CHAPTER I

Introduction

1. 1 Battery

An electrical battery is one or more electrochemical cells that convert stored

chemical energy into electrical energy by means of redox reactions.

1. 2 History of batteries

1748 – Benjamin Franklin first coined the term "battery" to describe an array of

charged glass plates.

1780 – Luigi Galvani was dissecting a frog affixed to a brass hook. When he

touched its leg with his iron scalpel, the leg twitched. Galvani believed the energy

that drove this contraction came from the leg itself, and called it "animal

electricity".

1800 – Volta invented the first true battery which came to be known as

the Voltaic Pile. It consisted of pairs of copper and zinc discs piled on top of each

other, separated by a layer of cloth or cardboard soaked in brine (i.e. the

electrolyte).

1836 – John Frederic Daniell invented the Daniell cell, which consisted of a

copper pot filled with a copper sulphate solution, in which was immersed an

unglazed earthenware container filled with sulphuric acid and a zinc electrode.

1844 – William Robert Grove invented Grove cell. It consisted of a zinc anode

dipped in sulfuric acid and a platinum cathode dipped in nitric acid, separated by

porous earthenware. The Grove cell provided a high current and nearly twice the

voltage of the Daniell cell.

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1859 – Gaston Plante invented the lead–acid battery, the first ever battery that

could be recharged by passing a reverse current through it. A lead acid cell

consists of a lead anode and a lead dioxide cathode immersed in sulphuric acid.

1866 – Georges Leclanche invented a battery that consisted of a zinc anode and

a manganese dioxide cathode wrapped in a porous material, dipped in a jar

of ammonium chloride solution. The manganese dioxide cathode had a little

carbon mixed into it as well, which improved electrolyte conductivity and

absorption.

1881 – Carl Gassner invented the first commercially successful dry cell battery

(zinc–carbon cell).

1899 – Waldemar Jungner invented the nickel–cadmium battery.

1901 – Thomas Alva Edison invented the alkaline storage battery.

1903 – Jungner invented the nickel–iron battery.

1970 – Lithium battery

1989 – Nickel/Metal hydride battery.

1980 – An American chemist John B. Goodenough led a research team at Sony

that would produce the lithium ion battery, a rechargeable and more stable version

of the lithium battery; the first ones were sold in 1991.

1996 – lithium ion polymer battery.

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1. 3 Categories and types of batteries

Batteries are classified into two broad categories.

Primary batteries irreversibly (within limits of practicality) transform chemical

energy to electrical energy. When the initial supply of reactants is exhausted,

energy cannot be readily restored to the battery by electrical means.

eg. Zinc–carbon batteries, Alkaline batteries

Secondary batteries can be recharged; that is, they can have their chemical

reactions reversed by supplying electrical energy to the cell, restoring their

original composition.

eg. Lead–acid batteries, Lithium ion batteries

1. 4 Battery cell types

There are many general types of electrochemical cells, according to chemical

processes applied and designs chosen. The variation includes galvanic cells, electrolytic

cells, fuel cells, flow cells and voltaic piles.

1. 4. 1 Wet cell

A wet cell battery has a liquid electrolyte. Other name is flooded cell, since the

liquid covers all internal parts, or vented cell, since gases produced during operation can

escape to the air. Wet cells may be primary cells (non–rechargeable) or secondary cells

(rechargeable). eg. Leclanche cell.

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1. 4. 2 Dry cell

A dry cell has the electrolyte immobilized as a paste, with only enough moisture

in the paste to allow current to flow. Compared to a wet cell, the battery can be operated

in any random position, and will not spill its electrolyte if inverted. eg. Zinc–carbon

battery.

1. 4. 3 Molten salt battery

A molten salt battery is a primary or secondary battery that uses a molten salt as

its electrolyte. eg. ZEBRA batteries (Na–NiCl2 battery).

1. 4. 4 Reserve battery

A reserve battery can be stored for a long period of time and is activated when its

internal parts (usually electrolyte) are assembled. For example, a battery for an electronic

fuze might be activated by the impact of firing a gun, breaking a capsule of electrolyte to

activate the battery and power the fuze's circuits. eg. Water–activated battery.

1. 5 Components of cell

Anode or negative electrode

Cathode or positive electrode

Electrolyte

Separator

Current collector

1. 5. 1 Anode

The electrode at which the oxidation occurs is called the anode. The charge on the

anode is negative.

