“Zincophilic-Hydrophobic” PAN/PMMA Nanofiber Membrane Toward High-Rate Dendrite-Free Zn Anode

Yanjie Wang; Ning Li; Huiyan Liu; Juan Shi; Yuequn Li; Xukai Wu; Zhuo Wang; Chao Huang; Kongyao Chen; Dianbo Zhang; Tianyu Wu; Ping Li; Cuixia Liu; Liwei Mi

doi:10.1007/s42765-023-00323-2

Advanced Fiber Materials ›› 2023, Vol. 5 ›› Issue (6) : 2002 -2015. DOI: 10.1007/s42765-023-00323-2

Research Article

“Zincophilic-Hydrophobic” PAN/PMMA Nanofiber Membrane Toward High-Rate Dendrite-Free Zn Anode

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¹Henan Key Laboratory of Functional Salt Materials, Center for Advanced Materials Research, Zhongyuan University of Technology, 450007, Zhengzhou, People’s Republic of China

²School of Energy and Environment, Zhongyuan University of Technology, 450007, Zhengzhou, People’s Republic of China

^j chenkongyao@zut.edu.cn

^q mlwzzu@163.com

Yanjie Wang

received her B.S. degree (2010) in Applied Chemistry and Ph.D. degree (2016) in Materials Science from Huazhong University of Science and Technology. From 2009 onward, she was a faculty member in Center of Advanced Materials Research, Zhongyuan University of Technology. She has been an associated professor since 2020. Her research is focused on functional materials for energy storage and conversion.

Ning Li

received his master degree (2023) in Materials and Chemical Engineering, Zhongyuan University of Technology, under the supervision of associated professor Yanjie Wang. His research interest is focused on designing new energy materials by electrospinning technology.

Huiyan Liu

is currently a master candidate in Materials and Chemical Engineering, Zhongyuan University of Technology, under the supervision of associated professor Yanjie Wang. Her research interest is developing new energy materials and devices.

Juan Shi

received her Ph.D. degree in Physical Chemistry from Wuhan University in 2017. She is currently a lecturer in Zhongyuan University of Technology. Her study is focused on lithium-ion battery, sodium-ion battery, solid electrolyte, organic electrolyte and investigating the interfaces in electrochemical energy storage devices.

Yuequn Li

is currently a master candidate in Materials and Chemical Engineering, Zhongyuan University of Technology. His research is focused on high-performance aqueous Zn-ion battery.

Xukai Wu

is currently a master candidate in Materials and Chemical Engineering, Zhongyuan University of Technology. His research is focused on high-performance Zn anode modified by electrospinning fiber membrane.

Zhuo Wang

received his Ph.D. degree in Materials Science and Engineering from Xiangtan University in 2019. From 2019 onward, he was a faculty member in Zhongyuan University of Technology. His research interests are focused on the field of energy storge materials and their mechano-electrochemical coupling mechanism.

Chao Huang

received his Ph.D. degree in Inorganic Chemistry from Zhengzhou University under the supervision of Prof. Hongwei Hou in 2016. Then he joined the school of Zhongyuan University of Technology. His research interests are in the field of organic-inorganic hybrid materials and devices.

Kongyao Chen

received his B.S. degree (2012) in Materials Chemistry from Henan University and Ph.D. degree (2017) in materials science from Huazhong University of Science and Technology (HUST). He is currently a lecturer in Zhongyuan University of Technology. His current research interests include functional materials and devices for Na-ion batteries and aqueous Zn-ion batteries.

Dianbo Zhang

received his B.S degree (2012) from Henan University and Ph.D. degree (2022) from Zhengzhou Universit. From 2015 onward, he was a faculty member of Zhongyuan University of technology. His research interest is in the field of new polymer functional material.

Tianyu Wu

is currently an undergraduate in Material Shaping and Control Engineering, Zhongyuan University of Technology. His research is focused on high-performance aqueous Zn-ion battery.

Ping Li

received her Ph.D. degree in Physical Chemistry from Xiamen University in 2019. She is currently a lecturer in Zhongyuan University of Technology. Her study is focused on theoretical study of organic reaction mechanism.

Cuixia Liu

received her Ph.D. degree from Huazhong University of Science and Technology in 2016. She is currently an assistant professor in Zhongyuan University of Technology. Her research is focused on the polymer-based functional material, high-value product development using microalgal biomass cultivated using wastewater.

Liwei Mi

received his B.S. degree (2005) and Ph.D. degree (2008) in Inorganic Chemistry from Zhengzhou University. From 2014 to 2023, he was a faculty member in Henan Key Laboratory of Functional Salt Materials and Center of Advanced Materials Research, Zhongyuan University of Technology. His research is focused on functional materials for energy storage and conversion and micro/nano composite structure design.

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Abstract

Uncontrollable Zn dendrites and side reactions seriously downgrade the cycling stability of the Zn anode, and restrict the commercialization of aqueous zinc ion batteries. Here, PAN-based (PAN, PAN/PMMA) nanofiber membranes with uniform “zincophilic-hydrophobic” sites have been in-situ electrospun on Zn to effectively prevent harmful side reactions and control Zn plating/stripping behavior. The abundant highly-negative functional groups (C≡N and C=O) of PAN/PMMA have strong coordination interactions with Zn²⁺, which can accelerate Zn²⁺ desolvation and increase the Zn²⁺ migration number. Furthermore, the even distribution of zincophilic sites can help create a uniform Zn deposition environment and enable horizontal Zn deposition. Simultaneously, the inherent “hydrophobicity” of the nonpolar carbon skeleton in PAN/PMMA can prevent Zn corrosion and hydrogen evolution reaction (HER) side reactions, thus improving the cycling stability of the Zn anode. As a result, PAN/PMMA@Zn symmetric cells demonstrated remarkable rate performance and long cycling stability, sustaining efficient operation for over 2000 cycles at 10 mA cm^− 2 with a low polarization voltage below 65 mV. This Zn anode modification strategy by in-situ constructed PAN-based nanofiber membrane has the advantages of simple-preparation, one-step membrane construction, binder-free, uniform distribution of functionalized units, which not only provides a specific scheme for developing advanced Zn anode but also lays a certain research foundation for developing “separator-anode” integrated Zn-based batteries.

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Yanjie Wang, Ning Li, Huiyan Liu, Juan Shi, Yuequn Li, Xukai Wu, Zhuo Wang, Chao Huang, Kongyao Chen, Dianbo Zhang, Tianyu Wu, Ping Li, Cuixia Liu, Liwei Mi. “Zincophilic-Hydrophobic” PAN/PMMA Nanofiber Membrane Toward High-Rate Dendrite-Free Zn Anode. Advanced Fiber Materials, 2023, 5(6): 2002-2015 DOI:10.1007/s42765-023-00323-2