CN114016063B - Solid oxide electrolytic cell and preparation method thereof - Google Patents

Solid oxide electrolytic cell and preparation method thereof Download PDF

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CN114016063B
CN114016063B CN202111536349.3A CN202111536349A CN114016063B CN 114016063 B CN114016063 B CN 114016063B CN 202111536349 A CN202111536349 A CN 202111536349A CN 114016063 B CN114016063 B CN 114016063B
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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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    • C25B9/00Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
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    • YGENERAL 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
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    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract

The invention discloses a low-temperature solid oxide electrolytic cell and a preparation method thereof, wherein the electrolytic cell comprises a hydrogen electrode layer, an electrolyte layer, an electron barrier layer, an interlayer and an oxygen electrode layer, wherein the hydrogen electrode layer is NiO and doped cerium oxide Ln x Ce 1‑x O 2 The electrolyte layer is doped cerium oxide-based material Ln x Ce 1‑x O 2 Ln is one or more of La, gd, sm, pr and Er, x is more than or equal to 0.1 and less than or equal to 0.5, and the electron blocking layer is a doped zirconia-based material M y Zr 1‑ y O 2 M is one or more of Y, sc, ce, yb, la, gd and Sm, Y is more than or equal to 0 and less than or equal to 0.5, and the interlayer is doped cerium oxide Ln x Ce 1‑x O 2 ,Ln x Ce 1‑x O 2 Ln is one or more of La, gd, sm, Y, pr and Er, x is more than or equal to 0.1 and less than or equal to 0.5, and the oxygen electrode is a perovskite oxide, a perovskite-like oxide or a composite material formed by the perovskite oxide and doped cerium oxide or the perovskite-like oxide and the doped cerium oxide. The electrolytic cell has excellent performance of low-temperature water electrolysis hydrogen production and power water electrolysis and carbon dioxide electrolysis.

Description

Solid oxide electrolytic cell and preparation method thereof
Technical Field
The invention relates to the field of fuel cells and electrolytic cells, in particular to a solid oxide electrolytic cell and a preparation method thereof.
Background
The Solid Oxide Electrolysis Cell (SOEC) can be regarded as the reverse process of the Solid Oxide fuel Cell, can electrolyze water vapor into hydrogen and oxygen at high temperature, or can be used for electrolyzing water vapor and carbon dioxide into synthesis gas, the apparent electrical efficiency can reach 100%, and the Solid Oxide electrolysis Cell is regarded as the most efficient electrolysis hydrogen production technology at present.
The high cost is an important reason that hinders the commercial application of solid oxide fuel cells or electrolyzers. In order to reduce the cost, the low temperature of the solid oxide fuel cell or the electrolytic cell has become a research hotspot in the field. The membrane electrode is the core component of the SOEC, and has a sandwich structure, a compact electrolyte layer is arranged in the middle, and porous hydrogen electrodes and oxygen electrodes are arranged on two sides. The ohmic resistance of the electrolyte layer is usually a major portion of the overall membrane electrode resistance. At present, a doped zirconia material is a commonly used SOEC electrolyte material, but the oxygen ion conductivity thereof is low at low temperature, resulting in a significant decrease in battery performance. The doped cerium oxide material has higher oxygen ion conductivity at low temperature, but it has a certain electron conductivity, resulting in a cell having an open circuit potential (OCV) lower than a theoretical value, decreasing the cell efficiency.
