CN114016072A - Solid oxide electrolytic cell - Google Patents

Solid oxide electrolytic cell Download PDF

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CN114016072A
CN114016072A CN202111539074.9A CN202111539074A CN114016072A CN 114016072 A CN114016072 A CN 114016072A CN 202111539074 A CN202111539074 A CN 202111539074A CN 114016072 A CN114016072 A CN 114016072A
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layer
cathode
nio
electrolytic cell
ysz
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赵哲
邵志刚
程谟杰
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Dalian Institute of Chemical Physics of CAS
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Dalian Institute of Chemical Physics of CAS
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/052—Electrodes comprising one or more electrocatalytic coatings on a substrate
    • C25B11/053—Electrodes comprising one or more electrocatalytic coatings on a substrate characterised by multilayer electrocatalytic coatings
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/02—Hydrogen or oxygen
    • C25B1/04—Hydrogen or oxygen by electrolysis of water
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
    • C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
    • C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

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  • Chemical Kinetics & Catalysis (AREA)
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Abstract

The invention discloses a solid oxide electrolytic cell which is characterized by comprising a cathode supporting layer, a cathode transition layer, a cathode active layer, an electrolytic cell layer, an interlayer and an anode layer, wherein the porosity of the cathode supporting layer is 50-70%, the porosity of the cathode transition layer is 50-60%, the porosity of the cathode active layer is 30-50%, the gradient change of the porosity of the cathode layer is beneficial to hydrogen/water vapor diffusion, the powder of the cathode active layer is uniformly mixed, the particle size is 100-500 nanometers, and more reaction active sites are provided. The electrolytic cell has very excellent electrolytic performance.

Description

Solid oxide electrolytic cell
Technical Field
The invention relates to the field of fuel cells and electrolytic cells, in particular to a solid oxide electrolytic cell.
Background
The Solid Oxide Electrolysis Cell (SOEC) can be coupled with industrial waste heat to electrolyze water vapor into hydrogen and oxygen at high temperature, the electric efficiency can reach 100%, and the Solid Oxide electrolysis Cell is considered as the most efficient water electrolysis hydrogen production technology.
The membrane electrode is the core component of the SOEC, and has a sandwich structure, a compact electrolyte layer in the middle, and porous cathodes and anodes on two sides. The conversion of water molecules into hydrogen molecules on the cathode involves the following processes: (1) bulk diffusion and surface diffusion of water molecules and hydrogen molecules in the cathode; (2) water molecules are dissociated into hydrogen molecules and oxygen ions; (3) oxygen ions are transported to the electrolyte/cathode interface by diffusion through the cathode bulk phase; (4) oxygen ions are implanted into the electrolytic cell and transferred to the anode. At present, the commonly used electrolytic cell structure comprises a cathode supporting type and an electrolytic cell supporting type, and compared with an electrolyte supporting type electrolytic cell, a cathode supporting type single cell has higher electrochemical performance. However, the cathode layer of the cathode-supported cell is thick, usually about 1mm, so that the diffusion resistance of water molecules in the cathode layer is large, and the further improvement of the performance of the cell is obviously limited by mass transfer diffusion at high current density.
Disclosure of Invention
In order to solve the technical problems, the invention provides a solid oxide electrolytic cell, which consists of a cathode supporting layer, a cathode transition layer, a cathode active layer, an electrolytic cell layer, an interlayer and an anode layer; the cathode supporting layer is NiO and Y0.15Zr0.85O2(YSZ) 50-70 wt% of NiO, and the balance YSZ, wherein the porosity of the cathode support layer is 50-70%, and the thickness of the cathode support layer is 0.5-2 mm; the cathode transition layer is a mixture of NiO and YSZ, the content of NiO is 40-60 wt%, the balance is YSZ, the porosity of the cathode transition layer is 50-60%, and the thickness of the cathode transition layer is 1-15 micrometers; the cathode active layer is a mixture consisting of NiO and YSZ, the NiO content is 30-50 wt%, and the balance is YSZ; the porosity of the cathode active layer is 30-50%, and the thickness of the cathode active layer is 1-10 microns; the electrolytic cell layer is YSZ, and the thickness of the electrolyte layer is 2-50 microns; the interlayer is Gd0.1Ce0.9O2The thickness of the interlayer is 0.2-5 microns; anode layer is La0.6Sr0.4Co0.2Fe0.8O3Or La0.6Sr0.4Co0.2Fe0.8O3With Gd0.1Ce0.9O2A composite of components.
