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A123 Systems' Nano-enbabled Battery for Electric Vehicles Runs into Manufacturing Snafu

At the time of its introduction A123 Systems's nano-enabled technology for lithium-ion batteries was heralded as a breakthrough  technology that would bring electric vehicles (EVs) one step closer to wide commercial adoption.

This rosy scenario started to reveal its thorny side when questions arose about whether Li-ion battery technology—nano-enabled or otherwise—could really meet the requirements of EV propulsion.This doubt was referred to by none other than U.S. Energy Secretary Steven Chu at the United Nations Climate Change Conference in Cancun in 2010.

With Ener1--another lithium-ion battery maker--filing for bankruptcy earlier this year, the market for nano-enabled Li-ion batteries for EVs needed some encouraging news.

Unfortunately, it did not get it this week with news that A123 will need to replace batteries used by electric sports car maker Fisker Karma among others. The recall will cost A123 Systems US $55 million.

It does not appear that there is any intrinsic problem with the batteries. Instead, one welding machine was calibrated incorrectly, resulting in a misalignment of some components in a battery cell. The problem can cause a break in the battery's electrical insulation and a potential short circuit, according to David Vieau, A123’s CEO.

While an unexpected $55-million manufacturing cost presents a problem, one can imagine that $249 million the company received from the federal government to build the plant in the first place should take some of the sting out of this unforeseen outlay. But it is probably the sagging demand for EVs that poses a far more worrisome problem for companies like A123 across the entire EV value chain.

For instance, Fisker Karma, one of the automobile manufacturers impacted by this battery manufacturing snafu, reported a net loss of $85 million this month in its fourth quarter on revenue of $40.4 million.

David Vieau may be correct in saying that problems like this manufacturing hitch are not totally unexpected in a new industry. However, this new industry may be facing a far more fundamental problem: not enough people want to buy the products they enable.

Thermoelectric Materials Turning Increasingly Towards Nanotechnology

Thermoelectric materials’ ability to generate an electrical current simply from differences in temperature has been a seductive proposition for providing sustainable energy solutions. And for good reason. If you placed a thermoelectric material next to a heat source, like a laptop battery, the electrons in the material would move to the cool side of the material thereby generating an electrical current. So, you can generate electricity just from waste heat from all sorts of machines and devices.

It’s an intriguing idea, but there are a couple of problems. The materials people have been experimenting with either possess a pretty poor thermoelectric conversion efficiency or they are prohibitively expensive for commercial uses.

With these challenges in mind, researchers are turning increasingly towards nanomaterials for solutions. Last month, I reported on Wake Forest researchers using multi-walled carbon nanotubes to fabricate a thin film that the researchers claim can convert differences in temperature into electrical energy more efficiently and more inexpensively than existing solutions.

The latest news comes from collaborative research between the California Institute of Technology, the Chinese Academy of Science's Shanghai Institute of Ceramics, Brookhaven National Laboratory and the University of Michigan. This international team has developed a liquid-like material in which selenium atoms make a crystal lattice and copper atoms flow through the crystal structure like a liquid.

"It's like a wet sponge," explains Jeff Snyder, a faculty associate in applied physics and materials science in the Division of Engineering and Applied Science at Caltech and a member of the research team. "If you have a sponge with very fine pores in it, it looks and acts like a solid. But inside, the water molecules are diffusing just as fast as they would if they were a regular liquid. That's how I imagine this material works. It has a solid framework of selenium atoms, but the copper atoms are diffusing around as fast as they would in a liquid."

The research, which was published in the journal Nature Materials, found that this unusual behavior of the copper ions around the selenium lattice resulted in very low thermal conductivity (bad at conducting heat) in what is otherwise a fairly simple semiconductor (good at conducting electricity), making it an excellent candidate as a thermoelectric material and a relatively inexpensive one.

