Lithium superoxide encapsulated in a benzoquinone anion matrix

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–C6H4O2) vapor, develops a deep blue color. This blue powder can be formally described as [Li2O2]0.3 · [LiO2]0.7 · {Li[p–C6H4O2]}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–C6H4O2] with a core of Li2O2. 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.

An inverse-breathing encapsulation system for cell delivery

Cell encapsulation represents a promising therapeutic strategy for many hormone-deficient diseases such as type 1 diabetes (T1D). However, adequate oxygenation of the encapsulated cells remains a challenge, especially in the poorly oxygenated subcutaneous site. Here, we present an encapsulation system that generates oxygen (O2) for the cells from their own waste product, carbon dioxide (CO2), in a self-regulated (i.e., “inverse breathing”) way. We leveraged a gas-solid (CO2–lithium peroxide) reaction that was completely separated from the aqueous cellular environment by a gas permeable membrane. O2 measurements and imaging validated CO2-responsive O2 release, which improved cell survival in hypoxic conditions. Simulation-guided optimization yielded a device that restored normoglycemia of immunocompetent diabetic mice for over 3 months. Furthermore, functional islets were observed in scaled-up device implants in minipigs retrieved after 2 months. This inverse breathing device provides a potential system to support long-term cell function in the clinically attractive subcutaneous site.

Nanoconfined growth of lithium-peroxide inside electrode pores: A noncatalytic strategy toward mitigating capacity-rechargeability trade-off in Lithium–Air battery

Capacity-rechargeability trade-off in Lithium–Air battery remains as one of the major challenges before its practical realization. As the discharge capacity increases, an uncontrolled growth of lithium-peroxide leads to passivation of...

A Modeling Study of Discharging Li-O2 Batteries With Various Electrolyte Concentrations

The mass transfer in the cathode electrode plays an important role in operating Li-O2 batteries. In this study, a two-dimensional, transient, and isothermal model is developed to investigate the mass transfer in discharging Li-O2 batteries. This model simulates the discharge performance of Li-O2 batteries with various electrolyte concentrations (0.1−1.0M) at various current densities (0.1, 0.3, and 0.5 mA/cm2). The O2 diffusivity and the ionic conductivity and diffusivity of Li+ are altered as the bis(trifluoromethane)sulfonimide lithium salt (LiTFSI) concentration in the electrolyte of tetraethylene glycol dimethyl ether (TEGDME) changes. The distributions of O2, Li+, and lithium peroxide (Li2O2) in the cathode electrode after discharge are calculated using this model. Modeling results show that when the concentration decreases from 0.5 to 0.25M, the discharge capacity of Li-O2 sharply drops at various current densities. The mass transfer of Li+ determines the discharge capacity of Li-O2 batteries with dilute electrolytes (≤0.25 M). In contrast, the O2 supply is dominant regarding the discharge capacity when the electrolyte concentration is larger than 0.5M. The highest discharge capacity (e.g., 6.09 mAh at 0.1 mA/cm2) is achieved using 0.5M electrolyte since it balances mass transfer of O2 and Li+.