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Materials Present in Batteries: Lithium-ion Battery

Daniela Delima

Batteries use diverse elements, which are harvested from the earth’s crust. It is thought provoking that most of these
materials are also shared by plants and living beings. We are made from stardust and anything that grows and
moves comes from these resources. As with all living organisms, the substances for batteries are chosen carefully
and in the right amount to achieve a harmonious interaction. Too much of one part could spoil a fine balance.

Background
Benjamin Franklin's famous experiment to attract electricity by flying a kite in a lightning storm was only one of many
late eighteenth- and early nineteenth-century experiments conducted to learn about electricity. The first battery was
constructed in 1800 by Italian Alessandro Volta. The so-called voltaic pile consisted of alternating discs of silver and
zinc separated by leather or pasteboard that had been soaked in salt water, lye, or some alkaline solution. Strips of
metal at each end of the pile were connected to small cups filled with mercury. When Volta touched both cups of
mercury with his fingers, he received an electric shock; the more discs he assembled, the greater the jolt he received.

Volta's discovery led to further experimentation. In 1813, Sir Humphrey Davy constructed a pile with 2,000 pairs of
discs in the basement of the Royal Institution of London. Among other applications, Davy used the electricity he
produced for electrolysis—catalyzing chemical reactions by passing a current through substances (Davy separated
sodium and potassium from compounds). Only a few years later, Michael Faraday discovered the principle of
electromagnetic induction, using a magnet to induce electricity in a coiled wire. This technique is at the heart of the
dynamos used to produce electricity in power plants today. (While a dynamo produces alternating current (AC) in
which the flow of electricity shifts direction regularly, batteries produce direct current (DC) that flows in one direction
only.) A lead-acid cell capable of producing a very large amount of current, the forerunner of
today's automobile battery, was devised in 1859 by Frenchman Gaston Planté.

In the United States, Thomas Edison was experimenting with electricity from both batteries and dynamos to power
the light bulb, which began to spread in the United States in the early 1880s. During the 1860s, Georges Leclanché
invented the wet cell, which, though heavy because of its liquid components, could be sold and used commercially.
By the 1870s and 1880s, the Leclanché cell was being produced using dry materials and was used for a number of
tasks, including providing power for Alexander Graham Bell's telephone and for the newly-invented flashlight.
Batteries were subsequently called upon to provide power for many other inventions, such as the radio, which
became hugely popular in the years following World War I. Today, more than twenty billion power cells are sold
throughout the world each year, and each American uses approximately 27 batteries annually [1].
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Introduction
Batteries are becoming more widely used. As the use of portable and mobile equipment increases, so does the use of
battery technology.

The increasing demands being placed on batteries has meant that the technology has developed considerably in the
past few years, and more development can be expected in the future.

With the huge demand for batteries, there is a wide variety of different battery and cell technologies available. These
range from the established non-rechargeable technologies such as zinc-carbon and alkaline batteries to rechargeable
batteries that have moved from NiCd through NiMH cells to the newer lithium ion rechargeable batteries. With a huge
need for batteries, there is a large amount of battery technology development underway and new types of cells and
batteries will no doubt become available offering even higher levels of performance.

Another area of battery technology that is becoming more important is the green or environmental aspects. Some of
the old battery technologies contain chemicals which can be considered as toxic. Now new designs are seeking to
use more environmentally friendly chemicals. Nickel cadmium cells are now considered as being environmentally
unfriendly and are not as widely used as they were previously. Other batteries also contain harmful chemicals and
this is likely to have a significant impact on the direction of future developments [2].

Basic Battery and Cell Concepts

Looking at the very basics of battery technology, a battery is a combination of two or more electrochemical cells.
These electrochemical cells store energy in the form of chemical energy, and this is converted into electrical energy
when connected to an electrical circuit in which an electrical current can flow.

Fig.1 The Cross-section of a Battery

The container of a typical alkaline battery, consisting of

preform inserted into a steel can, also doubles
as the cathode. The anode in the middle is a gel
composed primarily of zinc powder. The
separator between the anode and cathode is either
paper or synthetic fiber that has been soaked in an
electrolyte solution.
In the finished battery, a plastic seal, a steel nail, and a
metal top and bottom have been added. The
nail is welded to the metal bottom and extends about
two-thirds of the way into the can, through the
anode.

A cell consists of two electrodes with an electrolyte placed between them. The negative electrode is known as the
cathode, while the positive electrode is known as the anode. The electrolyte between them can either be a liquid or a
solid. Today many cells are enclosed in a special container, and there is an element known as a separator placed
between the anode and cathode. This is porous to the electrolyte and prevents the tow electrodes from coming into
contact with each other.
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The potential difference across the terminals of the battery is known as the terminal voltage. If the battery is not
passing any current, e.g. when it is not connected to any circuit, then the terminal voltage seen is the open circuit
voltage and this equals the EMF or electro-motive force of the battery.

It is found that all batteries have a certain level of internal resistance. As a result the terminal voltage falls when it is
connected to an external load. As the battery becomes exhausted it is found that the internal resistance rises and the
voltage under load falls.

