Unit 3

Energy Storage Systems

Content

1. Introduction
1.1. Energy crisis
1.2. Energy storage systems
1.3. Need of Energy storage systems
1.4. Methods of energy storage

2. Battery
2.1. Introduction
2.2. Battery characteristics
2.3. Types of batteries- Advantage, disadvantage and application
2.4. Li ion battery-construction, principle, working and application
2.5. Li polymer battery

3. Fuel Cell
3.1. Introduction
3.2. Fuel cell- construction, principle, working, advantage and
disadvantage
3.3. Types of fuel cells
3.4. Direct Methanol Fuel cell- construction, principle and working
3.5. Factors affecting the performance of DMFC
4. Hydrogen Production
4.1. What is hydrogen
4.2. Properties of hydrogen- physical, chemical, flammable and
hazardous
4.3. Uses of hydrogen
4.4. Need of hydrogen
4.5. Pathways of hydrogen production- steam reforming, coal
gasification, electrolysis, solar driven water splitting, biological
pathway and nuclear pathway.

5. Hydrogen storage
5.1. Need of hydrogen storage
5.2. Hydrogen economy
5.3. Different methods of hydrogen storage- physical and chemical

6. Future
 Unit: 3 Energy Storage Systems

1.Energy storage
Energy storage: is the capture of energy produced at one time and stored for use at a later
time or when need arises. Increasing population and development of human society demands
energy/electricity. Energy Storage Systems (ESS) are solutions for it. EES is the set of
methods or technologies involved in energy/electricity storage. Energy storage is a
promising way to store electrical energy so it's available to meet demand whenever needed.
Energy Storage System (ESS) provides a storage buffer when there is more supply than the
demand, and discharges the stored energy during peak demand periods.

Need of Energy Storage System

Electricity is generated either by non –renewable sources or by renewable sources of
energy. Energy generation based on the non-renewable sources includes combustion of fossil
fuels/carbon, natural gas and oil which give rise to emission of greenhouse gases and air
pollution. Against this, renewable energy sources (through sun, water and wind) are low cost
and clean energy system. However, continues and stable availability of energy is the major
limitation which needs to be resolved. Whatever is the pathway of energy generation, it is
finally transmitted to grids and in turn distributed to centralized and localized area. Therefore,
electricity which we receive in our house on daily basis travels through three stages:
generation, transmission and distribution as shown in figure below.
It is very well understood that GRIDs are the heart of the total system where generated energy
from the power plants reaches which is then transmitted and distributed to different sectors.
Therefore, grids are need to be stable and reliable to continuously balance the supply and
demand of energy. Therefore, to supply a smooth output power to the power grid, energy
storage systems are installed to the power generation system and it can also serve as back-up
power sources in an emergency promoting the efficient use of energy. Therefore, thumb rule
for modern society is electricity generation, storage, transmission and distribution, where
storage is crucial step.

Benefits of Energy storage system

1) ESSs stores energy when there is more supply than the demand, and discharges the stored
energy during peak demand periods. It can also serve as back-up power sources in an
emergency. In this way it enhances the reliability and flexibility of grid power.
2) By storing electrical energy in energy storage systems, electrical load is equalized,
promoting the efficient use of energy
3) Energy storage can also contribute to the decarbonisation of other economic sectors, and
integrate or support the use renewable energy (photovoltaics, hydropower, wind energy)
in transport, buildings or industry
4) Both distributed and centralised renewable electricity generation is expected to increase
reducing the toxic emission/pollution from conventional (non-renewable sources)
methods of electricity generation.
5) Instead of toxic pollution and centralized power supply, clean and localized power supply
can be achieved by ESS as they themselves act as energy dispatchers.

Energy storage system are categorized depending upon the mode of energy storage:
Electrical, mechanical, thermal and chemical/electrochemical. Among these, chemical
mode of energy storage has long time benefits and are reliable. Chemically energy
storage systems include devices like battery, fuel cell and hydrogen storage.
 2. Battery
1. Introduction
Electrical energy/power storage has widespread applications as can be seen in the sheer range
and diversity of batteries used as a source of electrical power. Batteries range from tiny button
cells storing mili watt hours of energy and delivering microwatt power, to gigantic load
levelling batteries situated within a factory size building, storing mega watt hours of energy
and delivering megawatts of power. It is predicted that in the year 2006 global demand for
batteries will reach £33 billion pounds.

2. Basic principles: The electrochemical series

Different metals (and their compounds) have different affinities for electrons. When two
dissimilar metals (or their compounds) are put in contact through an electrolyte, there is a
tendency for electrons to pass from one material to another. The metal with the smaller affinity
for electrons loses electrons to the material with the greater affinity, becoming positively
charged. The metal with the greater affinity becomes negatively charged. A potential
difference between the two electrodes is thus built up until it balances the tendency of the
electron transfer between the metals. At this point the potential difference is the equilibrium
potential: the potential at which the net flow of electrons is 0.
The electrochemical series represents the quantitative expression of the varying affinity of
materials relative to each other. In an aqueous electrolyte the standard electrode potential for
an electrode reaction is expressed with respect to a reference electrode. Conventionally this is
the H2/H+ cell, with reaction:
H+ + e ½ H2
3. What is a battery?
A battery is an electrochemical cell that converts chemical energy into electrical energy. It
comprises of two electrodes: an anode (the positive electrode) and a cathode (the negative
electrode), with an electrolyte between them. At each electrode a half-cell electrochemical
reaction takes place.

3.1. Discharge
Electrode 1 is an anode: the electrode is oxidised, producing electrons. Electrode 2 is a cathode:
the electrode is reduced, consuming electrons. In the fully charged state, there is a surplus of
electrons on the anode (thus making it negative) and a deficit on the cathode (thus making it
positive). During discharge, electrons therefore flow from the anode to the cathode in the
external circuit and a current is produced. Therefore, in simple terms batteries work as electron
pumps in the external circuit, preferably with only ionic current flowing through the electrolyte.
The electrical potential difference between the cathode and the anode, which can drive the
electrons in the external circuit, is called electromotive force (emf). Once all the active material
at the cathode has been reduced, and/or all the active anodic material is oxidised, the electrode
has effectively been used up, and the battery cannot provide any more power. It can then be
either disposed of or preferably recycled if it is a primary battery, or recharged if it is a
rechargeable (secondary) battery.

If the anode were zinc and the cathode were copper the half reactions would proceed as follows:
At the anode: Zn → Zn2+(aq) + 2e– Eo = 0.76V
At the cathode: Cu2+(aq) + 2e– → Cu Eo = 0.34V
Thus the total potential for this cell is 1.10 V.
During use as a battery, discharge leads to dissolution of Zn at the anode and the deposition of
Cu at the cathode. Such a cell is embodied in the Daniell Cell introduced in 1836. As a practical
cell this required two electrolytes (typically zinc sulphate and copper sulphate aqueous
solutions) to avoid polarisation. The electrolytes are separated from each other by a salt bridge
or a porous membrane, which allows the sulphate ions to pass and carry the ionic current, but
blocks metallic ions. The Daniell Cell is an effective battery but not practical for portability.
More recently, however, the idea of using two separate electrolytes has been resurrected in the
form of redox batteries.
3.2. Charge
When the cell potential is depleted the battery can be recharged. When a current is applied to
the cell in the opposite direction the anode becomes the cathode, and vice versa. Thus electrode
2 that was oxidised upon discharge is now reduced and the electrode 1 that was reduced is now
oxidised so the electrodes are returned to their former state, ready to be discharged again.
This time the anode would be copper and the cathode would be zinc, and the half reactions
would proceed as follows:
At the anode: Zn2+(aq) + 2e– → Zn Eo = -0.76V
At the cathode: Cu → Cu2+(aq) + 2e– Eo = -0.34V
The minimum potential required for charging will be 1.10 V, as this is the potential of the cell.
In reality much higher potentials will be required to overcome the polarisation.

4. Cell or battery?
A cell is a single encased electrochemical unit (one positive and one negative electrode) with
a voltage differential across its two terminals.

Different types of Cells

A battery is two or more cells that are electrically connected together and fitted with devices
such as a case, terminals, marking and protective devices that it needs to function properly. A
cell can be called as battery but a battery can’t be called as cell.

