ELECTROCHEMICAL POWER SOURCES

Batteries- types, characteristics. Fabrication and working of lechlanche cell,

primary lithium cell, lead- acid battery, Ni-metal hydride and lithium ion
batteries. Supercapacitors. Fuel cells - Classification, working principle,
components, applications of proton exchange membrane, direct methanol
and solid oxide fuel cells. Hydrogen as a fuel-production and storage.

BATTERIES
Leclanche cell / Dry cell
Lead-Acid battery
Nickel – metal hydride battery
Lithium battery
Supercapacitor
A battery is a device which stores chemical energy
and on demand convert it into electrical energy to
drive an external circuit.

Battery is a device consisting of more than one cell

arranged in series or parallel
 Battery (Ancient) History
1800 Voltaic pile: silver zinc
1836 Daniell cell: copper zinc
1859 Planté: rechargeable lead-acid cell
1868 Leclanché: carbon zinc wet cell
1888 Gassner: carbon zinc dry cell
1898 Commercial flashlight, D cell
1899 Junger: nickel cadmium cell
 Battery History
1946 Neumann: sealed NiCd
1960s Alkaline, rechargeable NiCd
1970s Lithium, sealed lead acid
1990 Nickel metal hydride (NiMH)
1991 Lithium ion
1992 Rechargeable alkaline
1999 Lithium ion polymer
 Series Connected Cells

Cells connected in series for higher voltage. Current rating is the same as for one cell. (a) Wiring.
(b) Schematic symbol for battery with three series cells. (c) Battery connected to lead resistance
RL.
 Parallel Connected Cells

The parallel connection is

equivalent to increasing
the size of the electrodes
and electrolyte, which
increases the current
capacity.

Cells connected in parallel for higher current rating. (a) Wiring. (b) Schematic symbol for battery
with three parallel cells. (c) Battery connected to lead resistance RL.
Copyright © The McGraw-Hill Companies, Inc. Permission required for reproduction or display.
 Series and Parallel Connected Cells

To provide a higher output voltage and more current capacity, cells

can be connected in series-parallel combination.
Fig. 12-16: Cells connected in series-parallel combinations. (a) Wiring two 3-V strings, each with
two 1.5-V cells in series. (b) Wiring two 3-v strings in parallel.
Copyright © The McGraw-Hill Companies, Inc. Permission required for reproduction or display.
 Series and Parallel Connected Cells

(c) Schematic symbol for the battery in (b) with output of 3 V. (d) Equivalent battery connected to
lead resistance RL.
Copyright © The McGraw-Hill Companies, Inc. Permission required for reproduction or display.
 The Electrochemical Cell
e
consumer

salt bridge

oxidation reduction
at zinc at copper
anode
ZnSO4 CuSO 4 cathode

Half Cell I Half Cell II

 The Electrochemical Cell (2)

• Zinc is (much) more easily oxidized than

Copper Zn   Zn 2  2e  (anode)
Cu 2  2e  
 Cu (cathode)
• Maintain equilibrium electron densities
• Add copper ions in solution to Half Cell II
• Salt bridge only carries negative ions
– This is the limiting factor for current flow
– Pick a low-resistance bridge
 Battery Characteristics
• Size
– Physical: button, AAA, AA, C, D, ...
– Energy density (watts per kg or cm3)
• Longevity
– Capacity (Ah (Ampere-hour), for drain of C/10 at
20°C)
– Number of recharge cycles
• Discharge characteristics (voltage drop)
 Further Characteristics
• Cost
• Behavioral factors
– Temperature range (storage, operation)
– Self discharge
– Memory effect
• Environmental factors
– Leakage, gassing, toxicity
– Shock resistance
 Primary (Disposable) Batteries
A primary cell cannot be recharged because the
internal chemical reaction cannot be reversed.

