CN113337834B - Asymmetric-structure electrolytic cell made of symmetric materials and preparation method thereof - Google Patents

Asymmetric-structure electrolytic cell made of symmetric materials and preparation method thereof Download PDF

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CN113337834B
CN113337834B CN202110621301.6A CN202110621301A CN113337834B CN 113337834 B CN113337834 B CN 113337834B CN 202110621301 A CN202110621301 A CN 202110621301A CN 113337834 B CN113337834 B CN 113337834B
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electrode
electrolytic cell
perovskite
electrolyte
solid oxide
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CN113337834A (en
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董德华
刘方升
李天培
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Zhejiang Zhongxin Degu New Material Technology Co.,Ltd.
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University of Jinan
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    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
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    • C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
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Abstract

The invention belongs to the technical field of solid oxide electrolytic cells, and particularly relates to an asymmetric-structure electrolytic cell made of a weighing material, a preparation method and application thereof. The symmetrical material asymmetric structure electrolytic cell consists of an electrode support body with a micro-channel structure, a thin electrolyte layer and a porous electrode layer; one end of the micro-channel structure penetrates through the support body, and the other end of the micro-channel structure is connected with the thin electrolyte layer; the symmetrical material for forming the porous electrode layer is formed by mixing NiO and an oxygen ion conductor material, or the symmetrical material for forming the porous electrode layer is a pure perovskite material or the mixture of perovskite and an oxygen ion conductor material. The method of the invention adopts three layers of Ni-based electrode or perovskite-based electrode and electrolyte to be co-fired, thus greatly increasing the bonding force of the electrode/electrolyte interface and simultaneously ensuring that the electrode has enough porosity for gas diffusion. The electrolytic cell prepared by the invention can select whether to adopt fuel to assist in electrolyzing CO according to application scenes 2 、H 2 O。

Description

Asymmetric-structure electrolytic cell made of symmetric materials and preparation method thereof
Technical Field
The invention belongs to the technical field of solid oxide electrolytic cells, and particularly relates to a material weighing asymmetric structure electrolytic cell and a preparation method thereof.
Background
The solid oxide electrolytic cell is an energy conversion device with an all-solid-state structure, and H is electrolyzed at a porous electrode by using electric energy 2 O、CO 2 Production of H 2 CO, or H 2 O and CO 2 Co-electrolysis for producing synthesis gas (CO and H) 2 Mixed gas of (2). The renewable energy storage device is combined with renewable energy sources such as solar energy and wind energy to store the renewable energy sources, and the problems of intermittence, fluctuation and the like of renewable energy source supply are solved. The efficiency of an electrolytic cell system directly affects its operating costs and is critical in determining the commercial application of this technology. In terms of equipment, raw materials, energy power (heat energy, electric energy) and other costs, the energy power cost accounts for about 60% of the total operating cost of high-temperature electrolysis, wherein the electric power cost accounts for a major portion of the energy power cost.
For conventional Ni-based cathodes, to avoid Ni being coated with H 2 O or CO 2 Oxidized to lose activity, H 2 Is fed to the cathode as a shielding gas, at this timePulling electrolytically generated oxygen ions from the cathode to the anode requires overcoming H 2 The potential difference formed by the air, most of the electric energy in the process is consumed, and the electric energy is greatly wasted. At present, two ways are generally adopted to reduce the power consumption of electrolysis: one is to use fuel gas, e.g. H 2 、CO、CH 4 Other hydrocarbon fuels assist electrolysis to reduce the oxygen partial pressure of the anode, so that the electrolysis power consumption is reduced, and although the hydrocarbon fuels have large reserves in the nature, the carbon deposition of the traditional Ni-based electrode can be caused after the hydrocarbon fuels are introduced; another approach is to use a perovskite electrode as the cathode, avoiding the use of H 2 As a shielding gas, the perovskite anode serves as a common oxygen evolution electrode, so perovskite-based materials are used for both electrodes of such batteries.
Disclosure of Invention
In order to solve the defects of the prior art, the invention aims to provide a preparation method of an asymmetric-structure electrolytic cell made of a symmetrical material.