Disclosure of Invention
Based on the above background technologies, the invention provides a low-temperature solid oxide electrolytic cell and a preparation method thereof, the electrolytic cell is based on a doped cerium oxide-based electrolyte, has lower ohmic resistance and higher OCV at low temperature, and realizes excellent performance output. The method comprises the following specific steps:
the low-temperature solid oxide electrolytic cell comprises a hydrogen electrode layer, an electrolyte layer, an electron barrier layer, an interlayer and an oxygen electrode layer, wherein the hydrogen electrode layer is NiO and doped cerium oxide Ln x Ce 1-x O 2 Composite material of NiO and Ln x Ce 1-x O 2 The mass ratio of the metal oxide to the metal oxide is 40: 60-70: 30, the thickness of the hydrogen electrode layer is 500-2000 nm, the porosity is 30-60%, ln in the hydrogen electrode layer is one or more of La, gd, sm, pr and Er, and x is more than or equal to 0.1 and less than or equal to 0.5; the electrolyte layer is doped cerium oxide (Ln) x Ce 1-x O 2 ) Ln is La,Gd. One or more of Sm, pr and Er, x is more than or equal to 0.1 and less than or equal to 0.5, the thickness of the electrolyte layer is 2-20 microns, and the electron blocking layer is a doped zirconia-based material (M) y Zr 1-y O 2 ) M is one or more of Y, sc, ce, yb, la, gd and Sm, Y is more than or equal to 0 and less than or equal to 0.5, the electron blocking layer is 2-500 nanometers, and the interlayer is doped cerium oxide (Ln) x Ce 1-x O 2 ) Ln is one or more of La, gd, sm, Y, pr and Er, x is more than or equal to 0.1 and less than or equal to 0.5, the thickness of the interlayer is 0.2-5 microns, the oxygen electrode is a composite material formed by perovskite oxide, perovskite-like oxide or perovskite oxide and doped cerium oxide or perovskite-like oxide and doped cerium oxide, the mass ratio of the perovskite oxide to the doped cerium oxide is 50: 50-80: 20, the mass ratio of the perovskite-like oxide to the doped cerium oxide is 50: 50-80: 20, the thickness of the oxygen electrode layer is 10-100 microns, and the porosity of the oxygen electrode layer is 30-60%.
Further, in the above technical solution, the hydrogen electrode preferably has a thickness of 800 to 1500 nm and a porosity of 40 to 55%.
Further, in the above technical solution, the electrolyte layer is doped cerium oxide (Ln) x Ce 1-x O 2 ) Ln is preferably one or more of Gd, sm, pr and Er, and the electrolyte layer thickness is preferably 5-10 microns.
Further, in the above technical solution, the electron blocking layer is a doped zirconia-based material (M) y Zr 1- y O 2 ) M is preferably one or more of Y, la, gd and Sm, and the electron blocking layer is preferably 5-50 nanometers.
Further, in the above technical solution, the spacer is doped cerium oxide (Ln) x Ce 1-x O 2 ) Ln is preferably one or more of La, gd, sm, pr and Er, and the thickness of the interlayer is preferably 0.2-2 microns.
Further, in the above technical solution, the oxygen electrode is preferably a composite material of a perovskite oxide and a doped cerium oxide or a perovskite-like oxide and a doped cerium oxide, the thickness of the oxygen electrode layer is preferably 20 to 50 μm, and the porosity of the oxygen electrode layer is preferably 40 to 55%.
The invention provides a preparation method of the electrolytic cell, which comprises the following steps of (1) mixing NiO and doped cerium oxide (Ln) x Ce 1- x O 2 ) Mixing and grinding the raw materials according to a certain mass ratio for 5-50 h to form hydrogen electrode powder, mixing and ball-milling the hydrogen electrode powder, toluene, ethanol, fish oil, polyethylene glycol, dioctyl phthalate and polyvinyl butyral for 10-100 h to form hydrogen electrode slurry, wherein the raw materials comprise: 100: 60-100: 20-50: 1-5: 3-6: 6-10, performing tape casting on the hydrogen electrode slurry to form a hydrogen electrode blank, drying the blank, and presintering the blank in a high-temperature furnace at 800-1200 ℃ for 2-20 h to form a hydrogen electrode support body; (2) Mixing and grinding electrolyte powder, n-butyl alcohol, o-benzene, polyvinyl butyral and fish oil for 10-100 h to form electrolyte slurry, wherein the raw materials are as follows: 100: 200-300: 10-40: 1-5, preparing the electrolyte slurry into a hydrogen electrode support body by adopting a screen printing or direct coating method, and sintering for 2-20 h at the high temperature of 1300-1500 ℃; (3) Preparing an electron barrier layer by adopting a magnetron sputtering method, and annealing at 200-600 ℃; (4) Preparing an interlayer on the electron barrier layer by adopting a magnetron sputtering method, and annealing at 800-1100 ℃; (5) Mixing and grinding the oxygen electrode powder, terpineol and ethyl cellulose for 2-50 h to form oxygen electrode slurry, preparing the oxygen electrode slurry on the interlayer by adopting a screen printing or direct coating method, and sintering at the high temperature of 800-1200 ℃ for 2-10 h to obtain the full cell.
