Singing

the Body Electric, while on Sabbatical

By Stephen O’Brien, Department of Chemistry & Biochemistry, The City College of New York
(Sabbatical Spring/Fall 2018)

On the way to school my daughter, Sophie, and I like to play a game called “punch-
buggy-Tesla” – a variation on a well known theme: if you spot a Tesla, you can punch
the other player in the arm. If it’s a white, black, red or grey Tesla it’s one punch, a
blue one grants two punches, while a Model X (the SUV) will award you three.
Sophie unfailingly spots them quicker than me, and so my arm and I are grateful for
two things: first, my daughter is softhearted and strikes gently. Second, there are
currently a few, but not yet too many, electric vehicles on the road.

The Tesla is a sleek, eye-catching vehicle, and this 21st
century, “mad-genius”-lead company has given the
public much to talk about. Some of us have driven a
Tesla and praised the superb acceleration, while
some of us find the lack of an engine sound kind of
creepy. Moreover, the self-driving car concept is both
a wonderful and sinister prospect to contemplate: A Tesla Model S. An all electric vehicle with
where will this take us? Will we all be living at the self-driving capabilities. The blue one is
beach, commuting two hours to the city with our feet worth two punches.
up watching Netflix? Will the machines make executive decisions on our behalf
regarding fault, choosing to run over the neighbor’s poor cat? More breakthroughs
in technology and regulation will have to come to pass before we get to fully
automated driving, but what many of us acknowledge, and what Tesla
wholeheartedly encourages, is that when we are looking at a Tesla we might be
looking at the future. This helps in part explain why Tesla’s market capitalization is
as high as GM, while selling about a tenth the number of cars. With Tesla
commandeering a significant portion, the total number of plug-in electric vehicles
(PEVs) sold in the United States in 2018 was 361,000.1 Not bad for a new comer, and
an 80% increase from 2017, but a mere fraction of the 17 million vehicles sold in the
U.S. each year.2

With the growing number of Tesla’s on the road, it is tempting to ponder the dawn
of the age of the electric vehicle (EV) as a path to this new, driverless future. Over
the past twenty years we have witnessed the maturity of an incredibly important
enabling technology: the rechargeable lithium-ion (Li-ion) battery. The Li-ion
battery (LIB) started out in our laptop computers, shrank for our cellphones, and
then morphed into every shape and size imaginable. Ankle breaking hoverboards,
eco-conscious thermostats, movie-making drones - pretty much any rechargeable
electronic you can think of - is based on LIBs. The Li-ion battery is in the Tesla. It
took a remarkable feat of engineering to make that happen. It is done with a
concatenation of battery cells about the size of AA batteries (Panasonic “18650”s,
now being replaced with “2170”s). To get the exciting acceleration and 300 mile

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range, 7,104 of these batteries are placed in the Tesla
model S in the base of the chassis, partitioned and
managed to deliver 85 kWh of energy.3 Some very
smart electrical engineers were involved in putting
together a computer controlled power electronics
system to manage charging the battery in a few
hours, and discharging it through the transmission
while you’re on the road. And in actual fact, the Tesla
doesn’t really have a transmission: it’s a single speed
gearbox – a triumph of torque, efficiency and
simplicity over the internal combustion engine.