The invention also aims to provide the electrolytic cell with high electrolytic efficiency prepared by the preparation method, and the electrolytic cell can select different auxiliary fuels for auxiliary electrolysis of CO according to application scenes 2 、H 2 O。
In order to achieve the purpose, the invention adopts the following technical scheme:
the electrode solid oxide electrolytic cell with the symmetrical material and the asymmetrical structure consists of an electrode support body with a micro-channel structure, a thin electrolyte layer and a porous electrode layer; one end of the micro-channel structure penetrates through the support body, and the other end of the micro-channel structure is connected with the thin electrolyte layer; the symmetrical material for forming the porous electrode layer is formed by mixing NiO and an oxygen ion conductor material, or the symmetrical material for forming the porous electrode layer is a pure perovskite material or the mixture of perovskite and an oxygen ion conductor material.
Preferably, the thickness of the electrode support body is 0.3 mm-2 mm, and the thickness of the thin electrolyte layer is 0.4 μm-30 μm; the diameter of the porous electrode layer/thin electrolyte interface micro-channel is 0.5-5 μm, and gradually combined and increased to 10-100 μm.
Preferably, the oxygen ion conductor material is (Y) 2 O 3 ) 0.08 Zr 0.92 O 2 、Gd 0.1 Ce 0.9 O 2 (ii) a The perovskite material is La 1-x Sr x MnO 3 、La 1-x Sr x CoO 3 、Sm 0.5 Sr 0.5 CoO 3 、(La 0.80 Sr 0.20 ) 0.95 FeO 3-x 、Ba x Sr 1-x Co 0.8 Fe 0.2 O 3-y 、La 1-x Sr x Co 1-y Fe y O 3 。
Preferably, the mass ratio of the NiO to the oxygen ion conductor material is 55-65: 35-45.
Preferably, the mass percentage of the perovskite in the mixture of the perovskite and the oxygen ion conductor material is 60% -100%.
A preparation method of the solid oxide electrolytic cell comprises the following steps:
(1) ball-milling and mixing the polymer, the solvent, the electrode powder and the dispersant to form slurry; the electrode powder is formed by mixing NiO and an oxygen ion conductor material, or is formed by mixing a pure perovskite material or a perovskite and an oxygen ion conductor material;
(2) preparing an electrode support body from the slurry obtained in the step (1) through a phase inversion process;
(3) pre-sintering the electrode support prepared in the step (2), and soaking the electrode support in electrolyte to form an electrolyte layer;
(4) directly spraying electrode slurry on the surface of the electrolyte layer of the electrode support prepared in the step (3);
(5) and (4) sintering the electrode support body sprayed with the electrode slurry in the step (4) to prepare the asymmetric electrode solid oxide electrolytic cell made of the symmetric material.
Preferably, the thickness of the spray electrode slurry in the step (4) is 10-30 μm;
preferably, the electrode slurry of step (4) is prepared by the following method: 3.6g of NiO and 2.4gGd were weighed 0.1 Ce 0.9 O 2 And putting the powder and 0.1g of PVP-40000 into a ball milling tank, adding 30ml of ethanol, and carrying out ball milling for 12 hours to obtain the electrode slurry.
Preferably, the sintering process in step (5) is: heating to 400 ℃ at a speed of 1-2 ℃/min, preserving heat for 1-2h, then heating to 1300 ℃ and 1400 ℃ at a speed of 1-2 ℃/min, preserving heat for 400min, and cooling to room temperature at a speed of less than 4 ℃/min.
Preferably, the preparation method of the electrolyte in step (3) comprises the following steps: 3g of electrolyte powder and 0.1g of PVP-40000 are weighed and poured into a ball milling tank, 30ml of ethanol is added, and ball milling is carried out for 12 hours. The electrolyte powder is Gd 0.1 C e0.9 O 2 、(Sc 2 O 3)0.10 (CeO 2 ) 0.01 (ZrO 2 ) 0.89 、(Y 2 O 3 ) 0.08 Zr 0.92 O 2 、Sm 0.2 Ce 0.2 O 2 And La 0.9 Sr 0.1 Ga 0.8 Mg 0.2 O 3 One or more of them are mixed.
