FUEL CELLS

Fuel cell

A fuel cell is an electrochemical device that

produces electricity without combustion by
combining hydrogen and oxygen to produce water
and heat.
Discovered German Scientist G H Shoenbein

First developed by William Grove

In 1839, Grove was experimenting on electrolysis

(the process by which water is split into hydrogen
and oxygen by an electric current), when he
observed that combining the same elements
could also produce an electric current
1930s -1950s Francis Thomas Bacon, a British
scientist, worked on developing alkaline fuel
cells.

He demonstrated a working stack in 1958.

The technology was licensed to Pratt and

Whitney where it was utilized for the Apollo
spacecraft fuel cells.
Advantages over conventional energy sources
They produce zero or very low emissions, especially Green
House Gases (GHGs) depending on the fuel used.

Have few moving parts and thus require minimal

maintenance, reducing life cycle costs of energy production.

Modular in design, offering flexibility in size and

efficiencies in manufacturing

Can be utilized for combined heat and power purposes,

further increasing the efficiency of energy production
 Working Principle
A fuel cell is a device that uses hydrogen (or hydrogen-rich
fuel) and oxygen to create electricity by an electrochemical
process.
A single fuel cell consists of an electrolyte sandwiched
between two thin electrodes (a porous anode and cathode)

Hydrogen, or a hydrogen-rich fuel, is fed to the anode where

a catalyst separates hydrogen's negatively charged electrons
from positively charged ions (protons)
At the cathode, oxygen combines with electrons and, in
some cases, with species such as protons or water, resulting
in water or hydroxide ions, respectively
The electrons from the anode side of the cell cannot pass
through the membrane to the positively charged cathode;
they must travel around it via an electrical circuit to reach
the other side of the cell. This movement of electrons is an
electrical current.

The amount of power produced by a fuel cell depends upon

several factors, such as fuel cell type, cell size, the
temperature at which it operates, and the pressure at which
the gases are supplied to the cell

Still, a single fuel cell produces enough electricity for only

the smallest applications. Therefore, individual fuel cells are
typically combined in series into a fuel cell stack. A typical
fuel cell stack may consist of hundreds of fuel cells.
Fuel cells are classified primarily by the kind of electrolyte
they employ. This determines the kind of chemical reactions
that take place in the cell, the kind of catalysts required, the
temperature range in which the cell operates, the fuel
required, and other factors.

There are several types of fuel cells currently under

development, each with its own advantages, limitations,
and potential applications.
 Classification of Fuel Cells
Based on the type of Electrolyte
1. Alkaline Fuel cell (AFC)
2. Phosphoric Acid Fuel cell (PAFC)
3. Polymer Electrolytic Membrane Fuel Cell (PEMFC)
Solid Polymer Fuel Cell (SPFC) and
Proton Exchange Membrane Fuel cell (PEMFC)
4. Molten Carbonate Fuel Cell (MCFC)
5. Solid Oxide Fuel Cell (SOFC)

Based on Types of Fuel and oxidant

1. Hydrogen (pure)-Oxygen (pure) fuel cell
2. Hydrogen rich gas-air fuel cell
3. Ammonia –air fuel cell
4. Synthesis gas- air fuel cell
5. Hydro carbon (gas)- air fuel cell
Based on operating temperature
 Alkaline Fuel Cells (AFC)

The alkaline fuel cell uses an alkaline electrolyte such as 40% aqueous
potassium hydroxide. In alkaline fuel cells, negative ions travel
through the electrolyte to the anode where they combine with
hydrogen to generate water and electrons.

It was originally used by NASA on space missions. NASA space shuttles

use Alkaline Fuel Cells. Alkaline fuel cells (AFCs) were one of the first
fuel cell technologies developed, and they were the first type widely
used in the U.S. space program to produce electrical energy and water
onboard spacecraft. These fuel cells use a solution of potassium
hydroxide in water as the electrolyte and can use a variety of non-
precious metals as a catalyst at the anode and cathode. High-
temperature AFCs operate at temperatures between 100ºC and 250ºC
(212ºF and 482ºF). However, more-recent AFC designs operate at
lower temperatures of roughly 23ºC to 70ºC (74ºF to 158ºF).
AFCs are high-performance fuel cells due to the rate at which chemical
reactions take place in the cell. They are also very efficient, reaching
efficiencies of 60 percent in space applications.

The disadvantage of this fuel cell type is that it is easily poisoned by

carbon dioxide (CO2). In fact, even the small amount of CO2 in the air
can affect the cell's operation, making it necessary to purify both the
hydrogen and oxygen used in the cell. CO2 can combine with KOH to
form potasium carbonate which will increase the resistance.
This purification process is costly. Susceptibility to poisoning also affects
the cell's lifetime (the amount of time before it must be replaced),
further adding to cost.

Cost is less of a factor for remote locations such as space or under the
sea. However, to effectively compete in most mainstream commercial
markets, these fuel cells will have to become more cost effective. AFC
stacks have been shown to maintain sufficiently stable operation for
more than 8,000 operating hours..
Anode Reaction: 2H2 + 4OH- »» 4H2O + 4e-
Cathode Reaction: O2 + 2H2O + 4e- »» 4OH-
Molten Carbonate Fuel Cells (MCFC):
The molten carbonate fuel cell uses a molten carbonate salt as the
electrolyte. It has the potential to be fuelled with coal- derived fuel
gases, methane or natural gas. These fuel cells can work at up to
60% efficiency
In molten carbonate fuel cells, negative ions travel through the
electrolyte to the anode where they combine with hydrogen to
generate water and electrons.
Molten carbonate fuel cells (MCFCs) are currently being developed for
natural gas and coal-based power plants for electrical utility, industrial,
and military applications. MCFCs are high-temperature fuel cells that
use an electrolyte composed of a molten carbonate salt mixture
suspended in a porous, chemically inert ceramic lithium aluminum
oxide (LiAlO2) matrix. Since they operate at extremely high
temperatures of 650ºC and above, nonprecious metals can be used as
catalysts at the anode and cathode, reducing costs.
Unlike alkaline, phosphoric acid, and polymer electrolyte membrane
fuel cells, MCFCs don't require an external reformer to convert more
energy-dense fuels to hydrogen. Due to the high temperatures at which
they operate, these fuels are converted to hydrogen within the fuel cell
itself by a process called internal reforming, which also reduces cost.

Although they are more resistant to impurities than other fuel cell
types, scientists are looking for ways to make MCFCs resistant enough to
impurities from coal, such as sulfur and particulates.

The primary disadvantage of current MCFC technology is durability. The

high temperatures at which these cells operate and the corrosive
electrolyte used accelerate component breakdown and corrosion,
decreasing cell life.

