Firenze University Press

[Link]/substantia

Energy on demand:
A brief history of the development of the battery
Citation: C. L. Heth (2019) Energy on
demand: A brief history of the devel-
opment of the battery. Substantia 3(2)
Suppl. 1: 73-82. doi: 10.13128/Sub- Christopher L. Heth
stantia-280
Minot State University, 500 University Ave. W, Minot, ND 58707
Copyright: © 2019 C. L. Heth. This is E-mail: [Link]@[Link]
an open access, peer-reviewed article
published by Firenze University Press
([Link] Abstract. Portable, readily available electrical energy provided by batteries is ubiq-
and distributed under the terms of the uitous in modern society and can easily be taken for granted. From the early Voltaic
Creative Commons Attribution License, piles to modern lithium ion cells, batteries have been powering scientific and techno-
which permits unrestricted use, distri- logical advancement for over two centuries. A survey of select notable developments
bution, and reproduction in any medi-
leading to modern batteries commercially available today are presented, with emphasis
um, provided the original author and
source are credited. on early technologies and also including some of the advancements made within the
last few decades. A brief discussion of the chemistry utilized by battery technology is
Data Availability Statement: All rel- also included.
evant data are within the paper and its
Supporting Information files. Keywords. Battery, electrochemical cell, Voltaic pile, Daniell cell.
Competing Interests: The Author(s)
declare(s) no conflict of interest.

INTRODUCTION

In the modern industrialized world, it can be difficult to imagine life

without ready access to on-demand electricity. Massive electrical infrastruc-
tures have been built allowing for safe, reliable, and constant delivery of elec-
trical energy to households, businesses, and industrial complexes throughout
much of the globe. By 1950, electric power consumption in the United States
was reported at 291 billion kilowatt hours.1 By the mid 1990’s usage topped
3,000 billion kilowatt hours, and demand has continued to increase with
consumption of 3,946 billion kilowatt hours reported for 2018, the bulk of
which is split between residential (37%) and commercial (35%) usage.1
While this infrastructure effectively provides fixed access to electrical
energy within relatively easy reach in homes, workplaces, and other loca-
tions, batteries are used as a source of power for a myriad of devices. From
cell phones to flashlights, wall clocks to children’s toys, more and more elec-
tronic devices utilize battery power. Medical devices, whether implanted
such as a pacemaker or external like an insulin pump, also require light-
weight mobile power sources, as do fully electric automobiles on an even
larger scale.
With a ready supply of electrical energy ubiquitous in industrialized
society, it can be easy to take this valuable resource for granted without con-
sideration for the process by which the development of the battery occurred,

Substantia. An International Journal of the History of Chemistry 3(2) Suppl. 1: 73-82, 2019
ISSN 1827-9643 (online) | DOI: 10.13128/Substantia-280
74 Christopher L. Heth