Preferably, the mass percentages of the electrode powder, the solvent, the polymer and the dispersant in the slurry in the step (1) are respectively as follows: 45-85%, 10-40%, 4-10% and 0.3-6%; the electrode powder is formed by mixing NiO and an oxygen ion conductor material or is a perovskite material.
Preferably, the polymer in step (1) is one or more of polyethersulfone, cellulose acetate, polyvinylidene fluoride, polysulfone, polyacrylonitrile, cellulose, polyimide, polyvinylidene fluoride, and polyamide; the solvent is one or more of N-methyl pyrrolidone, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, tetrahydrofuran, formylpiperidine, diacetic acid and dioxane; the dispersing agent is polyvinylpyrrolidone, polyvinyl butyral, propanol or polyethylene glycol; the mixing in the step (1) is to form slurry through ball milling, and the ball milling time is 24-48 h.
Preferably, the pre-sintering in the step (3) is to heat the anode blank to 400 ℃ at a speed of 1 ℃/min, keep the temperature for 1-2h, remove volatile substances, heat the anode blank to 1050 ℃ at a speed of 2 ℃/min, and keep the temperature for 2-3 h.
The invention utilizes the support electrode pore canal with the microchannel as the support electrode to prepare the thin electrolyte, the electrode slurry is sprayed on the surface of the thin electrolyte and then the thin electrolyte is sintered together, and the electrolytic cell prepared by one-step molding greatly improves the interface bonding force of the electrode/the thin electrolyte, increases the density of a three-phase interface, is suitable for auxiliary electrolysis modes of different types of fuels, and has high electrolysis efficiency and stable operation. The solid oxide electrolytic cell has excellent stability under high current and very high conversion efficiency in auxiliary electrolysis.
The electrolytic cell prepared by the asymmetric structure of the symmetrical material greatly increases the electrode/electrolyte interface bonding force in the co-sintering process, and simultaneously can prepare the electrode supporting electrolytic cell with a thin electrolyte structure due to the sintering resistance of the micro-channel structure, thereby greatly reducing the resistance of the electrolytic cell and reducing the power consumption of electrolysis. The Ni-based symmetric electrode material is adopted, and the micro-anode support body channel structure is utilized, so that the effective reforming of the hydrocarbon fuel can be realized. Therefore, the invention provides the electrolytic cell with the electrode of the asymmetric structure made of the symmetrical material, the thickness of the electrolyte of the electrolytic cell is reduced, so that the resistance is reduced, the electrolytic efficiency is improved, the interface binding force is improved by co-sintering, and the stability of the electrolytic cell is improved.
Advantageous effects
According to the electrolytic cell with the asymmetric structure and the symmetric material, the support electrode has the microchannel structure, the pores of the microchannel are resistant to sintering, and an effective way is provided for rapid gas diffusion; when the electrolyte and the two-side electrodes are co-fired, the binding force between a three-phase interface and an interface of a cathode and an anode is increased to the maximum extent; compared with other electrolytic cell preparation processes, the invention simultaneously considers two technical means of practical application and high performance, and is safe and efficient.