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Characteristics

 Efficiency as a reducing agent.

 High coulombic output (Ah/g)

 Good conductivity.

 Stability

Example

Metals

1. 5. 2 Cathode

The electrode at which reduction occurs is termed the cathode. The charge on the

cathode is positive.

Characteristics

 Good oxidizing agent.

 Must stable when contact with electrolyte.

 To achieve high performance.

 Should be conductive.

Example

Metallic oxides

1. 5. 3 Electrolyte

The ionic conductor–which provides the medium for transfer of charge, as ions,

inside the cell between the anode and cathode.

Characteristics

 Good ionic conductivity

 Low viscosity and high dielectric constant

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  Non reactivity with electrode materials

Example

Sulphuric acid, LiPF6 in 1: 1 (Ethylene carbonate and diethylene carbonate)

1. 5. 4 Separator

An ion permeable and electronically non conductive, spacer or material which

prevents electronic contact between electrodes of opposite polarity in the same cell.

Characteristics

 Chemical stability.

 Low thickness.

 Mechanical strength.

 High porosity & permeability.

Examples

Polypropylene, Glass, Non–Woven glass.

1. 5. 5 Current collector

An inert member of high electrical conductivity used to conduct current from or to

an electrode during discharge or charge.

Characteristics

 Excellent bulk electrical conductivity.

 Minimal thickness / weight.

 Excellent surface conductivity.

Examples

Aluminium foil, Copper foil and Nickel mesh.

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1. 6 Operating principle of cell

1. 6. 1 Discharge

The operation of a cell during discharge is shown schematically in Fig. 1. 1a.

When the cell is connected to an external load, electrons flow from the anode, which is

oxidized, through the external load to the cathode, where the electrons are accepted and

the cathode material is reduced. The electric circuit is completed in the electrolyte by the

flow of anions (negative ions) and cations (positive ions) to the anode and cathode,

respectively.

1. 6. 2 Charge

During the recharge of a rechargeable or storage cell, the current flow is reversed

and oxidation takes place at the positive electrode and reduction at the negative electrode,

as shown in Fig. 1. 1b. As the anode is, by definition, the electrode at which oxidation

occurs and the cathode, the one where reduction takes place, the positive electrode is now

the anode and the negative the cathode.

1. 7 Lithium batteries

Lithium batteries1 were first proposed by M. S. Whittingham at Binghamton

University, at Exxon, in the 1970s. Whittingham used titanium (II) sulfide as the cathode

and lithium metal as the anode. The reversible intercalation in graphite and intercalation

into cathodic oxides was also already discovered2 in the 1970s by J.O. Besenhard at TU

Munich. He also proposed the application as high energy density lithium cells. In 1979,

John Goodenough demonstrated a rechargeable3 cell with high cell voltage in the 4V

range using lithium cobalt oxide (LiCoO2) as the positive electrode and lithium metal as

the negative electrode. This innovation provided the positive electrode material which

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made lithium ion batteries (LIBs) possible. LiCoO2 is a stable positive electrode material

which acts as a donor of lithium ions, which means that it can be used with a negative

electrode material other than lithium metal. In 1985, Akira Yoshino4 assembled a

prototype cell using carbonaceous material into which lithium ions could be inserted as

the anode, and as the cathode lithium cobalt oxide (LiCoO2), which is stable in air. By

using an anode material without metallic lithium, safety was dramatically improved over

batteries which used lithium metal. The use of lithium cobalt oxide (LiCoO2) enabled

industrial–scale production to be achieved easily. This was the birth of the current

lithium–ion battery. In 1991, Sony and Asahi Kasei released the first commercial

lithium–ion battery.

1. 8 Advantages of lithium–ion battery

• High voltage

Lithium cells have voltages up to about 4V, depending on the cathode

material, compared with 1.5V for most other primary system. High open circuit

voltage in comparison to aqueous batteries (such as lead acid, nickel–metal hydride

and nickel–cadmium). This is beneficial because it increases the amount of power

that can be transferred at a lower current.

• High energy density and power density

The energy density (100–250 Wh/Kg) and power density (250 Wh/L) of

lithium cell is 2–4 or more times better than that of conventional batteries (Lead acid,

zinc anode and Ni/MH batteries).

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 • Operation over a wide temperature range

Many of the lithium cells will perform over a temperature range from –40 to

70°C.