Scientists are currently exploring corrosion-resistant materials for

components as well as fuel cell designs that increase cell life without
decreasing performance.
Anode Reaction: CO3-2 + H2 → H2O + CO2 + 2e-
Cathode Reaction: CO2 + ½O2 + 2e- → CO3-2
Overall Cell Reaction: H2 + ½O2 → H2O
Phosphoric Acid Fuel Cells (PAFC):
A phosphoric acid fuel cell (PAFC) consists of an anode and a cathode
made of a finely dispersed platinum catalyst on carbon and a silicon
carbide structure that holds the phosphoric acid electrolyte.
In phosphoric acid fuel cells, protons move through the electrolyte to the
cathode to combine with oxygen and electrons, producing water and
heat.
This is the most commercially developed type of fuel
cell and is being used to power many commercial
premises
Phosphoric acid fuel cells use liquid phosphoric acid as an electrolyte—
the acid is contained in a Teflon-bonded silicon carbide matrix—and
porous carbon electrodes containing a platinum catalyst.

The phosphoric acid fuel cell (PAFC) is considered the "first generation"
of modern fuel cells. It is one of the most mature cell types and the first
to be used commercially, with over 200 units currently in use.

This type of fuel cell is typically used for stationary power generation,
but some PAFCs have been used to power large vehicles such as city
buses

PAFCs are more tolerant of impurities

They are 85 percent efficient when used for the co-generation of
electricity and heat, but less efficient at generating electricity alone
(37 to 42 percent).

PAFCs are also less powerful than other fuel cells, given the same
weight and volume. As a result, these fuel cells are typically large
and heavy. PAFCs are also expensive.

Like PEM fuel cells, PAFCs require an expensive platinum catalyst,

which raises the cost of the fuel cell.
Polymer electrolyte membrane (PEM) fuel cells (PEMFC)

In polymer electrolyte membrane (PEM) fuel cells, protons move

through the electrolyte to the cathode to combine with oxygen and
electrons, producing water and heat.
Polymer electrolyte membrane (PEM) fuel cell uses a polymeric membrane
as the electrolyte, with platinum electrodes.
These cells operate at relatively low temperatures
These cells are the best candidates for cars, for buildings and smaller
applications. Polymer electrolyte membrane (PEM) fuel cells—also called
proton exchange membrane fuel cells—deliver high power density and offer
the advantages of low weight and volume, compared to other fuel cells. PEM
fuel cells use a solid polymer as an electrolyte and porous carbon electrodes
containing a platinum catalyst.
They only hydrogen, oxygen from the air, and water to operate and do not
require corrosive fluids like some fuel cells. They are typically fueled with
pure hydrogen supplied from storage tanks or onboard reformers
Polymer electrolyte membrane fuel cells
operate at relatively low
temperatures, around 80°C (176°F).

Low temperature operation allows them

to start quickly (less warm-up time) and results
in less wear on system
components, resulting in better durability.

However, it requires that a noblemetal

catalyst (typically platinum) be used to
separate the hydrogen's electrons
and protons, adding to system cost.

The platinum catalyst is also extremely

sensitive to CO poisoning, making it necessary
to employ an additional
reactor to reduce CO in the fuel gas if the
hydrogen is derived from an alcohol
or hydrocarbon fuel. This also adds cost.

Developers are currently exploring

platinum/ruthenium catalysts that are more
resistant to CO.
 Solid Oxide Fuel Cells (SOFC)
Work at higher temperatures

They use a solid ceramic electrolyte, such as

zirconium oxide stabilised with yttrium oxide,
instead of a liquid and operate at 800 to 1,000°C.
In solid oxide fuel cells, negative ions travel
through the electrolyte to the anode where they
combine with hydrogen to generate water and
electrons.
Efficiencies of around 60 per cent and are
expected to be used for generating electricity
and heat in industry and potentially for providing
auxiliary power in vehicles.
Anode Reaction: 2H2 + 2O–2 →
Since the electrolyte is a solid, the cells do not 2H2O + 4e–
have to be constructed in the plate-like Cathode Reaction: O2 + 4e– →
2O–2
configuration typical of other fuel cell Overall Cell Reaction: 2H2 + O2 →
types. 2H2O
High temperature operation removes the need for precious-metal
catalyst, thereby reducing cost.

They are not poisoned by carbon monoxide (CO), which can even be
used as fuel.

Sulphur resistant

This allows SOFCs to use gases made from coal.

Scientists are currently exploring the potential for developing lower-

temperature SOFCs operating at or below 800ºC that have fewer
durability problems and cost less.
Regenerative Fuel Cells (RFC):

This class of fuel cells produces electricity from

hydrogen and oxygen, but can be reversed and
powered with electricity to produce hydrogen and
oxygen; effectively storing energy or electricity
 Basic energy conversion of a fuel cell can be described as:

Chemical energy of fuel = Electrical energy + Heat energy

The input energy is that produced during

reactions at the electrodes.
 Performance
One measure of the energy conversion efficiency of a
fuel cell is the ratio of the actual voltage at a given
current density to the maximum voltage obtained under
no load (open circuit) conditions.

Ƞ = On load voltage / theoretical open circuit voltage

 Thermodynamic Analysis: 1st Law

It is usually formulated by stating that the change in the

internal energy (∆H) of a closed system is equal to the
amount of heat supplied (Q) to the system, minus the
amount of work (W) performed by the system on its
surroundings.
 Defining the work term
Electrical work is, in general, described by the relation: W = EIΔt
where E is the cell voltage and I is the current

In a fuel cell reaction, electrons are transferred from the anode to the
cathode, generating a current.

The amount of electricity (IΔt) transferred when the reaction occurs is

given by NF, where
N = number of electrons transferred
F = Faraday’s constant = 96,493 coloumbs

So the electrical work can be calculated as: W = NFE (Work done on

the surrounding)

The First Law then becomes: ΔH = Q - NFE

 Thermodynamic Analysis: 2nd Law

Consider the fuel cell to be ideal for now, meaning that it is reversible and thus
behaves as a perfect electrochemical apparatus :

“ If no changes take place in the cell except during the passage of

current, and all changes which accompany the current can be reversed by reversing
the current, the cell may be called a perfect elctrochemical
apparatus.”

Heat transferred during a reversible process was expressed as:

Q = T ΔS (1)
T = absolute temperature, ΔS = change in entropy
Combining the First and Second Law analysis, we get
ΔH = TΔS – NFE (2)
NFE = - (ΔH - TΔS ) (3)
Gibbs Free Energy is given by G= H – TS Max efficiency = NFE/ΔH
Or ΔG = ΔH-(T ΔS-S ΔT)
ΔG = ΔH-T ΔS (4)
As there is no change in temperature ΔT = 0
Eqn (2) becomes NFE = - Δ G)
Physical Interpretation of dG = dH - TdS

dH represents the total energy of the system.

TdS represents the “unavailable” energy (that which cannot

be converted to useful work).

