New Kid on the Plasmonic Block: Researchers Find Plasmonic Resonances in Semiconductor Nanocrystals

"We have demonstrated well-defined localized surface plasmon resonances arising from p-type carriers in vacancy-doped semiconductor quantum dots that should allow for plasmonic sensing and manipulation of solid-state processes in single nanocrystals," says Berkeley Lab director Paul Alivisatos, a nanochemistry authority who led this research."Our doped semiconductor quantum dots also open up the possibility of strongly coupling photonic and electronic properties, with implications for light harvesting, nonlinear optics, and quantum information processing."

Alivisatos is the corresponding author of a paper in the journalNature Materialstitled"Localized surface plasmon resonances arising from free carriers in doped quantum dots." Co-authoring the paper were Joseph Luther and Prashant Jain, along with Trevor Ewers.

The term"plasmonics" describes a phenomenon in which the confinement of light in dimensions smaller than the wavelength of photons in free space make it possible to match the different length-scales associated with photonics and electronics in a single nanoscale device. Scientists believe that through plasmonics it should be possible to design computer chip interconnects that are able to move much larger amounts of data much faster than today's chips. It should also be possible to create microscope lenses that can resolve nanoscale objects with visible light, a new generation of highly efficient light-emitting diodes, and supersensitive chemical and biological detectors. There is even evidence that plasmonic materials can be used to bend light around an object, thereby rendering that object invisible.

The plasmonic phenomenon was discovered in nanostructures at the interfaces between a noble metal, such as gold or silver, and a dielectric, such as air or glass. Directing an electromagnetic field at such an interface generates electronic surface waves that roll through the conduction electrons on a metal, like ripples spreading across the surface of a pond that has been plunked with a stone. Just as the energy in an electromagnetic field is carried in a quantized particle-like unit called a photon, the energy in such an electronic surface wave is carried in a quantized particle-like unit called a plasmon. The key to plasmonic properties is when the oscillation frequency between the plasmons and the incident photons matches, a phenomenon known as localized surface plasmon resonance (LSPR). Conventional scientific wisdom has held that LSPRs require a metal nanostructure , where the conduction electrons are not strongly attached to individual atoms or molecules. This has proved not to be the case as Prashant Jain, a member of the Alivisatos research group and one of the lead authors of the Nature Materials paper, explains.

"Our study represents a paradigm shift from metal nanoplasmonics as we've shown that, in principle, any nanostructure can exhibit LSPRs so long as the interface has an appreciable number of free charge carriers, either electrons or holes," Jain says."By demonstrating LSPRs in doped quantum dots, we've extended the range of candidate materials for plasmonics to include semiconductors, and we've also merged the field of plasmonic nanostructures, which exhibit tunable photonic properties, with the field of quantum dots, which exhibit tunable electronic properties."

Jain and his co-authors made their quantum dots from the semiconductor copper sulfide, a material that is known to support numerous copper-deficient stoichiometries. Initially, the copper sulfide nanocrystals were synthesized using a common hot injection method. While this yielded nanocrystals that were intrinsically self-doped with p-type charge carriers, there was no control over the amount of charge vacancies or carriers.

"We were able to overcome this limitation by using a room-temperature ion exchange method to synthesize the copper sulfide nanocrystals," Jain says."This freezes the nanocrystals into a relatively vacancy-free state, which we can then dope in a controlled manner using common chemical oxidants."

By introducing enough free electrical charge carriers via dopants and vacancies, Jain and his colleagues were able to achieve LSPRs in the near-infrared range of the electromagnetic spectrum. The extension of plasmonics to include semiconductors as well as metals offers a number of significant advantages, as Jain explains.

"Unlike a metal, the concentration of free charge carriers in a semiconductor can be actively controlled by doping, temperature, and/or phase transitions," he says."Therefore, the frequency and intensity of LSPRs in dopable quantum dots can be dynamically tuned. The LSPRs of a metal, on the other hand, once engineered through a choice of nanostructure parameters, such as shape and size, is permanently locked-in."

Jain envisions quantum dots as being integrated into a variety of future film and chip-based photonic devices that can be actively switched or controlled, and also being applied to such optical applications as in vivo imaging. In addition, the strong coupling that is possible between photonic and electronic modes in such doped quantum dots holds exciting potential for applications in solar photovoltaics and artificial photosynthesis

"In photovoltaic and artificial photosynthetic systems, light needs to be absorbed and channeled to generate energetic electrons and holes, which can then be used to make electricity or fuel," Jain says."To be efficient, it is highly desirable that such systems exhibit an enhanced interaction of light with excitons. This is what a doped quantum dot with an LSPR mode could achieve."