• Flat discharge characteristics

A flat discharge curve is typical for many lithium cells.

• No memory effect

• Superior shelf life

Self–discharge rate of approximately 5–10% per month, compared to over 30%

per month in common nickel metal hydride batteries, approximately 1.25% per month for

low self–discharge Ni–MH batteries and 10% per month in nickel–cadmium batteries.

1. 9 Electrochemistry of lithium–ion Battery

During charge, the positive material is oxidized and the negative material is

reduced. In this process, lithium ions are de–intercalated from the positive material and

intercalated into the negative material. (Intercalated – a reaction where lithium ions are

reversibly removed or inserted into a host without a significant structural change to the

host) The reverse process is present during a discharge cycle. The operation of a Lithium

ion cell is shown schematically in Fig. 1. 2.

The positive electrode half–reaction is

Charge
LiCoO2 Li1–xCoO2 + xLi+ + xe–

Discharge

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The negative electrode half–reaction is

Charge
+ –
xLi + xe + 6C LixC6

Discharge

The over all electrode reaction is

Discharge
CoO2 + LiC6 LiCoO2 + C6

Charge

1. 10 Classification of lithium batteries

Lithium batteries are classified into two broad categories.

Lithium battery

Li primary battery Li secondary battery

Soluble Solid Solid Lithium Lithium ion

cathode cathode electrolyte ion battery polymer
cells cells cells battery

1. 10. 1 Classification of lithium primary battery

Lithium primary cells classified on the basis of electrolyte used or cathode

material.

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a. Soluble–cathode cells

These use liquid or gaseous cathode materials that dissolve in the electrolyte or

the electrolyte solvent. Their operation depends on the formation of a passive layer on the

lithium anode resulting from a reaction between the lithium and the cathode material.

This prevents further chemical reaction (self– discharge) between anode and cathode or

reduces it to a very low rate. These cells are manufactured in many different

configurations and designs (such as high and low rate) and with a very wide range of

capacities. They are generally fabricated in cylindrical configuration in the smaller sizes,

upto about 35 Ah, using a bobbin construction for the low–rate cells and a spirally wound

(jelly–roll) structure for the high–rate designs. Prismatic containers, having flat parallel

plates, are generally used for the larger cells upto 10,000 Ah in size. Flator‘‘pancake–

shaped’’ configurations have also been designed. These soluble cathode lithium cells are

used for low to high discharge rates. The high–rate designs, using large electrode surface

areas, are noted for their high power density and are capable of delivering the highest

current densities of any active primary cell.

Eg. Li/SO2Cl2 cells

b. Solid–cathode cells

The second type of lithium anode primary cells uses solid rather than soluble

gaseous or liquid materials for the cathode. With these solid cathode materials, the cells

have the advantage of not being pressurized or necessarily requiring a hermetic–type seal,

but they do not have the high–rate capability of the soluble–cathode systems. They are

designed, generally, for low–to medium–rate applications such as memory backup,

security devices, portable electronic equipment, photographic equipment, watches,

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calculators and small lights. Button, flat, and cylindrical–shaped cells are available in

low–rate and the moderate–rate jelly–roll configurations. Eg. Li/V2O5 cell.

c. Solid–electrolyte cells

The third type of lithium anode primary batteries uses solid rather than liquid for

electrolytes. The solid electrolyte is formed in situ as the discharge product of the cell

reaction. However, the viscous liquid phase impart a plasticity to the cathode which

makes these solid state cells better able to adapt to volumetric changes during cell

discharge. These cells are noted for their extremely long storage life, in excess of 20

years, but are capable of only low–rate discharge in the micro ampere range. They are

used in applications such as memory backup, cardiac pacemakers, and similar equipment

where current requirements are low but long life is critical.