Further, in the above technical scheme, the electron blocking layer is prepared by adopting a magnetron sputtering method, the sputtering atmosphere is a mixed gas of oxygen and argon, the flow ratio of the oxygen to the argon is 1/1-1/40, the temperature of the sputtering substrate is 100-400 ℃, the sputtering pressure is 0.1 Pa-3.5 Pa, and the sputtering power density P = 3-35 Wcm -2
Further, in the technical scheme, the interlayer is prepared by adopting a magnetron sputtering method, the sputtering atmosphere is mixed gas of oxygen and argon, the flow ratio of the oxygen to the argon is 1/1-1/20, the temperature of a sputtering substrate is 100-600 ℃, the sputtering pressure is 0.1-2 Pa, and the sputtering power density p = 3-20 Wcm -2
Advantageous effects of the invention
(1) The invention is based on cerium oxide-based electrolyte, and an electron barrier layer M is prepared on the surface of the doped cerium oxide-based electrolyte y Zr 1-y O 2 And interlayer Ln x Ce 1-x O 2 Electron blocking layer M y Zr 1-y O 2 Effectively inhibiting the internal leakage problem of the doped cerium oxide, and avoiding the harmful reaction of the electron barrier layer and the high-activity Co/Fe-based perovskite-based oxygen electrode at high temperature by the interlayer. The method is applied to a solid oxide electrolytic cell, can be used for electrolyzing water to prepare hydrogen, and has reliable operation of the electrolytic cell.
(2) The electron barrier layer and the interlayer are prepared by the magnetron sputtering method, the uniformity of the electron barrier layer and the interlayer is better, the high-temperature sintering process is avoided, and the formation of high-resistance Ce-Zr solid solution between the electron barrier layer and the electrolyte layer and between the electron barrier layer and the interlayer in the high-temperature sintering process is avoided.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
Comparative example 1
A solid oxide electrolytic cell comprises a hydrogen electrode layer, an electrolyte layer and an oxygen electrode layer in this order. The hydrogen electrode was 1g, where NiO and Gd 0.2 Ce 0.8 O 2 0.5g, the thickness of the hydrogen electrode layer is 1000 nm, the porosity is 45 percent, and the electrolyte is Gd 0.2 Ce 0.8 O 2 The electrolyte layer thickness was 10 μm, and the oxygen electrode was La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3 -Gd 0.2 Ce 0.8 O 2 Has a mass of 0.01g, wherein La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3 0.006g of Gd 0.2 Ce 0.8 O 2 0.004g, the thickness of the oxygen electrode layer is 50 micrometers, and the porosity of the oxygen electrode layer is 50%. At 550 ℃, the OCV of the electrolytic cell is 0.97 when the absolute humidity of the hydrogen electrode side is 3%, the OCV of the electrolytic cell is 0.8V when the absolute humidity is 50%, and the current density is-0.12 Acm at 1.3V -2 . The OCV of the cell was 1.03V at an absolute humidity of 3% at the hydrogen electrode side at 450 ℃, 0.86V at an absolute humidity of 50%, and the current density was-0.03 Acm at 1.3V -2 . The electrolytic cell of comparative example 1 contained a hydrogen electrode layerElectrolyte layer and oxygen electrode layer, because the electric leakage in the electrolyte layer, the OCV and the performance of electrolytic cell are all lower.
