Battery Metals

A new way to use graphene oxide (GO) could add some backbone to hydrogel materials made from alginate, a natural material derived from seaweed.

In a paper in the journal Carbon, researchers describe a 3D printing method for making intricate and durable alginate-GO structures that are far stiffer and more fracture resistant that alginate alone.

“One limiting factor in the use of alginate hydrogels is that they’re very fragile—they tend to fall apart under mechanical load or in low salt solutions,” says Thomas Valentin, a PhD student in the School of Engineering at Brown University who led the work. “What we showed is by including graphene oxide nanosheets, we can make these structures much more robust.”

The material can also become stiffer or softer in response to different chemical treatments, meaning it could be used to make “smart” materials that react to their surroundings in real time, the research shows. In addition, alginate-GO retains alginate’s ability to repel oils, giving the new material potential as a sturdy antifouling coating.

TOUGHER STUFF

The 3D printing method researchers used to make the materials is called stereolithography. The technique uses an ultraviolet laser a computer-aided design system controls to trace patterns across the surface of a photoactive polymer solution. The light causes the polymers to link together, forming solid 3D structures from the solution.

The tracing process repeats until an entire object is built layer-by-layer from the bottom up. In this case, researchers made the polymer solution using sodium alginate mixed with sheets of graphene oxide, a carbon-based material that forms one-atom-thick nanosheets that are stronger pound-for-pound than steel.

One advantage of the technique is that the sodium alginate polymers link through ionic bonds. The bonds are strong enough to hold the material together, but certain chemical treatments can break them. That gives the material the ability to respond dynamically to external stimuli.

Previously, the researchers showed that they could use this “ionic crosslinking” to create alginate materials that degrade on demand, rapidly dissolving when treated with a chemical that sweeps away ions from the material’s internal structure.

For this new study, the researchers wanted to see how graphene oxide might change mechanical properties of alginate structures. They showed that they could make alginate-GO twice as stiff as alginate alone, and far more resistant to failure through cracking.

“The addition of graphene oxide stabilizes the alginate hydrogel with hydrogen bonding,” says senior author Ian Y. Wong, an assistant professor of engineering. “We think the fracture resistance is due to cracks having to detour around the interspersed graphene sheets rather than being able to break right though homogeneous alginate.”

QUICK CHANGE

The extra stiffness enabled the researchers to print structures that had overhanging parts, which would have been impossible using alginate alone. Further, the increased stiffness didn’t prevent alginate-GO from responding to external stimuli like alginate alone can.

The researchers showed that by bathing the materials in a chemical that removes its ions, the materials swelled up and became much softer. The materials regained their stiffness when ions were restored through bathing in ionic salts.

Experiments showed that the materials’ stiffness could be tuned over a factor of 500 by varying their external ionic environment.

That ability to change its stiffness could make alginate-GO useful in a variety of applications, the researchers say, including dynamic cell cultures.

“You could imagine a scenario where you can image living cells in a stiff environment and then immediately change to a softer environment to see how the same cells might respond,” Valentin says. That could be useful in studying how cancer cells or immune cells migrate through different organs throughout the body.

KEEPING THINGS CLEAN

Because alginate-GO retains the powerful oil-repellant properties of pure alginate, the new material could make an excellent coating to keep oil and other grime from building up on surfaces.

In a series of experiments, the researchers showed that a coating of alginate-GO could keep oil from fouling the surface of glass in highly saline conditions. That could make alginate-GO hydrogels useful for coatings and structures used in marine settings, the researchers say.

“These composite materials could be used as a sensor in the ocean that can keep taking readings during an oil spill, or as an antifouling coating that helps to keep ship hulls clean,” Wong says. The extra stiffness the graphene affords would make such materials or coatings far more durable than alginate alone.

The researchers plan to continue experimenting with the new material, looking for ways to streamline its production and continue to optimize its properties.

Additional coauthors are from Brown University, the University of Wisconsin, and the National University of Singapore.

The US Department of Education’s GAANN Training Grant in Applications and Implications of Nanotechnology, the National Science Foundation, and a Brown University Hibbitt Postdoctoral Fellowship funded the research.

Palladium has become the most precious of the precious metals, with prices topping gold Wednesday for the first time in 16 years as supplies remain tight amid strong automotive demand, traders and analysts said.

Spot palladium traded to a record high of $1,249.30 an ounce in overseas trading. Around 8:18 a.m. EST, the metal was up $20.50 to $1,246.55 an ounce. Gold was down $1.15 to $1,237.25.

