CN-121983587-A - Reversible solid oxide battery composite oxygen electrode and preparation method and application thereof

CN121983587ACN 121983587 ACN121983587 ACN 121983587ACN-121983587-A

Abstract

The invention relates to a reversible solid oxide battery composite oxygen electrode and a preparation method and application thereof, wherein the reversible solid oxide battery composite oxygen electrode comprises the steps of weighing soluble salts containing praseodymium, nickel and cobalt according to the stoichiometric ratio of PNCO, and dissolving the soluble salts in water to obtain a mixed solution; adding complexing agent into the mixed solution, stirring after ultrasonic treatment to obtain PNCO precursor liquid, transferring the PNCO precursor liquid to the surface of an LSC oxygen electrode for vacuum impregnation, placing the impregnated battery into a sintering furnace for calcination, and repeating the impregnation calcination cycle to obtain the PNCO-LSC composite oxygen electrode. According to the invention, the PNCO material with high oxygen ion conductivity is loaded on the surface of the LSC oxygen electrode with high electron conductivity by a solution impregnation method, so that the charge transmission capacity and the oxygen ion transmission rate of the oxygen electrode are obviously improved, the reactive sites are increased, the PNCO material has more excellent electrolysis current density in a CO 2 electrolysis mode, and the battery is ensured to maintain good stability in a long-term operation process.

Inventors

DU XIANLONG
LU LU
ZHANG YUQING
HOU JIANGUO
Dai Ruoyun
XIAO GUOPING
YAO HUICHAO
Miao Kaihong
WANG XIULIN
WANG JIANQIANG
Sui Yiyan

Assignees

中国科学院上海应用物理研究所
中海石油气电集团有限责任公司

Dates

Publication Date: 20260505
Application Date: 20251223

Claims (10)

1. The preparation method of the reversible solid oxide battery composite oxygen electrode is characterized by comprising the following steps: S1, weighing soluble salts containing praseodymium, nickel and cobalt according to the stoichiometric ratio of PNCO, and dissolving the soluble salts in water to obtain a mixed solution; S2, adding a complexing agent into the mixed solution, and stirring after ultrasonic treatment to obtain PNCO precursor liquid; S3, transferring the PNCO precursor solution to the surface of the LSC oxygen electrode for vacuum impregnation; And S4, placing the impregnated battery into a sintering furnace for calcination, and repeating the impregnation and calcination cycles of the steps S3 and S4 to obtain the PNCO-LSC composite oxygen electrode.
2. The method according to claim 1, wherein in the step S1, the praseodymium-containing soluble salt is praseodymium nitrate hexahydrate, the nickel-containing soluble salt is nickel nitrate hexahydrate, the cobalt-containing soluble salt is cobalt nitrate hexahydrate, and the mole fractions of the praseodymium nitrate hexahydrate, the nickel nitrate hexahydrate and the cobalt nitrate hexahydrate are each 5 to 90%.
3. The method according to claim 1, wherein in the step S2, the complexing agent is at least one selected from citric acid, ethylenediamine tetraacetic acid, polyvinylpyrrolidone, cetyltrimethylammonium bromide and sodium succinate, the molar ratio of the complexing agent to PNCO is 0.6:1-1.2:1, and the concentration of the PNCO precursor solution is 0.001-0.1 mol.L -1 .
4. The method of claim 1, wherein in step S3, the LSC oxygen electrode is from a Ni-ysz|ysz|gdc|lsc cell, wherein YSZ is yttria-doped zirconia and GDC is gadolinium-doped ceria.
5. The method of claim 1, wherein in step S3, the PNCO precursor liquid volume per impregnation is 5 to 100 μl and the impregnation effective area of the LSC oxygen electrode of the cell is 4cm x 4cm to 6cm x 6cm.
6. The method according to claim 1, wherein in step S4, the calcination process is performed by heating to 300-600 ℃ at a temperature programming rate of 1-5 ℃ per minute, maintaining the temperature for 0.1-5 hours, heating to 900-1100 ℃ at a temperature programming rate of 1-5 ℃ per minute, and sintering for 0.1-5 hours.
7. The method according to claim 1, wherein in step S4, the number of impregnation calcination cycles is 2 to 6.
8. A reversible solid oxide cell composite oxygen electrode, characterized in that it comprises an LSC base layer and a PNCO active layer coated on the surface of said LSC base layer, made according to the preparation method of any one of claims 1 to 7.
9. Use of a reversible solid oxide cell composite oxygen electrode according to claim 8, wherein the use encompasses a solid oxide fuel cell mode and a solid oxide electrolysis cell mode.
10. The use according to claim 9, characterized in that the use comprises an application in the electrolytic carbon dioxide recycling.

