Chemistry 362 Fall 2019

Professor Kim R. Dunbar

The Development of Lithium-Ion Batteries and

the Winners of the 2019 Nobel Prize in Chemistry

Bonnie Rankin
725002150

 Table of Contents

INTRODUCTION……...…………………………………………….. 1
Figure 1………………………………………………………..………… 1
Figure 2………………………………………………………………….. 2
Figure 3…………………………………………………..……………… 2
Figure 4……………………………………………………..…………… 3

MAJOR FINDINGS……….…………………………………………. 3
Figure 5………………………………………….………………………. 4
Figure 6…………………………………………..……………………… 4
Figure 7…………………………………………………….……………. 4

DISCUSSION…………….…………………………………………… 5
Figure 8…………………………………………………….……………. 5
Figure 9…………………………………………………….……………. 5

REFERENCES………………………………………………………... 6
Photo References………………..………………………………………. 7
INTRODUCTION

Lithium-ion batteries are in practically everything portable used on a daily basis. From
phones to cars, the rechargeable battery has played a large part in advancing the technology of
today. Since its first appearance on the commercial marketplace in 1992 this battery has
continued to be a large component of progress in green energy research and technological
advancements. The development of this battery is credited to three laureates, Dr. John B.
Goodenough, Dr. M. Stanley Whittingham, and Dr. Akira Yoshino, all of which won the Nobel
Prize in Chemistry in 2019. Twenty-seven years after the battery first appeared on the
marketplace. The process of creating the lithium-ion battery began in the 1970’s. The panic of
the oil crisis created a new interest in alternate sources of energy such as wind and solar. In order
to take advantage of these, it was necessary to have a way to store the energy captured in these
forms. A rechargeable battery was an idea that had been experimented on before, but the high
acidity and inefficiency of those available made it an unattractive and difficult solution to the
established use of fossil fuels.

A battery is made up of one or

more cells that store energy in an
anode or cathode electrode. For a
battery to charge the ions must move
from the anode to the cathode and
during discharging the ions move in
the opposite way as shown in Figure 1.
Between the two electrodes there is an
electrolyte that transports the ionic
component inside a cell while the
electric component is forced to the
external circuit. A rechargeable battery
Figure 1
can reverse the process. Before the
research began on the possibility of using lithium, European chemists had created rechargeable
batteries that were strongly acidic or alkaline and aqueous. The aqueous component limited the
voltage of the cell lowering the power that the battery could hold. These batteries were also
highly acidic and bulky, making them hard to transport and inefficient. More research was done
on rechargeable batteries in 1967 when Joseph Kummer and Neill Weber of the Ford Motor
Company discovered a sulfur rechargeable battery that used ceramic as the electrolyte, molten
sulfur with carbon as the cathode and molten sodium as the anode. The issue with this battery
was that it had to operate above 300°C, meaning it would not work for the commercial market
because the impracticality of the required temperature. These types of batteries paved the way
for Dr. Whittingham, Dr. Goodenough, and Dr. Yoshino to create the lithium-ion rechargeable
battery that was portable, capable of storing more energy, greener, and commercially viable.

Exxon Mobil wanted to be on the forefront of this new energy capacity. They hired Dr.
Stanley Whittingham as a materials scientist to develop the batteries. Dr. Whittingham
recognized the problems associated with the heavy metals of the current batteries and
hypothesized that lithium metal could be the anode in a battery due to its high electron release
tendency and its light weight. The only conditions were that the metal was protected from air and

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water. Dr. John B. Goodenough worked not long after Dr. Whittingham started his research. Dr.
Goodenough’s goal was to create a more eco-friendly energy source. He drew on the ideas of the
European rechargeable batteries and Dr. Whittingham’s previously researched disulphide
cathode. He reasoned that a battery could have more potential with the use of a metal oxide
cathode instead of a metal sulphide one. Dr. Yoshino was working for Sony and among those
researching a more efficient and commercial battery. He recognized the problem of the low
powered rechargeable batteries that existed and use of the wrong materials for this battery. He
used the research of both scientists to form the hypothesis that using a more durable carbonic-
based anode instead of a highly reactive lithium anode would create a more efficient
rechargeable battery without breaking down.

