Sunday, March 17, 2019

Bottled Lightning: Superbatteries, Electric Cars, and the New Lithium Economy

Book Review: Bottled Lightning: Superbatteries, Electric Cars, and the New Lithium Economy – by Seth Fletcher (Hill & Wang, 2011)

This is a great history of the development of battery technology and electric vehicles. Fletcher was a senior editor at Popular Science magazine when this was published. It seems likely that the 2020’s will see major adoption of EVs with the 2030’s being when they will come to dominate. As of now (2019) they are still a small percentage of total vehicles. 

This book begins with the beginnings of electricity itself. The development of the battery arose from a dispute about the nature of electricity among two Italian scientists, Galvani and Volta. Volta, after studying experiments involving the torpedo fish, came up with the first battery consisting of piles of metal, like sandwich cookies, made of zinc, copper, and brine-soaked cardboard. This was in 1800. Later in that century came Faraday and Maxwell, the discovery of the relationship between electricity and magnetism (now known as electomagnetism), and the development of bigger and more powerful batteries. Lead-acid batteries are of course still used to start our gasoline powered cars. At the beginning of powered transport electric cars did share the road with early gasoline vehicles but eventually proved impractical compared to them. Thomas Edison joined the search for a better battery. His nickel, iron, and potassium battery performed better than lead-acid batteries of his day and they powered some of the vehicles on the road early in the first decade of the 20th century. But the batteries began to leak and Edison was getting old with deteriorating health. Finally, the internal combustion engine was improving enough that battery-powered vehicles lost feasibility. Even though the leaking was fixed, his competitor ESB introduced a new battery, the Ironclad-Exide, using it to start gasoline engines. Thus, the battery was relegated to a supporting role in an increasingly petro-based world. Edison added nickel and lithium hydroxide to his battery in 1908 which gave it 10% more capacity and extended the time it could hold a charge. Lithium was the third element produced in the Big Bang after hydrogen and helium.

“Composed of three neutrons, three protons, and three electrons, lithium is the third element in the periodic table …”

Lithium was used in the 19th century to treat some illness. Lithium citrate was used in early formulations of the lemon-lime soda known as 7UP. The use of lithium chloride for heart patients in the 1940’s turned out to be harmful. People overdosed and died but data about what made a lethal dose became well defined. This slowed implementation of the promising results of lithium salts to treat mania. Lithium carbonate was approved as a psychiatric medication in 1970. It’s now considered one of the most effective medicines for mental illness and those with bipolar disorder. It is used as a mood stabilizer and the mechanism by which it works involves its effect on neurotransmitters and cell signaling. It increases serotonin production. The pharmaceutical industry only uses a tiny fraction of the lithium mined. Metal alloys, ceramics, lubricating greases, devices used to absorb CO2 on spacecraft and submarines, rocket propellant, and certain types of nuclear reactors are other uses. Its use in batteries is set to make it the main use for lithium. Its low atomic weight allows it to store more electricity in a smaller space and be lighter than other battery materials such as lead. Its eagerness to shed its outer electron leads it to make a more powerful battery. Lithium is unstable and so is reactive in its pure form. Under certain conditions a lithium battery can be an explosive but separating the electrodes with electrolyte bridges tames the explosive tendencies. Electricity has many advantages over other power sources such as burning fossil fuels (although much generated electric power comes from doing just that in big power plants), hydrogen, or biofuels like ethanol. The challenge for batteries is to be able to store more energy at reasonable cost. Incremental improvements have happened over the years and continue to do so but the high costs still limit higher implementation. 

