image: The 3D porous PFA-COOH-CNT artificial SEI membrane promoted the uniform deposition of zinc ions and hindered the direct contact between water and electrolyte through its zincophilic and hydrophobic properties, thus inhibiting the growth of zinc dendrites and the occurrence of hydrogen evolution reaction. At the current density of 1 mA‧cm−2, 1 mAh‧cm−2, the ultra-long cycle of 2200 h is achieved.
Credit: Nano Research, Chongqing Technology and Business university.
Professor Gu Xingxing's team at Chongqing Technology and Business University (CTBU) collaborated with Prof. Yanglong Hou’s team at Sun Yat-sen University recently developed a novel "zincophilic- hydrophobic" dual-function artificial SEI membrane based on biomass furfuryl alcohol (FA). In this study, carboxyl carbon nanotubes, COOH-CNT, with polar organic molecules (furfuryl alcohol, FA) experienced an in-situ reaction on the surface of zinc foil, to form an artificial SEI film (PFA-COOH-CNT) that is both zincophilic and hydrophobic to stabilize the Zn anode. With the PFA-COOH-CNT SEI film on Zn anode, during plating/stripping process, the Zn2+ ions deposition is uniform as well as the side reactions and Zn dendrite growth are effectively inhibited. Accordingly, the assembled PFA-COOH-CNT@Zn||Zn symmetric battery cycling stability can reach 2200 h at 1 mA‧cm−2,1 mAh‧cm−2, much longer than Zn||Zn symmetric battery (418 h). Meanwhile, the assembled PFA-COOH-CNT@Zn||V2O5 full cell also illustrates outstanding electrochemical performances, with the reversible capacity reaching 150.2 mAh‧g−1 at 1 A‧g−1 after 400 cycles. Therefore, the PFA-COOH-CNT artificial SEI film greatly improves the performance of aqueous zinc-ion batteries, provides a broader prospect for stability of zinc anode, and can also be applied in other energy storage batteries.
The team published their research article in the journal Nano Research on January 8, 2025.
"In the development of aqueous zinc-ion batteries, the protection of zinc anode is one of the important factors affecting its development." The corresponding author of the paper, Professor Xingxing Gu from Chongqing Technology and Business University, said, "At this stage, there are many problems affecting the cyclic performance of Zn anode in AZIBs, such as uneven electric field distribution caused by zinc dendrite growth, “dead zinc” and irreversible corrosion of zinc anode caused by hydrogen evolution reaction (HER). Among various protection strategies, the preparation method of artificial SEI film is relatively simple and effective. Additionally, it is found that the zincophilic properties of zinc anode can affect the uniform deposition of zinc ions, and thus affect the growth of zinc dendrites. Hydrophobicity will affect the occurrence of HER, thus affecting the corrosion resistance of zinc anode. Therefore, constructing a zincophilic and hydrophobic artificial SEI film to stabilize zinc anode is an efficient strategy”.
"Artificial SEI membranes are generally divided into inorganic SEI membranes, organic SEI membranes and hybrid SEI membranes." Miss Lingyao Kuang, first author of the paper, said, "However, during the cycle of AZIBs, the inorganic SEI film is easy to fall off due to continuous plating/stripping of zinc ions; Although the organic layer usually has good hydrophobic properties, the zincophile is not enough to meet the uniform deposition of zinc ions. Therefore, we constructed a hybrid artificial SEI membrane by using FA and COOH-CNT."
Under the acid condition, after heating, on the one hand FA and COOH-CNT were esterified to form a inorganic/organic framework with large amount of zincophilic groups, on the other hand the FA self-polymerized to form polyfurfuryl alcohol (PFA) to intersperse between COOH-CNTs and adhere them on the Zn anode surface to form an artificial SEI film. Such a film contains a large number of oxygen-containing functional groups, which greatly improves the zincophile of the zinc anode. Meanwhile, the densification of PFA and CNT provide zinc anode with the hydrophobic properties, which greatly improve the corrosion resistance of zinc anode.
The research team hopes that this study will provide more a simple, efficient, and easy to scale up strategy to protect the Zn anode. "This strategy can be achieved only by scalpel scraping and heating, using cost-effective raw reagents, which greatly improves the efficiency of stabilizing the zinc anode, and provides a broader prospect for future research on AZIBs." Professor Xing-Xing Gu said.
Other contributors include Bohui Xu and Zheshuai Lin from the Technical Institute of Physics and Chemistry, Chinese Academy of Sciences in Beijing, China.
This study was funded by the National Natural Science Foundation of China (Nos. 51902036, 22222902, 2263203, and 52111530236), the National Key R&D Program of China (No. 2022YFA1203902), Chongqing Bayu Scholars Support Program (No. YS2022050), the Natural Science Foundation of Chongqing Science & Technology Commission (No. CSTB2022NSCQ-MSX0828), and the Key Science and Technology Research Program of Chongqing Education Commission (No. KJZD-K202200807).
About the Authors
Prof. Xingxing Gu, Chongqing "Bayu Scholars" Young Scholar (2022), postgraduate tutor in Chongqing Technology and Business University. He is mainly engaged in the research of nano carbon materials for Li-S and lithium ion batteries and Li/Zn anode protection. He has been granted more than 10 grants, including National Natural Science Foundation Project. He has published over 40 papers as first author or corresponding author in journals such as Nature Communications, Advanced Functional Materials, Advanced Energy Materials, and Energy Storage Materials, etc. His total citation count exceeds 3,900, with an H-index of 33. He currently serves as an academic editor for the SCI journal of Rare Metals and a young editor broad member for Tungsten, Nano Materials Science, and Materials Reports: Energy, etc. https://ebes2014.ctbu.edu.cn/info/1212/7504.htm.
Prof. Yanglong Hou, Dean of the School of Materials, Sun Yat-sen University, Fellow of the Royal Society of Chemistry (FRSC) (2019) and Fellow of the Chinese Chemical Society (FCCS) (2022). As a national talent, Professor Hou has won many heavyweight awards and projects, including the Second Class National Prize of Natural Science, Second National Innovation Award, the National Natural Science Foundation Outstanding Youth Fund, the National Major Scientific Research Instrument Development Project, the National Key R&D Program of China, etc.
He is mainly engaged in the controlled synthesis, growth mechanism, self-assembly of magnetic materials and heterogeneous multifunctional materials and their application in the fields of biomedicine and energy. https://faculty.pku.edu.cn/houyanglong/zh_CN/zdylm/50575/list/index.htm.
About Nano Research
Nano Research is a peer-reviewed, open access, international and interdisciplinary research journal, sponsored by Tsinghua University and the Chinese Chemical Society, published by Tsinghua University Press on the platform SciOpen. It publishes original high-quality research and significant review articles on all aspects of nanoscience and nanotechnology, ranging from basic aspects of the science of nanoscale materials to practical applications of such materials. After 17 years of development, it has become one of the most influential academic journals in the nano field. Nano Research has published more than 1,000 papers every year from 2022, with its cumulative count surpassing 7,000 articles. In 2023 InCites Journal Citation Reports, its 2023 IF is 9.6 (9.0, 5 years), and it continues to be the Q1 area among the four subject classifications. Nano Research Award, established by Nano Research together with TUP and Springer Nature in 2013, and Nano Research Young Innovators (NR45) Awards, established by Nano Research in 2018, have become international academic awards with global influence.
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Journal
Nano Research
Article Title
Zincophilic and hydrophobic bifunctional PFA-COOH-CNT artificial SEI film for highly stable Zn anode
Article Publication Date
8-Jan-2025