Different types of batteries

5.Types of battery:
There are two types of battery: Primary and secondary
5.1. Primary batteries:
Primary batteries are not easily rechargeable, and consequently are discharged then disposed
of. Many of these are “dry cells” – cells in which the electrolyte is not a liquid but a paste or
similar. The cell electrochemical reactions are not easily reversible and cell is operated until
the active components in the electrodes are exhausted. Generally primary batteries have a
higher capacity and initial voltage than rechargeable batteries.
5.1.1. Applications:
1. Portable devices
2. Lighting
3. Toys
4. Memory back-up
5. Watches/clocks
6. Hearing aids
7. Radios
8. Medical implants
9. Defence related systems such as missiles
5.1.2. Advantages:
1. Inexpensive
2. Convenient
3. Lightweight
4. Good shelf life
5. High Energy density at low/moderate discharges

5.1.3. Disadvantages:
1. Can only be used once
2. Leads to large amount of waste batteries to be recycled
3.Batteries put into landfill sites have severe environmental impact
4.Life cycle energy efficiency < 2 %
5.1.4. The table below demonstrates the properties of various primary batteries:

Nominal
Cell Capacity
System Advantages Disadvantages Applications
Voltage (Wh/kg)
(V)

Low energy
Lowest cost; Torches; radios;
density; poor
Carbon/Zinc 1.50 65 variety of shapes electronic toys and
low-temperature
and sizes games
performance

Higher capacity High gassing on Military and aircraft

Mg/MnO2 1.60 105 than C/Zn; good discharge; receiver-
shelf life delayed voltage transmitters

Higher capacity
Personal stereos;
than C/Zn; good
Zn/Alk/MnO2 1.50 95 Moderate cost calculators; radio;
low-temperature
TV
performance

Hearing aids;
High Energy
Expensive; pacemakers;
density; flat
Zn/HgO 1.35 105 energy density photography;
discharge; stable
only moderate military
voltage
sensors/detectors

Good high and

low-temperature Expensive; low
Cd/HgO 0.90 45
performance; energy density
good shelf life

High Energy Watches;

density, good Expensive (but photography;
Zn/Ag2O 1.50 130
high rate cost effective) missiles; Larger
performance space applications
 Dependent on Watches; hearing
High Energy
environment; aids; railway
Zn/Air 1.50 290 density; long
limited power signals; electric
shelf life
output fences

High Energy Only low to Memory devices;

Li/SOCl2 3.60 300 density; long moderate rate standby electrical
shelf life applications power devices

High energy
density; best High-cost
Military and special
Li/SO2 3.00 280 low-temperature pressurized
industrial needs
performance; system
long shelf life

High energy
density; good Small in size, Electrical medical
Li/MnO2 3.00 200 low-temperature only low-drain devices; memory
performance; applications circuits; fusing
cost effective

5.2. Secondary batteries:

Secondary (rechargeable) batteries can be recharged by applying a reverse current, as the
electrochemical reaction is reversible. The original active materials at the two electrodes can
be reconstituted chemically and structurally by the application of an electrical potential
between the electrodes to “inject” energy. These batteries can be discharged and recharged
many times.

5.2.1. Applications:
These fall into two categories: (a) The battery is used as an energy storage device. It is
constantly connected to an energy source and charged by it. It can then release the stored energy
whenever needed, e.g. in
Car battery used to start engine
Aircraft systems
Standby power resources
Emergency no-fail systems
(b) The battery is used as a primary battery would be but is then recharged instead of being
disposed of, e.g. in
Electric vehicles
Mobile phones
Cameras
Power tools
Toys
Portable computers

5.2.2. Advantages:
High power density
High discharge rate
Good low temperature performance

5.2.3. Disadvantages:
Lower Energy density
Poorer charge retention
Safety issues
Lack of standards
High initial costs

5.2.4. The table below demonstrates the properties of various rechargeable batteries:

Nominal
Cell Capacity
System Advantages Disadvantages Applications
Voltage (Wh/kg)
(V)

Low cost; good

Low cycle life; low
high and low- Cars; lawn
Pb/Acid 2.00 35 energy density; poor
temperature mowers; aircraft
charge retention
operation
 Good physical
Aircraft;
durability; good High cost; memory
Ni/Cd 1.20 30 emergency power
charge retention; effect
applications
good cycle life

Good physical Low power and

Stationary
durability; long energy density; high
Ni/Fe 1.20 60 applications; fork
cycling and self discharge; high
lift trucks
standing life cost

High energy
density; low cost; Electric
Ni/Zn 1.60 27 good low- Poor cycle life scooters/bikes;
temperature military vehicles
performance

Military
Highest energy
High cost; low cycle equipment eg
density; low self
Zn/AgO 1.50 90 life; low performance torpedo
discharge; high
at low temperatures propulsion,
discharge rate
submarines

High energy
High cost; low
density; low self Portable power
Cd/AgO 1.20 55 performance at low
discharge; Good tools; satellites
temperatures
cycle life

High energy
High initial cost; self
density; good
discharge
Ni/H2 1.40 55 cycle life; can Aerospace
proportional to
tolerate over
H2 pressure
charge

High cost - limited to

High energy
military and
Ag/H2 1.40 80 density; good Aerospace
aerospace
cycle life
applications
 High specific High cost; expensive
energy; good shelf control methods
Li/Poly up to 4.2 135 Mobile phones
life; moldable; needed for
non-volatile charge/discharge

6) Battery characteristics
The following battery characteristics must be taken into consideration when selecting a battery:
1) Type
2) Voltage
3) Discharge curve
4) Capacity
5) Energy density
6) Specific energy density
7) Power density
8) Temperature dependence
9) Service life
10) Physical requirements
11) Charge/discharge cycle
12) Cycle life
13) Cost
14) Ability to deep discharge
15) Application requirements
6.1. Type
Primary and Secondary batteries.

6.2. Physical requirements

This includes the geometry of the cell, its size, weight and shape and the location of the
terminals.

6.3. Voltage
The theoretical standard cell voltage can be determined from the electrochemical
series using Eo values:
Eo (cathodic) – Eo (anodic) = Eo (cell)
This is the standard theoretical voltage. The theoretical cell voltage is modified by the Nernst
equation, which takes into account the non-standard state of the reacting component. The
Nernstian potential will change with time either because of use or self-discharge by which the
activity (or concentration) of the electro-active component in the cell is modified. Thus the
nominal voltage is determined by the cell chemistry at any given point of time.
The actual voltage produce will always be lower than the theoretical voltage due to polarisation
and the resistance losses (IR drop) of the battery and is dependent upon the load current and
the internal impedance of the cell. These factors are dependent upon electrode kinetics and thus
vary with temperature, state of charge, and with the age of the cell. The actual voltage appearing
at the terminal needs to be sufficient for the intended application.
Typical values of voltage range from 1.2 V for a Ni/Cd battery to 3.7 V for a Li/ion battery.

6.4. Capacity
The theoretical capacity of a battery is the quantity of electricity involved in the electro-
chemical reaction. It is denoted Q and is given by:
Q = xnF
where x = number of moles of reaction, n = number of electrons transferred per mole of
reaction and F = Faraday's constant
The capacity is usually given in terms of mass, not the number of moles:
Q = nFMr
where Mr = Molecular Mass. This gives the capacity in units of Ampere-hours per gram (Ah/g).
In practice, the full battery capacity could never be realised, as there is a significant weight
contribution from non-reactive components such as binders & conducting particles, separators
& electrolytes and current collectors & substrates as well as packaging. Typical values range
from 0.26 Ah/g for Pb to 26.59 Ah/g for H2.

6.5. Charge/Discharge cycle

There are many aspects of the cycle that need consideration, such as:
Voltage necessary to charge
Time necessary to charge
Availability of charging source
Potential safety hazards during charge/discharge
6.6 Discharge Curve
The discharge curve is a plot of voltage against percentage of capacity discharged. A flat
discharge curve is desirable as this means that the voltage remains constant as the battery is
used up.

6.7. Energy density

The energy density is the energy that can be derived per unit volume of the weight of the cell.

6. 8. Specific energy density

The specific energy density is the energy that can be derived per unit weight of the cell (or
sometimes per unit weight of the active electrode material). It is the product of the specific
capacity and the operating voltage in one full discharge cycle. Both the current and the voltage
may vary within a discharge cycle and thus the specific energy derived is calculated by
integrating the product of current and voltage over time. The discharge time is related to the
maximum and minimum voltage threshold and is dependent upon the state of availability of
the active materials and/or the avoidance of an irreversible state for a rechargeable battery.

6. 9. Power density
The power density is the power that can be derived per unit weight of the cell (W/kg).

