BOTTLED LIGHTING (COMPLETE)

Fletcher, Seth.  Bottled Lightning: Superbatteries, Electric Cars, and the New Lithium Economy.  New York: Farrar, Straus and Giroux, 2011.

This book is 273 pages in length (paperback version published by Hill and Wang, a division of Farrar, Strauss, and Giroux). 

Although I would have preferred a most recently published book on batteries, I could not find one that appears to give as much detail as this, although the focus is on the most commonly used battery type.  I decided to settle on this book because, even though it is 4 years old, its focus, lithium batteries, still dominates the energy storage field from smartphones to Tesla electric cars.

The author is a non-chemist but I did look at the bibliography and scanned through the chapters and noted that he based his information on reputable books and peer-reviewed journal articles.  After a quick review scan of the chapters, I did see some level of detail in the chemistry discussion and it gives me hope that this will be an informative book for me and my search for a more detailed understanding of battery technology.

Seth Fletcher is a science writer and senior editor at Scientific American. http://www.scientificamerican.com/pressroom/expert-directory/

CHAPTER 1: THE ELECTRICIANS

In this chapter, the author gives a brief but detailed history of the discovery of electricity and the battery. There was period in the history of the United States when it looked like the electric car would come out to be a dominant player in transportation.  The long time it took to come up with a better battery and the ease with which the gasoline engine became a more viable option ended the prospect of electric cars coming into the market.  While improving upon his battery designed for cars, adding a lithium compound to the electrolyte was one of Edison’s solution to his first failed attempt.  While this is not how lithium is used in so-called lithium batteries, the author used this as a starting off point to discuss lithium, its discovery, subsequent various uses, and its evolution into one of the most powerful elements to lead to increased energy density in today’s batteries.

·         First documented observation of electricity is by Thales the Greek philosopher who rubbed amber with cloth (elektron is the Greek word for amber) and observed feathers being attracted to it.

·         It was not until the beginning of the 17^thcentury that the term electricity (from elektron) was coined by William Gilbert who observed that many materials can be “electrified” by friction.

·         In the 1740’s, the Leyden jar was invented: a series of metals inside a jar immersed in some kind of electrolyte that acted like a capacitor, something that stores charge.

·         Galvani observed what he attributed to electricity in the twitching of a dissected frog’s legs upon contact with a scalpel.  Volta countered this with his own observation of metals contacting each other producing electricity. The two began a long-distance debate on the basis of this electrical phenomenon.

·         In 1800, Volta reported constructing a device consisting of zinc-copper metal sandwiches immersed in brine that produced electricity. The term battery came from connecting a “battery” of Leyden jars connected in series.

·         When this proved to be successful, bigger batteries were created to carry out all kinds of tests resulting in scientific discoveries: splitting of water into hydrogen and oxygen, breakdown minerals into newly discovered elements of potassium, magnesium, etc, electromagnetism, e.g.

·         By the beginning of the 20^th century, lead-acid batteries were being used to “power the telegraph, manage the load in the electrical-lighting substations, and support electric streetcar networks”.

·         In 1898, Thomas Edison began earnest research into a new type of battery that would replace the rechargeable lead-acid batteries commonly used. He believed that an alkaline type would be lighter and more long-lived. In 1904, Edison launched a nickel-iron battery using a potassium alkaline electrolyte that have better properties than the lead-acid batteries:  14 watt-hours per pound and 233 percent “better”.  Soon after, however, leaking and reduced capacities drove Edison to recall his batteries.  The prospect of electric cars followed suit as gasoline engines steadily improved and gasoline cars became more affordable. Edison and his co-workers continued to solve the leaking and capacity reduction problems and in 1909 came out with a much-improved second generation A cell battery.  Just around this time, however, the invention of an automatic starter for gasoline engines essentially wiped out any potential for the electric cars.  The batteries, instead of running cars, became support energy sources for gasoline engines.  Edison’s new battery saw use in running lamps and signals, telegraphy, and submarines but not electric cars.

·         The two improvements that saved Edison’s battery were: the addition of nickel flake to the electrode and lithium hydroxide to the electrolyte.

·         On lithium: as a metal, half the density of water, soft, very reactive with air and water.  The author uses the term “volatile”.  I think he means reactive.

·         Berzelius is credited for having discovered lithium in 1817.  Lithium is from the Greek word lithos meaning “stone”.

·         Lithium salts are now used commonly to treat mental illness, prescribed as mood-stabilizing drugs such as Eskalith, Lithobid, Lithonate, and Lithotabs. It affects neurotransmitters and cell signaling, and is known to increase the production of serotonin.

·         Of the 120,000 metric tons of lithium compounds mined each year, most go to metal alloys, ceramics, and lubricating greases.  In addition its pharmaceutical use, other minor uses of lithium are in compounds that absorb CO₂ in spacecrafts and other vessels, as rocket propellant, and in certain types of thermonuclear reactors.  And, of course, the subject of this book, in batteries.

·         An idea device for storing electricity is the smallest and lightest possible that can provide the largest stream of electrons. In lead-acid batteries, each electron comes from a heavy atom, lead, with an atomic weight of 207.  In lithium batteries, an electron can be squeezed out of a much smaller atom of lithium with an atomic weight of 7.

·         In addition, lithium’s reactivity and willingness to give up an electron means produces batteries that are high in energy density.

·         In 2010, Bill Gates noted that all the batteries in the world can store only 10 minutes of the global energy need.

·         The author has the following to say about the advantages of using electricity to run vehicles: "Mile by mile, it’s cheap compared with gasoline. It’s far more feasible than hydrogen, and in almost all circumstances it’s cleaner than ethanol.  It can come from almost any source – natural, gas, coal, nuclear, hydroelectric, solar, wind.  Even when it is generated by a coal-burning plant, it still produces less carbon dioxide per mile than a mile of gasoline.”

CHAPTER 2: FALSE START

We have only two modes— complacency and panic. —James R. Schlesinger, first U.S. secretary of energy

Fletcher, Seth (2011-05-10). Bottled Lightning: Superbatteries, Electric Cars, and the New Lithium Economy (p. 22). Farrar, Straus and Giroux. Kindle Edition.

In this chapter, the author tells the story of the revival of strong interest in electric cars due to increased air pollution reaching a crisis level and an international oil emergency and mismanagement that caused oil shortages in the late 1960’s to early 1970’s. These intersections of events catalyzed research in electric car batteries and, after 1973, Exxon was able to demonstrate a prototype of the first rechargeable lithium battery in a Society of Automotive Engineers conference. After 1973, Exxon was able to demonstrate a prototype of the first rechargeable lithium battery in a Society of Automotive Engineers conference.  After a few more attempts at trying other chemical material, in 1976, Whittingham published a paper in science on a LiTiS₂battery. The momentum continued as the world continues to have unreliable and affordable sources of petroleum. In 1973, the Arab Oil embargo began. In a Forbes magazine article, there were speculations of Exxon’s possible demise as there were indications of oil running out: “Unless the presently unexpected occurs, the world’s petroleum reserves are within a few years of their peak and will begin a slow decline to the point where oil and gas will be too valuable to use as energy”. In 1976 (during Ford’s presidency), Congress passed the Electric and Hybrid Vehicle Research, Development, and Demonstration Act, aimed to stimulate research, development, and production of alternatives to gasoline engines. Exxon marketed the first widespread use of lithium batteries for solar digital watches.  These lithium cells had a major advantage over nickel-cadmium batteries that bled energy away quickly and silver-zinc batteries that died after only 20-25 recharges. Exxon continued to invest in electrical devices, purchasing a company that made electric motors. GM got in the game as well building an electric car in 1979 while Exxon built a prototype hybrid car. But, the electric car industry never took off and interest in alternative fuels plummeted due to the following reasons: recession in 1979-1980 brought unprofitable ventures in to solar panels and batteries to a halt; by 1986, oil was again below $15 a barrel and supplies were steady as governments and oil companies ramped up their search for cheaply extracted oil reserves in the preceding years finding them in Alaska, the North Sea, and Mexico; and conservation measures mandated by the American Corporate Average Fuel Economy set average mpg at 27.5 saving 2 million barrels of oil a day between 1975 and 1985.  Reagan introduced further cutbacks in renewable energy programs when he came into office.  In the end, the best battery developed during that “false start era” could only store 30-35 watt-hours/kg, 500 times less energy density than gasoline. The following statement summed up how companies responded to this new era of oil abundance with respect to the development of batteries and other alternatives: “The key to the feasibility of advanced batteries of all types is the price and supply of oil”.