Description

Reversible solid oxide battery composite oxygen electrode and preparation method and application thereof Technical Field The invention relates to the field of electrochemical reduction of carbon dioxide and reversible solid oxide cells, in particular to a reversible solid oxide cell composite oxygen electrode, a preparation method and application thereof. Background With the continuous and rapid increase of global fossil energy consumption, a great amount of carbon dioxide (CO 2) is discharged into the atmosphere, so that a severe greenhouse effect is caused, the global climate environment is obviously influenced, and how to efficiently control the discharge of CO 2 and slow down global climate warming becomes an important topic to be solved in the global scope, and the method also attracts the wide attention of a plurality of researchers. The Solid Oxide Electrolytic Cell (SOEC) is used as a clean and efficient energy conversion device, CO 2 can be effectively reduced into carbon monoxide (CO) under the high-temperature condition, and an ideal way is provided for the resource utilization of CO 2. In the working process of the high-temperature SOEC CO 2 electrolysis system, CO 2 undergoes electrochemical reduction reaction on the cathode side to generate CO, oxygen ions generated in the reaction process are conducted to the anode (namely an oxygen electrode) side through oxygen vacancies in the electrolyte, electrochemical oxidation reaction (oxygen evolution reaction, OER) occurs on the surface of the oxygen electrode, and oxygen is generated after the oxygen ions lose electrons (O 2). From the reaction mechanism, the cathode reaction of the electrolysis of CO 2 only involves the transfer of two electrons, while the oxygen evolution reaction of the anode needs to complete the transfer of four electrons, and the reaction characteristic leads to the energy consumption of the electrolysis of CO 2 by high-temperature SOEC to be mainly concentrated in the anodic polarization process, so that the development of an oxygen electrode material with advanced performance becomes a key point for improving the electrolysis efficiency of CO 2. The ideal oxygen electrode material needs to have the following core properties of high ionic conductivity and electron conductivity, excellent stability in an oxidizing atmosphere and good catalytic activity on OER. At present, perovskite oxide materials are the most commonly used oxygen electrode (anode) materials in the SOEC field, typically representative including La1-xSrxMnO3±δ（LSM）、La1-xSrxCo1-yFeyO3-δ（LSCF） and PrBa 0.5Sr0.5Co1.5Fe0.5O5+δ (PBSCF), and the like. However, the problem of insufficient catalytic activity of Oxygen Evolution Reaction (OER) of the traditional perovskite oxide material generally exists, so that anode polarization loss is large in the process of electrolyzing CO 2 by SOEC, energy conversion efficiency is difficult to meet actual application requirements, and meanwhile, long-term working stability of the material is still to be further improved, which becomes a main technical bottleneck for restricting large-scale application of SOEC technology to CO 2 resource utilization. Disclosure of Invention In order to solve the problems of insufficient catalytic activity and large polarization loss of the existing perovskite oxide oxygen electrode material in the prior art, the invention aims to provide a reversible solid oxide battery composite oxygen electrode, and a preparation method and application thereof. The preparation method of the reversible solid oxide battery composite oxygen electrode comprises the following steps of S1, weighing soluble salts containing praseodymium, nickel and cobalt according to the stoichiometric ratio of PNCO, dissolving the soluble salts in water to obtain a mixed solution, S2, adding a complexing agent into the mixed solution, carrying out ultrasonic treatment, stirring to obtain PNCO precursor liquid, S3, transferring the PNCO precursor liquid to the surface of an LSC oxygen electrode for vacuum impregnation, S4, placing the impregnated battery into a sintering furnace for calcination, and repeating the impregnation and calcination cycles of the steps S3 and S4 to obtain the PNCO-LSC composite oxygen electrode. In a preferred embodiment, in the step S1, the praseodymium-containing soluble salt is praseodymium nitrate hexahydrate, the nickel-containing soluble salt is nickel nitrate hexahydrate, the cobalt-containing soluble salt is cobalt nitrate hexahydrate, and the mole fractions of the praseodymium nitrate hexahydrate, the nickel nitrate hexahydrate and the cobalt nitrate hexahydrate are all 5% -90%. In a preferred embodiment, in the step S2, the complexing agent is at least one selected from citric acid, ethylenediamine tetraacetic acid, polyvinylpyrrolidone, cetyltrimethylammonium bromide and sodium succinate, the molar ratio of the complexing agent to PNCO is 0.6:1-1.2:1, and the concentration of the PNCO precursor