6.10. Service life/Cycle life

The battery cycle life for a rechargeable battery is defined as the number of charge/recharge
cycles a secondary battery can perform before its capacity falls to 80% of what it originally
was. This is typically between 500 and 1200 cycles.
The battery shelf life is the time a battery can be stored inactive before its capacity falls to 80%.
The reduction in capacity with time is caused by the depletion of the active materials by
undesired reactions within the cell.
Batteries can also be subjected to premature death by:
Over-charging
Over-discharging
Short circuiting
Drawing more current than it was designed to produce
Subjecting to extreme temperatures
Subjecting to physical shock or vibrations
6.11. Temperature dependence
The rate of the reaction in the cell will be temperature dependant according to theories of
kinetics. The internal resistance also varies with temperature; low temperatures give higher
internal resistance. At very low temperatures the electrolyte may freeze giving a lower voltage
as ion movement is impeded. At very high temperatures the chemicals may decompose, or
there may be enough energy available to activate unwanted, reversible reactions, reducing the
capacity.
The rate of decrease of voltage with increasing discharge will also be higher at lower
temperatures, as will the capacity.

6.12 Ability to deep discharge

There is a logarithmic relationship between the depth of discharge and the life of a battery, thus
the life of a battery can be significantly increased if it is not fully discharged; for example, a
mobile phone battery will last 5-6 times longer if it is only discharged 80% before recharging.
Special deep discharge batteries are available for applications where this might be necessary.

6.13 Self - discharge

Self-discharge is a phenomenon in batteries in which internal chemical reactions reduce the
stored charge of the battery without any connection between the electrodes or any external
circuit

6.14 Cost
This includes the initial cost of the battery itself as well as the cost of charging and maintaining
the battery.
6.15 Application requirements
The battery must be sufficient for the intended application. This means that it must be able to
produce the right current with the right voltage. It must have sufficient capacity, energy and
power. It should also not exceed the requirements of the application by too much, since this is
likely to result in unnecessary cost; it must give sufficient performance for the lowest possible
price.

Comparison of different rechargeable batteries

Out of the available rechargeable batteries developed up till now, only Li metal and Li ion
battery delivers high specific power and specific energy. In case of pure Li metal battery,
chances of accidents are much more prevailing because of which much more focus is on Li ion
battery for commercial application.

7. Lithium batteries
The Royal Swedish Academy of Sciences awarded the Nobel Prize in Chemistry 2019 to John
B. Goodenough, of the University of Texas at Austin, USA, M. Stanley Whittingham, of
Binghamton University, State University of New York, USA, and Akira Yoshino of Asahi
Kasei Corporation, Tokyo, Japan, and Meijo University, Nagoya, Japan "for the development
of lithium-ion batteries. Li-ion batteries are now used in very high volumes in a number of
relatively new applications, such as in mobile phones, laptops, cameras and many other
consumer products.
7.1. Non- rechargeable lithium battery: Primary non- rechargeable lithium battery had been
well established for nearly two decades and become widely available since mid-1990s. In Li
metal battery pure form of Li metal was used as anode material. One of the main attractions of
lithium as an anode material is its position as the most electronegative 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. However, there were many
problems experienced whilst developing rechargeable lithium batteries, mainly due to the
extreme reactivity of lithium, and they lead huge explosions and accidents. In order to
overcome the problems associated with the high reactivity of lithium, the anode material is not
purely the metal, it is a non-metallic compound, e.g. carbon, which can store and exchange
lithium ions is used now in Li ion battery

7.2. Rechargeable Li ion battery

In Li ion battery (unlike Li battery) Li ion or Li compound is used to avoid the risk of
accidents and fire.

7.2.1. Construction of Li ion battery

The typical Li ion battery has four layered structure.

a) Cathode: Li containing or lithalated compounds are used as a cathode material which
are coated on Al collected electrode. The most common compounds used 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 range over which it is stable. LiNiO 2 is
more stable, however the nickel ions can disorder. LiMn2O4 is generally the best value
for money, and is also better for the environment.
b) Anode: The anode material is speciality carbon based, usually with
composition Li0.5C6. It is coated on current collected coated with Cu thin foil. This
lithium content is lower than would be ideal, however higher capacity carbons pose
safety issues.
c) 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. An electrolyte
made with lithium salt in an organic solvent. A typical electrolyte is LiPF6 dissolved in
an ethylene carbonate and dimethyl carbonate mixture. The electrolytes are selected in
such a way that there should be an effective transport of Li-ion to the cathode during
discharge The type of conductivity of electrolyte is ionic in nature rather than
electronic.
d) Separator: A separator is very essential component of battery and is made up of fine
porous polymer film.

7.2.2. Working
The traditional batteries are based on galvanic action but Lithium ion secondary battery
depends on an "intercalation" mechanism. This involves the insertion of lithium ions into the
crystalline lattice of the host electrode without changing its crystal structure.
During charging, lithium in positive electrode material (LiCoO 2) is ionized as Li+ and moves
from its host structure without disturbing it and inserted into the layers of negative electrode
(graphite/carbon). During discharge Li ions are dissociated from the anode and migrate across
the electrolyte and are inserted into the crystal structure of the host compound of cathode. At
the same time the compensating electrons travel in the external circuit and are accepted by the
host to balance the reaction. The process is completely reversible. This to and fro movement
of Li ion during charging and discharging cycle is called as “intercalation”. Thus the lithium
ions “rocks” back and forth between the electrodes during charging and discharging. Because
of this reason, the lithium ion batteries are called ‘Rocking chair, ‘Swing’ cells. During
discharge current flows through external circuit and light glows. During charging, the electrons
flows in the opposite direction
A typical Li-ion battery can store 150 watt-hours of electricity in 1 kilogram of battery as
compared to lead acid batteries can soar only 25 watt-hours of electricity in one kilogram. All
rechargeable batteries suffer from self-discharge when stored or not in use.

7.2.3. Principle

During charging Li ion migrates from its host structure towards anode and gets inserted
between the layers of graphite. During discharging the intercalated Li ion moves back to its
host structure. Simply, the Li-ion is transfers between anode and cathode through lithium
Electrolyte. Since neither the anode nor the cathode materials essentially change, the operation
is safer than that of a Lithium metal battery. After initial charging the following reactions take
place upon discharge:
7.2.4. Advantage of different components of battery

In cathode material, LiCoO2, the cobalt and oxygen bond together to form layers of octahedral
cobalt oxide open structures, where in between the layers Li ions can be inserted or intercalated.
It’s important that this structure allows the cobalt ions to change their valence states between
Co+3 and Co+4 (lose and gain a negatively-charged electron) when charging and discharging.
In anode, Li ion can easily be inserted in the layers of graphite which are held by Van der
Waal’s forces. Particularly, Li is chosen in cathode compound as it is the lightest element which
makes the electronic devise light in weight. Secondly, Li has excellent electrochemical
properties. It is highly reactive, so can easily lose the outermost electron and making easy to
get current flowing through a battery. It can achieve high energy and power density. It makes
the battery sec or rechargeable battery as lithium ions and electrons move
easily back into negative electrodes.

7.2.5. Advantages of Li ion battery

• They have high energy density ( > 100 Wh/Kg ) than other rechargeable batteries
• They are less in weight
• They produce high voltage out about 4 V as compared with other batteries.
• They have improved safety, i.e. more resistance to overcharge
• No liquid electrolyte means they are immune from leaking.
• Fast charge and discharge rate (80-90%)
 Long shelf life

7.2.6. Disadvantage
• They are expensive
• They are not available in standard cell types.

7.2.6. Applications
• The Li-ion batteries are used in cameras, calculators
• They are used in cardiac pacemakers and other implantable device
• They are used in telecommunication equipment, instruments, portable radios and TVs, pagers
• They are used to operate laptop computers and mobile phones and aerospace application.

7.2.7. Characteristics of Li Ion Battery:

In order to maximise the specific energy density, it is desirable to minimise the weight of the
cell, while maximising the ratio of weight of lithium to the weight of the cell. For the Li-ion
cell, for example, the theoretical stoichiometric value of the anodic multiplier (fA) is 10.3, while
for the cathode (fC) is 25. Thus the maximum theoretical specific energy density for a max 4.2
V is calculated to be between 380 to 460 Wh/kg, depending upon whether the weight of the
auxiliary components are taken into account.
The stoichiometric value for the carbon anode arises from the fact that lithium is intercalated
into the carbon structural layers at the max possible molar ratio of 1 Li atom to 6C atoms giving
rise to the limiting formula of LiC6. In practice, Li availability in the anode is only 50% of the
theoretical maximum corresponding to the formula Li0.5-xC6 where x can vary from 0 (fully
charged state) to 0.5 (fully discharged state). For the cathode, Li is intercalated into a perovskite
structure of LiCoO2. Although it appears that, theoretically, the maximum ratio of Li to CoO2 is
one, in practice the formula corresponds to Li0.5+xCoO2, where x=0 corresponds to the fully
charged state and x=0.5 corresponds to the fully charged state. Thus the available capacities for
both the anode and the cathode are more than halved, with the multipliers typically being, fA>21
and fC>50. The excess value arises from the weight of the binder and other additives. The
operating voltage during discharge decreases from a max value of 4.2 to a cut-off value of 2.8
V, giving an average value of 3.35 V over the discharge cycle. The practical specific energy
density is therefore in the region of 160 Wh/kg for a Li-ion cell.
The only practical method for increasing the specific energy density of a Li-ion cell is to
decrease the weight of the auxiliary components of the cell. It is widely believed that with a
considerable amount of research and development the maximum specific energy density that
can be achieved for a Li-ion cell within the next five years will reach 220 Wh/kg of the cell.
The cycle life of Li-ion batteries are between 500 to 1000 cycles.