Drawings
FIG. 1 is a schematic diagram of a conventional sintering process for preparing an electrolytic cell with an asymmetric structure made of symmetric materials;
FIG. 2 is a schematic diagram of a preparation process of an asymmetric-structured electrolytic cell co-sintering process for symmetric materials;
FIG. 3 is the electrochemical impedance spectra of hydrogen assisted electrolysis at 800 ℃ for the solid oxide electrolytic cell prepared in example 1, the co-sintering process and the conventional sintering process;
FIG. 4 is a current density-voltage (C-V) curve at 800 ℃ for a co-sintering process and a conventional sintering process for a solid oxide electrolytic cell prepared in example 1;
FIG. 5 shows electrochemical stability test of solid oxide cell prepared in example 1 at 800 deg.C operating temperature at 3A cm -2 Run at current density for 10 hours, 4A cm -2 No obvious attenuation is caused after the operation is carried out for 17 hours under the current density;
FIG. 6 is a SEM photograph of a solid oxide electrolytic cell prepared in example 1, co-fired at 1330 ℃ for 300 minutes;
FIG. 7 shows electrochemical stability test of an electrolytic cell prepared by a conventional sintering process at an operating temperature of 800 ℃ at 1A cm -2 Run at current density for 11.5 hours with slow decay, 1.5A cm -2 The current density is operated for 2.5 hours, and the attenuation is obvious;
FIG. 8 is an SEM photograph of an electrolytic cell prepared by a conventional sintering process;
FIG. 9 is the electrochemical impedance spectrum of ethanol-assisted electrolysis of a hydrocarbon fuel at 800 ℃ for an electrolysis cell prepared in example 2;
FIG. 10 is a current density-voltage (C-V) curve for hydrocarbon fuel ethanol assisted electrolysis at 800 ℃ for an electrolysis cell prepared in example 2;
FIG. 11 is a test of electrochemical stability of the cell prepared in example 2 at 800 ℃ for ethanol-assisted electrolysis of hydrocarbon fuel at 3A cm -2 No obvious attenuation is caused when the reactor is operated for 209 hours under the current density;
FIG. 12 is an SEM photograph of a perovskite electrode-supported electrolytic cell prepared in example 3;
FIG. 13 shows an electrolytic cell prepared in example 3 for electrolyzing pure CO at 800 deg.C 2 Current-voltage (I-V) curve of (a);
FIG. 14 shows an electrolytic cell prepared in example 3 for electrolyzing pure CO at 800 deg.C 2 The impedance spectrum of (a);
FIG. 15 is an impedance spectrum of the cells prepared in comparative example 1 and example 2 at 800 ℃ in hydrogen-assisted electrolysis;
FIG. 16 is a graph of current density versus voltage (C-V) at 800 ℃ for hydrogen-assisted electrolysis for the cells prepared in comparative example 1 and example 2.
Detailed Description
The present invention will be described in detail with reference to the following embodiments in order to further understand the features and technical means of the present invention, and to achieve the specific objects and functions of the present invention, and to analyze the advantages and application prospects of the present invention. However, it should not be understood that the scope of the present invention as defined above is limited to the following examples. All the technologies realized based on the above contents of the present invention belong to the scope of the present invention.
Example 1
36.99gNiO, 24.66g (Y) 2 O 3 ) 0.08 Zr 0.92 O 2 The powder, 4.3 g of polyethersulfone, 24 g N-methyl pyrrolidone and 0.43g of polyvinylpyrrolidone were weighed and placed in a ball mill jar and ball milled for 48 hours using a planetary ball mill to form a premix material. And filtering the premixed slurry, placing the premixed slurry into a vacuum stirring device for stirring and exhausting, setting the vacuum degree at-0.08 MPa, and stirring and exhausting for 20min to obtain the electrode slurry which does not contain bubbles and is uniformly mixed. The slurry was poured into a lower mold, a stainless steel mesh having a mesh opening of 70 μm was placed on the surface of the slurry so that the slurry slightly penetrated through the stainless steel mesh, and then an upper mold having both upper and lower ends open was pressed against the mesh, and a slurry having a thickness of 12mm was injected. Water was used as flocculant and poured from the top of the slurry to initiate the phase inversion process. And (3) carrying out phase inversion for 1.5h, then demoulding, tearing off the screen, placing the microchannel electrode blank in a beaker filled with water for soaking for 6h, and replacing the residual solvent. Then, the blank was placed in an oven to dry at 55 ℃ for 8 hours. And (3) sintering the dried blank at high temperature, heating to 400 ℃ at the speed of 1 ℃/min, preserving heat for 1h, removing volatile substances, heating to 1050 ℃ at the speed of 2 ℃/min, preserving heat for 2h, cooling to 500 ℃ at the speed of 5 ℃/min, and naturally cooling to obtain the Ni/YSZ pre-sintered blank.