·         Increasing air pollution that, in the extreme case, forced residents to wear nose masks indoors in LA, only 4 decades after the availability of the gasoline car drove the state of California to create laws to decrease the amount of air pollution created by cars.  It mandated that any new car manufactured should be built with a system that redirects any unburned fuel back to the engine for combustion instead of to the tailpipe as part of the exhaust.

·         Anti-gasoline car sentiments grew and politicians were driven to pass the Clean Air Act of 1970.

·         Around this time, the oil geopolitical crisis in the Middle East also started and international dispute and mismanagement caused an oil shortage that caused 1/5 of the gasoline stations in the US to run out of gasoline.

·         Although there were strong sentiments to revive electric cars, no battery technology existed at that time to replace the versatility and efficiency of the gasoline engine.  The electric car technology was behind gasoline technology 60 years by this time.

·         During that time, current research on the solid state ion movements had promising ideas for a new battery design.  The current design of lead acid batteries had reactions taking place only on the electrode surface in contact with the electrolyte leaving the core metal unused.  Therefore, much greater capacities can be attained if these reactions that produce electrons can take place in a three-dimensional volume.  (Robert Huggins’s and group at Stanford.)

·         In Ford in 1967, researchers have come out with a reversed battery design in which the electrodes are liquid (molten sodium and sulfur, heated at 300 C) separated by a solid ceramic electrolyte.  The ceramic was a form of aluminum oxide called beta-alumina that allowed ions to diffuse but not electrons.

·         By 1972, a conference was held on the very narrow topic of applications of solid state chemistry to battery design where participants wondered about and discussed exotic but theoretically possible pairings of elements for new batteries: sulfur-sodium, lithium-sulfur, magnesium-oxygen, zinc-air, aluminum-air, lithium-copper fluoride, etc.  At the same time, American car companies Ford, GM, Chrysler, and American Motors, Toyota, and German car companies were all working on electric cars.

·         In addition to the Belgirate conference group, Argonne National Lab, Bell Labs, Electric Power Institute, Dow Chemical, and General Electric were putting in their share of chemical research into batteries. Even Exxon got into it.

·         Whittingham at Exxon came up with a battery design with a theoretical energy density of 480 watt-hours per kilogram, more than twice what was generally thought necessary to run an electric car.  It uses titanium disulfide and lithium as the negative electrode (he first experimented with tantalum disulfide and realized this was too heavy to be viable car batteries).  At this point, Japan had already introduced the use of lithium in non-rechargeable batteries for lamps used by fishermen.

·         Exxon put in the money to build a prototype.  The step was to determine what suitable electrolyte to use:

o   Extremely low freezing point, -30 C

o   Not an electrical conductor but allow ions to flow through but not electrons

o   Able to dissolve salts that contain the right ions needed for the electrochemical reaction

·         After 1973, Exxon was able to demonstrate a prototype of the first rechargeable lithium battery in a Society of Automotive Engineers conference.  After a few more attempts at trying other chemical material, in 1976, Whittingham published a paper in science on a LiTiS₂ battery.

·         In 1976 (during Ford’s presidency), Congress passed the Electric and Hybrid Vehicle Research, Development, and Demonstration Act, aimed to stimulate research, development, and production of alternatives to gasoline engines.

·         In 1973, the Arab Oil embargo began. In a Forbes magazine article, there were speculations of Exxon’s possible demise as there were indications of oil running out: “Unless the presently unexpected occurs, the world’s petroleum reserves are within a few years of their peak and will begin a slow decline to the point where oil and gas will be too valuable to use as energy”.

·         The first ever rechargeable lithium battery to be sold in the market were button-size cells for watches.  The first widespread use of lithium batteries were for solar digital watches in which they were recharged by solar cells.   These lithium cells had a major advantage over nickel-cadmium batteries that bled energy away quickly and silver-zinc batteries that can died after only 20-25 recharges.

·         Exxon continued to invest in electrical devices, purchasing a company that made electric motors because as Exxon’s chairman said in July 1979, “We’re not finding as much oil as the world is using…in the long term, I’d say that you don’t ignore any source of energy. We can’t go back to the complacency of two years ago”.  The author notes that “Exxon had no desire to build electric cars itself, (Garvin) said, but through Reliance, he hoped to supply the motors, and through the Battery Division, the power”.

·         GM got in the game as well building an electric car in 1979 while Exxon built a prototype hybrid car.

·         But, the electric car industry never took off and interest in alternative fuels plummeted:

o   Recession in 1979-1980 brought unprofitable ventures in to solar panels and batteries to a halt

o   By 1986, oil was again below $15 a barrel and supplies were steady as governments and oil companies ramped up their search for cheaply extracted oil reserves in the preceding years finding them in Alaska, the North Sea, and Mexico.

o   Conservation measures mandated by the American Corporate Average Fuel Economy set average mpg at 27.5 saving 2 million barrels of oil a day between 1975 and 1985

o   “Reagan came in and cut back energy efficiency and renewable energy program by something like eighty percent”.

·         In the end, the best battery could only store 30-35 watt-hours/kg, 500 times less energy density than gasoline. The following statement summed up how companies responded to this new era of oil abundance with respect to the development of batteries and other alternatives: “The key to the feasibility of advanced batteries of all types is the price and supply of oil”.

CHAPTER 3: THE WIRELESS REVOLUTION

In this chapter, the author traces the development of wireless devices, ones that would later on become the major consumer of rechargeable lithium ion batteries.  Parallel to this is an account of the work done by the scientist Goodenough in developing the technology for the three major strains of lithium batteries in use today.  Aside from the invention and the eventual market debut of the wireless phone, a mini-electronic gadget explosion in Japan also provided the market motivation to develop better batteries with less toxic materials.  Pollution and accidental ingestion of batteries had reached a crisis point in Japan at that point due to their massive use of ever-smaller batteries.  Despite an initial partnership with Union Carbide to develop lithium battery technology, Sony eventually became the main owner and developer after the Bhopal accident led to the demise of Union Carbide.  In the late 1980’s, Sony came out with the newly developed lithium-ion battery that carried a 3.6 voltage (3 times that of NiCad and NiMH) and therefore a higher energy capacity, extraordinary recharging capability, and not subject to the memory effect that causes batteries recharged before they are dead to lose energy capacity.  Interspersed in the Sony success is the story of the failed lithium batteries developed and manufactured by Moli using a molybdenum lithium disulfide material.  This battery required metallic lithium.  Several fire accidents caused the company to lose its business which was sold to a Japanese company. Meanwhile, the cell phone industry flourished and was soon in need of a battery “with longer life and less weight”.  Battery size needed to keep up with the rapid miniaturization taking place with electronic gadgets as smaller processors are invented. In 1992, Sony came out with a lithium ion battery that was 30 percent smaller and 35 percent letter than then leading NiCad battery.  Its storage capacity was 90 watt hours per kilogram; triple that of lead-acid, nearly double that of NiCad, and 10-20 percent better than NiMH. At the same time, cell phone use continued to proliferate as it becomes smaller and lighter in size.  In 1993, 13 million cell phones have been sold in the US and the price was 25 percent cheaper than the year before.  In 1994, Motorola released the first cell phone run by a lithium ion battery, weighing a mere 3.9 pounds, lighter than a D-cell.  Sadly, Goodenough never got any monetary rewards for the work he did on lithium battery technology.  Further miniaturization occurred with the invention of the 3-volt RF amplifier allowed even smaller cell phones that now only require 1 lithium ion battery.  By 1998, there were more than 240 million cell phone subscribers.  By 1999, the cell phone began its evolution into a smart phone.  By 2002, 95% of cell phones were using lithium ion batteries, which the Economist called the “foot-soldiers of the digital revolution”.

·         In 1947, two Bell Labs scientists (Ringer and Young) were working on the development of a cell phone, one that is based wirelessly on a series of radio transmitters distributed over a large geographical are to provide cells of radio coverage.  By 1973, Motorola had developed the first mobile phone.

·         Goodenough would develop the three major strains of lithium cells used today.  Goodenough’s work on the lithium battery started with replacing the sulfide in Whittingham’s design with an oxide because he knew he can get more voltage out of it.  Tests on several variations of LiMO₂ (where M= transition element) resulted in a lithium cobalt oxide cathode which allowed removal of as much as half the lithium and still have a stable substance with a voltage of 4 volts, higher than Whittingham’s 2.4 volts. In addition, instead of building the battery fully charged, the battery was constructed in the discharged state allowing use of compounds that are stable at ambient conditions (obviating special lab conditions such as a dry room or an argon chamber). In 1980, Goodenough published his results on the lithium cobalt oxide type.

