Electrochemistry and

Its Application
TEKNIK KIMIA – UNIVERSITAS PERTAMINA 2019

Agung Nugroho
Performance of
Cell Battery
Performance of Cell Battery

 Ideal case: the discharge proceeds at the

theoretical voltage until all the active
materials are consumed.
 Curve 1:
 Initial voltage is lower due to internal
resistance.
 During discharge → voltage drop due to
accumulation resistance increase and
effect of polarization (activation and
concentration)
 Curve 2: higher internal resistance and
higher discharge rate.
Battery discharge characteristics

 Curve 1: during discharge , nearly no

change in reactants and reaction products
until the active materials are nearly
exhausted.
 Curve 2: two-step discharge indicating a
change in the reaction mechanism and
potential of the active material(s).
 Curve 3: is typical when the composition of
the active materials, reactants, internal
resistance, and so on, change during the
discharge.
 Terminology related to voltage

1. The theoretical voltage is a function of the anode and cathode materials, the composition
of the electrolyte, and the temperature (usually stated at 25°C).
2. The open-circuit voltage (OCV) is the voltage under a no-load condition and is usually a
close approximation of the theoretical voltage.
3. The closed-circuit voltage (CCV) is the voltage under a load condition.
4. The nominal voltage is one that is generally accepted as typical of the operating voltage of
the battery as, for example, 1.5 V for a zinc-manganese dioxide battery.
5. The working voltage is more representative of the actual operating voltage of the battery
under load and will be lower than the open-circuit voltage.
6. The end or cutoff voltage is designated as the end of the discharge. Usually it is the voltage
above which most of the capacity of the cell or battery has been delivered. The end
voltage may also be dependent on the application requirements.
Example:

 The lead-acid battery,

 the theoretical and open-circuit voltages are 2.1 V
 nominal voltage is 2.0 V,
 the working voltage is between 1.8 and 2.0 V, and
 the end voltage is typically 1.75 V on moderate and low-drain discharges
and 1.5 V for high-drain discharge.
 C rate

 In describing batteries, discharge current is often expressed as a C-rate in

order to normalize against battery capacity, which is often very different
between batteries.
 A C-rate is a measure of the rate at which a battery is discharged relative to
its maximum capacity.
 A 1C rate means that the discharge current will discharge the entire battery
in 1 hour.
 Example:
 For a battery with a capacity of 100 Ah, this equates to a discharge current of
100 A.
 A 5C rate for this battery would be 500 A, and a C/2 rate would be 50 A.
Primary Battery
 Dry Cell (Leclanche cell)

 The dry cell is a zinc-carbon battery.

 The zinc can serves as both a container and the
negative electrode.
 The positive electrode is a rod made of carbon
that is surrounded by a paste of manganese(IV)
oxide, zinc chloride, ammonium chloride, carbon
powder, and a small amount of water.

https://opentextbc.ca/chemistry/chapter/17-5-
batteries-and-fuel-cells/
 Dry Cell (Leclanche cell)

 Chemical reaction:
 Cathode: 2NH4+ + 2MnO2 +2e → Mn2O3 +2NH3 + H2O
 Anode: Zn → Zn2+ + 2e
 The difference of potential between the two electrodes is the output voltage (1.5
V).
 D, C, A, AA, and AAA batteries all have the same voltage rating
 Larger batteries can deliver more moles of electrons → higher capacity
Comparative Discharge Curves:
Size Effect
Comparative Discharge Curves:
Discharge Current
 Durability

The zinc container becomes thinner as the cell is used, because zinc metal is oxidized to zinc ions.
 Alkaline Battery

 Alkaline batteries were developed in the 1950s partly to address some

of the performance issues with zinc–carbon dry cells.
 As their name suggests, these types of batteries use alkaline
electrolytes, often potassium hydroxide.
 Alkaline batteries use zinc and magnesium dioxide.
 The alkaline dry cell lasts much longer as the zinc anode corrodes less
rapidly under basic conditions than under acidic conditions.
 Alkaline have higher energy density than the carbon-zinc batteries.
 Alkaline Battery

 Chemical reaction:
 Cathode: 2MnO2 + H2O + 2e → Mn2O3 + 2OH- Eo =-1.28V
 Anode: Zn + 2OH- → ZnO + H2O + 2e Eo = 0.15 V

 Overall : Zn + 2MnO2 → ZnO + Mn2O3 Eo = 1.43 V

 An alkaline battery can deliver about three to five times the
energy of a zinc-carbon dry cell of similar size.
 Alkaline batteries are prone to leaking potassium hydroxide, so
these should also be removed from devices for long-term
storage.
Secondary Battery
 Lead Acid Battery

 The lead acid battery is the type of secondary battery

used in your automobile.
 It is inexpensive and capable of producing the high
current required by automobile starter motors.
 Chemical reaction during discharge:
 Cathode: PbO2 + H2SO4 + 2e → PbSO4 + 2 H2O
 Anode: Pb + H2SO4 → PbSO4 + 2H+ + 2e

