A method for producing a current collecting layer of a ceramic-supported solid oxide cell

Abstract

The application discloses a preparation method of a current collecting layer of a ceramic support type solid oxide cell, and comprises the following steps: preparing a solid oxide cell substrate, mixing a silver nitrate solution and a dilute ammonia solution to obtain a silver-ammonia solution; treating the surface of a ceramic support of the solid oxide cell substrate with a sodium hydroxide solution first, then performing drying treatment, immersing the ceramic support in the silver-ammonia solution, adding a glucose solution to form a silver plating layer under water bath conditions, and then performing drying treatment; and performing high-temperature calcination on the formed silver plating layer of the solid oxide cell to prepare a silver layer on the surface of the ceramic support of the solid oxide cell, and the silver layer is the current collecting layer. The silver mirror reaction is utilized to form a silver layer with high conductivity in the ceramic support, an electrically conductive path is established between the electrode and the external circuit through the silver layer, the generated current is effectively collected and led out to the external circuit, and the internal resistance of the cell is reduced.

Description

Technical Field

[0001] This invention belongs to the field of solid oxide battery technology, specifically relating to a method for preparing a current collection layer in a ceramic-supported solid oxide battery. Background Technology

[0002] Against the backdrop of accelerated global energy transition, the large-scale consumption and efficient storage of renewable energy have become key challenges in achieving the "dual carbon" goal. Renewable energy sources such as solar and wind power are intermittent and fluctuating, necessitating energy conversion technologies to transform them into storable and easily transportable chemical energy carriers (such as hydrogen and synthetic fuels). Solid oxide cells (SOCs), as energy conversion devices with highly reversible characteristics, can flexibly switch between fuel cell mode (SOFC) and electrolyzer mode (SOEC), providing an ideal solution for the bidirectional conversion of renewable electricity and chemical energy. A solid oxide fuel cell consists of a fuel electrode, an air electrode, and an electrolyte. The electrolyte isolates the fuel and air at the fuel electrode and air electrode, respectively.

[0003] In the power generation mode (FC mode), under the influence of the chemical potential difference between the two electrodes, oxygen ions are transported to the anode through the electrolyte and react with the fuel at the fuel electrode (anode) to generate water and electrons. The electrons do work through the electrical appliances in the external circuit, forming a closed loop. In the electrolysis mode (EC mode), a certain electrolysis voltage is applied between the two electrodes of the electrolytic cell. Driven by this voltage, H2O dissociates into H2 and consumes electrons to generate oxygen ions. The oxygen ions are transported to the air electrode through the electrolyte and undergo an electrochemical reaction to release electrons and generate oxygen. The released electrons are then transported to the fuel electrode through the external circuit.

[0004] Therefore, both the air electrode and the fuel electrode must possess certain electronic and ionic conductivity to ensure efficient and stable reactions in both modes. In solid oxide electrode-supported batteries (including fuel electrode-supported and air electrode-supported batteries), porous pure ceramic support structures offer good mechanical strength and chemical compatibility, and the support material has low cost. However, the low electronic conductivity of porous ceramic support materials prevents effective current collection during battery operation. Therefore, designing and developing efficient current collection methods is crucial for achieving high-performance ceramic-supported solid oxide batteries and is of great significance. Summary of the Invention

[0005] The purpose of this invention is to provide a method for preparing a current collection layer for a ceramic-supported solid oxide battery. By utilizing a silver mirror reaction, a highly conductive silver layer is formed in the ceramic support. The silver layer establishes a conductive path between the electrode and the external circuit, effectively collecting the current generated during battery operation and exporting it to the external circuit.