Therefore G represents the “free” energy or the energy

available to do useful work.
 Fuel Cell Efficiency

Since fuel cells use materials that are typically burnt to release their
energy, the fuel cell efficiency is described as the ratio of the
electrical energy produced to the heat that is produced by burning
the fuel.

From the basic definition of efficiency: η = W / Qin

Hydrogen fuel cell:

Oxidation half reaction 2H2 4H+ + 4e- Energy formation (KJ/mole)
Reduction half reaction O2 + 4H+ + 4e- 2H2O -ΔHo = 286 -ΔGo = 237

The maximum efficiency of the fuel cell would be 83%.

 Classification of Losses in an Actual Fuel Cell

Activation Losses: These losses are caused by the slowness of the reaction
taking place on the surface of the electrodes. A proportion of the voltage
generated is lost in driving the chemical reaction that transfers the electrons.

Ohmic Losses: The voltage drop due to the resistance to the flow of
electrons
through the material of the electrodes. This loss varies linearly with current
density.

Concentration Losses: Losses that result from the change in concentration of

the reactants at the surface of the electrodes as the fuel is used.

Fuel Crossover Losses: Losses that result from the waste of fuel passing
through the electrolyte and electron conduction through the electrolyte.
This loss is typically small, but can be more important in low temperature
cells.
 Applications of 0D, 1D, 2D and 3D NSMs

The main active components are fuel electrode (anode), oxidant

electrode (cathode). The proton conducting solid membrane used
as electrolyte, is sandwiched between the anode and cathode
electrodes

Although the technology of such fuel cells was developed to an

extent, some problems remain unclear and only their solution can
result in wide-scale commercialization of fuel cells, especially as
the efficient current sources for portable devices. The most
important problem is the development of efficient catalysts,
which would provide the long-term operation of fuel cells without
sacrificing their characteristics.
The CO poisoning intrinsic to Pt based cathodes pose a further
barrier to fuel cell devices. Hence it is important to open up new
methods for making low cost and effective electrocatalysts.

It is well known that the catalytic activity attainable depends

significantly on the size of the Pt catalysts and their support.
However, there are two routes to overcome this problem. First,
the direct synthesis of novel 0D, 1D, 2D, and 3D NSMs (Pt or Pt
alloy catalysts) with high surface area for fuel cell devices.
Secondly, the synthesis of novel NSMs with high surface area as a
support of Pt or Pt alloys catalysts for fuel cell devices.
(SEM) and (TEM) image of different types of 0D NSMs, which is synthesized by
several research groups. (A) Quantum dots [20], (B) nanoparticles arrays, (C)
core–shell nanoparticles, (D) hollow cubes, and (E) nanospheres.
SEM image of different types of 1D NSMs, which is synthesized by several
research groups. (A) Nanowires, (B) nanorods , (C) nanotubes , (D) nanobelts ,
(E) nanoribbons, and (F) hierarchical nanostructures
SEM and TEM image of different kinds of 2D NSMs, which is synthesized by our and several
research groups.
(A) Junctions (continuous islands), (B) branched structures , (C) nanoplates , (D) nanosheets,
(E) nanowalls , and (F) nanodisks
Typical SEM and TEM image of different kinds of 3D NSMs, which is synthesized by several
research groups.
(A) Nanoballs (dendritic structures), (B) nanocoils , (C) nanocones, (D) nanopillers , and (E)
nanoflowers
During the past decade, the clusters stabilizing Pt nanoparticles
have attracted a considerable interest as catalysts for low
temperature fuel cell devices, such as polymer electrolyte fuel
cells (PEMFCs)and direct methanol fuel cells (DMFCs). The
clusters stabilizing Pt nanoparticles are formed in order to
maximize the active number of surface versus the inactive
number of Pt bulk atoms. However, one of the major problems
associated with the clusters stabilizing Pt catalysts are their
stability in the acid environment of DMFCs and PEMFCs. This is
because of after only 100 h of testing the reaction rate dropped
to half in such fuel cell devices. During this process the CO-ads
species were continuously formed, which strongly absorbs to the
clusters stabilizing Pt active sites to poison the fuel cell
performance devices.
Due to these problems of the clusters stabilizing Pt nanoparticles, researchers decided to
investigate the bimetallic clusters and colloids with nanometer-scale dimensions for fuel cell
device applications.
There are two main reasons for using the bimetallic clusters and colloids with nanometer-
scale dimensions, firstly, because they may serve as models for studying the formation of
different alloy catalysts.
Secondly, it is possible to save precious metal, such as Pt, by optimizing the synthetic
conditions so that only very thin surface layers occur . In most cases, Pt and Pt-based alloy
nanoparticles are used in the form of small nanoparticles, since small size offers high
surface area which is especially crucial for catalysis and fuel cell applications
A very recent report by Tiwari et al. showing perfect Pt nanocubes
had much higher electrocatalytic activity and stability for methanol
and ethanol oxidation than other nanostructures such as truncated
Pt nanocubes, truncated Pt (cubes + tetrahedra) and spherical Pt
nanoparticles.

Wang et al. reported the controlled synthesis of dendritic Au@Pt

core–shell nanomaterials.

Chen et al. synthesized the Co–Pt catalyst with a hollow sphere

structure via a very simple thermolytic reaction. The Co–Pt hollow
sphere catalyst showed the high surface area with a comparison to
the pure Pt nanoparticle catalyst and Co–Pt nanoparticles . In
addition, the Co–Pt hollow sphere catalyst showed enhanced
electrocatalytic activity for methanol oxidation with a comparison
to the pure Pt nanoparticle catalyst and Co–Pt nanoparticles at the
same Pt loading.
 1D NSMs

In the last few years, attention has been shifted towards the synthesis
of 1D NSMs because of their fundamental importance and potential
applications in fuel cells. To date, 1D NSMs (such as nanowires,
nanorods, nanobelts, and nanotubes) have been most extensively
studied because of their simplicity in preparation and its improved
catalytic properties as compared to bulk metallic materials

Ksar et al. fabricated the Pd nanowires in a hexagonal mesophase (as

soft templates) by electron beam irradiation. They also reported that
the average lengths of the Pd nanowires are controlled by the
amount of co-surfactant that assists the reduction/growth processes.
In addition, the electrochemical studies indicated that the Pd
nanowires had a very good electrocatalytic activity and stability for
ethanol oxidation.
Liu et al. prepared the nanoporous Pt–Co alloy nanowires by dealloying
electrodeposited by dealloying Pt-Co nanowires and examined their
electrochemical properties Pt–Co nanowires (15 h) had a superior
tolerance against CO poisoning.

