Highly Reversible Positive-Valence Conversion of Sulfur Chemistry for High-Voltage Zinc–Sulfur Batteries

Ze CHEN; Zhaodong HUANG; Jiaxiong ZHU; Dedi LI; Ao CHEN; Zhiquan WEI; Yiqiao WANG; Nan LI; Chunyi ZHI

doi:10.1002/adma.202402898

Highly Reversible Positive-Valence Conversion of Sulfur Chemistry for High-Voltage Zinc–Sulfur Batteries

Ze CHEN, Zhaodong HUANG, Jiaxiong ZHU, Dedi LI, Ao CHEN, Zhiquan WEI, Yiqiao WANG, Nan LI^*, Chunyi ZHI^*

^*Corresponding author for this work

Research output: Journal Publications › Journal Article (refereed) › peer-review

9 Citations (Scopus)

Abstract

Sulfur is a promising conversion-type cathode for zinc batteries (ZBs) due to its high discharge capacity and cost-effectiveness. However, the redox conversion of multivalent S in ZBs is still limited, only having achieved S⁰/S²⁻ redox conversion with low discharge voltage and poor reversibility. This study presents significant progress by demonstrating, for the first time, the reversible S²⁻/S⁴⁺ redox behavior in ZBs with up to six-electron transfer (with an achieved discharge capacity of ≈1284 mAh g⁻¹) using a highly concentrated ClO₄⁻-containing electrolyte. The developed succinonitrile–Zn(ClO₄)₂ eutectic electrolyte stabilizes the positive-valence S compound and contributes to an ultra-low polarization voltage. Notably, the achieved flat discharge plateaus demonstrate the highest operation voltage (1.54 V) achieved to date in Zn‖S batteries. Furthermore, the high-voltage Zn‖S battery exhibits remarkable conversion dynamics, excellent cycling performance (85.7% capacity retention after 500 cycles), high efficiency (98.4%), and energy density (527 Wh kg _S⁻¹). This strategy of positive-valence conversion of sulfur represents a significant advancement in understanding sulfur chemistry in batteries and holds promise for future high-voltage sulfur-based batteries.

Original language	English
Article number	2402898
Journal	Advanced Materials
Volume	36
Issue number	30
Early online date	11 Jun 2024
DOIs	https://doi.org/10.1002/adma.202402898
Publication status	Published - 25 Jul 2024
Externally published	Yes

Bibliographical note

Z.C. and Z.H. contributed equally to this work.

Publisher Copyright:
© 2024 The Author(s). Advanced Materials published by Wiley-VCH GmbH.

Funding

The work described in this paper was supported by a grant from the Research Grants Council of the Hong Kong Special Administrative Region, China (Project No. CityU C1002\u201021G). This work was also partially supported by a grant from Shenzhen Science and Technology Program (Program No. SGDX20211123151002003) and Innovation and Technology Fund (Grant No. GHP/191/21SZ).

Keywords

conversion-type cathode
eutectic electrolytes
positive-valence conversion of sulfur
sulfur cathode
zinc batteries

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title = "Highly Reversible Positive-Valence Conversion of Sulfur Chemistry for High-Voltage Zinc–Sulfur Batteries",

abstract = "Sulfur is a promising conversion-type cathode for zinc batteries (ZBs) due to its high discharge capacity and cost-effectiveness. However, the redox conversion of multivalent S in ZBs is still limited, only having achieved S0/S2− redox conversion with low discharge voltage and poor reversibility. This study presents significant progress by demonstrating, for the first time, the reversible S2−/S4+ redox behavior in ZBs with up to six-electron transfer (with an achieved discharge capacity of ≈1284 mAh g−1) using a highly concentrated ClO4−-containing electrolyte. The developed succinonitrile–Zn(ClO4)2 eutectic electrolyte stabilizes the positive-valence S compound and contributes to an ultra-low polarization voltage. Notably, the achieved flat discharge plateaus demonstrate the highest operation voltage (1.54 V) achieved to date in Zn‖S batteries. Furthermore, the high-voltage Zn‖S battery exhibits remarkable conversion dynamics, excellent cycling performance (85.7% capacity retention after 500 cycles), high efficiency (98.4%), and energy density (527 Wh kg S−1). This strategy of positive-valence conversion of sulfur represents a significant advancement in understanding sulfur chemistry in batteries and holds promise for future high-voltage sulfur-based batteries. ",

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AU - CHEN, Ze

AU - HUANG, Zhaodong

AU - ZHU, Jiaxiong

AU - LI, Dedi

AU - CHEN, Ao

AU - WEI, Zhiquan

AU - WANG, Yiqiao

AU - LI, Nan

AU - ZHI, Chunyi

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N2 - Sulfur is a promising conversion-type cathode for zinc batteries (ZBs) due to its high discharge capacity and cost-effectiveness. However, the redox conversion of multivalent S in ZBs is still limited, only having achieved S0/S2− redox conversion with low discharge voltage and poor reversibility. This study presents significant progress by demonstrating, for the first time, the reversible S2−/S4+ redox behavior in ZBs with up to six-electron transfer (with an achieved discharge capacity of ≈1284 mAh g−1) using a highly concentrated ClO4−-containing electrolyte. The developed succinonitrile–Zn(ClO4)2 eutectic electrolyte stabilizes the positive-valence S compound and contributes to an ultra-low polarization voltage. Notably, the achieved flat discharge plateaus demonstrate the highest operation voltage (1.54 V) achieved to date in Zn‖S batteries. Furthermore, the high-voltage Zn‖S battery exhibits remarkable conversion dynamics, excellent cycling performance (85.7% capacity retention after 500 cycles), high efficiency (98.4%), and energy density (527 Wh kg S−1). This strategy of positive-valence conversion of sulfur represents a significant advancement in understanding sulfur chemistry in batteries and holds promise for future high-voltage sulfur-based batteries.

AB - Sulfur is a promising conversion-type cathode for zinc batteries (ZBs) due to its high discharge capacity and cost-effectiveness. However, the redox conversion of multivalent S in ZBs is still limited, only having achieved S0/S2− redox conversion with low discharge voltage and poor reversibility. This study presents significant progress by demonstrating, for the first time, the reversible S2−/S4+ redox behavior in ZBs with up to six-electron transfer (with an achieved discharge capacity of ≈1284 mAh g−1) using a highly concentrated ClO4−-containing electrolyte. The developed succinonitrile–Zn(ClO4)2 eutectic electrolyte stabilizes the positive-valence S compound and contributes to an ultra-low polarization voltage. Notably, the achieved flat discharge plateaus demonstrate the highest operation voltage (1.54 V) achieved to date in Zn‖S batteries. Furthermore, the high-voltage Zn‖S battery exhibits remarkable conversion dynamics, excellent cycling performance (85.7% capacity retention after 500 cycles), high efficiency (98.4%), and energy density (527 Wh kg S−1). This strategy of positive-valence conversion of sulfur represents a significant advancement in understanding sulfur chemistry in batteries and holds promise for future high-voltage sulfur-based batteries.

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Highly Reversible Positive-Valence Conversion of Sulfur Chemistry for High-Voltage Zinc–Sulfur Batteries

Abstract

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Keywords

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