The potential for strongly coupled electronic and photonic modes in doped quantum dots arises from the fact that semiconductor quantum dots allow for quantized electronic excitations (excitons), while LSPRs serve to strongly localize or confine light of specific frequencies within the quantum dot. The result is an enhanced exciton-light interaction. Since the LSPR frequency can be controlled by changing the doping level, and excitons can be tuned by quantum confinement, it should be possible to engineer doped quantum dots for harvesting the richest frequencies of light in the solar spectrum.

Quantum dot plasmonics also hold intriguing possibilities for future quantum communication and computation devices.

"The use of single photons, in the form of quantized plasmons, would allow quantum systems to send information at nearly the speed of light, compared with the electron speed and resistance in classical systems," Jain says."Doped quantum dots by providing strongly coupled quantized excitons and LSPRs and within the same nanostructure could serve as a source of single plasmons."

Jain and others in Alivsatos' research group are now investigating the potential of doped quantum dots made from other semiconductors, such as copper selenide and germanium telluride, which also display tunable plasmonic or photonic resonances. Germanium telluride is of particular interest because it has phase change properties that are useful for memory storage devices.

"A long term goal is to generalize plasmonic phenomena to all doped quantum dots, whether heavily self-doped or extrinsically doped with relatively few impurities or vacancies," Jain says.

This research was supported by the DOE Office of Science.

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Super-Small Transistor Created: Artificial Atom Powered by Single Electrons

The researchers report inNature Nanotechnologythat the transistor's central component -- an island only 1.5 nanometers in diameter -- operates with the addition of only one or two electrons. That capability would make the transistor important to a range of computational applications, from ultradense memories to quantum processors, powerful devices that promise to solve problems so complex that all of the world's computers working together for billions of years could not crack them.

In addition, the tiny central island could be used as an artificial atom for developing new classes of artificial electronic materials, such as exotic superconductors with properties not found in natural materials, explained lead researcher Jeremy Levy, a professor of physics and astronomy in Pitt's School of Arts and Sciences. Levy worked with lead author and Pitt physics and astronomy graduate student Guanglei Cheng, as well as with Pitt physics and astronomy researchers Feng Bi, Daniela Bogorin,and Cheng Cen. The Pitt researchers worked with a team from the University of Wisconsin at Madison led by materials science and engineering professor Chang-Beom Eom, including research associates Chung Wun Bark, Jae-Wan Park, and Chad Folkman. Also part of the team were Gilberto Medeiros-Ribeiro, of HP Labs, and Pablo F. Siles, a doctoral student at the State University of Campinas in Brazil.

Levy and his colleagues named their device SketchSET, or sketch-based single-electron transistor, after a technique developed in Levy's lab in 2008 that works like a microscopic Etch A Sketch^TM, the drawing toy that inspired the idea. Using the sharp conducting probe of an atomic force microscope, Levy can create such electronic devices as wires and transistors of nanometer dimensions at the interface of a crystal of strontium titanate and a 1.2 nanometer thick layer of lanthanum aluminate. The electronic devices can then be erased and the interface used anew.

The SketchSET -- which is the first single-electron transistor made entirely of oxide-based materials -- consists of an island formation that can house up to two electrons. The number of electrons on the island -- which can be only zero, one, or two -- results in distinct conductive properties. Wires extending from the transistor carry additional electrons across the island.

One virtue of a single-electron transistor is its extreme sensitivity to an electric charge, Levy explained. Another property of these oxide materials is ferroelectricity, which allows the transistor to act as a solid-state memory. The ferroelectric state can, in the absence of external power, control the number of electrons on the island, which in turn can be used to represent the 1 or 0 state of a memory element. A computer memory based on this property would be able to retain information even when the processor itself is powered down, Levy said. The ferroelectric state also is expected to be sensitive to small pressure changes at nanometer scales, making this device potentially useful as a nanoscale charge and force sensor.

The research inNature Nanotechnologyalso was supported in part by grants from the U.S. Defense Advanced Research Projects Agency (DARPA), the U.S. Army Research Office, the National Science Foundation, and the Fine Foundation.

