Intro: form of MnO2, that could be reversibly

Intro:

Twenty-seven
years ago, the lithium-ion batteries came to the global market as a result of
creative work by Asahi Kasei, Yoshino and development by the Sony Corporation.
The creation of lithium-ion batteries came about rapidly and has continued to
display remarkable progress in capacity, energy, power and cost reduction. With
recent progress in new materials, lithium-ion batteries are presumed to
continue to improve in all of its properties with new battery concepts in active
materials, inert materials and cell designs. Initially, I wanted to look into
the future of lithium-ion batteries and where they are going (TESLA TESLA
TESLA) but then I started reading about lithium-ion batteries and their story
and it’s interesting how a concept can make it’s from an idea’s in someone’s
head to a billion systems spread around the world. Of course, this project
isn’t the history of all battery cells but a brief look at the steps taken to
get from the drawing board to the market.

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The beginning of the modern
lithium-ion battery:

Though
Sony was the first primary producer and vendor of lithium-ion batteries, there
were many pioneers that preclude the one sold in 1991. The concept of a cell in
which the lithium ions move reversibly between the Anode and Cathode was first
formulated by Armand in the late 1970s, by using intercalation materials of
different potentials for the two electrodes, and is often called a rocking
chair battery because of the flow of lithium ions back and forward between the
two electrodes.1 The idea was picked up by Lazzari and Scrosati soon after and
implemented with a lithiated tungsten dioxide electrode and a titanium
disulfide electrode. The potential voltage range was only between 0.8 to 2.1
volts and the electrodes both featured significant molecular weights, but the
principle was established. After the cell cycled for over 60 cycles, however,
the charge voltage required was about 2.2 V and discharge was approximately a
low return of 1.6 V.

A spark

A
discovery by the Goodenough laboratory was the ability of NaFeO2 from the
lithiated transition metal oxide family. The compound was able to both
deintercalate and intercalate lithium ions at relatively large potentials.
Nickel and cobalt as well as other combinations with Mn, Al, Fe, were all found
to have this ability and the later adoption of this patented material (LiCoO2)
formed the active positive material of Sony’s lithium-ion battery. Quickly
after this jump, J. C. Hunter of the Eveready Laboratories discovered a new
form of MnO2, that could be reversibly reduced and oxidized in a nonaqueous
electrolyte at a high potential similar to that of LiCoO2 with a similar
capacity. The compound finding of this compound was so groundbreaking that it’s
used to this day for a selected number of higher rate batteries.

The
discovery of suitable negative electrode materials was somewhat more
complicated than the positive electrode materials. Early work on graphite and
carbonaceous materials had shown that lithium ions can be intercalated. An
important finding by Fong, Von Sacken and Dahn, showed that petroleum coke was
much better than graphite for resistance to solvent co-intercalation and
reduction, while the addition of ethylene carbonate to PC greatly improved the
resistance on both graphite and petroleum coke. Yoshino and coworkers, from
Asahi Kasei (a Japanese battery supplier of separators and electrolytes), used
the benefits of lower temperature carbons such as petroleum coke in a seminal
patent that resulted in identifying Yoshino as the true inventor of the
lithium-ion battery.

The
reversible capacities of the cokes cycled at low rates which were only half
that of the graphite. Yoshino experimented with pure starting materials, rather
than petroleum. The purity of the coke was much higher than those used by
Dahn’s group. Both parties contributed to the evolution of the ion battery but
Yoshino’s model was superior through his more refined and mixtures of specific
chemicals salt, binding and electrode combinations. Asahi Kasei later formed a
joint venture to create A Battery Corp. to make lithium-ion batteries.

Ion batteries go corporate

A
was operating as a subsidiary company within Toshiba. While the main elements
of a lithium-ion battery were laid out by Yoshino, the battery was nowhere near
having a commercial battery with superior properties compared to nickel cadmium
and the newly discovered nickel metal hydride batteries. The need was great,
because of the deficiencies of these earlier batteries, particularly low specific
energy, poor charge retention and environmental problems with the cadmium
system. Additionally, the electronics industry was rapidly developing,
particularly in the sections of computations, communication and cameras. Sony
was one of the leading companies in consumer electronics and was willing to
bring new inventive products to the table unlike anything else on the market.
Sony was a relative newcomer to the battery business, learning the alkaline
primary cell technology, but severed that focus and began work in earnest on
rechargeable batteries.1

The new
generation of Cathodewere introduced; a hard carbon with higher specific
capacity was substituted for the coke. A still later development was the now
commonly used mesophase carbon microbeads (MCMB). This gave a still higher
specific capacity and a flat discharge profile. The positive electrode
material, LiCoO2, was carefully designed to have a coarser particle size and
good crystallinity.

A crash
project with Kureha Chemical Ind. Co. developed an improved material giving
greatly improved adhesion to the Al carrier foil. Sony’s role in producing
magnetic tape was helpful in manufacturing the coated electrodes and there is
no doubt that part of this experience involved the use of excellent production
coating machinery, but, as confirmed by Toru Nagaura,1 one of the key engineers
on the project, the particular kind of high energy mixing of the coating slurry
was also of great importance. This was also around the time where Nickel coated
iron cans were integrated into the system. Nickel coated iron cans were
critical to the success of the project because stainless cans originally
selected because of the presence of trace amounts of HF was found to have too
high resistance for the applications envisioned.

Sony’s final product

The cell
size selected was 18650 (this is based on the naming system for cylindrical
lithium primary cells, the first two numbers represent the diameter in mm and
the remaining numbers represent the height of the cell in tenths of mm – thus
the common a 18650 cell is 18 mm diameter and 65 mm in height) this is the
common size of AA batteries. This choice is close to the volume of subC
rechargeable nickel-based batteries, the most popular size at the time for
small electronic devices. The separator selected was a biaxially stretched
microporous polyethene material. The electrolyte chosen was ethylene carbonate
with a linear dialkyl carbonate and the salt was LiPF6 of high purity and state
of dryness. The all carbonate solvent had the important property of being
highly oxidation resistance. Subsequent improvements in electrolyte have mostly
involved the use of additives to improve the film on the negative material,
improve the oxidation stability of electrolyte to the positive active material.

Conclusion:

The
original Sony product with coke negative had roughly 5 times less energy
density than that of what it is today. Allowing for longer lasting battery
life, fewer battery recharges, and a refining of the core electrodes,
separators and to get larger numbers of recycles. While Sony remained the
industry leader for some time, competition from many other producers finally
led to a planned withdrawal of Sony from the battery market, but Sony and
Yoshino will forever have left the mark on the world of transportable power
that we live in today.

 

1.
Blomgren, George E.. “The Development and Future of Lithium Ion Batteries.”
jes.ecsdl.org. Journal of The Electrochemical Society, 164, 1 Dec. 2016. Web.
25 Jan. 2018. .

2. M. S.
Whittingham, “Lithium Batteries and Cathode Materials”, Chem. Reviews, 104,
4271 (2004).

3.
Thomas Waldmann, Jason B. Quinn, Karsten Richter, Michael Kasper, Alexander
Tost, Andreas Klein, Margret Wohlfahrt-Mehrens, Electrochemical, Post-Mortem,
and ARC Analysis of Li-Ion Cell Safety in Second-Life Applications, Journal of
The Electrochemical Society, 2017, 164, 13, A3154