“Gold has been toppled as the most valuable precious metal, as [the] demand-fueled rally over the past four months has driven palladium prices to record highs,” said a research note from commodities brokerage SP Angel.

Afshin Nabavi, head of trading at trading house MKS (Switzerland) SA, told Kitco News that there has been limited availability of metal, with the market as in backwardation. This is when nearby contracts are more expensive than deferred in any commodity. This is the opposite of the norm and is generally seen as a sign of supply tightness since users are willing to pay a premium to get metal right away. In fact, Nabavi described the backwardation spreads as “ridiculously wide” at times.

“The demand is rather high,” Nabavi said. “The Chinese have been good buyers of palladium.”

The biggest use for palladium is catalytic converters, with the metal historically used in gasoline-powered vehicles since – until a little more than a year ago – palladium was cheaper than sister metal platinum, which is required for diesel-powered cars. SP Angel reported that there has been a consumer shift from diesel- toward gasoline-powered cars, thus boosting palladium demand. While there has been conjecture that automakers may eventually substitute now-cheaper platinum for palladium in auto catalysts, so far they have not taken on this retooling, most observers say.

“Automakers aren’t likely to catch a break on palladium prices anytime soon as the metal used to reduce exhaust emissions is poised to extend its record-breaking rally,” SP Angel said.

The consultancy Metals Focus put out a report Tuesday saying that 2018 palladium supply is headed for the second-highest level this decade, but auto-catalyst demand is also strong, expected to hit a record 8.5 million ounces. The consultancy looks for a supply/demand deficit of 1.2 million palladium ounces.

While palladium posted a premium to gold for the first time since October 2002, platinum has weakened over the last four weeks, falling below $800 per ounce, analysts with Commerzbank pointed out.

“As a result, not only has the price gap to palladium widened significantly – the gap to gold has, too,” Commerzbank said. “The discount as compared to gold has now reached a record-high $440 per troy ounce.”

Palladium traded higher than gold just one day after Metals Focus issued a report saying it was likely to do so. However, Metals Focus also said gold is likely to eventually regain the upper hand.

Analysts said palladium will eventually encounter “some headwinds.” For starters, investors have been heavy buyers and eventually will have to sell in order to book profits.

“In addition, as we move through 2019 and U.S. growth slows, this will weigh on investor risk appetite, which in turn will affect palladium,” Metals Focus continued.

Meanwhile, the consultancy looks for gold to eventually strengthen, suggesting Federal Reserve policymakers at some point will adopt a more cautionary tone on interest-rate rises. Further, investors are net short in gold, meaning potential for buying in the form of short covering. Whenever U.S. economic growth slows, gold will become in favor again, Metals Focus says.

“Given how small the gold market is, this renewed investment will be sufficient to drive the price higher, during late 2019 and further ahead, in the process re-establishing a premium over palladium,” Metals Focus concluded.

Gold just got left behind by one of its sister metals. After a demand-fueled rally over the past four months that’s seen prices hit successive records, palladium topped gold.

Palladium, which hasn’t traded at a sustained premium to gold in 16 years, has gained as buyers scramble for supplies of the metal used in vehicle smog-control devices. Demand has risen as consumers turn away from diesel toward gasoline-powered cars, which tend to use more palladium in autocatalysts. The metal “should continue to benefit from strong fundamentals in 2019,” according to Bloomberg Intelligence.

While most metals have languished this year amid global trade concerns and a rising dollar, palladium climbed to records four times in November amid expectations that production will continue to fall short of demand. Holdings in exchange-traded products backed by palladium are at the smallest in almost a decade as investors pull the metal and offer the commodity for lease.

“People are grasping for whatever ounces of material they can get” in the palladium market, Tai Wong, head of base and precious metals trading at BMO Capital Markets, said before Wednesday’s levels were hit. “It’s very expensive to borrow, and that is perhaps the biggest factor driving the spot price higher.”

Palladium futures for March delivery climbed 0.4 percent to settle at a record $1,184.40 an ounce at 1:01 p.m. on Nymex in New York.

Palladium for immediate delivery climbed as much as 2.4 percent to a peak of $1,261.80 an ounce, and was at $1,241.47 in New York, according to Bloomberg pricing. Spot gold was 0.1 percent lower at $1,236.69 an ounce.

