Zenn, the motorcar company that took off thinking that the EEStor ultra capacitor was coming soon survives with essentially nothing for sale of note.  But the capital base has a few blocks left, enough to keep a board and officers chasing after the original dream. If EEstor gets to market anywhere close to the performance that’s been suggested, the Zenn firm will make out handsomely.  So they’re still in the hunt.

The interim Zenn CEO Jim Kofman, a lawyer by trade, attended the Zenn general meeting Tuesday March 27th, 2012 and explained Zenn’s position.

To start Kofman offered that EEStor would be making a public showing of their technology “before summer” due to a recently struck non-dilutive investment agreement between Zenn and EEStor.  The quote by Kofman being used states the agreement, “actually has very specific dates in it. And I guess all I’ll say to you is we’re expecting this before the summer if not well before that time.”

Where this becomes significant is the Zenn release of First Quarter 2012 Operating Results.  This document summarizes the financial activities reported to the shareholders.  This kind of thing is going to be very factual, brief and on point.  To quote the report it says, “The Company recently participated as a minority investor in an equity financing completed by EEStor . . . the Company was able to review certain aspects of the technology and obtain a covenant from EEStor regarding a timeline for near term public disclosure of the status of its technological development certified by an independent third party.”

Things pop out: EEStor is at work, it can raise money, it needs more working capital, the technology has properties that can be inspected, a disclosure timeline has been agreed to, and some form of independent third party certification could be forthcoming.

Now keep in mind, these are covenants in an agreement that can be: not met, renegotiated, cancelled, met, exceeded and so forth.

Bariumtitanate.blogspot quotes Kofman discussing the third party, “They know a lot about the space. We’ve been very careful choosing a firm that is extremely well known in the space.  Knows what they’re doing. Has been looking at this technology for a long time. And was able to be of significant assistance to us and also will be in the future.  But they are a firm that would be very well known to people who know the space. Very reputable and very independent. And were able to be responsive. Who knows a lot about the space.  Firm that is extremely well known in the space. Has been looking at this technology for a long time.”

In a bit of reassurance or perhaps optimism Kofman also notes on the EEStor public technology showing, “it’s coming and it’s very specific on what needs to be disclosed.  So we’re excited and we think that’s probably the most positive development you could look for.”

It is a bit of news.  In reality, outside of the investors in EEStor, no one has a ‘right’ to know what’s going on at EEStor.  The actual milestone is that EEStor has finally let an investor and license holder have enough intellectual property concession to stay afloat and engaged.

So far EEStor has raised funds, done its basic research, produced enough quality lab specimens to impress investors, and kept the lid on.  If one were to speculate on the progress, it seems with the public information, patents in particular, that they have the technology in the lab.  Most likely the tech poses considerable problems getting to prototype and commercial scale.  Perhaps they’ll get there, perhaps not.

The story it seems is more about the watchers than the watched.  We have no firm conclusions about the performance of the EEStor technology.  As much as we’d like to celebrate and congratulate and others would like to disparage and denigrate, EEStor is pressing on.

So we’ll wish the EEStor group good luck and God’s speed and the Zenn folks a good safe harbor and firmament of their capital base.  What ever happens this year, if anything does, it seems the EEStory will go on.

EC or electrochemical capacitor is a tech name for super or ultra capacitors.  With more capacity these aren’t the ones seen inside the computer or TV.  We’ve been watching closely as some firms like EEstor have attracted a lot of attention because the super or ultra capacitor could change the battery capacity needs of high demand applications like electric vehicles.

A real super or ultra capacitor that combines the power performance of capacitors with the high energy density of batteries would represent a significant advance in energy storage technology.

The UCLA team’s new electrodes are composed of an expanded network of graphene, a one-atom-thick layer of graphitic carbon that shows excellent mechanical and electrical properties as well as exceptionally high surface area.

Laser Eteched Graphene Capacitor Electrodes. Click image for the largest view.

Before we start, a Lightscribe DVD is one that can have an image burned on the label side by the laser in the DVD burner.  That noted:

The process is based on coating a DVD disc with a film of graphite oxide that is then laser treated inside a LightScribe DVD drive to produce graphene electrodes. Typically, the performance of energy storage devices is evaluated by two main figures, the energy density and power density. Suppose we are using the device to run an electric car.  The energy density tells us how far the car can go a single charge whereas the power density tells us how fast the car can go.

The UCLA devices made with Laser Scribed Graphene (LSG) electrodes exhibit ultrahigh energy density values in different electrolytes while maintaining the high power density and excellent cycle stability of ECs. Moreover, these ECs maintain excellent electrochemical attributes under high mechanical stress and thus hold promise for high power, flexible electronics.

The work comes out of the UCLA Department of Chemistry and Biochemistry, the Department of Materials Science and Engineering, and the California NanoSystems Institute.  That very thin layer of electrode burned on the disk demonstrates a high-performance graphene-based electrochemical capacitor that maintains excellent electrochemical attributes under high mechanical stress. The team’s paper has been published in the journal Science.