Further, in the technical scheme, the NiO content in the cathode supporting layer is preferably 55-65 wt%, the porosity of the cathode supporting layer is preferably 60-70%, and the thickness of the cathode supporting layer is preferably 0.8-1.5 mm.
Further, in the technical scheme, the content of NiO in the cathode transition layer is preferably 45-55 wt%, the porosity of the cathode transition layer is preferably 45-55%, and the thickness of the cathode transition layer is preferably 1-10 micrometers.
Further, in the technical scheme, the content of NiO in the cathode active layer is preferably 35-45 wt%, the porosity of the cathode active layer is preferably 35-45%, and the thickness of the cathode active layer is preferably 1-5 micrometers.
Further, in the technical scheme, the NiO and YSZ particle sizes selected for the cathode supporting layer are 1-20 micrometers, preferably 5-10 micrometers, the NiO and YSZ particle sizes selected for preparing the cathode transition layer are 0.5-5 micrometers, preferably 1-5 micrometers, and the NiO and YSZ particle sizes selected for preparing the cathode active layer are 0.1-1 micrometer, preferably 0.1-0.5 micrometer.
Further, in the technical scheme, the NiO and YSZ powder for preparing the cathode active layer are prepared by a one-time co-synthesis method, which comprises the following steps,
(1) preparing mixed liquid: preparing mixed liquid of nitrates of Ni, Y and Zr according to the mass ratio of NiO to YSZ in the cathode active layer, wherein the total concentration of metal ions in the mixed liquid is 0.5-3M, preferably 1-2M, one of ammonium citrate and glycine is added as a complexing agent, the molar concentration ratio of the complexing agent to the metal ions is 0.5: 1-3: 1, preferably 1.5: 1-2: 1, and the mixed liquid is heated at 60-80 ℃ for 5-10 h to form transparent sol;
(2) preparing mixed powder: adding a combustion improver into the transparent sol, wherein the combustion improver is one of propylene glycol or glycerol, transferring the sol into an evaporating dish, continuously heating the evaporating dish through an electric furnace until the sol is combusted to form initial mixed powder, and roasting the initial mixed powder at the high temperature of 800-1000 ℃ for 3-10 hours to form mixed powder. The invention has the following beneficial effects:
(1) the cathode layer of the solid oxide electrolytic cell comprises a supporting layer, a transition layer and an active layer, and the porosity is reduced in sequence, wherein the porosity of the cathode supporting layer is up to 70%, so that the solid oxide electrolytic cell is particularly beneficial to the diffusion of water vapor in pores, the concentration polarization of the electrolytic cell in a high current density region is obviously reduced, and the performance of the electrolytic cell is improved.