8. Lithium polymer batteries

Another way of overcoming the high reactivity of lithium is to use a solid polymer electrolyte.
Using lithium metal gives a higher energy density, higher cell potential and very low self
discharge, so if the safety issues can be overcome, it would be the preferred anode material.
Another problem to overcome is the high resistivity of the polymer electrolyte. One possible
solution is to use the electrolyte as a very thin film to decrease the total resistance.

8.1. Cell capacity and specific energy density

It is important to specify the exact steps taken when calculating the theoretical cell capacity
and the maximum specific energy density of a given lithium cell. For full lithium utilisation,
the cell capacity is 3860 mAh/g of lithium, simply calculated by Faraday’s laws. Thus, the
actual rated capacity of the cell in mAh is determined by the weight of lithium in the cell. The
actual specific capacity, on the other hand, is usually calculated as the actual rated capacity
divided by the weight of lithium in the cell (and quoted as mAh/g of Lithium) or, less
frequently, as the ratio of the rated capacity and the weight of the cell (and quoted as mAh/g of
the cell).
 3. Fuel Cells
1.Introduction
The future of battery technology now lies in the concept of fuel cells. A fuel cell, like a battery
is an electrochemical cell. It has an anode and a cathode, and an oxidation reaction and a
reduction reaction occur, however the electrodes act as catalysts, and are not used up in these
reactions. Instead, the reactions take place within a “fuel,” which provides the source for the
electrons. This is a very efficient method of producing electricity (up to 85% efficient – that’s
over three times as efficient as an internal combustion engine.) They are also very
environmentally friendly – the most environmentally friendly cells produce only water and
heat. At the moment the only disadvantage is that they are very costly, however it is very likely
that in the future fuel cells will be the power source of choice for many applications.

2. Fuel Cell:
A fuel cell is an electrochemical device that converts the chemical energy in fuels (e.g.
hydrogen, methane, butane or even gasoline and diesel) directly into electrical energy through
electrochemical process.
2.1. Why do we need fuel cell?
1) Worldwide energy crises are growing as the population is growing. To fulfil energy
demand we are dependent 80% on fossil fuels. As fossil fuel resources become more
and more pressed upon to deliver the worlds energy needs, as CO2 and global warming
loom ever nearer and as cities become ever increasingly crowded with polluting
automobiles the fuel cell seems to offer a golden solution to the world's energy
problems. It’s efficient, it’s clean, hydrogen can be produced by renewable energy and
the technology wouldn’t require any huge change in our way of life.
2) Conventional power plants convert chemical energy into electrical energy in three
steps:
 Production of heat by burning fuel
 Conversion of heat into mechanical energy
 Conversion of mechanical energy into electrical energy
The efficiency of the second step is limited (by the Second Law of Thermodynamics) to
the Carnot efficiency, since the conversion of heat into mechanical energy occurs in a closed-
cycle heat engine. An efficiency of about 41% can be reached by modern systems. A fuel cell
converts the chemical energy in fuels directly into electrical energy through electrochemical
process where efficiency of system lies till 70-80%. It exploits the natural tendency of oxygen
and hydrogen to react to form water which is clean by-product. The direct reaction is prevented
by the electrolyte, which separates the two reactants.

2.2. Construction and working of a fuel cell

A typical fuel cell has fuel –oxidant system. It has anode electrode, cathode electrode both
coated with catalyst and electrolyte. A fuel cell can run till the fuel system is available.
1. Hydrogen as a fuel enter fuel cell at anode where platinium catalyst causes the hydrogen to
split into positive hydrogen ions ad negatively charged electrons.
2. The positively charge hydrogen ions H+ react with hydroxyl ions in the electrolyte to form
water and the electron migrate through external circuit as they can’t travel through electrolyte.
3.At cathode oxidant or O2 enters and picks up the electrons coming from external circuit and
travels through electrolyte, where it combines with hydrogen ions.
4. Oxygen with electron combine hydrogen at anode and form water which drains out from the
cell.
2.3. The principle

Oxygen and hydrogen, when mixed together in the presence of enough activation energy have
a natural tendency to react and form water, because the Gibbs free energy of H 2O is smaller
than that of the sum of H2 and ½O2 added together (Hence, we don’t smoke our pipes on
Zeppelins!). If hydrogen and oxygen were combined directly, we would see combustion:

H2 + ½O2 → H2O
Combustion involves the direct reaction of H2 gas with O2. The hydrogen donates electrons to
the oxygen. We say that the oxygen has been reduced and the fuel oxidised. This combustion
reaction releases heat energy.
The fuel cell separates hydrogen and oxygen with a gas-impermeable electrolyte through which
only ions (e.g. H+, O2-, CO32–) can migrate. Hence two half reactions occur at the two
electrodes. The type of reactions at the electrodes is determined by the type of electrolyte.
Grove’s fuel cell is one of the simplest examples.

The half-reaction at the anode:

H2 → 2H+ + 2e–
The half-reaction at the cathode:
O2 + 4e–+ 4H+ → 2H2O
The net reaction is the combustion reaction:
H2 + ½O2 → H2O
Activation polarization is caused by the energy intensive activity of the making and breaking
of chemical bonds: At the anode, the hydrogen molecules enter the reaction sites so that they
are broken into ions and electrons. The resulting ions form bonds with the catalyst atoms and
the electrons remain in the vicinity until new hydrogen molecules start bonding with the
catalyst, breaking the bond between the earlier ion. The electrons migrate through the bipolar
plate if the bonding energy of the ion is low enough and the ions diffuse through the electrolyte.
A similar process occurs at the cathode: Oxygen molecules are broken up and react with the
electrons from the anode and the protons that diffused through the electrolyte to form water.
Water is then ejected as a waste product and the fuel cell runs (can supply a current), as long
as fuel and oxygen is provided
2.4. Advantages of fuel cell

1. High efficiency of energy conversion about 70-80%

2. Constant efficiency at low load.
3.Clean energy system and doesn’t produce polluting exhaust.
4.Excellant substitute for the use of fossil fuels hence saves fossil fuel.
5. Mostly by product is water and waste heat which is environmental friendly.
6. Low noise and less thermal pollution.
7. Low maintenance cost
8. Fuel cell performance s indepandant of the the power plant size, its MW or KW or W size.
9. Fast start up time for low temperature systems.
10. The demand for variations in power and energy densities is easiy met as required.e.g.
laptop, computers requires low power density and high energy density where as automobile
requires high power density , high energy density.Both can be pwered by fuel cells

2.5. Disadvantage of fuel cell

1. High initial cost

2. High cost of hydrogen fuel
3. Hydrogen storage is costly: H2 can be stored in lesser volume by liquefaction but liquefaction
itself require 30 % of stored energy.
4. Lack of infrastructure for distributing hydrogen.
5. life time of the cell is not accurately known

3. History of the technology

The fuel cell concept was first demonstrated by William R. Grove, a British physicist, in 1839.
The cell he demonstrated was very simple, probably resembling the given figure. By
application of a voltage across the two electrodes, hydrogen and oxygen could be extracted (the
process is called electrolysis) and captured as shown (William Nicholson first discovered this
in 1800). The fuel cell, or “gas battery” as it was first known, is the reverse of this process. In
the presence of platinum electrodes, which are necessary as catalysts, the electrolysis will
essentially run in reverse and current can be made to flow through a circuit between the two
electrodes.
 Electrolysis setup

Nobody tried to make use of the concept demonstrated by William R Grove until 1889 when
Langer and Mond tried to engineer a practical cell fuelled by coal gas. Further early attempts
carried on into the early 1900’s but the development of the internal combustion engine made
further research into the technology sadly unnecessary.
Francis Bacon developed the first successful fuel cell in 1932, running on pure O 2 and H2 and
using an alkaline catalyst and nickel electrodes. It was not until 1959 that Bacon and his
colleagues first demonstrated a 5 kW device; the 27-year delay is perhaps an indication of just
how difficult it is to make progress in this field of development. Harry Karl Ihrig demonstrated
a 20 bhp fuel cell tractor in the same year.
Around about this time, NASA started researching the technology with a view to produce a
compact electricity generator for use on spacecraft. Due to their astronomical budget, it was
not long before they got the job done. The Gemini program used early PEM fuel cells
(PEMFCs) in its later missions, and the Apollo program employed alkaline fuel cells. On a
spacecraft the water produced by the reaction was available for the spacemen to drink. NASA
continued to use alkaline cells in the space shuttle until the 90’s when PEMFC development
meant a switch back to PEMs was considered a possibility, however, the high cost of design,
development, test and evaluation prevented the switch, in spite of several technical advantages.
PEM fuel cells being installed in a Gemini 7 spacecraft (Source: Smithsonian Institution, from
the Science Service Historical Images Collection, courtesy of General Electric)

The alkaline fuel cell system as used on the space shuttles.

