Recipe for safer batteries — Just add diamonds

While lithium-ion batteries, widely used in mobile devices from cell phones to laptops, have one of the longest lifespans of commercial batteries today, they also have been behind a number of recent meltdowns and fires due to short-circuiting in mobile devices. In hopes of preventing more of these hazardous malfunctions researchers at Drexel University have developed a recipe that can turn electrolyte solution — a key component of most batteries — into a safeguard against the chemical process that leads to battery-related disasters.

Yury Gogotsi, PhD, Distinguished University and Bach professor in the College of Engineering, and his research team from the Department of Materials Science and Engineering, recently published their work — entitled “Nanodiamonds Suppress Growth of Lithium Dendrites” — in the journal Nature Communications. In it, they describe a process by which nanodiamonds — tiny diamond particles 10,000 times smaller than the diameter of a hair — curtail the electrochemical deposition, called plating, that can lead to hazardous short-circuiting of lithium ion batteries.

As batteries are used and charged, the electrochemical reaction results in the movement of ions between the two electrodes of a battery, which is the essence of an electrical current. Over time, this repositioning of ions can create tendril-like buildups — almost like stalactites forming inside a cave. These battery buildups, called dendrites, are one of the main causes of lithium battery malfunction. As dendrites form inside the battery over time, they can reach the point where they push through the separator, a porous polymer film that prevents the positively charged part of a battery from touching the negatively charged part. When the separator is breached, a short-circuit can occur, which can also lead to a fire since the electrolyte solution in most lithium-ion batteries is highly flammable.

To avoid dendrite formation and minimize the probability of fire, current battery designs include one electrode made of graphite filled with lithium instead of pure lithium. The use of graphite as the host for lithium prevents the formation of dendrites. But lithium intercalated graphite also stores about 10 times less energy than pure lithium. The breakthrough made by Gogotsi’s team means that a great increase in energy storage is possible because dendrite formation can be eliminated in pure lithium electrodes.

“Battery safety is a key issue for this research,” Gogotsi said. “Small primary batteries in watches use lithium anodes, but they are only discharged once. When you start charging them again and again, dendrites start growing. There may be several safe cycles, but sooner or later a short-circuit will happen. We want to eliminate or, at least, minimize that possibility.”

Gogotsi and his collaborators from Tsinghua University in Beijing, and Hauzhong University of Science and Technology in Wuhan, China, focused their work on making lithium anodes more stable and lithium plating more uniform so that dendrites won’t grow.

They’re doing this by adding nanodiamonds to the electrolyte solution in a battery. Nanodiamonds have been used in the electroplating industry for some time as a way of making metal coatings more uniform. While they are much, much smaller — and cheaper — than the diamonds you’d find in a jeweler’s case, nanodiamonds still retain the regular structure and shape of their pricey progenitors. When they are deposited, they naturally slide together to form a smooth surface.

The researchers found this property to be exceedingly useful for eliminating dendrite formation. In the paper, they explain that lithium ions can easily attach to nanodiamonds, so when they are plating the electrode they do so in the same orderly manner as the nanodiamond particles to which they’re linked. They report in the paper that mixing nanodiamonds into the electrolyte solution of a lithium ion battery slows dendrite formation to nil through 100 charge-discharge cycles.

If you think about it like a game of Tetris, that pile of mismatched blocks inching perilously close to “game over” is the equivalent of a dendrite. Adding nanodiamonds to the mix is kind of like using a cheat code that slides each new block into the proper place to complete a line and prevent a menacing tower from forming.

Gogotsi notes that his group’s discovery is just the beginning of a process that could eventually see electrolyte additives, like nanodiamonds, widely used to produce safe lithium batteries with a high energy density. Initial results already show stable charge-discharge cycling for as long as 200 hours, which is long enough for use in some industrial or military applications, but not nearly adequate for batteries used in laptops or cell phones. Researchers also need to test a large number of battery cells over a long enough period of time under various physical conditions and temperatures to ensure that dendrites will never grow.

“It’s potentially game-changing, but it is difficult to be 100 percent certain that dendrites will never grow,” Gogotsi said. “We anticipate the first use of our proposed technology will be in less critical applications — not in cell phones or car batteries. To ensure safety, additives to electrolytes, such as nanodiamonds, need to be combined with other precautions, such as using non-flammable electrolytes, safer electrode materials and stronger separators.”

Supervolcanoes: A key to America’s electric future?

Most of the lithium used to make the lithium-ion batteries that power modern electronics comes from Australia and Chile. But Stanford scientists say there are large deposits in sources right here in America: supervolcanoes.

