Electrochemical energy

systems

Batteries and Fuel Cells

Module -IV
 Module IV- An Insight
Electrochemical energy systems: Basic concepts of electrochemical
energy systems.

Conventional primary batteries: Dry cell.

Advanced primary batteries: Lithium and alkaline primary

batteries.

Conventional secondary batteries: Lead-acid, nickel-cadmium

secondary batteries.

Advanced secondary batteries: Nickel-Metal hydride and lithium-

ion secondary batteries.

Fuel cells: Hydrogen-oxygen fuel cells

New generation fuel cells
Electric vehicle application
Solid oxide fuel cells.
Over heated – over night charging
Don’t discharge continuously….
Use original battery
Use original charger
Do not modify the cell phone
No cheaper phone…. (China made!!!)
 Batteries

Energy Conversion---Storage---Delivery
 Batteries
• A Battery is a device that consists of one or more
galvanic cells connected in series and/or parallel,
which converts the chemical energy (redox
reaction) to electrical energy in a stored form and
can be used whenever required.
 Terminology
1. EMF of a battery -G=nEF

2. Capacity: Total quantity of electricity that can be withdrawn

from a full charged cell.

3. Energy Density: Voltage of the cell and amount of charge

that can be stored.

4. Long Self life Charging and

5. Safety Discharging??
6. Compact and light weight

7. Low price

8. Cycling
Classification (or) Types of batteries

Primary battery (Primary cells)

In which the cell reaction is not reversible. When all the reactants
have been converted to product, no more electricity is produced
and the battery is dead.
Ex: Dry cell, Leclanche Cell
Secondary battery (secondary cells)
In which cell reactions can be reversed by passing electric current
in the opposite direction. Thus it can be used for a large number of
cycles.
Ex: Lead-Acid Batteries, Ni-Cd, Li-ion

Flow battery and fuel cell

In which materials (reactants, products, electrolytes) pass through
the battery continuously,
 Types of batteries
 Primary batteries
Dry or lachlanche cell
Western-Cd cell, Clark Std Cell
 Advanced Primary batteries
Alkaline battery
Lithium batteries

 Secondary batteries
Lead acid
Nickel-Cadmium

 Advanced secondary batteries

Nickel Metal hydride
Lithium ion (or) Lithium polymer battery
 Zn-Carbon DRY cell (or) LACLANCHE Cell

The venerable carbon-zinc

cell or Lechlanche' cell was
invented in 1866 by
Georges lachlanche and
was the most common
small battery throughout
most of the 20th century

Representation: Zn| Zn2+ || NH4+ | MnO2| C

Construction of Zn-C Dry Cell
Carbon (graphite rod) electrode –
+ cathode
(coated with carbon black and
MnO2)

Paste of NH4Cl and ZnCl2

Zn metal (anode)

-
Non conducting metal
tube
 Discharging Reactions of a Dry Cell
Dry cell contains Zn, NH4Cl, ZnCl2 and MnO2
Anodic reaction : Zn(s)  Zn2+(aq) + 2e-

Cathodic reaction: 2MnO2(s) + 2H2O(l) + 2e-  2MnO(OH)(s) + 2OH-

Net Cell Reaction : Zn(s) + 2MnO2 (s) + 2H2O(l)  2MnO(OH)(s) + Zn2++2OH-

2MnO(OH)  Mn2O3 (s) + H2O(l)
Draw backs:
Some of the complexity of this reaction comes from the fact that the reduction of
the ammonium ion produces two gaseous products

2NH4+(aq) + 2e-  2NH3(g) + H2 (g)

which must be absorbed to prevent the buildup of gas pressure.

