Understanding Polymer Structure and Conductivity in Composite Electrolytes
Authors: Sand Sara , Rupp Jennifer , Yildiz Bilge 
Published: September 2023

Lithium ion batteries are a crucial technologies for electric vehicles and portable electronics due to their high energy density. However, flammable liquid electrolytes create a safety concern and transitioning to all solid state batteries allows for the potential of higher energy density by utilizing lithium metal anodes. Two classes of solid materials have been explored to replace liquid electrolytes: ceramic and polymer electrolytes. Composite electrolytes, typically in the form of dispersed ceramic particles or nanowires in polymer matrix, combine these two materials to have good ionic conductivity while maintaining the mechanical properties of the polymer. While they have achieved fairly high conductivity (typically 10-4 S/cm), the mechanism for such ion conduction is not well understood.
The polymer likely plays a crucial role as the ceramic volume fractions are typically under 20%.1,2 Four possible ways that polymers could increase in conductivity in the composite have been identified: decreased crystallinity, increased free volume, disruption of polymer alignment, and increased lithium ion dissolution due to acidic surface groups on the ceramic.1,3,4 We have developed thin film model systems to probe the interface of the polymer with and ceramic surfaces. We found that when confined to thin films, the conductivity of the polymer electrolyte increased compared to the bulk. We utilized differential scanning calorimetry to identify the crystallinity and found that the small crystallinity variation could not account for the variation in conductivity. Subsequently, we utilized surface conductivity and transference number measurements to understand the effects of acidic surface groups. X-ray Absorption measurements will be similarly utilized to probe the variation in lithium ion environments within these materials to understand any variation in the lithium salt dissolution. It was found that the variation in conductivity based on this effect is small.
In order to probe the possible variation in free volume, Small Angle Neutron Scattering will be utilized to quantify the free volume within thin films, bulk polymer, and composite electrolytes. This can quantify the volume associated with each monomer and therefore how much space is between polymer chains for lithium ion movement.5 Lastly, while the polymer chain alignment has not been extensively discussed composite literature, it has been identified that when polymer electrolytes are cast on a surface, polymer electrolytes typically show anisotropy with measurements parallel to the surface having higher conductivity due to the alignment of the chain.6 Therefore, ceramic fillers in the composites may disrupt this packing and allow for higher conductivity perpendicular to the cast surface, the direction in which they are most commonly measured. In order to probe this effect, we measure the anisotropy of both our thin film electrolytes as well as composite electrolytes to compare the significance of the anisotropy and utilize small angle x-ray scattering to measure any anisotropy in the structure.
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