In addition, nanoporous Pt–Co alloy nanowires exhibit an enhanced

electrocatalytic activity toward methanol oxidation (in comparison to
state-of-the art Pt/C and PtCo/C catalysts).
 2D NSMs
2D NSMs such as junctions (continuous islands), branched
structures, nanoprisms, nanoplates/ nanosheets, nanowalls, and
nanodisks are an especially promising form of nanoscale with a
rare combination of extremely high specific surface area,
exceptional thermal/electrical conductivity and stability

The utilization of 2D NSMs as a support to anchor catalyst

nanoparticles and facilitate electron transport opens up interesting
new possibilities for designing and building of next generation
catalysts for fuel cells. In addition, 2D NSMs can avoid aggregation and
maintain high specific surface areas; these factors are important in
increasing the accessibility of adsorbates to reactive sites
Li et al. fabricated the close-packed Au nanoprism thin films on the indium tin
oxide coated glass substrates. Au nanoprism are single crystalline, whose basal
surfaces are atomically flat {111} planes and lateral surfaces are {110} planes. A small
amount of Pt or Pd was deposited onto the Au nanoprism thin film electrodes and
studies their catalytic properties. They noticed that the Pt on Au nanoprism exhibited
greatly enhanced catalytic activity toward the oxidation of methanol and
much better CO poison resistance than commercial Pt-based catalysts

Wong’s group have synthesized Pd nanoplates array onto Au substrate by

electrochemical process.

the Pd nanoplate’s array electrode shows extraordinary electro-catalytic

activity towards the oxidation of methanol

Choi and Woo prepared a 2D Pt–Ru nanowire network using a SBA-15 nanoreactor and
showed that this nanostructured material displayed a higher performance than
commercial Pt–Ru (JM) in DMFC.
 2D continuous Pt island network on a flat Si substrate by
Tiwary group

This catalyst structure on the Si substrate has better electroactivity

toward methanol oxidation than the blanket Pt/Si and the Ru
decorated Pt film/Si electrodes. Recently many material scientists
and engineers have fabricated 2D graphene nanosheets as catalyst
supports for DMFCs

The electrochemical results of methanol oxidation indicate that Pt–

Ru/graphene nanosheets display excellent catalytic activity over
that of Pt–Ru/Vulcan. These results indicate that graphene
nanosheets could significantly increase the electrochemical active
surface area resulting in better catalyst utilization.
 3D NSMs

Compared to 0D, 1D, and 2D NSMs, the 3D NSMs hold a unique

morphology, which are expected to provide a larger surface area and to
facilitate the transport of reactants and products effectively, so that
electrochemical performance can be greatly improved.

Several research groups have fabricated 3D Pt nanoflowers as a catalyst

for fuel cell applications. Tong et al. prepared 3D Pt nanosheets
perpendicular to a boron-doped diamond (BDD) hybrid film surface,
synthesized by double template method
CVs of commercial Pt/C catalyst, Au–PF/Pt and the Au–PF/Au/Pt electrodes
in a 0.1 mol dm3 HClO4 + 0.4 mol dm3 CH3OH solution at a scan rate of 50
mV s1.
Zhang et al. prepared 3D Pt nanoflowers via a template-
free, direct electrodeposition method.
This electrochemical experiment demonstrates that Pt
nanoflowers have superior performance in aspects of
electrocatalytic activity and stability towards the oxidation of
methanol.
 Energy Storage

Energy is useful only if available when and where it is wanted.

Carrying energy to where it is wanted is called distribution or

transmission;

Keeping it available until when it is wanted is called storage

Since the use of renewable energy supplies constitutes a diversion of
a continuing natural flow of energy, there are problems in matching
supply and demand in the time domain, i.e. in matching the rate at
which energy is used.

This varies with time on scales of months (e.g. house heating in

temperate climates), days (e.g. artificial lighting) and even seconds
(e.g. starting motors)

In contrast to fossil fuels and nuclear power, the primary input

power of renewable energy sources is outside our control

we have the choice of either matching the load to the

availability of renewable energy supply or storing the
energy for future use.
Energy can be stored in many forms, i.e. chemical,
heat, electric, potential or kinetic energy.
 Electrical storage: batteries and accumulators

A device that has electricity both as input and output is called an

(electrical) accumulator or (electrical) storage battery. Batteries
are an essential component of most autonomous power systems
(especially with photovoltaic and small wind turbine generation),
of standby and emergency power systems, and of electric
vehicles.
 The lead acid battery

Although many electrochemical reactions are

reversible in theory, few are suitable for a
practical storage battery, which will be required
to cycle hundreds of times between charging and
discharging currents of 1–100A or more. The
most widely used storage battery is the lead acid
battery
As in all electrochemical cells, there are two electrode ‘plates’
immersed in a conducting solution (electrolyte).

In this case the electrodes are in the form of grids holding pastes of
lead (Pb) and lead dioxide respectively; the pastes are made from
powders to increase surface area in ‘spongy’ form.

Electrodes shaped as tubes give added mechanical strength and resist

‘shedding’ , and so are suitable for deep discharge
 The electrolyte is sulphuric acid, which ionises as follows:

During discharge, the reaction at the negative electrode is

The electrons so liberated travel through the external circuit

to the positive electrode, where they contribute to the
reaction:
The electrical current through the solution is carried by H+ and HSO−4
ions from the sulphuric acid electrolyte, which themselves take part
in the plate reactions.

Transportable ‘gelled cells’ have this electrolyte immobilised in

pyrogenic silica, with the fibrous glass mat separator giving open gas
paths for the release of hydrogen and oxygen in overcharge.

Although this makes them relatively expensive, they are safer to use
and transport, since there is no danger of spilling highly corrosive
sulphuric acid, and are ‘maintenance free’.
The theoretical cell-EMF at standard conditions for

Pb/PbSO4/H2SO4/PbSO4/PbO2 is cell = +1.92V

The actual cell EMF depends on the concentration of reagents,

and can be calculated by standard electrochemical methods. In
general, the open-circuit voltage of a cell differs by only a few per
cent from the theoretical cell voltage

In particular, lead acid batteries are produced at open-

circuit potential difference of 2.0V per cell.
In the specific case of the lead acid battery, the main reasons for
the ‘underachievement’ are:

A working battery necessarily contains non-active materials, e.g. the

case, the separators (which prevent the electrodes short-circuiting)
and the water in which the acid is dissolved. Moreover, the acid
concentration must not be too large, since the battery would then
discharge itself. Since the mass of actual battery contents exceeds the
mass of the active ingredients, the energy density based on the mass
of the whole battery is less than the theoretical value based on the
active mass alone.

However, this factor is not of great importance for stationary batteries.