[0006] To achieve the above objectives, this invention discloses a method for preparing a current collection layer in a ceramic-supported solid oxide battery, comprising the following steps:

[0007] (1) Preparation of solid oxide battery substrate;

[0008] (2) Prepare silver nitrate solution, dilute ammonia solution, sodium hydroxide solution and glucose solution;

[0009] (3) The silver nitrate solution is mixed with the dilute ammonia solution to obtain a silver ammonia solution;

[0010] (4) The surface of the ceramic support of the solid oxide battery substrate is first treated with sodium hydroxide solution, then dried, then immersed in silver ammonia solution, glucose solution is added and reduced under water bath conditions to form a silver plating layer, and then dried.

[0011] (5) The solid oxide battery with the formed silver plating layer is calcined at high temperature to obtain a silver layer on the surface of the ceramic support of the solid oxide battery, wherein the silver layer is a current collection layer.

[0012] Preferably, the silver nitrate solution contains 3%-7% silver nitrate by mass, the dilute ammonia solution is prepared from concentrated ammonia solution containing 2%-4% by mass, the sodium hydroxide solution contains 3%-7% sodium hydroxide by mass, and the glucose solution contains 3%-7% glucose by mass.

[0013] Preferably, the silver nitrate solution contains 5% silver nitrate by mass, the dilute ammonia solution is prepared from 3% concentrated ammonia by mass, the sodium hydroxide solution contains 5% sodium hydroxide by mass, and the glucose solution contains 5% glucose by mass.

[0014] Preferably, in step (3), dilute ammonia is added dropwise to the silver nitrate solution until the initially generated precipitate is completely dissolved to prepare a silver ammonia solution.

[0015] Preferably, in step (4), the reaction temperature under the water bath conditions is 70-90℃ and the time is 20-40 min; the drying temperature is 70-90℃.

[0016] Preferably, in step (4), the reaction temperature under the water bath condition is 80°C and the time is 30 min; the temperature of the drying treatment is 80°C.

[0017] Preferably, in step (5), the high-temperature calcination temperature is 800-900℃ and the time is 2-4 h.

[0018] Preferably, in step (5), the high-temperature calcination temperature is 850°C and the time is 3 hours.

[0019] Preferably, the ceramic support is a finger-shaped porous ceramic support structure.

[0020] The present invention also proposes a solid oxide battery, wherein a current collection layer prepared by the above preparation method is disposed on the ceramic support of the solid oxide battery.

[0021] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0022] This invention utilizes a silver mirror reaction to form a highly conductive silver layer in a finger-shaped porous ceramic support structure. The silver layer establishes a conductive path between the electrode and the external circuit, effectively collecting and discharging the current generated during battery operation to the external circuit, and also reducing the battery's internal resistance.

[0023] The silver mirror reaction in this invention is simple to implement and operates under mild conditions, effectively solving the problem of difficult current collection efficiency in ceramic-supported solid oxide batteries. Attached Figure Description

[0024] Figure 1 This is a comparison of the support side before and after the current collection layer of the ceramic-supported solid oxide battery is prepared according to the present invention;

[0025] Figure 2 These are SEM cross-sectional images of the current collection layer of the ceramic-supported solid oxide battery in this invention at different magnifications (a: scale of 40 μm; b: scale of 200 nm; c: scale of 100 nm).

[0026] Figure 3 This is the EDS energy spectrum of the current collection layer of the ceramic-supported solid oxide battery in this invention;

[0027] Figure 4 These are the IVP diagrams (a) and (b) of the solid oxide battery in SOFC mode and SOEC mode after the current collection layer is prepared in this invention. Detailed Implementation

[0028] The invention will now be further described with reference to the accompanying drawings.

[0029] Example 1:

[0030] Preparation of silver nitrate solution: Add about 20 mL of distilled water to a beaker, add 5% wt of silver nitrate according to the mass ratio, stir to dissolve, and obtain silver nitrate solution.

[0031] Preparation of dilute ammonia solution: Add about 20 mL of distilled water to a beaker, add 3% wt of concentrated ammonia solution according to the mass ratio, stir to dissolve, and obtain dilute ammonia solution.

[0032] Preparation of sodium hydroxide solution: Add about 20 mL of distilled water to a beaker, add 5% wt of anhydrous sodium hydroxide according to the mass ratio, stir to dissolve, and obtain a dilute sodium hydroxide solution.

