Lithium, Timing, Bolivia, Socialist Dreams

Every technology has a ‘shelf life’. Some are longer than others. The shelf life of “8 Track Tape” was fairly short (though perhaps not as short as Betamax Tape). Silver based photography ruled for nearly 180 year (from about 1820 to near 2000) and has now nearly died in a puff of digital smoke… and with it, the demand for silver took a big hit.

So now we come to the Green Dream of a world driven by electric cars, with lithium ion batteries in them.

Folks all over the world are madly looking for Lithium Mines. These tend to be located in dry lake beds behind mountain ranges. There are not very many places in the world where, for thousands of years, just enough rain has fallen to wash lithium from the mountains, down the backside into broad shallow pans, and with just the right differential evaporation to concentrate the Lithium salts in one part, the other salts in another part. One of them is Bolivia.

Bolivia has recently elected a very socialist oriented government. They have spent a lot of time sitting on one of the worlds largest lithium reserves. Demanding that the evil capitalists give them a giant payment for this resource. Demanding that exorbitant development costs for the country be born by the evil foreigners, the greedy capitalists… Planning how to build their Socialist Dream on the foundation of these salty sands.

This “Times” article spells it out:

http://www.time.com/time/world/article/0,8599,1872561,00.html

For Lithium Car Batteries, Bolivia Is in the Driver’s Seat
[…]
But at Detroit’s International Auto Show this month, the excitement surrounding the Big Three’s announcements that they’re shifting from gasoline to voltage has been tempered by another realization: most of the lithium used to make the batteries for those cars is found in Bolivia, whose leftist President isn’t too fond of the U.S.
[…]
Small, impoverished Bolivia, in fact, is the Saudi Arabia of lithium. It’s home to 73 million metric tons of lithium carbonate, more than half the world’s supply. The largest single deposit is the Salar de Uyuni, a vast, 4,085-square-mile (6,575-sq-km) salt desert in the southern Potosi region that is also one of Bolivia’s biggest tourist attractions.

President Evo Morales, Bolivia’s first indigenous head of state, prides himself on state control over natural resources he nationalized the country’s (massive natural gas reserves in 2006). If the past is any indication, electric carmakers should look to the Andes with sober eyes. “This is a unique opportunity for us,” says Bolivian Mining Minister Luis Alberto Echazu. “The days of U.S. car companies buying cheap raw materials to sell expensive cars are over.” Indeed, Bolivia’s lithium abundance could put car manufacturers in the position of replacing one energy-rich Latin American U.S. critic — Venezuelan President Hugo Chavez — with another.

and this article from The New York Times is similar:

http://www.nytimes.com/2009/02/03/world/americas/03lithium.html

In Bolivia, Untapped Bounty Meets Nationalism
[…]
Japanese and European companies are busily trying to strike deals to tap the resource, but a nationalist sentiment about the lithium is building quickly in the government of President Evo Morales, an ardent critic of the United States who has already nationalized Bolivia’s oil and natural gas industries.
[…]
None of this is dampening efforts by foreigners, including the Japanese conglomerates Mitsubishi and Sumitomo and a group led by a French industrialist, Vincent Bolloré. In recent months all three have sent representatives to La Paz, the capital, to meet with Mr. Morales’s government about gaining access to the lithium, a critical component for the batteries that power cars and other electronics.

“There are salt lakes in Chile and Argentina, and a promising lithium deposit in Tibet, but the prize is clearly in Bolivia,” Oji Baba, an executive in Mitsubishi’s Base Metals Unit, said in La Paz. “If we want to be a force in the next wave of automobiles and the batteries that power them, then we must be here.”

I even wrote an article that pointed out this bind, and that suggested we really ought to just turn our massive coal reserves into “oil products” as South Africa does, rather than sign on to yet another Socialist Dictator and yet another single country dominated resource.

https://chiefio.wordpress.com/2009/09/23/lithium-electric-cars-and-bolivian-socialists/

And that is the Achilles’ Heel of the electric car movement. They can only be built at a slow rate in proportion with the global supply of those two metals or they will run into the inelastic supply curve of those metals. When excess demand meets inelastic supply, prices rise dramatically. This will “rate limit” the introduction of electric cars on a global basis. The only way out of this problem is to build many more and larger mines. Not exactly the darling of the same environmentalists who insist that the electric car will save the planet. Oh, and what do we do if Bolivia says that they do not want to dig up all the lithium at that rate?

