PNNL team pinpoints cause of dendrites and whiskers in lithium batteries; ethylene carbonate a culprit
Researchers at Pacific Northwest National Laboratory (PNNL) have uncovered a root cause of the growth of dendrites and whiskers that plague lithium batteries, sometimes causing a short circuit, failure, or even a fire.
The team, led by Chongmin Wang, has shown that the presence of certain compounds in the electrolyte prompts the growth of dendrites and whiskers. The team hopes the discovery will lead to new ways to prevent their growth by manipulating the battery’s ingredients. The results were published in Nature Nanotechnology.
Dendrites are tiny, rigid tree-like structures that can grow inside a lithium battery; their needle-like projections are called whiskers. Both can pierce the separator inside a battery. They also increase unwanted reactions between the electrolyte and the lithium, speeding up battery failure. Dendrites and whiskers are holding back the widespread use of lithium metal batteries, which have higher energy density than their commonly used lithium-ion counterparts.
The PNNL team found that the origin of whiskers in a lithium metal battery lies in a structure known as the solid-electrolyte interphase (SEI), a film where the solid lithium surface of the anode meets the liquid electrolyte. Further, the scientists pinpointed a culprit in the growth process: ethylene carbonate, an indispensable solvent added to electrolyte to enhance battery performance.
Li whisker formation during electrochemical deposition of Li in a CO2 environment. a–c, Sequential TEM snapshots of Li particle nucleation. d–f, Whisker growth process. g, Whisker collapse. The red arrow in f indicates that the Li whisker sprouts up from the whisker–electrolyte interface. Blue dotted lines indicate the nucleus. Red dotted lines highlight the side surface and shape of the Li whisker. h, Deflection of the AFM tip and vertical growth rate of the whisker during the process. i,j, Li particle in another nucleation case and corresponding electron diffraction pattern. The spring constant of the AFM cantilever is ~0.4 N m–1. He et al.
The team’s findings include videos that show the step-by-step growth of a whisker inside a nanosized lithium metal battery specially designed for the study.
A dendrite begins when lithium ions start to clump, or “nucleate,” on the surface of the anode, forming a particle that signifies the birth of a dendrite. The structure grows slowly as more and more lithium atoms glom on, growing the same way that a stalagmite grows from the floor of a cave. The team found that the energy dynamics on the surface of the SEI push more lithium ions into the slowly growing column. Then, suddenly, a whisker shoots forth.
To capture the action, the scientists integrated an atomic force microscope (AFM) and an environmental transmission electron microscope (ETEM). The team used the AFM to measure the tiny force of the whisker as it grew. The PNNL team measured the force of the growing whisker by pushing down on its tip with the cantilever of the AFM and measuring the force the dendrite exerted during its growth.
The team found that the level of ethylene carbonate directly correlates with dendrite and whisker growth. The more of the material the team put in the electrolyte, the more the whiskers grew. The scientists experimented with the electrolyte mix, changing ingredients in an effort to reduce dendrites. Some changes, such as the addition of cyclohexanone, prevented the growth of dendrites and whiskers.
We don’t want to simply suppress the growth of dendrites; we want to get to the root cause and eliminate them. We drew upon the expertise of our colleagues who have expertise in electrochemistry. My hope is that our findings will spur the community to look at this problem in new ways. Clearly, more research is needed.—Chongmin Wang
Understanding what causes whiskers to start and grow will lead to new ideas for eliminating them or at least controlling them to minimize damage, added first author Yang He. He and the team tracked how whiskers respond to an obstacle, either buckling, yielding, kinking, or stopping. A greater understanding could help clear the path for the broad use of lithium metal batteries in electric cars, laptops, mobile phones, and other areas.
The work was funded by DOE’s Office of Energy Efficiency and Renewable Energy’s Vehicle Technologies Office. The work was made possible thanks to the unique combination of capabilities available at EMSL, the Environmental Molecular Sciences Laboratory, a DOE Office of Science user facility located at PNNL.
Yang He, Xiaodi Ren, Yaobin Xu, Mark H. Engelhard, Xiaolin Li, Jie Xiao, Jun Liu, Ji-Guang Zhang, Wu Xu & Chongmin Wang (2019) “Origin of lithium whisker formation and growth under stress” Nature Nanotechnology doi: 10.1038/s41565-019-0558-z