The inner workings of Li-ion batteries

Latest findings by MIT researchers explain the unexpectedly high power and long cycle life of lithium-ion batteries.

The researchers studied the electrode material lithium iron phosphate (LiFePO₄) and found that inside this electrode, during charging, a solid-solution zone (SSZ) forms at the boundary between lithium-rich and lithium-depleted areas - the region where charging activity is concentrated, as lithium ions are pulled out of the electrode. The material is considered especially promising for lithium-based rechargeable batteries; it has already been demonstrated in applications ranging from power tools to electric vehicles to large-scale grid storage.

The observations help to resolve a longstanding puzzle about LiFePO₄: in bulk crystal form, both lithium iron phosphate and iron phosphate (FePO₄, which is left behind as lithium ions migrate out of the material during charging) have very poor ionic and electrical conductivities. Yet when treated - with doping and carbon coating - and used as nanoparticles in a battery, the material exhibits an impressively high charging rate.

The findings appear in a paper in the journal Nano Letters co-authored by MIT postdoc Jun Jie Niu, research scientist Akihiro Kushima, professors Yet-Ming Chiang and Ju Li, and three others. Li says that this SSZ “has been theoretically predicted to exist, but we see it directly for the first time” in transmission electron microscope (TEM) videos taken during charging.

The SSZ is a “metastable” state, persisting for at least several minutes at room temperature. Replacing a sharp interface between LiFePO₄ and FePO₄ that has been shown to contain many additional line defects called “dislocations”, the SSZ serves as a buffer, reducing the number of dislocations that would otherwise move with the electrochemical reaction front. “We don’t see any dislocations,” Li says. This could be important because the generation and storage of dislocations can cause fatigue and limit the cycle life of an electrode.

Unlike conventional TEM imaging, the technique used in this work, developed in 2010 by Kushima and Li, makes it possible to observe battery components as they charge and discharge, which can reveal dynamic processes. “In the last four years, there has been a big explosion of using such in situ TEM techniques to study battery operations,” Li says.

A better understanding of these dynamic processes could improve the performance of an electrode material by allowing better tuning of its properties, Li says. Despite an incomplete understanding to date, lithium iron phosphate nanoparticles are already used at an industrial scale for lithium-ion batteries, Li explains. “The science is lagging behind the application,” he says. “It’s already scaled up and quite successful on the market. It’s one of the success stories of nanotechnology.”

“Compared to traditional lithium-ion, [lithium iron phosphate] is environmentally friendly and very stable,” Niu says. “But it’s important for this material to be well understood.”

While the discovery of the SSZ was made in LiFePO₄, Li says, “The same principle may apply to other electrode materials. People are looking for high-power electrode materials, and such metastable states could exist in other electrode materials that are inert in bulk form. … The phenomenon discovered could be very general, and not specific to this material.”

The research was supported by the National Science Foundation.