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1. Designing electrolytes with polymerlike glass-forming properties and fast ion transport at low temperatures

   https://doi.org/10.1073/pnas.2004576117  

   Zhao, Qing ; Liu, Xiaotun ; Zheng, Jingxu ; Deng, Yue ; Warren, Alexander ; Zhang, Qiyuan ; Archer, Lynden ( October 2020 , Proceedings of the National Academy of Sciences)

   In the presence of Lewis acid salts, the cyclic ether, dioxolane (DOL), is known to undergo ring-opening polymerization inside electrochemical cells to form solid-state polymer batteries with good interfacial charge-transport properties. Here we report that LiNO₃, which is unable to ring-open DOL, possesses a previously unknown ability to coordinate with and strain DOL molecules in bulk liquids, completely arresting their crystallization. The strained DOL electrolytes exhibit physical properties analogous to amorphous polymers, including a prominent glass transition, elevated moduli, and low activation entropy for ion transport, but manifest unusually high, liquidlike ionic conductivities (e.g., 1 mS/cm) at temperatures as low as −50 °C. Systematic electrochemical studies reveal that the electrolytes also promote reversible cycling of Li metal anodes with high Coulombic efficiency (CE) on both conventional planar substrates (1 mAh/cm²over 1,000 cycles with 99.1% CE; 3 mAh/cm²over 300 cycles with 99.2% CE) and unconventional, nonplanar/three-dimensional (3D) substrates (10 mAh/cm²over 100 cycles with 99.3% CE). Our finding that LiNO₃promotes reversibility of Li metal electrodes in liquid DOL electrolytes by a physical mechanism provides a possible solution to a long-standing puzzle in the field about the versatility of LiNO₃salt additives for enhancing reversibility of Li metal electrodes in essentially any aprotic liquidmore »electrolyte solvent. As a first step toward understanding practical benefits of these findings, we create functional Li||lithium iron phosphate (LFP) batteries in which LFP cathodes with high capacity (5 to 10 mAh/cm²) are paired with thin (50 μm) lithium metal anodes, and investigate their galvanostatic electrochemical cycling behaviors.

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2. On the crystallography and reversibility of lithium electrodeposits at ultrahigh capacity

   https://doi.org/10.1038/s41467-021-26143-9  

   Zhao, Qing ; Deng, Yue ; Utomo, Nyalaliska W. ; Zheng, Jingxu ; Biswal, Prayag ; Yin, Jiefu ; Archer, Lynden A. ( December 2021 , Nature Communications)

   Abstract Lithium metal is a promising anode for energy-dense batteries but is hindered by poor reversibility caused by continuous chemical and electrochemical degradation. Here we find that by increasing the Li plating capacity to high values ( e.g ., 10–50 mAh cm −2 ), Li deposits undergo a morphological transition to produce dense structures, composed of large grains with dominantly (110) Li crystallographic facets. The resultant Li metal electrodes manifest fast kinetics for lithium stripping/plating processes with higher exchange current density, but simultaneously exhibit elevated electrochemical stability towards the electrolyte. Detailed analysis of these findings reveal that parasitic electrochemical reactions are the major reason for poor Li reversibility, and that the degradation rate from parasitic electroreduction of electrolyte components is about an order of magnitude faster than from chemical reactions. The high-capacity Li electrodes provide a straightforward strategy for interrogating the solid electrolyte interphase (SEI) on Li —with unprecedented, high signal to noise. We find that an inorganic rich SEI is formed and is primarily concentrated around the edges of lithium particles. Our findings provide straightforward, but powerful approaches for enhancing the reversibility of Li and for fundamental studies of the interphases formed in liquid and solid-state electrolytes using readily accessible analytical tools.
3. Stable, high-performance, dendrite-free, seawater-based aqueous batteries

   https://doi.org/10.1038/s41467-020-20334-6  

   Tian, Huajun ; Li, Zhao ; Feng, Guangxia ; Yang, Zhenzhong ; Fox, David ; Wang, Maoyu ; Zhou, Hua ; Zhai, Lei ; Kushima, Akihiro ; Du, Yingge ; et al ( January 2021 , Nature Communications)