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Solar Power Without Solar Cells: A Hidden Magnetic Effect of Light Could Make It Possible

The researchers found a way to make an"optical battery," said Stephen Rand, a professor in the departments of Electrical Engineering and Computer Science, Physics and Applied Physics.

In the process, they overturned a century-old tenet of physics.

"You could stare at the equations of motion all day and you will not see this possibility. We've all been taught that this doesn't happen," said Rand, an author of a paper on the work published in theJournal of Applied Physics."It's a very odd interaction. That's why it's been overlooked for more than 100 years."

Light has electric and magnetic components. Until now, scientists thought the effects of the magnetic field were so weak that they could be ignored. What Rand and his colleagues found is that at the right intensity, when light is traveling through a material that does not conduct electricity, the light field can generate magnetic effects that are 100 million times stronger than previously expected. Under these circumstances, the magnetic effects develop strength equivalent to a strong electric effect.

"This could lead to a new kind of solar cell without semiconductors and without absorption to produce charge separation," Rand said."In solar cells, the light goes into a material, gets absorbed and creates heat. Here, we expect to have a very low heat load. Instead of the light being absorbed, energy is stored in the magnetic moment. Intense magnetization can be induced by intense light and then it is ultimately capable of providing a capacitive power source."

What makes this possible is a previously undetected brand of"optical rectification," says William Fisher, a doctoral student in applied physics. In traditional optical rectification, light's electric field causes a charge separation, or a pulling apart of the positive and negative charges in a material. This sets up a voltage, similar to that in a battery. This electric effect had previously been detected only in crystalline materials that possessed a certain symmetry.

Rand and Fisher found that under the right circumstances and in other types of materials, the light's magnetic field can also create optical rectification.

"It turns out that the magnetic field starts curving the electrons into a C-shape and they move forward a little each time," Fisher said."That C-shape of charge motion generates both an electric dipole and a magnetic dipole. If we can set up many of these in a row in a long fiber, we can make a huge voltage and by extracting that voltage, we can use it as a power source."

The light must be shone through a material that does not conduct electricity, such as glass. And it must be focused to an intensity of 10 million watts per square centimeter. Sunlight isn't this intense on its own, but new materials are being sought that would work at lower intensities, Fisher said.

"In our most recent paper, we show that incoherent light like sunlight is theoretically almost as effective in producing charge separation as laser light is," Fisher said.

This new technique could make solar power cheaper, the researchers say. They predict that with improved materials they could achieve 10 percent efficiency in converting solar power to useable energy. That's equivalent to today's commercial-grade solar cells.

"To manufacture modern solar cells, you have to do extensive semiconductor processing," Fisher said."All we would need are lenses to focus the light and a fiber to guide it. Glass works for both. It's already made in bulk, and it doesn't require as much processing. Transparent ceramics might be even better."

In experiments this summer, the researchers will work on harnessing this power with laser light, and then with sunlight.

The paper is titled"Optically-induced charge separation and terahertz emission in unbiased dielectrics." The university is pursuing patent protection for the intellectual property.

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New Way to Control Magnetic Properties of Graphene Discovered

The finding by a team of Maryland researchers, led by Physics Professor Michael S. Fuhrer of the UMD Center for Nanophysics and Advanced Materials is the latest of many amazing properties discovered for graphene.

A honeycomb sheet of carbon atoms just one atom thick, graphene is the basic constituent of graphite. Some 200 times stronger than steel, it conducts electricity at room temperature better than any other known material (a 2008 discovery by Fuhrer, et. al). Graphene is widely seen as having great, perhaps even revolutionary, potential for nanotechnology applications. The 2010 Nobel Prize in physics was awarded to scientists Konstantin Novoselov and Andre Geim for their 2004 discovery of how to make graphene.

In their new graphene discovery, Fuhrer and his University of Maryland colleagues have found that missing atoms in graphene, called vacancies, act as tiny magnets -- they have a"magnetic moment." Moreover, these magnetic moments interact strongly with the electrons in graphene which carry electrical currents, giving rise to a significant extra electrical resistance at low temperature, known as the Kondo effect. The results appear in the paper"Tunable Kondo effect in graphene with defects" published this month inNature Physics.

The Kondo effect is typically associated with adding tiny amounts of magnetic metal atoms, such as iron or nickel, to a non-magnetic metal, such as gold or copper. Finding the Kondo effect in graphene with vacancies was surprising for two reasons, according to Fuhrer.