Dr. Whittingham had done previous work

that illustrated titanium disulphide could be a
cathode and store charged lithium ions. Using this
knowledge he created a battery in 1976 made of
lithium and titanium disulphide. Lithium was
chosen based on his hypothesis. He discovered
that in addition to being a lighter solution to the
heavy batteries of the time it was also
rechargeable. Upon multiple repeated testing of
recharging, anode dendrites, or lithium whiskers,
started to form a long connection to the cathode.
They created a short-circuit that was explosive
proving to be a challenge of the battery. These
lithium whiskers are shown in Figure 2. The end
of the oil crisis prompted Exxon Mobil to shut Figure 2
down the experiment as it was no longer pertinent
to them to create an alternate energy source to
fossil-fuels. Due to the cancelation of the research he was not able to achieve a long term
working battery, making the people who employed him his biggest challenge that he was not
able to overcome. Although Dr. Whittingham’s battery failed to achieve a continuously
functional system, his work started the path towards lithium ions in batteries. This was the basis
Dr. Goodenough and Dr. Yoshino worked off of.

Dr. Goodenough was doing research at the

University of Oxford on lithium extraction. During
this research he formulated the theory that a metal
oxide would create a battery with greater potential.
His research focused on the amount of lithium that
can be extracted from layered lithium cobalt oxide
and lithium nickel oxide without changing the
structure of the molecule. This led to the discovery
that a large portion of the lithium could be
extracted with lithium cobalt oxide (LiCoO2) or
Figure 3

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lithium nickel oxide (LiNiO2) cathodes. He then reasoned that using these materials as cathodes
would create higher movement of lithium electrons and a higher potential. Figure 3 shows how
lithium ions would be transferred while using a LiCoO2 cathode. During this time he also
reasoned that a battery could be formed while in a discharged state as it could be formed in a
charged state. The largest challenge was the length of time it took to test multiple metal oxides
for the right combination then testing them in a battery form. The information Dr. Goodenough
discovered about lithium ions and the metal oxide helped Dr. Yoshino form his own hypothesis
and create the final product that so many were hoping to achieve.

Dr. Yoshino was employed at Sony when working on

a commercial rechargeable battery that had enough power to
be placed in Sony’s products. His hypothesis centered on a
carbon based anode and his big challenge was finding a
carbon material that would be durable enough for multiple
uses yet reactive enough. He tested different types of carbon-
based material with a LiCoO2 cathode. A functioning battery
was created with polyacetylene but it was found to have too
low of a capacity. A petroleum coke anode was then tested
and found to work the best due to its ability to be charged
and discharged multiple times without deteriorating. The
result of the petroleum coke anode and LiCoO2 cathode was
a commercial rechargeable battery that could be recharged
multiple times without lowering the power of the battery.
The final product that employed research of lithium ions
from Dr. Whittingham, the LiCoO2 cathode, and the
formation of a battery in a discharged state theory of Dr. Figure 4
Goodenough is shown in Figure 4.

MAJOR FINDINGS

Each of these three men discovered a component that would be used to achieve the
objective of a rechargeable battery. Dr. Whittingham started the path to fossil fuel-free energy
technology. As opposed to the heavy toxic metal rechargeable batteries of that day, he looked
into the lighter metal lithium that had a high tendency to discharge its electrons. His investigation
and creation of a rechargeable lithium and titanium disulphide battery was the first of its type to
successfully hold a charge. Thus, he discovered the possibility of the use of lithium, which was
the first part of the puzzle. Dr. Goodenough was also interested in creating a more ecofriendly
battery and used Dr. Whittingham’s research with his own background to try metal oxide as a
cathode. He found LiCoO2 supported his idea of a reverse or discharged state of battery. This flip
on the original battery design standard and use of a LiCoO2 cathode created a more powerful
battery and is what lead Dr. Yoshino to create the first commercialized lithium ion battery. His
invention was the breakthrough that created a boom for technology. Without the research and
findings Dr. Whittingham and Dr. Goodenough, Dr. Yoshino may not have put these
components together and created the lithium-ion battery.