Example 1
A solid oxide electrolytic cell comprises a hydrogen electrode layer, an electrolyte layer, an electron barrier layer, an interlayer, and an oxygen electrode layer in sequence, wherein the hydrogen electrode is 1g, niO and Gd 0.2 Ce 0.8 O 2 0.5g, hydrogen electrode layer thickness of 1000 nm, porosity of 45%, and electrolyte Gd 0.2 Ce 0.8 O 2 The thickness of the electrolyte layer was 10 μm, and the material of the electron blocking layer was Y 0.15 Zr 0.85 O 2 The thickness of the electron barrier layer is 100 nanometers, and the interlayer material is Gd 0.2 Ce 0.8 O 2 The thickness of the interlayer is 1 micron, and the oxygen electrode is La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3 -Gd 0.2 Ce 0.8 O 2 Has a mass of 0.01g, wherein La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3 0.006g of Gd 0.2 Ce 0.8 O 2 0.004g, the thickness of the oxygen electrode layer is 50 microns, and the porosity of the oxygen electrode layer is 50%. At 550 ℃, the OCV of the electrolytic cell is 1.02 when the absolute humidity of the hydrogen electrode side is 3%, the OCV of the electrolytic cell is 0.86V when the absolute humidity is 50%, and the current density is-0.35 Acm at 1.3V -2 . At 450 deg.C, the OCV of the electrolytic cell is 1.10 when the absolute humidity of the hydrogen electrode side is 3%, the OCV of the electrolytic cell is 0.94V when the absolute humidity is 50%, and the current density is-0.15 Acm at 1.3V -2
The above-described electrolytic cell is prepared as follows,
(1) NiO (50 g) was mixed with Gd 0.2 Ce 0.8 O 2 (50g) Mixing and grinding the mixture for 24 hours to form hydrogen electrode powder, mixing and ball-milling the hydrogen electrode powder, toluene, ethanol, fish oil, polyethylene glycol, dioctyl phthalate and polyvinyl butyral for 50 hours to form hydrogen electrode slurry, wherein the dosage of the raw materials is respectively as follows: 100g, 80g, 25g, 1g, 3g and 8g, carrying out tape casting on the hydrogen electrode slurry to form a hydrogen electrode blank, drying the blank, and presintering the blank in a high-temperature furnace at 1000 ℃ for 5 hours to form a hydrogen electrode support body;
(2) Gd electrolyte is added 0.2 Ce 0.8 O 2 Mixing and grinding the powder with n-butyl alcohol, o-benzene, polyvinyl butyral and fish oil for 10-100 h to form electrolyte slurry, wherein the dosage of the raw materials is respectively as follows: 10g, 25g, 1.5g, 2g and 0.2g, preparing the electrolyte slurry on a hydrogen electrode support body by adopting a screen printing method, and sintering at the high temperature of 1400 ℃ for 10 hours;
(3) Preparing an electron barrier layer by magnetron sputtering, wherein the sputtering atmosphere is a mixed gas of oxygen and argon, the flow ratio of the oxygen to the argon is 1/15, the temperature of a sputtering substrate is 400 ℃, the sputtering pressure is 0.15Pa, and the sputtering power density P =10Wcm -2 Annealing the sputtered electron blocking layer at 300 ℃;
(4) Preparing an interlayer on the electron barrier layer by magnetron sputtering, wherein the sputtering atmosphere is oxygen and argon mixed gas, the flow ratio of the oxygen and the argon is 1/10, the temperature of a sputtering substrate is 400 ℃, the sputtering pressure is 0.5Pa, and the sputtering power density P =15Wcm -2 Annealing the sputtered interlayer at 1000 ℃ for 5 hours;
(5) La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3 (6g)、Gd 0.2 Ce 0.8 O 2 (4g) Mixing and grinding the mixture for 10 hours, mixing the mixture with terpineol (4.7 g) and ethyl cellulose (0.3 g), grinding the mixture for 24 hours to form oxygen electrode slurry, preparing the oxygen electrode slurry on an interlayer by adopting a screen printing method, and sintering the oxygen electrode slurry for 3 hours at the high temperature of 1000 ℃ to obtain the full cell.
Example 2
A solid oxide electrolytic cell comprises a hydrogen electrode layer, an electrolyte layer, an electron barrier layer, an interlayer, and an oxygen electrode layer in sequence, wherein the hydrogen electrode is 1g, niO and Gd 0.2 Ce 0.8 O 2 0.5g, hydrogen electrode layer thickness of 1000 nm, porosity of 45%, and electrolyte Gd 0.2 Ce 0.8 O 2 The thickness of the electrolyte layer is 10 microns, and the material of the electron barrier layer is Y 0.15 Zr 0.85 O 2 The thickness of the electron barrier layer is 100 nanometers, and the interlayer material is Gd 0.2 Ce 0.8 O 2 The thickness of the interlayer is 1 micron, and the oxygen electrode is La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3 -Gd 0.2 Ce 0.8 O 2 Mass 0.01g, wherein La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3 0.006g of Gd 0.2 Ce 0.8 O 2 0.004g, the thickness of the oxygen electrode layer is 50 microns, and the porosity of the oxygen electrode layer is 50%.