Primary and Secondary Cells

Although there are many different types of battery, there are two main categories of cell or battery that can be used to
provide electrical power. Each type has its own advantages and disadvantages and therefore each type of battery is
used in different applications, although they can often be interchanged [2]:

Primary batteries
Primary batteries are essentially batteries that cannot be recharged. They irreversibly transform chemical energy to
electrical energy. When the chemicals within the battery have all reacted to produce electrical energy and they are
exhausted, the battery or cell cannot be readily restored by electrical means.

Secondary batteries
Secondary batteries or secondary cells are different to primary ones in that they can be recharged. The chemical
reactions within the cell or battery can be reversed by supplying electrical energy to the cell, restoring their original
composition.

Cell Types
There are many different types of cell or battery technology that are available. Each different type of battery
technology has its own advantages and disadvantages. Accordingly different types of cell or battery technology may
be used in different applications. The table below gives a summary of some of the different types that are in more
common use today [2].

BATTERY TYPES & THEIR PROEPRTIES

CELL TYPE NOMINAL VOLTAGE CHARACTERISTICS
V
Primary cells and
batteries
Alkaline manganese 1.5 Widely available, providing high capacity. Shelf life normally up to
dioxide about five years. Capable of providing moderate current.
Lithium thionyl 3.6 Good for low to medium currents. High energy density and long
chloride shelf life.
Lithium manganese 3.0 Long shelf life combined with high energy density and moderate
dioxide current capability.
Mercury oxide 1.35 Used for button cells but are virtually phased out now because of
the mercury they contain.
Silver oxide 1.5 Good energy density. Mainly used for button cells.
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BATTERY TYPES & THEIR PROEPRTIES

CELL TYPE NOMINAL VOLTAGE CHARACTERISTICS
V
Zinc carbon 1.5 Widely used for consumer applications. Low cost, moderate
capacity. Operate best under intermittent use conditions.
Zinc air 1.4 Mostly used for button cells. Have a limited life once opened and
low current capability but a high energy density.
Secondary cells and
batteries
Nickel cadmium 1.2 Were in very common use, but now giving way to NiMH cells and
NiCd batteries in view of environmental impacts. Low internal resistance
and can supply large currents. Long life if used with care.
Nickel metal hydride 1.2 Higher capacity but more expensive than NiCads. Charging must be
NiMH carefully controlled. Being used in many applications where NiCads
were previously used.
Lithium ion Highest capacity and they are now widely used in many laptops,
Lion mobile phones, cameras . . etc. Charging must be carefully
controlled and often have a limited life ~ typically 300 charge
discharge cycles.
Lead acid 2.0 Widely used for automotive applications. Relatively cheap, but life
expectancy often short.

The performance of battery technology has improved considerably in recent years. As the demands being required of
batteries has increased with greater capacity being required in smaller spaces and greater levels of reliability, so
considerable amounts of research have been invested in trying to meet the new requirements.

The research has resulted in much longer times between charge, higher capacity levels and greater degrees of
reliability. For the future, the demands being placed on batteries will only increase, and no doubt the technology will
improve beyond all measure [2].

Principles and Basics of Lithium-ion Batteries

Fig. 2 Lithium Ion Battery

Li-ion batteries, as one of the most advanced recharchable batteries,

are attracting much attention in the past few decades. They are
currently the dominant mobile power sources of portable electronic
devices, exclusively used in cell phones and laptops [3].

The smallest working unit in a battery is the electrochemical cell,

consisting of a cathode and an anode separated and connected by an
electrolyte. The electrolyte conducts ions but is an insulator to electrons.
In a charged state, the anode contains a high concentration of
intercalated lithium while the cathode is depleted of lithium. During the
discharge, a lithium ion leaves the anode and migrates through the
electrolyte to the cathode while its associated electron is collected by
the current collector to be used to power an electric device.

The cell designs and combinations in modules and packs differ greatly. To establish a base understanding, this paper
shows the main cell designs and then focuses on materials, processing, and manufacturing with special emphasis on
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batteries for transportation [3].

The electrodes in lithium-ion cells are always solid materials. One can distinguish between cell types according to
their electrolytes, which may be liquid, gel, or solid-state components. The electrolytes in gel and solid-state cells
represent a structural component and do not need additional separators for the effective separation of electrodes and
avoidance of short circuits. Cells come in button, cylindrical, and prismatic forms [3].

For low-energy and low-power applications, a cell often represents a full battery. For high-energy and high-power
applications such as transportation or stationary storage, a number of cells are packaged in a module, and a number
of modules are packaged in a battery [3].

A Li‐ion battery is constructed by connected basic Li‐ion cells in parallel (to increase current), in series (to increase
voltage) or combined configurations. Multiple battery cells can be integrated into a module. Multiple modules can be
intergrade into a battery pack. For example, the 85 kWh battery pack in a typical Tesla car contains 7104 cells.
Typically, a basic Li‐ion cell consists of a cathode (positive electrode) and an anode (negative electrode) which are
contacted by an electrolyte containing lithium ions. The electrodes are isolated from each other by a separator,
typically micro porous polymer membrane, which allows the exchange of lithium ions between the two electrodes but
not electrons. In addition to liquid electrolyte, polymer, gel, and ceramic electrolyte have also been explored for
applications in Li‐ion batteries [3].