or the technological advancements that followed. A com- In simple electrochemical cells (Figure 1), these
plete and exhaustive accounting of all these advances processes occur at the surface of electronic conductors,
would be an undertaking beyond the scope of this work termed electrodes. These electrodes may be composed of
and may well be out-of-date prior to publication, as work a redox-active material or more electrochemically inert
currently continues to design and produce smaller, light- materials such as platinum, mercury, gold, or graph-
er, and longer lasting batteries for mobile electronics. As ite.5 Oxidation occurs at the anode, while the reduction
such, this work will focus on the earliest battery devel- process occurs at the cathode. Between the electrodes is
opments as well as the more significant general develop- an electrolyte, an ionic conductor necessary to reduce
ments within the past several decades. polarization and allow current to flow. Wire or another
electrically conducting material connects the two elec-
trodes to a load, completing the circuit, allowing the
THE ELECTROCHEMICAL CELL battery to discharge and work to be done. The overall
system must remain charge-neutral in order to continue
The term “battery” has several different meanings functioning. If a build up of charge occurs, polarization
which may at first glance appear unrelated.2 The com- results and the electric current is reduced and ultimately
mon thread within these varied definitions is the ref- stopped completely.
erence to multiple parts working in concert, whether Batteries are often classified as either primary or
artillery pieces, a pitcher and a catcher in baseball, or a secondary batteries. In both cases, chemical poten-
collection of electrochemical cells. Benjamin Franklin tial energy is converted to electrical energy. For pri-
is attributed with one of the first uses of the term “Elec- mary batteries, the chemical reactants are consumed
trical Battery”, included in a letter describing his work in a process which is not easily reversible, resulting in
with static electricity using Leyden jars to English natu- a battery which can only be discharged a single time.
ralist Peter Collinson in 1749: Examples of primary batteries include common alka-
line batteries, silver button cells and watch batteries,
Upon this We made what we call’d an Electric Battery, and the homemade “lemon battery” consisting of piec-
consisting of eleven Panes of large Sash Glass, arm’d with es of iron and copper stuck into the flesh of the acidic
thin leaden Plates,…with Hooks of thick Leaden Wire one citrus fruit.
from each Side standing upright, distant from each other;
Secondary batteries also convert chemical potential
and convenient Communications of Wire and Chain from
the giving Side of one Pane to the receiving Side of the oth- energy to electrical energy, but do so through revers-
er; that so the whole might be charg’d together, and with ible chemical process which render the resulting bat-
the same Labour as one single Pane;…3 tery rechargeable. Application of electrical energy from
an external source such as a generator or another bat-
Over time, the term “battery” has come to refer to tery can regenerate the initial chemical reactants, restor-
both a collection of connected electrochemical cells and ing the battery’s charge and allowing repeated charge/
a single working cell, and will be generally used without discharge cycles. Because of this ability to store energy,
specificity throughout this work.4 these types of cells are also known as “storage batteries”.
Batteries produce electrical energy through oxida- Common examples of storage batteries include lead-acid
tion-reduction (redox) processes, wherein one substance
loses electrons through oxidation while another sub-
stance gains electrons through reduction. It is some-
times convenient to examine the oxidation and reduc-
tion processes independently as half reactions, an exam-
ple of which is shown below. However, it is important to
note that oxidation cannot occur without a correspond-
ing reduction process also occurring and vice versa,
although the two processes do not necessarily need to
occur at the same physical location.

Oxidation:  Zn(s) → Zn2+(aq) + 2 e-
Reduction: Cu2+(aq) + 2 e- → Cu(s)

Overall:      Zn(s) + Cu2+(aq) → Zn2+(aq) + Cu(s)

Figure 1. A simple electrochemical cell.
Energy on demand: A brief history of the development of the battery 75

batteries used in most automobiles and lithium-ion bat- a “crown of cups”, a series of what would modernly be
teries found in mobile consumer electronics. described as simple wet cells.14
Discharging Volta’s pile resulted in visible corrosion
occurring on the zinc (or tin) discs, the result of oxida-
THE VOLTAIC PILE tion of the anode. A slight corrosion was also sometimes
noted on the silver (or copper) cathode discs, but not to
Prior to 1800, studies of electricity were limited to the same extent as seen on the anode. At the time this
what could be achieved through collection and discharge led him to believe the current was solely the result of the
of static electricity.6–8 While arcs with rather large volt- anodic reaction. Considering it is now known that oxi-
ages could be achieved, their application was limited by dation cannot occur without reduction, and with Volta
the small current and extremely short duration of the and others noting problematic polarization resulting
discharge.6 Despite this limitation, the study of electri- from bubbles of hydrogen gas adhering to the electrode
cal phenomenon spanned from attempts to split water surfaces, it seems evident that the corresponding reduc-
through electrolysis, to studies with frogs predating tion process in Volta’s pile was the reduction of hydro-
Luigi Galvani’s well-known work, to Franklin’s famous gen from water, as seen in the overall electrochemical
lightning experiments.9–13 reaction below.
In March of 1800, Alessandro Volta (Figure 2), pro-
fessor of natural philosophy at the University of Pavia Zn(s) + 2H2O(l) → Zn2+(aq) + H2(g) + 2OH-(aq)
in Lombardy, Italy, in a correspondence to Joseph
Banks, President of the Royal Society of London, It should be noted that the reduction process is often
described a device which could provide a continuous incorrectly attributed to reduction of the cathode mate-
supply of electrical power. 8,14 This apparatus (Figure rial (half reactions seen below for silver and copper).
3), later known as the “Voltaic Pile” consisted of discs However, this would require ions of the cathode material
of tin or zinc paired with discs of copper, brass, or sil- to be already present in order to occur. While it is pos-
ver, with layers of water-soaked paper, fiber board, or sible some advantageous oxidized cathode material may
leather between the disc pairs. Wire contacts with the
discs on the top and bottom of the pile allowed the
experimenter access to a constant electric current.
Also included was a description of what Volta termed