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 Dr. Whittingham’s experiments
included creating electricity from the
contact of lithium ions being held
between titanium sulfide plates. The
design he used was comprised of
titanium sulfide, 2.5-volt material, and a
removable way to insert ions. His
hypothesis was centered on the use of
lithium with his previously discovered
titanium sulfide cathode therefore, the
tests he ran consisted of a battery made
of those materials. During multiple
testing rounds of charging, running, and
Figure 5 recharging, dendrites formed between
the cathode and anode that eventually
led to an explosion. The lithium dendrites short-circuited the battery on multiple attempts, and
the battery was found to be too volatile because of the explosions it caused. Figure 5 illustrates
the battery that Dr. Whittingham created. The figure also shows the battery produced two volts
while functioning.

Dr. Goodenough focused on metal oxides in

his experiments. He and his students worked
through oxide group structures to find the
maximum voltage of lithium that could be taken
from the metal oxide without sacrificing the
structure. LiCoO2 and lithium nickel oxide
(LiNiO2) were the two metal oxides he found that
could have half the lithium taken out. When testing
these as cathodes he found four volts would be
created from a battery using LiCoO2 as the cathode.
This was a higher voltage than Dr. Whittingham’s Figure 6
battery and became closer to a more efficient battery.
Figure 6 shows the battery created using this information.

Dr. Yoshino worked off of Dr.

Goodenough’s findings. He analyzed the
objective and the problems that other types of
rechargeable batteries had. By using lithium ions
and research done by Dr. Goodenough he
determined that a carbon-based material for a
negative electrode would pair with the LiCoO2
cathode. Through a process of studying different
types of materials and using information about
carbon-based materials such as graphite, he
determined it was necessary to have not only a
Figure 7

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carbon based material but one that was not a solid. This was so it did not have the tendency to
break down. Materials were systematically eliminated as possible materials and remaining
possibilities were tested. Polyacetylene created a functioning battery but did not produce a high
voltage that was desired. A carbon-based material with a crystalline structure was necessary, and
petroleum coke was found to work the best for the battery because of its structure and the voltage
it produced. This combination of petroleum coke and LiCoO2 produced four volts and was much
more desirable and is shown in Figure 7. In order to deem a commercially viable product, Dr.
Yoshino proceeded to conduct many experiments with handmade prototypes to prove its ability
and safety.

DISCUSSION

The experiments done by all three laureates began by

analyzing the information already known, then conducting a trial and
error system based on their hypotheses. Their collected data through
the processes helped determine if each of their discoveries
successfully created the lithium-ion battery. Failures and
shortcoming were recorded in the data and led the next person to the
proper material. Dr. Whittingham’s tests and data collected provided
information on lithium and its potential for following scientists to
work from. Exxon documented his discovery, and he is shown in
Figure 8 describing his work. Dr. Goodenough worked from Dr.
Whittingham’s research, and the data he collected not only provided Figure 8
a more in depth understanding of lithium but gave a new way of
thinking about the lithium-ion battery as it was
paired with an oxide instead of a sulphide. Data
from both these experiments were used with
previous knowledge by Dr. Yoshino to form a
hypothesis and test. Dr. Yoshino’s success and
explanation in his data, such as Figure 9 illustrating
the replica of the functional battery, will continue to
help improve the performance of the lithium-ion
battery and create one that is even more efficient.

These three laureates achieved their goal of

creating a fossil fuel-free energy and a more
efficient, portable battery. The work that the three
Figure 9 of them did combined to create a battery that has
transformed the world. The lithium-ion battery is in
use by practically every individual today. The invention and application of it has been under
discussion for years in order to fully understand the possible applications. Dr. M. Stanley
Whittingham, Dr. John B. Goodenough, and Dr. Akira Yoshino’s work and data will continue to
transform the world as people continue to try and improve upon it to make an even more
efficient battery that does not depend on and can compete with fossil fuels. They truly did make
an impact on the world and people’s everyday life; this innovation and impact merited the Nobel
Prize.