ZnCl2 (aq) + 2NH3 (g)  Zn(NH3)2Cl2 (sparingly soluble salt)

2MnO2 (s) + H2(g)  Mn2O3(s) + H2O(l)
 Applications and disadvantages
• Used in flash lights, transistor radios, calculators etc
• Disadvantages of dry cell

• The voltage of this cell is initially about 1.5 volts, but decreases as
energy is taken from the cell. Due to the accumulation of the
products on electrodes. It also has a short shelf life and
deteriorates rapidly

• Oxidation of the zinc wall eventually causes the contents to leak

out, so such batteries should not be left in electric equipment for
long periods.
ALKALINE DRY CELLS - Primary Alkaline Battery

• Alkaline cells overcome some of the problems with Zn-Carbon primary batteries
by using potassium hydroxide in place of ammonium chloride in the
electrolyte.

• Potassium hydroxide is a base or alkaline material, hence the name "alkaline"

batteries.
 Construction of Alkaline Battery
Positive

Steel can
Cathode (HgO/Ag2O
Separator and Carbon black)
Cellulose + 40% KOH

Anode (Zn rod + HgO)

Negative
Vent
 Discharging Chemistry of Alkaline Cell

• The zinc anode does not form the container but it is in the form of a powder,
giving a large surface area. The following half-cell reactions take place inside the
cell:

• At the anode: Zn (s) + 2OH– (aq) → ZnO (s) + H2O(l) +2e–

• At the cathode: HgO (s) + H2O(l) + 2e – → Hg(s) + 2OH– (aq)

• Net Cell Reaction : Zn(s) + HgO(s) → Hg(s) + ZnO(s)

Advantages and Uses

1. Zinc does not dissolve as readily in alkaline medium
2. Long life, maintain it’s voltage
3. Used in calculators and watches
4. These cells have much longer shelf life and perform better under drain
and in cold weather.
5. They avoid the use of the zinc-corroding ammonium ions and do not
produce any gaseous products.
 Drawbacks
Alkaline batteries are prone to leaking potassium hydroxide,
a caustic agent that can cause respiratory, eye and skin irritation.

This can be avoided by

1. Not attempting to recharge disposable alkaline cells,
2. Not mixing different battery types in the same device,
3. Replacing all of the batteries at the same time,
4. storing in a dry place,

Caution
1. Once a leak has formed due to corrosion of the outer steel shell, potassium hydroxide
forms a feathery crystalline structure that grows and spreads out from the battery over
time, following up metal electrodes to circuit boards where it commences oxidation of
copper tracks and other components, leading to permanent circuitry damage.
2. The leaking crystalline growths can also emerge from seams around battery covers to
form a furry coating outside the device, that corrodes any objects in contact with the
leaking device.

Ref : [Link]
 Primary Lithium batteries
Introduction
• One of the main attractions of lithium as an anode material in its position as
the most electropositive metal in the electrochemical series combined with its
low density, thus offering the largest amount of electrical energy per unit
weight among all solid elements.

• Li cannot be used with the traditional aqueous electrolytes due to the very
vigorous corrosive reaction between Li and water with inflammable hydrogen
as the product.

• In the 1980s progress was made in the use of Li as an anode material with
MnO2, liquid SO2 (or) thionyl chlorides as the cathode, and hexaflurophosphate
dissolved in propylene carbonate as a typical organic electrolyte.

• Li cells are generally properly sealed against contact with air and moisture
While the primary lithium battery has been well established for nearly two
decades,
 Li Primary batteries
Li Cells with solid cathode Li Cells with Soluble cathode Li Cells with Solid electrolyte

Anode: Li  Li+
Li Cells with solid cathode
3 to 3.2 V High energy density, good low-temperature
performance; cost effective. Small in size, long self life,
Electrical medical devices; memory circuits
Anode: Li,

Cathode: MnO2 or V2O5 mixed with 10% graphite

Electrolyte: Lithium salt in organic solvent

Cathode: Mn4+  Mn3+

V5+  V4+
 Li Primary batteries
Li Cells with Soluble cathode:
Anode: Li,
Cathode: SOCl2or SO2Cl2 dissolved in electrolyte
Electrolyte: Lithium salt in organic solvent