"First, we were studying a system of nothing but carbon, without adding any traditionally magnetic impurities. Second, graphene has a very small electron density, which would be expected to make the Kondo effect appear only at extremely low temperatures," he said.

The team measured the characteristic temperature for the Kondo effect in graphene with vacancies to be as high as 90 Kelvin, which is comparable to that seen in metals with very high electron densities. Moreover the Kondo temperature can be tuned by the voltage on an electrical gate, an effect not seen in metals. They theorize that the same unusual properties of that result in graphene's electrons acting as if they have no mass also make them interact very strongly with certain kinds of impurities, such as vacancies, leading to a strong Kondo effect at a relatively high temperature.

Fuhrer thinks that if vacancies in graphene could be arranged in just the right way, ferromagnetism could result."Individual magnetic moments can be coupled together through the Kondo effect, forcing them all to line up in the same direction," he said.

"The result would be a ferromagnet, like iron, but instead made only of carbon. Magnetism in graphene could lead to new types of nanoscale sensors of magnetic fields. And, when coupled with graphene's tremendous electrical properties, magnetism in graphene could also have interesting applications in the area of spintronics, which uses the magnetic moment of the electron, instead of its electric charge, to represent the information in a computer.

"This opens the possibility of 'defect engineering' in graphene -- plucking out atoms in the right places to design the magnetic properties you want," said Fuhrer.

This research was supported by grants from the National Science Foundation and the Office of Naval Research.

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New Spin on Graphene Makes It Magnetic

The results, reported inScience, could be a potentially huge breakthrough in the field of spintronics.

Spintronics is a group of emerging technologies that exploit the intrinsic spin of the electron, in addition to its fundamental electric charge that is exploited in microelectronics.

Billions of spintronics devices such as sensors and memories are already being produced. Every hard disk drive has a magnetic sensor that uses a flow of spins, and magnetic random access memory (MRAM) chips are becoming increasingly popular.

The findings are part of a large international effort involving research groups from the US, Russia, Japan and the Netherlands.

The key feature for spintronics is to connect the electron spin to electric current as current can be manipulated by means routinely used in microelectronics.

It is believed that, in future spintronics devices and transistors, coupling between the current and spin will be direct, without using magnetic materials to inject spins as it is done at the moment.

So far, this route has only been demonstrated by using materials with so-called spin-orbit interaction, in which tiny magnetic fields created by nuclei affect the motion of electrons through a crystal. The effect is generally small which makes it difficult to use.

The researchers found a new way to interconnect spin and charge by applying a relatively weak magnetic field to graphene and found that this causes a flow of spins in the direction perpendicular to electric current, making a graphene sheet magnetised.

The effect resembles the one caused by spin-orbit interaction but is larger and can be tuned by varying the external magnetic field.

The Manchester researchers also show that graphene placed on boron nitride is an ideal material for spintronics because the induced magnetism extends over macroscopic distances from the current path without decay.

The team believes their discovery offers numerous opportunities for redesigning current spintronics devices and making new ones such as spin-based transistors.

Professor Geim said:"The holy grail of spintronics is the conversion of electricity into magnetism or vice versa.

"We offer a new mechanism, thanks to unique properties of graphene. I imagine that many venues of spintronics can benefit from this finding."

Antonio Castro Neto, a physics professor from Boston who wrote a news article for theSciencemagazine which accompanies the research paper commented:"Graphene is opening doors for many new technologies.

"Not surprisingly, the 2010 Nobel Physics prize was awarded to Andre Geim and Kostya Novoselov for their groundbreaking experiments in this material.

"Apparently not satisfied with what they have accomplished so far, Geim and his collaborators have now demonstrated another completely unexpected effect that involves quantum mechanics at ambient conditions. This discovery opens a new chapter to the short but rich history of graphene."

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Physicists Discover New Way to Visualize Warped Space and Time

"We've found ways to visualize warped space-time like never before," says Kip Thorne, Feynman Professor of Theoretical Physics, Emeritus, at the California Institute of Technology (Caltech).

By combining theory with computer simulations, Thorne and his colleagues at Caltech, Cornell University, and the National Institute for Theoretical Physics in South Africa have developed conceptual tools they've dubbed tendex lines and vortex lines.

Using these tools, they have discovered that black-hole collisions can produce vortex lines that form a doughnut-shaped pattern, flying away from the merged black hole like smoke rings. The researchers also found that these bundles of vortex lines -- called vortexes -- can spiral out of the black hole like water from a rotating sprinkler.

