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Nonuniform electrodeposition and dendritic growth of lithium metal coupled to its chemical incompatibility with liquid electrolytes are largely responsible for poor Coulombic efficiency and safety hazards preventing the successful implementation of energy-dense Li metal anodes. Artificial solid electrolyte interface (ASEI) layers have been proposed to address the morphological evolution and chemical reactions in Li metal anodes. In this study, an ASEI layer consisting of a lithium phosphorus oxynitride (LiPON) thin film electrolyte and gold-alloying interlayer was developed and shown to promote the electrodeposition of smooth, homogeneous, mirror-like Li metal morphologies. The Au layer alloyed with Li, reducing the nucleation overpotential and resulting in a more spatially uniform metal deposit, while the LiPON layer provided a physical barrier between the Li metal and aprotic liquid electrolyte. The effectiveness and integrity of the LiPON protective layer was assessed using in operando impedance spectroscopy and ex situ SEM/EDS characterization. Smooth, homogeneous Li morphologies were realized in capacities up to 3 mAh cm -2 plated at 0.1 mA cm -2 . At higher current densities up to 1 mA cm -2 or increased deposition capacities of 6 mAh cm -2 , the LiPON coating fractured due to the localized, nonuniform lithium deposits and rough, dendritic Li morphologies were observed. This approach represents a new strategy in the design of artificial SEIs to enable Li metal anodes with practical areal capacities.

Mechanically and thermally robust separators offer an alternative approach for preventing battery failure under extreme conditions such as high loads and temperatures. However, the trade-off between electrochemical performance and mechanical and thermal stability remains an ongoing challenge. Here, we investigate aramid nanofiber (ANF) separators that possess high moduli and self-extinguishing characteristics. The ANF separators are formed from the dissolution of bulk Kevlar fibers and their subsequent vacuum-assisted self-assembly. Thermogravimetric analysis shows a high 5 wt % decomposition temperature of 447 °C, which is over ∼175 °C higher than commercial Celgard separators. The ANF separator also possesses a high Young's modulus of 8.8 GPa, which is ∼1000% higher than commercial separators. Even when dry or when soaked in battery electrolyte, the ANF separators self-extinguish upon exposure to flame, whereas commercial separators melt or drip. We show that these features, although adventitious, present a trade-off with electrochemical performance in which a lithium nickel manganse cobalt (NMC) oxide-based battery possessed a reduced capacity of 123.4 mA h g -1 . Considering the separator holistically, we propose that the ANF separator shows an excellent balance of the combined properties of high modulus, flame-resistance, thermal stability, and electrochemical stability and might be suitable for extreme environment applications with further testing.

We present a method to prepare shear thickening electrolytes consisting of silica nanoparticles in conventional liquid electrolytes with limited flocculation. These electrolytes rapidly and reversibly stiffen to solidlike behaviors in the presence of external shear or high impact, which is promising for improved lithium ion battery safety, especially in electric vehicles. However, in initial chemistries the silica nanoparticles aggregate and/or sediment in solution over time. Here, we demonstrate steric stabilization of silica colloids in conventional liquid electrolyte via surface-tethered PMMA brushes, synthesized via surface-initiated atom transfer radical polymerization. The PMMA increases the magnitude of the shear thickening response, compared to the uncoated particles, from 0.311 to 2.25 Pa s. Ultrasmall-angle neutron scattering revealed a reduction in aggregation of PMMA-coated silica nanoparticles compared to bare silica nanoparticles in solution under shear and at rest, suggesting good stabilization. Conductivity tests of shear thickening electrolytes (30 wt % solids in electrolyte) at rest were performed with interdigitated electrodes positioned near the meniscus of electrolytes over the course of 24 h to track supernatant formation. Conductivity of electrolytes with bare silica increased from 10.1 to 11.6 mS cm -1 over 24 h due to flocculation. In contrast, conductivity of electrolytes with PMMA-coated silica remained stable at 6.1 mS cm -1 over the same time period, suggesting good colloid stability.

Using neutron reflectometry, we have determined the thickness and scattering length density profile of the electrode-electrolyte interface for the high-voltage cathode LiMn(1.5)Ni(0.5)O4 in situ at open circuit voltage and fully delithiated. Upon exposure to a liquid electrolyte, a thin 3.3 nm Li-rich interface forms due to the ordering of the electrolyte on the cathode surface. This interface changes in composition, as evident by an increase in the scattering length density of the new layer, with charging as the condensed layer evolves from being lithium rich to one containing a much higher concentration of F from the LiPF6 salt. These results show the surface chemistry evolves as a function of the potential.