·         Despite this, there was no movement partly due to the federal government taking about a decade to decide on regulations of frequencies companies can use to carry calls. 

·         Outside the US, however, in the early 80’s, cell phone towers were going up in Japan, Bahrain, Saudi Arabia, Mexico, and the Scandinavian countries.

·         In October 1983, the first US cellular network was launched, using the Bell Labs vision of distributed low-power cell towers to carry the signals with a phone assigned a new frequency as it moved to the next “cell” region. In 1984, the first handheld mobile phone went on sale.

·         During this time, a mini-electronic gadget craze in Japan has fueled a battery pollution crisis and ingestion health hazard due to ever-smaller batteries being used. This provided an impetus to develop better batteries that have less toxic materials.  In the US, however, there was no strong response and new battery development remained largely unmotivated and Goodenough’s new lithium batteries did not find any takers.  The focus was on semi-conductor instead, ceding the R & D on lithium battery technology to Japanese companies.

·         Although a partnership eventually developed between Japans Sony Corp and Union Carbide, the Bhopal Disaster (release of methyl isocyanate that killed thousands) led to the dismantling of Union Carbide.  Sony bought all of the lithium battery technology and decades of publications by Whittingham, Goodenough and others.  In the late 1980’s, the Sony team came up with a safe and cheap lithium battery for commercial production and sale.  It uses a carbon anode and a cobalt oxide cathode and the following reaction:

o   LiC₆ + CoO₂ àC₆ + LiCoO₂.

o   P = IV, V = 3.6 volts; the higher voltage allows greater power at the same current

o   This represented a major jump in voltage and doubling of energy capacity.

o   As a comparison, it took 6 of a nickel-cadmium 1.2 V batteries connected in series to provide the 7 volts needed to run a mobile phone. It would only take two of the new lithium batteries.

o   Sony’s lithium battery lasts longer too because it is “extraordinarily” rechargeable.

o   Did not suffer from “memory effect” like the NiCad and NiMH that causes loss of energy capacity if recharged before completely dead.

o   Sony named these batteries lithium ion batteries.

·         Interspersed in the Sony success is the story of the failed lithium batteries developed and manufactured by Moli using a molybdenum lithium disulfide material.  This battery required metallic lithium.  Several fire accidents caused the company to lose its business which was sold to a Japanese company.

·         Meanwhile, the cell phone industry flourished and was soon in need of a battery “with longer life and less weight”.  Battery size needed to keep up with the rapid miniaturization taking place with electronic gadgets as smaller processors are invented.

·         In 1992, Sony came out with a lithium ion battery that was 30 percent smaller and 35 percent letter than then leading NiCad battery.  Its storage capacity was 90 watt hours per kilogram; triple that of lead-acid, nearly double that of NiCad, and 10-20 percent better than NiMH.

·         In 1993, 13 million cell phones have been sold in the US and the price was 25 percent cheaper than the year before.  In 1994, Motorola released the first cell phone run by a lithium ion battery, weighing a mere 3.9 pounds, lighter than a D-cell.

·         In a side note, Goodenough never got any monetary rewards for the work he did on lithium battery technology.

·         By the late 1990’s, the invention of the 3-volt RF amplifier allowed even smaller cell phones that now only require 1 lithium ion battery.

·         By 1998, there were more than 240 million cell phone subscribers.  By 1999, the cell phone began its evolution into a smart phone.

·         By 2002, 95% of cell phones were using lithium ion batteries, which the Economist called the “foot-soldiers of the digital revolution”.

CHAPTER 4: REVIVING THE ELECTRIC CAR

In this chapter, the author starts off by telling a brief story of the Tesla Company that now builds electric cars “that compete on performance rather than price”. One of the founders, Eberhard, used money from the sale of his company to put together a group of people that would build the “hottest” electric car around.  In 2003, Tesla Motors was incorporated. Eberhard had lithium ion batteries in mind even at the start. Their battery pack design consisted of 6,831 laptop batteries.  One of the things they had to deal with was a thermal runaway problem associated with lithium ion cells.  In one test, they watched a pack of lithium ion cells catch fire and turn into an inferno after deliberately overheating it. In July 2006, Eberhard et al went public and showed the Tesla Roadster.  Meanwhile, over at GM, Bob Lutz was steaming with frustration as he watched the launch of the Tesla and the popularity of the Prius rise while his ideas of a GM electric car were held back by lack of enthusiastic support from the company. To Lutz” Nothing less than an electrically driven car would appease these critics. Lutz’s argument was, “Whether we like it or not, there are the environmentally conscious people, the government people in California, the car people— everybody seems to believe that the electric vehicle is the answer. And with the advent of lithium-ion batteries, I think that we’re getting to the point where it is feasible.”” In 2007, GM finally came out with the Chevy Volt with much positive press.  “Lutz described the drivetrain and the specifications. Forty miles on lithium-ion batteries alone. If you’re one of the 78 percent of Americans who live within twenty miles of work, and you charge the car every night, “You will never need to buy gasoline during the entire life of the vehicle,” he said, and that line drew enthusiastic applause. “And you would save five hundred gallons of gasoline and eliminate 4.4 metric tons of carbon dioxide a year from the tailpipe.” If you drive sixty miles a day, you’ll get the equivalent of 150 mpg, he said. Use E85 and you’ll get more than five hundred miles per equivalent petroleum gallon.”

CHAPTER 5: THE BLANK SPOT AT THE HEART OF THE CAR

In this chapter, the author gives an account of the historical struggles of the electric cars due to various social, cultural, economical, and infrastructure issues, starting back in the late 19th century.  In the number of false starts described by the author, however, a common denominator was the limitations imposed by the battery system, referred to by the author as "the blank spot at the heart of the car".  When the concept of an electric car was first introduced, electricity was still a mysterious phenomenon for most people.  But, in the late 19th century and early 20th century, what eventually killed any prospects for the electric car is the development of gas powered engines.  Electric cars were plagued with limited range, charging, and battery maintenance issues that made it easy for the gasoline engine to take it over as the engine of choice.

In the 1950's and 1960's, increasing pollution problems from gasoline combustion stimulated some interest again in developing electric cars.  A few electric car prototypes came out of Detroit in 1966 but even the oil crisis of the 1970's did not result in the further development of electric cars.  In the 1990's, the California Air Resources Board issued a mandate for 2% of all cars sold in CA starting 1998 must be emission-free.  This created a short but doomed "boomlet" of electric car production by GM and its competitors.  A quote from the New York Times given by the author provides a cynical interpretation that GM was producing an electric car simply to prove the government wrong about its viability and marketability. The EV1 was produced and there was higher than expectation demand for a lease but eventually the state capitulated by postponing the deadline.  In the author's words, "But while GM was rolling in positive press as a result of the EV1, it was simultaneously lobbying the state of California to dismantle the CARB regulations. The company argued that this legislation was forcing a private enterprise to produce, at enormous."..."General Motors and DaimlerChrysler eventually succeeded in beating CARB  down. GM built the last EV1s in 1999; that generation used nickel- metal- hydride batteries and could run up to 150 miles on a charge." Eventually, GM recalled all the EV1's ever leased, hauled them out to the desert where they  were all crushed to death.

GM's next and latest attempt at an electric vehicle came several years later in its announcement of the new Chevy Volt electric car, a car cynically referred to by a New York Times op ed as truly a car of the future considering when the concept was released, there was not battery technology available to run it.  Even the Wall Street Journal was scathing in its criticism that GM simply wanted to appear fuzzier to further encourage government bailout.  Nevertheless, there were serious efforts to launch the Volt which started with a hunt and competition for the best batteries.  The final contenders in this search were CP1 and A123.  The specifications required by GM included: "Each supplier had to prove that its product could store 16 kilowatt- hours of energy, drive the Volt forty miles on electricity alone, launch the car from zero to sixty in eight seconds, run for at least ten years, withstand five thousand full discharges, lose no more than 10 percent of its charge capacity along the way, fit into the tunnel that houses a conventional car’s driveshaft, weigh no more than four hundred pounds, and cost as little as possible. And never, ever explode." The final battery pack for the first test cars consisted of 200 3.6 volt lithium ion cells packed in groups of three surrounded by a cooling liquid.  " A computerized monitoring system inside each battery pack conducted this little orchestra, coordinating the actions of the individual cells, balancing voltage, and watching, above all, for any indication that a cell might be failing, shorting out, or otherwise threatening the stability of the system. The batteries were engineered to propel the 3,520- pound Volt forty miles." This time, the atmosphere that the Volt was announced in portend a more motivated market for the electric car: gas was $4 a gallon, there was desperation among the American carmakers brought on by the recession, global warming was becoming a more serious public issue, and lastly, the blank at the center of the heart of the electric car has now been filled by a more improved lithium ion battery technology.