[0033] Preparation of glucose solution: Add about 20 mL of distilled water to a beaker, add 5% wt of anhydrous glucose according to the mass ratio, stir to dissolve, and obtain glucose solution.

[0034] Preparation of silver ammonia solution: Pour 3 mL of silver nitrate solution into an empty beaker, and gradually add dilute ammonia solution dropwise into the silver nitrate solution until the precipitate disappears to obtain silver ammonia solution.

[0035] Preparation of solid oxide battery substrate:

[0036] 3% Y2O3-stabilized ZrO2 (3YSZ) | LSM (La) was prepared by phase transformation casting technology. 0.8 Sr 0.2 ) 0.95 MnO 3-δ A green body with a bilayer finger-porous ceramic structure of -SSZ (Sc2O3-stabilized ZrO2) was sintered at 900℃ for 3 h. Then, an SSZ electrolyte layer structure was prepared by impregnation technology and sintered at 1250℃ for 4 h to obtain a 3YSZ | LSM-SSZ | SSZ half-cell structure. A NiO-SZZ fuel electrode structure was prepared by screen printing technology and sintered at 1200℃ for 3 h to obtain a 3YSZ | LSM-SSZ | SSZ | NiO-SSZ single cell.

[0037] Preparation of the silver layer:

[0038] The NiO-SSZ fuel electrode side was sealed with waterproof tape, while the 3YSZ ceramic support side was exposed. The solid oxide batteries were placed in an empty beaker, and sodium hydroxide solution was poured into the beaker. After standing at room temperature for 5 minutes, the solid oxide batteries were removed and placed in an oven at 80°C to dry. Then, the solid oxide batteries were transferred to an empty beaker, and silver ammonia solution was poured into the beaker to a volume of 10 mL. The beaker was placed in a vacuum chamber and vacuum-sealed for 5 minutes. Then, 3-6 mL of glucose solution was quickly added, and the beaker was sealed with sealing film. The beaker was then placed in a water bath at 80°C for 30 minutes. After removing the beaker, the solid oxide batteries were placed in an oven at 80°C to dry.

[0039] The dried solid oxide battery was transferred to a muffle furnace and calcined at 850°C for 3 h to obtain an Ag@3YSZ|LSM-SSZ|SSZ|NiO-SSZ battery with a silver plating layer. The silver layer was prepared on the pore walls of the finger-like porous structure of the ceramic support using a silver mirror reaction, that is, a current collection layer was prepared on the pore walls of the finger-like porous structure of the ceramic support.

[0040] like Figure 1 As shown, the ceramic-supported solid oxide battery before the current collection layer is located to the right of the ceramic-supported solid oxide battery after the current collection layer is fabricated. After the solid oxide battery undergoes silver mirror reaction silvering treatment, the color of the support side surface changes from the original white of the ceramic to black. This color change indicates that the silver layer has been successfully deposited on the surface of the ceramic support of the solid oxide battery. Furthermore, as... Figure 2 and Figure 3 The scanning electron microscope (SEM) and energy dispersive spectroscopy (EDS) results shown indicate that the silver layer is uniformly loaded on the pore walls of the ceramic support, confirming that the silver layer has a good deposition effect on the pore surface of the ceramic support.

[0041] The ceramic support is a finger-shaped porous ceramic support structure. The oriented arrangement of the finger-shaped pores provides a deposition substrate for the silver layer. Compared with traditional sponge-like pores, the finger-shaped pore walls are smoother and the pore channels are more interconnected, which allows the silver layer to cover the pores evenly without clogging them.

[0042] Example 2: Testing of solid oxide batteries:

[0043] This invention, after preparing a current-collecting layer, tested a solid oxide battery with good current collection performance. The test results are as follows: Figure 4 As shown, the tests were conducted in both power generation and electrolysis modes.