The reactions cannot be allowed to go to completion. If all the lead
were consumed by reaction there would be no electrode left
for the reverse reaction to operate, i.e. the battery could not be
cycled.
Similarly, if the concentration of H2SO4 is allowed to reduce too
much, the electrolyte ceases to be an adequate conductor.
In practice, many battery types should not be allowed to discharge
more than about 50% of total potential stored energy, or they may
be ruined. However, specially designed batteries do allow ‘deep
discharge’ beyond 50%.
The other main factor limiting the life of even a well-maintained
battery is self-discharge of the positive electrode. This is particularly
acute in vehicle SLI (Starting, Lighting and Ignition) batteries in
which the grid is not pure Pb but usually a lead–antimony–calcium
alloy. Electrode plates with antimony are physically stronger and
better able to stand the mechanical stresses during motion.
Development of improved lead acid batteries still continues,
producing a variety of models with performance optimised for
different applications, in terms of reliability, long life, cost,
power/weight ratio, etc. Key developments over the last few decades
include polypropylene for inert leak-proof enclosures, ‘absorbent
glass mat’ technology for plate separators, valve regulated
lead acid batteries
 SEM (a) and TEM (b) image of nanostructured
lead oxide PbO

discharge capacity v.s. cycle number for the

nanostructured lead oxide
Supercapacitors
Supercapacitors represent an important component for energy
storage devices, particularly for short-acting high power batteries.
Batteries suffer from a relatively slow power delivery or uptake, faster
and higher-power energy storage systems are needed in a number of
applications, and this role has been given to the supercapacitors
The highest performance supercapacitors are currently based on NSMs, given that
increased electrode surface area improves the capacitance. It is the reason why so
many researchers have been involved in working on different kinds of NSMs.

In brief, supercapacitors are formed by two polarizable electrodes, a separator and

an electrolyte. They utilize double layer capacitance where the ions of the
electrolyte are adsorbed on the charged electrode, resulting in a Helmholtz layer

The Helmholtz double layer thickness is defined as half the diameter of the
adsorbed solvated ions at the electrode/solution interface

The power density of supercapacitors is lower than that of batteries. Therefore,

the development of supercapacitors aims to improve the power density and
significantly reduce cost. These electrochemical devices are also known as
ultracapacitors, pseudo capacitors, and double layer capacitors.
 0D and 1D NSMs
Initially researchers synthesized NSMs with zero-dimensional atomic clusters (quantum dots) for
supercapacitors. Atomic clusters, nanoparticles, filaments and similar spatially confined molecula
systems are defined as zero modulation dimensionality (0D or more correctly quasi-zero
dimensional) and possess an aspect ratio from one to infinity. Atomic clusters are spherical and
composed of several thousands atoms. However, the possibility of designing atomic clusters is no
very promising at present.

Two major problems still exist in the synthesis of atomic clusters. First, it is difficult to produce
mass-selected clusters in large quantities.

Secondly, to make atomic cluster materials, one has to consider other cluster–cluster interactions
and make sure that this would not lead to coalescence of clusters that would change its original
physical and chemical characteristics.

However, well-controlled and mass-producible atomic clusters will likely increase with more
advanced research and their applications in the future.
many research groups have found that electrode-active materials
with nanoscale crystalline particle size usually show better discharge life due to their high
specific surface areas. Additionally, nanoscale particles dramatically change surface
reaction rates, causing a dramatic improvement in power density when compared to
conventional capacitor. As a result, researchers have tried to develop some transition metal
oxides nanoparticles, such as hydrous IrO2, SnO2 , amorphous RuO2 , hydrous and
anhydrous crystalline RuO2 nanoparticles , for supercapacitor applications due to their high
pseudocapacitance charge-storage mechanism

The charge-storage mechanism of metal oxides {XO2 (X = Ir, Ru, Sn, Mn, etc.)} as proposed
is based on the novel concept of redox (oxidation–reduction) reactions associated with
the surface reac-tion and the insertion of metallic cations, for instance, H+, Li+, Na+, K+
into the metal oxides. The simple
reaction on charge-storage mechanism can be written as follows:

Where X and C+ represent the metal and proton or alkalimetal cation, respectively
The supercapacitive behavior of various metal oxides, such as RuO2 , IrO2 , NiOx MnO2 Ni3(-
Fe(CN)6)2(H2O) and SnO2 have already been evaluated. Among these materials, RuO2 (specific
capacitance 720 F g1) and IrO2 (specific capacitance 550 F g1) have been recognized as the most
promising candidates for supercapacitor electrodes due to their very large specific capacitance
values. The weakness of these nanoparticles are their low specific surface area; therefore
one of the key-issues to address increasing their specific surface area.

1D NSMs are able to solve the problem of specific surface area and thus improve the utilization
of electrode active materials.

Most recently, 1D MnO2 nanorods , Co3O4 nanorods, polyaniline nanowires , singleand

multi-walled carbon nanotubes , Li4Ti5O12 with nanotubes/nanowires , MnO2 nanobelts
, and c-MnO2 nanoneedles have been used.

These 0D and 1D NSMs still do not resolve the fundamental limitations of the materials
for next generation electrochemical supercapacitors. In addition, high material cost limits
the commercial use, so it is urgent to look for a substitute materials to replace RuO2.
 2D NSMs

2D NSMs dramatically change surface reaction rates and electrical transport

throughout the material, causing a dramatic improvement in specific power density
when compared to conventional capacitor.

Recent reports by various groups have shown that 2D NSMs (such as nanosheets,
nanobelts, nanowalls, nanofibers, and nanoplates) enhance the average specific
capacitance

A direct synthesized single-crystalline Ni(OH)2 hexagonal nanoplates on lightly oxidized

graphene nanosheets exhibit a high specific capacitance of 1335 F g1 at a charge and
discharge current density of 2.8 A g1 and 953 F g1 at 45.7 A g1 with remarkable cycling
ability .
Fabricated PANI nanobelts onto a conducting substrate via an electrochemical route.
These PANI nanobelts on conducting substrate showed large capacitances of 873 F
g1 at 10 mV s1 and excellent stability over 1000 cycles.

Recently, Wu et al. prepared composite films of chemically converted graphene (CCG)

and PANI nanofibers (PANI-NFs) and applied them as electrodes for supercapacitors.
They found that the conductivity of the composite film is about 10 times that of a PANI-
NF film. This conductive composite film showed a large electrochemical capacitance
(210 F g1) at a discharge rate of 0.3 A g1.