The researchers explain tendex and vortex lines -- and their implications for black holes -- in a paper that's published online on April 11 in the journalPhysical Review Letters.

Tendex and vortex lines describe the gravitational forces caused by warped space-time. They are analogous to the electric and magnetic field lines that describe electric and magnetic forces.

Tendex lines describe the stretching force that warped space-time exerts on everything it encounters."Tendex lines sticking out of the moon raise the tides on the Earth's oceans," says David Nichols, the Caltech graduate student who coined the term"tendex." The stretching force of these lines would rip apart an astronaut who falls into a black hole.

Vortex lines, on the other hand, describe the twisting of space. If an astronaut's body is aligned with a vortex line, she gets wrung like a wet towel.

When many tendex lines are bunched together, they create a region of strong stretching called a tendex. Similarly, a bundle of vortex lines creates a whirling region of space called a vortex."Anything that falls into a vortex gets spun around and around," says Dr. Robert Owen of Cornell University, the lead author of the paper.

Tendex and vortex lines provide a powerful new way to understand black holes, gravity, and the nature of the universe."Using these tools, we can now make much better sense of the tremendous amount of data that's produced in our computer simulations," says Dr. Mark Scheel, a senior researcher at Caltech and leader of the team's simulation work.

Using computer simulations, the researchers have discovered that two spinning black holes crashing into each other produce several vortexes and several tendexes. If the collision is head-on, the merged hole ejects vortexes as doughnut-shaped regions of whirling space, and it ejects tendexes as doughnut-shaped regions of stretching. But if the black holes spiral in toward each other before merging, their vortexes and tendexes spiral out of the merged hole. In either case -- doughnut or spiral -- the outward-moving vortexes and tendexes become gravitational waves -- the kinds of waves that the Caltech-led Laser Interferometer Gravitational-Wave Observatory (LIGO) seeks to detect.

"With these tendexes and vortexes, we may be able to much more easily predict the waveforms of the gravitational waves that LIGO is searching for," says Yanbei Chen, associate professor of physics at Caltech and the leader of the team's theoretical efforts.

Additionally, tendexes and vortexes have allowed the researchers to solve the mystery behind the gravitational kick of a merged black hole at the center of a galaxy. In 2007, a team at the University of Texas in Brownsville, led by Professor Manuela Campanelli, used computer simulations to discover that colliding black holes can produce a directed burst of gravitational waves that causes the merged black hole to recoil -- like a rifle firing a bullet. The recoil is so strong that it can throw the merged hole out of its galaxy. But nobody understood how this directed burst of gravitational waves is produced.

Now, equipped with their new tools, Thorne's team has found the answer. On one side of the black hole, the gravitational waves from the spiraling vortexes add together with the waves from the spiraling tendexes. On the other side, the vortex and tendex waves cancel each other out. The result is a burst of waves in one direction, causing the merged hole to recoil.

"Though we've developed these tools for black-hole collisions, they can be applied wherever space-time is warped," says Dr. Geoffrey Lovelace, a member of the team from Cornell."For instance, I expect that people will apply vortex and tendex lines to cosmology, to black holes ripping stars apart, and to the singularities that live inside black holes. They'll become standard tools throughout general relativity."

The team is already preparing multiple follow-up papers with new results."I've never before coauthored a paper where essentially everything is new," says Thorne, who has authored hundreds of articles."But that's the case here."

This research was supported by the National Science Foundation, the Sherman Fairchild Foundation, the Brinson Foundation, NASA, and the David and Barbara Groce Fund.

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Research Into Batteries Will Give Electric Cars the Same Range as Gas Cars, Experts Say

The electric car was introduced by Edison as early as 1900. But, as we all know, Henry Ford's vehicle concept with a noisy, smelly combustion engine won the race to become people's most treasured individual means of transport, despite the fact that in principle, the combustion engine is hopeless.

Then, as now, the Achilles' heel of the electric car was the limited energy density of the batteries, which will only sustain short drives. Now -- 110 years later -- the battery technology, combined with the effect electronics and the electric engine, have come so far in performance, size and price that the electric car is again becoming interesting. The electric car does not pollute locally and it can, if used cleverly, be utilised to introduce more renewable energy into the electricity supply.

Electric cars are a good match for a society that has abandoned the use of fossil fuels.

