Hi Frank - I've been watching the posts on lithium-"X" batteries with interest.
In fact, research here is both more advanced than generally realized, and in other ways, more retarded. Perhaps the best phrase to describe the difference between North American R&D versus foreign competitors is "less coherent, but more diverse".
The following could be a book, but it's just a quick overview.
Geoffrey Ballard (whose work eventually resulted in the Ballard fuel cell) was a pioneer, back in the 70's. The following except notes some of the limitations to alternative energy R&D in the U.S. at the time, and also describes graphically the pioneering work that differs so dramatically from the carefully planned and funded Japanese efforts.
Tangentially, it deals with some of the competitive issues you've alluded to.
"The fact that the battery they were developing was intended for a submarine did not distract them from this larger vision. "We looked at the sub as a test bed," says Ballard. If you could perfect the rechargeable battery, "you could then apply it to a car." In fact, for test purposes the submarine had advantages. "Being able to experiment with these batteries and having a strong pressure hull between you and this thing was a nice idea. Having it under water also made it a lot safer. We expected failures." And failure could be dangerous.
They were careful, but mishaps occurred. Ballard unlocked the lab one morning to find solvents and chemical beads splattered all over, and shards of glass embedded in the ceiling. A large ion exchange column, the glass apparatus used to manufacture batches of lithium dithionite, had exploded during the night. Fortunately, nobody was around. A similar thing happened another time. The amounts of dithionite involved on these occasions were relatively small, so the damage was minor but unsettling nonetheless.
The actual battery for Horton's submarine, however, was a different story. Each unit was a spool-shaped device about the size of a large hatbox. Designed to be ganged together and fit into a cylindrical pod attached outside the pressure hull, it held two kilograms of lithium dithionite, which, as Prater had already found out, was an extremely unstable substance. And, in chemical jargon, "unstable" is often a euphemism for explosive. "We thought we'd got it pretty well under control," says Ballard. "We had it in acetyl nitryl. We didn't think it was dangerous. But it turns out, in hindsight, that we didn't know that much about it. In fact, we had created quite a dodgy situation. A high-powered battery is basically just a controlled bomb. Whenever you put chemical compounds together that create electricity, you've essentially got an explosive situation." He shakes his head and laughs. "If it had decided to detonate, there would have been another Crater Lake down there in Arizona. And no more motel, I'll tell you! We were very, very lucky."
islandnet.com
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Ballard's pioneering work was eventually bought out, and the proceeds used to advance the Ballard PEM fuel cell.
Recently, a spate of stories has surfaced about an alleged "shortage" of lithium...
"Lithium surge lacks staying power"
... To put the situation into perspective, consider that to make 60 million plug-in hybrid vehicles a year containing a small lithium-ion battery would require 420,000 tonnes of lithium carbonate – or six times the current global production annually.
But in reality, you'd want a decent-sized battery, so it's more likely you'd have to increase global production 10-fold. And this excludes the demand for lithium in portable electronics.
So the automakers and electric-vehicle enthusiasts have to ask themselves whether the focus on lithium-ion technology is a jump from the frying pan into the fire; from peak oil to peak lithium.
Tahil believes so, and suggests that the industry should focus more on battery technologies based on more common metals, such as nickel or zinc. This would include sodium nickel chloride or "Zebra" batteries and zinc air batteries... "
thestar.com
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The most concise informed response I've seen to Tahil's comments is here (among other alternative energy esoterica):
"Re: Reality check on lithium-ion hype
by Anonymous
Mr. Tahil’s basis for a Lithium shortage is built upon a statement in his paper: meridian-int-res.com On page 12 of this report he states; “Existing LiIon/LiMP “Energy Batteries” for EVs require about 0.3kg of Lithium metal equivalent per kWh, in the form of Lithium Carbonate.” He then continues in this paper to state that it takes 1.4kg/kWh of Lithium Carbonate Li2CO3 to build each kilowatt hour of an EV battery. This premise is completely in error & I show why below. Saft, which is one of best known, most respected & oldest Lithium Ion battery manufacturers in the world publishes the ‘lithium content’ of their Li-Ion batteries. Let’s take a look at some Saft Li-Ion rechargeable batteries that use lithium carbonate in their makeup. One can open the following Link & navigate down to their ‘Lithium – ion batteries’ to confirm the figures I post below: saftbatteries.com If you click on the ‘MP 176065’ as provided in the following link: saftbatteries.com You will see that this Li-ion battery is rated as follows: Nominal voltage: 3.75 Volts Capacity: 6.8 Ah Lithium equivalent content: 2.0 g Nominal energy: 26 Wh Now let’s do the math for everyone to see: 1kWh or 1,000Wh / 26Wh = 38.46 of these batteries to make 1kWh 38.46 Saft MP 176065 batteries X 2.0g Lithium equivalent each = 76.92g of lithium equivalent If you add up the molecular weight of lithium carbonate (Li2CO3) & then figure what the percentage of lithium is, you find that lithium makes up 18.8% or .188 of Li2CO3. 