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In Li–S batteries, the insulating nature of sulfur and Li 2 S causes enormous challenges, such as high polarization and low active material utilization. The nucleation of the solid discharge product, Li 2 S, during the discharge cycle, and the activation of Li 2 S in the subsequent charge cycle, cause a potential challenge that needs to be overcome. Moreover, the shuttling of soluble lithium polysulfide intermediate species results in active material loss and early capacity fade. In this study, we have used thiourea as an electrolyte additive and showed that it serves as both a redox mediator to overcome the Li 2 S activation energy barrier and a shuttle inhibitor to mitigate the notorious polysulfide shuttling via the investigation of thiourea redox activity, shuttle current measurements and study of Li 2 S activation. The steady-state shuttle current of the Li–S battery shows a 6-fold drop when 0.02 M thiourea is added to the standard electrolyte. Moreover, by adding thiourea, the charge plateau for the first cycle of the Li 2 S based cathodes shifts from 3.5 V (standard ether electrolyte) to 2.5 V (with 0.2 M thiourea). Using this additive, the capacity of the Li–S battery stabilizes at ∼839 mA h g −1 after 5 cycles and remains stable over 700 cycles with a low capacity decay rate of 0.025% per cycle, a tremendous improvement compared to the reference battery that retains only ∼350 mA h g −1 after 300 cycles. In the end, to demonstrate the practical and broad applicability of thiourea in overcoming sulfur-battery challenges and in eliminating the need for complex electrode design, we study two additional battery systems – lithium metal-free cells with a graphite anode and Li 2 S cathode, and Li–S cells with simple slurry-based cathodes fabricated via blending commercial carbon black/S and a binder. We believe that this study manifests the advantages of redox active electrolyte additives to overcome several bottlenecks in the Li–S battery field.
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Redox-couple investigations in Si-doped Li-rich cathode materials
In this investigation, the improved electrochemical behavior in Si-doped Li-rich cathodes is studied with scanning transmission electron microscopy (STEM) and electron energy loss spectroscopy (EELS). Z-contrast images show a layered structure that develops a thin, spinel-like surface layer after the first charge cycle. Si-doping increases discharge capacity by ∼25% and appears to retard the surface phase transformation. Based on electron energy loss spectra, the surface layer in the doped material has an altered oxygen electronic environment, which supports the STEM findings. Furthermore, Si-doping changes the redox behavior during the activation cycle. Density functional theory calculations indicate that Si-doping can increase oxygen vacancy formation, and change the sequence of the redox couples by introducing more oxygen vacancies before or during the typical high voltage activation process. The results of this work indicate that the type of doping employed here is an effective strategy for controlling the complex charge compensation mechanisms in lithium-rich cathodes.
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- PAR ID:
- 10273943
- Date Published:
- Journal Name:
- Physical Chemistry Chemical Physics
- Volume:
- 23
- Issue:
- 4
- ISSN:
- 1463-9076
- Page Range / eLocation ID:
- 2780 to 2791
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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- Free Publicly Accessible Full Text
-
Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1039/D0CP05737A