Figure 2. Alessandro Volta (1745-1827) (public domain). Figure 3. Volta’s crown of cups and several piles (public domain).
76 Christopher L. Heth

have been present, it is unlikely there would be enough Further advances rapidly followed. Electrodeposition
to support much electric current out of the device. of metals was reported by Nicholson and Carlisle along
with William Cruickshank in England, and indepen-
Cu2+(aq) + 2 e- → Cu(s) dently by J.W. Ritter in Bavaria in 1800.18–20 In 1805, Rit-
Ag+ + e- → Ag(s) ter was reported to have developed a modified pile uti-
lizing a single metal which could be charged, a precursor
Volta’s description of his pile was quite complete and to the storage battery.21 Humphry Davy confirmed that
its design was elegant yet simple, allowing experimental- charcoal could substituted for the wires connected to the
ists to very quickly build replicas in their laboratories for pile (a phenomenon originally reported by Volta), and
application to their own work. Volta in this same letter is reported to have used charcoal to produce impressive
described experiments where he applied the leads from sparks as early as 1802.22 By 1808, Davy had used the
his pile to his lips and tongue, describing the results: Voltaic pile to discover and isolate several of the alkali
and alkaline-earth elements, including sodium, potas-
In fact, once the circuit is closed in a convenient manner, sium, barium, calcium, strontium, and magnesium.23,24
one will excite simultaneously…a sensation of light in the
eyes, a convulsion on the lips and even in the tongue, a
painful prick at the point of the tongue, finally followed by
EARY IMPROVEMENTS TO THE BATTERY
a sensation of taste.15

While undoubtedly a monumental improvement

IMPACT OF VOLTA’S PILE over static discharge collecting devices of the time, the
Voltaic pile was not without its imitations. The use-
This new development had an almost immedi- ful lifetime of the pile was limited, as corrosion of the
ate impact on the study of electricity. Possibly due to metal discs, while a necessary result of the chemical pro-
hostilities between France and England at the time, cesses driving the output, would occur quite rapidly and
Volta sent the first four pages of the letter to Banks in require the pile to be rebuilt.25 In addition, polarization
March, with the remainder sent several months later.8 of the electrodes would result in a decrease in output
As a result, Volta’s letter was not formally read into the over time. Within a year, numerous attempts to improve
Society until June 26, 1800.14 However, Banks shared the Voltaic pile were made. One such modification was
the contents of the first four pages with a number of the the trough battery developed by Cruickshank (Figure
members of the Society, allowing them to build devices 4).25 A grooved wooden trough was used, with soldered
for their own work prior to the paper’s reading. William pairs of zinc and silver plates affixed in the grooves
Nicholson specifically mentions these circumstances in with rosin or wax to create a number of sealed cham-
his accounts of this new “electrical or Galvanic appara- bers. These chambers were then filled with a solution
tus” published in July, 1800, indicating he felt it proper of ammonium nitrate, effectively replacing the wetted
to delay publication of his own work until Volta’s entire paper discs of the pile with a fluid solution. This ensured
paper had been read to the Society.16 a more ready supply of electrolyte at the surface of the
In this same paper, Nicholson describes work he plates, and allowed the plates to be more easily cleaned
performed with Anthony Carlisle which included the as corrosion occurred through treatment with hydro-
electrolysis of water, with application of electric current chloric acid solution.25
for a period of 13 hours to produce 1.17 cubic inches of Charles Wilkinson modified Cruickshank’s trough
gas.16 This was a significant improvement in both yield battery, using wooden partitions instead of metal plates,
and efficiency from earlier works using static discharge. and attached wires to separated zinc and copper plates,
For comparison, George Pearson reported collecting one allowing the plates to be removed at the conclusion of
third of a cubic inch of gas utilizing over 14,600 static the battery’s daily usage while leaving the electrolyte in
discharges.9 While times for that specific experiment are the trough.26 Wilkinson had previously noted the power
not given by Pearson, based upon times given for other of the device was not related to the contact area between
experiments in the same paper, the process likely took the copper or silver plate and the zinc plate, and pro-
approximately 18 hours to complete. Later that same posed an increase in available zinc surface area resulted
year, Humphry Davy produced isolated hydrogen and in increased output.27 With the zinc and copper plates
oxygen gases from samples of water in separate glasses completely separated, Wilkinson reported his plunge-
using a Voltaic pile, completing the circuit through his type device with four inch plates was the equal of a
own body by inserting a finger in each glass of water.17 Cruickshank-type trough battery with six inch plates.26
Energy on demand: A brief history of the development of the battery 77