The commercial cells are typically assembled in discharged state. The discharged cathode materials (e.g., LiCoO 2,
LiFePO4) and anode materials (e.g., carbon) are stable in atmosphere and can be easily handled in industrial
practices. Yohsino made a significant contribution to the commercial production of Li‐ion batteries by using
discharged electrode materials in full cells for the first time. During charging process, the two electrodes are
connected externally to an external electrical supply. The electrons are forced to be released at the cathode and
move externally to the anode. Simultaneously the lithium ions move in the same direction, but internally, from cathode
to anode via the electrolyte. In this way the external energy are electrochemically stored in the battery in the form of
chemical energy in the anode and cathode materials with different chemical potentials. The opposite occurs during
discharging process: electrons move from anode to the cathode through the external load to do the work and Li ions
move from anode to the cathode in the electrolyte. This is also known as “shuttle chair” mechanism, where the Li ions
shuttle between the anode and cathodes during charge and discharge cycles [3].

Fig.3 The Basic Components and Operation

Principle of A Li-ion Cell.
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Materials Used in Lithium-Ion Batteries

Cathode Materials

State-of-the-art cathode materials include lithium-metal oxides [such as LiCoO 2, LiMn2O4, and Li(NixMnyCoz)O2],
vanadium oxides, olivines (such as LiFePO4), and rechargeable lithium oxides. Layered oxides containing cobalt and
nickel are the most studied materials for lithium-ion batteries. They show a high stability in the high-voltage range but
cobalt has limited availability in nature and is toxic, which is a tremendous drawback for mass manufacturing.
Manganese offers a low-cost substitution with a high thermal threshold and excellent rate capabilities but limited
cycling behavior. Therefore, mixtures of cobalt, nickel, and manganese are often used to combine the best properties
and minimize the drawbacks. Vanadium oxides have a large capacity and excellent kinetics. However, due to lithium
insertion and extraction, the material tends to become amorphous, which limits the cycling behavior. Olivines are
nontoxic and have a moderate capacity with low fade due to cycling, but their conductivity is low. Methods of coating
the material have been introduced that make up for the poor conductivity, but it adds some processing costs to the
battery[3].

Anode Materials

Anode materials are lithium, graphite, lithium-alloying materials, intermetallics, or silicon. Lithium seems to be the
most straight forward material but shows problems with cycling behavior and dendritic growth, which creates short
circuits. Carbonaceous anodes are the most utilized anodic material due to their low cost and availability. However,
the theoretical capacity (372 mAh/g) is poor compared with the charge density of lithium (3,862 mAh/g). Some efforts
with novel graphite varieties and carbon nanotubes have tried to increase the capacity but have come with the price
of high processing costs. Alloy anodes and intermetallic compounds have high capacities but also show a dramatic
volume change, resulting in poor cycling behavior. Efforts have been made to overcome the volume change by using
nanocrystalline materials and by having the alloy phase (with Al, Bi, Mg, Sb, Sn, Zn, and others) in a nonalloying
stabilization matrix (with Co, Cu, Fe, or Ni). Silicon has an extremely high capacity of 4,199 mAh/g, corresponding
with a composition of Si5Li22. However, cycling behavior is poor, and capacity fading not yet understood [3].

Electrolytes

A safe and long-lasting battery needs a robust electrolyte that can withstand existing voltage and high temperatures
and that has a long shelf life while offering a high mobility for lithium ions. Types include liquid, polymer, and solid-
state electrolytes. Liquid electrolytes are mostly organic, solvent based electrolytes containing LiBC 4O8 (LiBOB),
LiPF6, Li[PF3(C2F5)3], or similar. The most important consideration is their flammability; the best performing solvents
have low boiling points and have flash points around 30°C. Therefore, venting or explosion of the cell and
subsequently the battery pose a danger. Electrolyte decomposition and highly exothermic side reactions in lithium-ion
batteries can create an effect known as “thermal runaway.” Thus, selection of an electrolyte often involves a tradeoff
between flammability and electrochemical performance.

Separators have built-in thermal shutdown mechanisms, and additional external sophisticated thermal management
systems are added to the modules and battery packs. Ionic liquids are under consideration due to their thermal
stability but have major drawbacks, such as lithium dissolution out of the anode.

Polymer electrolytes are ionically conductive polymers. They are often mixed in composites with ceramic
nanoparticles, resulting in higher conductivities and resistance to higher voltages. In addition, due to their high
viscosity and quasi-solid behavior, polymer electrolytes could inhibit lithium dendrites from growing and could
therefore be used with lithium metal anodes.

Solid electrolytes are lithium-ion conductive crystals and ceramic glasses. They show a very poor low-temperature
performance because the lithium mobility in the solid is greatly reduced at low temperatures. In addition, solid
electrolytes need special deposition conditions and temperature treatments to obtain acceptable behavior, making
them extremely expensive in use, although they eliminate the need for separators and the risk of thermal runaway [3].