Richard B. Kaner, professor of chemistry & materials science and engineering, points out the impressive expectation saying, “Our study demonstrates that our new graphene-based supercapacitors store as much charge as conventional batteries, but can be charged and discharged a hundred to a thousand times faster.”  We’ll need weights and volumes soon to validate that.

Maher F. El-Kady, a graduate student in Kaner’s lab and the study lead author sums up the study saying, “Here, we present a strategy for the production of high-performance graphene-based ECs through a simple all solid-state approach that avoids the restacking of graphene sheets.”

The team fabricated LSG electrodes without the problems of activated carbon electrodes that have so far limited the performance of commercial ECs. First, The LightScribe laser causes the simultaneous reduction and exfoliation of graphite oxide and produces an open network of LSG with substantially higher and more accessible surface area. This results in a sizable charge storage capacity for the LSG supercapacitors. The open network structure of the electrodes helps minimize the diffusion path of electrolyte ions, which is crucial for charging the device. This can be accounted for by the easily accessible flat graphene sheets, whereas most of the surface area of activated carbon resides in very small pores that limit the diffusion of ions. This means that LSG supercapacitors have the ability to deliver ultrahigh power in a short period of time whereas activated carbon cannot.

That begs the question of how much more capacity could be gained by a laser cutting expressly for the maximum capacity.  A common DVD burner is a stroke of genius for an experiment, but the potential must be considerable higher.

The graphene laid thin and flat is a mechanically robust and shows high conductivity (>1700 S/m) compared to activated carbons (10-100 S/m). This means that LSG electrodes can be directly used as supercapacitor electrodes without the need for binders or current collectors as is the case for conventional activated carbon ECs. Furthermore, these properties allow LSG to act as both the active material and current collector in the EC. The combination of both functions in a single layer leads to a simplified architecture and makes LSG supercapacitors cost-effective devices.

Today’s commercially available ECs consist of a separator sandwiched between two electrodes with liquid electrolyte that is either spirally wound and packaged into a cylindrical container or stacked into a button cell.  Unfortunately, these device architectures not only suffer from possible harmful leakage of electrolytes, but their design makes it difficult to use them for practical flexible electronics.

The research team replaced the liquid electrolyte with a polymer gelled electrolyte that also acts as a separator, further reducing the device thickness and weight and simplifying the fabrication process as it does not require special packaging materials.

In order to evaluate under real conditions the potential of this all solid-state LSG-EC for flexible storage, the research team placed a sample under constant mechanical stress to analyze its performance, it had almost no effect on the performance of the device.

Kaner explains, “We attribute the high performance and durability to the high mechanical flexibility of the electrodes along with the interpenetrating network structure between the LSG electrodes and the gelled electrolyte.  The electrolyte solidifies during the device assembly and acts like glue that holds the device components together.”

It looks as though the choices the team has made improves the mechanical integrity and increases the life cycle of the device even when tested under extreme conditions.

The press release seems to be driving to flexible and or portable device applications. There might be a bias or some unsaid circumstance, perhaps graphene costs or the electrolyte gel that suggests a smaller higher value first market.

That’s OK, its best to get to a market and build some experience before trying to hit the biggest market of all.

The UCLA team took a difficult challenge and answered with clever, innovative and simple solution. It will be a while before we know if the idea can get to mass production scale and at what prices.

Meanwhile – its sure looks good.

To refresh, silicon’s advantage is a high capacity for energy storage comes from taking on a much larger charge than today’s electrodes. Silicon’s disadvantage is that it swells up when charged, expanding up to 3 times its discharged size. The expansion and contraction over charge and discharge cycles quickly destroys the silicon structure that makes an electrode.

The PNNL study examines a new type of silicon-carbon nanocomposite electrode revealing details of how they function and how repeated use could wear them down.  The study also provides clues to why this material performs better than silicon alone.

Right off the silicon-carbon electrode equipped battery has an electrical capacity five times higher than conventional lithium battery electrodes.  There’s a strong motive in place for more research because silicon-carbon nanocomposite electrodes could lead to longer-lasting, cheaper rechargeable batteries for electric vehicles.  A five-fold increase changes the economics for consumers in a major way.

Wang explains the PNNL role, “The electrodes expand as they get charged, and that shortens the lifespan of the battery. We want to learn how to improve their lifespan, because silicon-carbon nanofiber electrodes have great potential for rechargeable batteries.”

Silicon Carbon Electrode for Lithium Ion Battery

Wang led a multi-institution effort to test the nano-sized electrodes consisting of carbon nanofibers coated with silicon. The carbon’s high conductivity, which lets electricity flow, nicely complements silicon’s high capacity, which stores it.  Researchers at Department of Energy’s Oak Ridge National Laboratory and Applied Sciences Inc. and General Motors Global R&D Center created the silicon-carbon nanofibers and forwarded the electrodes to the team at PNNL to probe their behavior while functioning.