Figure 4. 19th Century illustration of a trough battery (public

domain).

As previously mentioned, corrosion of the anode

material was recognized to occur during discharge of
a battery. However, corrosion would also occur, albe-
it more slowly, even when the battery was left idle or
stored for a period of time. While removal of the anode
metal from the electrolyte solution as seen in plunge- Figure 5. A drawing of a Daniell Cell. This later design utilizes a
type batteries was an effective means to halt this sec- ceramic cell container and paper divider, with copper sheet and
zinc rod electrodes.
ondary corrosion, the two-fluid cell would prove to be
another approach with historical significance.6
One particularly noteworthy modification of the
Daniell cell was developed by William Grove.34,35 While
THE DANIELL CELL investigating the action of a mixture of nitric and hydro-
chloric (muriatic) acids on gold foil, he discovered con-
While aspects of a two-fluid cell had previously been necting the gold foil to an isolated pool of nitric acid
described independently by Becquerel and Wach, the suc- via a wire resulted in the dissolution of the gold foil.34
cessful invention is generally credited to J. Frederic Dan- He also proposed that using nitric acid and an inactive
iell.6,28 In letters to Michael Faraday, Daniell describes cathode such as platinum in one chamber of a Daniell
a cell composed of a copper cylinder with a membrane cell, with a zinc anode in the other, should produce a
tube “formed of a part of the gullet of an ox” suspended greater electric current than the standard configura-
by collars inside (Figure 5).29–31 Within the membrane was tion.34 While nitric acid had been used as an electrolyte
contained a zinc rod as well as a solution of either sul- previously, this is believed to be the first time nitric acid
furic acid or zinc sulfate, with the copper cylinder filled was recognized as a cathodic reactant.6 The half reac-
with a copper(II) sulfate solution. Additionally, a siphon tions, as well as the combined overall redox reaction, can
tube was included to allow removal of saturated zinc be seen below.
sulfate solution from the bottom of the membrane tube.
Thus, fresh acid and copper(II) sulfate could be added Oxidation: Zn(s) → Zn2+(aq) + 2 e-
as needed. Later other materials such as paper dividers Reduction: 2 H+(aq) + 2 HNO3(aq) + 2 e- →
or porous ceramic were used to separate the two solu- 2 H2O(l) + 2 NO2(g)
tions.6,32,33 The presence of copper ions in the outer solu-
tion, and the need to occasionally add copper(II) sulfate Overall: Zn(s) + 2 H+(aq) + 2 HNO3(aq) →
to the cell, indicate the reduction reaction for the Daniell Zn2+(aq) + 2 H2O(l) + 2 NO2(g)
cell was not hydrogen reduction as seen in the Voltaic pile
and the trough battery, but rather the reduction of copper Further improvement of the Grove cell occurred
ion, resulting in the following overall reaction. through the inclusion of carbon as an inert electrode
material.6 While many investigators, including Volta
Zn(s) + Cu2+(aq) → Zn2+(aq) + Cu(s) and Davy, had already explored charcoal and graph-
78 Christopher L. Heth