Cathode: 2SOCl2 + 4e-  4Cl- + S +SO2

SO2Cl2 + 2e-  2Cl- + SO2

Li Cells with Solid Electrolyte:

Anode: Li,
Cathode: MnO2, V2O5
Electrolyte: Solid electrolyte Such as LiX in PEO (Polyethylene oxide)

Long Life due to no evaporation of electrolyte

Secondary (or) Rechargeable Batteries

1. Lead Acid storage battery

2. Ni-Cd (NiCad) Battery

Advanced Secondary (or) Rechargeable Batteries

1. Lithium ion battery

2. Nickel Metal Hydride Battery
3. Li-ion polymer battery
 Lead-Acid storage Battery
Lead-acid batteries, invented in 1859 by French physicist Gaston
Plante, are the oldest type of rechargeable battery.

This acts both as electrochemical cell and electrolytic cell. While discharging it
acts as electrochemical (voltaic cell) and on charging it acts as electrolytic cell.
The maximum emf = 12V
Representation of Lead Storage Cell : Pb / PbSO4(s), H2SO4 (aq) / PbO2(s), Pb
 Construction of Lead acid Battery +ve

Discharge Reactions
-ve
At Anode Pb
Pb + SO42-  PbSO4 + 2e-
At Cathode
PbO2

PbO2 + 4H++ SO42- + 2e-  PbSO4 + 2H2O

Charging
Pb + PbO2 + H2SO4 PbSO4 + 2H2O + Energy
Discharging
~30% H2SO4

While discharging specific gravity of sulphuric acid falls below 1.2

 Disadvantage of Pb-Acid Battery
• Accumulation of PbSO4 causes the electrodes to collapse
under stress.
• Short cirucuit due to breakage of active materials

Overcharging
• Because of the open cells with liquid electrolyte in
most lead-acid batteries, overcharging with high
charging voltages will generate oxygen and hydrogen
gas by electrolysis of water, forming an explosive mix.
 Uses /Applications

For constant power supply for electrical vehicles,

Gas engine ignition,
Telephone exchangers,
Trains,
Mines,
Laboratories,
Hospitals,
Automobiles and in power Stations
 Nickel Cadmium battery

• The nickel-cadmium battery (commonly abbreviated NiCd or Nicad) is a type

of rechargeable battery using Nickel oxy hydroxide NiO(OH) and metallic
cadmium (Cd) as electrodes and an alkaline potassium hydroxide KOH
electrolyte.

• The first NiCd battery was created by of Sweden in 1899. But only
introduced in the early 1960's
• 1.4 V battery
• Energy density about double that of lead
acid batteries.
• Their small size and high rate discharge
capacity made portable tools and other
consumer applications practical for the
first time.

Representation NiCd battery: Cd | CdO | KOH (aq) || NiO(OH) | Ni

Construction

-ve +ve

KOH

Cd
NiO(OH)
 Discharge and charge Chemistry
Discharging
At anode: Cd(s) + 2OH-  Cd(OH)2(s) +2e-

At cathode : 2NiO(OH) +2H2O(l) +2e-  2Ni(OH)2 (s) + 2OH- (aq)

Net reaction: 2NiO(OH)(s) + Cd(s) +2H2O(l) Cd(OH)2(s) + 2Ni(OH)2(s)

Advantages
• Constant voltage (1.4V)
• No gaseous products
• Wide temperature range (Up to 70°C)

• Charging process is strongly endothermic-the battery cools during charging. This

makes it possible to charge very quickly

• Rapid charge typically 2 hours, but can be as low as 10 to 15 minutes.

• The sealed nickel-cadmium cell can be stored in the charged or discharged state
without damage.

• Available in a large variety of sizes and capacities

 Applications

• Motorized equipments
• Power tools
• Transistors
• Electronic calculators
• Commercial and industrial portable products
• Medical instrumentation
• Emergency lighting
• Toys
• Cordless and wireless telephones

Medical equipment
Personal care
Professional lighting
Radio communication and tracking
equipment
Professional tooling
Military equipment
Professional electronic devices
 Nickel Metal Hydride Batteries
• Their basic structure is identical to that of Ni-Cd

• The NiMH battery was patented in 1986 by Stanford Ovshinsky.