Then the PNNL team tested how much lithium the electrodes could hold and how long they lasted using a small testing battery called a half-cell. At 100 charge-discharge cycles, the electrodes still maintained a very good capacity of about 1000 milliAmp-hours per gram of material. That’s 5 to 10 times the capacity of conventional electrodes in lithium ion batteries.  So far so good.

The team knew the expansion and contraction of the silicon could be a problem for the battery’s longevity, since stretching tends to wear things out.  (Like kinking a wire quickly back and forth till it separates – note smaller wires take longer to break than large ones – so stay with this.)

To see how well the electrodes weather the repeated stretching, Wang popped a specially designed, tiny battery into a transmission electron microscope, which can view objects nanometers wide.  They zoomed in on the tiny battery’s electrode allowing the team to study the electrode in use, and they took images and video while the tiny battery was being charged and discharged.  There are images and videos on the study’s Supporting Information page – so click here!

Previous work has shown charging causes lithium ions to flow into the silicon.  The PLLN team’s study showed lithium ions flowed into the silicon layer along the length of the carbon nanofiber at a rate of about 130 nanometers per second. This is about 60 times faster than silicon alone, suggesting that the underlying carbon improves silicon’s charging speed.  There’s a bonus worth more examination.

The team expected the silicon layer to swell up about 300 percent as the lithium entered.  But the combination of the carbon support and the silicon’s unstructured quality allowed it to swell evenly.  That compares favorably to silicon alone, which swells unevenly, causing imperfections.

Beyond the swelling up, lithium is known to cause other changes to the silicon. The combination of lithium and silicon initially form an unstructured, glassy layer. Then, when the lithium to silicon ratio hits 15 to 4, the glassy layer quickly crystallizes, as seen in previous researcher’s work.

The team examined the crystallization process in the microscope to better understand it. In the microscope video, they could see the crystallization advance as the lithium filled in the silicon and reached the 15:4 ratio.

Here’s the breakthrough – the team found that this crystallization is different from the classic way that many substances crystallize, which builds from a starting point. Rather, the lithium and silicon layer snapped into a crystal all at once when the ratio hit precisely 15 to 4. Computational analyses of this crystallization verified its snappy nature, a type of crystallization known as congruent phase transition.

And the crystallization isn’t permanent. Upon discharging, the team found that the crystal layer became glassy again, as the concentration of lithium dropped on its way out of the silicon.

That’s the key to the huge capacity.

On the longevity front the team charged and discharged the tiny battery 4 times. Comparing the same region of the electrode between the first and fourth charging, the team saw the surface become rough, similar to a road with potholes.

Wang has an explanation about the changes being likely due to lithium ions leaving a bit of damage in their wake upon discharging, “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.”

The fact that the silicon layer is very thin makes it more durable than thicker silicon. In thick silicon, the holes that lithium ions leave behind can come together to form large cavities. “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,” is Wang’s metaphor.

For the future work the team expects to explore the thickness of the silicon layer and how well it bonds with the underlying carbon to optimize the performance and lifetime of the electrodes.

Lots of possibility here.  Great work and a great start.  And a big thanks to the American Chemical Society for making the images and videos available.  Seeing an electrode in action is quite a treat as well as highly instructional.

So far this is the best solution seen to getting the silicon advantage into the lithium ion battery chemistry.  Silicon has tempted and bedeviled for years.  The potential using the preliminary numbers are tremendous bait – a 5 to 10 fold increase in capacity could double range for 40% of the mass.  Plus those flow rates suggest very quick charges and discharges offering simpler engineering, better performance and fast recharge.  This is a technology to watch very carefully.

The world record looks secure for now, the battery prototype has third party tests confirming the energy density at the 400 watt hours per kilogram.  In comparison, one of the currently manufactured at scale batteries is made by Panasonic rates at 245 Wh/Kg.  That’s a battery model a person can buy.

Across from the new density rating are the projected costs.  Envia’s Sujeet Kumar, Co-founder, President & CTO explains the demonstration prototype packaged as a 40 Ah pouch cell, in a new system could lower Li-ion cell costs to $180/kWh with further reductions to come.

A lot of people from the mainstream media to bloggers run numbers projecting a deep cut in electric vehicle prices.  It’s not been easy to notice or find the specific number of charging cycles being talked about.  There is graphic suggesting that by 300 cycles the battery is still at 91% capacity.  This isn’t thousands of cycles, but hundreds. Lets all calm down.  Envia still has work to do.

What has Envia way out in front are the electrodes.  Envia calls the cathodes “high capacity Manganese rich” (HCMR), which is a lithium-rich layered-layered Li2MnO3·LiMO2 composite. The HCMR composite cathode material offers twice the specific capacity and lower cost compared to more conventional cathode materials.

