The fine detail of what happens in an electrode during charging and discharging is just one of many factors that determine battery life, but it’s one that, until this study, was not adequately understood. We have found a new way to think about battery degradation.

—William Chueh of SIMES, senior author

The results, Chueh said, can be directly applied to many oxide and graphite electrodes used in today’s commercial lithium ion batteries and in about half of those under development.

An important source of battery wear and tear is the swelling and shrinking of the negative and positive electrodes as they absorb and release ions from the electrolyte during charging and discharging.

For this study scientists looked at a lithium iron phosphate cathode material. If most or all of the nanoparticles in the material actively participate in charging and discharging, they’ll absorb and release ions more gently and uniformly. However, if only a small percentage of particles take in the ions, they’re more likely to crack and get ruined, degrading the battery’s performance.

Previous studies produced conflicting views of how the nanoparticles in the cathode material behaved. To probe further, researchers made small coin cell batteries, charged them with different levels of current for various periods of time, quickly took them apart and rinsed the components to stop the charge/discharge process. Then they cut the electrode into extremely thin slices and took them to Berkeley Lab for examination with intense X-rays from the Advanced Light Source synchrotron, a DOE Office of Science User Facility.

We were able to look at thousands of electrode nanoparticles at a time and get snapshots of them at different stages during charging and discharging. This study is the first to do that comprehensively, under many charging and discharging conditions.

—Yiyang Li, lead author

Analyzing the data using a model developed at MIT, the researchers discovered that only a small percentage of nanoparticles absorbed and released ions during charging, even when it was done very rapidly. However, when the discharge rate increased above a certain threshold, more and more particles started to absorb ions simultaneously, switching to a more uniform and less damaging mode. This suggests that scientists may be able to tweak the electrode material or the process to get faster rates of charging and discharging while maintaining long battery life.

The next step, Li said, is to run the battery electrodes through hundreds to thousands of cycles to mimic real-world performance. The scientists also hope to take snapshots of the battery while it’s charging and discharging, rather than stopping the process and taking it apart.

This should yield a more realistic view, and can be done at synchrotrons such as ALS or SLAC’s Stanford Synchrotron Radiation Lightsource, also a DOE Office of Science User Facility. Li said the group has also been working with industry to see how these findings might apply in the transportation and consumer electronics sectors.

Research funding came from the Samsung Advanced Institute of Technology Global Research Outreach Program; the School of Engineering and Precourt Institute for Energy at Stanford; the Samsung-MIT Program for Materials Design in Energy Applications; and the US Department of Energy; and the National Science Foundation.

Resources

• Yiyang Li, Farid El Gabaly, Todd R. Ferguson, Raymond B. Smith, Norman C. Bartelt, Joshua D. Sugar, Kyle R. Fenton, Daniel A. Cogswell, A. L. David Kilcoyne, Tolek Tyliszczak, Martin Z. Bazant & William C. Chueh (2014) “Current-induced transition from particle-by-particle to concurrent intercalation in phase-separating battery electrodes” Nature Materials doi: 10.1038/NMAT4084