Separators
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The battery separator separates the two electrodes physically from each other, thus avoiding a short circuit. In the
case of a liquid electrolyte, the separator is a foam material that is soaked with the electrolyte and holds it in place. It
needs to be an electronic insulator while having minimal electrolyte resistance, maximum mechanical stability, and
chemical resistance to degradation in the highly electrochemically active environment. In addition, the separator often
has a safety feature, called “thermal shutdown;” at elevated temperatures, it melts or closes its pores to shut down
the lithium-ion transport without losing its mechanical stability. Separators are either synthesized in sheets and
assembled with the electrodes or deposited onto one electrode in situ. Cost wise, the latter is the preferable method
but poses some other synthesis, handling, and mechanical problems. Solid-state electrolytes and some polymer
electrolytes need no separator [3].

The Lithium-Ion Batteries

In general, Li-ion batteries can be characterized as energy storage systems that rely on insertion reactions from both
electrodes where lithium ions act as the charge carrier [4]. Given this broad definition, there are several different cell
chemistries that make up the Li-ion battery family. Most Li-ion batteries use a negative electrode principally made
from carbon (e.g., graphite) or lithium titanate (Li4Ti5O12), with some novel materials under development, namely, Li
metal and Li(Si) alloys. The electrolyte used varies based on the choice of electrode materials, but is typically
composed of a mixture of lithium salts (e.g., LiPF 6) and an organic solvent (e.g., diethyl carbonate) to allow for ion
transfer—these components will be discussed in more detail below. A separating membrane is used to allow lithium
ions to pass between the electrodes while preventing an internal short circuit [5].

This arrangement is shown conceptually in Figure 2, with the transport aspects of the battery when operating as an
energy source (i.e., a galvanic device) illustrated—the electrons travel from the negative electrode to the positive
electrode while simultaneously the Li+ ions travel from the negative electrode through the electrolyte to the positive
electrode to maintain electroneutrality. When the system is operated in charge mode (i.e., as an electrolytic device)
the electron current and Li+ ion flow is reversed.

Figure 2. The schematic construction of a Li-ion

battery showing the positive and negative
electrodes, the electrode connecting electrolyte
that includes a porous separator membrane
intended to prevent direct contact between the two
electrodes. When the battery acts as a galvanic
device, the electrons travel from the negative
electrode to a current collector to the load, and
then via a second current collector to the positive
electrode. Simultaneously, the Li+ ions travel from
the negative electrode through the electrolyte to the
positive electrode to maintain electroneutrality.
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There are therefore many choices of materials for the positive and negative electrode materials, the electrolyte, and
the separator. The technological limitations of the various materials are driven by their function, as detailed below.

The electrolyte must offer the highest possible lithium ion transport under use conditions. The batteries must
operate in the general environment, likely to extend from, e.g., −30 ◦ C for a vehicle that has been parked for a
period of time in extreme cold, to +60 ◦ C for a battery that has heated as a consequence of the combination of
environmental conditions and heat generated by charging [5]. The separator must likewise offer the highest possible
lithium ion conduction under the same operational conditions and must offer the ability for a rapid thermal shutdown
if significant overheating occurs to prevent a thermal runaway process .

A suitable combination of negative and positive electrode materials must exist that leads to a cost-effective high
capacity battery. A summary of battery electrode materials and their electrochemical half cell potentials vs. a Li/Li +
reference can be found in Figure 3. The eventual cell voltage is the difference between the chosen pair of electrode
materials, and further modified by cell losses, such as necessary over potentials to achieve current flows, or IR losses
due to poor Li+ ion transport through the electrolyte. For example, if LiFePO was chosen as the positive half-cell,
4
and Li4Ti5O12 as the negative half-cell, the nominal open circuit voltage would be V OC = V+ − V− = 1.95 V, where V+
represents the half-cell potential of the positive electrode and V− that of the negative electrode.

Likewise, the cell capacity is dictated by the specific capacity of each of the electrode materials present in the cell,
and the fact that equal capacities are present for the positive and negative electrodes.

For example, using the capacities presented in Figure 3 to construct conceptual pairs, and choosing the same
LiFePO4 (170 Ah kg−1) paired with Li4Ti5O12 (175 Ah kg−1), assuming an idealized ratio of positive and negative
electrode materials in a manner proportionate to their conceptual capacity, the idealized ratio of LiFePO4:Li4Ti5O12 =
170 Ah kg−1:175 Ah kg−1 = 0.97, meaning that an idealized battery with 170 Ah of capacity would contain 1 kg
LiFePO4 and 0.97 kg Li4Ti5O12. Therefore, because of the mass of both electrodes combined, and using an approx.
15% weight allowance for the balance of plant shown in Figure 2 (i.e., electrolyte, separator, current collectors) and a
battery enclosure, a battery with a specific capacity of ca. ((170 Ah)/(1 kg+0.97 kg))/1.15 = 75 Ah kg −1 would result.
Using the same positive electrode paired with a carbon negative electrode (370 Ah kg−1, resulting in an electrode
mass ratio of 170 Ah kg −1:370 Ah kg−1 = 0.46), and the same 15% allowance for balance of plant would result in a
battery that is about 101 Ah kg−1. The specific energy of the battery would then be obtained by multiplying this
resulting capacity by the expected cell voltage for this combination of electrode materials.
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Figure 3. A summary of some present and future electrode chemistry options for Li-ion batteries.
The proposed capacity of the Li(Si) is 50% of the theoretical capacity of the material, similar to the
case found for some of the positive electrode materials.