Envia Coated Cathode. Click Image for more info.

Envia’s Kumar explains by engineering the cathode composition, structure, dopants, morphology and nano-coating, they’re able to precisely control and tune the specific capacity, cycle life, calendar life, rate capability and physical properties of the material to match any application.  This suggests there can be trade offs among the specifications to get to specific applications.  Retuned for cycles over 1000 the capacity is between 220 and 295 Wh/kg.

On the anode side Envia engineered at nano size with Si-C anodes at a resulting high capacity at 1530 mAh/g reversible capacity, a good rate capability running 95.5% capacity retention and good cycling performance  – 90% capacity retention after 50 cycles in a half cell.  On the anode side there doesn’t seem to be any easy quotes to reassure the careful observer.  Again, this cycling performance isn’t a setup for mass marketing.

Envia Silicon Based Anode. Click image for more info.

The company says it can see light now at the end of the tunnel for its working prototype based on lithium-ion chemistry and also said it will prove other scientists wrong who have said lithium-ion chemistry is limited in how inexpensive and energy dense it could be made to be.

Add to the electrodes technology the electrolyte is a proprietary compound.  It’s very interesting to look at the effect of the nail gun test.  Punch a nail through a conventional battery and the results are quite flammable spreading collateral damage, a nightmare potential in a serious collision or impact.  The Envia website shows a proprietary pouch with a nail driven through that has, well, a hole in it – lacking the flame burned ripped apart imagery.  Of course this is a proprietary test, but its quite an attractive property for a lithium-ion battery.

Envia Nail Penetration Test Result. Click image for the largest view.

Congratulations are in order for getting to a rechargeable silicon anode based lithium-ion battery.  This is no small feat.  It seems the Envia team thinks it can drive to better results in the next few years.  Keep in mind the requirements for cell phones and other small rechargeables, laptops and other mid-sized devices and electric vehicles have very different specifications and consumer expectations.  Envia could get to some markets sooner than others.

But for electric vehicles a rebattery job at 1,000 cycles isn’t going to cut it or even come close.  Your humble writer has looked at numerous studies over the years and today, subject to revision, is thinking electric vehicle batteries have to get to 300 Wh/kg charged over 3000 cycles at better than 90% capacity for under $130.

Lets say Envia gets to 400 W/kg and recharges 3000 times at $125. Then you will have a revolution.

Meanwhile – lets all stay calm.  So, go get ‘em Envia!

Ranjan previously found that capacitors, which contained the polymer polyvinylidene fluoride, or PVDF, in combination with another polymer called CTFE, were able to store up to seven times more energy than those currently in use.

Scanning Electron Micrographs of Polyvinylidene Fluoride or PVDF

Ranjan said, “We knew that this material makes an efficient capacitor, but wanted to understand the mechanism behind its storage capabilities.”

The findings should lead to much more powerful and efficient electric cars.  Liquid fuels offer a stored energy per unit weight or volume that hasn’t been bettered by anything practical yet. That has slowed to a near stop the widespread adoption of electric vehicles.  Vehicle dynamics require essentially two rates of energy flow, a steady state and high power.  Batteries directly store electricity and use a chemical reaction to generate electricity then discharge it slowly, which works for the steady state.  Capacitors go to work in applications requiring quick delivery of energy.

Roughly explained, capacitors are made from two metal surfaces separated by a dielectric and the capacitance can be improved by bringing the surfaces closer together and by using a separator with high dielectric permittivity.

Ranjan and his colleagues predict that mixing a ferroelectric polymer with a pinch of another polymer could yield a sevenfold increase in stored energy compared to the pure dielectric.

Using calculations the team shows insights at the molecular level about how that could occur.  The activity is the polymer atoms collectively rearrange from a nonpolar to polar state.  The computer simulations are reported in Physical Review Letters.  

The work has also revealed a “transition path” with low activation energies and the path is accessible at technologically “reasonable” temperatures. The path explores a complex torsional and rotational manifold suggesting suitable copolymers significantly alter the energy barriers between phases providing tunability of both the energy density and the critical fields.

Ranjan and fellow NC State physicist Dr. Jerzy Bernholc and Dr. Marco Buongiorno-Nardelli from the University of North Texas, used computer simulations to see how the atomic structure within the polymer changed when an electric field was applied. Applying an electric field to the polymer causes atoms within it to polarize, which enables the capacitor to store and release energy quickly.

They found that when an electrical field was applied to the PVDF mixture, the atoms performed a synchronized dance, flipping from a non-polar to a polar state simultaneously, and requiring a very small electrical charge to do so.

There’s the “Aha!” moment.  Ranjan explains, “Usually when materials change from a polar to non-polar state it’s a chain reaction – starting in one place and then moving outward. In terms of creating an efficient capacitor, this type of movement doesn’t work well – it requires a large amount of energy to get the atoms to switch phases, and you don’t get out much more energy than you put into the system.”