   Metal anode instability, including dendrite growth, metal corrosion, and hetero-ions interference, occurring at the electrolyte/electrode interface of aqueous batteries, are among the most critical issues hindering their widespread use in energy storage. Herein, a universal strategy is proposed to overcome the anode instability issues by rationally designing alloyed materials, using Zn-M alloys as model systems (M = Mn and other transition metals). An in-situ optical visualization coupled with finite element analysis is utilized to mimic actual electrochemical environments analogous to the actual aqueous batteries and analyze the complex electrochemical behaviors. The Zn-Mn alloy anodes achieved stability over thousands of cycles even under harsh electrochemical conditions, including testing in seawater-based aqueous electrolytes and using a high current density of 80 mA cm⁻². The proposed design strategy and the in-situ visualization protocol for the observation of dendrite growth set up a new milestone in developing durable electrodes for aqueous batteries and beyond.
4. The early-stage growth and reversibility of Li electrodeposition in Br-rich electrolytes

   https://doi.org/10.1073/pnas.2012071118  

   Biswal, Prayag ; Kludze, Atsu ; Rodrigues, Joshua ; Deng, Yue ; Moon, Taylor ; Stalin, Sanjuna ; Zhao, Qing ; Yin, Jiefu ; Kourkoutis, Lena F. ; Archer, Lynden A. ( December 2020 , Proceedings of the National Academy of Sciences)

   The physiochemical nature of reactive metal electrodeposits during the early stages of electrodeposition is rarely studied but known to play an important role in determining the electrochemical stability and reversibility of electrochemical cells that utilize reactive metals as anodes. We investigated the early-stage growth dynamics and reversibility of electrodeposited lithium in liquid electrolytes infused with brominated additives. On the basis of equilibrium theories, we hypothesize that by regulating the surface energetics and surface ion/adatom transport characteristics of the interphases formed on Li, Br-rich electrolytes alter the morphology of early-stage Li electrodeposits; enabling late-stage control of growth and high electrode reversibility. A combination of scanning electron microscopy (SEM), image analysis, X-ray photoelectron spectroscopy (XPS), electrochemical impedance spectroscopy (EIS), and contact angle goniometry are employed to evaluate this hypothesis by examining the physical–chemical features of the material phases formed on Li. We report that it is possible to achieve fine control of the early-stage Li electrodeposit morphology through tuning of surface energetic and ion diffusion properties of interphases formed on Li. This control is shown further to translate to better control of Li electrodeposit morphology and high electrochemical reversibility during deep cycling of the Li metal anode. Our results show that understandingmore »and eliminating morphological and chemical instabilities in the initial stages of Li electroplating via deliberately modifying energetics of the solid electrolyte interphase (SEI) is a feasible approach in realization of deeply cyclable reactive metal batteries.

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5. Solid electrolyte interphases for high-energy aqueous aluminum electrochemical cells

   https://doi.org/10.1126/sciadv.aau8131  

   Zhao, Qing ; Zachman, Michael J. ; Al Sadat, Wajdi I. ; Zheng, Jingxu ; Kourkoutis, Lena F. ; Archer, Lynden ( November 2018 , Science Advances)

   Electrochemical cells based on aluminum (Al) are of long-standing interest because Al is earth abundant, low cost, and chemically inert. The trivalent Al 3+ ions also offer among the highest volume-specific charge storage capacities (8040 mAh cm −3 ), approximately four times larger than achievable for Li metal anodes. Rapid and irreversible formation of a high-electrical bandgap passivating Al 2 O 3 oxide film on Al have, to date, frustrated all efforts to create aqueous Al-based electrochemical cells with high reversibility. Here, we investigate the interphases formed on metallic Al in contact with ionic liquid (IL)–eutectic electrolytes and find that artificial solid electrolyte interphases (ASEIs) formed spontaneously on the metal permanently transform its interfacial chemistry. The resultant IL-ASEIs are further shown to enable aqueous Al electrochemical cells with unprecedented reversibility. As an illustration of the potential benefits of these interphases, we create simple Al||MnO 2 aqueous cells and report that they provide high specific energy (approximately 500 Wh/kg, based on MnO 2 mass in the cathode) and intrinsic safety features required for applications.