(2) The cathode active layer of the solid oxide electrolytic cell is prepared in one step by adopting a co-synthesis method, and the particle size of NiO and YSZ is 0.1-0.5 micron. The NiO and the YSZ particles prepared by the method are highly and uniformly mixed, and a stable interface is formed between the NiO and the YSZ particles through high-temperature (up to 1000 ℃) heat treatment during combustion, so that the nano NiO and the YSZ particles are prevented from rapidly growing up in the sintering process of the cathode active layer, the dissociation reaction active sites of water molecules are obviously increased, and the performance of the electrolytic cell is improved.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
Comparative example 1
A solid oxide electrolytic cell comprises a cathode layer, an electrolyte layer, an interlayer and an anode layer, wherein the cathode layer is composed of NiO and Y0.15Zr0.85O2(YSZ), wherein the total mass of the cathode layer is 1g, the NiO is 0.55g, the YSZ is 0.45, the porosity of the cathode layer is 45%, and the thickness of the cathode layer is 1 mm; the electrolytic cell layer is YSZ, and the thickness of the electrolyte layer is 10 microns; the interlayer is Gd0.1Ce0.9O2The thickness of the interlayer is 1 micron; the anode layer is La0.6Sr0.4Co0.2Fe0.8O3. The electrolytic cell is operated in an electrolytic water mode, and the electrolytic current density is-1.7 Acm under the conditions that the absolute humidity is 70 percent, the temperature is 800 ℃ and the voltage is 1.5V-2。
Example 1
A solid oxide electrolytic cell comprises a cathode supporting layer, a cathode transition layer, a cathode active layer, an electrolytic cell layer, an interlayer and an anode layer; the cathode supporting layer consists of NiO and YSZ, the total mass of the cathode supporting layer is 1g, wherein the NiO is 0.65g, the YSZ is 0.35g, the porosity is 60%, and the thickness of the cathode supporting layer is 1 mm; the total mass of the cathode transition layer is 0.02g, wherein NiO is 0.01g, YSZ is 0.01g, the thickness is 15 microns, and the porosity is 50%; the mass of the cathode active layer is 0.02g, wherein NiO is 0.008g, YSZ is 0.012g, the thickness is 5 microns, and the porosity is 40%; the electrolytic cell layer is YSZ, and the electrolyte layer is thickThe degree is 10 microns; the interlayer is Gd0.1Ce0.9O2The thickness of the interlayer is 1 micron; the anode layer is La0.6Sr0.4Co0.2Fe0.8O3The mass of the oxygen electrode was 0.008 g.
The electrolytic cell is prepared as follows:
preparing a cathode supporting layer: NiO and YSZ with the particle size of 5-10 microns are selected, mixed and ground with n-butyl alcohol, o-benzene, polyvinyl butyral and fish oil, cast to form a biscuit, and then pre-sintered for 5 hours at 1000 ℃.
Preparing a cathode transition layer: NiO and YSZ with the particle size of 1-5 microns are selected, mixed and ground, then mixed and ground with terpineol and ethyl cellulose to form cathode transition layer slurry, the transition layer slurry is prepared on a cathode supporting layer through screen printing, and then presintering is carried out for 5 hours at 1100 ℃.
Preparing a cathode active layer: ni (NO) is configured according to the mass ratio of NiO to YSZ in the active layer3)2·6H2O、Y(NO3)3·6H2O and Zr (NO)3)4·5H2100mL of O mixed solution, controlling the total concentration of metal ions in the mixed solution to be 2M, adding glycine, wherein the molar concentration ratio of the glycine to the metal ions is 2: 1, and heating the mixed solution at 80 ℃ for 5 hours to form transparent sol; adding propylene glycol into transparent sol, transferring the sol into an evaporation dish, continuously heating the evaporation dish through an electric furnace until the sol is combusted to form initial mixed powder, roasting the initial mixed powder at the high temperature of 1000 ℃ for 10 hours to form a NiO and YSZ mixture with the particle size of 0.1-0.5 micrometer, mixing and grinding the NiO and YSZ mixture with terpineol and ethyl cellulose to form cathode active layer slurry, preparing the transition layer slurry on a cathode supporting layer through screen printing, and then pre-sintering the transition layer slurry at the temperature of 1100 ℃ for 5 hours.
Preparing an electrolyte layer: mixing and grinding 30-50 nm YSZ particles, terpineol and ethyl cellulose to form electrolyte layer slurry, preparing the electrolyte layer slurry on a cathode active layer through screen printing, and sintering at 1300 ℃ for 10 hours.
