We Could Use A Moore's Law For Rechargeable Battery Life

Well this is just cool...

Forgetful Scientists Accidentally Quadruple Lithium-Ion Battery Lifespan

Battery technology goes through periodic bouts of breakthroughs followed by long, long, periods of quiescence characterized by product development.

I like the article's focus on chemical elements -- lithium and aluminum.

I found this article while googling tips to conserve lithium-ion battery life.

Seek and ye shall find.

Putting the "Up" in 7-Up

Slenderizing..lithiated...dispels hangovers...takes the 'ouch' out of grouch...

Lithium put the "up" in old 7up

Remember these?

Time For Cocktails: The Vesper

"A dry martini," [Bond] said. "One. In a deep champagne goblet." 

"Oui, monsieur."

"Just a moment. Three measures of Gordon's, one of vodka, half a measure of Kina Lillet.* Shake it very well until it's ice-cold, then add a large thin slice of lemon peel. Got it?"

"Certainly, monsieur." The barman seemed pleased with the idea.

"Gosh, that's certainly a drink," said Leiter.

Bond laughed. 'When I'm...er...concentrating,' he explained, "I never have more than one drink before dinner. But I do like that one to be large and very strong and very cold and very well-made. I hate small portions of anything, particularly when they taste bad. This drink's my own invention. I'm going to patent it when I can think of a good name."

—Ian Fleming, Casino Royale (1953)

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*Kina Lillet used to contain quinine, a muscle relaxant. Kinda like how Coca-Cola used to contain cocaine, and 7-Up contained lithium citrate.

Electrons Have Consequences

The valence electrons of lithium and beryllium metal are spherically shaped and easily lost. Once lost, the remaining two electrons revert back to being helium-like electrons except that the kernel, being laden with more charge than helium, sucks in the remaining two even closer. This explains the extremely small sizes of both Li⁺ and Be²⁺ and ultimately why lithium is such an effective battery material and why even tinier beryllium is found in many brilliant gemstones.

Things change dramatically when we move on to boron, a favorite element of mine. The electrons actually reach out further and take shapes.

Can Lithium Help Detroit?

Bolivian Lithium

Back to chemblogging for a bit.  Hmmm, let's see...I left off quite a while ago with lithium, helium, and hydrogen. I'll finish off lithium before moving onto beryllium, the fourth element.

Lithium Pharmacology
Lithium (or more accurately Li⁺) is pharmacologically active and is used to treat bipolar disorder. It's not at all clear to me (nor to Wiki) how this works.  Let's improvise. Here's my armchair analysis:
Observations: (1) In the body, Li⁺ is awash with lots of similar cations, namely, sodium (Na⁺) and potassium (K⁺). Moreover, there's realistically no way that one could swamp the body with so much Li⁺ that it would simply displace Na⁺ and K⁺; moreover, both sodium and potassium are essential and we'd die without them. Better to look for something that Li⁺ does better than Na⁺ and K⁺ do.
(2) Lithium is found in nature as lithium carbonate (in nature, elements tend to be found with other elements for which they have natural affinity). There is also experimental evidence that Li⁺ binds better to carboxylate groups, –CO₂^(-) than do either Na⁺ or K⁺:  ref.  In other words, Li⁺ has a higher affinity for the carboxylate functional group¹ and could displace a greater concentration of Na⁺ and K⁺. The pharmacists already know about this special affinity and Li⁺ is commonly formulated as lithium citrate:

Notice that the citrate has three carboxylate groups. Lithium citrate was once an ingredient in 7-Up, the Uncola, but was removed in 1950. It's important to realize that once in the body, the citrate part is easily chewed up and metabolized, leaving three Li⁺ cations, each in search of a carboxylate. 
(3) Carboxylates are ubiquitous, being the terminal side chain of common amino acids aspartic acid and glutamic acid.
(4) Glutamate is implicated in all kinds of neurochemical functions.

Hypothesis: Li⁺ displaces Na⁺ to such an extent as to affect the role of glutamate. The carboxylate functional groups are intimately involved in how neurotransmissions occur.  Essentially what lithium does is to monkey wrench this somehow. Anyway, it's just food for thought. Prove it wrong. A cursory Google search suggests there is something to this: ref, ref, and ref.

There are other proposed mechanisms of action for lithium and, if interested, check out the Wiki page here.  I love ill-defined chemical mechanisms, especially when an element is involved.  I'll return to this theme when I consider the essential role of boron (element 5, after beryllium) in plants. Meanwhile, I hope a lithium expert finds this blogpost and jumps in to correct me. I will retract the hypothesis.

Lithium Ion Batteries
Lithium ion batteries power lots of everyday electronic gadgets like cellphones, laptops and other electronic gadgets and, hopefully soon, lots of electric cars. Several generations of rechargeable batteries include lead-acid, nickel-cadium, nickel-metal hydride (NMH), lithium, and now lithium ion. By far and away the lithium ion battery is superior--enough to revolutionize the small gadget industry. Why is that?
First, it's very light. Lead-acid (think 12 V car batteries) and NMH batteries (think Prius batteries) are very heavy. Old fashioned carbon-zinc batteries are light but are not rechargable). Weight is very counterproductive deadweight when you're trying to move something around.
Second, lithium has a relatively high redox potential² for conversion of Li⁺ to lithium metal. Early lithium batteries did in fact use lithium metal and lithium ions, however it was quickly realized that the dangers of using lithium metal could not be overcome.  Lithium is a highly electropositive element and would seem well suited for 3 V applications. If you consider that the nominal voltage of common batteries: viz., AA, AAA, C, and D is, 1.5 V you'll realize that a 3.0 V battery would be useful, given that 3 V is commonly acheived by using two 1.5 V batteries in series. (This is why so many devices use two such batteries head to tail).
Lithium’s exceptional light weight is currently wasted in present generation batteries, especially automobile-sized ones: the battery train for the Chevy Volt weighs about 600 lbs. Much of this weight is due to cobalt oxide present. However, next generation breathing batteries intend to do away with the relatively heavy cobalt or iron-based components. I really hope the Volt does well and I suspect it will. Detroit needs a home run like the Toyota Pruis. I think the Volt is especially suited for the urban coastal hipsters. Me? I'll stick with diesel for the time being.