“In the case of the PVDF mixture, the atoms change their state all at once, which means that you get a large amount of energy out of the system at very little cost in terms of what you need to put into it. Hopefully these findings will bring us even closer to developing capacitors that will give electric vehicles the same acceleration capabilities as gasoline engines.”

The study paper is sure to get some very curious examiners.  Flipping the polarity state as a means to store energy is an exciting idea. It’s already known the chemistry functions.  As Ranjan said, the tunability is now up for trials by many ideas.  The clue will also encourage other materials and perhaps designer materials to get legs for more research.

The team has made a significant stride in both establishing the PVDF material and a protocol to use calculation to explore other ideas.  With EEStor gone missing for now, and using polymers that might be very inexpensive to produce, ultra capacitors are very welcome back into the news.

To start, a flow battery or accurately a Redox Flow Battery (RFB) is a type of rechargeable electrochemical system that relies on the redox states of various chemicals for the purpose of storing energy.  The electroactive components, anolyte and catholyte, are liquids held in tanks.  Charging and discharging of these batteries happens through a redox process in the cell.  RFBs are attractive because in addition to the rapid charge/discharge ability is they can scale way up.

Process Graph of Metal Based Ionic Liquids used in a Flow Battery. Click image for the largest view.

To increase the energy stored in this type of system requires simply to only increase the size of the anolyte and catholyte tanks.  Likewise, increasing the power output of the flow battery only necessitates the addition of more cells.

So far the problems have been charge cycle efficiencies, low energy densities, raw material costs, cross contamination of the anolyte and catholyte, plus corrosiveness and safety issues all have contributed to an unacceptably high cost per kWh.

The Sandia research published in Dalton Transactions, might lead to devices that can help economically and reliably incorporate large-scale intermittent renewable energy sources, like solar and wind, into the nation’s electric grid.

Anthony Medina, director of Sandia’s Energetic Components Realization program opens the discussion, “The U.S. and the world need significant breakthroughs in battery technology for renewable energy sources to replace today’s carbon-based energy systems. MetILs are a new, promising battery chemistry that might provide the next generation of stationary storage battery technology, replacing lead-acid and lithium-ion batteries and providing significantly higher energy storage density for these applications.”  The electrical grid was designed for steady power sources, making fluctuating electricity from intermittent renewable energy difficult to accommodate.  Battery based energy storage techniques can help even out the flow from fluctuating sources.

Sandia’s Travis Anderson is leading a team developing the next generation of flow batteries.  In a flow battery a pump moves a solution of free-floating charged metal ions, dissolved in an electrolyte substance, with free-floating ions that conducts electricity, from an external tank through an electrochemical cell to convert the chemical energy into electricity. Flow batteries are rapidly charged and discharged by changing the charge state of the electrolyte.  The electroactive material can be easily re-used many times. Anderson said flow batteries can sustain more than 14,000 cycles in the lab, equivalent to more than 20 years of energy storage.  Sounds great.

But flow battery grid storage systems are roughly the size of a house and can cost more than equivalent lithium-ion batteries. So the Sandia group goal is to make flow batteries smaller and cheaper, while increasing the amount of energy stored for a given volume, or energy density.  So far some flow batteries are out there, mostly using zinc bromine and vanadium redox, but they are moderately toxic and vanadium has big price fluctuations, plus they are vulnerable to the temperature.  The Sandia group’s leaders hope to build a battery without water and solve these issues.

The Sandia team is multidisciplinary experts including electrochemist David Ingersoll, organic chemist Chad Staiger and chemical technologists Harry Pratt and Jonathan Leonard. What they’ve designed is a new family of electrochemically reversible, metal-based ionic liquids, or MetILs, which are based on inexpensive, non-toxic materials that are readily available within the U.S., such as iron, copper and manganese. They have a home run on new flow battery cathode materials.

Sandias Ionic Liquid Metal Salt Electrolyte Samples. MetILs are, from left to right: copper-based compound, cobalt-based compound, manganese-based compound, iron-based compound, nickel-based compound, and vanadium-based compound. Click the link above to the Sandia press release for more info and larger views.

Anderson takes up the explanation, “Instead of dissolving the salt into a solvent, our salt is a solvent. We’re able to get a much higher concentration of the active metal because we’re not limited by saturation. It’s actually in the formula. So we can cost-effectively triple our energy density, which drastically reduces the necessary size of the battery, just by the nature of the material.”

Here’s the payoff – The electrochemical efficiency, or ability to reverse charge, in MetILs is far greater than anything else published to date. The team has prepared nearly 200 combinations of cations, anions and ligands, and of those, five outperform the electrochemical efficiency of ferrocene, which has long been considered the efficiency gold standard.