California especially has had a problem with internal combustion engine (ICE) vehicles due to the susceptibility of the cities in the southern part of the state to smog. Anti-ICE advocates in California were given another boost by the Middle East energy crisis in the 1970’s. These situations revived interest in electric vehicle (EV) development. Battery research was ongoing at Stanford and at the Ford Motor Company. Solid state electro-chemistry, aka solid state ionics, took off in the early 70’s with the search for better anodes, cathodes, and insulating materials in batteries. By 1972, Chevy, GM, Ford, Chrysler, AMC, and Toyota were all working on EVs. Exxon was also deeply involved in battery research. In fact, Exxon had the only battery model that used lithium that functioned at room temperature, which was a big advantage. Exxon’s early lithium batteries were dangerous if not handled correctly. Gas buildup would lead to explosions. By 1976 the US government was supporting battery research for EVs. There were fears then of oil supplies running out and Exxon wanted to diversify. The first Exxon rechargeable lithium battery to reach the market was very small. The button cell battery was to be used for a solar powered watch. The digital watch thus became the first wearable battery, a trend that we now all know well with our smart phones. The recession of 1979-1980 crashed the battery and EV momentum. Exxon wanted out of battery R&D and ended up licensing their discoveries to other companies like Eveready, then Union Carbide. With the election of Reagan US government interest in alternative energy waned. The rebound of oil supply in the 1980’s also kept EV and battery research underfunded. Getting things to market is more challenging when oil and gasoline prices are low. 

Bell Labs research in the 1970’s led to breakthroughs in cellular communications. Motorola and AT&T were vying for a prototype. Motorola was the first to conduct a cell phone call in New York City in 1973 when a call was made to their competitor, Bell Labs. The story of Oxford’s John Goodenough is told (the author gives some detailed descriptions of different contributors to battery storage, their academic and work histories). Goodenough first decided to replace the lithium sulfides with lithium oxides. These could reach a higher voltage. Goodenough also proved that a battery did not have to be built fully charged as previously believed. It could use compounds stable at ambient air condition and build them discharged. Essential for getting the lithium battery into the marketplace was the lithium-cobalt-oxide cathode which Goodenough notes is what started the wireless revolution. He published in 1980. Motorola started selling cell phones in 1984 but they would be quite rare for years to come. Japanese companies in the 1980’s were very interested in battery research, maybe especially since at the time they made a lot of battery operated digital devices. Sony had planned to joint venture with Union Carbide/Eveready when the disaster in Bhopal, India hit and Union Carbide was in litigation and split up. Sony was able to buy Eveready out at a bargain. By 1987 they were focused on developing a mass-market rechargeable lithium battery. Sony came up with a carbon anode to go with the lithium-cobalt-oxide cathode. The voltage was higher yet at 3.6 volts. This would mean that more power weighed a little less and that battery power was smaller and could fit in smaller gadgets. Another benefit of Sony’s new battery was that it would last longer due to a reversible chemical reaction with little damage from recharges. They could also be recharged before being run completely dead, unlike nickel-cadmium (NiCad) batteries. They announced them ready for use in 1990, calling them lithium-ion batteries, perhaps to distinguish them from Exxon’s flaming lithium batteries of the 1970’s. However. Another company, Moli, had failed mass marketing of lithium batteries in the late 1980’s due to fires caused by unforeseen charging-discharging scenarios. 

In 1990 the nickel-metal-hydride battery replaced the NiCad and was mass marketed. However, in 1992 Sony offered a $60 optional lithium-ion battery for a camcorder that was smaller and lighter the NiCad and stored more energy than nickel-metal-hydride. In 1994 Motorola released the first small cell phone with 45 minutes of talk-time and the first phone with voice mail. It was now realized that the small and light lithium-ion battery was enabling a portable electronics revolution. Japanese companies dominated the industry. RF power amplification allowed phones and devices to become even smaller and lighter and by 1996 small cell phones were the icon of power that big ones used to be. By 1999 the cell phone began transforming into the smart phone. Constant connectivity and its advantages and disadvantages (never-ending work day) were being realized as well. By 2002 95% of cell phones used lithium-ion batteries. 

By the early 2000’s lithium-ion tech was a hope of EV entrepreneurs. In July of 2003, Silicon Valley entrepreneurs Martin Eberhard and Marc Tarpenning incorporated Tesla Motors. The idea of Tesla was to compete via performance rather than price and to a considerable extent that is still true today with Elon Musk at the helm. Their first battery-pack idea consisted of 6831 laptop cells. Musk joined as a major investor and chairman in 2004. The first early launch (earlier than they would have preferred) of a Tesla vehicle was in July 2006. Of course, Toyota was mass producing the lithium-ion powered hybrid Prius a few years before that. It first went on limited sale in 2001. I bought one the first week in January of 2006 and 13 years and almost 500,000 miles later it is still on the road doing fine (although the battery was replaced a few years ago). The Tesla was 100% plug-in electric and built for power and luxury. In 2006, the movie, Who Killed the Electric Car? premiered at Sundance. It painted GM as insincere in their quest for alt-fuel vehicles like hydrogen and EVs. At first, GM did not consider Toyota’s Prius a threat but eventually had to because of its sales success. GM’s Bob Lutz was in charge of coming up with GM’s EV, the Chevy Volt. GM and others had had other unmarketable prototypes with EVs from the early 1900’s through the 1970’s and 1990’s. From 1996-1999 GM had leased 800 EV1 cars but eventually collected them up and destroyed them in the desert – thus “killing” the electric car. They were not affordable nor profitable. They did not want to lose more money maintaining them. GM had lost about $1 billion of the EV1.