Lithium ion batteries have one of the highest coulombic efficiency (CE) ratings in rechargeable batteries (more than
99%). CE describes the charge efficiency by which electrons are transferred in batteries and is the ratio of the total
charge extracted from the battery to the total charge put into the battery over a full cycle. The coulombic efficiency of
Li-ion batteries improves with cycling. To prove this, Panasonic, E-one Moli, Sony, LG and Samsung Li-ion batteries in
18,650 cell format where cycled. Some cells began with a coulombic efficiency of 99.1% and improved to 99.5% with
15 cycles. Some started at 99.5% and reached 99.9% with 30 cycles. The consistency on repeat tests was high,
reflecting in Li-ion being a very stable battery system [6].

Positive Electrode

Positive electrodes generally are intercalation compounds from which Li + ions can diffuse out or back in. Well known
examples of materials used, as detailed in Figure 3, include LiCoO 2 (~140 Ah kg−1, ~3.9 V vs. Li/Li+), LiFePO4
(~170 Ah kg−1, ~3.45 V vs. Li/Li+), Li(Ni Mn Co )O (e.g., NMC811 where 1−x−y = 0.8, x = 0.1 and y = 0.1,
1−x−y x y 2

Li(Ni1−x−yCoxAly)O2 (NCA, ~200 Ah kg−1, ~3.8 V vs. Li/Li+), and LiMn2O4 (~110 Ah kg−1, ~4.1 V vs. Li/Li+) [7].
Individual materials will be discussed briefly below.

(LiCoO2)
First developed by Sony in 1991, the lithium cobalt oxide battery has been the battery of choice for most personal
electronics (laptops, cameras, tablets, etc.) due to their high energy density, long life cycle and ease of
manufacturing. Lithium cobalt batteries are very reactive and therefore suffer from poor thermal stability and must be
monitored during operation to ensure safe use.

Lithium Nickel Oxide (LiNiO2)

LiNiO2 was recognized as a promising material for high voltage batteries (i.e., an approx. 4 V vs. Li/Li+ electrode
potential), because it is a lower cost material (it is Co free) and has a high theoretical capacity of 250 Ah kg−1.
However, difficulties with its use, especially the formation of a self-passivation layer at the surfaces caused difficulties
with its use. Because stoichiometric LiNiO2 requires great care in manufacture, and is a somewhat less practical
electrode material, solid solutions of this material with Co], Fe, Mn, Al , Ti, and Mg were developed, from which the
current “NMC 811” (i.e., “Nickel 0.8 Manganese 0.1 Cobalt 0.1”) and related materials were developed.

Lithium Manganese Oxide (LiMn2O4)

Lithium manganese oxide batteries (LMO) were first introduced in the early 1980’s, though they took nearly 15 years
to commercialize. The architecture forms a three-dimensional spinel structure that improves ion flow on the electrode,
which results in lower internal resistance and improved current handling. Low internal cell resistance enables fast
charging and high-current discharging. Li-manganese can be discharged at currents of 20–30 A with moderate heat
buildup in an 18,650 package. This chemistry provides better thermal stability than the lithium cobalt oxide battery but
results in approximately 33% lower capacity and a lower life span.

Most Li-manganese batteries blend with lithium manganese cobalt oxide (NMC) to improve the specific energy and
prolong the life span.

One of the main research efforts in the field of lithium-manganese oxide electrodes for Li-ion batteries involves
developing composite electrodes using structurally integrated layered Li 2MnO3 and spinel LiMn2O4, with a chemical
formula of xLi2MnO3 (1−x)Li1+yMn2−yO4. The combination of both structures provides increased structural stability
during electrochemical cycling while achieving higher capacity and rate-capability].

Lithium Iron Phosphate (LiFePO4)

In 1996, researchers at the University of Texas in Austin found that phosphate materials could be used in Li-ion
battery positive electrodes. LiFePO4 (LFP) offers good electrochemical performance with low resistance, besides high
current rating and long cycle life. The phosphate helps to stabilize the electrode against overcharging and provides a
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higher tolerance to heat which limits the breakdown of the material. These batteries have a wide temperature range
and can operate between +60 ◦ C to −30 ◦ C and are much less likely to suffer from a thermal runaway. LiFePO4 has a
higher self-discharge than other Li-ion batteries, which can cause balancing issues with aging. This can be mitigated
through the use of sophisticated control electronics, at increased battery pack cost. Further, moisture seems to
significantly limit the lifetime of the battery. With the efficient power-to-weight ratios, high safety features and the
chemistry’s resistance to thermal runaway, LiFePO4 batteries are achieving popularity for use in motor homes.