ite for charge collection or as electrical conductors, it is carbon matrix.6 As with the Daniell and Grove cells, the
Robert Bunsen who is commonly credited with initiat- Leclanché cell also served as an important stepping stone
ing its widespread use in batteries.6 The replacement of toward the eventual development of the dry cell battery.
the expensive platinum cathode with carbon helped Numerous attempts were made through the years to
reduce the cost of Grove-type batteries, which undoubt- immobilize the electrolyte and create a “dry cell”, thus
edly increased their usage. However, the disadvantages reducing or eliminating risk of leaking or spillage. Volta’s
inherent to the use of nitric acid were still present, par- original pile immobilized the electrolyte by absorbing it
ticularly the production of noxious nitrogen oxides (NO, in paper or leather.14 Attempts with other materials were
N2O4). Eventually oxidants other than nitric acid were reported, including starch pastes, sand, asbestos, wool,
explored, including chromic acid, permanganate, and and gelatin.6,36 In 1887, Carl Gassner, Jr. filed a patent in
chlorates, and modified Grove cells were used for the the United States outlining the use of zinc oxide mixed
next several decades for certain applications.6 However, with plaster surrounding a MnO2/C cathode inside a zinc
the greatest value in both the Daniell and Grove cells cylinder, which served as both anode and cell container
may have been in laying the groundwork for what would for a battery.37 While this approach was not particularly
eventually become the modern dry cell battery. successful, likely due to extremely limited ion mobility
within the solid plaster, it does bear a striking resem-
blance to the modern dry cell configuration.
TOWARD THE MODERN DRY CELL Alkaline electrolytes were reported in a French pat-
ent in 1881, followed by a U.S. patent in 1883, by Felix de
One significant downside to the Cruickshank, Dan- Lalande and Georges Chaperon, although it is likely the
iell, and Grove batteries, as well as their derivatives, use of alkaline solutions was investigated far earlier. 38
was the need for liquid electrolytes, often times corro- Lalande and Chaperon used caustic potash or caustic
sive acid solutions. These solutions resulted in batteries soda with zinc anodes and copper oxide as the cathode
that were quite heavy, prone to spillage if moved, and material to good effect, and in 1889 a manufacturing
susceptible to messy leaks. This combination of factors plant was producing alkaline zinc and copper oxide cells
was especially problematic for applications requiring a in the United States.38,39
mobile source of power, such as on railroads, street cars,
or eventually for carriage lighting.
A significant step toward a solution to this problem
occurred with the design of a cell by Georges Leclan-
ché, patented in France in 1866. 36 The Leclanché cell
continued to utilize a zinc rod as the anode, but made
use of a porous ceramic pot filled with a mixture of
manganese(IV) oxide and carbon with a carbon rod cur-
rent collector as the cathode (Figure 6). Reduction of the
manganese from +4 to +3 occurred at the cathode, and
can be seen below.7 A solution of saturated ammonium
chloride was used as the electrolyte.6

Oxidation: Zn(s) → Zn2+(aq) + 2 e-

Reduction: 2 H+(aq) + 2 MnO2(s) + 2 e- → 2 MnO(OH)(s)

Overall: Zn(s) + 2 H+(aq) + 2 MnO2(s) →

Zn2+(aq) + 2 MnO(OH)(s)

While still a wet cell, and thus still suffering from

some of the same limitations of its predecessors, the
elimination of acid served to improve the stability of the
cell, and reduced the hazards associated with leaks and
spills. Unfortunately, current outputs were limited under
prolonged use, with only a slight improvement over the
Daniell cell, possibly due to the limited redox availabil-
ity of the MnO2 residing in microdomains within the Figure 6. Leclanché wet cell (public domain).
Energy on demand: A brief history of the development of the battery 79