Eg. Li/LiI/I2 (P2VP)

1. 10. 2 Classification of lithium secondary batteries

Lithium secondary cells classified on the basis of electrolyte used.

a. Lithium–ion battery

The three primary functional components of a lithium–ion battery are the anode,

cathode, and electrolyte. The anode of a conventional lithium–ion cell is made from

carbon, the cathode is a metal oxide, and the electrolyte is a lithium salt in an organic

solvent. The most commercial popular anode material is graphite. The cathode is

generally one of three materials: a layered oxide (such as lithium cobalt oxide), a

polyanion (such as lithium iron phosphate), or a spinel (such as lithium manganese

oxide). The electrolyte is typically a mixture of organic carbonates such as ethylene

carbonate or diethyl carbonate containing complexes of lithium ions. These non–aqueous

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electrolytes generally use non–coordinating anion salts such as lithium

hexafluorophosphate (LiPF6), lithium hexafluoroarsenate monohydrate (LiAsF6. H2O),

lithium perchlorate (LiClO4), lithium tetrafluoroborate (LiBF4), and lithium triflate

(LiCF3SO3). Depending on materials choices, the voltage, capacity, life, and safety of a

lithium–ion battery can change dramatically.

b. Lithium–ion polymer battery

Lithium–ion polymer batteries, polymer lithium ion, or more commonly lithium

polymer batteries (abbreviated Li–poly, Li–Pol, LiPo, LIP, PLI or LiP) are rechargeable

batteries (secondary cell batteries). This battery consists of a carbon anode and Li+

insertion material cathode and solid polymer electrolyte, in which lithium ions swing

between the two electrodes. Lithium polymer batteries have the same basic chemistry as

lithium ion batteries. However, the polymer cells use a porous separator that, when

exposed to the electrolyte, turns to a gel because the gel isn't flammable, lithium polymer

batteries have a different architecture, with the anode and cathode developed as a plate

and stacked on top of each other. Polymer electrolytes/separators can be solid polymers

(e.g., polyethylene oxide) and LiPF6, or other conducting salts and SiO2, or other fillers

for better mechanical properties. Lithium polymer batteries do not need a metal shell the

way that lithium ion batteries do. In fact, the shell of lithium polymer batteries is often

plastic.

1. 11 Components of lithium ion cells

1. 11. 1 Anode

The anode is the electrode at which oxidation takes place and electrons are fed

into the external circuit. Different type of anode materials are used in currently used

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lithium ion batteries such as lithium metal, carbonaceous materials, Sn, SnO based

materials and Intermetallic alloys etc.,

Criteria

The potential of lithium insertion and deinsertion in the anode Vs Li must be as

low as possible.

The amount of lithium which can be accommodated by the anode material should

be as high as possible to achieve a high specific capacity.

The anode should endure repeated Li insertion and deinsertion without any

structural change to obtain long cycle life.

Examples. Li, graphite, metal and metal oxides.

1. 11. 2 Cathode

The cathode is the electrode at which reduction takes place and into which

electrons are fed from the external circuit. A guest spaced such as lithium can be inserted

interstitially into the host lattice and extracted during recharge with little or no structural

modification of the host. The intercalated compounds are classified as follows

 LiMO2 based materials (M = Co, Ni, Mn)

 LiMPO4 based materials (M = Fe, Co, Ni and Mn)

 LiMn2O4 based materials

Criteria

The insertion compound LixMyXz (X – anion) should have a high lithium

chemical potential (µLi(c)) to maximize the cell voltage.

The insertion compound LixMyXz should allow an insertion/extraction of a

large amount of lithium, to maximize the cell capacity.

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The lithium insertion/extraction process should be reversible with no or

minimal changes in the host structure over the entire range x of lithium

insertion/extraction in order to provide a good cycle life for the cell.

The insertion compound should support mixed conduction. It should have

good electronic conductivity σe and lithium ion conductivity σLi to

minimize polarization losses during the discharge/charge process and

thereby to support a high current density and power density.

The insertion compound should be chemically stable without undergoing

any reaction with the electrolyte over the entire range, x of lithium

insertion/extraction.

Examples. LiCoO2, LiMn2O4, LiFePO4 etc.

1. 11. 3 Electrolyte

Electrolytes can be defined as to serve as the medium for the transfer of charges,

which are in the form of ions, between a pair of electrodes. The vast majority of the

electrolytes are electrolytic solution types that consists of salts dissolved in either water

(aqueous) or organic molecules (nonaqueous) and are in a liquid in the service

temperature range.

Criteria

It should be a good ionic conductor and electronic insulator

It should have wide electrochemical window

It should also be inert to other cell components

It should be robust against other various abuses, such as electrical, mechanical or

thermal ones.

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Its components should be environmentally friendly.