• Zinc carbon (flashlights, toys)

• Heavy duty zinc chloride (radios, recorders)
• Alkaline (all of the above)
• Lithium (photoflash)
• Silver, mercury oxide (hearing aid, watches)
• Zinc air
Secondary (Rechargeable) Batteries
A secondary cell, or storage cell, can be recharged
because its chemical reaction is reversible.
• Nickel cadmium
• Nickel metal hydride
• Alkaline
• Lithium ion
• Lithium ion polymer
• Lead acid
 Standard Alkaline Batteries
• Chemistry
Zinc (-), manganese dioxide (+)
Potassium hydroxide aqueous electrolyte
• Features
+ 50-100% more energy than carbon zinc
+ Low self-discharge (10 year shelf life)
± Good for low current (< 400mA), long-life use
– Poor discharge curve
 Leclanche Cell/ Dry cell
Fabrication
 Constituents
1. Anode:
Zinc – Moderate reduction potential,
Good dimensional stability.

2. Cathode:
Graphite – Highly porous, Good mechanical strength,
Fabricated to any shape.

3. Electrolytes:
- A paste of 26 % NH4Cl & 9 % ZnCl2 made with wheat flour.
- NH4Cl is highly soluble and have high conductance.
- ZnCl2 helps to maintain acidic pH of electrolyte for
proper gel structure
(products of electrolysis are alkaline)
4. Depolariser:
- Gas Polarisation occurs at Cathode
- H+ reduces to H atom and forms H2 molecules.
- H2 molecule gets adsorbed on graphite surface &
increases its resistance, output voltage of cell decreases.
- Increases cell pressure and battery ultimately bursts.
- MnO2 is used as a depolariser
- MnO2 oxidizes H2 to water
- MnO2 is a bad conductor, hence mixed with graphite
powder and made a paste with NH4Cl and water.
- Tied up in a muslin cloth.

5. Special additives:
- Added to avoid self-corrosion (Zn), increase shelf-life of battery
- Wheat flour: Two enzymes mesonine & gliadine, shows
negative catalysis on oxidation of Zn & minimises
self-corrosion.
Reactions
The redox reaction in a Leclanché cell involves the two following half-
reactions:

Anode (oxidation of Zn): Zn → Zn2+ + 2e−

Cathode (reduction of Mn(IV)):
2 MnO2 + 2NH4+ + 2e− → 2 MnO(OH) + 2 NH3

The chemical process which produces electricity in a Leclanché cell begins

when zinc atoms on the surface of the anode oxidize, i.e. they give up both
their valence electrons to become positively charged Zn2+ ions. As the
Zn2+ ions move away from the anode, leaving their electrons on its surface,
the anode becomes more negatively charged than the cathode. When the
cell is connected in an external electrical circuit, the excess electrons on the
zinc anode flow through the circuit to the carbon rod, the movement of
electrons forming an electric current.
After passing through the whole circuit, when the electrons enter the cathode
(carbon rod), they combine with manganese dioxide (MnO2) and water (H2O),
which react with each other to produce manganese oxide (Mn2O3) and
negatively charged hydroxide ions. This is accompanied by a secondary acid-
base reaction in which the hydroxide ions (OH–) accept a proton (H+) from
the ammonium ions present in the ammonium chloride electrolyte to produce
molecules of ammonia and water.

Zn(s) + 2MnO2(s) + 2NH4Cl(aq) → ZnCl2(aq) + Mn2O3(s) + 2NH3(aq) + H2O(l)

or if one also considers the hydration of the Mn2O3(s) sesquioxide into Mn(III)

oxy-hydroxide:

Zn(s) + 2 MnO2(s) + 2 NH4Cl(aq) → ZnCl2(aq) + 2 MnO(OH)(s) + 2 NH3(aq)