The cost to borrow palladium for a month was at a record 22 percent, more than seven times higher than the 10-year Treasury yield. Holdings of exchange-traded products backed by the metal are at the lowest since February 2009.

Palladium’s deficit is set to widen to about 1.4 million ounces in 2019, adding to a shortfall of 1.2 million ounces this year, according to London-based Metals Focus Ltd. Supply is likely to remain broadly stable in 2019, while there will be growing demand from the automotive sector, according to Junlu Liang, a senior analyst at the consultancy.

Consumption of palladium in autocatalysts could rise in-line with the production of electric vehicles amid the global effort to cut emissions for cleaner air, Eily Ong, an analyst at Bloomberg Intelligence, said in a report. “The EU has a binding target of cutting emissions by at least 40 percent by 2030 from 1990 levels, while China aims for 26-28 percent cuts from 2005 levels,” she wrote.

When five geologists fell on hard times during the 2014 commodities crash, they packed their bags and traveled to the Australian Outback in search of fresh mineral riches to mine.

The friends, who met at university in Perth, began exploring for tantalum, a corrosive-resistant metal used in electronic equipment such as mobile phones. But within weeks of drilling holes on a prospect in the remote Pilbara region — think Mad Max — they unearthed a massive lithium deposit, the latest in a wave of discoveries that has transformed Australia into the world’s biggest supplier of the key ingredient in rechargeable lithium-ion batteries.

“Australia is now the lithium capital of the world and Pilgangoora is one of the biggest lithium mines on the planet,” says Neil Biddle, one of the five geologists and co-founder of Pilbara Minerals, which opened its mine and processing plant this month. “We [Australia] are already global leaders in gold and iron ore and we can do the same with lithium.”

Pilgangoora is one of six lithium mines opened in Western Australia over the past 24 months in response to a global boom in demand for battery raw materials driven by bullish forecasts for sales of electric vehicles and energy storage systems.

By 2020, UBS forecasts, Australia will have streaked ahead of competitors in Latin America and will be producing half the world’s lithium, positioning a country better known for exporting highly polluting coal and iron ore at the forefront of a green energy revolution.

The lithium boom is attracting billions of dollars of investment in new mines, as well as 3 billion Australian dollar commitments to build five lithium hydroxide refineries. These investors range from heavyweights such as Albermarle Corp. of the U.S., Chile’s Sociedad Química y Minera (SQM) and China’s Tianqi Lithium as well as a plethora of junior miners and new entrants in Western Australia. It is part of a wider push by global miners to discover, dig up and process battery raw materials, including nickel, cobalt and graphite.

Australia is seeking to cash in on the frantic activity by encouraging companies to move beyond mining and processing ore and invest in the more complex business of making precursors — the mix of metals and chemicals that go into battery cathode production. This is the most lucrative end of the supply chain that will power a global lithium-ion battery market forecast to grow from $60 billion in 2017 to $100 billion by 2025, says the World Economic Forum.

The state government in Perth is even investigating whether Western Australia could become a hub for building niche batteries, the type of value-added activity it was unable to attract during the recent iron ore boom.

“The reason we were never able to succeed in iron and steel is there are other people already in the space,” says Bill Johnston, Western Australia’s minister for mines. “But this is about new demand, not existing demand … a multibillion-dollar opportunity.”

Not everyone is convinced. Skeptics warn that the supply boom could turn to bust if electric vehicle sales disappoint or bullish forecasts that lithium demand will triple within a decade prove overly optimistic. Advances in battery technologies could yet produce alternatives to the metal, which may dent demand. Others warn lithium pricing is volatile and lacks the transparency of other battery materials, such as nickel, which are traded on the London Metal Exchange.

Prices for lithium carbonate — the most widely used form of the metal — have fallen by a third in Asia since the start of the year and are trading at two-year lows, according to data compiled by research group Benchmark Mineral Intelligence. Morgan Stanley estimated in February that prices will fall 45 percent by 2021 due to a coming wave of low-cost lithium brine projects in Chile — a development that it predicts will challenge the new generation of Australian and Chinese producers.

“We expect these supply additions to swamp forecast demand growth. As a result, we forecast 2018 to be the last year of global lithium deficit, followed by significant surpluses emerging from 2019,” Morgan Stanley told clients.