Mixing 3g of (Y) 2 O 3 ) 0.08 Zr 0.92 O 2 Electrolyte powder and 0.1g of PVP-40000 are weighed and poured into a ball milling tank, 30ml of ethanol is added, and ball milling is carried out for 12 hours. And then, dipping a layer of thin electrolyte on the smooth surface of the Ni/YSZ pre-sintered blank by using a dip-coating method, and finally, drying the blank in an oven at the drying temperature of 50-60 ℃ for more than 30 mm until the blank is completely dried.
3.6g of NiO and 2.4g of 2.4gGd were weighed 0.1 Ce 0.9 O 2 Putting the powder and 0.1g of PVP-40000 into a ball milling tank, adding 30ml of ethanol, and carrying out ball milling for 12 hours. A12 mm diameter punch was used to punch a hole through the weighing paper, and the hole was aligned right in the middle of the YSZ electrolyte impregnated support electrode blank and pressed into an evaporation dish. And (3) placing the evaporating dish on a heating table, setting the temperature of the heating table to be 120 ℃, and then uniformly spraying the electrode slurry on the surface of the electrolyte by using a spray gun, wherein the thickness of the electrode is 10-30 micrometers. And raising the temperature of the sprayed pre-sintered battery to 400 ℃ at a speed of 1 ℃/min, preserving the heat for 1h, removing volatile substances, raising the temperature to 1330 ℃ at a speed of 2 ℃/min, preserving the heat for 5h, finally cooling to 500 ℃ at a speed of 2 ℃/min, naturally cooling, and directly sintering in one step to prepare the full battery.
Example 2
When the hydrocarbon fuel is used for assisting electrolysis, a high-efficiency catalytic reaction bed is required to be prepared by utilizing the micro-channel, so that the aims of catalyzing the hydrocarbon fuel and preventing carbon deposition are fulfilled. The full cell preparation process was the same as in example 1.
Preparing a catalytic reaction bed:
PD-Gd 0.1 Ce 0.9 O 2 catalyst precursor: weighing 0.0444 g Gd (NO) 3 ) 3 ·6H 2 O（≥99%），0.3936 g Ce(NO 3 ) 3 ·6H 2 O (99%) 4.72 g N, N-dimethylformamide and 0.102 g polyvinylpyrrolidone (PVP, molecular weight 1300000) were placed in a beaker and dissolved thoroughly. 0.0533 g Pd (NO) were weighed 3 ) 3 ·2H 2 O (more than or equal to 99 percent) is dissolved in 1g of the prepared solution. Then, the resultant was immersed in the supported electrode microchannel of the full cell prepared in example 1, and sintered at 750 f for 2 hours, which was repeated 2 times.
Ru-Gd 0.1 Ce 0.9 O 2 Fiber catalyst: 0.3173 g are weighedGd(NO 3 ) 3 ·6H 2 O（≥99%），0.1313 g RuCl 3 ，2.7475 g Ce(NO 3 ) 3 ·6H 2 O (more than or equal to 99 percent), 8 g of distilled water, 2 g of absolute ethyl alcohol (more than or equal to 99 percent) and 0.8 g of polyvinylpyrrolidone (PVP, molecular weight of 1300000) are placed in a beaker, and magnetons are added to stir for more than 10 hours until the mixture is clear, transparent and bubble-free. Then preparing a fiber catalyst by using an electrostatic spinning machine, and sintering for 2 hours at 800 ℃. Grinding the phase-formed fiber catalyst, placing a certain mass into a glass vial, adding ethanol, sufficiently crushing in ultrasonic wave, adding into a support electrode microchannel impregnated with the catalyst precursor by using a negative pressure (-2-1 bar) auxiliary addition mode, drying, and repeatedly operating to ensure 241 mm 3 The mass of the fiber catalyst in the support body is 3 mg-10 mg, and the full battery with the anode having the catalytic reaction bed is prepared.
