Reducing Voltage Hysteresis in Li-Rich Sulfide Cathodes by Incorporation of Mn

• Published in: Chemistry of materials 2024-05, Vol.36 (11), p.5687-5697
• Main Authors: Li, Xiaotong, Kim, Seong Shik, Qian, Michelle D., Patheria, Eshaan S., Andrews, Jessica L., Morrell, Colin T., Melot, Brent C., See, Kimberly A.
• Format: Article
• Language: English
• Subjects: Anions; ENERGY STORAGE; Hysteresis; Materials; Redox reactions; Transition metals
• ISSN: 0897-4756; 1520-5002
• DOI: 10.1021/acs.chemmater.4c00736

Conventional intercalation-based cathode materials in Li-ion batteries are based on charge compensation of the redox-active cation and can only intercalate one mole of electron per formula unit. Anion redox, which employs the anion sublattice to compensate charge, is a promising way to achieve multielectron cathode materials. Most anion redox materials still face the problems of slow kinetics and large voltage hysteresis. One potential solution to reduce voltage hysteresis is to increase the covalency of the metal–ligand bonds. By substituting Mn into the electrochemically inert Li1.33Ti0.67S2 (Li2TiS3), anion redox can be activated in the Li1.33–2y/3Ti0.67–y/3Mn y S2 (y = 0–0.5) series. Not only do we observe substantial anion redox, but the voltage hysteresis is significantly reduced, and the rate capability is dramatically enhanced. The y = 0.3 phase exhibits excellent rate and cycling performance, maintaining 90% of the C/10 capacity at 1C, which indicates fast kinetics for anion redox. X-ray absorption spectroscopy (XAS) shows that both the cation and anion redox processes contribute to the charge compensation. We attribute the drop in hysteresis and increase in rate performance to the increased covalency between the metal and the anion. Electrochemical signatures suggest the anion redox mechanism resembles holes on the anion, but the S K-edge XAS data confirm persulfide formation. The mechanism of anion redox shows that forming persulfides can be a low hysteresis, high rate capability mechanism enabled by the appropriate metal–ligand covalency. This work provides insights into how to design cathode materials with anion redox to achieve fast kinetics and low voltage hysteresis.