The team has worked up the early solutions.  Usually when mixing up positively and negatively charged molecules, the molecules will start clumping together, eventually causing the solution to turn gummy and clog up the battery membrane and electrode surfaces. The team solved that challenge by developing asymmetric cations, or positively charged ions, that resemble a soccer ball. In this analogy, the black pentagons represent negatively charged areas and the white hexagons represent positively charged regions. Such an arrangement lowers the melting point by preventing the ionic liquid constituents from bonding and becoming a solid, while the partial charge still allows electrons to flow freely through the cell to generate a current.  It’s sort of “pre clumped” and works better for it – just don’t let it completely discharge.

Imre Gyuk, energy storage systems program manager at the Department of Energy’s Office of Electricity Delivery and Energy Reliability said, “The MetILs approach represents an ingenious, out-of-the-box solution to the cathode/electrolyte paradigm. Because it is based on readily available, inexpensive precursors, it may well lead to innovative, cost-effective storage systems with major impacts on the entire U.S. grid.”

Next up for the Sandia team is to find similar materials for the flow battery anodes.  The team is encouraged by their progress so far.

Anderson said, “There are three things you’re juggling at the same time, and they aren’t always related: viscosity, electrical conductivity and the fundamental electrochemical efficiency. The excitement of having all three things go right at the same time, it’s like finding the treasure, but without the map. We’re creating that map, and we’re very excited by the possibilities.”

Lets see . . . low or non-toxic, 14,000 cycles, temperature tolerance, highest density so far, capacity by tank size . . .  is anyone else thinking miniaturization?

Advanced batteries are the major barrier to electrification of a significant share of transport and for better, lighter and cheaper electronics.

The research group’s technique is described in the journal Nature Materials.  As well as a look inside without destruction the technique may also improve battery performance and safety by offering diagnostics of battery internal operations.  Therein lies the breakthrough.

MRI Image From Inside a Battery. Click image for more info.

The MRI has been extremely successful in the medical field for visualizing disorders and assessing the body’s response to therapy.  But an MRI isn’t usually used in the presence of a lot of metal, a primary component in many batteries’ shells, as part of the anode and cathode and in many cases the electrolyte.  The problem is metallic surfaces and dense concentrations conduct electricity that effectively block the radio frequency fields that are used in a MRI to see beneath surfaces or inside the human body.  With the radio waves shielded or absorbed and converted to electrical current – there isn’t anything to see.

The research group has cleverly turned this limitation into a virtue. Because radio frequency fields do not penetrate metals, one can actually perform very sensitive measurements on the surfaces of the conductors.  Using popular lithium-ion batteries, for example, the team was able to directly visualize the build-up of lithium metal deposits on the electrodes after charging the battery. Those deposits can also detach from the electrode surface, eventually leading to overheating, battery failure, and, in some cases – to a fire or an explosion.

This breakthrough is sure to speed development up because the ability to visualize small changes on the surface of the batteries’ electrodes, which would allow in principle, for testing of many different battery designs and materials while operating under normal conditions.

The breakthrough comes from a collaboration between Clare Grey, associate director of the Northeastern Center for Chemical Energy Storage and a professor at Cambridge and Stony Brook universities, and Alexej Jerschow, a professor in the Department of Chemistry at New York University who heads a multi-disciplinary MRI research laboratory.  The group isn’t saying whose brainstorm found the virtue in the limitation, but that’s OK.

Jerschow illustrates the import by explaining, “New electrode and electrolyte materials are constantly being developed, and this non-invasive MRI technology could provide insights into the microscopic processes inside batteries, which hold the key to eventually making batteries lighter, safer, and more versatile. Both electrolyte and electrode surfaces can be visualized with this technique, thus providing a comprehensive picture of the batteries’ performance-limiting processes.”

Grey points out why the technique offers such an advantage, “MRI is exciting because we are able to identify where the chemical species inside the battery are located without having to take the battery apart, a procedure which to some degree defeats the purpose. The work clearly shows how we can use the method to identify where lithium deposits form on metal electrodes.” Grey adds, “The resolution is not yet where we want it to be and we would like to extend the method to much larger batteries, but the information that we were able to get from these measurements is unprecedented.”

It’s a start that works.  Other team members include S. Chandrashekar, a postdoctoral fellow at both Stony Brook and New York Universities; Nicole Trease, a postdoctoral fellow at Stony Brook University; and Hee Jung Chang, a Stony Brook University graduate student.

Looking ahead the group offers that the method could lead to the study of irregularities and cracks on conducting surfaces in the materials sciences field. In addition, they add, the methods developed here could be highly valuable in the quest for enhanced battery performance and in the evaluation of other electrochemical devices, such as fuel cells.

They might want to consider more thoroughly the impact the technique might have on catalysts – but that field will surely find them quite soon.

Chandrashekar sums up briefly, “We still have some way to go to make the images resolve better and make imaging time shorter. However, we feel that with this work, we have made the field wide open for interesting applications.”