There is gathering evidence, that the new generation
of PEVs (Plug-in Electric Vehicles) are good enough
to compete with, and possibly displace the ICE
(Internal Combustion Engine). Yet modern car
engines are complex, precision instruments of
transportation perfected over 100 years. And
although gasoline is pollutive, the cause of economic The chassis of a Tesla Model S is filled with
7,104 batteries, wired together to produce a
disparity and even wars, this liquid fuel is a very fine 85 kWh powertrain.
source of portable energy the world over. Gasoline
has an energy density of about 34 MJ/liter whereas the Li-ion battery is around 1-3.
What this means is, to drive the car, you have to carry around a lot more battery.
Cars typically do 20-30 miles per gallon (mpg); a small electric car can drive about 4
miles on 1 kilowatt hour (kWh) of electricity. The compact Tesla Model 3, for
example, has a range of 220 miles with a fully charged 50-kWh battery pack. Since 5-
7 kWh is equivalent to 1 gallon, you need 80-100 lbs of battery for only 1 gallon (6.3
lb) of gasoline. How the weight of the battery is actually calculated, and whether you
choose to include the casing or electronics complicates the final value, but the range
is 140-250 Wh/kg. The comparison is not exactly fair because PEVs don’t need a
combustion engine or transmission, but suffice to say the battery is much heavier
than we’d like. Furthermore, the more weight you have to lug around, the more
energy you need to turn the wheels – a sort of catch 22. This is a major impediment
to extending range and reducing the cost of a PEV, which in turn pushes that clean
driverless future further away from us. So, why can’t we make the lithium-ion
battery lighter weight?

The basics of a modern rechargeable battery are that you need two electrodes (an
anode and a cathode) and a liquid electrolyte. Charge is shuttled between the
electrodes using the electrolyte. When using the battery, charge flows in the
direction caused by a favorable chemical reaction that produces electricity, while
the reverse direction of this chemical reaction can be induced to occur when you
recharge the battery by supplying electricity. One direction yields electrons to
produce electricity; the other direction takes the electrons back. The perfect set of
electrodes will allow this to occur over and over efficiently and safely, without
degradation. The LIB can do this an average of one thousand times, following a

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“rocking chair” mechanism between two compounds, LixC6 + Li1-xMO2 ⇌ C6 +
LixCoO2.4

The invention of the LIB is in turn a remarkable
story, with discoveries and breakthroughs that
span the American, European and Asian continents.
Electrode development for LIBs started in the
1970s with the development of specific
intercalation compounds by Stanley Whittingham
and co-workers at Exxon.5 In 1979 John
Goodenough and co-workers discovered the
lithium cobalt oxide material at Oxford University.6
Lithium cobalt oxide and its descendants serve as
the cathode. During the 1980s, SONY and Union
Carbide had a joint venture to develop lithium-ion Basic mechanism of a Lithium-ion battery.
batteries. SONY later bought out Union Carbide.
Under the management of Keizaburo Tozawa (and later Koichi Tsunoda) SONY
brought about LIB commercialization in 1991, shipping thousands of units that year
for camcorders.7 At this point the LIB comprised a stable cathode and anode. SONY’s
anode was a lithium-graphite intercalation compound.

Over the years LIB battery designers have improved
by iteration the design, filed thousands of patents, and
come up with the best liquids and materials for the
lightest weight, cheapest version. Things don’t always
work out, such as the explosive incidents and recalls
over Dell laptops, the Samsung Galaxy 7, and the
Boeing Dreamliner. The safety issue stems from
several factors: the battery is in essence a controlled Opps. There goes my Christmas present
thanks to poor LIB manufacture.
chemical reaction. But any contaminants or
microscopic failures can cause side reactions. The so-called thermal runaway is a
complex series of chemical reactions initiated by a short in the cell, or by excessive
heat from outside the cell. The “runaway” is when one cell overheats, causing it’s
neighbor to overheat and starting a chain reaction. Among the reactions that lead to
fire is the electrolyte - an organic liquid, which, rather like gasoline, can flare up,
especially when it comes into contact with the lithium in the anode.8

Lithium-ion is a high energy density, long-lasting and
safe rechargeable battery. However, despite the green
feeling we get around a PEV, and the touting of lithium-
ion batteries as cleantech enabling, LIB manufacturing
is hardly free of environmental, political or
humanitarian impacts. The effects of fossil fuel
consumption are mitigated, including significantly
curbed greenhouse gas emissions, but the raw
minerals required for battery production are derived Artisanal cobalt miners in Kaili, DRC.
(Photo by Julien Harneis | Flickr
Commons.)