CHAPTER 6: THE LITHIUM WARS

In the late 1990’s, Goodenough’s group from UT and a Quebec company collaborated on studying and developing a type of battery which uses lithium iron phosphate.  Armand, representing the Quebec company who bought the rights from Goodenough and his post-doc, wanted to create a battery that makes use of cheap, ubiquitous metal like iron. They found that by synthesizing nanoparticles of the lithium iron phosphate gave it a dramatic boost in electric conductivity.  In addition, Armand’s group found a second key thing to make the material work even better: starting with the precursor material containing the iron, oxygen, and phosphorus, they then added a lithium compound which when burned, coated the nano particles with carbon.  This boosted the conductivity even higher.

A few years later, Yet-Ming Chiang’s started working on self-assembling batteries by working on the attractive and repulsive forces that will drive anode and cathode material so self-assemble. In one experiment, they doped various olivines (a group of materials of which lithium iron phosphate is a member).  They had some good results.  For example, when a graduate student doped lithium iron phosphate with niobium or zirconium atoms in just the right areas in the crystalline structure, there was a large increase in conductivity.  (“Doping – adding tiny, targeted dashes of impurities to a material in order to tweak its electronic structure and therefore change its behavior.”). In a paper published by Chiang and his group, they described the battery constructed from this material as having the ability to be completely discharged in three minutes and that this result would allow the design of a new lithium battery that has the highest power density yet. In an editorial that was mostly positive, however, it was pointed out that carbon contamination may have contributed significantly to the high conductivity observed (these were olivine powders synthesized from carbon-containing precursors).  Armand was not happy about this and carried out experiments to try to reproduce Chiang’s results.  In 2003, he published the following rebuttal in the journal Natural Materials, ““We suggest that the effects seen by Chung et al.”— Chiang’s student Sung-Yoon Chung was the first author on the paper—“ are due to carbon for low-temperature samples, and to low-valency iron derivatives … It is beyond, not the scope, but the length of this letter to discuss the juggling of point defect chemistry equations to justify the results … . Unambiguously, it is the polyolefin worn from jars, subsequently charred into carbon, which is responsible for the good use of the LiFePO4 electrode.”  He claimed that carbon from the jar lining was charred into the particles and that a metallic compound of iron, Fe₂P, had coated the particles, and that these two were what enabled the high conductivity observed and not the doping.  Chiang offered another rebuttal, noting that procedures by Armand were significantly different and that they have addressed the possible carbon contamination and showed that the increase in conductivity is not correlated with the amount of carbon.  In 2004, however, an independent academic group reproduced Chiang’s experiments and showed that the “The description of a highly electronically conductive phosphate challenges conventional wisdom”.  The back and forth among these three, with Armand’s company and the University of Texas joining in continued and reached the courts as Chiang continuously tried to rebut every accusation of misrepresentation of data.  These scientific back-and-forth discussions and rebuttal on the “scientific merit” as Nazar put it would continue on including a slew of court cases which involved patent disputes, many of them still ongoing at the time of writing.  Toward the end, the author gave a detailed account a series of company sales and changes of what used to be known as Hydro Quebec, causing Armand to lose control of two types of battery technologies he helped develop.  One of these eventual companies was Avestor who sold lithium metal polymer batteries to ATT for use in its U-Verse boxes.  Two of these exploded and some caught fire. Avestor went into bankruptcy.  One other company, Phostech Lithium, was unable to produce high-quality lithium iron phosphate to make batteries that people would buy.  This was run by Armand’s friend and Armand’s laboratory supported the research. Here is what Armand had to say after moving to France, “too disillusioned to work”: Batteries are the only hope for changing the fuels in transport. We know that the fuel cell won’t make it for years. So I mean everything is in the hands of the battery people”.  At the end of the chapter, Armand was also quoted as saying, “The number one property of lithium iron phosphate is that it is an excellent catalyst for human greed”.

CHAPTER 7: THE BRINK

The development of the Volt in late 2008 after the battery battle was resolved between the competing companies Compact Power and A123 continued with the CEO Rick Wagoner going to Washington twice to receive funding from the government.  At the second try, GM was granted an emergency loan and they used some of this to keep working on the Volt.  Two weeks later after providing demonstration drives to journalists, GM filed for bankruptcy.  Besides the battery problem, most of the further development work (from its original fist launch) went into improving the aerodynamics, down to the smallest tweaks to earn the Volt another quarter mile in range, spending 700 hours in the wind tunnel, twice the normal time.

Around the same time, Nissan was working on the first purely battery-powered electric car for mass marketing, the Leaf.  Its battery pack consists of a floorboard full of lithium manganese oxide batteries which turned out to be the same type of battery built by Compact Power for the Chevy Volt.

Several paragraphs of the chapter were devoted to mostly negative criticisms of the Volt in the media and by other automakers.  As the author notes, however, “the critiques were predictable because they always favored the technology in which the carmaker had invested the most money”. Some of these critiques targeted the battery technology in general with a Toyota person noting that plug-ins are still expensive and that the battery technology is not optimal yet. A Mercedez Benz person person simply trashed batteries as being environmentally disastrous in terms of their disposal and an Audi person hailed the diesel engine as the better alternative.  On the media front, the author gave an extensive transcript of Letterman shows in which Elon Musk of Tesla was the guest and in the other, Bob Lutz of GM.

By the 2010 international car show, GM’s Volt, an e6 car being marketed by a Chinese company, a BMW electric car, and a Tesla roadster were there to show off their latest electric car offerings.  A congressional delegation led by Nancy Pelosi was also there to get a close-up look at how the government investment in GM is going.

·         Story of the Volt: The development of the Volt in late 2008 after the battery battle was resolved between the competing companies Compact Power and A123 continued with the CEO Rick Wagoner going to Washington twice to receive funding from the government.  At the second try, GM was granted an emergency loan and they used some of this to keep working on the Volt.  Two weeks later after providing demonstration drives to journalists, GM filed for bankruptcy.  Besides the battery problem, most of the further development work (from its original fist launch) went into improving the aerodynamics, down to the smallest tweaks to earn the Volt another quarter mile in range, spending 700 hours in the wind tunnel, twice the normal time.

·         Around the same time, Nissan was working on the first purely battery-powered electric car for mass marketing, the Leaf.  Its battery pack consists of a floorboard full of lithium manganese oxide batteries which turned out to be the same type of battery built by Compact Power for the Chevy Volt.

·         Several paragraphs of the chapter were devoted to mostly negative criticisms of the Volt in the media and by other automakers.  As the author notes, however, “the critiques were predictable because they always favored the technology in which the carmaker had invested the most money”. Some of these critiques targeted the battery technology in general with a Toyota person noting that plug-ins are still expensive and that the battery technology is not optimal yet. A Mercedez Benz person simply trashed batteries as being environmentally disastrous in terms of their disposal and an Audi person hailed the diesel engine as the better alternative.  On the media front, the author gave an extensive transcript of Letterman shows in which Elon Musk of Tesla was the guest and in the other, Bob Lutz of GM.

·         By the 2010 international car show, GM’s Volt, an e6 car being marketed by a Chinese company, a BMW electric car, and a Tesla roadster were there to show off their latest electric car offerings.  A congressional delegation led by Nancy Pelosi was also there to get a close-up look at how the government investment in GM is going.