Three such modules were installed in each shuttle

Recent developments are thick and fast as the technology begins to come to fruition.
Automotive applications are high on the agenda due to the huge consumer market and the need
for an environmentally friendly, renewable alternative to the internal combustion engine and
fossil fuels.

Honda fuel cell car

 4. Types of fuel cells
Fuel cells are categorised according to their type of electrolyte, since it is the property-
determining component. The six main types of fuel cells are outlined below.

Fuel cell type DMFC PEMFC AFC PAFC MCFC SOF

C

Electrolyte Polymeric ion Polymeric ion Immobilise Immobilis Immobilise Cera

type exchange exchange d alkaline ed liquid d liquid mic
membrane membrane salt phosphori molten
solution c acid carbonate

Operating 20 – 90 30 – 100 50 – 200 ~220 ~650 500 –

temperature 1000
(°C)

Charge carrier H+ H+ OH– H+ H32– O2–

Power range 1 – 100 1 – 100k 500 – 10k 10k – 1M 100k – 1k –

(W) 10M+ 10M+

Applications and main advantages:

Portable Higher energy density than batteries and

electronics faster recharge.

Cars boats and Zero emissions and higher

spaceships efficiency.

Domestic Efficiency and

CHP reliability

Distributed Efficiency,
power emissions and less
noise
generation,
CHP, busses

Able to
internally
× √ √
reform CH4 × × ×
(see Fuelling
section)

The phosphoric acid fuel cell (PAFC) was however the first type of fuel cell to be commercially
produced and enjoys widespread terrestrial use. Many 200 kW systems are in place in USA
and Europe.

The diagram below shows the mechanisms by which the different fuel cell types operate:
5. Direct Methanol Fuel cell (DMFC)

5.1. Construction and working

Methanol is a high-energy fuel that can be combusted with oxygen to generate 4800 Wh of
heat per kilogram of methanol. The fuel cell consists of two catalytic electrodes (anode and
cathode) separated by a proton-exchange membrane. In a “direct” methanol fuel cell a solution
of methanol dissolved in water (approximately 3 wt %) is circulated past the negative electrode,
while oxygen is flown past the positive electrode. As electricity is generated, the methanol is
oxidized to carbon dioxide at the negative electrode while oxygen is reduced to water at the
positive electrode and protons are conducted across the membrane. Also, the formed CO 2 is
expelled out.

5.2. Principle

1.Methanol should oxidised spontaneously above anode potential (0.046 V vs RHE)

2.Oxygen should reduced spontaneously below cathode potential (1.23 V)
6. Factors affecting the output/performance of DMFC fuel cell

1. Kinetic losses : Any kind of reaction/electrochemical reaction rate when slows down due
to some issues is called Kinetic losses. Such losses lowers the efficiency of fuel cell.
2. Ohmic losses : Losses due to internal resistance or barriers with in the cell

6.1. Kinetic losses :

a) Methanol crossover : The role fuel (methanol) is to produce protons which will pass
through the membrane and electrons which will pass through external circuit but instead
it itself pass/diffuses through the membrane without reacting and reaches cathode. By
this crossover of methanol much more fuel is wasted and more fuel feed is required to
run the fuel cell. Secondly, efficiency and output of cell lowers. Third, if it reacts with
O2 after reaching cathode it lowers the cell voltage

b) CO2 crossover : Small amount of catalyst is used at cathode and anode electrode lining
which accelerates the rate of reaction. During the methanol oxidation reaction CO 2 is
formed, which strongly adsorbs onto the platinum catalyst,either reducing or
deactivating the number of available reaction sites. This is called as poisoning of the
catalyst which and lowers the performance of the cell.
7. Limitations of DMFC

1. Capital cost
2. Excessive methanol cross over
3.CO2 poisoning
4. Slow dynamic response
5. Membrane used is Nafion (sulfonated tetrafluroethylene co-polymer
6.Cost of platinium catalyst

Both Battery and Fuel cell are electrochemical cell which have capacity to store energy.
Unlike fuel cell, battery doesn’t have fuel-oxidant system and it undergoes charging and
discharging.

The International Energy Association (IEA) estimates that, in order to keep global warming
below 2 degrees Celsius, the world needs 266 GW of energy storage by 2030, up from 176.5
GW in 2017. Under current trends, Bloomberg New Energy Finance predicts that the global
energy storage market will hit that target, and grow quickly to a cumulative 942 GW by 2040
(representing $620 billion in investment over the next two decades).
 4. Hydrogen Production
1) Hydrogen
Hydrogen is a simplest lightest and abundant element of all which has single orbiting electron
around the central dense nucleus. Chemically, such atomic arrangement is highly reactive and
for this reason hydrogen atoms combine easily to form molecular H 2 instead of just H. It is
rarely found in pure form in atmosphere.

Figure 1. Structure of hydrogen

2. Physical Properties of hydrogen.

1) It is a colourless, odourless, tasteless and gaseous in nature.
2) It is sparingly soluble in water.
3) It does not support respiration although it is not poisonous.
4) It is a better conductor of heat than other gases, its conductivity is about five times that
of air

3. Chemical Properties of hydrogen.

1) Hydrogen reacts with most elements.
2) Hydrogen burns in oxygen or air to form water
2H2 + O2 → 2H2O
3) A mixture of hydrogen with O2 or air explodes violently when kindled, provided either
gas is not present in excess.
4) Reaction with Non-metals
H2 + F2 ---------- 2HF
H2 + Cl2------  2HCl
N2 + 3H2 --------  2NH3
5) Reducing properties:
When passed over heated metallic oxides( copper oxide, iron oxide, lead oxide) they
are reduced to metals
CuO + H2 → Cu + H2O
4. Hazardous properties of hydrogen/disadvantage of hydrogen
1) Undetectability : H2 gas is colourless ,odourless and not detectable by human senses.
Therefore, H2 leakage is a huge disaster.
2) Flammability: Mixtures of H2 with air, O2 or other oxidizers are highly flammable over
wide range of composition and leads to explosion.
3) Auto ignition : Temperature of about 565̊ C are usually required for mixtures of H2 with
air or O2 to auto ignite at 14.7 psi. However, at pressures from 3-8psi, autoignition have
occurred near 650 .

5. Combustible properties of hydrogen/Properties which make H2 an ideal fuel/ Safe

Handling is required for hydrogen
1) Wide range of flammability: 45 to 75%
2) Low ignition energy: 0.02 mJ
3) Small quenching distance: 0.064 cm
4) High auto ignition temperature: 585̊ C
5) High octane number: 130
6) High flame speed
7) High Diffusivity
8) Very low density
9) Hydrogen flames are very pale blue and are almost invisible in daylight due to absence
of soot.

6. Uses of hydrogen.
1) Commercial fixation of nitrogen from the air in the Haber ammonia process
2) Hydrogenation of fats and oils
3) In reactions: hydro-de-alkyaltion, hydrocracking, hydro de- sulphurization, methanol
production
4) Hydrogenation of unsaturated oils in oil and petroleum industries
5) Production of hydrochloric acid
6) Rocket fuel
7) welding
8) reduction of metallic ores
9) Authorized food additive that allows the check on leakage in food packaging
10) Hydrogen fuel cell to run automobiles

7. Importance or advantage of Hydrogen/Need to study hydrogen

1) It is readily available and abundant in nature.
2) It is an efficient future fuel with zero-emission (when burned or used no toxic by-product
is produced) when burned with oxygen. It is non-polluting, inexhaustible and cost effective
carrier of energy.

