Thursday, 2 June 2016: 11:00
Aqua 305 (Hilton San Diego Bayfront)
It is well established that lithium-ion batteries (LIBs) exhibit reduced performance with increasing electrochemical cycles (quantified as capacity fade or impedance growth), and it has also been demonstrated that the electrochemical driving forces for ion insertion and removal from the active electrode materials cause mechanical strain that can even lead to fracture of the active, brittle particles. In other words, battery storage capacity fades over repeated electrochemical cycles, and cathode particles can exhibit fracture over repeated cycles. However, the direct correlation between fracture events due to electrochemomechanical coupling and the performance reduction of LIB cathodes has not been established fully. Thus, although the fracture mechanics of electrode materials have been modeled extensively, it is not well understood whether, when, and how fracture initiates and progresses to result in changes in late-life performance of LIBs. Here, we monitored acoustic emission events during repeated cycling of LiMn2O4 and LiNi0.5Mn1.5O4 electrodes to consider the temporal correlations of electrode particle fracture and changes in capacity and impedance. We varied the electrochemical cycling rate to intensify fracture driving forces, and thus identified any temporal correlations between fracture, capacity fade, and impedance growth as a function of cycle characteristics. We analyzed performance degradation using electrochemical impedance spectroscopy, including the dependences on temperature and state-of-charge. Such analysis of how fracture relates to capacity fade and impedance growth in this class of brittle ionic conductors informs the design of Li-ion batteries with increased durable useful lifetimes.