76.92 / .188 = 409.15g of Lithium Carbonate in 1kWh of this Saft Li-ion battery. This is only 0.409kg/kWh --- NOT 1.4kg/kWh, Mr. Tahil’s basis for this article. 0.409kg/kWh is extremely close to the figure (0.431) that the UN & the US-DOT & several Li-Ion battery companies tell us we need to use when determining the lithium content of a Li-ion battery. They are having us figure a little high for transportation safety reasons. Go ahead and open the other data sheets for the other Saft Li-ion batteries & do the analysis on each battery displaying the Lithium contents. They all fall in at around 0.409kg to 0.426kg per kWh which is extremely close to the 0.431kg/kWh as stated in an above commentary. This means that we can build in excess of 1.5 Billion PHEV20 (more than 2 X all the world’s current vehicles) & use only 5,799,918 tonnes of Li2CO3. The USGS tells us in a 2000 study that we have 12,000,000 tonnes of Li2CO3 …. HOWEVER, Lithium can be & is being recycled from Li-Ion batteries. See TOXCO @: toxco.com As can be seen, lithium is quite recyclable so, in reality we won’t even begin to approach using up half the world’s reserves by the time we have gotten around to building 1.5 billion PHEV vehicles; if we EVER make that many. It is estimated that the whole world only has 0.6 billion vehicles today. Wayne Brown --- privatenrg.com"
tyler.blogware.com
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The following IEEE article has a quick overview of the state of the art...
"... Better batteries through chemistry
The cathodes of current lithium-ion batteries are made of lithium-cobalt metal oxide (LiCoO2). This material is pricey, and it can become unstable and release oxygen if the cell is overcharged. One alternative is to replace the cobalt in the cathodes with iron phosphates, which won’t release oxygen under any charge and therefore will not burn.
A123Systems, in Watertown, Mass., first launched a lithium-ion phosphate battery this past fall in Black & Decker’s DeWalt power tools. A123Systems claims its batteries can be recharged 10 times as often as conventional lithium-ion designs, charge to 90 percent capacity in 5 minutes, and charge fully in less than 15 minutes. Conventional lithium-ion models, by contrast, can take twice as long.
In May, the company unveiled a battery pack it said could be ready for electric vehicle use within three years. It’s smaller than a carton of cigarettes and weighs barely 4.5 kg (10 lbs.), one-fifth as heavy as an equivalent NiMH battery. A123 is taking part in one of the two joint ventures to which GM has awarded battery development contracts. Its partner is Cobasys, of Orion, Michigan, itself a joint venture of Chevron Technology Ventures and Energy Conversion Devices Inc. GM's other contract is with a joint venture between Johnson Controls, of Milwaukee, and Saft Advanced Power Systems, of Paris.
Austin, Texas–based Valence Technology also uses iron-phosphate cathodes for its Saphion battery. The technology is used in the Segway, the self-stabilizing scooter, and in unofficial conversions that aim to increase the range of a Toyota Prius.
Customarily, the anode of a lithium-ion battery is made of graphite, which can store only a limited amount of energy. Researchers at Sandia National Laboratories, in Livermore, Calif., have developed anodes using a composite of graphite and silicon that can quadruple storage capacity.
Late this year, 3M Co., in St. Paul, Minn., will deliver still another kind of anode, based on amorphous silicon, which the company says will store twice the energy of today’s lithium batteries. Other researchers are trying to make anodes of alloys of lithium and two other metals, generally antimony mixed with either copper, manganese, or indium. Such three-metal alloys should also increase storage capacity.
Cells now being developed by Altair Nanotechnologies, based in Reno, Nev., switch the lithium from the cathode to the anode, forming a compound called lithium-titanate spinel (Li4Ti5O12). The company says that the cells recharge in 3 minutes and deliver three times as much power as the conventional design, and at a great operating range of temperatures: –30 °C to 249 °C (–22 °F to 480 °F). It also says that its batteries can keep on ticking after 9000 recharging cycles, compared with 1000 for conventional cells. Altair’s battery, however, is not yet in production.... "
spectrum.ieee.org
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This post hardly does justice to the subject, but may be a starting point for those who wish to go further.
Jim |
