Narrowing the gap between theoretical and actual capacity in key Li-based battery systems can be achieved through improvements in both electronic and ionic conductivities of materials, via addition of conductive species. Additives do, however, penalize both volumetric and gravimetric properties, and also limit liquid transport and high rate performance. In this work, we developed techniques to design and optimize cathode system based directly on the relationships among ionic and electronic conductivities, and specific energy. We also investigated formation mechanisms, and resulting geometric characteristics in nanoparticle agglomerates, to systematically study percolation and conductivity in self-assembled structures.
In our study of selection of conductive additives, architectures of model composite cathodes, comprised of active material, graphite, carbon black, and PVDF, were generated using our prior approach in simulating polydisperse arrangements. A key finding of this portion of the work, was that the conductive coatings strongly influence conductivity, via reduction of contact resistance. Thus, we conclude that neither surface nor bulk modifications of active material particles conductivities seem to be desirable targets for improvement of laminate conductivity, for the ranges of materials studied. In the cathode optimization study, our results quantified trade-offs among ionic and electronic conductivity, and conductivity and specific energy. We also provided quantitative relationships for improved utilization and specific power, with higher specific energy. Finally, we provided quantitative guidance for design of high energy density Li(Ni1/3Co1/3Mn1/3)O2 cells using conductive additives, and also provided guidelines for design of cathode systems, based directly on solid and liquid phase transport limitations.
In the agglomeration and aggregation study, 3D, branch-like nanoparticle agglomerates were systematically studied via use of new algorithms in generation of such structures. Our findings in this portion of the study included the conclusion that Coulomb forces concentrated on the tip are likely root causes of the long chain-like shapes of observed clusters, creating branch-like soot agglomerates; particles tend to form a more compact and smaller cluster with van der Waals force. Under a certain combination of forces, including Coulomb and van der Waals forces, nanoparticles form self-similar structures with a specific fractal dimension.