The modern alkaline battery can be considered a

culmination of many of the advances described above,
although 50 years would pass before its invention. A
zinc casing serves as the anode as used by Gassner. Con-
tained within the cell is a cathode composed of the car-
bon rod collector made popular by Bunsen surrounded
by a MnO2/C paste similar to that found in the Leclan-
ché cell. A caustic soda paste serves as the electrolyte
as described by de Lalande and Chaperon. The alkaline
electrolyte and the cathode materials are separated with
a layer of paper, reminiscent of the separators used in
Volta’s original pile. Patents were granted for this config-
uration to Lewis Urry, Paul Marsal, and Karl Kordesch
Figure 7. Diagram of a lead-acid battery.
in 1947 in Great Britain, and in the United States over
a decade later in 1960.40 One additional development to
improve safety was the use of small amounts of mercu- The increased surface area of the lead grid allows for
ry to suppress hydrogen gas production inside the cell a greater current output than could be achieved using
which could cause the cell to rupture.41 Due to the tox- similar sized plates. A solution of 20-30% aqueous sulfu-
icity of mercury, its use eventually fell out of favor, and ric acid serves as the electrolyte.
there is now a worldwide ban on the use of mercury in Although the battery was capable of being
commercial batteries. recharged, the technology needed to generate the current
to efficiently charge it had not yet been developed, and
as such the only way to recharge a lead acid battery was
LEAD-ACID BATTERY to exhaust a number of primary batteries such as Dan-
iell or Grove cells. It wasn’t until the 1880’s when large
While Ritter’s “charging pile” should be recognized as scale electrical power production allowed storage batter-
the first storage battery, its application did not gain trac- ies to flourish.6 Even today, the lead-acid battery holds a
tion at the time.21 The first widely utilized secondary bat- worldwide market share of over $35 billion USD annu-
tery was the lead-acid battery. The use of lead plates to ally, with automotive batteries as the primary market.44
store electrical charge was first described by W.J. Sinsteden
in 1854.42 However, it was Gaston Planté several years later
who would develop a version which would be viable on a NICKEL STORAGE BATTERIES
useful scale, although its usefulness was still limited and it
could be considered to be ahead of its time.43 While the lead-acid battery was (and continues to
Sinsteden, for unknown reasons, used lead plates be) quite serviceable for many static applications, its
to connect batteries to a voltammeter instead of using weight and acidic electrolyte made it less-than-ideal
silver, platinum, or copper wires as was commonly for more portable purposes. The first secondary bat-
done.42,43 He noted a small secondary current that could tery to successfully compete with the lead-acid battery
be measured, which increased with subsequent charge/ was developed by E.W. Jungner. In a patent filed in his
discharge cycles. He also noted the formation of lead native Sweden, Jungner first described a nickel-iron cell
oxides on one of the plates. Planté looked at this phe- in 1897, followed in 1901 by a patent replacing iron with
nomenon more closely, comparing the results of a num- cadmium.45,46 In 1901, Thomas Edison also obtained
ber of different metals including aluminum, silver, cop- a United States patent for a nickel-iron secondary bat-
per, lead, iron, and gold.43 He also compared electrolyte tery.47 It is unclear if Edison was aware of the work of
acidified with sulfuric acid to other options. Jungner at the time.
The modern lead-acid battery utilizes a series of Owning to the lower density of nickel and cadmium
cells, each containing a lead-alloy grid as one electrode, (7.81 and 8.00 g/cm3, respectively) versus that of lead
and a lead(IV) oxide-coated lead plate or grid as the oth- (10.66 g/cm3), these cells showed a significant decrease in
er electrode (Figure 7). The overall redox process results weight when compared to their lead-acid counterparts.48
in both oxidation and reduction of lead, as seen below. Jungner also utilized an alkaline electrolyte rather than
acid, which would eventually allow for dry cell develop-
Pb(s) + PbO2(s) + 2H2SO4(aq) → 2PbSO4(s) + 2 H2O(l) ment. However, mass production of NiCd (sometimes
80 Christopher L. Heth

