Revisiting the Impact of Anion Selection on Sulfur Redox Reaction Kinetics for High Sulfur Loading Lithium–Sulfur Batteries

Fei, Yue; Li, Matthew; Li, Zhenfeng; Guan, Dichang; Jia, Wenting; Zhang, Hao; Amine, Khalil; Li, Ge

doi:10.1002/adma.202507459

Revisiting the Impact of Anion Selection on Sulfur Redox Reaction Kinetics for High Sulfur Loading Lithium–Sulfur Batteries

Journal Article · Wed Jul 09 04:00:00 EDT 2025 · Advanced Materials

DOI:https://doi.org/10.1002/adma.202507459· OSTI ID:3000110

Fei, Yue ^[1]; Li, Matthew ^[2]; Li, Zhenfeng ^[1]; Guan, Dichang ^[3]; Jia, Wenting ^[1]; Zhang, Hao ^[1]; Amine, Khalil ^[2]; ^[1]

Univ. of Alberta, Edmonton, AB (Canada)
Argonne National Laboratory (ANL), Argonne, IL (United States)
Univ. of Alberta, Edmonton, AB (Canada); Central South University, Changsha (China)

Lithium bis(trifluoromethane)sulfonimide (LiTFSI) is widely used in lithium–sulfur (Li–S) battery electrolytes due to its stability with lithium polysulfides (LiPSs) and moderate compatibility with lithium metal anodes. However, LiTFSI presents environmental concerns due to its association with per- and polyfluoroalkyl substances (PFAS), which are environmentally persistent and potentially toxic, raises sustainability concerns. This research also reveals that LiTFSI limits sulfur redox reactions (SRRs), making it less effective than other lithium salts. Additionally, some salts previously considered incompatible with Li-S systems due to their reactivity with LiPSs are demonstrated to perform effectively. For the first time, a protective, porous cathode electrolyte interphase (CEI) formed in situ through reactions between salt anions and LiPS is reported. The cells delivered a high specific capacity of 1230.8 mAh g⁻¹ at 0.05 C with a sulfur loading of ≈6 mg cm⁻², limited lithium anode, maintaining a capacity retention of 76.2% after 100 cycles at 0.1 C. Under harsh conditions, such as high sulfur loading, lean electrolyte conditions (3 µL mg⁻¹), and in anode-free cells, the cells continued to deliver outstanding capacity. This work provides valuable guidelines for understanding and selecting lithium salts to advance electrolyte design for Li–S batteries.

View Accepted Manuscript (DOE)

Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Organization:: USDOE Office of Science (SC); Natural Sciences and Engineering Research Council of Canada (NSERC)

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 3000110

Journal Information:: Advanced Materials, Journal Name: Advanced Materials Journal Issue: 39 Vol. 37; ISSN 1521-4095; ISSN 0935-9648

Publisher:: WileyCopyright Statement

Country of Publication:: United States

Language:: English

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