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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                            A metal-free all-organic ammonium-ion battery with low-temperature applications
                        
                    
    
            Current commercial batteries are mainly metal based, with metal elements in charge carriers and/or electrode materials, which poses potential economic and environmental concerns due to the heavy use of nonrenewable metals. Thus, metal-free batteries present a unique opportunity as sustainable energy storage devices, though the relevant research is still in its infancy. Herein, we present an all-organic metal-free NH 4 + ion full battery that can operate at a low temperature of 0 °C, by using polypyrrole (PPy) as the cathode, polyaniline (PANI) as the anode, and 19 m ammonium acetate aqueous solution as electrolyte. For the first time, PPy is demonstrated as a high-capacity host material for both NH 4 + and K + storage, when cycled in water in salt electrolytes (WiSEs). When tested in a three-electrode cell containing 25 m NH 4 CH 3 COO electrolyte, PPy exhibits an impressive capacity of 125 mA h g −1 at a specific current of 1 A g −1 and retains 43.61 mA h g −1 at 25 A g −1 . Additionally, a full battery is assembled using the PPy cathode and PANI anode coupled with 19 m NH 4 CH 3 COO WiSE. This battery is found to deliver a capacity of 78.405 mA h g −1 at 25 °C and 49.083 mA h g −1 at 0 °C with a capacity retention of 71.83% after 200 cycles, demonstrating its potential for operations at low temperatures. Additionally, the physiochemical properties of NH 4 + -based WiSEs are examined by Raman and nuclear magnetic resonance (NMR) spectroscopies, to explore their electrochemical behaviors and the fundamental effect of salt concentration on the electrolyte characteristics. This study presents the first non-metal battery with potential for low-temperature applications and opens the door to future metal-free electronics that would generate long-term benefits to the environment. 
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                            - Award ID(s):
- 2019046
- PAR ID:
- 10465410
- Date Published:
- Journal Name:
- Journal of Materials Chemistry A
- Volume:
- 11
- Issue:
- 6
- ISSN:
- 2050-7488
- Page Range / eLocation ID:
- 2814 to 2825
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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