This is why electric cars have been reborn as an important factor in the vision of a society without fossil fuels, and the first electric cars have already hit the roads, albeit in very limited numbers and with very short ranges between recharges.

The advantages of the electric car are first and foremost that it can be integrated into the electricity system and potentially serve as a buffer in the electricity system of tomorrow, where most of our electricity originates from fluctuating renewable energy. Where there is excess electricity from e.g. wind turbines, the electric cars can be charged. When there is a shortage of electricity, some of the power can be returned to the electricity grid. The other major advantage is that, if mass-produced, the electric car could be cheaper to produce than the current cars.

2 tonnes of batteries or 50 litres of gasoline

Today, battery packs are expensive and are only able to store a relatively low amount of energy. Researchers all over the world are working to change that. In the current setting, an electric car is no good if you are taking the family on holiday to Lake Garda in Italy. For electric cars to become the consumers' preferred mode of transport, the battery capacity must be significantly increased. In Risø Energy Report 9, page 58, you can read that the energy density in today's batteries is almost two orders lower than that of fossil fuels. This means that a battery pack containing energy corresponding to 50 litres of petrol, would weigh between 1.5 and 2 tonnes.

Lithium is a soft, silver-white metal -- the lightest of all metals. Lithium is extremely reactive and corrodes quickly in a humid atmosphere. There, lithium is typically stored under kerosene or in a protective atmosphere to avoid contact with oxygen and water.

The most promising electric car batteries are based on the metal lithium (Li). Lithium is a soft, silver-white metal -- the lightest of all metals. Lithium is extremely reactive and corrodes quickly in a humid atmosphere. There, lithium is typically stored under kerosene to avoid contact with oxygen and water. The lightness is one of the strengths of lithium. Traditional car batteries are based on lead (Pb), which is one of the heaviest metals in existence. To reduce the weight of batteries, lithium is the way to go, which is also substantiated by the prominence of rechargeable Li-ion batteries in e.g. mobile phones, cameras and MP3 and MP4 players. These batteries have the highest energy density among rechargeable batteries.

The lithium battery market is going to grow exponentially, and a discussion has already emerged whether there is going to be enough lithium to electrify the entire world's car park. Lithium is naturally occurring with approx. 65 g per tonne in top soil and approx. 0.1 g per tonne of water and can be extracted from soil as well as water, but if the lithium content is small, the extraction is costly.

In addition to the use in batteries, lithium is used in anti-depressants, ceramics, glass, aluminium production, lubricants and synthetic rubber. In the future (after 2050), lithium will probably also be used in fusions reactors for electricity production. The world's lithium reserves are found in countries such as Chile, China, Australia, Russia, Argentina, the USA, Zimbabwe and Bolivia. Lately, large deposits have been found in Afghanistan -- so large that the USA has dubbed the country 'the Saudi Arabia of lithium'. In Bolivia, lithium is found in large quantities under Salar de Uyuni -- the world's largest salt lake. Last year, Bolivia's president Morales announced that the country is going to invest DKK 5 billion in extracting lithium from the dried-out salt lake that covers more than 10,000 square kilometres and contains more than a quarter of the world's total lithium deposits.

The fight over the world's lithium resources will intensify in the future, but the upside is that the lithium part of batteries can be recycled, so when the batteries are worn out, the lithium can be extracted and form part of a new battery.

Li-air batteries could have the same efficient energy density as gasoline

Li-air batteries are a promising opportunity in the long term."If we succeed in developing this technology, we are facing the ultimate break-through for electric cars, because in practice, the energy density of Li-air batteries will be comparable to that of petrol and diesel, if you take into account that a combustion engine only has an efficiency of around 30 per cent," says Tejs Vegge, senior scientist in the Materials Research Division. If batteries with an energy density this great become a reality, one could easily imagine electrically powered trucks. Li-air batteries are thus a promising research area, but there are many research challenges to overcome before the batteries find their way to the electric cars.

The development of rechargeable batteries has moved slowly since the invention of the traditional lead-acid batteries, which are still used in the majority of e.g. starter batteries for conventional cars. The development of the Li-ion batteries marked a significant leap in the energy density of the rechargeable batteries. The final break-through may belong to the Li-air batteries which, in practice, could have the same efficient energy density as petrol. Source: Lithium -- Air Battery: Promise and Challenges, G. Girishkumar, B. McCloskey, A.C. Luntz, S. Swanson and W. Wilcke, IBM Research, published in J.Phys.Chem.Lett.2010,1,2193-2203.