The “two metals” were lithium and copper.

This Wall Street Week article even called it “peak lithium”

http://blogs.wsj.com/environmentalcapital/2009/02/03/peak-lithium-will-supply-fears-drive-alternative-batteries/

Peak Lithium: Will Supply Fears Drive Alternative Batteries?

By Keith Johnson

Saudis like to say that the stone age didn’t end for a lack of stones. But could a lack of lithium end the electric car age before it begins?

“Peak lithium” is back in focus, as the New York Times looks at Bolivia’s quest to cash in on the world’s biggest reserves of lithium, a key component in batteries. Simply put, global automakers and battery makers need to ensure a steady supply of lithium to power the expected electric-car revolution, but Bolivia’s populist government and its embrace of resource nationalism raises a lot of concerns about access to the country’s mineral wealth. TIME recently did a big takeout on Bolvia’s lithium, too.

Concerns about global supplies of lithium are a lot like the debate over peak oil. Some experts believe the huge increase in electric cars will actually strain the world’s lithium supplies in a few years; as with peak oil, “above-ground” factors like Bolivia’s politics may be just as critical as geology.
[…]
So what’s the alternative? Skip lithium altogether. Just as thin-film solar-power companies gained in appeal when global polysilicon supplies were tight, batteries that use materials other than lithium are gaining attention now. “Forward-thinking automakers will aggressively pursue alternative chemistries. As auto manufacturers come to terms with limited lithium supplies, they will increasingly consider alternative chemistries like zinc-air or other batteries made from more abundant elements,” Lux said in the report.

Toyota started researching a zinc-air battery, initially out of safety concerns (lithium-ion batteries sometimes explode). Germay’s RWE recently poured more research money into zinc-air batteries, too. Zinc-air and other metal-air batteries sidestep the lithium supply issue.

But if alternative batteries are still in the lab, that’s because they face a host of hurdles lithium-ion and nickel-metal hydrate batteries don’t share. Most importantly, zinc-air batteries aren’t rechargable and have a short lifespan—crucial negatives for the auto market. Some alternative batteries suffer from other shortcomings, too, including weight. That will leave lithium and existing nickel-metal batteries to share the global market in coming years, Lux figures.

But I fixated on the same chemistries. Things like zinc-air and aluminum-air and the problems with heated sulphur batteries.

But Things Change

I’d figured that the LiIon battery probably had a very long shelf life. It’s made with one of the lightest metals on the planet, and with one of the highest electrical potentials in its ions. It would take a lot of work to find a suitable alternative. Though, in honesty, I did wonder about sodium and potassium as similar metals in the same column of the periodic table of the elements and why there were not batteries made with them? I figured they had been tried, as an obvious alternative, and discarded for some reason.

It turns out, I ought to have thought about that a bit longer…

In this article, I looked at Lithium as a traded metal, and used it has an example in reading trading charts. It trades at fairly high prices, especially compared to things like potassium and sodium.

https://chiefio.wordpress.com/2011/05/04/lithium-example/

Here are two charts of a relatively new ETF, one that trades Lithium as a basket of miners.

That ETF, ticker “LIT”, has stocks in it that do the actual mining of lithium. From

Top 10 Holdings (91.97% of Total Assets)	 
Company	                        Symbol	% Assets
Sociedad Quimica y Minera S.A. 	SQM	24.52
FMC Corporation Common Stock	FMC	19.30
AVALON RARE METALS INC.	        AVL.TO	10.51
Rockwood Holdings, Inc. Common 	ROC	8.88
Exide Technologies	        XIDE	5.66
SAFT GPE 	                SAFT.PA	5.25
	                        6764	4.79
	                        CLQMF.TO 4.60
	                        6674	4.48
	                        6764	3.98

Some of these, like SQM and FMC, mine more than just lithium. Others are small miners who may be more focused, but also less known.

At present, the price of a pound of lithium is about $28. See:

http://www.metalprices.com/FreeSite/metals/li/li.asp

for current quotes.