The above-described electrolytic cell was prepared as follows,
(1) NiO (50 g) was mixed with Gd 0.2 Ce 0.8 O 2 (50g) Mixing and grinding the mixture for 24 hours to form hydrogen electrode powder, mixing and ball-milling the hydrogen electrode powder, toluene, ethanol, fish oil, polyethylene glycol, dioctyl phthalate and polyvinyl butyral for 50 hours to form hydrogen electrode slurry, wherein the dosage of the raw materials is respectively as follows: 100g, 80g, 25g, 1g, 3g and 8g of hydrogen electrode slurry are subjected to tape casting to form a hydrogen electrode blank, the blank is dried and then presintered in a high temperature furnace at 1000 ℃ for 5 hours to form a hydrogen electrode support body;
(2) Gd electrolyte is added 0.2 Ce 0.8 O 2 Mixing and grinding the powder with n-butyl alcohol, o-benzene, polyvinyl butyral and fish oil for 10-100 h to form electrolyte slurry, wherein the dosage of the raw materials is respectively as follows: 10g, 25g, 1.5g and 2 g: 0.2g, preparing the electrolyte slurry into a hydrogen electrode support body by adopting a screen printing method, and sintering at the high temperature of 1400 ℃ for 10 hours;
(3) Preparing an electron blocking layer by screen printing, and adding Y 0.15 Zr 0.85 O 2 (10g) Mixing with terpineol (10 g) and ethyl cellulose (0.5 g), grinding for 24h to obtain electron barrier layer slurry, printing the electron barrier layer slurry on an electrolyte layer, and sintering at the high temperature of 1200 ℃ for 10h;
(4) Preparing interlayer by screen printing method, and adding Gd 0.2 Ce 0.8 O 2 (8g) Mixing with terpineol (10 g) and ethyl cellulose (0.5 g), grinding for 24h to obtain interlayer slurry, printing on an electronic barrier, and sintering at 1280 ℃ for 10h;
(5) La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3 (6g)-Gd 0.2 Ce 0.8 O 2 (4g) Mixing and grinding for 10h, mixing with terpineol (4.7 g) and ethyl cellulose (0.3 g), grinding for 24h to obtain oxygen electrode paste, and screen printingPreparing the materials on the interlayer, and sintering at the high temperature of 1000 ℃ for 3h to obtain the full cell.
The OCV of the electrolytic cell is 0.99V at 550 deg.C and 3% absolute humidity of hydrogen electrode, 0.82V at 50% absolute humidity, and-0.15 Acm at 1.3V -2 . At 450 deg.C, the OCV of the cell was 1.06 at an absolute humidity of 3% at the hydrogen electrode side, 0.89V at an absolute humidity of 50%, and a current density of-0.05 Acm at 1.3V -2
As can be seen from the comparison of the examples, the electrolytic cell effectively improves the performance of the electrolytic cell by adding the electron barrier layer and the interlayer, wherein the electrolytic cell with the electron barrier layer and the interlayer prepared by the magnetron sputtering method has more excellent performance.

Claims (10)

1. A low temperature solid oxide electrolytic cell, characterized in that: the electrolytic cell sequentially comprises a hydrogen electrode layer, an electrolyte layer, an electron barrier layer, an interlayer and an oxygen electrode layer; the hydrogen electrode layer is NiO and Ln x Ce 1-x O 2 A composite of components;
the electrolyte layer is Ln x Ce 1-x O 2 (ii) a The electron blocking layer is M y Zr 1-y O 2 M is one or more of Y, sc, ce, yb, la, gd and Sm, Y is more than or equal to 0 and less than or equal to 0.5, and the electronic barrier layer is 2 to 500 nanometers; the interlayer is Ln x Ce 1-x O 2 The thickness of the interlayer is 0.2 to 5 microns; wherein Ln in the hydrogen electrode layer, the electrolyte layer and the interlayer x Ce 1-x O 2 Ln is independently selected from one or more of La, gd, sm, Y, pr and Er, and x is more than or equal to 0.1 and less than or equal to 0.5.
2. The low temperature solid oxide electrolytic cell of claim 1, wherein: niO and Ln of hydrogen electrode layer x Ce 1-x O 2 The mass ratio of (1) is 40 to 70, the thickness of the hydrogen electrode layer is 500 to 2000 nanometers, and the porosity is 30 to 60 percent;
the thickness of the electrolyte layer is 2 to 20 micrometers;
the oxygen electrode layer is a perovskite oxide, a perovskite-like oxide, or a composite material formed by the perovskite oxide and doped cerium oxide, or a composite material formed by the perovskite-like oxide and the doped cerium oxide, the thickness of the oxygen electrode layer is 10-100 micrometers, and the porosity of the oxygen electrode layer is 30-60%.