Preparing an interlayer: size of the particlesGd of 50 to 100 nm0.1Ce0.9O2Mixing with terpineol and ethyl cellulose, grinding to form interlayer slurry, preparing the interlayer slurry on the electrolyte layer by screen printing, and sintering at 1200 ℃ for 5 h.
Preparing a cathode layer: la0.6Sr0.4Co0.2Fe0.8O3The electrode paste was prepared on the spacers by screen printing and then sintered at 1000 ℃ for 5 h.
The electrolytic cell is operated in an electrolytic water mode, and the electrolytic current density is-3.3 Acm under the conditions that the absolute humidity is 70 percent, the temperature is 800 ℃ and the voltage is 1.5V-2。
Example 2
A solid oxide electrolytic cell comprises a cathode supporting layer, a cathode transition layer, a cathode active layer, an electrolytic cell layer, an interlayer and an anode layer; the cathode supporting layer consists of NiO and YSZ, the total mass of the cathode supporting layer is 1g, wherein the NiO is 0.7g, the YSZ is 0.3g, the porosity is 55%, and the thickness of the cathode supporting layer is 1.5 mm; the total mass of the cathode transition layer is 0.02g, wherein NiO is 0.01g, YSZ is 0.01g, the thickness is 15 microns, and the porosity is 50%; the mass of the cathode active layer is 0.02g, wherein NiO is 0.008g, YSZ is 0.012g, the thickness is 5 microns, and the porosity is 40%; the electrolytic cell layer is YSZ, and the thickness of the electrolyte layer is 10 microns; the interlayer is Gd0.1Ce0.9O2The thickness of the interlayer is 1 micron; the anode layer is La0.6Sr0.4Co0.2Fe0.8O3The mass of the oxygen electrode was 0.008 g.
The electrolytic cell is prepared as follows:
preparing a cathode supporting layer: NiO and YSZ with the particle size of 5-10 microns are selected, mixed and ground with n-butyl alcohol, o-benzene, polyvinyl butyral and fish oil, cast to form a biscuit, and then pre-sintered for 5 hours at 1000 ℃.
Preparing a cathode transition layer: NiO and YSZ with the particle size of 1-5 microns are selected, mixed and ground, then mixed and ground with terpineol and ethyl cellulose to form cathode transition layer slurry, the transition layer slurry is prepared on a cathode supporting layer through screen printing, and then presintering is carried out for 5 hours at 1100 ℃.
Preparing a cathode active layer: ni (NO) is configured according to the mass ratio of NiO to YSZ in the active layer3)2·6H2O、Y(NO3)3·6H2O and Zr (NO)3)4·5H2100mL of O mixed solution, controlling the total concentration of metal ions in the mixed solution to be 2M, adding glycine, wherein the molar concentration ratio of the glycine to the metal ions is 2: 1, and heating the mixed solution at 80 ℃ for 5 hours to form transparent sol; adding propylene glycol into transparent sol, transferring the sol into an evaporation dish, continuously heating the evaporation dish through an electric furnace until the sol is combusted to form initial mixed powder, roasting the initial mixed powder at the high temperature of 1000 ℃ for 10 hours to form a NiO and YSZ mixture with the particle size of 0.1-0.5 micrometer, mixing and grinding the NiO and YSZ mixture with terpineol and ethyl cellulose to form cathode active layer slurry, preparing the transition layer slurry on a cathode supporting layer through screen printing, and then pre-sintering the transition layer slurry at the temperature of 1100 ℃ for 5 hours.
Preparing an electrolyte layer: mixing and grinding 30-50 nm YSZ particles, terpineol and ethyl cellulose to form electrolyte layer slurry, preparing the electrolyte layer slurry on a cathode active layer through screen printing, and sintering at 1300 ℃ for 10 hours.
Preparing an interlayer: gd with the particle size of 50-100 nanometers0.1Ce0.9O2Mixing with terpineol and ethyl cellulose, grinding to form interlayer slurry, preparing the interlayer slurry on the electrolyte layer by screen printing, and sintering at 1200 ℃ for 5 h.