Battery development has been racing ahead for a decade when many used to believe little progress could be made.  Now we have a technology that puts the activity inside a battery in view. Should Chandrashekar’s prognosis come to pass soon and at high resolution and high speed “shutter speed” so to speak, development for batteries should gather much more momentum and achieve results faster and at lower cost.

But that’s just one field.  The fuel cell field and other catalyst processes can use a boost of high-speed development diagnostics, too.

This is great news.  Congratulations are in order.  We’d sure like to know though, who was the person or who were the folks who had the brainstorm?  That would be a double up on the congratulations.

This week the UWO scientists report that using nitrogen-doped graphene nanosheets (N-GNSs) as cathode materials significantly increases the performance of a non-aqueous lithium-oxygen battery by about 33% more than the high-performance pristine graphene nanosheets announced in August.

The paper has been published in the journal Electrochemistry Communications.

The research team led by Professor Xueliang (Andy) Sun found that their nitrogen-doped graphene nanosheet cathode materials delivered a discharge capacity of up to 11,660 mAh g^-1 compared to the pristine graphene nanosheet capacity of up to 8,706 mAh g^-1.

Nitrogen Doped Graphene NanoSheet Diagram from researchers at University of Western Ontario .

The team had been following recent studies where nitrogen doping was applied to carbon powder and nanotubes.  Those research efforts showed higher discharge capacities.  The UWO team then set out to try nitrogen doping on carbon nanosheets by testing for electrocatalytic activity of N-GNSs for oxygen reduction in the non-aqueous electrolyte.  The nitrogen doping for oxygen reduction result is 2.5 times that of the pristine graphene nanosheet. The team is attributing the excellent electrochemical performance of N-GNSs to the defects and functional groups as active sites introduced by the nitrogen doping.

The team is pointing out the finding not only shows that N-GNSs are promising electrode materials, but also gives a rational direction to modify other carbon materials for application in lithium-oxygen batteries.

The hard numbers reported in the study show the initial discharge capacity of the GNS electrode was 8,530 mAh g^-1 at a current density of 75 mA g^-1, while the N-GNS electrode delivered 11,660 mAh g^-1 for N-GNSs an increase about 37% higher.

Keep in mind these are lab research batteries and other questions are coming up.  Another worthwhile consideration is as the current densities increased, the discharge capacities of both samples decreased.  At a current density doubled to 150 mA g^-1 discharge capacities were 5,333 mAh g^-1 for GNS and 6,640 mAh g^-1 for N-GNS.  At 300 mA g^-1 capacities went to 3,090 mAh g^-1 for GNS and 3,960 mAh g^-1 N-GNS.  These results are pretty much linear with no big surprises.

Nitrogen isn’t especially expensive, but graphene nano sheets aren’t a common item yet.  In fact graphite is usually mined rather than made from petroleum.  Thus for now the new cathodes are anything but cheap.  But mass markets and scaling up have amazing effects on pricing product components.

Meanwhile . . . down in the U.S. the IBM effort has been working on air batteries too.  One or the other of these or perhaps others are going to find a practical and affordable way to store very high capacities of electricity one day. Things have come a long way from carbon dry cells and lead acid.

Maybe the Canadians up at Western can provoke a bit of news out of IBM.  Air battery news isn’t coming at raging speed, but the bits we’re getting are encouraging.

An EMB (a technical description of a flywheel) stores energy through spinning a composite flywheel with an electric motor that’s built in, driving the rotating mass to speed making the system into a battery. Then use the electricity by using the motor as a generator that slows the flywheel down.  EMBs aren’t quite dead, the once widely admired Beacon Power flywheel builder that’s in bankruptcy has found a buyer that may put the intellectual property back to work and return a chunk of a federal loan to the taxpayers.

Mr. Peart’s idea is quite futuristic. Aside from the problems of either lifting the whole thing into orbit or building a manufacturing system in orbit, the concept does overcome the twin drags on rotating masses, the friction of air and bearings blocking gravity’s effect.  Peart is suggesting the flywheel spin at speeds in excess of 60,000 RPM. The flywheels would float (through the use of magnets) in a frictionless vacuum chamber, removing almost all friction and drag.  That would enable the storage of energy for years on end.

Peart's Orbital ElectroMechanicalBattery Layout. Click image for the largest view.

Peart’s satellite would collect energy through an incorporated solar array.  Once the energy is stored the system would seem conventional with other ideas – the energy can be transferred through the use of a microwave antenna and then converted back into electricity through a rectenna (receiving antenna), located down on Earth. The antenna could be repositioned so to allow energy transfer to multiple reactenna locations on Earth, from a single position in orbit.

Peart's Solar Energy Collector and Storage Satellite. Click image for the largest view.

The idea has some thought in it; the satellite would incorporate a system of easy access doors to allow the servicing or removal of worn batteries. The batteries would be oriented on a circular plate that rotates allowing the removal of a set of batteries in a series. The batteries would be mounted with alternating clockwise and counter-clockwise rotations to balance out the gyroscopic effects.  That way two in pairs would speed up twisting opposite to each other leaving the satellite undisturbed.