Moreover, the electrochemical capacitances are much higher than those of

supercapacitors based on pure CCG or PANI-NF films, mainly due to the synergic effect
of both components. This means 2D NSMs exhibit high specific capacitance and
remarkable rate capability as well as promise for applications in supercapacitors with
both high energy and power densities. The weakness of these 2D NSMs are their low
specific surface area, therefore, present research and development for these materials
are focusing on increasing their specific surface area.
 3D NSMs

3D NSMs may not only improve surface reaction rates, chemical stability, and electrical
transport,but also greatly enhance the specific surface area throughout the material,
causing a dramaticimprovement in storage capacity when compared with the 2D based
supercapacitors

Recently, Liu et al. prepared hybrid supercapacitor electrodes by coaxially coating

manganese oxide on a vertically aligned carbon nanofiber array . These ordered core–shell
nanostructures have a very large surface area, which is 10 times higher than that of the
flat surface. This large surface area offers a highly conductive and robust core for reliable
electrical connection to the MnO2 shell, which ensures the rapid completion of the redox
reactions and offer easy electrolyte access to a large-volume of active electrode materials.
The specific capacitance value of core–shell nanostructure in a 0.10 M
Na2SO4 aqueous electrolyte is 365 F g1.
Kim et al. synthesized 3D vertically aligned CNTs onto
conductive carbon papers and applied them as electrodes for supercapacitors.
Remarkable supercapacitor properties were obtained by using the directly
integrated, naturally patterned, and vertically aligned CNTs. The specific
capacitance, energy, and power density were 200 F g1, 20Wh kg1, and 40 kW kg1
respectively

Hence, the 3D nanostructured electrode materials that boost high surface area exhibit
good chemical stability, and have an ordered macro-porous structure increases the
electrode/electrolyte interfacial area and facilitate ion transfer in the system with
improved storage capacity. Moreover, we believe that 3D NSMs are able to resolve
fundamental limitations of materials for next-generation scaling of advanced
supercapacitors devices.
 Superconducting electromagnetic energy
storage (SMES)

A superconducting electromagnetic energy storage (SMES)

system is a device for storing and very quickly discharging
large quantities of electric power, e.g. 10MW for <1 s.

It stores energy in the magnetic field created by the

flow of DC in a coil of superconducting material that has
been cryogenically cooled to ∼4K).

At these very low temperatures, certain materials have

essentially zero resistance to electric current and can
maintain a DC current for years without appreciable loss.
SMES systems have been in use for some years to improve industrial
power quality and to provide a premium quality service for those
electricity users who are particularly vulnerable to voltage
fluctuations. An SMES recharges within minutes and can repeat the
charge/discharge cycle thousands of times without any degradation
of the magnet.

Although there have been proposals to use SMES more generally for
storing large amounts of electrical energy, the cost appears to be
prohibitive
First SC device in a grid
Some HTS SMES
 Li–ion batteries

Li-ion batteries consist of a three primary functional components. The

main components of a Li-ion battery device are the positive electrode,
negative electrode and the electrolyte, for which a variety of materials
may be used.

Generally, the most useful material for the positive electrode is one of
three materials: lithium cobalt oxide, lithium iron phosphate, or a
spinel such as lithium MnO2.

On the other hand, the most common materials for the negative
electrode are carbon based compounds and lithium- containing alloys.
Upon charging, lithium ions are extracted from the positive electrode material and inserted
into the
negative electrode material. Upon discharging, the reverse process takes place. Common
batteries
should exhibit three characteristics: (a) high energy and power capacity, (b) high charging
rate, and
(c) long lifetime (cycling stability). Although Li-ion batteries are available commercially, the
performance
of Li-ion batteries is limited by the current electrode and electrolyte materials. For future
generations
of rechargeable Li-ion batteries, not only for applications in portable electronic devices but
especially for clean energy storage and use in hybrid electric vehicles, further improvements
of materials
are essential. We need to find new, efficient and effective ways to improve the physical and
chemical characteristics of the materials for use in electrochemical Li-ion batteries
One avenue that is opening up is that of NSMs for electrochemical Li-ion batteries devices.
However, the selection of NSMs for use as negative electrode, positive electrode, and
electrolyte, as well as their voltage, capacity, life, and safety abilities in electrochemical Li-ion
battery devices can dramatically improve. Recently, great efforts have been made toward the
development of improved electrolyte, negative and positive electrodes materials

It has been demonstrated that the morphology of nanostructures can be optimized to achieve
higher energy and charge densities in electrochemical Li-ion battery devices. Therefore,
nanoarchitecture is another consideration that can be optimized for further improvement. In
this regard, research on . NSMs is expanding rapidly into the assembly of nanoparticles in 0D
and 1D structures.
Recently, some research groups have tried to synthesize 0D nanoparticles to avoid the
problem of poor Li+ ion diffusivity and electron conductivity, which would eliminate either metal
doping or carbon coating.

0D nanoparticles with high-crystallinity are particularly advantageous when the aim as above
mentioned is to achieve faster lithium-ion diffusion. They also display a better rate capability,
which indicates its possible use in electrochemical Li-ion battery devices.

However, 0D NSMs are not very stable and very difficult to make in large quantities. Various
efforts have been implemented to synthesize novel 0D NSMs but have been met with very
limited success in the improvement of electrochemical Li-ion battery device performance.
Due to this, researchers have fabricated new 1D NSMs that will make electrochemical Liion
battery devices more efficient due to their unique mechanical, thermal, electrical properties
and structural versatility. Various efforts have been made by the scientific community to
fabricate novel 1D NSMs such as nanotubes, nanorods, and nanobelts . The figure bekow
shows the schematic diagram of a Li+ ion pathway in 1D NSMs.
They also constructed a full cell composed of a LiCoO2 cathode and a car-bon–
silicon core–shell nanowire anode. Significantly, using these core–shell nanowires
they achieved high mass loading and an area capacity of 4mA h cm2.

Importantly, the capacity of a Li-ion full cell consisting of a cathode of LiCoO2 and anode
of Si nanotubes shows a higher capacity than commercially available graphite even after
200 cycles. However, a new problem arose for 1D NSMs are low surface area and slow
diffusion rates. Due to low surface area, slow diffusion rates and poor conductivity, 1D
NSMs show the poor energy density and poor rate capacities. Consequently,
improvement in surface area to volume ratio, diffusion rates and conductivity is
necessary.
 2D NSMs

2D NSMs are a useful approach to improve the electrode performances in higher overall
capacity, high-rate capability, and longer cycling life. 2D NSMs normally exhibit small
crystalline size, high surface area, large surface-to-volume ratio, and favorable structural
stability over 1D, and 0D NSMs. The development of a 2D nanostructure gives the right
structure necessary for a fast mass transport, for instance.

Recently, Zhou et al. synthesized a Si/TiSi2 heteronanostructure on Ti foil in a CVD

chamber with TiCl4, SiH4 and H2 as precursors. The Si/TiSi2 heteronanostructure
was used as an anode material for Li+ batteries. In this heteronanostructure, Si
nanoparticles acts as an active component to store and release Li+ while TiSi2
serves as the inactive component to support Si and to facilitate charge transport.
The Si/TiSi2 heteronanostructures show fast and superior charge/discharge
capacities.
 3D NSMs
In order to further achieve higher energy and charge densities in
electrochemical Li-ion battery devices, 3D nanostructured
electrodes may be needed. As 3D NSMs electrode have a higher
surface area, larges surface-to-volume ratio, and more favorable
structural stability over 2D, 1D, and 0D NSMs. The 3D NSMs can
be flooded with electrolyte, ensuring a high specific surface area
in contact with the electrode and hence a high flux of Li+ ion
across the interface.