• Now NiMH batteries have begun to find use in high voltage automotive
applications. The energy density is more than double that of Lead acid
and 40% higher than that of NiCads

The NiMH battery uses a

hydrogen-absorbing alloy (TiNi)
for the negative electrode
instead of cadmium.
Ni-MH Battery
 Components
• Instead of cadmium, hydrogen absorbing alloy is used as the active
element at a hydrogen-absorbing negative electrode (anode).

• This electrode is made from a metal hydride (MH, ZrH2)) usually

alloys of Lanthanum and rare earths that serve as a solid source of
reduced hydrogen that can be oxidized to form protons.

• The components of NiMH batteries include a cathode of Nickel-oxy hydroxide,

an anode of Hydrogen absorbing alloys
• Potassium-hydroxide (KOH) electrolyte.
• They are more expensive than Lead-acid and NiCad batteries, but they are
considered better for the environment.
• The electrolyte is alkaline potassium hydroxide. Cell voltage is 1.2-1.5 Volts
The Construction and chemistry
MH
The chemistry of NiMH Battery

Anode KOH

Charging
MH + OH- 2H2O + M + e-
Discharging
Cathode
Charging
2NiO(OH) + 2OH-+ 2e- 2Ni(OH)2 +2OH-
Discharging NiO(OH)

Overall Reaction
Charging
MH2 + 2NiO(OH) Ni(OH)2 + M
Discharging
 Advantages
• High energy density

• Rapid charge possible in 1 hour

• overcharging can cause deterioration of the battery. Chargers should

therefore incorporate a timer to prevent overcharging.

• Because of potential pressure build up due to gassing they usually

incorporate a re-sealable vent valve

• Reconditioning is possible.

• Environmentally friendly (No cadmium, mercury or lead)

Secondary Lithium ion batteries
 History of battery specific energy

300

?
(Wh/kg)

250
Energy

200
Specific Energy

150 Li-Ion

100
Lead Ni-Cd
Acid Ni-MH
50

0
1850 1900 1950 2000
Year 34
 Lithium batteries

• The main attractions of lithium as an anode material is

– It is the most electropositive metal in the electrochemical series
– It has very low density,
– Means, the largest amount of electrical energy per unit weight

• But Li cannot be used with the traditional aqueous

electrolytes
– due to the very vigorous corrosive reaction between Li and water
– with flammable hydrogen as the product.
 Materials Used
Anode
• The anode material is carbon based.
• This lithium content is lower then would be ideal, however higher capacity
carbons pose safety issues.

Electrolyte
• Since lithium reacts violently with water, and the cell voltage is so high that
water would decompose, a non-aqueous electrolyte must be used.
• A typical electrolyte is LiPF6 dissolved in an ethylene carbonate and dimethyl
carbonate mixture.
• Polymer electrolyte

Cathode materials
• The most common compounds used for cathode materials are LiCoO2, LiNiO2
and LiMn2O4.
• Of these, LiCoO2 has the best performance but is very high in cost, is toxic and
has a limited lithium content
• LiNiO2 is more stable, however the nickel ions can disorder.
• LiMn2O4 is generally the best value for money, and is also better for the
environment.
 Lithium ion-battery

Electrolyte:
• Liquid organic
solvents
• Polymers
• Gels

Anode: Cathode:
• Carbon-based • Transition-metal oxides
• Alloys and intermetallics
• Oxides
• Lithium-metal
 Working

Charging Discharging
• The following reactions take place upon working

At the Cathode: LiCoO2 Charging

Discharging
Li1-xCoO2 + xLi+ + xe-
Charging
At the Anode: xLi+ + C + Xe- Discharging
CLix
Charging
Overall: LiCoO2 + C Discharging Li1-xCoO2 + LixC
 Chemistry and Construction

• Anode here is a non-metallic compound, e.g. carbon, which can store

and exchange lithium ions.