Lithium Nickel Manganese Cobalt Oxide (Li(NixMnyCo1−x−y)O2)

Lithium Nickel Manganese Cobalt Oxide (NMC) electrodes can be designed for high specific energy or power with
high density. The secret of NMC lies in combining nickel and manganese: nickel is known for its high specific energy
but poor stability; manganese has the benefit of forming a spinel structure to achieve low internal resistance but offers
a low specific energy. The mix of the various metals (nickel and manganese) varies by manufacturer and is a very
closely guarded formula. Researchers are using nickel-rich electrodes to increase energy density, while reduction in
cobalt is also helpful since it lowers costs. Companies have switched from NMC111 (discharge capacity: 154 Ah kg−1
at 0.1 C) to NMC442 to NMC622, and now NMC811 (discharge capacity: >185 Ah kg −1 at 0.1 C) is slated for
introduction. NMC111 means equal parts nickel, manganese and cobalt.

Combining nickel and manganese enhances each other’s strengths, making NMC the most successful Li-ion system
and suitable for EV power trains. These batteries are currently in high demand given the high specific energy and
excellent thermal characteristics.

Negative Electrode

Two main types of negative electrodes being used include lithium titanate and carbon-based electrodes, and new
types of electrodes under development include lithium metal and lithium-metal alloys with a special focus on lithium-
silicon alloys, and conversion electrodes [8].

Carbon Based Electrodes

Carbon, and usually synthetic graphite, still remains the active material of choice for the negative electrode, due to its
relatively high specific capacity of ~370 Ah kg−1, low average voltage (150 mV vs. Li/Li+) and a relatively flat
voltage rendering a high overall cell voltage and high roundtrip energy efficiency. Further, because it is a very
abundant, low cost and non-toxic material, it is a particularly good choice of electrode and therefore widely used.
Regrettably, under some specific conditions, carbon reacts with atmospheric oxygen, and in the case of a thermal
runaway event, the electrode can catch fire.

Lithium Titanate (Li4Ti5O12)

Batteries with lithium titanate negative electrodes have been known since the 1980s. Li-titanate (LTO) replaces the
graphite in the negative electrode of a typical Li-ion battery and the material forms into a spinel structure. The
counter-electrode can be lithium manganese oxide or NMC. Spinel lithium titanate has been regarded as a highly
useful electrode material because of the zero volume change during lithiation, leading to an extremely long
operational lifetime for the electrode, coupled with the improved safety owing to an extremely flat discharge and
charge plateau at about 1.55 V vs. Li/Li +. This material has low electronic conductivity and the Li + diffusion
coefficient of this material can result in poor performance at high power levels, though this can be improved through
the reduction of the lithium ion transport path lengths through proper nanostructuring, and the improvement of the
electronic conductivity through doping, surface coating, and forming composites with better electronic conductors
such as carbon materials.

Lithium Metal
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With a very large capacity (3860 Ah kg−1) and the lowest negative electrochemical potential, it is natural to
consider Li metal electrodes for the negative electrode in a Li-ion battery since the significant electrode capacity
may decrease the mass of the negative electrode by an order of magnitude, and possibly decrease the mass of
the overall battery by about a third. Unfortunately, Li metal electrodes in secondary batteries have proved
challenging due to the growth of metallic dendrites during Li plating/stripping, with short circuit caused by the
dendrites leading to thermal runaway and a risk of fire/explosion .

Alloy Based Electrodes

Constructing the negative electrode from metals that electrochemically alloy with lithium at close to room
temperature presents opportunities for the creation of Li-ion batteries with higher specific capacity than that
offered by conventional graphite electrodes. For this reason, a number of metals and metalloids, like aluminum, tin,
and silicon which react with lithium to form alloys by electrochemical processes that are partially reversible, are
under study. Unfortunately, the accommodation of so much lithium is accompanied by enormous volume
changes in the host metal plus phase transitions. The mechanical strain generated during the alloying/de-
alloying processes leads to cracking and crumbling of the metal electrode and a marked loss of capacity to
store charge, in the course of a few cycles.

Silicon Based Electrodes

The lithium–silicon alloy has, in its fully lithiated composition, Li15Si4, a theoretical specific capacity of 4200 Ah kg−1
which is even higher than the 3860 Ah kg −1 for metallic lithium . The major issue with this electrode chemistry is
the significant volumetric change of the electrode material, where the transition between Si and Li 15Si4 causes a
280% volumetric change, generating high internal strain in the active materials. The resulting strain leads to cracking
and eventual disintegration of the Si material leading to significant reversible capacity fade. Additional drawbacks of
Si are a low Li+ diffusion coefficient and high electrical resistivity. Manufacture of composite electrodes composed of
nanostructured Si, better able to accommodate volume expansion, and using heavily doped Si embedded in
conductive matrices appears to lead to significantly improved mechanical and electrical properties.

Electrolyte

As mentioned, the electrolyte is an essential part of the battery, providing ionic conductivity enabling Li+ ions to
shuttle between the two electrodes, while not being electronically conductive. Two major classes of electrolytes
exist: liquid (aqueous and organic) and solid (polymer and ceramic) [8].