CHAPTER 8: THE STIMULUS

In this chapter, the author gives a brief history of the beginning of battery boom, funded partly by a US stimulus package of 2.4 billion dollars released in August of 2009 to help build the battery industry in the US.  The 5 US companies receiving the largest funding were Johnson Controls, A123, Dow Kokam, Compact Power, and Enerdel.  Even though Enerdel is an American company, its electrode powder was imported from China. The author gives the following example of the general procedure for producing lithium ion cells:  The electrode powder is blended with a clear liquid solvent, carbon black, and a chemical binder forming a slurry painted onto a long sheet of aluminum for the positive electrode and copper for the negative electrode.  The cured reels of electrode material are then cut up into rectangular portions, brushed and then vacuumed to remove any contaminant particles.  A separator is inserted between the positive and electrodes to prevent them from making contact.  This sandwich of electrodes and separators are then immersed in a liquid electrolyte inside plastic pouches that are then vacuum-sealed.  After a testing and aging process, the cells are wired into a battery pack and the cooling and heating mechanisms, voltage monitoring circuitry, and thermistors for detecting overheating are added. Several paragraphs were devoted to the authors meeting with Chiang, founder of A123 and involved in the lithium disputes of the early 2000, his short biography and the his foray into companies that developed superconductors and batteries based on academic research results on high-temperature superconductors and later to lithium ion batteries made possible by the Bayh-Dole Act which allowed universities to keep title of their own inventions and license them.  These companies were American Superconductor and, of course, A123.  A plant section of the A123 factory was dedicated to making, testing, and characterizing electrochemically active materials which are then packed into a battery for testing.  Unlike Enerdel which manufactures prismatic (rectangular) batteries, A123 packages their batteries into the typical and more familiar cylindrical cells.  In another assembly plant, the author was given a tour of the projects A123 was involved in at the time of writing: a lithium ion starter battery for a new “supercar”, the first and only FAA-approved lithium ion aircraft battery, and a 770 lb lithium ion battery that can produce 200 kilowatts of power on demand for use by buses.  The advantage of cylindrical cells over prismatic cells is that the winding process is cheaper than the cut and stack process.  Prismatic cells, however, have the advantage of allowing more surface area accessible to the cooling material.

The author provided a chronicle and list of Japanese, Korean, and Chinese players in the battery manufacturing field even before the US stimulus funding to US battery manufacturing companies: Sanyo, Panasonic, Mitsubishi, and Nissan-NEC in Japan; LG Chem and Samsung in South Korea; and BYD in China.  In 2008, many of these companies were getting into up to billion dollar deals with carmakers like Volkswagen, Audi, Bosch, and Nissan to produce lithium ion cell batteries.  In addition to actual manufacturing of proven battery technology, Asian companies were also spending large amounts of money on research and development.  During this time, it was clear that the US was not winning the “boxing match” of battery production, but the James Greeneberger noted that the US’s “left hook” is technology. In the author’s interview with Eberhard who was then director of electric vehicles for Volkswagen-Audi, Eberhard opined that research into increased energy density and lower costs trump that of safety which was the priority of A123 systems.  He contrasted the marketability of a battery system that provides 50 kWh weighing 200 pounds and costing $20,000 versus the same battery but weighing 1,000 pounds and costing $4,000; it’s clear to him that option number 2 is the more desirable one, “game over for gasoline”. [Incidentally, at the time I was reading this section (May 2, 2015), Tesla Motors just came out with a lithium ion battery for home use with dimensions measuring 1300 mm x 860 mm x 180 mm with a 10 kWh capacity for $3500 excluding installation.].  It was clear to Greenberger as well that electrochemical energy storage cost was the limiting factor back then. An electric car industry that is dependent on wealthy buyers and government subsidies is not sustainable.Chiang was optimistic, noting that unlike the expense of platinum catalysts for hydrogen fuel cells, there is more room for price-cuts in lithium ion cells. Back then, the economics for grid batteries were more feasible as the “electrical grid is so idiotically inefficient today that spending a small fortune on giant lithium ion batteries to hook into the system could actually be a moneymaker”.  This was primarily why A123 got the contract from the global energy company AES to produce grid batteries; it was “financially-driven”. Enerdel built 1-megawatt batteries for Portland General Electric that it will use to store wind and solar energy.  At that time, no one knew what the cost floor of lithium ion batteries was. Besides the cost of production, the other concern was the availability of lithium

·         In this chapter, the author gives a brief history of the beginning of battery boom, funded partly by a US stimulus package.

·         In August 2009, the US released 2.4 billion dollars of stimulus funding to help build the battery industry in the US.  The 5 US companies receiving the largest funding were Johnson Controls, A123, Dow Kokam, Compact Power, and Enerdel.

·         Enerdel process for battery production: Even though Enerdel is an American company, its electrode powder was imported from China. The electrode powder is blended with a clear liquid solvent, carbon black, and a chemical binder.  The electrode slurry is then painted onto a long sheet of aluminum for the positive electrode and copper for the negative electrode.  These sheets are then heated in an oven for curing. The cured reels of electrode material are then cut up into rectangular portions, brushed and then vacuumed to remove any contaminant particles.  a separator is inserted between the positive and electrodes to prevent them from making contact.  This sandwich of electrodes and separators are then immersed in a liquid electrolyte inside plastic pouches that are then vacuum-sealed.  The next step is to pre-charge the cells enough to start the chemical reaction, opening the pouch to allow gas to escape.  It is then vacuumed and re-sealed, charged to 60% capacity, and allowed to age for 24 days to monitor for any defects.  In the final steps, cells are wired into a battery pack and the cooling and heating mechanisms, voltage monitoring circuitry, and thermistors for detecting overheating are added.  The packs are then bundled into larger modules and packed into a black box that becomes the car battery.

·         Several paragraphs were devoted to the authors meeting with Chiang, founder of A123 and involved in the lithium disputes of the early 2000, his short biography and the his foray into companies that developed superconductors and batteries based on academic research results on high-temperature superconductors and later to lithium ion batteries made possible by the Bayh-Dole Act which allowed universities to keep title of their own inventions and license them.  These companies were American Superconductor and, of course, A123.  A plant section of the A123 factory was dedicated to making, testing, and characterizing electrochemically active materials which are then packed into a battery for testing.  Unlike Enerdel which manufactures prismatic (rectangular) batteries, A123 packages their batteries into the typical and more familiar cylindrical cells.  In this process, the electrode-separator sandwich is fed into a winding machine which turns the long sandwich sheets into “jelly rolls”, turning out cells that are slightly larger than the AA battery.  Several batteries are then wired in series, the number of cells depending on the required battery for the electronic device such as a laptop.  At the time of writing A123 had five factories in China.  Chiang noted that China’s advantage is not the savings in labor (battery production is not particularly labor-intensive) but the ease and short time it takes to build a factory there and to acquire the materials needed; the drawback is intellectual property theft that has created competitors in China for the same battery technology. In another assembly plant, the author was given a tour of the projects A123 was involved in at the time of writing: a lithium ion starter battery for a new “supercar”, the first and only FAA-approved lithium ion aircraft battery, and a 770 lb lithium ion battery that can produce 200 kilowatts of power on demand for use by buses.

·         The advantage of cylindrical cells over prismatic cells is that the winding process is cheaper than the cut and stack process.  Prismatic cells, however, have the advantage of allowing more surface area accessible to the cooling material.

·         The author provided a chronicle and list of Japanese, Korean, and Chinese players in the battery manufacturing field even before the US stimulus funding to US battery manufacturing companies: Sanyo, Panasonic, Mitsubishi, and Nissan-NEC in Japan; LG Chem and Samsung in South Korea; and BYD in China.  In 2008, many of these companies were getting into up to billion dollar deals with carmakers like Volkswagen, Audi, Bosch, and Nissan to produce lithium ion cell batteries.  In addition to actual manufacturing of proven battery technology, Asian companies were also spending large amounts of money on research and development.  During this time, it was clear that the US was not winning the “boxing match” of battery production, but the James Greeneberger noted that the US’s “left hook” is technology. 

·         In the author’s interview with Eberhard who was then director of electric vehicles for Volkswagen-Audi, Eberhard opined that research into increased energy density and lower costs trump that of safety which was the priority of A123 systems.  An example of this is the advantage of building battery factories near the car production facilities which cuts down substantially on the shipping costs.  “Dollars per kilowatt-hour stored is all that matters”, according to Eberhard.  He contrasted the marketability of a battery system that provides 50 kWh weighing 200 pounds and costing $20,000 versus the same battery but weighing 1,000 pounds and costing $4,000; it’s clear to him that option number 2 is the more desirable one, “game over for gasoline”. [Incidentally, at the time I was reading this section (May 2, 2015), Tesla Motors just came out with a lithium ion battery for home use with dimensions measuring 1300 mm x 860 mm x 180 mm with a 10 kWh capacity for $3500 excluding installation.].  It was clear to Greenberger as well that electrochemical energy storage cost was the limiting factor back then. An electric car industry that is dependent on wealthy buyers and government subsidies is not sustainable.

