BOTTLED LIGHTNING (Chapter 2)

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 LiTiS₂ battery. 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”.