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1. High Performance Air Breathing Flexible Lithium–Air Battery

   https://doi.org/10.1002/smll.202102072  

   Ahmad Jaradat, Chengji Zhang (January 2021, Small)

   null (Ed.)

   Lithium–oxygen (Li–O2) batteries possess the highest theoretical energy density (3500 Wh kg−1), which makes them attractive candidates for modern electronics and transportation applications. In this work, an inexpensive, flexible, and wearable Li–O2 battery based on the bifunctional redox mediator of InBr3, MoS2 cathode catalyst, and Fomblin-based oxygen permeable membrane that enable long-cycle-life operation of the battery in pure oxygen, dry air, and ambient air is designed, fabricated, and tested. The battery operates in ambient air with an open system air-breathing architecture and exhibits excellent cycling up to 240 at the high current density of 1 A g−1 with a relative humidity of 75%. The electrochemical performance of the battery including deep-discharge capacity, and rate capability remains almost identical after 1000 cycle in a bending fatigue test. This finding opens a new direction for utilizing high performance Li–O2 batteries for applications in the field of flexible and wearable electronics. 

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2. Regulating Li‐Ion Transport through Ultrathin Molecular Membrane to Enable High‐Performance All‐Solid‐State–Battery

   https://doi.org/10.1002/smll.202303625  

   Rajendran, Sathish; George, Antony; Tang, Zian; Neumann, Christof; Turchanin, Andrey; Arava, Leela_Mohana_Reddy (June 2023, Small)

   Abstract Solid‐state lithium metal batteries with garnet‐type electrolyte provide several advantages over conventional lithium‐ion batteries, especially for safety and energy density. However, a few grand challenges such as the propagation of Li dendrites, poor interfacial contact between the solid electrolyte and the electrodes, and formation of lithium carbonate during ambient exposure over the solid‐state electrolyte prevent the viability of such batteries. Herein, an ultrathin sub‐nanometer porous carbon nanomembrane (CNM) is employed on the surface of solid‐state electrolyte (SSE) that increases the adhesion of SSE with electrodes, prevents lithium carbonate formation over the surface, regulates the flow of Li‐ions, and blocks any electronic leakage. The sub‐nanometer scale pores in CNM allow rapid permeation of Li‐ions across the electrode–electrolyte interface without the presence of any liquid medium. Additionally, CNM suppresses the propagation of Li dendrites by over sevenfold up to a current density of 0.7 mA cm⁻²and enables the cycling of all‐solid‐state batteries at low stack pressure of 2 MPa using LiFePO₄cathode and Li metal anode. The CNM provides chemical stability to the solid electrolyte for over 4 weeks of ambient exposure with less than a 4% increase in surface impurities. 

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3. Lithium superoxide encapsulated in a benzoquinone anion matrix

   https://doi.org/10.1073/pnas.2019392118  

   Nava, Matthew; Zhang, Shiyu; Pastore, Katharine S.; Feng, Xiaowen; Lancaster, Kyle M.; Nocera, Daniel G.; Cummins, Christopher C. (December 2021, Proceedings of the National Academy of Sciences)

   Lithium peroxide is the crucial storage material in lithium–air batteries. Understanding the redox properties of this salt is paramount toward improving the performance of this class of batteries. Lithium peroxide, upon exposure to p –benzoquinone ( p –C 6 H 4 O 2 ) vapor, develops a deep blue color. This blue powder can be formally described as [Li 2 O 2 ] 0.3   · [LiO 2 ] 0.7   · {Li[ p –C 6 H 4 O 2 ]} 0.7 , though spectroscopic characterization indicates a more nuanced structural speciation. Infrared, Raman, electron paramagnetic resonance, diffuse-reflectance ultraviolet-visible and X-ray absorption spectroscopy reveal that the lithium salt of the benzoquinone radical anion forms on the surface of the lithium peroxide, indicating the occurrence of electron and lithium ion transfer in the solid state. As a result, obligate lithium superoxide is formed and encapsulated in a shell of Li[ p –C 6 H 4 O 2 ] with a core of Li 2 O 2 . Lithium superoxide has been proposed as a critical intermediate in the charge/discharge cycle of Li–air batteries, but has yet to be isolated, owing to instability. The results reported herein provide a snapshot of lithium peroxide/superoxide chemistry in the solid state with redox mediation. 