Another Way

Seems that other folks, too, were looking at the periodic chart. As I’d looked a the question of chemistry of LENR cells I ran into the idea of hydrogen “intercalated” in a metal lattice and they pointed out that other ions did this with graphite. Specifically, Lithium in a lithium ion battery. And that Potassium and Sodium would do this too. Well, if they do that too, they ought to make a battery too… and with nearly no effort (once I bothered to think “perhaps it CAN be done”) I found the “Potassium Ion Battery”.

I was familiar with “intercalated” as a term of art from calendars ( it is the process of stuffing in odd days to make the months and years work… like leap year). Guess all that time looking at Stonehenge and sundials has had SOME benefit ;-) In chemistry it has a related meaning:

http://en.wikipedia.org/wiki/Intercalation_(chemistry)

Materials science

Many layered solids intercalate guest molecules. A famous example is the intercalation of potassium into graphite. Intercalation expands the “van der Waals gap” between sheets, which requires energy. Usually this energy is supplied by charge transfer between the guest and the host solid, i.e., redox. Aside from graphite, well-known intercalation hosts are the layered dichalcogenides such as tantalum disulfide and iron oxychloride. In characteristic manner, intercalation is analyzed by X-ray diffraction, since the spacing between sheets increases, and by electrical conductivity, since charge transfer alters the number of charge carriers.

http://en.wikipedia.org/wiki/Li_ion

During charging, an external electrical power source (the charging circuit) applies a higher voltage (but of the same polarity) than that produced by the battery, forcing the current to pass in the reverse direction. The lithium ions then migrate from the positive to the negative electrode, where they become embedded in the porous electrode material in a process known as intercalation.
[…]
The three primary functional components of a lithium-ion battery are the anode, cathode, and electrolyte. The anode of a conventional lithium-ion cell is made from carbon, the cathode is a metal oxide, and the electrolyte is a lithium salt in an organic solvent.

The most commercially popular anode material is graphite. The cathode is generally one of three materials: a layered oxide (such as lithium cobalt oxide), a polyanion (such as lithium iron phosphate), or a spinel (such as lithium manganese oxide).

The electrolyte is typically a mixture of organic carbonates such as ethylene carbonate or diethyl carbonate containing complexes of lithium ions. These non-aqueous electrolytes generally use non-coordinating anion salts such as lithium hexafluorophosphate (LiPF6), lithium hexafluoroarsenate monohydrate (LiAsF6), lithium perchlorate (LiClO4), lithium tetrafluoroborate (LiBF4), and lithium triflate (LiCF3SO3).
[…]
The reversible intercalation in graphite and intercalation into cathodic oxides was also already discovered in the 1970s by J.O. Besenhard at TU Munich. He also proposed the application as high energy density Lithium cells

Primary lithium batteries in which the anode is made from metallic lithium pose safety issues. As a result, lithium-ion batteries were developed in which both anode and cathode are made of a material containing lithium ions. In 1981, Bell Labs developed a workable graphite anode to provide an alternative to the lithium metal battery. Following cathode research performed by a team led by John Goodenough, in 1991 Sony released the first commercial lithium-ion battery. Their cells used layered oxide chemistry, specifically lithium cobalt oxide.

The article goes on to explore many variations possible on the chemistry. The only critical material in limited supply or with few options is the Lithium.

So about that “potassium” alternative:

http://en.wikipedia.org/wiki/Potassium-ion_battery

That wiki doesn’t say much. Here is the entire text of the body:

Potassium battery or potassium-ion battery was first invented by the American/Iranian chemist, Ali Eftekhari, in 2004 as an alternative to lithium-ion batteries. The battery uses Prussian blue as the cathode material for its stability, the prototype could be successfully used for millions of cycles. The prototype was made of KBF4 electrolyte though almost all common electrolyte salts of lithium batteries (their potassium salts) can be used for the construction of potassium battery. The potassium battery designed had some valuable advantages in comparison with similar lithium batteries: the cell design is simple, and both the material used and the procedure needed for the cell fabrication are cheaper. The chemical diffusion coefficient of K+ in the cell is higher than that of Li+ in lithium batteries, which is due to a smaller Stoke’s radius of K+ in electrolyte solution (solvated ions).