• A lithium ion-accepting material (Intercalation), for example CoO2, is

then used as the cathode material, and lithium ions are exchanged back
(deintercalation) and forth between the two during discharging and
charging. These are called intercalation electrodes.

• This type of battery is known as a “rocking chair battery” as the ions

simply “rock” back and forth between the two electrodes.
 Lithium Polymer Battery
Electrolyte is a polymer
Lithium battery-battery of the future

• Imagine your electrical equipment powered by Lithium

ion battery refuse to die out of charge.

• Imagine your 2 hour battery backup of your laptop

increases to 20 hours.

• 6 days of standby time of cell phones increases to 60 days

i.e 2 months ( charging a mobile just 6 times a year)

Stanford University have found a way to use silicon nanowires to

produces 10 times the amount of electricity of existing lithium-ion,
known as Li-ion, batteries that power laptops, iPods, video cameras,
cell phones, and countless other devices. A laptop that now runs on
battery for two hours could operate for 20 hours.
 Fuel Cells
An electrochemical cell in which the energy of a reaction between a
fuel (such as liquid hydrogen) and an oxidant (such as liquid
oxygen) is converted directly and continuously into electrical
energy.

Primary Battery: irreversible

Secondary Battery: Reversible but charging is required.

Fuel cell: Operates with continuous replenishment of fuels at

electrodes which doesn’t require charging.

Representation: fuel| electrode| electrolyte| electrode| Oxidant

At Anode: Fuel → Oxidized product + ne

At Cathode: Oxidant +ne → reduced product
 Fuel Cells
Classification :
1. Low Temperature fuel cells (< 100oC)
2. Moderate Temperature fuel cells (100 to 250oC)
3. High Temperature fuel cell (> 500oC)

Types :
• Alkaline Fuel Cells (AFC): US spacecraft

• Phosphoric Acid Fuel Cells (PAFC): Stationary power generation, city buses

• Molten Carbonate Fuel Cells (MCFC): Military application, power plants

• Polymer Electrolyte Membrane Fuel Cells (PEMFC): Car, Bus

• Solid Oxide Fuel Cells (SOFC): Industry

• Biochemical Fuel cells (BCFC)

 Alkaline Fuel Cells (or) H2- O2 Fuel Cells

Unreacted Oxygen
Unreacted H2 or Air free from CO2

- +
e- e-

2H2 + 4 OH-  H2O + 4e- (Anode)

O2 + 2H2O + 4 e-  4OH- (Cathode)

2H2 + O2  2H2O (Net reaction)

K+OH-

Voltage :1.15 V
Power: 10-100 KW
Porous carbon Anode with Pt/Ni catalyst
 Solid oxide fuel cells (SOFC)
electrolyte all made up of ceramic substances

• Anode : porous carbon

• Cathode: Thin porous carbon layer where oxygen reduction
occurs
• Fuel: Hydrogen
• Electrolyte : Solid oxide or ceramic electrolyte - Dense layer of
oxygen conducting ceramic. - mixture of Ni, ZrO2 and CaO coated
on either side by porous electrode materials. Others include
yettrium stabilized zirconia (YSZ) and gadolinium doped ceria
(GDC)
• Operating Temp: >1000 0C
• Efficiency: 50-60% due to low conductivity solid oxide electrolyte
 Construction

• High efficiency
• Long term stability
• Fuel flexibility
• Low emissions
• High operating temp – longer start up times
• Mechanical / Chemical compatibility issues.
 Applications
• Auxiliary power units in vehicles
• Stationary power generation
• By product gases – channeled to turbines to generate more electricity –
cogeneration of heat and power and improves overall efficiency
 Micro Fuel Cell Powered Small Gadgets

music player cell phone

fuel cartridge