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4. Surface molecular engineering to enable processing of sulfide solid electrolytes in humid ambient air

   https://doi.org/10.1038/s41467-024-55634-8  

   Liu, Mengchen; Hong, Jessica J; Sebti, Elias; Zhou, Ke; Wang, Shen; Feng, Shijie; Pennebaker, Tyler; Hui, Zeyu; Miao, Qiushi; Lu, Ershuang; et al (December 2025, Nature Communications)

   Abstract Sulfide solid-state electrolytes (SSEs) are promising candidates to realize all solid-state batteries (ASSBs) due to their superior ionic conductivity and excellent ductility. However, their hypersensitivity to moisture requires processing environments that are not compatible with today’s lithium-ion battery manufacturing infrastructure. Herein, we present a reversible surface modification strategy that enables the processability of sulfide SSEs (e. g., Li₆PS₅Cl) under humid ambient air. We demonstrate that a long chain alkyl thiol, 1-undecanethiol, is chemically compatible with the electrolyte with negligible impact on its ion conductivity. Importantly, the thiol modification extends the amount of time that the sulfide SSE can be exposed to air with 33% relative humidity (33% RH) with limited degradation of its structure while retaining a conductivity of above 1 mS cm^-1for up to 2 days, a more than 100-fold improvement in protection time over competing approaches. Experimental and computational results reveal that the thiol group anchors to the SSE surface, while the hydrophobic hydrocarbon tail provides protection by repelling water. The modified Li₆PS₅Cl SSE maintains its function after exposure to ambient humidity when implemented in a Li_0.5In | |LiNi_0.8Co_0.1Mn_0.1O₂ASSB. The proposed protection strategy based on surface molecular interactions represents a major step forward towards cost-competitive and energy-efficient sulfide SSE manufacturing for ASSB applications. 

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5. Investigating dry room compatibility of sulfide solid-state electrolytes for scalable manufacturing

   https://doi.org/10.1039/D1TA09846B  

   Chen, Yu-Ting; Marple, Maxwell A.; Tan, Darren H.; Ham, So-Yeon; Sayahpour, Baharak; Li, Wei-Kang; Yang, Hedi; Lee, Jeong Beom; Hah, Hoe Jin; Wu, Erik A.; et al (March 2022, Journal of Materials Chemistry A)

   All-solid-state batteries (ASSBs) are viewed as promising next-generation energy storage devices, due to their enhanced safety by replacing organic liquid electrolytes with non-flammable solid-state electrolytes (SSEs). The high ionic conductivity and low Young's modulus of sulfide SSEs make them suitable candidates for commercial ASSBs. Nevertheless, sulfide SSEs are generally reported to be unstable in ambient air. Moreover, instead of gloveboxes used for laboratory scale studies, large scale production of batteries is usually conducted in dry rooms. Thus, this study aims to elucidate the chemical evolution of a sulfide electrolyte, Li 6 PS 5 Cl (LPSCl), during air exposure and to evaluate its dry room compatibility. When LPSCl is exposed to ambient air, hydrolysis, hydration, and carbonate formation can occur. Moreover, hydrolysis can lead to irreversible sulfur loss and therefore LPSCl cannot be fully recovered in the subsequent heat treatment. During heat treatment, exposed LPSCl undergoes dehydration, decomposition of carbonate species, and reformation of the LPSCl phase. Finally, LPSCl was found to exhibit good stability in a dry room environment and was subject to only minor conductivity loss due to carbonate formation. The dry room exposed LPSCl sample was tested in a LiNi 0.8 Co 0.1 Mn 0.1 O 2 |LiIn half-cell, exhibiting no significant loss of electrochemical performance compared with the pristine LPSCl, proving it to be compatible with dry room manufacturing processes. 

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