3) It has highest energy density (120-142 MJ/Kg) among the existing hydrocarbon fuels as
shown in figure 2. below. It has high calorific value compared to other fuels.

4) If it is produced from renewable sources of energy such as sun and water then it is a green
and sustainable fuel.

Figure 2. Comparison of power density of different fuels with hydrogen

Energy density (MJ/Kg) is the amount of energy in a given mass (or volume) of fuel.

Power density (KWh/Kg) is the amount of power in a given mass (or volume) of fuel.

1kg of H2 contains 33.33 KWh of usable energy whereas petrol and diesel gives only 12
KWh/Kg.
8. Different pathways/resources of hydrogen production

Figure 3. Schematic diagram of different pathways of hydrogen production.

Hydrogen can be produced from diverse resources which includes fossils fuels (oil, coal and
gas), nuclear energy and renewable energy sources (solar, hydro, wind, geothermal, biomass).
The different pathways are listed below in detail.

1) Steam methane reforming (SMR):

Catalytic steam reforming is, at present, the most efficient, economical and widely used
technique for the production of hydrogen. Almost 50% of the H2 is produced by this method
and is popular at industrial scale. SMR is a chemical synthesis process to produce syngas (H2+
CO) from hydrocarbon feedstock and later H2 is isolated and procured. It is produced in a
reformer at high temperature (700̊ C-1100̊ C) and pressure (2-25 bar or at 2MPa) by reaction
of steam with hydrocarbon such as methane in the presence of metal based catalyst (Ni). It is a
strongly endothermic reaction.

CH4 + H2O ↔ CO + 3H2 ∆H= 206.1 KJ/mol

Later, hydrogen is obtained by reaction of produced CO with water which is also called as
water-gas shift reaction (WGSR). It is mildly exothermic reaction.

CO + H2O ↔ CO2 + H2 ∆H= - 41.2 KJ/mol

The sulphur content of the methane feedstock is first removed and then mixed with steam. The
mixture is then passed through steel tubes, which contain Ni catalysts. The H2 generated in this
first step contains some methane and carbon monoxide. To remove CO and CH4, the gas passes

Figure 4. Schematic diagram of different pathways of hydrogen production.

through a heat recovery step. The gas is fed to a water gas shift reactor where additional
hydrogen is produced. The gas finally passes through a gas purifier where CO 2 is removed by
wet scrubbing with amine solution. The purity of gas produced by this method is 98%.
Partial Oxidation
If the methane and other hydrocarbons in natural gas undergo reaction in limited supply of
oxygen stock, then it undergoes partial oxidation process. With less than the stoichiometric
amount of oxygen available, reaction produces primarily hydrogen and carbon monoxide. In
WGSR, CO reacts with water to form more amount of hydrogen.
CH4 + 1/2O2 ↔ CO + 2H2 (+ heat)
CO + H2O ↔ CO2 + H2
As it can be seen from the reaction that it produces less hydrogen initially than the SMR
process.

Advantages of SMR
1) Efficient net conversion efficiency of 65-70%.
2) SMR doesn’t require external heat source as it is an exothermic reaction.
3) Stable during the transition of operation.
4) Natural gas is convenient and easy to handle.
 5) It is a potential way to provide fuel to fuel cells.

Disadvantages of SMR

1) SMR is dependent on fossil fuels for the feedstock of methane which are at the edge
of extinction and their combustion emits toxic gases in atmosphere causing air
pollution.
2) Depending on the scale of the production, SMR has high capital cost.
3) SMR requires high operating temperature which sows the start up.
4) Sulfur compounds produced during the reaction deactivates/poisons the catalyst
which slows sown the reaction with period of time. Also, it provokes the need of
sulphur tolerant catalyst for SMR

2) Coal Gasification:
Coal gasification is the technology which converts coal directly into hydrogen. In this
method coal is combined with steam and oxygen to produce synthesis gas (CO+H2) along
with waste gases, char and ash. Coal gasification is represented by following equation:
CmHn + 0.5mO2 ↔ mCO + 0.5 n H2
Where, ‘m’ and ‘n’ depends on the composition of coal.The gasification of coal generally
consists of four steps:
 Pre-treatment of Coal: Coal is dried to remove the moisture content of it and then crushed
or pulverised
 Gasification: The pre-treated coal is charged into the gasification reactor where it reacts
with oxygen (air) and steam. The gasification reaction usually takes place at high
temperatures from 800 to1900°C and high pressure up to 10 MPa. When coal is burned
with less than a stoichiometric quantity of air, with or without steam, the product is a low-
heat-content gas, which after purification can be used as fuel gas. Using oxygen in place of
air produces medium-heat content gas. Some of CO must be reacted with steam by shift
conversion to get additional hydrogen. The ashes from gasifier are removed as molten slag
or dry condition.
 Gas cleaning: The gas products from the gasifier contain a mixture of different gases such
as, carbon monoxide, carbon dioxide, hydrogen, methane, other organic vapours and
hydrogen sulfide in different concentrations. Nitrogen is also present in gas products if air
is used. Other impurities are particulates, and water vapour. The product gas is then purified
prior to their combustion through the removal of particulate matters, such as, coal dust, ash
 and tar aerosols. The tar and oil are removed by gas quenching method, and then the acid
gas is removed by solvent treatment technology. The tar and oils are condensed in the gas
quenching and cooling section of the plant. Ammonia is removed from the gas in a scrubber
by using either aqueous or organic liquid. Acid gases such as H2S, COS, CS2, mercaptans,
and CO2 can be removed from gas by an acid gas removal step, where it is treated with a
solvent to absorb the acid gases. Methanol may be used as a solvent to separate acid
gasessuch as hydrogen sulfide and carbon dioxide from feed gas streams.
 Gas beneficiation: In the shift conversion process, H2O and a portion of the CO
catalytically react to form CO2 and H2. After passing through an absorber for CO2 removal,
CO and H2 remain in the producer gas. They are reacted in a methanation reactor to yield
CH4 and H2O. Many processes are directly related with a coal gasification process, such as,
oxygen plant, power and steam plant, sulfur recovery unit etc.

Almost 18% of the H2 is produced by coal gasification at commercial level. The most important
advantage of this technique is has 99.8% conversion of carbon into fuel. However, disadvantage
lies in burning of less abundant fossil fuels which makes it most expensive hydrocarbon to use for
hydrogen production. Secondly, combustion of coal causes emission of toxic has which are threat
to environment and human health.

3) Electrolysis: ‘Electrolysis’ word implies lysis (splitting) of water by applying electrical

bias or passing a direct current through it. Water electrolysis involves splitting of water
into hydrogen and oxygen. This method doesn’t rely on fossil fuels. When voltage (< 1.23
V) is applied in electrochemical cell/set up containing two or three electrode system
immersed in current conducting electrolyte/water, it splits water into oxygen and
hydrogen. The most common electrolyte used is potassium hydroxide (KOH) as it is
excellent conductor of electricity and corrosion resistant.

Figure 5. Electrolysis set up

The produced H2 and O2 are regulated and stored. The three electrode system consists of anode
(working electrode), cathode (counter electrode) and reference electrode (Ag/AgCl). In order
to to increase the rate of hydrogen production catalyst material is coated/aaplied on the
electrode surfaces which catalyses the water splitting reaction

Thermodynamically (theoretically) minimum potential required to split water is 1.23 V but in

practical practice it is greater than 1.23 to 1.5 V. The additional potential (V applied -1.23 V) is
called as overpotential. This overpotential is the excess energy which is required to overcome
the various activation barriers. Minimum is the overpotential greater is the efficiency of catalyst
coated on the electrode. This technique delivers about 80% of energy efficiency. Over all
reaction governed by electrolysis is

2 H2O(l) → 2 H2(g) + O2(g)

4) Solar driven water splitting or Photocatalysis:

The electric energy require for water splitting can be replaced or minimized by sun energy
by utilizing nanomaterials making the system cost effective and clean. Even electricity
generated by photovoltaics can be employed for water splitting. Soar driven water
splitting has two pathways:
a) Photocatalytical water splitting b) Photoelectrochemical water splitting

Photo-catalytic (PC) water splitting

In photocatalytical water splitting semiconductor photocatalyst is immersed in
water/electrolyte and irradiated with sunlight. The generated photoelectron hole pair with
in the semiconductor performs the function of water reduction and oxidation on its surface
to produce H2 and O2. In order to facilitate surface reaction and better charge separation
many times photocatalyst is modified with co-catalyst or buffer layers as shown in Figure.
In this catalysis photocatalyst has to satisfy stringent criteria to perform PC water splitting,
that is, a) narrow band gap to maximize the absorption spectrum and b) appropriate
conduction and valence band edges w.r.t. to redox potential of water and c) it should be
stable. Although many materials are available which satisfy the properties required for
 a b

Figure 6. Photocatalysis mechanism with band gap structure of photocatalysis

water splitting but it is difficult to have single material which can satisfy all the requirements.
Moreover, main bottle neck lies in low quantum yield where most of the photo generated charge
carriers recombine after excitation. To solve this issue photoelectrochemical water splitting
emerged as an efficient path way of solar driven water splitting.