 Each cell produces 2 V, so six cells are connected in series to produce a

12-V car battery.
Lead Acid Battery
 Anode : Pb + SO42- → PbSO4 +2e
 Cathode : PbO2 + SO42- +4H+ +2e → PbSO4 +2H2O
Discharge-Charge Mechanism
 Comparative Discharge Curves: Effect
of Temperature

Higher discharge voltages and capacities are obtained at the higher temperatures and lower discharge rates.
 Ni-Cd batteries

 Negative electrode: Cadmium (Cd) –

instead of the MH in Ni-MH batteries
 Positive electrode: nickel oxyhydroxide
(NiO(OH)) – the same than in Ni-MH batteries
 Electrolyte: Potassium hydroxide (KOH)
solution
 The positive and negative plates, which are
prevented from shorting by the separator,
are rolled together and put into the case.
 This is a “jelly-roll” design and allows the NiCd
cell to deliver much more current than a
similar-sized alkaline battery.
Saft batteries
Ni-Cd batteries

 The voltage is about 1.2 V to 1.25 V

as the battery discharges.
 NiCd battery can be recharged
about 1000 times.
 Cadmium is a toxic heavy metal so
NiCd batteries should never be
opened or put into the regular
trash.
 Ni-Cd batteries

• Chemical reaction (discharge)

• Positive electrode 2NiO(OH) + 2H2O + 2e- 2Ni(OH)2 + 2OH-

Through electrolyte
Through load
• Negative electrode Cd + 2OH- Cd(OH)2 + 2e-

• Overall 2NiO(OH) + Cd + 2H2O 2Ni(OH)2 + Cd(OH)2

• The electrolyte is not affected because it does not participate in the reaction.
Discharge Characteristics
Charge Characteristics
 Nickel Metal Hydride
(Ni-MH) batteries

 Negative electrode: Metal Hydride such as

 AB2 (A=titanium and/or vanadium, B= zirconium or
nickel, modified with chromium, cobalt, iron, and/or
manganese)
 AB5 (A=rare earth mixture of lanthanum, cerium,
neodymium, praseodymium, B=nickel, cobalt,
manganese, and/or aluminum)
 Positive electrode: nickel oxyhydroxide (NiO(OH))
 Electrolyte: Potassium hydroxide (KOH)
 Ni-MH batteries

• Chemical reaction (discharge)

• Positive electrode NiO(OH) + H2O + e- Ni(OH)2 + OH- Eo =0.52 V

Through electrolyte Through load

• Negative electrode MH + OH- M + H2O + e- Eo =0.83V

• Overall NiO(OH) + MH Ni(OH)2 + M Eo =1.35V

• The electrolyte is not affected because it does not participate in the reaction.
Ni-MH batteries

The negative electrode

material must be an alloy
capable of large amount
of hydrogen adsorption

LaNi5
TiN2
ZrNi
Ti2Ni

Typical electrodes can adsorb

up to 2wt% hydrogen when charged
Discharge Characteristics
Lithium Ion Battery
 Lithium Battery Development

 Pioneering work for the lithium battery

began in 1912 by G. N. Lewis but it was
not until the early 1970’s when the first
non-rechargeable lithium batteries
became commercially available.
 In the 1970’s, Lithium metal was used
but its instability rendered it unsafe.
There are two types of Lithium
Batteries

Lithium
(metallic)
Lithium ion
(intercalated lithium compound)

Non-rechargeable Rechargeable
- Instrumentation
- Mobile phones
- Oil drilling
- Laptops
- Power tools
- Electric powertrains
Li Battery
 Li/MnO2 Primary Battery

 Electrolyte containing lithium salts in a mixed organic solvent, such as propylene

carbonate and 1,2-dimethoxyethane
 Manganese dioxide, an intercalation compound, is reduced from the tetravalent to the
trivalent state, producing LixMnO2 as the Li+ ion enters into the MnO2 crystal lattice.
 Lithium Battery Development

 Attempts to develop rechargeable

lithium batteries followed in the
eighties, but failed due to safety
problems.
 The Lithium-Ion battery has a slightly
lower energy density than Lithium
metal, but is much safer.
 Introduced by Sony in 1991.
 Lithium secondary battery

 1972 Define the concept of chemical

intercalation
 In chemistry, intercalation is the reversible
inclusion of a molecule between two other
molecules.
 Ex: graphite intercalation compounds.
 Graphite intercalation compounds are complex
materials where an atom, ion, or molecule is inserted
(intercalated) between the graphite layers. In this type
of compound the graphite layers remain largely intact
and the guest species are located in between.

Source: J.-M. Tarascon and M. Armand , Nature, 414, 359, 2001.

