Highly Reversible Zn Anodes Achieved by Enhancing Ion-Transport Kinetics and Modulating Zn (002) Deposition

Zhenhai Shi; Meng Yang; Yufeng Ren; Yizhou Wang; Junhong Guo; Jian Yin; Feili Lai; Wenli Zhang; Suli Chen; Husam N Alshareef; Tianxi Liu

doi:10.1021/acsnano.3c08197

Highly Reversible Zn Anodes Achieved by Enhancing Ion-Transport Kinetics and Modulating Zn (002) Deposition

ACS Nano. 2023 Nov 14;17(21):21893-21904. doi: 10.1021/acsnano.3c08197. Epub 2023 Oct 28.

Authors

Zhenhai Shi¹, Meng Yang¹, Yufeng Ren¹, Yizhou Wang², Junhong Guo¹, Jian Yin², Feili Lai³, Wenli Zhang⁴, Suli Chen¹, Husam N Alshareef², Tianxi Liu¹

Affiliations

¹ The Key Laboratory of Synthetic and Biological Colloids, Ministry of Education, School of Chemical and Material Engineering, Jiangnan University, Wuxi 214122, China.
² Materials Science and Engineering, Physical Science and Engineering Division, King Abdullah University of Science and Technology, Thuwal 23955-6900, Saudi Arabia.
³ John A. Paulson School of Engineering and Applied Sciences, Harvard University, Cambridge 02138, Massachusetts, United States.
⁴ School of Chemical Engineering and Light Industry, Guangdong University of Technology, Guangzhou 510006, China.

PMID: 37897736
DOI: 10.1021/acsnano.3c08197

Abstract

Uncontrolled dendrite growth and water-related side reactions in mild electrolytes are the main causes of poor cycling stability of zinc anodes, resulting in the deterioration of aqueous zinc-based batteries. Herein, a multifunctional fluorapatite (Ca₅(PO₄)₃F) aerogel (FAG) interface layer is proposed to realize highly stable zinc anodes via the integrated regulation of Zn²⁺ migration kinetics and Zn (002) orientation deposition. Owing to the well-defined aerogel nanochannels and the rich Zn²⁺ adsorption sites resulting from the ion exchange between Ca²⁺ and Zn²⁺, the FAG interface layer could significantly accelerate the Zn²⁺ migration and effectively homogenize the Zn²⁺ flux and nucleation sites, thus promoting rapid and uniform Zn²⁺ migration at the electrode/electrolyte interface. Additionally, during the cycling process, the F atoms from FAG promote the in situ generation of ZnF₂, which facilitates the manipulation of the preferred Zn (002) orientation deposition, thus efficiently suppressing dendrite growth and side reactions by combining with the above synergistic effects. Consequently, the FAG-modified Zn anode displays a stable cycle life of over 4000 h at 1 mA cm^-2 and exhibits highly reversible Zn plating/stripping behavior. Meanwhile, the Zn||MnO₂ full cells exhibit improved cycle stability over 2000 cycles compared with that of the bare Zn, highlighting the virtues of the FAG protective layer for highly reversible Zn anodes. Our work brings the insight in to stabilize Zn anodes and power the commercial applications of aqueous zinc-based batteries.

Keywords: Aerogels; Dendrite growth; Ion exchange-adsorption; Zn (002) deposition; Zn anodes.