TY - JOUR

T1 - An Aqueous Electrolyte Regulator for Highly Stable Zinc Anode Under −35 to 65 °C

AU - Wang, Rui

AU - Ma, Quanwei

AU - Zhang, Longhai

AU - Liu, Zixiang

AU - Wan, Jiandong

AU - Mao, Jianfeng

AU - Li, Hongbao

AU - Zhang, Shilin

AU - Hao, Junnan

AU - Zhang, Lin

AU - Zhang, Chaofeng

N1 - Funding Information: R.W. and Q.M. contributed equally to this work. The authors thank the financial support from the National Natural Science Foundation of China (52172173), Natural Science Foundation of Anhui Province for Distinguished Young Scholars (2108085J25), Excellent Research and Innovation Team Project of Anhui Province (2022AH010001), Natural Science Foundation of Anhui Province (2208085QE130). The authors acknowledge the High‐performance Computing Platform of Anhui University for providing computing resources. The authors thank infrared spectroscopy and microspectroscopy beamline (BL01B) of National Synchrotron Radiation Laboratory (NSRL) for the help in characterizations. The authors also thank Biolin Scientific AB for offering the experiment help and data analysis for EQCM‐D.

PY - 2023/10/27

Y1 - 2023/10/27

N2 - The reversibility and long-term cycling stability of aqueous zinc-ion batteries (AZIBs) in a wide temperature range have rarely been explored. Herein, diethylene glycol monoethyl ether (DG) is introduced as an electrolyte additive to enhance Zn performance within a wide temperature range of −35 to 65 °C. Operando synchrotron Fourier transform infrared spectroscopy analysis combined with molecular dynamics simulations reveal that the introduction of DG disrupts the initial hydrogen bonding network of the aqueous electrolyte, restructuring the solvation structure surrounding Zn2+ ions and mitigating water-induced parasitic reactions. Adding DG reduces the freezing point of the aqueous electrolyte without compromising its incombustibility. Moreover, operando electrochemical quartz crystal microbalance with dissipation monitoring (EQCM-D) and X-ray photoelectron spectroscopy demonstrated that the coordinated DG and OTF− undergo reductive decomposition, forming a self-healing solid electrolyte interphase comprising an inorganic/organic ZnF2-ZnS, which can effectively suppress the notorious side reactions and guide the uniform Zn deposition. Consequently, the symmetric Zn/Zn cells demonstrate excellent cycling stability for 3500 h under 1 mA cm−2 at 25 °C, and for 1000 h under 1 mA cm−2 at both −35 and 65 °C. Full batteries with a DG-containing electrolyte exhibit a long lifespan of 5000 cycles at 2 A g−1.

AB - The reversibility and long-term cycling stability of aqueous zinc-ion batteries (AZIBs) in a wide temperature range have rarely been explored. Herein, diethylene glycol monoethyl ether (DG) is introduced as an electrolyte additive to enhance Zn performance within a wide temperature range of −35 to 65 °C. Operando synchrotron Fourier transform infrared spectroscopy analysis combined with molecular dynamics simulations reveal that the introduction of DG disrupts the initial hydrogen bonding network of the aqueous electrolyte, restructuring the solvation structure surrounding Zn2+ ions and mitigating water-induced parasitic reactions. Adding DG reduces the freezing point of the aqueous electrolyte without compromising its incombustibility. Moreover, operando electrochemical quartz crystal microbalance with dissipation monitoring (EQCM-D) and X-ray photoelectron spectroscopy demonstrated that the coordinated DG and OTF− undergo reductive decomposition, forming a self-healing solid electrolyte interphase comprising an inorganic/organic ZnF2-ZnS, which can effectively suppress the notorious side reactions and guide the uniform Zn deposition. Consequently, the symmetric Zn/Zn cells demonstrate excellent cycling stability for 3500 h under 1 mA cm−2 at 25 °C, and for 1000 h under 1 mA cm−2 at both −35 and 65 °C. Full batteries with a DG-containing electrolyte exhibit a long lifespan of 5000 cycles at 2 A g−1.

KW - electrolyte additives

KW - electrolyte engineering

KW - electrolyte modification

KW - Zn ion batteries

UR - http://www.scopus.com/inward/record.url?scp=85170659674&partnerID=8YFLogxK

U2 - 10.1002/aenm.202302543

DO - 10.1002/aenm.202302543

M3 - Article

AN - SCOPUS:85170659674

VL - 13

JO - Advanced energy materials

JF - Advanced energy materials

SN - 1614-6832

IS - 40

M1 - 2302543

ER -