 Li-ion batteries

• Positive electrode: Lithiated form of a transition

metal oxide (lithium cobalt oxide-LiCoO2 or
lithium manganese oxide LiMn2O4)
• Negative electrode: Carbon (C),
• usually graphite (C6)
• Electrolyte: solid lithium-salt electrolytes
• (LiPF6, LiBF4, or LiClO4)
• and organic solvents (ether)

http://www.fer.hr/_download/repository/Li-ION.pdf
 Li-ion batteries

•Chemical reaction
Comparison of secondary batteries
See You on Next Lecture
https://www.youtube.com/watch?v=OvGB4ZyMvBU
 Cathode Current Collector

More details on the transport of Li-ions

 Both the anode and cathode are made from a collection of powder
particles which are bonded together into a 3-D porous body (electrode).
 During discharge, ion transport in the electrode occurs as follows (green
6
line)
1. Li-ion starts in the bulk of an anode particle. 5

2. It undergoes solid state diffusion in the particle.

4
3. At the surface it disassociates from the and enters the electrolyte
e-
which occupies the pores of the electrode. 4 Electrolyte
4. The ion is transported through the electrolyte (liquid phase diffusion) to
the cathode. MPI
5. It undergoes solid state diffusion in the cathode. 4 work
 At the same time, the electron must pass through the collection of solid
particles to a metal current collector where it can be extracted from the 3 1shop
2
cell and used to power a device (red line). It can not travel in the ,
electrolyte.
WPI,
2008Collector
Anode Current 45
Source:http://www.math.wpi.edu/MPI2008/TIAX/MPI-web.ppt#256,1,Modeling battery electrode properties
 Electrodes

Cathode Current
 Electrodes typically contain high surface area Collector
carbon to increase the electrical conductivity
between particles.
 A small amount of polymer binder is used to hold the
particles in place.
 Typical particle size ~10um.
 Typical electrode thickness 50-75 μm.
 Cathode current collector typically Al
 Anode current collector typically Cu
Electrodes

10mm

1mm
10mm
 Key Battery Attributes

 Energy Density: Total amount of energy that can be stored per unit mass or
volume. How long will your laptop run before it must be recharged?
 Power Density: Maximum rate of energy discharge per unit mass or volume. Low
power: laptop, i-pod. High power: power tools.
 Safety: At high temperatures, certain battery components will breakdown and
can undergo exothermic reactions.
 Life: Stability of energy density and power density with repeated cycling is
needed for the long life required in many applications.
 Cost: Must compete with other energy storage technologies.
 Advantages of Using Li-Ion Batteries

 POWER – High energy density means

greater power in a smaller package.
 160% greater than NiMH
 220% greater than NiCd
 HIGHER VOLTAGE – a strong current
allows it to power complex mechanical
devices.
 LONG SELF-LIFE – only 5% discharge loss
per month.
 10% for NiMH, 20% for NiCd
Packaging and Configurations
Packaging
and Type
F
Size (mm)
33x90
History
1896 for lantern, later for radios, NiCd only
Configurations E N/A 1905 for lantern and hobby, discontinued
1980
D 34x61 1898 for flashlight, later radios
C 25.5x50 1900 as above for smaller form factor
B N/A 1900 for portable lighting, discontinued
2001
A 17x50 NiCd only, also in half-sizes
AA 14.5x50 1907 for WWI; made standard in 1947
AAA 10.5x44.5 1954 for Kodak, Polaroid to reduce size
AAAA 8.3x42.5 1990 for laser pointers, flashlights, PC stylus
4.5V 85x61x17.5 Flat pack for flashlight, common in Europe
In ca. 1917, the National 9V 48.5x26.5x17.5 1956 for transistor radios
Institute of Standards and
18650 18x65 Early 1990s for Li-ion
Technology established the
alphabet nomenclature. 26650 26x65 Larger size for Li-ion
 Cylindrical cell

➢ Classic packaging for

primary & secondary cells

➢ High mechanical stability,

economical, long life

➢ Holds internal pressure without deforming

case

➢ Inefficient use of space

➢ Metal housing adds to weight

 Button cell

➢ Also known as coin cells;

small size, easy to stack

➢ Mainly reserved as primary batteries in watches, gauges

➢ Rechargeable button cells do not allow fast charging

➢ Limited new developments

➢ Must be kept away from children, harmful if swallowed

(voltage)
Prismatic cell

➢ Best usage of space

➢ Allows flexible design

➢ Higher manufacturing cost

➢ Less efficient thermal

management

➢ Shorter life
 Pouch cell

➢ Light and cost-effective to manufacture

➢ Simple, flexible and lightweight solutions

➢ Exposure to humidity, hot temperature shorten

life

➢ Loss of stack pressure; swelling due to gassing

➢ Design must include allowance for 8-10%

swelling

Some cells may bloat

Active materials for
rechargeable Li-based cells
 The road map for developing advanced
Li-ion batteries

High energy density battery

High capacity electrode

materials

 Output voltage and capacity mainly determined by the

electrodes
 Vast majority of commercial Li battery utilize carbon based
anode material
 Silicon and tin = large capacity, but have volumetric
Yoo et al, Materials Today, 17(3), 2014 expansion problem
 Electrodes in LIB

Cathode Materials Anode Materials

Nitta et al, Materials Today, 18(5), 2015

Electrodes in LIB
 Electrodes of LIB

 Cathode Materials for LIB

 Triclinic structured Materials
 Spinal type Materials
 Layered Materials
 Olivine structured Materials
 Rhombohedral structured Materials
 Anode materials for LIB
 Insertion-type materials.
 Alloy/de-alloy materials.
 Conversion materials.
See You on Next Lecture