[0044] In the power generation mode, the fuel electrode side is in a hydrogen atmosphere (H2), and the air electrode side is in an air atmosphere;

[0045] In electrolysis mode, the fuel electrode side is a mixed atmosphere of 50% H2O and 50% H2, while the air electrode side remains an air atmosphere.

[0046] At temperatures of 700℃, 750℃, 800℃, and 850℃, the maximum power density of the solid oxide battery in power generation mode is 66.21 mW / cm². -2 108.78 mW cm -2 159.51 mW cm -2 and 219.50 mW cm -2In electrolysis mode, at 1.3 V, the electrolysis current of the solid oxide battery is 61.89 mA cm⁻¹. -2 114.05 mA cm -2 197.02mA cm -2 and 288.83 mA cm -2 .

[0047] The above results indicate that the silver layer formed by the silver mirror reaction can establish a conductive path between the electrode and the external circuit, effectively collecting and discharging the current generated during battery operation to the external circuit, thereby reducing the battery's internal resistance.

[0048] It should be understood that the above description is only a preferred embodiment of the present invention. For those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

[0049] The above are merely preferred embodiments of the present invention and do not constitute any limitation on the present invention. Any equivalent substitutions or modifications made by those skilled in the art to the technical solutions and content disclosed in the present invention without departing from the scope of the present invention shall be deemed to have remained within the protection scope of the present invention.

Claims

1. A method for preparing a current collection layer in a ceramic-supported solid oxide battery, characterized in that, Includes the following steps: (1) Preparation of solid oxide battery substrate; (2) Prepare silver nitrate solution, dilute ammonia solution, sodium hydroxide solution and glucose solution; (3) The silver nitrate solution is mixed with the dilute ammonia solution to obtain a silver ammonia solution; (4) The surface of the ceramic support of the solid oxide battery substrate is first treated with sodium hydroxide solution, then dried, then immersed in silver ammonia solution, glucose solution is added and reduced under water bath conditions to form a silver plating layer, and then dried. (5) The solid oxide battery with the formed silver plating layer is calcined at high temperature to obtain a silver layer on the surface of the ceramic support of the solid oxide battery, wherein the silver layer is a current collection layer.

2. The preparation method according to claim 1, characterized in that, The silver nitrate solution contains 3%-7% silver nitrate by mass, the dilute ammonia solution is prepared from concentrated ammonia solution with a mass percentage of 2%-4%, the sodium hydroxide solution contains 3%-7% sodium hydroxide by mass, and the glucose solution contains 3%-7% glucose by mass.

3. The preparation method according to claim 2, characterized in that, The silver nitrate solution contains 5% silver nitrate by mass, the dilute ammonia solution is prepared from 3% concentrated ammonia solution by mass, the sodium hydroxide solution contains 5% sodium hydroxide by mass, and the glucose solution contains 5% glucose by mass.

4. The preparation method according to claim 1, characterized in that, In step (3), dilute ammonia is added dropwise to the silver nitrate solution until the initially formed precipitate is completely dissolved to prepare a silver ammonia solution.

5. The preparation method according to claim 1, characterized in that, In step (4), the reaction temperature under the water bath conditions is 70-90℃ and the time is 20-40 min; the drying temperature is 70-90℃.

6. The preparation method according to claim 5, characterized in that, In step (4), the reaction temperature under the water bath conditions is 80°C and the time is 30 min; the temperature of the drying treatment is 80°C.

7. The preparation method according to claim 1, characterized in that, In step (5), the high-temperature calcination temperature is 800-900℃ and the time is 2-4 h.

8. The preparation method according to claim 7, characterized in that, In step (5), the high-temperature calcination temperature is 850°C and the time is 3 hours.

9. The preparation method according to claim 1, characterized in that, The ceramic support is a finger-shaped porous ceramic support structure.

10. A solid oxide battery, characterized in that, The ceramic support of the solid oxide battery is provided with a current collection layer prepared by the preparation method according to any one of claims 1 to 9.

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