There was another battery safety issue that began in December 2005 with Sony laptop batteries catching fire. By August 2006, 4.1 million laptops were recalled by Dell. By October, Sony had recalled 10 million batteries worldwide. The explanation was that during manufacture of a certain batch some metal fragments got into the electrolyte and caused short circuiting. 

By 2007 Eberhard was out as CEO of Tesla and Musk was in. GM was still making the case for the Chevy Volt, that electrification would be better than other alternative fuels and vehicles.

In the late 90’s and early 2000’s it was discovered that adding carbon improved conductivity in lithium iron phosphate. This later became known as “doping.” Doped lithium iron phosphate could make a battery cathode that would discharge completely very quickly which was a desired feature for EV batteries. There were disagreements about how the doping actually worked to increase conductivity. Was it doped metals the led to it or carbon contamination from the jars used in experiments? Later, as early experiments were reproduced it was found that doping did work even though the idea of a highly electrically conductive phosphate challenged conventional wisdom.  Then it was thought to be a coating of lithium phosphide that contaminated the experiment producing the unexpected effect. There were arguments between potential patent holders and companies that could be made or broken by what was determined to be the process. These became known as the “lithium wars.” Litigation and patent disputes marred the battery industry as they had in the late 1800’s. These disputes were still ongoing to some extent when this book was published so I’m not sure what has happened since then. There are several stories of early developers of technologies, both in academia and industry, not getting any royalties when later developers did. John Goodenough did not profit from his work but the marketers of his work did.

The development and successive unveilings of the Chevy Volt is recounted in detail. The first unveiling was in 2007 as a concept car. After some considerable redesign it was unveiled again in Sept. 2008. Meanwhile GM and other car companies were struggling through the economic downturn and amidst government bailouts and restructuring. The early Obama administration was very interested in EVs and battery research and billions of stimulus dollars would be invested. One might think of it as a ‘Green New Deal’ of sorts. Chevy had spent billions getting the Volt ready and even nowadays (2019) EVs are barely profitable for carmakers. The Volt’s competition was announced in 2008 as Japan’s Nissan announced plans to build the Nissan Leaf. In late 2010 both cars were being sold. The year before, Elon Musk appeared on David Letterman, trashing the Volt. Of course, his competition, the Tesla Roadster, was then priced at a hundred grand. At that price it sure would have to be better than the Volt at 40K. 

Aided by the economic stimulus and venture capitalists, many new battery start-ups were popping up. Obama supported the battery industry and wanted more American companies to build batteries as Japan and Korea cornered a big segment of the market. Some companies designed in the U.S. and manufactured in China to take advantage of cheap labor. Big mergers and acquisitions in the battery business were becoming commonplace globally. An EV revolution would feed battery manufacturers indefinitely. Batteries are heavy and so shipping costs are an issue. That is why some companies building cars strategized that battery manufacturing plants near car production plants were a good idea.  Important as cost and weight and related is energy density. Not enough energy density and the weight gets too high to make a battery pack that gets range. Cost per KWh (kilowatt-hour) is another benchmark for batteries. Mass marketing of batteries will probably eventually reduce costs for consumers as will better energy density of the batteries. One hurdle in hydrogen fuel-cells, a competitive alternative fuel, is the cost of the platinum catalyst, which is unlikely to drop or be replaced by something else. 