Preparing a cathode layer: la0.6Sr0.4Co0.2Fe0.8O3The electrode paste was prepared on the spacers by screen printing and then sintered at 1000 ℃ for 5 h.
The electrolytic cell is operated in an electrolytic water mode, and the electrolytic current density is-2.7 Acm under the conditions that the absolute humidity is 70 percent, the temperature is 800 ℃ and the voltage is 1.5V-2。
Example 3
A solid oxide electrolytic cell comprises a cathode supporting layer, a cathode transition layer, a cathode active layer, an electrolytic cell layer, an interlayer and an anode layer; the cathode supporting layer is composed of NiO and YSZThe total mass of the cathode supporting layer is 1g, wherein NiO is 0.65g, YSZ is 0.35g, the porosity is 60%, and the thickness of the cathode supporting layer is 1 mm; the total mass of the cathode transition layer is 0.02g, wherein NiO is 0.01g, YSZ is 0.01g, the thickness is 15 microns, and the porosity is 50%; the mass of the cathode active layer is 0.02g, wherein NiO is 0.008g, YSZ is 0.012g, the thickness is 5 microns, and the porosity is 40%; the electrolytic cell layer is YSZ, and the thickness of the electrolyte layer is 10 microns; the interlayer is Gd0.1Ce0.9O2The thickness of the interlayer is 1 micron; the anode layer is La0.6Sr0.4Co0.2Fe0.8O3The mass of the oxygen electrode was 0.008 g.
The electrolytic cell is prepared as follows:
preparing a cathode supporting layer: NiO and YSZ with the particle size of 5-10 microns are selected, mixed and ground with n-butyl alcohol, o-benzene, polyvinyl butyral and fish oil, cast to form a biscuit, and then pre-sintered for 5 hours at 1000 ℃.
Preparing a cathode transition layer: NiO and YSZ with the particle size of 1-5 microns are selected, mixed and ground, then mixed and ground with terpineol and ethyl cellulose to form cathode transition layer slurry, the transition layer slurry is prepared on a cathode supporting layer through screen printing, and then presintering is carried out for 5 hours at 1100 ℃.
Preparing a cathode active layer: NiO and YSZ with the particle size of 0.1-0.5 micrometer are selected, mixed and ground, then mixed and ground with terpineol and ethyl cellulose to form cathode active layer slurry, the transition layer slurry is prepared on a cathode transition layer through screen printing, and then presintering is carried out for 5 hours at 1100 ℃.
Preparing an electrolyte layer: mixing and grinding 30-50 nm YSZ particles, terpineol and ethyl cellulose to form electrolyte layer slurry, preparing the electrolyte layer slurry on a cathode active layer through screen printing, and sintering at 1300 ℃ for 10 hours.
Preparing an interlayer: gd with the particle size of 50-100 nanometers0.1Ce0.9O2Mixing with terpineol and ethyl cellulose, grinding to obtain interlayer slurry, screen printing to obtain interlayer slurry, and firing at 1200 deg.CKnot 5 h.
Preparing a cathode layer: la0.6Sr0.4Co0.2Fe0.8O3The electrode paste was prepared on the spacers by screen printing and then sintered at 1000 ℃ for 5 h.
The electrolytic cell is operated in an electrolytic water mode, and the electrolytic current density is-2.3 Acm under the conditions that the absolute humidity is 70 percent, the temperature is 800 ℃ and the voltage is 1.5V-2。
Example 4
A solid oxide electrolytic cell comprises a cathode supporting layer, a cathode transition layer, a cathode active layer, an electrolytic cell layer, an interlayer and an anode layer; the cathode supporting layer consists of NiO and YSZ, the total mass of the cathode supporting layer is 1g, wherein the NiO is 0.65g, the YSZ is 0.35g, the porosity is 60%, and the thickness of the cathode supporting layer is 1 mm; the total mass of the cathode transition layer is 0.02g, wherein NiO is 0.01g, YSZ is 0.01g, the thickness is 15 microns, and the porosity is 50%; the mass of the cathode active layer is 0.02g, wherein NiO is 0.001g, YSZ is 0.001g, the thickness is 5 microns, and the porosity is 50%; the electrolytic cell layer is YSZ, and the thickness of the electrolyte layer is 10 microns; the interlayer is Gd0.1Ce0.9O2The thickness of the interlayer is 1 micron; the anode layer is La0.6Sr0.4Co0.2Fe0.8O3The mass of the oxygen electrode was 0.008 g.