Lithium in Synthetic Organic Chemistry

The wonderful and unique properties of lithium just go on and on. A single inorganic compound, LiAlH₄ or LAH in the parlance, enabled the synthesis of entirely new classes of compounds, including pharmaceuticals. Organolithiums are a class of compounds wherein lithium replaces a hydrogen atom.  They are useful because they allow carbon in a hydrocarbon to behave as a negatively charged anion-a carbanion. Carbon normally engages in chemical reactions as an electrophile, i.e., having a tendency to attract negatively charged coupling partners. An obvious example of this is peptide synthesis in which donor nitrogen meets acceptor carbon.
Alkali metals, Li, Na, potassium, etc. dissolve in liquid ammonia to give intense blue solutions. Liquid ammonia itself is colorless, and so are solutions of Li⁺.  The blue color comes from solvated electrons:
              Na   --------> Na⁺ [e^–]
                        NH₃
The compound is called sodium electride.  You can watch it form here

Worries About Lithium Supplies
Worries about Bolivia becoming the Saudi Arabia of lithium are overblown. First of all, the photos (see above) are deceptive: those miles and miles of white salt flats are not heaps of lithium salt: it’s mainly just dried up sodium chloride. The salts are enriched in lithium carbonates. Unlike fossil fuels, the lithium inside batteries is not destructively consumed. Lithium is not a source of energy: remember that the energy has to put back inside the batteries. We have ample domestic sources for the time being from the brines of Searles Lake, CA and in Nevada.

Last but not least, don't forget the dilithium crystals!
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¹Functional Group defined
² Redox Potential is term of art and usually refers to chemical element's potential to gain or lose an electron. In lithium, there is a high propensity for the metal to lose one electron and thus obtain the noble gas electronic configuration of helium.

Lithium: Part 2/3

Link

(bummer about the link)

Lithium (1/3)

The other day at Costco I noticed one of those bilingual signs: “Batteries/Piles.” The Spanish word pila echoes the historical origin of batteries (cf. the obvious name from the photo above). In the year 1800, Alessandro Volta (the guy the Chevy Volt is indirectly named after) invented what became known as the voltaic pile, thus enabling the first systematic studies of how electricity interacts with matter.

Sir Humphry Davy seized upon the idea of electrolyzing dry molten salts and metal oxides with voltaic pile electrodes (the two wire thingies in the photo above). Davy prepared several elements for the first time, producing blobs of highly reactive metals at one wire when he electrolyzed molten natrium and kalium salts. Davy gave the new metals “ium” names derived from their material origins: sodium from caustic soda and potassium from potash. Davy was so persuasive, and his demonstrations so dramatic, that he successfully renamed the elements: natrium became sodium and kalium became potassium. Today, only the Germans use the older names, though they do survive in the modern chemical symbols, Na and K.

Lithium was discovered in mineral ore samples in 1817. Its discover, J. A. Arfvedson, thought it appropriate to name the new element after the Greek word lithos = stone [cf. lithosphere], to distinguish it from the chemically similar elements sodium and potassium, both of which had been first found in sea and land plant ashes. A year later Sir Humphry prep'd lithium metal by electrolyzing molten lithium oxide.

Metallic lithium is the lightest of metals, so light that it floats on oil; it would float on water too if it didn’t spontaneously react and produce combustible hydrogen gas: see link. The brilliant red color briefly seen in that video comes from gaseous lithium atoms “cooling” in the outer reaches of the flame by giving up red photons. Today lithium salts are used in pyrotechnics to give brilliant red colors.

Lithium sits near the extreme upper left corner of the Periodic Table, directly beneath hydrogen.* Lithium follows helium in sequential order, but the two elements couldn’t be more different. Explaining why helium and the other noble gases are so chemically stable requires a plunge into quantum mechanics (at least at the level of an elementary text book); suffice it to say that when moving from helium to lithium, the third electron that elemental lithium requires cannot share the same space as its first two electrons and must be held at a greater distance, i.e., be more weakly bound. The third electron is said to be a valence electron. The concept of valency comes from a Latin word meaning "combining power of an element" and refers to an element’s ability to gain, lose or share electrons.

Lithium doffs its third electron with ease, becoming lithium ion (Li⁺) and by so doing regains the magic electronic configuration of helium. By analogy, Na⁺ has the magic noble gas configuration of neon, and K⁺ has the noble gas configuration of argon.

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*Hydrogen is not an alkali metal however it is classed in Group I, the western edge of the Periodic Table. Hydrogen shares some chemical properties with lithium and the other alkali metals, namely the oxidation state of +1. On the other hand, hydrogen also can also be a hydride, having pseudo-halide properties.