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 REFERENCES

Rathi, A. Winners of the 2019 Nobel Prize in chemistry developed lithium-ion batteries.
https://qz.com/1724449/nobel-prize-in-chemistry-winners-developed-lithium-ion-batteries/
(accessed Nov 29, 2019).

Nevelius, E. Press Release: The Nobel Prize in Chemistry 2019.

https://www.nobelprize.org/prizes/chemistry/2019/press-release/ (accessed Nov 29, 2019).

Goodenough, J. B. Nature Electronics. March 2018, pp 204–204.

Nobel Prize in Chemistry 2019: Lithium-ion batteries.

https://www.sciencedaily.com/releases/2019/10/191009082508.htm (accessed Nov 29, 2019).

Krämer K. Chemistry Nobel prize 'finally' goes to developers of lithium-ion batteries.

https://www.chemistryworld.com/news/chemistry-nobel-prize-finally-goes-to-developers-of-
lithium-ion-batteries/4010482.article (accessed Nov 29, 2019).

Temming, M.; Lambert, J. The development of the lithium-ion battery has won the chemistry
Nobel Prize. https://www.sciencenews.org/article/lithium-ion-battery-chemistry-nobel-prize
(accessed Nov 29, 2019).

Guarino, B. Nobel Prize in Chemistry awarded for rechargeable lithium-ion batteries.

https://www.washingtonpost.com/science/2019/10/09/nobel-prize-chemistry-awarded-lithium-
ion-batteries/ (accessed Nov 29, 2019).

Pioneers of innovation: The battery that changed the world.

https://energyfactor.exxonmobil.com/science-technology/battery-changed-world/ (accessed Nov
29, 2019).

LeVine, S. At 92, the man who brought you the lithium-ion battery is still having creative
breakthroughs. https://qz.com/338767/the-man-who-brought-us-the-lithium-ion-battery-at-57-
has-an-idea-for-a-new-one-at-92/ (accessed Nov 29, 2019).

Yoshino, A. https://www.asahi-kasei.co.jp/asahi/en/r_and_d/interview/yoshino/pdf/lithium-
ion_battery.pdf (accessed Nov 29, 2019).

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 PHOTO REFERENCES

Figure 1
Dilluh. Lithium ion battery primer. https://areweanycloser.wordpress.com/2013/05/20/lithium-
ion-battery-primer/ (accessed Nov 29, 2019).

Figure 2
Fernholm, A. The Nobel Prize in Chemistry 2019.
https://www.nobelprize.org/prizes/chemistry/2019/popular-information/ (accessed Nov 29,
2019).
Figure 3
Gregg, H. The University of Chicago Magazine. The University of Chicago 2016.

Figure 4
Goodenough, J. B. Nature Electronics. March 2018, pp 204–204.

Figure 5
Temming, M.; Lambert, J. The development of the lithium-ion battery has won the chemistry
Nobel Prize. https://www.sciencenews.org/article/lithium-ion-battery-chemistry-nobel-prize
(accessed Nov 29, 2019).

Figure 6
Temming, M.; Lambert, J. The development of the lithium-ion battery has won the chemistry
Nobel Prize. https://www.sciencenews.org/article/lithium-ion-battery-chemistry-nobel-prize
(accessed Nov 29, 2019).

Figure 7
Temming, M.; Lambert, J. The development of the lithium-ion battery has won the chemistry
Nobel Prize. https://www.sciencenews.org/article/lithium-ion-battery-chemistry-nobel-prize
(accessed Nov 29, 2019).

Figure 8
Pioneers of innovation: The battery that changed the world.
https://energyfactor.exxonmobil.com/science-technology/battery-changed-world/ (accessed Nov
29, 2019).

Figure 9
Yoshino, A. https://www.asahi-kasei.co.jp/asahi/en/r_and_d/interview/yoshino/pdf/lithium-
ion_battery.pdf (accessed Nov 29, 2019).