Microstructural Analysis of Lithium-Ion Battery Cathode Carbon-Binder Domain across Processing Conditions
Authors: Brenneis Willa , Liu Qingsong , Richards Jeffrey J. , Lopez Jeffrey 
Published: August 2024

Improvement of lithium-ion battery (LIB) energy density and rate capability is necessary to increase adoption of electric vehicles (EVs) and curb transportation emissions. The cathode structure must support facile ion and electron transport, enabling rapid charging while maintaining near-theoretical capacity. Much investigation focuses on active material design for fast-charging cathodes, [1] but less is understood about the effect of electrode processing on carbon-binder domain (CBD) structure and its impact on rate capability. As conductive carbon facilitates electron transfer, slow Li+ diffusion through cathode micropores is rate-limiting and prevents full active material utilization at high charge rates. [2,3] However, efforts to improve Li+ diffusion, such as increasing porosity, introduce charge-transfer limitations. [4] Thus, cathode processing conditions and resulting microstructure must be carefully designed to optimize for both electronic and ionic conductivity. For example, an increase in coating shear rate and decrease in slurry solid content improves long-range electronic pathways [5,6] and calendaring strengthens active material-carbon contacts to reduce charge-transfer resistance. [2] However, the impact of processing variations on ionic transport pathways, which can be described by CBD porosity and tortuosity, is not well understood. Further, because the CBD is traditionally characterized as a single phase, the distinct influences of insulating binder and conductive carbon distributions on structure and performance are poorly defined.
In this talk, I will discuss how electrode coating conditions impact pathways available to Li+ and electrons within the CBD with the goal of identifying optimal microstructures for efficient transport. We fabricate cathodes with varying solid content, coating shear rate, and degree of calendaring to explore disparate CBD microstructures. We use electrochemical impedance spectroscopy (EIS) with a symmetric cell & blocking electrolyte to determine cathode resistivity and tortuosity and plasma focused ion beam scanning electron microscopy (PFIB-SEM) to examine CBD morphology over a representative cathode volume (~80 x 80 x 50 µm3). We then use small-angle neutron scattering (SANS) with solvent contrast variation to distinguish between binder and carbon distributions and determine the surface area of each component within the CBD. Relationships between processing conditions, structural variations, and rate capability will be discussed, informing the design of the CBD for facile transport and improved fast charging performance. Further, reducing ionic transport limitations through intentional design of LIB cathodes will enable thicker electrodes to increase cell energy density.
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