termed “nicad”) batteries did not occur until the mid-

dle of the 20th century, upon development of a means
of dealing with gases that can be produced during the
redox processes, allowing for creation of a completely
sealed battery.49
While quite popular in the second half of the 20th
century, NiCd cells had several downsides. First, they
were prone to memory effects, requiring a full dis-
charge prior to recharging to avoid loss of charge capac- Figure 8. Intercalation of lithium ions.
ity. Additionally, the toxic nature of the cadmium cath-
ode was a disposal concern, and in 2009 the European
Union prohibited their use in most applications.7 magnesium, beryllium, and aluminum) was obtained,
Improvements to NiCd batteries were investigat- although the patent application was filed in 1961. 55
ed as early as the 1960’s. Efforts to improve the capac- An organic solvent with salts of the anode material is
ity of the nickel hydroxide electrode through inclusion specified, avoiding the problems associated with aque-
of didymium hydrate (a mixture of rare-earth oxides, ous electrolyte solutions. Also mentioned are cathodes
primarily lanthanum and neodymium) were granted composed of redox-active organic polymers including
a United States patent in 1967.50 Development of what polymers of quinones, sulfoxides, hydroxylamines, and
would become known as nickel-metal hydride batteries azo compounds. Another approach was described by
occurred in the 1990’s, when Stanford Ovshinsky and D.A.J. Swinkels in 1966, wherein a molten lithium chlo-
coworkers expanded the scope of additives to include ride electrolyte was used.56 Unfortunately, this system
many rare-earth and transition metals.51,52 These addi- required a minimum operating temperature of 650 °C,
tives allowed the cadmium cathode to be replaced with making it impractical for widespread use.
a nickel-metal alloy. These cathodes allowed for the One practical application of lithium metal anodes
storage and discharge of hydrogen (as hydride) through was the lithium-iodine battery.57 Its development had a
charge/discharge cycles, increasing the charge capacity significant positive impact in medicine, improving the
and greatly reducing memory effects compared to stand- performance of pacemakers implanted in cardiac patients
ard NiCd batteries.7 Having led the work that directly by decreasing the weight and increasing the battery life
allowed commercialization of nickel-metal hydride bat- compared to previous battery options of the time. 58
teries, Ovshinsky, a prolific inventor, is often referred to While not necessarily a problem for pacemaker applica-
as the inventor of the nickel-metal hydride battery.53 tions, the lithium-iodine battery was a primary battery,
and could not be effectively recharged. With pure metal
anodes, ions produced through oxidation upon discharge
THE RISE OF LITHIUM must be reduced and redeposited onto the anode when
the cell is recharged. Unfortunately, for several reasons,
While zinc was the predominant anode material for lithium often does not redeposit evenly on the electrode
almost two centuries, potential was seen for lithium as a surface but instead can form dendrites which can grow to
replacement. Lithium has a higher activity and a lower sufficient length to short circuit the cell.58
density than zinc, which would allow for lighter batter- In the mid 1970’s, intercalation of ions, including
ies with increased voltage output than zinc cells. Gil- lithium ions, into a host framework had been recognized
bert Lewis and Frederick Keys successfully measured and described.59 Rather than relying upon a pure lithium
the potential of the lithium electrode as early as 1913.54 metal electrode with the inherent risks associated with
Unfortunately lithium, like the rest of the alkali met- it, electrodes composed of materials capable of accepting
als, reacts with water, rendering it unusable with aque- lithium ion insertion within its solid structure (Figure
ous electrolytes. Additionally, lithium metal reacts read- 8) were explored. Attempts to develop cells based upon
ily with atmospheric nitrogen at ambient temperatures intercalating electrodes proceeded through the 1980’s.58
to produce a surface coating of lithium nitride, gener- The most successful of these, which would form the
ally with some amount of lithium oxide as well, thereby basis for the lithium ion batteries now common, utilized
requires inconvenient inert atmosphere conditions to a lithium cobalt oxide (LiCoO2) material developed by
successfully work with lithium metal. J.B. Goodenough and coworkers in 1981.60 Other mate-
In was not until 1965 when a patent for a secondary rials were also found to support lithium ion insertion,
battery utilizing lithium (as well as sodium, potassium, including TiS2, V4O10, and graphite.61 Intercalating elec-
Energy on demand: A brief history of the development of the battery 81

trodes are now commonly used for both the anode and 7. M. Nentwich, B. Störr, J. Hanzig in Electrochemical
the cathode in lithium ion batteries, with lithium ions Storage Materials: From Crystallography to Manufac-
shuttled between them during charge or discharge pro- turing Technology (T. Leisegang, M. Zschornak, H.
cesses.62 Stöcker), De Gruyter, Boston, MA, 2018, 41-74.
8. B. Dibner, Alessandro Volta and the Electric Battery,
Franklin Watts, New York, 1964.
CONCLUSIONS 9. G. Pearson, Philos. Trans. R. Soc. London 1779, 87,
142.
As society relies more and more on portable electric 10. A. P. van Troostwijk, J. R. Deiman, Obs. sur la Phys.
power, there is little doubt that significant effort will be 1789, 35, 369.
expended to further improve battery technology. The 11. H.A.M. Snelders, Ambix 1979, 26, 116.
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