Date(s) - 03/28/2023
9:15 am - 10:15 am
New Engineering Building – Room 201
Bryan D. McCloskey, Ph.D.
Chair of Chemical and Biomolecular Engineering
The Warren and Katharine Schlinger Distinguished Professor in Chemical Engineering
Chemical & Biomolecular Engineering
University of California, Berkeley
Energy Storage and Distributed Resources Division, Lawrence Berkeley National Laboratory
Title: Ion transport in charged polymer electrolytes: the pursuit of high Li+ transference number
Abstract: Conventional Li-ion battery electrolytes have been designed to optimize numerous desirable properties, including interfacial and thermal stability, conductivity, and low flammability. However, all Li+-bearing electrolytes still possess low Li+ transference (t+) numbers, where current passed through them is primarily carried by the counteranion, resulting in large concentration gradients that limit battery performance, particularly at high discharge and charging rates. The development of high t+ electrolytes—those in which most (or all) current is carried by the Li+ ion—could enable safer battery cycling, faster charging rates, and thicker, more energy-dense cathode designs in Li-ion batteries.
This presentation will outline our attempts to develop polymer-based high t+ electrolytes wherein anions are appended to a polymer (polyanions) and neutralized with Li ions. In this configuration, Li ions, when appropriately solvated, have hydrodynamic radii much smaller than the polymer’s radius of gyration, ostensibly allowing them to diffuse or migrate faster than their appended counteranions, and hence enable high t+ electrolytes. Ultimately, I show this picture to be oversimplified, and that anion-anion and cation-anion correlations severely limit the t+ of high conductivity polyanionic solutions.
Initially, I will present studies that highlight the inherent tradeoff between segmental motion and ion content that has generally limited room temperature conductivity of dry polymer electrolyte systems. We show that blending of a small molecule diluent breaks the apparent tradeoff between segmental dynamics and charge carrier concentration in dry polymer electrolytes, motivating the pursuit of polyelectrolyte solutions (charged polymers dissolved in solvent) as potential high t+ electrolytes. In the second part of the presentation, I discuss our efforts to understand and characterize the full transport properties of a model, monodisperse, battery-relevant oligomeric polyelectrolyte system. Intriguingly, for polyelectrolytes with larger molecular weights, we observe that the average velocity of Li ions in an electric field is in the direction opposite than expected, evidence of a negative t+ due to correlated motion through Li ion condensation on the polyelectrolyte chain. While this result is a negative outcome in our pursuit of high t+ electrolytes, we anticipate many of the capabilities and insights gleaned throughout our studies to be of general use to those studying novel, concentrated electrolyte solutions where strong, non-ideal ion-ion correlations are observed.
Bio: Bryan McCloskey is the Department Chair and Warren & Katharine Schlinger Distinguished Professor in Chemical Engineering in the Department of Chemical and Biomolecular Engineering at the University of California, Berkeley. He also holds a joint appointment as a Faculty Engineer in the Energy Storage and Distributed Resources Division at Lawrence Berkeley National Laboratory. His laboratory explores numerous applications of electrochemistry to energy sustainability, conversion, and storage. Current projects focus on electrochemical regeneration of alkaline sorbents for direct air CO2 capture, elucidating the fundamental electrochemistry of metal-air batteries, and understanding a variety of challenges facing Li-ion batteries, including high voltage cathode stability, advanced cathode material development (Ni-rich and Li- rich NMC oxides and Li-excess disordered rocksalt materials), extreme fast charging, and low temperature and high transference number electrolyte formulations. He has co-authored 150 articles and has won numerous awards for his research, including The Electrochemical Society Charles Tobias Award, The International Society of Electrochemistry Tajima Prize, and the VW/BASF Science Award- Electrochemistry. More information about the McCloskey Lab can be found at the Lab’s website: www.mccloskeylab.com