Peart's Orbital Power Station EMB Service Door. Click image for the largest view.

The proposal has ten series mounted vertically in a column, and six columns are mounted in each individual satellite making a total of 360 batteries mounted in each satellite. The satellite images shown here are small-scale examples, full power satellites would contain several thousand batteries. Each battery would have capacity ratings about 25kWh.

An orbital power station offers the cleanest renewable energy storage and production so far imagined.  Such power station satellites would provide energy on a constant basis, and could answer demand at peak power consumption times with the stored energy.  Peart also points out orbital power stations can also be used as a practical means to sell power services worldwide.

The problem is going to be the capital investment.  Lifting simply a very large solar array is going to challenge the economics.  Adding in batteries at current orbital lift prices doesn’t seem practical for now.

Yet the concept has great stimulating value.  The Republican primary race has one candidate that sees the future of mankind returning to the solar system, which is for now a government sized job and one best done by the free people of earth instead of despots.

Almost everyone it seems has forgotten the root of the information age is the American effort to put a man on the moon. Without the research and development during the 1960s searching for small, lightweight and energy efficient devices, primarily integrated circuits, the information age we now know would not exist as we know it.  Societies have myopic views of the past; it will always be a challenge to avoid a myopic view of the future.

Peart’s concept has value, a measure of thought that can solve problems, worthy of note and keeping saved for those in the future who can build off planet.  Peart’s idea is part of that vision thing that is so painfully lacking in American political and economic discourse.

It’s a pity that virtually all political energy is devoted to cutting up the proceeds of the past, dividing up the production of the present and promising the potential of the future – without investing in the ideas that make future filled with possibilities, challenges and opportunity.  We’re missing that vision thing.

The assertion now is IBM believes it has solved a fundamental problem that may lead to the creation of a rechargeable battery with a 500-mile (800-kilometre) range – letting EVs potentially compete with most petroleum fueled engines.  That would solve the major concern with owning an electric vehicle (EV), the range anxiety – a driver’s estimation that the battery charge will not get the vehicle to the destination on the charge.

As the technology sits today the best offerings of EVs use lithium-ion batteries, which still occupying a large volume and rarely provide 100 miles (160 kilometers) of driving before they’re discharged.

IBM is well into their Battery 500 Lithium/Air Battery project.  The original idea is to come up with and electrical storage solution as good as gasoline, runs out 500 miles and is fully electric with size weight and pricing comparable to a gasoline internal combustion drive.

A lithium-air cell has more potential because it has theoretical energy densities more than 1000 times greater than conventional lithium-ion battery chemistry, setting up an energy density comparable to gasoline.  Lithium-air cells use carbon, instead of metal oxides for the positive electrode, which is lighter and reacts with oxygen from the air around it to produce an electrical current.

The problem has been chemical instabilities limiting the recharging cycles, making lithium-air impractical for use in cars.

Wilcke said, “We now have one which looks very promising.”  No disclosure is being made about what material it is but he says that several research prototypes have already been demonstrated.

To get to this point Wilcke studied the underlying electrochemistry of lithium-air cells using a form of mass spectrometry. What he learned was that oxygen is reacting not just with the carbon electrode, as it was known to, but also with the electrolytic solvent – the conducting solution that carries the lithium ions between the positive and negative electrodes.  When the electrolyte reacts with the oxygen as the battery is used it will eventually be depleted.

Wilcke teamed up with colleague Alessandro Curioni at IBM’s Zurich research labs in Switzerland.  Curioni explains they used a Blue Gene supercomputer to run extremely detailed models of the reactions to look for alternative electrolytes. This included a form of atomistic modeling right down to the quantum mechanics of the components.

The pair’s work is part of the Battery 500 project, where IBM is leading a coalition involving four US national laboratories and commercial partners, with the hope to have a full-scale prototype ready by 2013, with commercial batteries to follow by around 2020.

Graham-Rowe found Phil Bartlett, head of electrochemistry at the University of Southampton, UK for his counter point who offers, “Lithium in water spontaneously catches fire.”

But if the IBM lead consortium has come up with an anode and cathode that works with the oxygen in an electrolyte that doesn’t react with the oxygen they would have solved a major obstacle with lithium-air batteries.  Keeping the H2O molecules out would be a much less challenging matter.

So we’re bursting with questions!  Have the Battery 500 folks got both of the electrode materials sorted out and a selection of electrolytes?  Is the oxygen transport inbound handling the nitrogen, water vapor and trace gasses or are the barriers at the electrodes and electrolytes?  Perhaps both methods are under study?  The questions just take off from there.

This is good news and congratulations are in order for the Battery 500 team people and Mr. Graham-Rowe for finding the news and getting it out.