The nanowalls between the NSMs, of equal dimensions

throughout, ensure very short diffusion paths for Li ions on
intercalation and deintercalation, and hence homogeneous rates
of transports.
An excellent reversible capacity was obtained for these
MnO2/CNT nanotube array electrodes. The coaxial
MnO2/carbon nanotube arrays offer the following
advantages: (a) presence of carbon nanotube improves the
electrical conductivity
(b) homogeneous electrochemical accessibility and better
ionic conductivity is achieved by avoiding agglomerative
binders and other additives
(c) well-directed coaxial alignment provides a better
conductive path

(d) MnO2/CNT hybrid nanostructures offer a unique dual-

binding mechanism of lithium storage (insertion–deinsertion
in the case of carbon nanotubes and formation and
decomposition of Li2O in the case of MnO2 nanotubes).
The use of 3D NSMs is increasing rapidly in the field of Li-ion battery devices because of
their substantial
advantages in terms of mass transport. Transport in 3D NSMs typically encompasses
shorter
transport length for Li+ ions and electrons, better electrode–electrolyte contact area, and
great merits
to permit reproducible Li+ insertion and extraction. This verifies their promising application
as electrode
materials for Li-ion batteries.
Hydrogen Storage
• Physical storage of H2
•Compressed •Metal Hydride
•Cryogenically liquified •Carbon nanofibers

• Chemical storage of hydrogen

•Sodium borohydride •Methanol

•Ammonia •Alkali metal hydrides
• Physical storage of H2

• Chemical storage of hydrogen

• New emerging methods

The current hydrogen market is, dominated by uses for oil
refining, food production, metals treatment, and fertilizer
manufacture. Power production uses relatively little of
the hydrogen, perhaps on the order of 10-20 million
kilograms per year in the US, or about 0.1% of the total
Hydrogen Storage Technologies
Gaseous Hydrogen
The most traditional way of storing hydrogen is in the gaseous form
in pressure vessels. Since hydrogen behaves very much like an ideal
gas in the ambient temperature (and the temperatures below) it
satisfies the ideal gas law PV = nRT ,

where n is the amount of hydrogen in moles and R is the gas

constant
Gaseous hydrogen can be stored either in aboveground portable or
stationary containers or in different kinds of earth caves.
For a given volume and temperature the energy density of storage is
increased when increasing the pressure of storage vessel. The only
problem of this is the safety features and regulations that limit the
allowable pressure.

One of the best properties of pressure vessels is that they do not

leak. The losses of the storage capacity are thus virtually non-
existent . Some leaks may occur through connectors but with proper
fittings and regulators these leaks can be minimized.

The most common hydrogen storage systems can withstand the

pressure of 20 MPa, while light weight composite cylinders can
withstand the pressure up to 80 MPa . When hydrogen is stored at
such high pressures, very thick wall tank has to be used.
 Compressed
•Volumetrically and Gravimetrically inefficient, but
the technology is simple, so by far the most common in
small to medium sized applications.
1. Research on material embrittlement, using new ad hoc
fracture mechanics techniques.
2. Development of stronger and lower cost construction
materials, especially carbon fibers.
3. Development of an efficient and clean (without oils) high
pressure compressor.
 Liquid H2 (Cryogenic)
Cryogenic hydrogen, usually simply referred to as liquid hydrogen (LH2),
has a density of 70.8 kg/m3 at normal boiling point (-253C). (Critical
pressure is 13 bar and critical temperature is –240°C). The theoretical
gravimetric density of LH2 is 100%, but only 20 wt. % H2 of this can be
achieved in practical hydrogen systems today

On a volumetric basis the same respective values are 80 kg/m3 and 30

kg/m3. This means that liquid hydrogen has a
much better energy density than the pressurized gas solutions
mentioned above. However, it is important to recall that about a 30-
40% of the energy is lost when LH2 is produced. The other main
disadvantage with LH 2 is the boil off losses during dormancy, and the
fact that a super insulated cryogenic container is needed.
 Liquid (Cryogenic)

•Gravimetrically and volumetrically efficient but very costly to compress

Hydrogen in the liquid form is used widely as a
principal fuel in space programs due to its high
volumetric density (70.8 kg/m3)

Liquid hydrogen has been demonstrated in commercial

vehicles (particularly by BMW)
The main R&D tasks are

1.Develop more efficient liquefaction processes.

2. Lower costs and improve the insulated
containers.
3. Develop systems that automatically capture the
boil off and re-liquefy the fuel
 Metal Hydrides
•Technically a chemical reaction, but
acts like a physical storage method
•Hydrogen is absorbed like in a
sponge.
•Operates at 3-30 atm, much lower
than for compressed gas tanks
•Comparatively very heavy, but with
good volumetric efficiency, good for
small storage, or where weight
doesn’t matter
Metal hydrides are composed of metal atoms that constitute of
a host lattice and hydrogen atoms that are trapped in
interstitial sites, such as lattice defects. The trap site can be a
vacancy or a line defect. In the case of a line defect, a string of
hydrogen atoms may accumulate along the defect. Such a
string increases the lattice stress, especially if two adjacent
atoms recombine to form molecular hydrogen.

Since adsorption of hydrogen increases the size of lattices , the

metal is usually ground to a powder
There are two possible ways of hydriding a metal, direct
dissociative chemisorption and electrochemical splitting
of water. These reactions are, respectively

where M represents the metal. In electrochemical splitting there has to be a catalyst,

such as palladium, to break down the water
As a hydrogen molecule approaches the metal surface, weak van Der Waal’s
forces begin to act upon it drawing it closer. The molecule reaches the potential
well Ep at distance zp, and very large forces would be required to force it any
closer the surface in a molecular form. However, the dissociation energy of
hydrogen molecule is exceeded by the chemisorption energy. Thus the
hydrogen molecule dissociates and individual hydrogen atoms are attracted to
the surface by chemisorptive forces and they reach the potential well ECH. From
this point sometimes even the ambient temperature’s thermal energy is enough
to increase the vibrational amplitude of hydrogen atoms which can thus reach
and enter the metal surface
Metal and hydrogen usually form two different kinds of hydrides, a-
phase and b- phase hydride. In a-phase there is only some hydrogen
adsorbed and in b-phase the hydride is fully formed. For example,
Mg2Ni forms hydrides of Mg2NiH0.3 and Mg2NiH4

A study of nano-scaled particles shows that when the metal grains are in
the range of 5 to 50 nm, the kinetics of both absorption and desorption is
improved by an order of magnitude because of improved thermal
conductivity

Hydrogen is a highly reactive element and is known to form hydrides

and solid solutions with thousands of metals and alloys
Hydrogen in Carbon Structures
Hydrogen can be stored into the nanotubes by chemisorption or
physisorption. The methods of trapping hydrogen are not known very
accurately but density functional calculations have shown some
insights into the mechanisms .