The liquid quality of the material limits the heat-carrying vibrations so they can only travel in longitudinal waves, which results in the material being less thermally conductive than a solid material. Then in combination with the crystal structure of the selenium, which helps conduct electricity, the copper-selenium material has the thermoelectric figure of merit (thermoelectric efficiency) of 1.5 at 1000 degrees Kelvin, one of the highest values for a bulk material, according to the researchers.

Interestingly, NASA scientists had worked with a copper-selenium material 40 years ago, but because the material had this liquid-like property they found it difficult to work with. Now with this research that identifies and explains why the material has such excellent thermoelectric properties, Snyder believes that it could open up liquid-like thermoelectric materials for further research.

Custom IC Boosts Speed of Nanopore Measurements in DNA Sequencing

In the march toward inexpensive DNA sequencing, so-called “nanopore sequencing” has shown itself to be a promising technology.

However, there has been one major drawback with the nanopore solution: The weakness of the signals generated from the nanopores when the DNA passes through them. To compensate for this, researchers have mainly tried to slow the DNA as it moves through the nanopores.

Late last year, IEEE Spectrum reported on research coming from a Harvard team that was taking a different approach. Instead of trying to slow down the DNA, the team, which is part of chemistry professor Charles Lieber’s laboratory, looked at boosting the signal from the electronics.

Now researchers at Columbia, led by electrical engineering professor Ken Shepard, together with colleagues at the University of Pennsylvania, have followed in this vein by developing a custom integrated circuit using commercial semiconductor technology that should boost the signal from the nanopores and speed up the measurements. The research was described in an article on Physorg.com.

"We put a tiny amplifier chip directly into the liquid chamber next to the nanopore, and the signals are so clean that we can see single molecules passing through the pore in only one microsecond," says Jacob Rosenstein, a Ph.D. candidate in electrical engineering at Columbia and lead author of the paper. "Previously, scientists could only see molecules that stay in the pore for more than 10 microseconds."

The research team, which has published its work in the journal Nature Methods, found previous circuitry simply wasn't up to the task.

"We saw that nearly everybody else measures nanopores using classical electrophysiology amplifiers, which are mostly optimized for slower measurements," Physorg quoted Shepard as saying. "So we designed our own integrated circuit instead."

Their measurement platform involves a CMOS preamplifier with solid-state nanopores in thin silicon nitride membranes.

Shepard and his team appear confident that they can produce dramatic improvements to the technology. "With a next-generation design, we may be able to get a further 10X improvement, and measure events that last only 100 nanoseconds,” says Shepard. “Our lab is also working with other electronic single-molecule techniques based on carbon nanotube transistors, which can leverage similar electronic circuits. This is an exciting time!"

Graphene-Silicon Anodes for Li-ion Batteries Go Commercial

 

Recently researchers at the U.S. Department of Energy's Pacific Northwest National Laboratory have been examining the problem of limited charge-discharge cycles in the lives of nanostructured silicon anodes on lithium-ion batteries.

While nanostructured silicon anodes have a longer life than the pure silicon variety, they are still not up to the standards set by lowly old graphite in this respect. But it appears that one company is undeterred by this drawback.

California Lithium Battery Inc. (CalBattery) announced last week that it has entered into a Work for Others (WFO) agreement with Argonne National Laboratory (ANL) to commercialize what is being dubbed the “GEN3” lithium-ion battery. The GEN3 battery is largely based on Argonne’s provisionally patented silicon-graphene battery anode process

(On a bit of a side note, the researchers who were named in the anode patent are all part of the Hersam Research Group at Northwestern University, which seems to be growing into a leader in the development of graphene-based silicon anodes.)

In the press release and the video below, CalBattery says that it can produce the GEN3 battery in the United States at a cost reduction of 70 percent. I’m not sure what they're comparing it to—nor if that means they are reducing the production costs by 70 percent or the actual purchase price of the Li-ion battery by that amount. But in any case, it seems they believe that this cost reduction will be a “huge breakthrough.”

 

 

According to Phil Roberts, CEO of CalBattery, the plan is to use a Very Large Format (VLF) battery and apply the new graphene-enabled silicon anodes to them.