Lithium reserves and mining is the next subject. Lithium is abundant and should not shoot up in price although it is concentrated in certain areas and somewhat subject to potential political upheavals of those areas that might occur. A 2006 paper titled – The Trouble with Lithium – by energy analyst William Tahil, suggested that lithium was another finite resource we would become dependent on like oil. The border between Chile and Bolivia and somewhat into Argentina has the most concentrated lithium-bearing brines in the world. China also has a decent amount. There are other places as well but the high concentrations of the “lithium triangle” in South America make it the world’s lowest cost lithium. The Salar de Atacama is the largest of the salt flats that contains the concentrated lithium. At the time the reserves were counted at just under 30 million tons of lithium in the form of lithium carbonate. While lithium may be relatively abundant, other resources used in EVs (and wind turbines, military apps, and other modern conveniences) are not so abundant. These are rare earth minerals and other minerals such as cobalt. The rare earth minerals required for the magnets in electric-drive vehicles are mostly mined in China, although they exist elsewhere at higher costs to develop. Cobalt is extensively mined in Africa, sometimes by child miners and other exploited workers.

There are basically three companies that supply the majority of the world’s lithium. They became known as the Oligopoly. One is a Chilean company, one a German company, and one was originally an American company. They all have some reserves in the lithium triangle. Bolivia has been more protective of its reserves, being suspicious of capitalist impulses of would-be developers. However, they may have the largest reserves of all. While there are other supplies, the Oligoply is the cheapest and is likely to remain so because of the high concentration of lithium. I am not sure if things have changed much since 2011 when this book was published. The company SQM extracts 30% of the world’s lithium supply from a single salt flat in Chile, the Salar de Atacama, in the high Andean desert. The US has some lithium reserves in the west, mostly in Nevada, but it would be costlier to develop than to buy from South America. However, there is some value in having a domestic source, so development is likely. A company called Western Lithium was involved in planning mines in Nevada at the time. 

The author traveled to the South American salt flats to see the lithium mining operations for himself. Brine evaporation pools are how the lithium carbonate is extracted. First, he goes to Bolivia, one of the poorest nations in South America with a history of exploitation by mineral extractive industries that has led to massive distrust of any proposed developments. With the continent’s largest natural gas reserves and possibly the world’s largest lithium reserves – both remain undeveloped. Leader Evo Morales, an indigenous Bolivian, nationalized the natural gas industry and notoriously shunned the U.S. and Chile in a potential pipeline deal to bring Bolivian gas to Chile for export. He wanted any company that led lithium extraction in Bolivia to also begin an EV industry in Bolivia. Morales is known to rail about the evils of neo-liberalism and transnational companies. But their reserves are huge and they have time. With their attitude toward resources it is virtually assured that Bolivian lithium will be the slowest and most complicated to be developed. A French company was trying to develop the lithium but had been bogged down by Bolivian politics.

Potassium, magnesium, and boron are other valuable components of the salt flats so the development of all evaporite minerals needs to be considered. In Bolivia, potassium is actually more valuable than lithium. At press time, the first lithium production plant was scheduled to come online in 2014, Thus, they are years behind Chile and Argentina. Lithium availability and price are basically a direct function of how fast EV production takes off and that has been pretty slow so far. 

Lithium mining, or evaporatives mining in general, involves evaporation pools of considerable aerial extent. After the mineral ores/salts evaporate out they are raked into piles and transported via truck for further processing. Lithium, however, is transported to processing as a concentrated brine.The lifeless Atacama Desert is the driest place on earth. The SQM lithium mining sites the author visited in Chile were far more developed and professional than those across the border in Bolivia. The Chilean operations are also lower in elevation and closer to the coast which gives economic advantages. At the time SQM supplied 31% of the world’s lithium yet that only accounted for 8% of the company’s revenues. They produce 50% (at the time) market share of the world’s plant nutrition through their nitrogen-based fertilizers that include caliche, saltpeter (potassium), and iodine – they supply 25% of the world’s iodine. In the desert, however, the products are lithium, potassium, and boron. At the time SQM was producing 40,000 metric tons of lithium carbonate per year. The lithium concentration in the salt in the Salar de Atacama is on average about 2700 parts per million. Another advantage of the desert is that since there is literally no rain (millimeters per decade) it makes an ideal environment to extract evaporatives. It has one of the highest evaporation rates on the planet, three times higher than in the flats in Bolivia. In Bolivia there is a wet season that floods the salt flats. Chilean lithium in the Atacama also has a very low magnesium-to-lithium ratio, which makes extraction easier and cheaper than in Bolivia. SQM also benefitted from their existing copper mining infrastructure in the area and think they can triple their extraction rates to meet rising demand easily. 