Example 3
17.7 g of Polyethersulfone (PESF) and 0.72 g of polyvinylpyrrolidone (PVP) were dissolved in 100 g N-methylpyrrolidone (NMP) and stirred magnetically for 4 hours. Then, 43.16 g (La) 0.80 Sr 0.20 ) 0.95 FeO 3-X (LSF 20) and 18.50 g Gd 0.1 Ce 0.9 O 2 (GDC-TC) powder 28.32 g of the above solution was added and ball-milled with a planetary ball mill for 48 hours to form a uniform slurry. The slurry was cast into a stainless steel mold and a stainless steel mesh was immersed in the slurry. After 2 hours of using water as a coagulant on top, the slurry was converted into a green body of perovskite electrode support, with the perovskite electrode support having a microchannel structure formed over the mesh. The green anode formed was dried at 60 ℃ overnight and then presintered at 1050 ℃ for 2 h.
GDC and (Y) 2 O 3 ） 0.08 Zr 0.92 O 2 The (YSZ) bilayer was dip-coated on the perovskite electrode support and then co-sintered at 1350 ℃ for 5h to form a dense GDC-YSZ electrolyte membrane. 10 wt% YSZ (YSZ-U1) and 0.38 wt% PVP powders were dispersed in ethanol by ball milling for 24 hours and GDC slurry was prepared using the same method. By mixing LSF powder with 4 wt% GDC powder and0.38 wt% PVP powder was mixed in ethanol for 24 hours to prepare LSF-GDC electrode slurry. The LSF-GDC slurry was sprayed on the dense electrolyte membrane to form another electrode, and sintered at 1250 ℃ for 2 h. And obtaining the perovskite electrode supported full cell.
Conventional sintering
And heating the support electrode blank body soaked with the YSZ electrolyte to 400 ℃ at the speed of 1 ℃/min, preserving heat for 1h, removing volatile substances, heating to 1350 ℃ at the speed of 2 ℃/min, preserving heat for 5h, cooling to 500 ℃ at the speed of 2 ℃/min, and naturally cooling to prepare the half cell. 3.6g of NiO and 2.4gGd were weighed 0.1 Ce 0.9 O 2 Putting the powder and 0.1g of PVP-40000 into a ball milling tank, adding 30ml of ethanol, and carrying out ball milling for 12 hours to prepare electrolyte slurry. A hole is punched in the label paper by a puncher with the diameter of 10 mm, the hole is aligned with the middle of the half cell and is stuck in an evaporation dish. And (3) placing the evaporating dish on a heating table, setting the temperature of the heating table to be 120 ℃, and then uniformly spraying the electrode slurry on the surface of the electrolyte by using a spray gun, wherein the thickness of the electrode is 20-30 micrometers. Heating the sprayed half cell at 1 deg.C/min to 400 deg.C, maintaining for 1h, removing volatile substances, heating at 2 deg.C/min to 1280 deg.C, maintaining for 2h, cooling to 500 deg.C at 2 deg.C/min, and naturally cooling
A full cell was prepared at warm temperature and the rest of the operation was identical to example 1.
Comparative example 1
In the comparative example, the sprayed pre-sintered battery is heated to 400 ℃ at a speed of 1 ℃/min, the temperature is kept for 1h, volatile substances are removed, the temperature is heated to 1350 ℃ at a speed of 2 ℃/min, the temperature is kept for 5h, finally the temperature is reduced to 500 ℃ at a speed of 2 ℃/min, then the temperature is naturally reduced, the whole battery is prepared by direct one-step sintering, and the rest operations are the same as those in the example 1.
Comparative example 2
In the comparative example, the sprayed pre-sintered battery is heated to 400 ℃ at a speed of 1 ℃/min, the temperature is kept for 1h, volatile substances are removed, the temperature is heated to 1310 ℃ at a speed of 2 ℃/min, the temperature is kept for 5h, finally the temperature is reduced to 500 ℃ at a speed of 2 ℃/min, then the temperature is naturally reduced, the whole battery is prepared by direct one-step sintering, and the rest operations are the same as those in the example 1.