3. A low temperature solid oxide electrolysis cell according to claim 1 wherein: the thickness of the hydrogen electrode is 800 to 1500 nanometers, and the porosity is 40 to 55 percent; the electrolyte layer is Ln x Ce 1-x O 2 Ln is one or more of Gd, sm, pr and Er, and the thickness of the electrolyte layer is 5 to 10 micrometers.
4. A low temperature solid oxide electrolysis cell according to claim 1 wherein: the electron blocking layer is M y Zr 1-y O 2 M is one or more of Y, la, gd and Sm, and the electronic barrier layer is 5 to 50 nanometers.
5. A low temperature solid oxide electrolysis cell according to claim 1 wherein: the interlayer is Ln x Ce 1- x O 2 Ln is one or more of La, gd, sm, pr and Er, and the thickness of the interlayer is 0.2 to 2 microns.
6. A low temperature solid oxide electrolysis cell according to claim 1 wherein: the oxygen electrode layer is a composite material formed by a perovskite oxide and doped cerium oxide or a perovskite-like oxide and doped cerium oxide, the mass ratio of the perovskite oxide to the doped cerium oxide is 50 to 80, the mass ratio of the perovskite-like oxide to the doped cerium oxide is 50; the perovskite is (La, sr) (Co, fe) O 3 ,(Ba,Sr)(Co,Fe)O 3 , (La,Sr)CoO 3 ,(Sm,Sr)CoO 3 ,(Pr,Sr)CoO 3 One of the perovskite-like compounds is (La, sr) 2 CoO 4 ,(Pr,Sr) 2 CoO 4 ,(La,Sr) 2 NiO 4 One of them.
7. The method of making a low temperature solid oxide electrolysis cell of any one of claims 1~6 comprising the steps of:
(1) NiO is mixed with Ln x Ce 1-x O 2 Mixing and grinding the materials according to a mass ratio for 5 to 50h to form hydrogen electrode powder, mixing the hydrogen electrode powder, toluene, ethanol, fish oil, polyethylene glycol, dioctyl phthalate and polyvinyl butyral, and performing ball milling for 10 to 100h to form hydrogen electrode slurry, performing tape casting on the hydrogen electrode slurry to form a hydrogen electrode blank, drying the blank and then pre-sintering to form a hydrogen electrode support body;
(2) Mixing and grinding electrolyte powder, n-butyl alcohol, o-benzene, polyvinyl butyral and fish oil for 10 to 100h to form electrolyte slurry, preparing the electrolyte slurry on a hydrogen electrode support body by adopting a screen printing or direct coating method, and sintering;
(3) Preparing an electron barrier layer M on the electrolyte layer of the hydrogen electrode support obtained in the step (2) by adopting a magnetron sputtering method y Zr 1-y O 2 Annealing at 200 to 600 ℃;
(4) Preparing interlayer Ln on electron barrier layer by magnetron sputtering method x Ce 1-x O 2 Annealing at 800 to 1100 ℃;
(5) And preparing the oxygen electrode slurry on the interlayer by adopting a screen printing or direct coating method, and sintering to obtain the full cell.
8. The method of making a low temperature solid oxide electrolysis cell as claimed in claim 7, wherein: in the step (1), the hydrogen electrode powder, toluene, ethanol, fish oil, polyethylene glycol, dioctyl phthalate and polyvinyl butyral are prepared by the following raw materials in proportion: 100:60 to 100:20 to 50:1~5:3~6:3~6:6 to 10, drying the green embryo, and then pre-sintering in a high-temperature furnace at 800 to 1200 ℃ for 2 to 20h;
in the step (2), the proportion of the electrolyte powder to the n-butyl alcohol, the o-benzene, the polyvinyl butyral and the fish oil is as follows: 100:200 to 300:10 to 40:10 to 40:1~5, sintering the hydrogen electrode support body at the high temperature of 1300-1500 ℃ for 2-20h;
in the step (5), the oxygen electrode powder, terpineol and ethyl cellulose are mixed and ground for 2 to 50h to form oxygen electrode slurry, the oxygen electrode slurry is prepared on an interlayer by adopting a screen printing or direct coating method, and the mixture is sintered for 2 to 10h at the high temperature of 800 to 1200 ℃ to obtain the full-cell.