The electrolytic cell is prepared as follows:
preparing a cathode supporting layer: NiO and YSZ with the particle size of 5-10 microns are selected, mixed and ground with n-butyl alcohol, o-benzene, polyvinyl butyral and fish oil, cast to form a biscuit, and then pre-sintered for 5 hours at 1000 ℃.
Preparing a cathode transition layer: NiO and YSZ with the particle size of 1-5 microns are selected, mixed and ground, then mixed and ground with terpineol and ethyl cellulose to form cathode transition layer slurry, the transition layer slurry is prepared on a cathode supporting layer through screen printing, and then presintering is carried out for 5 hours at 1100 ℃.
Preparing a cathode active layer: ni (NO) is configured according to the mass ratio of NiO to YSZ in the active layer3)2·6H2O、Y(NO3)3·6H2O and Zr (NO)3)4·5H2100mL of O mixed solution, controlling the total concentration of metal ions in the mixed solution to be 2M, adding glycine, wherein the molar concentration ratio of the glycine to the metal ions is 2: 1, and heating the mixed solution at 80 ℃ for 5 hours to form transparent sol; adding propylene glycol into transparent sol, transferring the sol into an evaporation dish, continuously heating the evaporation dish through an electric furnace until the sol is combusted to form initial mixed powder, roasting the initial mixed powder at the high temperature of 1000 ℃ for 10 hours to form a NiO and YSZ mixture with the particle size of 0.1-0.5 micrometer, mixing and grinding the NiO and YSZ mixture with terpineol and ethyl cellulose to form cathode active layer slurry, preparing the transition layer slurry on a cathode supporting layer through screen printing, and then pre-sintering the transition layer slurry at the temperature of 1100 ℃ for 5 hours.
Preparing an electrolyte layer: mixing and grinding 30-50 nm YSZ particles, terpineol and ethyl cellulose to form electrolyte layer slurry, preparing the electrolyte layer slurry on a cathode active layer through screen printing, and sintering at 1300 ℃ for 10 hours.
Preparing an interlayer: gd with the particle size of 50-100 nanometers0.1Ce0.9O2Mixing with terpineol and ethyl cellulose, grinding to form interlayer slurry, preparing the interlayer slurry on the electrolyte layer by screen printing, and sintering at 1200 ℃ for 5 h.
Preparing a cathode layer: la0.6Sr0.4Co0.2Fe0.8O3The electrode paste was prepared on the spacers by screen printing and then sintered at 1000 ℃ for 5 h.
The electrolytic cell is operated in an electrolytic water mode, and the electrolytic current density is-2.9 Acm under the conditions that the absolute humidity is 70 percent, the temperature is 800 ℃ and the voltage is 1.5V-2。

Claims (9)

1. A solid oxide electrolytic cell characterized by: the electrolytic cell consists of a cathode supporting layer, a cathode transition layer, a cathode active layer, an electrolytic cell layer, an interlayer and an anode layer in sequence;
the cathode supporting layer is a mixture of NiO and YSZ, wherein the NiO content is 50-70 wt%, the porosity of the cathode supporting layer is 50-70%, and the thickness of the cathode supporting layer is 05-2 mm; the YSZ is Y0.15Zr0.85O2；
The cathode transition layer is a mixture of NiO and YSZ, the content of NiO is 40-60 wt%, the porosity of the cathode transition layer is 50-60%, and the thickness of the cathode transition layer is 1-15 micrometers;
the cathode active layer is a mixture of NiO and YSZ, the content of NiO is 30-50 wt%, the porosity of the cathode active layer is 30-50%, and the thickness of the cathode active layer is 1-10 micrometers;
the porosity of a cathode supporting layer, a cathode transition layer and a cathode active layer of the electrolytic cell is reduced in sequence;
the powder of the cathode active layer is prepared by the following method,
(1) preparing mixed liquid: preparing mixed solution of nitrates of Ni, Y and Zr according to the content of NiO and YSZ in the cathode active layer, adding a complexing agent, and heating to form transparent sol;
(2) preparing mixed powder: adding a combustion improver into the transparent sol, continuously adding the transparent sol to the sol for combustion to form initial mixed powder, and roasting the initial mixed powder to form mixed powder.