Alternately, the reduction reaction of Mn(IV) can proceed further, forming

Mn(II) hydroxide.
Zn(s) + 2MnO2(s) + 2 NH4Cl(aq) → ZnCl2(aq) + Mn(OH)2(s) + 2 NH3(aq)
1. Produces 2 to 6 Ah current capacity
2. Addition of Sodium and Potassium chromates increases
corrosion resistance to Zn
3. Addition of small amount of mecuric compounds leads to
suppression of Hydrogen discharge.
4. A period of rest is to be given.
5. Since the electrolyte is a paste migration of ions occurs slow.
6. When not in use, battery should be removed from device.
7. Maximum battery efficiency is expected with low current
withdrawals and intermittent use.
Lead Acid Accumulator / Lead Acid Battery/
Lead Acid Storage cell
 Electrochemistry

First Charging Overall Reaction

• The secondary batteries used in vehicles have
a reversible chemical process.
Discharge: The battery reacts by producing
current flow in an external load circuit and
produces lead sulfate and water.
D
Pb + PbO2 + 2H2SO4 2PbSO4 + 2H2O
C
Charge: The battery reacts to a reverse current from
an external energy source and produces lead, lead
peroxide, and sulfuric acid.
– This cell is a widely applied type of secondary cell,
used extensively in vehicles and other applications
requiring high values of load current.
– The positive electrode is made of lead peroxide.
– The negative electrode is made of spongy lead metal.
– The electrolyte is sulfuric acid.
– The output is about 2.1 volts per cell.
– Cells are typically used in series combinations of 3 (6-
V battery) or 6 (12-V battery).
 Nickel – Metal Hydride Battery
Nickel-metal hydride batteries are essentially an extension of
the proven sealed nickel-cadmium battery technology with
the substitution of a hydrogen-absorbing negative electrode
for the cadmium-based electrode.

General Characteristics
• Typically can be recharged hundreds of times.
• Efficient at high rate discharges.
• Significantly higher capacity than nickel-cadmium batteries.
• Typical expectancy life is 2 to 5 years.
• Operates well at a wide range of temperatures:
Charging 0° C to 50° C Discharging 0° C to 50° C
Construction
• Anode (-ve) - Metal hydride, MH [LaNi5 alloy grid]
• Cathode (+ve) - Nickel oxy hydroxide/ Ni
• Electrolyte - KOH

A synthetic non-woven material separates two electrodes, serves

as a medium for absorbing electrolyte
Electrochemistry:
The electrochemistry of the nickel-metal hydride battery is generally
represented by the following charge and discharge reactions:
Charge
At the negative electrode, in the presence of the alloy and with an
electrical potential applied, the water in the electrolyte is
decomposed into hydrogen atoms, which are absorbed into the alloy,
and hydroxyl ions as indicated below.
Alloy + H2O + e‾ Alloy (H) + OH ‾
At the positive electrode, the charge reaction is based on the
oxidation of nickel hydroxide just as it is in the nickel-cadmium
couple.
Ni(OH)2 + OH ‾ NiOOH + H2O + e ‾
Discharge
At the negative electrode, the hydrogen is desorbed and combines
with a hydroxyl ion to form water while also contributing an electron
to the circuit.
Alloy (H) + OH ‾ Alloy + H2O + e ‾
At the positive electrode, nickel oxyhydroxide is reduced to its lower
valence state, nickel hydroxide.
NiOOH + H2O + e ‾ Ni(OH)2 + OH ‾
Advantage of Ni-MH over Ni-Cd battery

• Higher energy density can be achieved.

• Smaller amount of –ve electrode in Ni-MH battery is sufficient.
• Larger volume of +ve electrode, results in higher capacity or
longer service life.
• Ni-MH battery is free of Cd, hence disposal is feasible and eco-
friendly.

Advantages

• High capacity
• No maintenance required
• Minimum environmental problem
• Rapid recharging capability
• Long cycle life and long shelf life
Lithium Ion Battery – Lithium
primary battery

https://prezi.com/l0mxnhjqdxud/lithium-ion-batteries-presentation/

https://www.youtube.com/watch?v=no4vRKvKxcU
 Supercapacitor

https://www.youtube.com/watch?v=W4bE5zD_GxI

https://www.youtube.com/watch?v=wkM-8m0HpO8