“Incredibly, some energy storage systems providers and independent power producers today are using hundreds of thousands, if not millions, of small cylindrical cell batteries in massive utility-scale storage systems. This approach is simply too costly and not viable. Large storage must be built from large batteries, not small batteries originally designed for powered hand tools. Our VLF battery has a clear performance and cost advantage in providing the massive currents needed with the minimum materials and battery management components, resulting in a more affordable lithium-ion battery for wide-scale use.”

It is encouraging news that some commercial interests are looking to bring a recently developed nanotechnology-enabled solution for improving Li-ion batteries to market . However, my enthusiasm is somewhat tempered by the emphasis that is being placed on refining the battery for electric vehicle (EV) applications. 

I suppose this interest in the EV market is why they decided to apply the graphene-silicon anodes to the VLF batteries. Maybe that can make the difference in an arena where so many companies are struggling or have failed outright.

 

Engineering of Graphene Gives it Piezoelectric Properties

Researchers at Stanford University are extending the capabilities of graphene by engineering piezoelectric capabilities into the material.

"The physical deformations we can create are directly proportional to the electrical field applied and this represents a fundamentally new way to control electronics at the nanoscale," says Evan Reed, head of the Materials Computation and Theory Group at Stanford and senior author of the study. "This phenomenon brings new dimension to the concept of 'straintronics' for the way the electrical field strains—or deforms—the lattice of carbon, causing it to change shape in predictable ways."

The concept of ‘straintronics’ in Graphene was demonstrated at least as far back as 2010 when Lawrence Berkeley National Laboratory research, led by Michael Crommie, professor of physics at UC Berkeley and a faculty researcher at LBNL, serendipitously discovered that when graphene was grown on platinum a strain pattern was created.

It should be noted that the Stanford research, which was published in the journal ACS Nano,  was conducted within modeling and simulation software. Nonetheless the researchers achieved their piezoelectric effect quite deliberately in the models by depositing lithium, hydrogen, potassium and fluorine atoms on one side of the graphene lattice. They expected this to generate a piezoelectric effect, but not on the scale they witnessed in the models.

“We thought the piezoelectric effect would be present, but relatively small. Yet, we were able to achieve piezoelectric levels comparable to traditional three-dimensional materials," said Reed. "It was pretty significant."

While the level of the piezoelectric effect was unexpected, the real breakthrough here may be that they were able to control the effect by depositing the atoms in specific locations within the graphene.

"We were further able to fine tune the effect by pattern doping the graphene—selectively placing atoms in specific sections and not others," said Mitchell Ong, a post-doctoral scholar in Reed's lab and first author of the paper. "We call it designer piezoelectricity because it allows us to strategically control where, when and how much the graphene is deformed by an applied electrical field with promising implications for engineering."

It should be interesting to see if anyone takes on these simulations and starts running physical experiments. If it can be duplicated in physical experiments, it could open the possibility for this kind of doping to be used on other nanomaterials that could open their use in a number of application areas, ranging from energy harvesting to chemical sensing and high-frequency acoustics.

Carbon Nanofibers Improve Silicon Electrodes for Li-ion Batteries, But Is It Enough?

For the last couple of years the big news for lithium-ion (Li-ion) batteries has been the replacement of graphite in the anodes with silicon.

This move from graphite to silicon has been eagerly pursued in order to address one of the fundamental operations of Li-ion batteries: the movement of lithium ions from the cathode to the anode and their storage there. The more lithium ions that the anode can store, the longer the battery will stay charged. The charge can be increased by a factor of ten by replacing the graphite with silicon.

But there is a drawback with these silicon electrodes. They swell to three times their original size when charged and the charging and discharging of the battery soon renders the silicon useless as an electrode in a battery. For this reason, researchers have been working with various nanostructured silicon materials that take advantage of the superior storage capacity of silicon but are not as susceptible to the deterioration caused by charge-discharge cycles.