Photoelectrochemical (PEC) catalytic water splitting

In PEC water splitting two (or three) electrode system immersed in conducting electrolyte
where working electrode may be n/p- type material and counter of metallic type or second
option is n-type material as photoanode and p-type material as photocathode (Figure). When
sunlight is incident on working electrode, electron hole pair is generated where they migrate
through electrolyte to respective electrodes. Electrons from external circuit reaches
photocathode for water reduction and hole at photoanode does water oxidation. So the two
processes occur at two different electrodes unlike photocatalytical water splitting. In this kind

Figure 7. Photoelectrochemical water splitting

of water splitting small bias (V< 1.23 V) can be applied to narrow band gap materials which
can absorb in visible region but their conduction band edge is below the water reduction
potential. In feasibility of applying small bias can separate the charges efficiently increasing
the solar to fuel conversion efficiency.

5) Biohydrogen production process: Biological hydrogen (biohydrogen) production

processes is a hydrogen production technology that utilise renewable energy resources by
using microorganisms. The process is operating at ambient temperature and atmospheric
pressure, and use less energy. These biohydrogen production technologies are possible
candidate for sustain the world power energy supply, potential to replace fossil fuels and
do not discharge greenhouse gases such as carbon dioxide. The biohydrogen is generating
by three differents mechanism which can be categorised as light dependent (biophotolysis
and photo fermentation) and independent (dark fermentation).

The biological agents such as enzymes, bacteria or plant extract (algae) are also used for
photolysis (water splitting using sunlight) of water into O2 and H2 which is called as
‘Biophotolysis’. Cyanobacteria (blue green algae) are ideal organism for producing hydrogen
due to their ability to perform prosynthetic CO2 fixation using water as electron donor. In some
processes, the photosynthetic organism is not powerful enough to split water even with light as
a source of energy. In such a case it utilizes organic acids as an electron donor to produce
hydrogen and no oxygen is produced in this process. This is called as photo fermentation
method. The advantage of the process is that non-sulfur prosynthetic bacteria produces 100%
electron from the organic substrate. Therefore, waste rich in organic content such as whey,
starches, sugar refinery waste, agricultural waste or industrial waste can be employed as
substrate. The prosynthetic bacteria are usually grown in anerobic conditions and immobilized
for hydrogen production.
Dark fermentation or anerobic digestion (hydrogen production from biomass) is yet
another biohydrogen pathway utilizing bacteria for hydrogen production by series of
biochemical reactions. It is independent of light energy and consumes no oxygen and therefore
called as anerobic digestion. It utilizes ‘Biomass” material which is organic in nature. Waste
and Wastewaters such as food processing, animal waste and agricultural waste are rich in
carbohydrates which act as source of nutrients for bacteria which ultimately produces
hydrogen. Moreover, it reduces treatment and disposal cost both which is currently needed for
the waste streams. Treating these waste streams to protect public health and the environment
while producing a clean energy source makes biological hydrogen production an attractive
alternative to fossil fuels.

C6H12O6 + 2H2O → 2CH3COOH + 4H2 + 2CO2

6) Nuclear hydrogen system:

Figure 8. Nuclear hydrogen system

This technique is based on the fundamental concept of using heat liberated from the nuclear reactors
to generate hydrogen. The nuclear fission reaction of splitting of helium molecule using radioactive
particles liberates huge amount of heat. The heat liberated from nuclear reaction is utilized in steam
reforming or thermochemical process or high temperature electrolysis to directly produce
hydrogen. Sometimes thermal energy is utilized to turn the turbine which generate electricity. The
generated electricity is in turn used in water electrolysis to produce hydrogen as shown in flow
chart. This technique ensures large scale and consistent production of hydrogen with zero emission
of greenhouse gases. The two major drawback of nuclear powered technique is its high cost along
with management and disposal of nuclear waste.
 5.Hydrogen Storage

1. ‘Hydrogen Economy”
The term “Hydrogen Economy” refers to the infrastructure which is used to support the energy
requirements of society, based on the use of hydrogen in place of fossil fuels. The hydrogen
economy infrastructure comprises of five key elements—production, delivery, storage,
transportation, and applications/use, which are in different stages of technological
advancement.

2. Hydrogen storage
Hydrogen economy makes sense when hydrogen production, storage, transportation and its
use are superior than the distribution of electricity by wires. However, the main bottleneck in
hydrogen economy is hydrogen storage. As H2 can be produced by various methods (as seen
in earlier chapter) and can be transported for the use but its storage is a huge problem due to
the following reasons:
1) Hydrogen is lighter and low density gas which can easily escape to the atmosphere
causing leakage in the storage system.
2) High flame speed, high flammability and low ignition energy of hydrogen increases
high risk of explosion or fire.
3) The major requirement of hydrogen is in fuel cell governed vehicles where, on board
H2 generation is insufficient to provide the required amount of H 2 as well as on borad
storage is the main barrier to fuelling vehicles. Therefore, efficient storage systems are
required.

3. Different methods of hydrogen storage

There are two major methods for H2 storage: Physical method and chemical method or
materials based method. Physical method Includes
a) Compressed gas storage
b) Cryogenic liquid storage
c) Cryo-compressed storage
Material based H2 storage includes different category of materials which store H2 by different
mechanism.
4. Physical methods of H2 storage
a) Compressed gas storage: Compressed hydrogen is a storage form where hydrogen is stored
in gas form at room temperature in high-strength tanks and is kept under pressures to increase
the storage density. Compressed hydrogen in hydrogen tanks at 350 bar (5,000 psi) and 700
bar (10,000 psi) is used for hydrogen tank systems in vehicles. Car manufacturers have been
developing this solution, such as Honda or Nissan. For this method, lighter stronger tanks
capable of holding more amount of hydrogen is required which increases its cost. Additionally,
compressing the hydrogen gas at the filling station require about 20% as much energy as is
contained in the fuel.
b) Cryogenic liquid storage: Hydrogen is stored in liquid form. Hydrogen is liquified by
reducing its temperature to -253°C, similar to liquified natural gas (LNG) which is stored at -
162°C.BMW is working on this method for cars. As a liquid, hydrogen contains almost 3 times
more energy than equal weight of gasoline but also requires 2.7 times more space to store.
Liquefaction of hydrogen requires heavily insulated tanks and liquefaction at the filling station
requires about 40% as much energy as in contained in the fuel. Another disadvantage of this
method is the ‘dormancy’ (Dormancy is defined as the period of inactivity before a vessel
releases H2 to reduce pressure build-up). Despite the insulation, some heat leaks into the tanks
eventually boiling off the hydrogen.
c) Cryo- compressed storage: A ‘cryopressure’ system stores liquid hydrogen in a pressure
vessel like that used for compressed gaseous storage, allowing containment of the boiled off
gas. This solution helps with the issue of dormancy and increases storage life but on the other
hand increases weight and size. A cryo-compressed storage system consists of a composite
pressure vessel with a metallic liner that is encapsulated in a secondary insulated jacket, whose
role is to limit heat transfer between the hydrogen and the environment. A cryo-compressed
system operating at a maximum pressure of 345 bar. Around 10.4 kg H2 vessel is installed on
board by Toyota Prius.

5. Chemical methods of H2 storage

Hydrogen can be stored in vast variety of materials under diverse conditions of pressure and
temperature or can be made to store in case of certain materials using the process of a)
Physisorption and b) chemical storage. High pressure and cryogenic hydrogen storage is
impractical for vehicular application and has safety concerns and volumetric constraints. This
has prompted intensively for solid state hydrogen storage in materials.
a) Physisorption Method:
It is a process in which H2 molecules get weakly adsorbed at the surface of the material. One
way to improve the kinetics of storage is to maintain the molecular identity of H 2 during the
process which is possible by Physisorption. The most widely studied materials are porous
materials, such as carbon materials (fullerenes, Nanotubes and graphene), zeolites, metal
organic frameworks (MOFs), covalent organic frameworks (COFs), micro porous metal
coordination materials (MMOMs), clatherates and organotransition metal complexes.

