Kevlar-based layered nanoscale membrane

suppresses dendrite growth in lithium-ion battery

Materials Research Society/MRS Bulletin | Published: 20 February 2015

SEM image of the tip of a copper dendrite. Credit: Nicholas Kotov.

Boeing did not experience a pleasant start to 2013. Within the first few weeks of the
year, several of its much-anticipated 787 Dreamliner aircraft were grounded or had to
conduct an emergency landing due to smoke being detected in their electrical
compartments. In one incident, a fire even broke out on a plane parked at Boston’s
Logan International Airport. Authorities in both the United States and Japan were
searching for answers.
The culprit behind the accident turned out to be the Dreamliner’s lithium-ion batteries.
Lithium atoms from the batteries’ anodes had leaked through tiny holes in the separator
membrane, meant to insulate the anode and cathode. As more and more atoms built up,
they formed dendrites--branch-like structures. When the dendrites found their way from
the anode to the cathode, the battery circuit shorted, causing overheating and
sometimes a fire or explosion.
The tips of the dendrites are just 20–50 nm across, making their containment an
extremely difficult task for engineers. Now, a research team from the University of
Michigan has built a battery membrane with pores that are just 15–20 nm in diameter—
large enough to allow lithium ions to pass, but small enough to prevent dendrites from
growing. “We were able to make a matrix of individual polymeric filaments with very
small pores so they could transport charge, but still apply pressure on the growing
dendrites to stop them,” says Nicholas Kotov, a materials scientist and chemical
engineer, and senior author of the article. “This requires several properties that are
contradictory to each other: stiffness, toughness, high-temperature stability, and ion
mobility,” he says. While carbon nanotubes, due to their strength, would have seemed
like the obvious choice for the membrane given their superior strength, their electrical
conductivity ruled them out.

Instead, Kotov and his colleagues turned to Kevlar TM—the ultra-strong threads made
from aramid polymer, used in bulletproof vests—to find a solution to the dendrite
problem. KevlarTM is both an insulating material and has very high mechanical properties.
Moreover, they knew that immersing KevlarTM in a solution of dimethylsulfoxide and
water caused the macroscale threads to transform into nanoscale aramid fibers.
Combining this method with a technique called layer-by-layer assembly, the researchers
built a thin membrane composed of nanoscale aramid nanofibers and polyethylene oxide.
As they reported in Nature Communications, the team first tested the aramid nanofiber
membrane for its ability to suppress copper and lithium dendrites. Under normal
conditions, copper and lithium electrodes quickly and aggressively form dendrites, but
when the aramid nanofiber separator was in place, the researchers found no evidence of
dendrites. “The layering process achieves unmatched dispersion uniformity of nanofibers
that produces high-density, high-performance films,” says Jaime Grunlan, a professor of
mechanical engineering at Texas A&M University, who was not involved in the work.
“These membranes shut down dendrite formation as a result, which has not been
demonstrated by any other ion conducting technology.”
Following this success, Kotov and his colleagues turned their attention to lithium. They
created a battery with a metallic lithium anode, and then tested it under normal
conditions using a standard industry separator made by Celgard TM, whose membranes
are composed of polyethylene or polypropylene. Dendrites, as expected, eventually
formed. When the team replaced the Celgard TM separator with the aramid nanofiber
sheet, however, dendrites did not form. Examining the electrical parameters of the
battery additionally revealed that the charge-discharge cycles remained stable when
using the aramid nanofiber separator, but not the CelgardTM one. The aramid nanofiber
separator can also operate at higher temperatures than standard models, an asset for
increasing a battery’s operational range.
“It is no easy task to find a material that can both stop dendrite formation in its tracks
and conduct ions, as Kotov and co-workers have demonstrated here,” says Jodie
Lutkenhaus, an assistant professor of chemical engineering at Texas A&M University,
who was not involved in the research. “This work represents a big leap forward for
mechanically robust ion conducting membranes.”
In addition to its possibility of improving batteries used in airplanes and electronic
vehicles, the new membrane could find application in consumer electronics such as in
mobile phones and tablet computers, as well as in biomedical devices. Kotov and his
colleagues have already been approached by a number of companies interested in their
work, and Kotov has co-founded a startup, Elegus Technologies, to commercialize the
membranes. “Next, we are working on scaling up the separator,” he says. “We have to
transition from the lab to real-world processing.”