Now researchers at Pacific Northwest National Laboratory (PNNL) are taking a closer look at why these nanostructured silicon electrodes perform better than the graphite variety. "The electrodes expand as they get charged, and that shortens the lifespan of the battery," lead researcher Chongmin Wang at the Department of Energy's Pacific Northwest National Laboratory, was quoted as saying. "We want to learn how to improve their lifespan, because silicon-carbon nanofiber electrodes have great potential for rechargeable batteries."

The research, which was published in the journal Nano Letters, first tested how much lithium the electrodes could hold and how long they would last by putting the electrodes—which were made from carbon nanofibers wrapped by a thin layer of silicon—into a half-cell.

The researchers were initially impressed by the results, which showed that material maintained a very good capacity of about 1000 milliAmp-hours per gram of material after 100 charge-discharge cycles, five to 10 times the capacity of conventional electrodes in lithium ion batteries. However, they remained skeptical that the material would withstand continued charge-discharge cycles.

What they discovered while looking at the electrode through a transmission electron microscope confirmed some previous research and revealed some new phenomena. The research observed, as previous work has shown, that charging the battery does cause lithium ions to flow into the silicon. But what this research discovered was that the addition of the carbon to the silicon speeds up this process considerably—as much as 60 times faster than silicon alone.

It also turns outjust as expectedthat the silicon nanocomposite electrode does swell to three times its size just as its silicon cousin, but it does so evenly avoiding the imperfections that are caused by the uneven expansion of silicon alone.

Another interesting discovery from this research builds on previous work that discovered that once the ratio of lithium to silicon reached 15 to 4 in these electrodes the material crystallizes. The PNNL research discovered that the crystallization happens all at once rather than gradually—it ‘snaps’ into its crystallized form—a phenomenon known as congruent phase transition.

The key determination though was to find out how this charging and discharging affected the electrode. The results were not encouraging. It turns out the charge-discharge process leaves the surface of the electrode looking like a potholed stretch of road.

"We can see the electrode's surface go from smooth to rough as we charge and discharge it. We think as it cycles, small defects occur, and the defects accumulate," said Wang.

While this may not sound like good news, there is the positive side in that the thin silicon reacts better than thicker silicon and is more durable. “"In the current design, because the silicon is so thin, you don't get bigger cavities, just like little gas bubbles in shallow water come up to the surface. If the water is deep, the bubbles come together and form bigger bubbles," says Wang.

The researchers will next be looking into optimizing the bonding between the carbon nanofibers and the silicon to improve both the performance and the lifetime of the electrodes.

HyperSolar's Zero-carbon Process for Hydrogen Gas Production

Last week, I covered nanotechnology research that mimics photosynthesis to split water molecules into hydrogen gas. The resulting gas could be used for powering fuel cells.

Despite the comments being led off into an odd tangent about this development depriving the earth of its water resources, the aim of this line of research is to find sustainable and environmentally friendly methods for producing hydrogen gas.

In keeping with this spirit, Santa Barbara, CA-based HyperSolar, Inc. has announced this week that they have plans for producing “the world’s first nanotechnology-based, zero-carbon process for the production of renewable hydrogen and natural gas.”

I suppose in anticipation of some concern that potable water would be used in the proposed process, Tim Young, CEO of HyperSolar, made it clear in the press release that waste water would be used in the hydrogen production.

“Our research and development to date gives us a high degree of confidence that our innovative process can achieve commercial viability,” said Young. “Starting with a negative value feedstock in the form of wastewater and operating in low cost reactors, we believe that our artificial photosynthesis process of extracting hydrogen from water will be cost effective.”

There are not a lot of details about the process that Hypersolar is planning to adopt. We know from the quote above that it will be an “artificial photosynthesis process” like those I blogged on last week. And we know that nanoparticles will be used to detoxify the wastewater to “produce clean water and pure hydrogen in the presence of sunlight.” But we don’t know what nanoparticles will be used—except that they will be made from low-cost semiconducting materials—nor how they will be used in the process. Nonetheless Hypersolar has said that they expect to have a robust prototype of its process by 2013.