In a study published today in Nature Communications, scientists detail a new method for locating lithium in supervolcanic lake deposits. The findings represent an important step toward diversifying the supply of this valuable silvery-white metal, since lithium is an energy-critical strategic resource, said study co-author Gail Mahood, a professor of geological sciences at Stanford’s School of Earth, Energy & Environmental Sciences.

“We’re going to have to use electric vehicles and large storage batteries to decrease our carbon footprint,” Mahood said. “It’s important to identify lithium resources in the U.S. so that our supply does not rely on single companies or countries in a way that makes us subject to economic or political manipulation.”

Supervolcanoes can produce massive eruptions of hundreds to thousands of cubic kilometers of magma — up to 10,000 times more than a typical eruption from a Hawaiian volcano. They also produce vast quantities of pumice and volcanic ash that are spread over wide areas. They appear as huge holes in the ground, known as calderas, rather than the cone-like shape typically associated with volcanoes because the enormous loss of magma causes the roof of the chamber to collapse following eruption.

The resulting hole often fills with water to form a lake — Oregon’s Crater Lake is a prime example. Over tens of thousands of years, rainfall and hot springs leach out lithium from the volcanic deposits. The lithium accumulates, along with sediments, in the caldera lake, where it becomes concentrated in a clay called hectorite.

Exploring supervolcanoes for lithium would diversify its global supply. Major lithium deposits are currently mined from brine deposits in high-altitude salt flats in Chile and pegmatite deposits in Australia. The supervolcanoes pose little risk of eruption because they are ancient.

“The caldera is the ideal depositional basin for all this lithium,” said lead author Thomas Benson, a recent PhD graduate at Stanford Earth, who began working on the study in 2012.

Since its discovery in the 1800s, lithium has largely been used in psychiatric treatments and nuclear weapons. Beginning in the 2000s, lithium became the major component of lithium-ion batteries, which today provide portable power for everything from cellphones and laptops to electric cars. Volvo Cars recently announced its commitment to only produce new models of its vehicles as hybrids or battery-powered options beginning in 2019, a sign that demand for lithium-ion batteries will continue to increase.

“We’ve had a gold rush, so we know how, why and where gold occurs, but we never had a lithium rush,” Benson said. “The demand for lithium has outpaced the scientific understanding of the resource, so it’s essential for the fundamental science behind these resources to catch up.”

Working backward

To identify which supervolcanoes offer the best sources of lithium, researchers measured the original concentration of lithium in the magma. Because lithium is a volatile element that easily shifts from solid to liquid to vapor, it is very difficult to measure directly and original concentrations are poorly known.

So, the researchers analyzed tiny bits of magma trapped in crystals during growth within the magma chamber. These “melt inclusions,” completely encapsulated within the crystals, survive the supereruption and remain intact throughout the weathering process. As such, melt inclusions record the original concentrations of lithium and other elements in the magma. Researchers sliced through the host crystals to expose these preserved magma blebs, which are 10 to 100 microns in diameter, then analyzed them with the Sensitive High Resolution Ion Microprobe in the SHRIMP-RG Laboratory at Stanford Earth.

“Understanding how lithium is transported in magmas and what causes a volcanic center to become enriched in lithium has never really systematically been done before,” Benson said.

The team analyzed samples from a range of tectonic settings, including the Kings Valley deposit in the McDermitt volcanic field located on the Nevada-Oregon border, which erupted 16.5 to 15.5 million years ago and is known to be rich in lithium. They compared results from this volcanic center with samples from the High Rock caldera complex in Nevada, Sierra la Primavera in Mexico, Pantelleria in the Strait of Sicily, Yellowstone in Wyoming and Hideaway Park in Colorado, and determined that lithium concentrations varied widely as a function of the tectonic setting of the supervolcano.

“If you have a lot of magma erupting, it doesn’t have to have as much lithium in it to produce something that is worthy of economic interest as we previously thought,” Mahood said. “You don’t need extraordinarily high concentrations of lithium in the magma to form lithium deposits and reserves.”

Improving identification

In addition to exploring for lithium, the researchers analyzed other trace elements to determine their correlations with lithium concentrations. As a result, they discovered a previously unknown correlation that will now enable geologists to identify candidate supervolcanoes for lithium deposits in a much easier way than measuring lithium directly in melt inclusions. The trace elements can be used as a proxy for original lithium concentration. For example, greater abundance of easily analyzed rubidium in the bulk deposits indicates more lithium, whereas high concentrations of zirconium indicate less lithium.

“We can essentially use the zirconium content to determine the lithium content within about 100 parts per million,” Benson said. “Now that we have a way to easily find more of these lithium deposits, it shows that this fundamental geological work can help solve societal problems — that’s really exciting.”