Application example 1
Hydrogen assisted electricitySolving: electrochemical stability testing at an operating temperature of 800 ℃ was performed by sealing the cell prepared in example 1 in an alumina ceramic tube with a ceramic high temperature sealing adhesive, raising the temperature to 260 ℃ at 2 ℃/min, holding the temperature for 1h, and raising the temperature to 800 ℃ at 4 ℃/min. Introducing Ar to the cathode and the anode for emptying, and introducing H 2 Reducing, and introducing 30% Ar +60% CO into the cathode 2 +10%H 2 Anode is introduced with H 2 A gas. The cells were first tested for ac impedance using an electrochemical workstation with a high frequency setting of 100000HZ and a low frequency setting of 0.1HZ, the results of which are shown in figure 2. The resistance of the electrolytic cell prepared by the co-firing process is obviously reduced. The cells were then tested for current density-voltage (C-V) curves using an electrochemical workstation with a cut-off voltage of no more than 1.5V, and the results are shown in fig. 3. The performance of the electrolytic cell prepared by the co-firing process is greatly improved. Finally, stability test is carried out, and the co-firing electrolytic cell is 3A cm -2 The current density is operated for 10 hours and then increased to 4A cm -2 The current density was run for 17 h without significant attenuation and the results are shown in figure 4.
Application example 2
And (3) hydrocarbon fuel assisted electrolysis: a catalytic reaction bed was prepared by example 2 supporting electrodes in microchannels.
And (3) testing the electrochemical stability at the operation temperature of 800 ℃, sealing the electrolytic cell in an alumina ceramic tube by using a ceramic high-temperature sealing adhesive, heating to 260 ℃ at the temperature of 2 ℃/min, preserving the temperature for 1h, and heating to 800 ℃ at the operation temperature of 4 ℃/min. Introducing Ar to the cathode and the anode for emptying, and introducing H 2 Reducing, and then introducing 60% Ar +30% H into the cathode 2 O+10%H 2 And 92.5% Ar +7.5% C is introduced into the anode 2 H 5 OH gas. The cells were first tested for ac impedance using an electrochemical workstation with a high frequency setting of 100000HZ and a low frequency setting of 0.1HZ, the results of which are shown in figure 8. The cells were then tested for current density-voltage (C-V) curves using an electrochemical workstation with a cut-off voltage of no more than 1.5V, and the results are shown in fig. 9. Finally, stability test is carried out, and the battery is at 3A cm -2 Run at current density of 209H without significant decay, see FIG. 10, with cathode producing a large amount of H 2 Simultaneous anodic production of large quantities of synthesis gas (CO + H) 2 ）。
Application example 3
Hydrogen-protection-free electrolysis of pure CO 2 : the LSF-GDC supported SOEC with microchannels prepared in example 3 was first fed with pure CO on the cathode side 2 And performing performance test at 800 ℃. The cross section of the cell is shown in figure 11, the electrolytic cell is sealed in an alumina ceramic tube by using a ceramic high-temperature sealing adhesive, the temperature is raised to 260 ℃ at the speed of 2 ℃/min, the temperature is kept for 1h, and the temperature is raised to 800 ℃ at the speed of 1 ℃/min. Ar is introduced into the cathode for evacuation, and pure CO is introduced 2 . First, a current-voltage (I-V) curve of the battery was measured using an electrochemical workstation, and as a result, as shown in fig. 12, the battery did not exhibit an activated polarization phenomenon during electrolysis of pure CO2, and then, the ac impedance of the battery was measured using an electrochemical workstation, with a high frequency set at 100000HZ and a low frequency set at 0.1HZ, and as a result, as shown in fig. 13, the total resistance of the battery was 1.32 Ω cm 2 。

Claims (6)