9. The method of making a low temperature solid oxide electrolysis cell as claimed in claim 7, wherein: in the step (3), an electron barrier layer is prepared by adopting a magnetron sputtering method, the sputtering atmosphere is a mixed gas of oxygen and argon, the flow ratio of the oxygen to the argon is 1/1~1/40, the temperature of a sputtering substrate is 100-400 ℃, the sputtering pressure is 0.1Pa-3.5Pa, and the sputtering power density is P = 3-35Wcm -2
10. The method of making a low temperature solid oxide electrolysis cell as claimed in claim 7, wherein: in the step (4), the interlayer is prepared by adopting a magnetron sputtering method, the sputtering atmosphere is a mixed gas of oxygen and argon, the flow ratio of the oxygen to the argon is 1/1~1/20, the temperature of a sputtering substrate is 100-600 ℃, the sputtering pressure is 0.1Pa-2Pa, and the sputtering power density is P = 3-20Wcm -2
CN202111536349.3A 2021-12-14 2021-12-14 Solid oxide electrolytic cell and preparation method thereof Active CN114016063B (en)

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CN114597424A (en) * 2022-04-06 2022-06-07 北京理工大学 Metal support solid oxide electrolytic cell adopting GDC electrolyte
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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005310737A (en) * 2004-03-23 2005-11-04 Toto Ltd Solid oxide fuel cell
WO2014057218A2 (en) * 2012-10-10 2014-04-17 Universite De Bourgogne Method for preparing a fuel cell
CN108103524A (en) * 2016-11-25 2018-06-01 中国科学院大连化学物理研究所 A kind of electrolytic tank of solid oxide and preparation method thereof
CN111244470A (en) * 2018-11-29 2020-06-05 中国科学院大连化学物理研究所 Nano composite cathode and preparation and application thereof
CN111910201A (en) * 2020-08-17 2020-11-10 广东电网有限责任公司广州供电局 Hydrogen electrode of solid oxide electrolytic cell, preparation method of hydrogen electrode and solid oxide electrolytic cell
CN112382774A (en) * 2020-11-13 2021-02-19 中国科学院大连化学物理研究所 Preparation method of electrolyte supporting type electrolytic cell barrier layer
CN112779555A (en) * 2020-12-25 2021-05-11 山东科技大学 High-performance solid oxide electrolytic cell and preparation method thereof

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005310737A (en) * 2004-03-23 2005-11-04 Toto Ltd Solid oxide fuel cell
WO2014057218A2 (en) * 2012-10-10 2014-04-17 Universite De Bourgogne Method for preparing a fuel cell
CN108103524A (en) * 2016-11-25 2018-06-01 中国科学院大连化学物理研究所 A kind of electrolytic tank of solid oxide and preparation method thereof
CN111244470A (en) * 2018-11-29 2020-06-05 中国科学院大连化学物理研究所 Nano composite cathode and preparation and application thereof
CN111910201A (en) * 2020-08-17 2020-11-10 广东电网有限责任公司广州供电局 Hydrogen electrode of solid oxide electrolytic cell, preparation method of hydrogen electrode and solid oxide electrolytic cell
CN112382774A (en) * 2020-11-13 2021-02-19 中国科学院大连化学物理研究所 Preparation method of electrolyte supporting type electrolytic cell barrier layer
CN112779555A (en) * 2020-12-25 2021-05-11 山东科技大学 High-performance solid oxide electrolytic cell and preparation method thereof

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
Aline Léon等.Effect of scaling-up on the performance and degradation of long-term operated electrolyte supported solid oxide cell, stack and module in electrolysis mode.《Journal of Power Sources》.2021,第510卷第230346页. *
Development of LSCF–GDC composite cathodes for low-temperature solid oxide fuel cells with thin film GDC electrolyte;Yongjun Leng等;《International Journal of Hydrogen Energy》;20080606;第33卷(第14期);摘要和正文第8-9页 *
Effect of scaling-up on the performance and degradation of long-term operated electrolyte supported solid oxide cell, stack and module in electrolysis mode;Aline Léon等;《Journal of Power Sources》;20210827;第510卷;正文第4页 *

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