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from some toxic and energy consumptive refining processes, and, sadly, not of all of
the mining can be considered humanitarian. Among the issues are the cobalt, a
relatively rare element for which 58% of global production comes from the
Democratic Republic of Congo.9,10

All things considered, we’d like a rechargeable battery that is akin to the LIB, but
doesn’t rely on cobalt, is safer, and weighs less. Dealing with these three issues is
somewhat of a global R&D mission at universities, government labs and industry.
Reducing the cobalt is ongoing, with the design of new cathode materials that
contain more manganese, nickel, or rely on alternative compounds like lithium iron
phosphate.5 Research into better electrolytes is an interesting and complex problem
for both organic chemists to attempt to solve - the use of a solid electrolyte is
possible – a completely liquidless battery that could be far safer.11 We can also
contemplate finding completely alternative substitutes to the LIB.12

The focus on weight reduction takes on many forms. One thing to do is get rid of all
the graphite in the LIB and make a so-called lithium metal battery. The graphite in
the LIB houses the lithium ions and insures they cycle well. Reverting to a pure
lithium metal anode would dispense with the need for graphite and generate a good
voltage range for a battery. However, lithium metal reacts with the electrolyte. It
does not usually cycle well, often forming dendrites, or uneven deposits leading to
failure after a few charge/discharge cycles. But there is hope: advances in
electrolytes and alternative chemistries could allow lithium metal to be the anode of
the future: the search for the lithium metal battery marches onward.

For part of my sabbatical, I was a professor in residence at Alpha-En Corporation,
located in Yonkers, New York. Alpha-En Corp. is small technology firm devoted to
the development of lithium metal (Li-M) films for next generation battery
technology. They have developed a unique process for lithium metal (Li-M) film
production: a low-energy consumption, room temperature procedure that relies on
aqueous mineral feedstocks. Lithium is ordinarily made by traditional
“electrowinning” - molten lithium chloride electrolysis at around 500 °C, with high
energy requirements. The idea of taking mineral solutions that you can almost
extract directly from the ground, and converting them to lithium metal is very
appealing. A second feature is the use of a membrane that filters lithium from other
base metals, such as sodium, potassium and calcium. This extraction process could
also save time and money while producing high purity lithium, just what is needed
for batteries. Finally, battery manufacturers want ultra thin films of lithium to
sandwich together in preparation of a functional anode. Such a form factor is hard to
attain when starting with a chunk of metal. Traditionally, for manufacturers of
primary lithium batteries (like Energizer), the lithium is extruded from an ingot into
a foil typically limited to thicknesses above 75 microns and often prepared as an
alloy foil, to maintain mechanical strength. Making thin lithium films that are less
than 50 microns requires rethinking the whole approach.

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Alpha-En Corp.’s process can claim controllable film
thicknesses in the 5-50 micron range. Purity with
respect to base metals content is extremely high and
deposition conditions can control morphology. These
features have the potential to drastically improve
behavior for cycling of lithium anodes in
electrochemical cells. Alpha-En is currently exploring
partnerships with leading global battery producers.
The goal is to become a producer of Li-M anodes that
can be used in conjunction with a range of cathodes
for the development of next generation batteries. The
Li-M anode should be thought of as a technology - a
departure from thinking simply in terms of providing
the raw material. Not least because the ultimate
behavior of the lithium in a battery can be controlled
by the method of production and treatments
involved. One additional, fascinating feature of Alpha-
En lithium metal is the morphology (called
microstructure) that can be created. Under specific
deposition conditions, they are able to grow uniform
rods of lithium metal. These rods are 300-400 Lithium metal thin films prepared via the
alpha-En process. The underlying
nanometers in diameter, with lengths of tens of morphology is a set of rods. The
microns. The result is quite beautiful, and leads to macroscopic effect is a smooth, beautiful
bright blue film.
another astounding observation, brilliant blue
colored films, unique to this morphology. While the
mechanism of color may be different, it is reminiscent of the phenomenon of
structural coloration, which causes the wings of the morpho butterfly to be an
iridescent blue.