This year they will be attempting to meet the following milestones:

1.      A proof-of-concept microparticle for hydrogen production using conventional photovoltaic elements

2.      Analysis of the feedstock potential of multiple wastewater sources

3.      A complete photoreactor prototype for sustained hydrogen production

4.      Design of nanoparticles using low-cost semiconducting materials

I am pleased to see a company make such a grand proposal and I wish them luck. However, if they are successful in finding a cheap and environmentally friendly method for producing hydrogen gas for fuel cells, maybe they can turn their attention to finding a cheap and safe way of creating an infrastructure to distribute the hydrogen to cars powered by fuel cells.

Nanowire Forest Splits Water with Sunlight

Nanotechnology has a checkered past in improving fuel cell technology. I have cataloged some of the missteps previously. At the time, the areas in which researchers were attempting to apply nanotechnology to fuel cells—namely improved catalysts and hydrogen storage—didn’t address the real problems that have prevented fuel cells from receiving wider adoption.

One of the fundamental problems with fuel cells has been the cost of producing hydrogen. While hydrogen is, of course, the most abundant element, it attaches itself to other elements like nitrogen or fluorine, and perhaps most ubiquitously to oxygen to create the water molecule. The process used to separate hydrogen out into hydrogen gas for powering fuel cells now relies on electricity produced from fossil fuels, negating some of the potential environmental benefits. So in the last few years, a new line of research has emerged that uses nanomaterials to imitate photosynthesis and break water down into hydrogen and oxygen thereby creating a more cost-effective and environmentally-friendly method for producing hydrogen.

Angela Belcher at MIT reported on just such a method two years ago when she used man-made viruses to serve as a scaffold to attract molecules of the catalyst iridium oxide and a biological pigment (zinc porphyrins). Once these two molecules attached themselves to the scaffold, the viruses would become “wire-like,” which enabled them to split the water molecules into hydrogen and oxygen because of the precise spacing in the wire.

Now researchers at University of California, San Diego have developed a quite different approach to mimicking photosynthesis for splitting water molecules by using a 3D branched nanowire array that looks like a forest of trees.

According to Deli Wang, professor in the Department of Electrical and Computer Engineering at the UC San Diego Jacobs School of Engineering, this tree-like structure enables both trees and the nanowire arrays to capture the maximum amount of solar energy. To illustrate what he means, Wang points to satellite imagery in which flat surfaces like oceans or deserts simply reflect the light back and forests remain dark because they are absorbing the light.

The nanowire forest that Wang and his colleagues have created uses the process of photoelectrochemical water-splitting to produce hydrogen gas. The method used by the researchers, which was published in the journal Nanoscale, found that the forest structure of the nanowires, which has a massive amount of surface area, not only captured more light than flat planar designs, but also produced more hydrogen gas.

“With this structure, we have enhanced, by at least 400,000 times, the surface area for chemical reactions,” said Ke Sun, a PhD student in electrical engineering who led the project.

While it appears from the press release that the researchers are more interested in pursuing the photosynthesis aspect of this research to expand its use into capturing carbon dioxide, it could be a cost-effective way for producing hydrogen gas.

Nokia and Cambridge Look at Applying Nanotechnology to Super-Hydrophobic Phones

Mobile phone giant Nokia and Cambridge University have been working for a number of years on  nanotechnology applications for cell phones. In 2008, they announced the much-ballyhooed Morph phone that featured plastic electronics; the flexible circuits allowed the handset, which I like to call it the Dick Tracy phone, to wrap around your wrist like a watch.

I guess it’s impressive to duplicate a tech gadget used by a comic book character developed in the 1930s, but I never could see the point. Adding to the head scratching on that one was their admission that they didn’t expect to commercialize that phone for another 20 years.

