Discovery pinpoints LiFePO4 electrode high charging rates
The electrode material studied, lithium iron phosphate (LiFePO4), is a promising material for lithium-based rechargeable batteries and has already been demonstrated in applications ranging from power tools to electric vehicles to large-scale grid storage. The MIT researchers found that inside the 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.
By using transmission electron microscope (TEM) videos taken during charging Professor Ju Li, the Battelle Energy Alliance Professor of Nuclear Science and
Engineering and a professor of materials science and engineering, found that the SSZ “has been theoretically predicted to exist, but we see it directly for the first time.”
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 poor ionic and electrical conductivities. Yet when treated – with doping and carbon coating – and used as nanoparticles in a battery, the material exhibits a high charging rate.
“It was quite surprising when this [rapid charging and discharging rate] was first demonstrated,” admitted Li. “We directly observed a metastable random solid solution that may resolve this fundamental problem that has intrigued [materials scientists] for many years”.
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,” said Li. This could be important because the generation and storage of dislocations can cause fatigue and limit the cycle life of an electrode.
Diagram illustrates the process of charging or discharging the lithium iron phosphate (LFP) electrode. As lithium ions are removed during the charging process, it forms a lithium-depleted iron phosphate (FP) zone, but in between there is a solid solution zone (SSZ, shown in dark blue-green) containing some randomly distributed lithium atoms, unlike the orderly array of lithium atoms in the original crystalline material (light blue).
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,” revealed Li.
Li beleives that a better understanding of the dynamic processes could improve the performance of an electrode material by allowing better tuning of its properties.
Despite an incomplete understanding to date, lithium iron phosphate nanoparticles are already used at an industrial scale for lithium-ion batteries. “The science is lagging behind the application,” explained Li. “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,” said co-author and MIT postdoc Jun Jie Niu. “But it’s important for this material to be well understood.”
While the discovery of the SSZ was made in LiFePO4, Li said: “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 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.
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