Such concerns were noticeably absent at Pilbara Mineral’s opening of its Pilgangoora mine this month, when guests dined on fresh prawns, oysters and roast beef in the 40-degree Celsius heat, about 930 miles from Perth. Several of the investors attending the event became multimillionaires by taking a punt on the Perth-based company, which has transformed from a penny stock worth millions five years ago into an AU$1.4 billion industry leader.

“The big surprise [is] the dominance of Western Australian supply of lithium raw materials,” says Ken Brinsden, CEO of Pilbara Minerals, who has dubbed the area “Lithium Valley.” He rejects Morgan Stanley’s bearish predictions and forecasts that the region will dominate the supply of the metal for years to come due to bountiful supply and a mining culture able to deliver projects on time and on budget.

Overlooking Pilgangoora, Brinsden points to two neighboring lithium mines owned by Altura Mining and Mineral Resources, which have recently opened. Together they will produce annually 2 million metric tons of spodumene concentrate, a pale-gray material that contains about 6 percent lithium.

This powdery substance is currently shipped to China, where refineries convert it into lithium hydroxide and lithium carbonate products used in batteries. At full production, the three mines would provide enough lithium for batteries to power roughly 8 million electric vehicles per year.

Between 2016 and 2020, Australian-based miners will almost triple annual production of lithium to 188,000 metric tons, far outstripping rivals in Chile, Argentina and China and accounting for about half the world’s total supply. Australia’s market dominance is being driven by delays to Latin American projects, the rapid delivery of schemes Down Under and a growing preference among customers for lithium hydroxide, rather than carbonate, products due to changes in battery chemistry.

Until recently lithium carbonate — used in everything from pharmaceuticals to cement and batteries — dominated the global trade in the metal. But battery manufacturers are increasingly using lithium hydroxide, a material with a higher percentage of the metal than its carbonate equivalent.

Hard-rock mining can make lithium hydroxide products more competitive, leading analysts to predict a more rapid growth in the use of hydroxides than carbonates in coming years.

“The evidence for the shift to hard-rock mining is in all the new mines like ours which are attracting finance and big players such as Albermarle targeting expansion of hard-rock investments,” says Brinsden.

Albermarle, the world’s biggest lithium producer, this month put on hold a planned expansion of its brine operations at Chile’s Salar de Atacama lithium project while simultaneously accelerating a plan to build a $400 million lithium hydroxide processing plant in Kemerton, Western Australia. It cited growth in demand for lithium hydroxide from battery-makers in its decision.

The U.S. producer also agreed to pay $1.15 billion for a 50 percent stake in the Wodgina mine owned by Mineral Resources, which neighbors the Pilgangoora mine. And in a boost to the state government’s plan to attract value-added activities, Albermarle will build a processing plant to convert spodumene ore to lithium hydroxide.

“This is a big test for Australia, which hasn’t added a lot of value to its mining exports in the past,” says Scott Winter, a former coal mining expert who recently joined Mineral Resources as chief operating officer. “We want to make lithium hydroxide rather than transport large volumes of lower-grade material to China for processing.

“A metric ton of spodumene concentrate sells for $961 while a metric ton of lithium hydroxide sells for as much as $18,000 — so it’s a real value-add for us [and] the economy in general,” he adds.

Mineral Resources is not alone in moving into lithium hydroxide processing. China’s Tianqi Lithium is investing hundreds of millions of dollars in a new processing plant near Perth and an expansion of the Greenbushes mine, which it jointly owns with Abermarle. Chile’s SQM and Australia’s Kidman Resources plan to build a third plant to process ore from its Mount Holland mine, which has signed deals with Elon Musk’s Tesla and the Japanese giant Mitsui.

BHP, the world’s biggest miner by market capitalization, is also seeking to ride the battery boom by investing in its Nickel West Australia division — a subsidiary that faced closure until the growth in the electric vehicle market. It is also investing tens of millions of dollars in a nickel sulfate plant, with a goal to sell 90 percent of the metal into the fast-growing battery market by 2020, rather than the lower-margin steel industry. “We want to go from digging rocks in the ground to making precursor on a scale that doesn’t exist anywhere on the planet,” says Eduard Haegel, president of BHP Nickel West.

Haegel says Western Australia is blessed with minerals but also benefits from its geographical location near Japan, South Korea and China, the world’s pre-eminent battery-makers.

Yet some commentators warn that the sharp falls in lithium prices this year highlight the volatility of the battery market, where technologies, fiscal incentives and supply chains are changing rapidly. Spot prices of lithium carbonate in China — the world’s biggest consumer of the metal — have more than halved this year following cuts to subsidies for electric vehicles and growth in Australian supply.