·         The key then is to keep lowering the cost per kilowatt-hour.  At the time of writing, the magic number was the $200/kWh mark; by the spring of 2010, battery costs have come down to $600/kWh.  [Tesla’s 2015 home battery system is still clearly too expensive but much improved at $350 kWh without installation].  Chiang was optimistic, noting that unlike the expense of platinum catalysts for hydrogen fuel cells, there is more room for price-cuts in lithium ion cells. Back then, the economics for grid batteries were more feasible as the “electrical grid is so idiotically inefficient today that spending a small fortune on giant lithium ion batteries to hook into the system could actually be a moneymaker”.  This was primarily why A123 got the contract from the global energy company AES to produce grid batteries; it was “financially-driven”. Enerdel built 1-megawatt batteries for Portland General Electric that it will use to store wind and solar energy.  At that time, no one knew what the cost floor of lithium ion batteries was. Besides the cost of production, the other concern was the availability of lithium.

CHAPTER 9: THE PROSPECTORS

In this chapter, the author features the many different companies and countries vying for a share of high concentrations of lithium in a limited number of regions.  He starts off by providing a context to what was then the sides of the coin when it came to the amount of lithium reserves.  In a rebuttal to an article written by an energy analyst, William Tahil, in December 2006 entitled “The Trouble with Lithium”, a leading lithium research geologist wrote that the current world lithium deposits sit at 28.4 million metric tons of lithium or 150 million metric tons of lithium carbonate.  At that time, the annual world use of lithium was 16,000 metric tons.  At the second Lithium Supply and Markets Conference that the author attended, the oligopoly of lithium extraction and mining each separately gave a talk to“deliver warnings” to prospectors that each one of them was sitting in vast reserves of lithium that no one else can compete with.  These three are:

o   Sociedad Quimica y Minera de Chile that owns Salar de Atacama, a 280,000 hectare salt-encrusted depression high in the Atacama desert contained 40 million tons of lithium carbonate equivalent, the largest known commercially exploitable reserves in the world. In 2009, they produced 40,000 tons of lithium carbonate.

o   Chemetall, a German company, claimed that it has the ability to reopen a dormant mine in Kings Mountain, North Carolina which is full of lithium containing spodumene rock.

o   FMC or Food Machinery Corporation bought the Lithium Corporation of America produced processed lithium powders, ingots, and solutions.

Each of these companies runs at least one major operations in the Lithium Triangle in South America (where Bolivia, Argentina, and Chile intersect), the world’s richest source of lithium.  Bolivia probably has the most deposit of lithium, some 8.9 million tons of lithium in just the Salar de Uyuni region.  During the same conference, the author visited what could be the largest scale lithium mine in the US, with enough deposits to supply the entire US and maybe even the world.  Western Uranium took over Chevrons claim of this lithium-rich region and spun off Western Lithium that now holds 2,000 mining claims. In this volcanic region, lithium and water were left behind when common elements “made their way into freshly baked granite” as the magma cooled.  The “leftover juices” crystallized into pegmatites; spodumene is the type of pegmatite that contains a lot of lithium. These rocks melted again and re-cooled forming a type of rhyolite rich in sodium, potassium, and lithium.  The lithium in Western Lithium’s mine is trapped in clay. Tests on long cylinders of earth done during that time showed that the mine area contained an economically viable 4,000 + ppm lithium.  Back then, Western Lithium claimed that the area contained the equivalent of 500,000 tons of lithium carbonate, “theoretically enough to satisfy the current world demand for four years”.  The clay is processed by crushing, calcination, and then mixing with a solution of sulfates.  A water leach step comes next and the addition of soda ash which causes lithium carbonate to precipitate. At full operation, the mine was projected to produce 27,000 tons of lithium carbonate a year and 115,000 tons of potassium sulfate as a by-product.  At the time of writing, it was projected that it will take 89 cents to process a pound of lithium.

·         In a rebuttal to an article written by an energy analyst, William Tahil, in December 2006 entitled “The Trouble with Lithium”, the geologist wrote that the current world lithium deposits sit at 28.4 million metric tons of lithium or 150 million metric tons of lithium carbonate.  Then, the annual world use of lithium was 16,000 metric tons.

·         At the second Lithium Supply and Markets Conference that the author attended, the oligopoly of lithium extraction and mining each separately gave a talk “deliver warnings” to prospectors that each one of them was sitting in vast reserves of lithium that no one else can compete with.  These three are:

o   Sociedad Quimica y Minera de Chile that owns Salar de Atacama, a 280,000 hectare salt-encrusted depression high in the Atacama desert contained 40 million tons of lithium carbonate equivalent, the largest known commercially exploitable reserves in the world. In 2009, they produced 40,000 tons of lithium carbonate.

o   Chemetall, a German company, claimed that it has the ability to reopen a dormant mine in Kings Mountain, North Carolina which is full of lithium containing spodumene rock.

o   FMC or Food Machinery Corporation bought the Lithium Corporation of America produced processed lithium powders, ingots, and solutions.

·         Each of these companies runs at least one major operations in the Lithium Triangle in South America (where Bolivia, Argentina, and Chile intersect), the world’s richest source of lithium.  Bolivia probably has the most deposit of lithium, some 8.9 million tons of lithium in just the Salar de Uyuni region.

·         At the time of writing, the author visited what could be the largest scale lithium mine in the US, with enough deposits to supply the entire US and maybe even the world.  This site was first explored by Chevron in the early 1970’s when they were prospecting for Uranium in the McDermitt Caldera where they detected “anomalous clay lens” that was extraordinarily high in lithium.  They abandoned the idea when recession hit and oil became cheap again.  Western Uranium took over and spun off Western Lithium that now holds 2,000 mining claims of the lithium-rich area.

·         In this volcanic region, lithium and water were left behind when common elements
“made their way into freshly baked granite” as the magma cooled.  The “leftover juices” crystallized into pegmatites; spodumene is the type of pegmatite that contains a lot of lithium. These rocks melted again and re-cooled forming a type of rhyolite rich in sodium, potassium, and lithium.  The lithium in Western Lithium’s mine is trapped in clay. Tests on long cylinders of earth done during that time showed that the mine area contained an economically viable 4,000 + ppm lithium.  Back then, Western Lithium claimed that the area contained the equivalent of 500,000 tons of lithium carbonate, “theoretically enough to satisfy the current world demand for four years”.

·         When the author asks a company representative what the environmental impact would be of extracting lithium from this site, his response was honest:  “Mining lithium from clay makes much less of an impact than many other extractive industries – there are no toxic chemicals involved, and no blasting – but mining is never impact-free. ‘I mean, we’re going to put a big hole in the side of that mountain.  But, you have to weigh the net costs.”

·         The clay is processed by crushing, calcination, and then mixing with a solution of sulfates.  A water leach step comes next and the addition of soda ash which causes lithium carbonate to precipitate. At full operation, the mine was projected to produce 27,000 tons of lithium carbonate a year and 115,000 tons of potassium sulfate as a by-product.  At the time of writing, it was projected that it will take 89 cents to process a pound of lithium.

CHAPTER 10: THE LITHIUM TRIANGLE

In this chapter, the author reports about his visit to Salar di Uyuni and the region referred to as the Lithium Triangle, a lithium-rich site where Bolivia, Chile, and Argentina intersect. Salar is the term for the extensive span of white substance composed of 47 billion cubic meters of salt, gypsum, brine, mud, and fossilized brine-shrimp feces.  This is possibly the world’s richest source of lithium. In 2011, the plan for Salar di Uyuni is to produce 30,000 tons per year of lithium carbonate and 700,000 tons of potassium starting 2014.  Projections for worldwide demand for lithium in 014 were not clear back in 2011.  If countries adopt electric car vehicles at a 5% level in 2020, this would require about 60,000 tons of lithium carbonate; existing lithium capacity will not be able to meet this.  US Geological Survey estimates that the Salar di Uyuni then held about 9 million tons of lithium carbonate, much lower than the Bolivian estimate of one hundred million tons according to Roelants. The constant influx of minerals from the Rio Grande is what made the area rich in potassium, lithium, and boron.  During a flood, the salar is under 1.5 feet of water.  The evaporation pools in which brine from the salar will sit and evaporate will be lined with PVC plastic.  The concentrated brine will then be piped back to the plant. According to the Bolivian writer Juan Carlos Zuleta, there were three things that are a hindrance to the progress of the lithium industry in Salar di Uyuni: political, social, and technical and logistical problems of low evaporation rate, high magnesium to lithium ratio, and the difficulty of access to the sea.

