Citation: Gao Dunfeng, Wei Pengfei, Li Hefei, Lin Long, Wang Guoxiong, Bao Xinhe. Designing Electrolyzers for Electrocatalytic CO₂ Reduction[J]. Acta Physico-Chimica Sinica, ;2021, 37(5): 200902. doi: 10.3866/PKU.WHXB202009021 shu

Designing Electrolyzers for Electrocatalytic CO₂ Reduction

Gao Dunfeng ^1,, ,
Wei Pengfei ¹ ,
Li Hefei ^1,2 ,
Lin Long ^1,2 ,
Wang Guoxiong ^1,2,, ,
Bao Xinhe ¹

1.
State Key Laboratory of Catalysis, Dalian National Laboratory for Clean Energy, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning Province, China
2.
University of Chinese Academy of Sciences, Beijing 100049, China

Author Bio: Dunfeng Gao is currently an associate professor at the Dalian Institute of Chemical Physics, Chinese Academy of Sciences (DICP, CAS). He obtained B.Sc. degree from China University of Petroleum in 2009 and Ph.D. degree from the DICP in 2015. Then he worked as a postdoctoral researcher at the Ruhr University Bochum and the Fritz Haber Institute of the Max Planck Society in Germany (2015-2019). In 2019, he moved back to the DICP as an associate professor. His research focuses on electrocatalysis including CO₂ electroreduction, CH₄ electrooxidation and water electrolysis

Guoxiong Wang is currently a full professor at the Dalian Institute of Chemical Physics, Chinese Academy of Sciences (DICP, CAS). He obtained B.Sc. degree from Wuhan University in 2000 and Ph.D. degree from the DICP in 2006. After a one-year stay at the DICP as an assistant professor (2006-2007), he worked as a postdoctoral researcher at the Hokkaido University in Japan (2007-2010). In December 2010, he moved back to the DICP as an associate professor and promoted to a full professor in 2015. His research focuses on energy storage and conversion, electrocatalytic CO₂ reduction and fuel cell
Corresponding author: Gao Dunfeng, dfgao@dicp.ac.cn Wang Guoxiong, wanggx@dicp.ac.cn
Received Date: 4 September 2020
Revised Date: 24 September 2020
Accepted Date: 24 September 2020
Available Online: 9 October 2020
Fund Project: the CAS Youth Innovation Promotion Y201938Dalian Institute of Chemical Physics, China DICP DMTO201702Dalian National Laboratory for Clean Energy, China DNL180404the National Key R & D Program of China 2016YFB0600901Dalian National Laboratory for Clean Energy, China DNL201924Dalian Outstanding Young Scientist Foundation, China 2017RJ03the Strategic Priority Research Program of the Chinese Academy of Sciences XDB17020200the National Natural Science Foundation of China 21573222This project was supported by the National Key R & D Program of China (2016YFB0600901), the National Natural Science Foundation of China (21573222, 91545202, 22002155), Dalian National Laboratory for Clean Energy, China (DNL180404 and DNL201924), Dalian Institute of Chemical Physics, China (DICP DMTO201702), Dalian Outstanding Young Scientist Foundation, China (2017RJ03) and the Strategic Priority Research Program of the Chinese Academy of Sciences (XDB17020200) and the CAS Youth Innovation Promotion (Y201938)the National Natural Science Foundation of China 22002155the National Natural Science Foundation of China 91545202

The electrocatalytic CO₂ reduction reaction (CO₂RR) driven by renewable energy is an efficient approach to achieve the conversion and utilization of CO₂. In this context, CO₂RR has become an emerging research focus in the field of electrocatalysis over the past decade. While a large number of nanostructured catalysts have been developed to accelerate CO₂RR, the tradeoff between activity and selectivity usually renders the overall electrocatalytic performance very poor. Beyond catalyst design, rationally designing electrolyzers is also of substantial importance for improving the CO₂RR performance and achieving its scale-up for practical applications. To a large extent, the electrolyzer configuration determines the local reaction environment near an electrode by affecting the process conditions, thereby resulting in remarkably different electrocatalytic performances. To be techno-economically viable, the performance of CO₂ electrolyzers is expected to be at least comparable to that of the current state-of-the-art proton exchange membrane (PEM) water electrolyzers, with regard to their activity, selectivity, and stability. Researchers have made great progress in the development of CO₂ electrolyzers over the past few years, but they are also facing many issues and challenges. This review aims to provide an in-depth analysis of the research progress and status of current CO₂ electrolyzers including H-cell, flow-cell, and membrane electrode assembly cell (MEA-cell) electrolyzers. Herein, operation at industrial current densities (> 200 mA∙cm⁻²) is set as a basis when these electrolyzers are discussed and compared in terms of the four main figures of merit (current density, Faradic efficiency, energy efficiency and stability) that describe the CO₂RR performance of an electrolyzer. The advantages and drawbacks of each electrolyzer are discussed and highlighted with emphasis on the key achievements reported to date. Compared to conventional H-cell electrolyzers that work well in mechanistic studies, the newly developed electrolyzers using gas diffusion electrodes, both flow-cell and MEA-cell electrolyzers, are able to break the limitation of CO₂ solubility in water and acquire industrial current densities. Although flow-cell electrolyzers have achieved current densities exceeding 1 A∙cm⁻², they suffer from low energy efficiencies because of the significant iR drop and poor stability owing to the use of alkaline electrolytes. These issues can be overcome in the case of zero-gap MEA-cell electrolyzers with ion exchange membranes being as solid electrolytes. The anion exchange membrane (AEM)-based CO₂ electrolyzers are at the center of the current research, as they demonstrate promising activity and selectivity toward specific CO₂RR products and exhibit excellent stability for over thousands of hours in few cases. Meanwhile, the crossover of CO₂ and liquid products from the cathode to the anode through the membrane tends to lower the utilization efficiency of the CO₂ supplied to the AEM electrolyzers. MEA-cell electrolyzers using cation exchange membranes and bipolar membranes have also been explored; however, neither of them have shown satisfactory CO₂RR performance. The development of new polymer electrolyte membranes and ionomers would help address these problems. While issues and challenges still exist, MEA-cell electrolyzers hold the greatest promise for practical applications. As concluding remarks, research strategies and opportunities for the future have been proposed to accelerate the development of CO₂RR technology for practical applications and to deepen the mechanistic understanding behind improved performance. This review provides new insights into rational electrolyzer design and guidelines for researchers in this field.
- CO₂ electrolyzers,
- Electrocatalytic reduction,
- Energy efficiency,
- Industrial current density,
- Flow cell,
- Membrane electrode assembly
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Designing Electrolyzers for Electrocatalytic CO2 Reduction

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Designing Electrolyzers for Electrocatalytic CO₂ Reduction