Aqueous Electrolytes
As in all electrochemical systems, the cell potential is limited by the electrochemical window of the electrolyte.
Although aqueous electrolytes may conceptually be safer and have lower potential environmental impacts, the
restricted electrochemical voltage window (1.23 V) precludes its use in Li-ion batteries—indeed, all negative electrode
materials spontaneously react with water to produce free hydrogen. While it has been demonstrated that by creating
“water in salt” electrolytes (aqueous mixtures of salts and water at high salt concentrations of the salt, and in which
the number of salt particles exceeds the number of water molecules) can increase this electrochemical window and
enable demonstration Li-ion batteries, this approach is not close to commercialization.

Organic Liquid Electrolytes

In order to achieve a wider electrochemical window, Li-ion battery electrolytes are usually based on an organic
solvent loaded with a lithium salt. A common system is the use of an organic carbonate, such as Ethyl carbonate,
propylene carbonate, and dimethyl carbonate, with dissolved LiPF6, LiBF4 or LiClO4. Using appropriate blends of
these solvents and salts, electrolytes with good electrochemical stability and with suitably high Li+ ion conductivities
of approx. 10 mS/cm are needed for a high-performance battery. A new development in the field is the use of Room
Temperature Ionic Liquids (RTILs) which mitigates the flammability and volatility of organic electrolytes issue.

Polymer Electrolytes
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Because the use of an organic liquid electrolyte poses an environmental contamination risk due to leakage, coupled
with a flammability issue, the development of solid polymer electrolytes (SPEs) are promising alternatives to enhance
the safety performance of batteries. Composite electrolytes
based on POE (poly(oxyethylene)) and similar matrices have been developed that can have gel-like (low molecular
weight) or solid (high polymer molecular weight) properties for Li-ion cell applications.

Ceramic Electrolytes
Recent advances in battery technology involve using ceramics as the electrolytes, in particular the use of LiSICONs
(Lithium Super Ion Conductors) and including glassy materials with similar compositions, result in higher
conductivities overall due to higher conductivity at grain boundaries. Work to improve the conductivity of ceramic
electrolytes to yield materials with performance similar to that of liquid electrolytes continues, with some promising
results.

Solid Electrolyte Interphase

A final resistance to Li+ ion transport in the batteries that must be considered to understand the performance of the
Li-ion battery is the presence of the Solid Electrolyte Interphase (SEI). At the electrode surfaces, this passivation
layer (SEI) is formed from decomposition products of the electrolytes. The SEI allows Li+ transport while blocking
further electrolyte decomposition. While not completely understood, this nanometer scale SEI film is of paramount
importance to the performance of the battery, but materials modeling is starting to reveal its nature.

Raw Materials in Lithium-Ion Battery

Aluminum Aluminum is a silvery-white, soft, nonmagnetic metal with symbol Al.

Derived from bauxite, it is the third most abundant element in the
earth's crust after oxygen and silicon. When exposed to air,
aluminum forms a passivation layer that protects the metal from
corrosion. Aluminum is used as cathode material in some lithium-ion
batteries [9].

Manganese Manganese with symbol Mn is produced by mining iron and other

minerals. The metal is a relatively abundant and is mined worldwide
except in North America. Steel manufacturing uses roughly 90
percent of manganese production; the remaining 10% is used in
specialty chemical and agricultural. High grade, high purity
manganese is in growing demand for Li-ion batteries. Manganese is
named after the region of “Magnesia” in Greece where the black
mineral was found. Manganese is used to prevent steel corrosion
and serves as cathode material in Li-ion, zinc-carbon and alkaline
batteries [9].

Spinel Spinel is a hard glassy mineral consisting of an oxide of magnesium

and aluminum that forms a three-dimensional chemical structure.
Spinels were known as rubies, and now belong to the most famous
gemstones in shades of red, blue, green, yellow, brown and black.
 Page 13 of 16

Manganese-based Li ion batteries consist of a spinel structure in

which the cathode forms a three-dimensional framework that appears
after initial formation. Spinel batteries are known for their low
resistance [9].

Tantalum The name comes from Tantalus, a villain from the Greek mythology.
Tantalum (Ta) is a rare, hard, blue-gray, lustrous transition metal that
is highly corrosion-resistant and commonly used for electronic
components, such as capacitors and high-power resistors. The
dielectric layer of a capacitor is very thin and achieves high
capacitance in a small volume.

Africa is a large supplier of tantalum but this could change as

tantalum is a by-product of lithium mining that is increasing in
Australia. The need for tantalum capacitors is growing for demanding
environments such as high heat. The Internet of Things (IoT), 5G
infrastructure and autonomous vehicles are further area of growth for
tantalum capacitors [9].

Tin Tin (Sn) is a silvery, malleable metal that does not oxidize easily in
the air. Appearing after bronze in ancient times, the first pure metallic
tin was produced in 600 BC. Today, it is combined with many alloys,
most notably tin/lead solder and corrosion-resistant tin plating of
steel. Low toxicity makes tin-plated metal suitable for food packaging.
Tin is also found in batteries [9].

Titanate Titanate usually refers to inorganic compounds composed of titanium

oxides. The materials are white and have a high melting point,
making them suitable for furnaces. Titanate is also used for anode
material of some lithium-based batteries. Lithium-titanate batteries
can be fast-charged with little stress. They are more durable than
regular Li-ion with graphite anodes but hold less energy and are
more expensive [9].