The author also visited Salar de Atacama, the “world’s purest and most productive lithium source”. SQM  runs the bigger of the two lithium operations in Salar de Atacama and is the world’s largest supplier of lithium at the time of writing (up to 31% of the world’s lithium).  They also provide 50% of the world’s nitrogen-based fertilizer (from saltpeter or caliche) and 25% of the world’s iodine. Here at SQM, mining was in full operation, with more than 100 evaporation ponds lined with black plastic and into which the brine from under the salar is pumped and baked in the sun. The concentrated brine is the source of lithium, magnesium, and boron. At that time, SQM was also marketing waste magnesium chloride for treating unpaved roads forming a firm smooth surface.  As with Salar di Uyuni, the Salar de Atacama is rich in lithium brought by freshwater flowing down from the mountains carrying minerals from volcanic rock.  SQM claimed back then that there were 40 million tons of lithium carbonate equivalent reserves there, the measure economically extractable portion.  It produces 40,000 metric tons of lithium carbonate equivalent per year.  The lithium concentration is equivalent to 2,700 ppm. Extraction of the abundant lithium is helped by the fast evaporation rate of water in the region, 3500 mm per year.  In Uyuni, water evaporation rate is 1300-1700 mm per year. The Atacama brine also has a lower magnesium to lithium ratio which makes the extraction and processing of pure lithium easier. In the evaporation pools, the serial precipitation of different salts starts with sodium chloride which precipitates first and settles to the bottom.  It is followed by potassium chloride or potash, then carnallite (a salt of potassium and magnesium).  Then comes bischofite containing a magnesium salt. The potassium chloride salt is sold as fertilizer.

·         In this chapter, the author reports about his visit to Salar di Uyuni and the region referred to as the Lithium Triangle, a lithium-rich site where Bolivia, Chile, and Argentina intersect.

·         Salar is the term for the extensive span of white substance composed of 47 billion cubic meters of salt, gypsum, brine, mud, and fossilized brine-shrimp feces.  This is possibly the world’s richest source of lithium.

·         Oscar Ballivian, a Bolivian geologist was the first to make rigorous measurements of the lithium deposits in Salar de Uyuni in 1981.

·         Political and social turmoil from 2002 culminating in the election of Evo Morales, the first indigenous president of Bolivia.  Relationship with the US soured resulting in ambassador to each country being recalled in 2008.  Meanwhile, Japanese and Chinese companies were wooing Morales’ to get a share of Bolivia’s lithium deposits.  Several paragraphs were devoted to a detailed summary of the development of the Salar di Uyuni lithium and potassium mines headed by a Belgian (Roelants) appointed by President Morales.  According to Roelants, Salar di Uyuni contain a lot more potassium, magnesium, and boron than lithium and therefore it was more appropriate to refer to evaporatives when talking about the development of Salar as a mining site. Potassium chloride is more abundant and cheaper to extract so even though it is 1/10^th the price of lithium per ton, it is the more lucrative material to mine from Salar; the volume of potassium is 25 times higher than lithium. Despite the abundance of both potassium and lithium, Bolivia cannot sell more than 30 percent of the world market as this will cause the price of lithium to go down. In 2011, the plan for Salar di Uyuni is to produce 30,000 tons per year of lithium carbonate and 700,000 tons of potassium starting 2014.  Projections for worldwide demand for lithium in 014 were not clear back in 2011.  If countries adopt electric car vehicles at a 5% level in 2020, this would require about 60,000 tons of lithium carbonate; existing lithium capacity will not be able to meet this.  US Geological Survey estimates that the Salar di Uyuni then held about 9 million otns of lithium carbonate, much lower than the Bolivian estimate of one hundred million tons according to Roelants.

·         The constant influx of minerals from the Rio Grande is what made the area rich in potassium, lithium, and boron.  During a flood, the salar is under 1.5 feet of water.  The evaporation pools in which brine from the salar will sit and evaporate will be lined with PVC plastic.  The concentrated brine will then be piped back to the plant.

·         The author also visited Salar de Atacama, the “world’s purest and most productive lithium source”. SQM  runs the bigger of the two lithium operations in Salar de Atacama and is the world’s largest supplier of lithium at the time of writing (up to 31% of the world’s lithium).  They also provide 50% of the world’s nitrogen-based fertilizer (from saltpeter or caliche) and 25% of the world’s iodine. “If the Bolivian pilot plant was the lithium mining equivalent of a subsistence farm under construction, SQM was an agribusiness giant.  Here at SQM, mining was in full operation, with more than 100 evaporation ponds lined with black plastic and into which the brine from under the salar is pumped and baked in the sun. The concentrated brine is the source of lithium, magnesium, and boron. At that time, SQM was also marketing waste magnesium chloride for treating unpaved roads forming a firm smooth surface.  All of the land where the salar is located used to belong to Bolivia until they lost it to Chile during the Saltpeter War in 1884 along with its coastline. This area now belonging to Chile is still a rich source of nitrates, copper, and other minerals.

·         As with Salar di Uyuni, the Salar de Atacama is rich in lithium brought by freshwater flowing down from the mountains carrying minerals from volcanic rock.  SQM claimed back then that there were 40 million tons of lithium carbonate equivalent reserves there, the measure economically extractable portion.  It produces 40,000 metric tons of lithium carbonate equivalent per year.  The lithium concentration is equivalent to 2,700 ppm. Extraction of the abundant lithium is helped by the fast evaporation rate of water in the region, 3500 mm per year.  In Uyuni, water evaporation rate is 1300-1700 mm per year. The Atacama brine also has a lower magnesium to lithium ratio which makes the extraction and processing of pure lithium easier. In the evaporation pools, the serial precipitation of different salts starts with sodium chloride which precipitates first and settles to the bottom.  It is followed by potassium chloride or potash, then carnallite (a salt of potassium and magnesium).  Then comes bischofite containing a magnesium salt. The potassium chloride salt is sold as fertilizer.

·         The lithium evaporating pools are colored chartreuse due to the yellow hue of magnesium and lithium. The final product is a “sickly yellow-green” solution containing 6% lithium, taking about 14 months to go from 0.2 to 6%.  A higher concentration will cause the lithium to precipitate. The concentrated brine is then processed in white lithium carbonate.

·         According to the Bolivian writer Juan Carlos Zuleta, there were three things that are a hindrance to the progress of the lithium industry in Salar di Uyuni: political, social, and technical and logistical problems of low evaporation rate, high magnesium to lithium ratio, and the difficulty of access to the sea.

                                                                                                                               

CHAPTER 11: THE GOAL

This chapter is the best one by far in terms of the chemistry content and interesting battery science, albeit outdated (2011).  The author begins this chapter by offering two suggestions for what battery scientists should keep aiming for: keep looking for novel substances that can contribute incremental improvements to battery technology and keep investigating technology even though their commercialization is still a long way off.

He starts off with revisiting Whittingham whose work for Exxon on lithium batteries in the 1970’s did not get off the ground.  After doing some work on solid state semiconductors, Whittingham is back working on battery technology.  He lists the following as the still existing challenges to battery technology: availability of cheaper materials, good electrolyte, better separator, and better geometries.  As the author noted, this list is generalized by Jon Lauckner as follows: “The ideal goal will be to have the same energy density as gasoline or diesel fuel.  That is where we’d say, okay, we’ve arrived.”  In Whittingham’s current lab, the focus of investigation is on electrodes.  The molecular or crystalline structure of the new electrode material is determined using x-ray diffractometry.  The process for making these new electrodes is described by the author as follows: “Mix a couple of teaspoons of the powdered battery material with binder, an equal measure of carbon black, and a solvent. Paint that concoction onto a sheet of aluminum foil. Bake it in a miniature curing oven. Transfer it to a vacuum chamber that extracts every trace of moisture. Remove the film of cathode material and use an industrial-grade hole punch to slice out a quarter-size circle of pencil-lead-gray electrode material.”  The next steps involve assembling the battery cells in a glove box filled with either argon or helium to prevent the lithium from reacting. The test battery that results is a coin cell into which the cathode, the separator soaked with about 5-6 drops of electrolyte, and the slice of lithium metal anode are pressed. To test the cells, the batteries are charged and discharged  repeatedly while measuring how much energy it can store, how quickly it can discharge that energy, how many times it can be cycled, etc.