Some see an echo of what happened in the iron ore market a few years ago, at least in the short to medium term.

“There was a big spike in iron ore prices when demand outstripped supply a few years back, which drew new entrants into the sector,” says Andrew Driscoll, head of resources research at CLSA Asia-Pacific Markets. “But when prices returned to normal levels after a supply response, some companies with lower-quality assets were squeezed out.”

But, he says, the longer-term outlook is good, with lithium demand set to triple by 2025 as sales of electric vehicles grow.

Australia is already a world leader in extracting battery minerals and will soon become a major processor of lithium hydroxide. Moving further up the value chain to manufacture battery precursors, cathode material and niche batteries is a much tougher challenge, however. The current world leaders China, South Korea and Japan have first-mover advantage, expertise and lower cost bases than Australia.

“From lithium in the ground to becoming a battery there is a need for ore, spodumene, hydroxide, precursor chemical, anode and cathode battery. At the moment we have a dominant position in the first two and we are close to having a very large place in the hydroxide market,” says Johnston. “[We now need] to make sure that we have every step along the pathway and then, perhaps in the future, there will be specific reasons to have batteries manufactured in Australia.”

Most automakers are undertaking ambitious plans to add more electric cars to their lineups in order to keep up with consumer trends and future-proof their businesses, but financial analysts at HSBC are skeptical. The firm believes high prices for lithium and cobalt—two metals used in current electric-car batteries—could hinder future sales, according to Bloomberg.

“High lithium and cobalt prices–but also limited supply and lower demand for pure EVs–now favor more plug-in hybrids in the short to medium term versus our previous expectation.” HSBC analysts Alexandre Falcao and Augusto Ensiki said in a report. They predicted that by 2025, global market share for electric cars will reach 9.4 percent, compared to a previous estimate of 10.5 percent. But the analysts increased their predicted plug-in hybrid market share rose from 2.4 percent to 5.5 percent.

Lithium supplies will remain “reasonably tight” due to low availability and increased demand for batteries, the analysts said. However, they noted that electric cars will likely still see a sales boost around 2020, due to lower battery prices and an influx of new models. But the analysts believe that the costs for battery materials will cap growth.

HSBC isn’t the first organization to point to materials costs as a potential obstacle for electric cars. Earlier this year, Bloomberg predicted that cobalt supplies would not be able to keep up with automakers’ demand. The metal is already proving difficult to source. Most of the world’s cobalt comes from the Democratic Republic of the Congo, which has a poor human rights record. Panasonic has come under scrutiny for accidentally supplying batteries to Tesla containing Cuban cobalt, violating the United States sanctions against Cuba.

Companies have discussed creating cobalt-free batteries, or investing in solid-state batteries, a much-touted alternative to today’s lithium-ion batteries. But these ideas are still under development. Meanwhile, automakers are preparing to launch more electric cars. For now, they’ll have to make the most of limited lithium and cobalt supplies.

Protean Energy has landed a big fish to advise its fledgeling battery subsidiary KORID Energy, bringing in a leading authority on emerging energy storage systems.

Protean’s 60 per cent-owned subsidiary has appointed Dr Soowhan Kim as technical advisor to help develop the $9.7m 1MW/4MWh vanadium redox flow battery (VRFB) system managed by the Korean Institute of Energy Technology Evaluation and Planning (KETEP).

Dr Kim has over 20 years experience working for large research associations and energy corporations and is also the administrator of the KETEP grant for the project.

These postings include senior roles in fuel cell development for Hyundai Motor Company since 1998, and research director at KOSDAQ-listed OCI Company Ltd, a global leader in green energy, and chemicals that operates in six countries.

“We are extremely pleased to have Dr Kim involved in the development of the KETEP trial battery project,” said Protean chairman Bevan Tarratt.

“This appointment grants the company access to over 20 years of experience in leading industry and research bodies. The combination of Korean government support and a world-class technical team provides significant value accretion to Protean’s South Korean operations.”

Dr Kim is currently based out of Sunkyunkwan University, South Korea, where he works as an ‘industry collaboration’ professor. He gained his PhD in engineering from Pennsylvania State University.

Dr Kim was the senior research scientist for Pacific Northwest Laboratories and led a team developing redox flow battery systems, including providing technical support to a 1MW/8MWh VRFB installation conducted by Ashlawn Energy.