Activating the Stepwise Intercalation-Conversion Reaction of Layered Copper Sulfide toward Extremely High Capacity Zinc-Metal-Free Anodes for Rocking-Chair Zinc-Ion Batteries

Zeheng Lv; Bo Wang; Minghui Ye; Yufei Zhang; Yang Yang; Cheng Chao Li

doi:10.1021/acsami.1c21168

Activating the Stepwise Intercalation-Conversion Reaction of Layered Copper Sulfide toward Extremely High Capacity Zinc-Metal-Free Anodes for Rocking-Chair Zinc-Ion Batteries

ACS Appl Mater Interfaces. 2022 Jan 12;14(1):1126-1137. doi: 10.1021/acsami.1c21168. Epub 2021 Dec 21.

Authors

Zeheng Lv¹, Bo Wang¹, Minghui Ye¹, Yufei Zhang¹, Yang Yang², Cheng Chao Li¹

Affiliations

¹ School of Chemical Engineering and Light Industry, Guangdong University of Technology, Guangzhou 510006, People's Republic of China.
² State Key Lab of Physical Chemistry of Solid Surfaces, State-Province Joint Engineering Laboratory of Power Source Technology for New Energy Vehicle, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, People's Republic of China.

PMID: 34933560
DOI: 10.1021/acsami.1c21168

Abstract

Conventional zinc-ion batteries (ZIBs) are severely hindered by the inherent drawbacks of Zn metal anodes including dendrite growth, side reactions, and interface passivation. Developing intercalation-type anodes to fabricate rocking-chair ZIBs is a promising approach to overcome the above issues. However, the low capacity resulting from the limited transfer electron number of intercalation reactions impedes their practical applications. Herein, we report an effective strategy to break the capacity limit of layered CuS materials as a Zn-metal-free anode through activating its intrinsic conversion reaction. It is found that the preintercalation of cetyltrimethylammonium bromide in CuS (CuS@CTMAB) significantly lowers the energy barrier of the conversion reaction, thus realizing a record-breaking capacity (367.4 mAh g^-1 at 0.1 A g^-1) as a Zn-metal-free anode based on the reversible conversion of Cu²⁺/Cu⁰. Theoretical calculation, ex situ microscopy, and spectroscopy results verify that the characteristic stepwise intercalation-conversion reaction route occurred in CuS@CTMAB. Moreover, the moderate structure transformation and good electronic conduction during the phase evolution process led to excellent cycling stability and high rate performance. Consequently, the rocking-chair ZIB full battery system utilizing CuS@CTMAB and Zn²⁺-preintercalated MnO₂ as the anode and cathode, respectively, exhibits exceptional capacity retention of 93.9% up to 8000 cycles at 2 A g^-1. Besides, the CuS@CTMAB anode is also compatible with high-voltage Prussian blue cathodes, demonstrating its outstanding practicality.

Keywords: anode material; copper sulfide; intercalation−conversion reactions; record-breaking capacity; rocking-chair-type aqueous zinc-ion batteries.