Another notable figure featured by the author is Elton Cairns, now at UCB/LBL, whose work focuses on the next generation (at the time of writing) lithium batteries in the form of lithium sulfur battery: lithium metal is the anode, elemental sulfur is the cathode, and the electrolyte is a mixture of ionic liquids, liquid polymers, and a lithium salt run by a simple reaction, the formation of lithium sulfide.  It is projected at that time that it could store up to 5 times the energy of the current lithium ion batteries used then.  It eliminates carbon from the equation and the reduction in weight can be replaced by more lithium metal; LiC₆ is only 10% lithium by mass. There are also weight savings on the cathode side because sulfur is considerably lighter than the cobalt-oxide used in the current lithium batteries and one sulfur atom can bond to two lithium atoms.  This has the potential to store hundreds of watt hours per kilogram increasing the mileage driving range considerably.  The problem is sulfur’s poor electrical conductivity which requires nanoscale engineering before it can improve its conductivity performance.

Another elemental contender which is closer to reality at the time of writing (it was projected to be sold by 2013 by Panasonic) is silicon.  This new (back then) lithium battery makes use of a silicon alloy anode with an energy capacity of 4 amp-hours which was a 30% improvement back then. Silicon nanowires have also been shown to hold more lithium ions (up to 4.4 million compared to 1 with 6 carbon atoms) back in 2008.  Bonding of silicon and lithium ions, however, results in swelling and compression during charging and discharging that can stress the electrodes leading to material breakdown.  Yi Cui, the original investigator and called somewhat of a battery savant by the author, suggested that the way to get around this is to make the components smaller to the point where mechanical strain is no longer an issue.  Cui also came up with novel battery ideas such as paper soaked in a carbon nanotube or nanowire solution which turns the paper into a highly conductive material that can be used as a substrate for lithium ion batteries. “Paper is very light and its internal structure is made of cellulose fibers so it soaks (the active battery material) up like ink. Once you put the materials in, they can be accessed by the electrolyte very fast for high power.”

David Sadoway’s approach was to reverse the thinking on batteries and find a solution to the problem that batteries like to store charge but they don’t like high current.  This precludes their use in the electric grid where they had “quickly soak up a load of electricity from a fast running windmill, to quickly dump it into the system when the wind dies down and everyone in the neighborhood turns up the air conditioner.”  He proposes starting with a material that can take high current with no problems and “teach” it how to store charge.  An ideal material for this is an aluminum smelter.  Upon initial investigation, he and a grad student realized that to build this kind of battery would require liquid metals. Looking at the periodic table gave him the epiphany he needed: magnesium as the cathode and antimony as the anode. Even though antimony is a semimetal and less of a nonmetal with an electronegativity of 2.05, magnesium’s low electronegativity of 1.3 is enough to “intimidate” antimony into receiving electrons.  In addition, the two elements have similar melting points but with very different densities which would allow phase separation (because they are also insoluble in the third component, the liquid electrolyte) and the stratified layers required for separation in a battery without the need for a solid separator.  Sadoway also noted that this design is highly scalable to large size batteries needed for a grid-scale application.

The battery technology that appears closest to beating gasoline is lithium-air. As a comparison, lead acid batteries can store up to 40 watt-hours per kilogram; lithium ion at 200 watt-hours per kilogram and a theoretical limit of 400 watt-hours per kilogram; but the lithium-air has a theoretical maximum of 11,000 watt-hours per kilogram.  The way the author wrote about this makes it sound like the dream battery of all time: “Even after handicapping to take into account weight, efficiency, and other foreseeable technological obstacles – after assuming that, for the sake of argument, the lithium-air battery will be able to deliver only 15 percent of its theoretical energy capacity – it still matches what gasoline, because of the terrible efficiency of the internal combustion engine, can deliver.”  Lithium-air is possibly the simplest battery design in terms of elemental composition, lithium being the lightest metal and carbon and oxygen components of all living matter.  In this design, lithium acts as the anode and the positive electrode is porous carbon that traps oxygen from the air.  The electrolyte can be an organic or polymeric solvent like that used in current lithium ion batteries.  The reaction between lithium and oxygen produces lithium peroxide (Li₂O₂), a solid.  In the recharging phase, the solid lithium peroxide decomposes into lithium ions and oxygen is reformed and pumped back into the air.  The highest profile research department is (at the time of writing) the one created by IBM which is aiming for a 500-mile range electric car battery. A couple of problematic issues identified then for this type of battery are the slowness of the lithium-oxygen reaction resulting in lower power and the ability of replating lithium metal smoothly on the negative electrode instead of forming fuzzy spikes during recharging.  A possible solution for the power problem is to use nanoparticles to increase the surface area of interaction and/or to use a catalyst. The safety of lithium metal has also always been an issue but as one scientists suggests the battery design has to be proven first before spending considerable time and resources on studying its safety.

One company who is putting considerable research into making the use of lithium safe is PolyPlus. They got their start studying lithium sulfur batteries and determined that one safe way to keep lithium and sulfur from reacting uncontrollably and undesirably is by coating the lithium with a conductive solid electrolyte like a thin glass layer.  PolyPlus also developed a lithium-air battery that separates the lithium from the air through a ceramic barrier that allows lithium “to engage in the right reactions while keeping it completely isolated from moisture”.  According to

PolyPlus’ CTO, “you can hold it in your hand, you can put it in a glass of water, and it’ll just sit there…it’s completely stable”.  This lithium-air battery, however, is still non-rechargeable because at the time of writing PolyPlus has not resolved the recharging issue of lithium not re-plating smoothly back on the electrode.

At the time of writing, the author notes that purely electric car vehicles are still some time away from being the primary car for various reasons and one of these is the problem of charging stations and the time it takes for a full charge.  According to Elton Cairns, a car battery that holds 25 kilowatt-hours will require a 100-kilowatt substation to recharge the battery in 15 minutes and 50-kilowatt hours battery like in the Tesla will require a 200-kilowatt substation to recharge in 15 minutes.  A house runs at 1 kilowatt.  To run a charging station like a gas station will require multimegawatts of power.

So, the proliferation of electric car either requires batteries that have a 500-mile range obviating infrastructure requirements for charging stations.  In Wilcke’s words, “I would rather tackle a really difficult technical problem…It’s confined to being a technical problem and you don’t need a zillion dollars’ infrastructure”.  This was echoed by Peter Bruce that the focus should be on solving the energy density problems.

EPILOGUE

During the week before Christmas 201, the first fleet of 45 dealer-ready plug-in hybrid Chevy Volt was rolled out on their way to New York City and Washington DC; another 300 are bound for CA and TX at the end of that week.  On the first roll-out of test vehicles, the backlash was fierce and sometimes sourced from a twisted interpretation of information: it is not a true EV because the tires are still run by gas engine, the New York Times called it an “electric lemon”, it was referred to as a “government brainstorm” demanded by the Obama administration in exchange for bailout money, the price tag of $41,000 was steep and thus a failure, etc., with the “polarization over the volt largely confined to the spheres of auto journalism and political hackery”. Nevertheless, the Volt overcame this and GM later announced that another 1000 jobs are being developed in addition to the 2000 currently existing to build the Volt.  GM stocks raised 20 billion dollars in the largest IPO in American history.

The Nissan Leaf’s roll-out, on the other hand, was without drama despite the fact that it was a riskier venture because it is a pure EV.  This implies, as the author suggests, that all the backlash was against GM and not electric cars.

Soon, announcements were made of other EV’s being released by Ford, Toyota, and Mitsubishi followed by Volkswagen, Audi, and Porsche.

In 2011, the momentum for electric cars was there and was sweeping the battery industry alongside it, with A123, Panasonic, Enerdel, and Tesla which was developing silicon anodes that will increase the energy density of the lithium ion battery by 30% by 2013.  According to the author, however, the biggest threat to the battery industry could be politics.  Much of the initial momentum in building these start-ups came from one-time stimulus funds that will run out eventually.  Even though the EPA is still charged with regulating greenhouses, with the Republican takeover of congress in 2010, the author opines that “it is clear that the brief window in which any kind of comprehensive climate-change legislation was possible has been closed”.  The other government alternative is to invoke the Corporate Average Fuel Economy (CAFÉ) standards which mandate mpg requirements for new cars, 35.5 mpg by 2016 and 62 mpg by 2025.  The former Department of Energy secretary Stephen Chu noted that the stimulus funds should be a “downpayment” on a long-term investment on energy R&D.  According to Chu, “some level of government direction of the private sector is necessary because the benefits of clean-energy technology – clean air, better national security, less risk of dangerous climate change, stability of energy prices – are ‘neither recognized nor rewarded by the free market’”.