The Li-air battery is designed with a lithium electrode (the anode), and electrolyte and a porous carbon electrode (the cathode), which attracts the oxygen from the air when the battery is in operation. The battery is therefore, so to speak, open at one end, or it has an oxygen supply of its own. During discharge, oxygen reacts with lithium to form lithium peroxide (Li2O2), and during charging, this process is reversed to release oxygen. Both reactions take place on the surface of the porous carbon electrode.

Battery resembles humans: Gains weight and becomes short of breath

The interaction with air requires the electrode to have a very large surface area. The prototypes being worked on now have a current density of approx. 1 milliamp per square centimetre surface area, and this has to be increased by at least one order before the batteries are ready to be used in real life.

The fact that the battery absorbs oxygen atoms from the air means that the battery gains weight as it being discharged. Theoretically, the battery can more than double its weight.

At the same time, the electrode could become short of breath, so to speak. The oxygen absorbed by the battery reacts with lithium to form lithium peroxide, which may cause clogging of aggregates in the battery's channels, causing them to become blocked and preventing the supply of further oxygen."In our trials, we use pure oxygen, so we are okay, but the problems accumulate when the oxygen has to be extracted from ordinary air," says Søren Højgaard Jensen from the Fuel Cells and Solid State Chemistry Division. Ordinary air also contains moisture, and it must be taken into consideration that, as mentioned above, lithium and humidity do not make an attractive combination.

Difficult to charge

En extremely high overvoltage is required to recharge the battery again after a discharge. The so-called equilibrium voltage for the Li-air battery is 3 volts. When the battery is discharged, the voltage drops to 2.6-2.7 volts. But when you want to recharge the battery, the voltage must be increased to 4.5 volts. In comparison, a Li-ion battery can be recharged at an overvoltage of only 10 per cent.

"The discharge process is proceeding really well. Our problem is that the reverse process has a very high energy loss," says senior scientist Poul Norby, Materials Research Division."The high overvoltage for recharging is hard going for the current battery components, which limits the number of times the battery can be recharged," says Poul Norby. The cyclic energy loss in charging/recharging is about 40 per cent in Li-air batteries. The challenge is to reduce this number to 10 per cent, corresponding to Li-ion batteries.

In order to solve this issue, Tejs Vegge performs extensive computer calculations, so-called DFT calculations (Density Functional Theory), on the Li-air batteries. Using this method, it is possible -- at atom level applying an approximation to the famous Schrödinger equation, to calculate how the lithium and oxygen atoms interact."In this way, we hope to find an explanation of the high overvoltage and a solution to what we can do to reduce it, e.g. by adding an appropriate catalyst," says Tejs Vegge.

In addition to the computer calculations, the batteries are examined using X-ray and neutron rays. These techniques allow the scientists to study how ions and electrons move in the electrode-electrolyte interfaces when the battery is charged and discharged."We focus particularly on solid-state electrolytes because they offer safety and transport advantages. Large lithium batteries with liquid electrolytes could pose a safety risk in the event of accidents," says Tejs Vegge.

Finally, the battery properties are tested in practice. Testing of large lithium batteries takes place in a converted chest freezer in the laboratories of the Fuel Cells and Solid State Chemistry Division."The batteries have to be able to withstand heavy frost and extreme heat, and we can subject them to that in our converted chest freezer, which is able to cool objects down to -60°C and heat them to around 50°C," says Søren Højgaard Jensen.

Must recharge quickly -- and at least 300 times

Today, metal-air batteries are only used as disposable batteries for special purposes with high energy density requirements, e.g. for military equipment, and zinc-air batteries are used as disposable batteries in e.g. hearing aids.

If the battery is to withstand a car running e.g. 250,000 kilometres during its lifetime, and the battery is able to deliver approx. 800 kilometres from one charge, it must be able to handle full charging and discharging at least 300 times. Li-air battery prototypes can currently handle 50 charges, so the researchers are faced with other scientific challenges.

In addition to the number of charges the battery must be able to withstand, it must also be possible to charge it quickly."Think about the volume of energy transferred when you put petrol into your car. It takes a couple of minutes, and then you can go another 800-1000 kilometres. This is a true challenge for the Li-air batteries, because they may potentially be able to contain the same amount of energy as petrol, but it takes considerably longer to refuel," says Tejs Vegge.

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