The evaporatives evaporate out in an orderly way: first sodium chloride (halite) settles on the bottom. Then the brine is transferred to other pools where potassium chloride (potash), a fertilizer, precipitates out. Then a mineral called carnallite, a magnesium and potassium salt settles out, then comes bischofite, another magnesium salt. The brines, now higher in lithium, are transferred to new pools. These become yellow due to magnesium and lithium. Finally, a 6% lithium brine is produced which is yellow-green. It takes about 14 months to get this 6% lithium brine (from 0.2% lithium brine) – any higher concentration and the lithium will begin to precipitate. The 6% lithium brine is transferred via truck to processing plants. Here it is processed into lithium carbonate, a white powder. 

The challenges for battery makers and battery power in general include making it cheaper and more efficient so that it can compete better with oil and gasoline, eventually without government subsidies. This is basically increasing energy density. Improvements have been steady but incremental and small. There is still considerable research going on looking for breakthroughs. Assembly of new batteries for research involves the use of glove boxes (assembly by gloves in sealed off chamber filled with inert gas like argon or helium to prevent chemical reaction. Sealed in cathodes make coin cells which can be tested with lithium (anode) and electrolyte. The cells are repeatedly charged and discharged so that their performance can be observed. How these things go may result in better zero-to-sixty times and highway passing power for EVs. In fact, EVs, once considered low power, now can have immense power. Research continues into the possibilities of a lithium-sulfur battery which does not need carbon:

“If a lithium-sulfur battery could be made to work correctly, it could store hundreds of watt-hours per kilogram, enough to jump up into the realm of the several-hundred-mile electric car.”

However, since sulfur is a poor conductor the limits have yet to be overcome. Nanoscale engineering is being used to address these issues. Lithium batteries that use silicon may be in the market now – were set to be sold by Panasonic by 2013 – giving 30% increase in energy capacity. Silicon may be tweaked even further and again nanoengineering (silicon nanowires) is being used for such tweaks. Always with lithium there are safety concerns due to its reactivity. Lithium-air batteries are another area of research with plain old air being involved in the battery cell structure. 

Many other materials and techniques are involved with battery research and it is perhaps one of the most promising tech sectors but even in recent years improvements have been small, “incremental” is the word usually used. Battery use for grid storage is happening all over the world. However, it still is not competitive to natural gas “peaker” plants which can be started quickly to provide back-up power for wind and solar resources that are intermittent. Those peaker plants are forced to run inefficiently and so increase the costs of wind and solar considerably. These are one of the main “hidden costs” of wind and solar and are often referred to as grid integration costs. More recently, gas peaker plants can utilize small battery-assist for instantaneous start-up for grid balancing. 

Other hurdles remain for mass adoption of electric vehicles. Charging infrastructure is inadequate in many areas. Charging times are an issue. These days one can have a level 2 charger (which still takes hours) installed at home or business. Some states charge a road-use tax of EVs. If EVs were adopted en masse the revenue from gasoline and diesel taxes would drop dramatically and such revenue funds many things at federal, state, and local levels. The bottom line is that higher energy density solutions are needed and the outlook is not great at the moment. Pure EVs still have a long way to go to compete with the ICE (internal combustion engine) but many products on the market, hybrids and plug-in hybrids can be quite economic and advantageous. I just bought a new PHEV (plug-in hybrid) last week. Other advantages include quietness and needing to stop for fuel way less often due to longer overall range. The tax credit helps the economics a lot as does the EV power which is currently much cheaper than gas or diesel power per mile. Another advantage is less wear and tear on the gasoline engine, less oil changes (none in a pure EV), and other parts that wear out slower than in a gas or diesel engine. Of course, depending on where one lives EVs may be powered by whatever powers the local electrical grids, be it coal, natural gas, nuclear, or renewables. Aside form hardcore “greener-than-thou” enthusiasts that like to power their EVs with solar panels and can afford it, it is more likely that many EVs are powered mostly by fossil fuels. 

Great book for the historical perspective and the overall perspective of electrification.

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