2. A solid oxide electrolytic cell according to claim 1, wherein:
the electrolytic cell layer is YSZ, and the thickness of the electrolyte layer is 2-50 microns;
the interlayer is Gd0.1Ce0.9O2The thickness of the interlayer is 0.2-5 microns;
the anode layer is La0.6Sr0.4Co0.2Fe0.8O3Or La0.6Sr0.4Co0.2Fe0.8O3With Gd0.1Ce0.9O2A composite of components;
the powder of the cathode active layer is prepared by the following method,
in the step (1), the total concentration of metal ions in the mixed solution is 0.5-3M, the molar concentration ratio of the complexing agent to the metal ions is 0.5: 1-3: 1, and the mixed solution is heated at 60-80 ℃ for 5-10 h;
in the step (2), a combustion improver is added into the transparent sol, the sol is transferred into an evaporation vessel, the evaporation vessel is continuously heated by an electric furnace until the sol is combusted, so as to form initial mixed powder, and the initial mixed powder is roasted at a high temperature of 800-1000 ℃ for 3-10 h to form mixed powder.
3. The solid oxide electrolytic cell of claim 1, wherein the cathode support layer has a NiO content of 55 to 65 wt%, a cathode support layer porosity of 60 to 70%, and a cathode support layer thickness of 0.8 to 1.5 mm.
4. A solid oxide electrolytic cell according to claim 1, wherein: the NiO content in the cathode transition layer is 45-55 wt%, the porosity of the cathode transition layer is 45-55%, and the thickness of the cathode transition layer is 1-10 micrometers.
5. A solid oxide electrolytic cell according to claim 1, wherein: the content of NiO in the cathode active layer is 35-45 wt%, the porosity of the cathode active layer is 35-45%, and the thickness of the cathode active layer is 1-5 microns.
6. A solid oxide electrolytic cell according to claim 1, wherein: NiO and YSZ particle sizes selected for preparing the cathode supporting layer are 1-20 micrometers, NiO and YSZ particle sizes selected for preparing the cathode transition layer are 0.5-5 micrometers, and NiO and YSZ particle sizes selected for preparing the cathode active layer are 0.1-1 micrometer.
7. A solid oxide electrolytic cell according to claim 1, wherein: NiO and YSZ particle sizes selected for preparing the cathode supporting layer are 5-10 micrometers, NiO and YSZ particle sizes selected for preparing the cathode transition layer are 1-5 micrometers, and NiO and YSZ particle sizes selected for preparing the cathode active layer are 0.1-0.5 micrometer.
8. A solid oxide electrolytic cell according to claim 1 or 2, wherein: in the preparation step (1) of the active layer powder, the total concentration of metal ions in the mixed solution is 1-2M, the molar concentration ratio of the complexing agent to the metal ions is 1.5: 1-2: 1, and the complexing agent is one of ammonium citrate and glycine.
9. A solid oxide electrolytic cell according to claim 1 or 2, wherein: in the active layer powder preparation step (2), the combustion improver is one of propylene glycol or glycerol.
CN202111539074.9A 2021-12-15 2021-12-15 Solid oxide electrolytic cell Pending CN114016072A (en)

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