Vanadium Vanadium is a hard, silvery gray metal with symbol V. Discovered in

1801 in Mexico, vanadium is found in about 65 minerals, and the
metal forms a stable oxide layer once isolated. Vanadium also occurs
naturally in fossil fuel deposits and is produced in China and Russia
from steel smelter slag and other by-products, including uranium
mining. Vanadium is used for specialty steel alloys such as high-
speed tools, including the Flow Battery. The price of vanadium
increased in part due to reduced availability caused by closing mines
in South Africa and Russia, as well as shutdowns in China related to
iron and steel markets and stricter environmental laws that also
includes a ban on the import of vanadium-bearing stags. Besides the
flow battery, vanadium is also used for high-strength rebar and other
superior steel products. The Rensselaer Polytechnic Institute, USA,
is experimenting with high charge rates on Li-ion by replacing cobalt
oxide with vanadium disulfide [9].

Zinc Zinc (Zn) is chemically similar to magnesium; combining zinc with

copper turns into brass, an alloy that has been used since the 10th
century BC in Judea and the 7th century BC in Greece. Zinc metal
was not produced on a large scale until the 12th century in India and
the late 1500s in Europe. By 1800, Luigi Galvani and Alessandro
Volta uncovered the electrochemical properties of zinc for batteries.
Other uses are corrosion-resistant zinc plating of iron and light metal
 Page 14 of 16

castings. It is also an ingredient in anti-dandruff shampoos. Zinc is an

essential mineral for our physical development and well-being. Zinc
deficiency affects about two billion people in the developing world.
The symptoms are retardation in growth, delayed sexual maturity,
vulnerable to infection and diarrhea. Excess zinc can lead to lethargy
and copper deficiency [9].

Battery Definitions, Terms, and Terminology

Anode
The definition for the anode is the electrode at which an oxidation reaction occurs. This means that the anode
electrode is a supplier of electrons. However the electron flow reverses between charge and discharge activities.
As a result, the positive electrode is the anode during charging and the negative electrode is the anode during
discharging[10].

Battery
A battery is the generic name for a unit that creates electrical energy from stored chemical energy. Strictly it
consists of two or more cells connected in an appropriate series / parallel arrangement to provide the required
operating voltage and capacity to meet its operating requirements. The term battery is also frequently used to refer
to a unit consisting of a single cell, especially when it contains battery management circuitry [10].

Cathode
The definition of a cathode is the electrode in a battery or other system at which a reduction reaction occurs. The
electrode takes up electrons from an external circuit. Accordingly, the, the negative electrode of the battery or cell
is the cathode during charging and the positive electrode is the cathode during discharging [10].

Capacity
The capacity of a battery or cell is defined as the amount of energy that it can deliver in a single discharge. Battery
capacity is normally specified in amp-hours (or milli-amp-hours) or as watt-hours [10].

Cell
The definition of the cell is the basic electrochemical unit that is used to create electrical energy from stored
chemical energy or to store electrical energy in the form of chemical energy. A basic cell consists of two electrodes
with an electrolyte between them [10].

Cycle Life
The capacity of a rechargeable cell or battery changes over its life. The definition of the battery life or cycle life of a
battery is number of cycles that a cell or battery can be charged and discharged under specific conditions, before
the available capacity falls to a specific performance criteria - normally 80% of the rated capacity [10].

NiMH batteries typically have a cycle life of 500 cycles, NiCd batteries can have a cycle life of over 1,000 cycles
and for NiMH cells it is less at around 500 cycles. Lithium -ion cells currently have cycle life times of around 300
cycles, although with development this is improving. The cycle life of a cell or battery is greatly influenced by the
type depth of the cycle and the method of recharging. Improper charge cycle cut-off, particularly if the cell is over-
charged or reverse charged significantly reduces the cycle life.

Deep Cycle
A charge discharge cycle in which the discharge is continued until the battery is fully discharged. This is normally
take to be the point at which it reaches its cut-off voltage, typically 80% of discharge [10].

Electrode
The electrodes are the basic elements within an electrochemical cell. There are two in each cell: one positive and
one negative electrode. The cell voltage is determined by the voltage difference between the positive and the
negative electrode [10].

Electrolyte
The definition of the electrolyte within a battery is that it is the medium that provides the conduction of ions
between the positive and negative electrodes of a cell [10].

Self-Discharge
 Page 15 of 16

It is found that batteries and cells will lose their charge over a period of time, and need re-charging. This self-
discharge is normal, but various according to a number of variables including the technology used and the
conditions. Self-discharge is defined as the recoverable loss of capacity of a cell or battery. The figure is normally
expressed in a percentage of the rated capacity lost per month and at a given temperature. The self-discharge
rate of a battery or cell is very dependent upon the temperature [10].

Separator
This battery terminology is used to define the membrane that is required within a cell to prevent the anode and
cathode shorting together. With cells being made more compact, the space between the anode and cathode
becomes much smaller and as a result the two electrodes could short together causing a catastrophic and
possibly explosive reaction. The separator is an ion-permeable, electronically non-conductive material or spacer
that is placed between the anode and cathode [10].
 Page 16 of 16

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