1. The electrode solid oxide electrolytic cell with the symmetrical material and the asymmetrical structure is characterized in that the electrode solid oxide electrolytic cell with the symmetrical material and the asymmetrical structure consists of an electrode support body with a micro-channel structure, a thin electrolyte layer and a porous electrode layer; one end of the micro-channel structure penetrates through the support body, and the other end of the micro-channel structure is connected with the thin electrolyte layer; the symmetrical material forming the porous electrode layer is formed by mixing NiO and an oxygen ion conductor material, or the symmetrical material forming the porous electrode layer is a pure perovskite material or the mixture of perovskite and an oxygen ion conductor material;
wherein the thickness of the electrode support body is 0.3 mm-2 mm, and the thickness of the thin electrolyte layer is 0.4 μm-30 μm; the diameter of the porous electrode layer/thin electrolyte interface micro-channel is 0.5-5 μm, and the diameter is gradually increased to 10-100 μm;
the mass ratio of the NiO to the oxygen ion conductor material is 55-65: 35-45, wherein the mass percent of the perovskite in the mixture of the perovskite and the oxygen ion conductor material is 60% -100%;
the electrolytic cell is prepared by the following steps:
(1) ball-milling and mixing the polymer, the solvent, the electrode powder and the dispersant to form slurry; the electrode powder is formed by mixing NiO and an oxygen ion conductor material, or is formed by mixing a pure perovskite material or a perovskite and an oxygen ion conductor material;
(2) preparing an electrode support body by the slurry obtained in the step (1) through a phase inversion process;
(3) pre-burning the electrode support prepared in the step (2), and soaking the electrode support in an electrolyte to form an electrolyte layer;
(4) directly spraying electrode slurry on the surface of the electrolyte layer of the electrode support prepared in the step (3);
(5) sintering the electrode support body sprayed with the electrode slurry in the step (4) to prepare the asymmetric electrode solid oxide electrolytic cell made of the symmetric material;
the sintering process in the step (5) comprises the following steps: raising the temperature to 400 ℃ at a speed of 1-2 ℃/min, preserving the heat for 1-2h, then raising the temperature to 1320-.
2. The solid oxide electrolysis cell of claim 1, wherein said oxygen ion conductor material is (Y) 2 O 3 ) 0.08 Zr 0.92 O 2 、Gd 0.1 Ce 0.9 O 2 And Sm 0.2 Ce 0.8 O 2 (ii) a The perovskite material is La 1-x Sr x MnO 3 、La 1-x Sr x CoO 3 、Sm 0.5 Sr 0.5 CoO 3 、(La 0.8 0Sr 0 .20 ) 0.95 FeO 3-x 、Ba x Sr 1-x Co 0 .8 Fe 0 .2 O 3-y 、La 1-x Sr x Co 1-y Fe y O 3 。
3. The solid oxide electrolysis cell according to claim 1, wherein the thickness of the sprayed electrode slurry of step (4) is 10 μm to 30 μm.
4. The solid oxide electrolysis cell of claim 1, wherein the electrode slurry of step (4)The preparation method comprises the following steps: 3.6g of NiO and 2.4gGd were weighed 0.1 Ce 0.9 O 2 And putting the powder and 0.1g of PVP-40000 into a ball milling tank, adding 30ml of ethanol, and carrying out ball milling for 12 hours to obtain the electrode slurry.
5. The solid oxide electrolysis cell of claim 1, wherein the electrolyte of step (3) is prepared by the following method: 3g of electrolyte powder and 0.1g of PVP-40000 are weighed and poured into a ball milling tank, 30ml of ethanol is added, and ball milling is carried out for 12 hours.
6. The solid oxide electrolysis cell according to claim 5, wherein the electrolyte powder is Gd 0.1 Ce 0.9 O 2 、(Sc 2 O 3 ) 0.10 (CeO 2 ) 0.01 (ZrO 2 ) 0.89 、(Y 2 O 3 ) 0.08 Zr 0.92 O 2 、Sm 0.2 Ce 0.2 O 2 And La 0.9 Sr 0.1 Ga 0.8 Mg 0.2 O 3 One or more of them are mixed.
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CN104779409A (en) * 2015-04-27 2015-07-15 上海邦民新能源科技有限公司 Solid oxide fuel cell and preparation method thereof
CN112250437A (en) * 2019-11-05 2021-01-22 济南大学 Solid oxide electrolytic cell supported by oxygen electrode and preparation method thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104779409A (en) * 2015-04-27 2015-07-15 上海邦民新能源科技有限公司 Solid oxide fuel cell and preparation method thereof
CN112250437A (en) * 2019-11-05 2021-01-22 济南大学 Solid oxide electrolytic cell supported by oxygen electrode and preparation method thereof

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