Classification

Electrolytes can be roughly divided into three groups as follows

Liquid electrolytes eg. LiPF6 in 1: 1 (EC: DEC)

Solid polymer electrolyte eg. LiClO4 – PEO

Gel polymer electrolyte eg. PVDF – HFP

1. 11. 4 Separators

A separator is a porous membrane placed between electrodes of opposite polarity,

permeable to ionic flow but preventing electrical contact of the electrodes.

Criteria

Electronic insulator

Minimal electrolyte (ionic) resistance

Mechanical and dimensional stability

Sufficient physical strength to allow easy handling

Chemical resistance to degradation by electrolyte, impurities and electrode

reactants and products

Effective in preventing migration of particles or colloidal or soluble species

between the two electrodes

Readily wetted by electrolyte

Uniform in thickness and other properties

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Classification

Separators for batteries can be divided into different types, depending on their

physical and chemical characteristics. They can be molded, woven, non–oven,

microporous, bonded, papers, or laminates.

Eg. Polypropylene, cellulose, nonwoven fabric and celgard etc.

1. 11. 5 Current collectors

A structural part of a complicated electrode assembly. Its primary purpose is to

conduct the electricity between the actual working (reacting) parts of the electrode and

the terminals. Current collectors must be electrochemically stable when in contact with

the cell component during the potential operation window of an electrode. In lithium

batteries Al can be used as current collector for positive electrode and Cu foil for

negative electrode. The rough surface of substrate enhanced the adhesive force between

an active material and a current collector. Therefore, surface roughness of substrate is an

important factor to improve the cycleability of Li–ion cell.

a. Aluminium foil

For high voltage5 (>3.5 V Vs Li/Li+) LIBs, Al is the material of choice. It is used

extensively with lithiated transition metal oxides upto 5V Vs. Li/Li+. In air and aqueous

solutions, Al can be protected by a thin and dense oxide passive layer, Al2O3. Its low

price and good electrical conductivity due to a high purity of Al metal expand the

potential application for lithium batteries.

b. Copper foil

Almost all commercial, rechargeable lithium batteries use carbonaceous materials

applied to a copper foil substrate as the negative electrode. As lithium ions, which are

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released from the positive electrodes, are intercalated to the carbonaceous negative

electrode materials, the resulting potential6 reaches between 0.25 and 0.01 V Vs. Li/Li+.

In this state, the negative electrode materials, the Cu current collector, and the electrolyte

are electrochemically reduced. Cu metal surface is likely to reduce the electrolyte at the

potential 3 V Vs. Li/Li+, generating the cathodic current beecause of this, Cu metal is

stable at a lower narrow potential range and is generally acceptable for negative electrode

current collectors.

1. 12 Applications of lithium primary and secondary batteries

Lithium primary and secondary batteries are widely used in consumer, industrial,

medical, automotive and military devices.

General usage

Lithium–ion batteries can be used both in devices that need recharging, such as

cell phones, and in products whose batteries are difficult, expensive or impossible to

recharge or replace, such as cardiac pacemakers.

Portable electronics

In portable electronics, batteries needs to be recharged many times, and the

lithium–ion battery can handle hundreds of recharges. Products that use the lithium–ion

battery include iPods, cell phones, PCs, laptops, watches and digital cameras.

Medical applications

Implantable electronic devices cannot be recharged or replaced without great

expense, so the batteries used need to be small and able to last for years. Implantable

products that use lithium–ion batteries include cardiac pacemakers, cardiac defibrillators,

neuro stimulators and drug infusion systems.

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Military applications

The lithium–ion battery's long life and light weight make it the battery used in

many military functions, including providing power for the computers in missiles.

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1. 13 References

1. M. S. Whittingham, Science 192 (1976) 1126.

2. R. Schallhorn, R. Kuhlmann, J. O. Besenhard, Mater. Res. Bull. 11 (1976) 83.

3. USPTO search for inventions by "Goodenough, John".

4. US 4668595, Yoshino; Akira, "Secondary Battery", issued 10 May 1985, assigned

to Asahi Kasei.

5. S. T. Myung, Y. Hitoshi, Y. K. Sun, J. Mater. Chem. 21 (2011) 9891.

6. K. L. Lee, J. Y. Jung, S. W. Lee, H. S. Moon, J. W. Park, J. Power Sources 129

(2004) 270.

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 Fig. 1. 1 Operation of cell a) Discharge b) Charge

Fig. 1. 2 Lithium – ion battery – operating principle (source: www.marklines.com)

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