Lithium-sulfur (Li-S) batteries are highly regarded as the next-generation energy-storage devices because of their ultrahigh theoretical energy density of 2600 Wh kg . Sulfurized polyacrylonitrile (SPAN) is considered a promising sulfur cathode to substitute carbon/sulfur (C/S) composites to afford higher Coulombic efficiency, improved cycling stability, and potential high-energy-density Li-SPAN batteries. However, the instability of the Li-metal anode threatens the performances of Li-SPAN batteries bringing limited lifespan and safety hazards. Li-metal can react with most kinds of electrolyte to generate a protective solid electrolyte interphase (SEI), electrolyte regulation is a widely accepted strategy to protect Li-metal anodes in rechargeable batteries. Herein, the basic principles and current challenges of Li-SPAN batteries are addressed. Recent advances on electrolyte regulation towards stable Li-metal anodes in Li-SPAN batteries are summarized to suggest design strategies of solvents, lithium salts, additives, and gel electrolyte. Finally, prospects for future electrolyte design and Li anode protection in Li-SPAN batteries are discussed.
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http://dx.doi.org/10.1002/anie.201912701 | DOI Listing |
Angew Chem Int Ed Engl
December 2024
State Key Laboratory of Material Processing and Die & Mould Technology, Institute for Materials Science and Engineering, Huazhong University of Science and Technology, Wuhan, Hubei, 430074, China.
Sulfurized polyacrylonitrile (SPAN) presents an opportunity to replace elemental sulfur as a "shuttle-free" cathode for secondary Li-S batteries, which can be an ideal choice for stationary energy storage due to its abundance, low cost, and sustainability. The electrolyte options for the state-of-the-art SPAN batteries have been limited to the flammable carbonate and ether ones, which raises safety concerns. Here, we explored the use of a non-flammable acetonitrile (AN) electrolyte for SPAN battery for the first time and identified the irreversible cleavage of C-S bonds of SPAN as the main reason for the failure of SPAN in AN electrolyte.
View Article and Find Full Text PDFACS Nano
November 2024
Engineering Research Center of Polymer Green Recycling of Ministry of Education, Fujian Key Laboratory of Pollution Control & Resource Reuse, College of Environmental and Resource Sciences and College of Carbon Neutral Modern Industry, Fujian Normal University, Fuzhou, Fujian 350000, China.
The electrolyte plays an essential role in the advancement of lithium-sulfur batteries (LSBs), as it not only transports the charge carriers but also extensively influences sulfur conversion mechanisms and electrode-electrolyte interphases formed on the electrode surface, thereby directly impacting battery performance. However, the majority of existing electrolytes suffer from incompatibility with either the Li anode or the sulfur cathode. Here, we develop a densely packed ion-cluster electrolyte (DPIE) through the strategic combination of a weakly solvating solvent and an inert diluent, resulting in the self-assembly of abundant compact ion-pair aggregates within its structure.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
November 2024
Frontiers Science Center for New Organic Matter, Key Laboratory of Advanced Energy Materials Chemistry (Ministry of Education), State Key Laboratory of Advanced Chemical Power Sources, College of Chemistry, Nankai University, Tianjin, 300071, China.
Sulfurized polyacrylonitrile (SPAN) is recognized as a promising organic cathode for long-lifespan lithium metal batteries. Nevertheless, the irreversible cleavage/formation of multiple sulfur-sulfur (S-S) bonds of SPAN within conventional ether-based electrolytes results in loss of active S species, severe capacity fading and shuttle effects. Herein, we propose a new electrolyte based on dipropyl ether (PE) solvent for Li-SPAN batteries.
View Article and Find Full Text PDFACS Appl Mater Interfaces
November 2024
Department of Chemical Engineering, Shanghai Jiao Tong University, Shanghai 200240, P. R. China.
As one of the most promising battery systems, the lithium sulfur battery is expected to be widely used in fields of high energy density demands. Owing to the unique solid-solid conversion mechanism, there is no shuttle effect for the Li-SPAN (sulfurized polyacrylonitrile) battery. However, the compatibility between Li anode and carbonate electrolyte has not been resolved, which prevents the SPAN from practical applications.
View Article and Find Full Text PDFAdv Mater
August 2024
Department of Chemical and Biomolecular Engineering, University of Maryland, College Park, MD, 20742, USA.
Sulfurized polyacrylonitrile (SPAN) recently emerges as a promising cathode for high-energy lithium (Li) metal batteries owing to its high capacity, extended cycle life, and liberty from costly transition metals. As the high capacities of both Li metal and SPAN lead to relatively small electrode weights, the weight and specific energy density of Li/SPAN batteries are particularly sensitive to electrolyte weight, highlighting the importance of minimizing electrolyte density. Besides, the large volume changes of Li metal anode and SPAN cathode require inorganic-rich interphases that can guarantee intactness and protectivity throughout long cycles.
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