As a marketing tool—as I’ve heard the Morph phone described—it was effective in that it got a lot of press coverage. But it left me thinking: Does Nokia really have a handle on what nanotechnology can do for mobile phones?

It seems the researchers there did. In fact, Nokia published an entire book on the subject back in 2010 called “Nanotechnologies for Future Mobile Devices.” So there remained considerable hope that Nokia would focus its attention on the technologies that would really make a difference in cell phones, namely longer lasting batteries.

So, when news came out this week that the big breakthrough it had made in pairing cellular telephony  with nanotechnology was to make handsets waterproof, I couldn’t help but be disappointed.

Okay, I'll admit that waterproofing is a good feature—and sure is a step up from a Dick Tracy phone. But really, Nokia? Five years of collaboration with Cambridge University and this is the result? I have ‘water-resistant’ nanotechnology on my cycling apparel. At this point, water resistance is just not one of those added features made available by nanotechnology that I can get too excited about anymore, even if it is the super-hydrophobic variety.

Sure, duplicating the lotus effect and other biomimicry on the nanoscale is a worthy feature for a score of products, but some of these products have already been on the market for nearly a decade now.

While I know people who have ruined their phones by dropping it in water, when Chris Bower, the principal scientist at Nokia Research Center in Cambridge, claimed in the video that a coating of the super-hydrophobic material could manage to help a phone dropped in water survive, he seemed less than certain and I was less than impressed.  Don’t get me wrong. Keeping a phone from becoming waterlogged is a big deal. I suppose I just expected an even bigger one. Worse still for Nokia, at least one news report seems to have contradicted Bower's claim, pointing out that because of all the openings on a cell phone, water would still find its way into the electronics.

I'll give the researchers their due: The graphene sensor they rigged up to help them film the water droplet falling on the coating in super slow motion is quite impressive. But it seems I’m still going to have to wait for Nokia and Cambridge to announce a mobile phone that will operate for a month without recharging .

China Surges ahead of India in Nanotechnology: Does it Matter?

I am not certain why there is this hullabaloo about the so-called nanotech race. To me it just seems as though scientists around the world are working on their research, they publish it in journals, other scientists read it and then build on that research and so it goes. I don’t see how that translates into a competition between countries, but it seems to be a matter for which some are enormously preoccupied.

The latest news is that China is “soaring ahead” of India in nanotechnology research.  China and India are nearly always discussed in this great nanotechnology race. This is to be expected. These two countries represent two of the fastest growing economies in the world, and much of that growth has been leveraged upon technology.

However, it’s not always clear that these countries’ efforts in the field of nanotechnology should give Europe, North America or any other advanced OECD countries in nanotechnology any reason for alarm. One day it seems one of these countries (China, in this instance) has a lead and then the next it doesn’t.

In this latest study published in Scientometrics, once you get past the quantification of the race (i.e. how many articles are published, how many times they are cited, etc.), you discover the interesting bit. It seems China is focusing its efforts in nanotechnology research on “nanomaterials and their applications” whereas India is focusing their work on addressing their developmental problems, such as clean drinking water.

To be honest though, I’m not clear on how this makes China more “sophisticated” than India in its nanotechnology development. Further there seems to be a distinction here without much difference: India’s aim of developing nanotechnology solutions for clean drinking water will clearly require “nanomaterials and their applications”. I think what the study is trying to say is that  China is approaching nanomaterials development in a more systematic way.

Nonetheless when all is said and done, what matters is the impact nanotechnology can have on a country or life in that country. Cientifica has its measuring stick for this impact. But ultimately perhaps the impact that comes to China and India from nanotechnology may not originate from research in those countries, but from somewhere else entirely, which still leaves me wondering why all of this measuring of which country publishes what matters.

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Nanoclast

IEEE Spectrum’s nanotechnology blog, featuring news and analysis about the development, applications, and future of science and technology at the nanoscale.

 
Editor
Dexter Johnson
Madrid, Spain
 
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Rachel Courtland
Associate Editor, IEEE Spectrum
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