C; Step S4: Heat solution C at 100°C to evaporate water until a viscous gel is obtained; then, dry the gel at 300°C for 20 hours to obtain a dry gel precursor. Step S5: Sinter the dry gel precursor at 600~800℃ for 2~10h to obtain the nanostructured active layer material NiO-BaCe. 1-x Zr x O3.

3. The method for preparing the active layer material of the electrolytic cell according to claim 2, characterized in that, In step S1, the volume ratio of deionized water to anhydrous ethanol is 1:

3.

4. The method for preparing the active layer material of the electrolytic cell according to claim 2, characterized in that, In step S2, the complexing agent is any one or more of citric acid, ethylenediaminetetraacetic acid, and ethylene glycol, and the molar ratio of the complexing agent to nickel ions is 1.5:

1.

5. The method for preparing the active layer material of the electrolytic cell according to claim 2, characterized in that, In step S5, the sintering temperature of the dry gel precursor is 700°C and the sintering time is 5 hours.

6. An electrolytic cell, characterized in that, It includes an active layer and an electrolyte layer arranged sequentially. The active layer is prepared based on the active layer material prepared by the method for preparing the active layer material of the electrolytic cell according to any one of claims 2-5. The electrolyte layer is prepared based on an electrolyte, wherein the electrolyte is an SDC electrolyte.

7. A method for preparing an electrolytic cell as described in claim 6, characterized in that, Includes the following steps: Step T1: Mix nickel oxide and pure phase ceramic powder, then add organic solvent, binder and dispersant, and roll mill to prepare slurry; degas the obtained slurry and cast it to obtain a film tape with a thickness of 100µm; the pure phase ceramic is 3YSZ, the organic solvent is anhydrous ethanol, and the binder is PVB; Step T2: Stack several layers of film strips and hot press them together to prepare a support. Step T3: Prepare slurries for the active layer and electrolyte layer based on the active layer material and electrolyte, respectively. Then, after degassing, print the slurries for the active layer and electrolyte layer onto the support and dry them. Step T4: After isostatic pressing of several layers of the support body treated in step T3, high-temperature debinding and sintering are performed to obtain a half-cell of all-solid-state electrolytic cell. Step T5: Print perovskite electrode paste on the half-cell of the all-solid-state electrolytic cell and sinter it to obtain the all-solid-state high-temperature co-electrolytic cell.

8. The method for preparing an electrolytic cell according to claim 7, characterized in that, In step T2, the pressure of the stacked hot pressing is 20 MPa; in step T4, the temperature of the isostatic pressing is 80°C; the sintering temperature is 1400°C and the heating rate is 2°C / min; in step T5, the sintering temperature is 1100°C.

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