Since the electrochemical potential of K+ is identical to that of Li+, the cell potential is similar to that of lithium-ion. Potassium batteries can accept a wide range of cathode materials with excellent rechargeability, cheaper materials, etc. A noticeable advantage of potassium battery is the availability of Potassium graphite, which is used as an anode material in current Lithium-ion_battery. Its stable structure guarantees a reversible intercalation/de-intercalation of potassium ions during the charging/discharging process.

A potassium battery that uses molten electrolyte of KPF6 was patented.. China’s Starsway Electronics marketed the first potassium battery-powered PMP as a high energy device.

PMP is “portable media player”.

While I’ve not found a current vendor, and these folks look to have failed to beat Apple in the PMP market (even with a cheaper battery), once a chemistry is known, it tends not to be forgotten.

In Conclusion

I have no idea why we are not already seeing a flood of Potassium-Ion batteries onto the market. It looks to me like the chemistry is well understood and there does not look to be any significant manufacturing hurdle. All I can figure is that it takes a long time to go from ‘just invented’ to ‘in your hand’ and it’s “in process” somewhere. Either that, or the Lithium Industry is slowing it down with the usual tricks of patent suits, buying up companies and shelving them, committing merger, or price predation. (It is also possible they are just not willing to pay the royalties asked by the inventor and are inventing other chemistries to bypass his patents or just waiting out the patent clock.)

What is very clear, though, is that the “self life” of Lithium is far more limited that I’d originally expected, the alternatives are clearly in existence and cheap, and that any Socialist Utopia built on the sands of Lithium will be rapidly eroded by a Potassium salt flood…

Or, perhaps, a sodium ion flood…

http://en.wikipedia.org/wiki/Sodium-ion_battery

Sodium-ion batteries are a type of reusable battery that uses sodium-ions as a way to store power in a compact system. This type of battery is still in a developmental phase but is forecasted to be a cheaper, more durable way to store energy than commonly used lithium-ion batteries. Unlike sodium-sulfur batteries, sodium ion batteries can be made portable and are able to work at room temperature (approx. 25˚C).
[…]
A sodium ion battery stores energy in chemical bonds in its cathode. When the battery is charging Na+ ions intercolate or migrate towards the interior of the battery where the cathode is.

(I think the wiki writer needs to learn that it’s “intercalate” not “intercolate” ;-)

But they still have a bit of work to do to make the “millions of cycles” of the potassium cell:

A normal sodium cell voltage is 3.6 volts and is able to maintain 115 mA·hr g-1 after 50 cycles. Which means the battery approximately has a storage capacity of 400 W·hr kg-1 Yet, sodium-ion batteries are still unable to maintain a strong charge after repeated charge and discharge. After 50 cycles most sodium-ion batteries tend to store about 50% of original capacity. Researchers are now looking at different anode and cathode materials that will allow a sodium cell to maintain its original charge.

Na/NaxC6

In 1999, D.A. Stevens and J.R. Dahn were the first to test a new anode material made of carbons, (NaxC6). They found the average voltage on the low potential platau was higher on the Na cells compared to the Li cells. They also showed a glucose precursor can be used to make carbon meterials with a high reversable capacity.

NaV1−xCrxPO4F

This type of sodium-ion battery was tested by Haitao Zhuoa, Xianyou Wanga, Anping Tanga, Zhiming Liua, Sergio Gamboab and P.J. Sebastianb. They found that through the reaction:
NaF + (1−x)VPO4 + xCrPO4 → NaV1−xCrxPO4F
the introduction of the Cr helped the battery retain more energy through cycles of charge and discharge. The chart below (from their study) shows the differences between the battery with and without Cr.

The chart has one cell with a 91% capacity after 20 cycles. Quite livable for many uses.

Ov course, you could just replace lithium in half of the cell and still cut the demand dramatically:

Na2FePO4F

In 2007 researchers B. L. Ellis, W. R. M. Makahnouk, Y. Makimura, K. Toghill, and L. F. Nazar tested Na2FePO4F and Li2FePO4F cathode materials in rechargeable batteries along with a mixture of the two cathode materials. They found the sodium iron phosphate cathode easily replaces a lithium iron phosphate in a Li cell. The combined lithium-ion and sodium-ion make up would lower the overall price of the battery.

Ah, “scarcity” going down in flames… Love the smell of “resource substitution” in the morning…

LIT LIthium ETF / Miners fund

I think it’s time for cup of coffee #2… or maybe I’ll have tea this time ;-)

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