By leveraging their proprietary process for making thin films of lithium,
demonstrating superior performance of these films as anodes, and scalability to
production volumes, Alpha-En aims to become a supplier of lithium metal anodes to
major battery manufacturers. It is hoped that the lithium metal anode can propel
battery research forward by a significant margin in terms of energy density and
cost, with major potential for aiding next generation battery technology
development. Production of new lithium metal batteries could, if successful, lead to
a tipping point in PEV adoption as well as other technology advancements in
portable electronics. Definitely something to strive for, and more than enough to
think about when the next Tesla passes by.

Like all interesting companies, the story behind alpha-En Corporation is one of
people. The founder and Chairman is Jerome Feldman. I consider Jerry to be a good
friend and we’ve worked together for several years now. Jerry was a lawyer by
training with a law degree from NYU. Many years ago, as he tells it, he got bored of
practicing law and got into science and technology. He founded a company called
National Patent Corporation, which later brought the IP to America that enabled the

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soft contact lens revolution. Several intrepid lives later he met an ingenious inventor
and former Navy engineer by the name of Larry Swonger. Their overlapping interest
in energy technology, minerals extraction and lithium, culminated in this current
venture. More recently, Sam Pitroda, a founder of six technology companies and
former Cabinet Minister of the government of India joined the team. While Vinder
Sokhi, an early investor, board member and expert in tech-to-market enterprises,
signed up to be chief operating officer. Working amongst them has been an honor
and true education. I am very grateful to the whole team at alpha-En for having
granted me this opportunity, and to the City College of New York (including my
colleagues at the Department of Chemistry and Biochemistry) for allowing me time
away from campus to delve into such an interesting and satisfying pursuit.

***


References

(1) Navigant Research. https://www.navigantresearch.com/news-and-views/us-
pev-sales-update-2018.
(2) Detroit News.
https://www.detroitnews.com/story/business/autos/2019/01/03/2018-
auto-sales-results/2466909002/.
(3) Wikipedia: Tesla Model S. Https://En.Wikipedia.Org/Wiki/Tesla_Model_S.
(4) Hausbrand, R.; Cherkashinin, G.; Ehrenberg, H.; Gröting, M.; Albe, K.; Hess, C.;
Jaegermann, W. Fundamental Degradation Mechanisms of Layered Oxide Li-
Ion Battery Cathode Materials: Methodology, Insights and Novel Approaches.
Mater. Sci. Eng. B Solid-State Mater. Adv. Technol. 2015, 192, 3–25.
(5) Whittingham, M. S. History, Evolution, and Future Status of Energy Storage.
Proc. IEEE 2012, 100, 1518–1534.
(6) K.Mizushima; P.C.Jones; P.J.Wiseman; J.B.Goodenough. LixCoO2 (0<x<-1): A
New Cathode Material for Batteries of High Energy Density. Mater. Res. Bull.
1980, 15, 783–789.
(7) SONY Global Corporate History.
https://www.sony.net/SonyInfo/CorporateInfo/History/SonyHistory/2-
13.Html.
(8) Galushkin, N. E.; Yazvinskaya, N. N.; Galushkin, D. N. Mechanism of Thermal
Runaway in Lithium-Ion Cells. J. Electrochem. Soc. 2018, 165, A1303–A1308.
(9) CBS News. https://www.cbsnews.com/news/the-toll-of-the-cobalt-mining-
industry-congo/.
(10) Wall Street Journal YouTube report.
https://www.youtube.com/Watch?V=a5GQpST7gvg.
(11) Zheng, F.; Kotobuki, M.; Song, S.; Lai, M. O.; Lu, L. Review on Solid Electrolytes
for All-Solid-State Lithium-Ion Batteries. J. Power Sources 2018, 389, 198–213.
(12) Crabtree, G.; Kócs, E.; Trahey, L. The Energy-Storage Frontier: Lithium-Ion
Batteries and Beyond. MRS Bull. 2015, 40, 1067–1078.