Carbon Materials based storage system: Hydrogen gets adsorbed on the surface of carbon
through Van der Waals bonding (~6 kJ mol−1). There are many unique carbon structures with
high surface area such as carbon foam, carbon nanotubes, carbon aero gels and activated
carbon. Current systems store as much as 4% hydrogen by weight and is expected to take leap
till 8%. Carbon Nanotubes (CNTs) are microscopic tubes of carbon with two nanometers
thickness across that can store hydrogen in their microscopic pores or within the tube structures.
Nanotubes have single or multiple wall structure, multiple adsorption sites, high packing
density and possess an estimated capacity of 6 wt%. The interaction between hydrogen and
graphene can be tuned by adjusting the distance between adjacent layers or by simply tuning
the sheet curvature or by chemical functionalization of the material, which enables controlled
adsorption and desorption of hydrogen. The method involves storing hydrogen between layers
of graphite and allowing the release of hydrogen only when heated to a temperature of around
450 °C. It is more efficient than carbon nanotubes as it is not only cheap but also safe and easy
to prepare.

“Zeolite” is derived from the two Greek words “zeo” meaning “to boil” and “lithos” meaning
“stone”. In zeolites, the H2 are forced to move into the cavities of the molecular sieve under
elevated temperatures and pressure which are of different pore architecture and composition.
When zeolites are cooled to room temperature, H2 gets trapped inside its cavity, which can then
be made to release by raising the temperature of the system. The results suggest that zeolites
containing sodalite cages showed a hydrogen storage capacity of 9.2 cm3 g−1 at 573 K and
10.0 MPa. Zeolites are known for their high thermal stability, low cost and adjustable
composition.

Metal–organic frameworks are a family of nano-porous materials that are composed of well
defined building blocks, polar metal oxide centers (connectors) and non polar organic linkers.
MOFs which contain oxides are stable even when their pores have been emptied/heated. MOFs
have good stability, high void volume, well defined tailor able cavities of uniform size, large
surface area, adjustable pore size, controllable properties and acceptable thermal stability.
These are also efficient H2 storing materials that possess pore dimensions comparable to the
length of molecular diameter of H2. They are composed of open channels based on the aromatic
carbons. Their internal surfaces can be easily modified to change their channel curvature, thus
enhancing H2 adsorbing interactions. These structures include metal building units and possess
pore dimensions which can be systematically tuned for purpose of modifying and improving
hydrogen uptake and adsorption / desorption properties.
Glass microspheres are small, hollow, glass microballons whose diameter vary from about 25
microns to 500 microns and wall thickness are about 1 micron. They can be used in large beds
to store hydrogen at high pressures. The microspheres are filled with hydrogen gas at 200 to
400 C temperatures. The high temperature makes the glass walls permeable and the gas fills
the spheres. Once the glass is cooled to room temperature, the hydrogen is trapped inside the
spheres. The hydrogen can be released as needed by heating the spheres or by crushing it.

b) Chemical storage could offer high storage performance due to the strong binding of
hydrogen (chemisorption) and the high storage densities. However, the regeneration of
storage material is still an issue. Chemical storage uses technologies in which hydrogen is
generated through a chemical reaction. The materials which store hydrogen through
chemical storage are ammonia (NH3), metal hydrides, formic acid, carbohydrates, synthetic
hydrocarbons and liquid organic hydrogen carriers (LOHC).

Metal hydrides are famous for their unique ability to absorb hydrogen and release it later,
either at room temperature or through heating of the tank. They store hydrogen in the interatom
spaces of a granular metal as shown in figure. Metal hydrides possess hydrogen storing capacity
of 5–7 wt% but only when heated to temperatures of 2500 °C or higher. Metal hydrides tend
to bind strongly with hydrogen creating a need for high temperatures of around 120–200 °C to
release their hydrogen content. Hydrides chosen for storage applications provide low reactivity
(high safety) and high hydrogen storage densities. Metal hydrides are very effective for storing
large amounts of hydrogen in a safe and compact way. All the reversible hydrides working
around ambient temperature and atmospheric pressure consist of transition metals.
Apart from metal hydrides, complex metal hydrides such as NaAlH4, LiBH4, Mg(BH4)2,
ammonia borane (NH3BH3), amide/imide systems, Li2NH, Li3NH, LiAlH4 and MgH2 are
currently the only hydrides which are able to accomplish the 9 wt% gravimetric goal set for the
year 2015 by US Department of Energy. Complex metal hydrides (CMHs) formed by light
elements, such as boron, nitrogen, or aluminium often have extreme hydrogen densities but
also poor thermodynamic and kinetic properties and limited reversibility. Typical complex
metal hydride system include amide –hydride system, borohydrides and alanates.
Chemical hydride for hydrogen storage includes Sodium Borohydrate NaBH4 solution. It is
the most popular of many hydrate solutions where solution is passed through a catalyst to
release H2. Because of their high hydrogen content, sodium borohydride (NaBH4), AB
(NH3BH3), and FA-based chemical hydrogen storage materials are potential hydrogen sources
for proton exchange membrane fuel cells. Chemical hydrides may offer options with high
energy densities and potential ease of use, in which hydrogen is stored in these materials via
strong chemical bonds and is released by thermal decomposition or other chemical reaction. In
particular, hydrogen desorption from chemical hydrides is exothermic in nature, consequently
being irreversible because they cannot be reconstituted simply by applying an overpressure of
hydrogen gas at modest temperature and pressure. As a result, chemical hydrides are intended
as “one-way” single-use fuels, that is, the leftover by-product must be removed from the
vehicle for off-board regeneration. A few prominent examples of chemical hydrides including
ammonia borane (NH3BH3) and alane (AlH3) are currently under investigation. Hydrides
suffer from serious limitations as they react violently upon exposure to moist air, are
cumbersome to handle and recycle as they cause skin or eyes irritation and also cause
absorption of impurities into the tank during the uptake of hydrogen. This leads to reduction in
tank’s lifetime as the impurities occupy the spaces inside the metal which where once occupied
by hydrogen. Secondly, weight of hydrogen storage units is about 10-20 times higher than
gasoline tanks.

6. Comparison between different methods:

The efficiency of storage is usually measured by two parameters:
a) Gravimetric density (GD): the weight percentage of hydrogen stored of the total
weight of the system (hydrogen + container), and
b) Volumetric density (VD): the stored hydrogen mass per unit volume of the system.
Compact, light and efficient hydrogen storage technology is a key enabler for fuel cell vehicles
and the use of renewable energy in vehicles. A vision of hydrogen as a vehicle energy carrier
offers the possibility of an eventual transition to use of a wide range of renewable resources for
vehicles. Better hydrogen storage could lead to cost reduction of hydrogen fuel as it could allow
the use of remote resources and long distance transport. Up till now the hydrogen storage is the
main barrier due to weight, volume and fuelling infrastructure. Therefore, material
development for improving the hydrogen storage is the necessity.
 6. Future

Advanced energy storage provides an integrated solution to the critical energy needs:
electric grid modernization, reliability, and resilience; sustainable mobility; flexibility
for a diverse and secure, all-of-the-above electricity generation portfolio; and enhanced
economic competitiveness for remote communities and targeted micro-grid solutions.
For grid applications, electricity must be reliably available 24 hours a day. Even second-
to-second fluctuations can cause major disruptions that could potentially cost billions
of dollars. At the global level, energy storage can also curb climate change by
decreasing emissions from electricity, heating and cooling needs. At the community
level, energy storage can involve more resilient and flexible energy systems with higher
levels of energy security through integration of locally produced energy. From the
citizen perspective, energy storage holds the benefit of improved control of energy costs
and origin. For the private sector, energy storage can open new business opportunities
with constant innovation of offered services. These can range from energy-storage-as-
a-service enterprises to market actors expanding to installation of storage systems,
charging stations and virtual power plants.
The concept of effectively storing energy is a game changer. Coupled with smart billing
technologies and strategic partners, ESS technology will revolutionize how utilities
manage grid resources. The efforts to lift our power generation and electrical grid into
the 21st century is a multipronged effort. It needs a new generation mix of low-carbon
sources that include hydro, renewables and nuclear, ways to capture carbon that don’t
cost a zillion dollars, and ways to make the grid smart. However, there is risk in this
transition of revolutionization will be hindered by variety of obstacles. The main
challenge to overcome is cost, safety, durability and infrastructure. New approaches to
maximize energy storage capacity are essential to bring intermittent renewables into the
grid and effectively manage electricity generation to meet peak demand. DOE seeks to
enable a smarter, more flexible electric grid and electric vehicles on roads by advancing
research on novel materials and system components that resolve key challenges for
energy storage systems. Dream of smart city and a well-developed country is
conceivable by the amalgamation of ESS.