Calculations indicate that hydrogen can be adsorbed at the exterior of

the tube wall by H-C bonds with a H/C coverage 1.0 or inside the tube
by H-H bonds with a coverage up to 2.4 as shown in Figure .

The adsorption into the interior wall of the tube is also possible but
not stable. The hydrogen relaxes inside the tube forming H-H bonds.

The numbers in the figure tell the bond lengths in 10-10 m.

Hydrogen adsorption in a nanotube. a) exterior adsorption with H/C coverage 1.0,
b) interior adsorption with coverage 1.0, c) interior adsorption with coverage 1.2,
d) interior adsorption with coverage 2.4
Multi-walled nanotubes, in which two or more single
tubes are rounded up each other with van Der Waal’s
attraction, can adsorb hydrogen between the single-wall
nanotubes.

The hydrogen causes the radius of the tubes to increase

and thus makes a multi-walled nanotube less stable . In
nanotube bundles hydrogen can also be adsorbed in the
middle of different tubes
Recent results on hydrogen uptake of single-walled nanotubes
are promising. At 0.67 bar and 600 K about 7 wt% of hydrogen
have been adsorbed and desorped with a good cycling stability .
Another result at ambient temperature and pressure shows
that 3.3 wt% can be adsorbed and desorped reproducibly and
4.2 wt% with a slight heating.
Even though the price of the nanotubes is still high they
have a good potential in storing hydrogen. When the
manufacturing techniques are improved and some
engineering problems solved, they may be highly
competitive against other hydrogen storage technologies.

There are also some other forms of carbon that adsorb hydrogen.
These are graphite nanofibers, fullerenes, and activated carbon.
Compare with palladium decorated carbon nanotubes
The increase in hydrogen storage capacity in palladium decorated
carbon nanotubes is due to 2 mechanisms;
Pure CNT

1. Adsorption of the hydrogen molecules on the

surface and interior regions of CNTs.
2. Dissociation of H2molecules on the palladium
particles and atomic H spills over to the spaces
between adjacent carbon layers of CNTs
 Cycle stability
Besides the high storage capacity and reversibility of the hydrogen storage, the storage
medium has to be stable under repeated hydrogenation/dehydrogenation cycles.

This stability is largely determined by the microstructure and chemical changes during the
hydrogen absorption and de-sorption process.

The combination of temperature, pressure, hydrogen absorption/desorption (expansion

and contraction) can result in a change in microstructure and chemical composition of
the storage material which in combination with the sensitivity to oxidation and
contamination makes the cycle stability one of the more difficult targets to achieve.

For metal – hydride based batteries, metals (or combinations of) like Ce, La,Nd, Pr and
metal oxides like Cr2O3, Al2O3 and CeO2are often used to improve the cycle stability . For
this reason these types of materials are also considered for improving the stability of the
hydrogen storage materials .

A good cycling stability is reported for over-stoichimetric La(Ni,M)5+x (with M = Mn, Cu) .
In addition one also has to keep in mind that the depth of hydrogen charge and discharge
are of considerable influence on the cycle stability of the storage material.
 Chemical storage
The technology is based on a very simple redox reaction of magnetite

Fe3O4 must first be reduced with hydrogen at suburban

H2production plants or at residential gas stations.

Step 1: chemical H2storage.

Fe3O4+4H2→3Fe+4H2O
Then, the reduced iron oxide (mainly Fe) is packed in cassettes. The cassettes will be
transported to the gas stations and be mounted on PEFC vehicles. Addition of water
into the cassettes would produce pure hydrogen and regenerate Fe3O4according to
equation below.

The hydrogen could be supplied directly to the PEFC on the vehicles without any
purification treatment for CO.

Step 2: H2recovery.
3Fe+4H2O→Fe3O4+4H2
The cassettes with Fe3O4 after water decomposition are to be
exchanged for the new ones packed with Fe at residential gas
stations or service stations. The used Fe3O4should
be recycled many times. According to the equation the theoretical
amount of hydrogen being chemically stored is 4.8 wt.% of Fe
 Chemical hydrogen storage: hydrogen generation from
ammonia borane
Generation of hydrogen from suitable carriers is a safe alternative to hazardous
physical hydrogen storage. In this regard, boron hydrides with high gravimetric
content of hydrogen are considered to be promising materials as carriers of
hydrogen for portable applications

Ammonia borane (H3N·BH3, AB) with 19.6 wt% of hydrogen has been attracting
immense interest as a hydrogen storage medium in recent years

It possesses a volumetric density of 146 g H2/lit and a gravimetric density of 196 g

H2/kg. These values are well above the US Department of Energy targets (2015) of a
volumetric density greater than 82 g H2/lit and a gravimetric density greater than 90
g H2/kg
Ammonia borane is a stable white solid and a safe material to handle under
ambient conditions, which makes it very attractive for practical applications.
Ammonia borane was first synthesized by Shore and Parry in 1958 using
NaBH4and NH4Cl in ether solvent

Release of hydrogen from AB can be accomplished either by thermolysis (neat or

metal catalyzed) in the solid state and non-aqueous medium (ethereal solvents) or
metal catalyzed reactions in solvents (water and methanol)
In early 2010, Honda Motor Company in Torrance, California opened a new more
compact and efficient solar-hydrogen refueling station. Pictured below , the new station
is designed to demonstrate what could be envisioned at the household level, where solar
PV panels would be used to produce the electricity needed for hydrogen production
through electrolysis. The system uses a 48-panel, 6-kilowatt solar PV system.

Honda’s New Solar Hydrogen Fueling System (Source: Honda Motor Company, 2010)
Electrolysis of Water Electrolysis is the
process by which water molecules are split
directly into hydrogen and oxygen molecules
using electricity and an electrolyzer device.
The overall electrolysis reaction is:

The two most common types of electrolyzers

are alkaline (use a potassium hydroxide
electrolyte) and PEM (use a solid polymer
membrane electrolyte). A schematic of an
alkaline electrolysis system is provided in
Figure. The electrolysis reaction produces
pure oxygen as a by-product along with pure
hydrogen. The oxygen can then be used for
productive purposes such as enriching the
oxygen content of greenhouses for food
production.
 The requirements for effective on-board
hydrogen storage are

1) Appropriate thermodynamics (favourable enthalpies of hydrogen

absorption and desorption)
2) Fast kinetics (quick uptake and release)
3) High storage capacity (specific capacity to be determined by usage)
4) Effective heat transfer
5) High gravimetric and volumetric densities
6) Long cycle lifetime for hydrogen absorption/desorption
7) High mechanical strength and durability
8) Safety under normal use and acceptable risk under abnormal
conditions
9) Cheap components and materials
From literature it is clear that to meet the requirements for hydrogen storage, the
current status of the technology is insufficient.

For example to give an idea about the system requirements,

to drive with an average car 100 km one needs 3 litre of
gasoline (2.21 kg) (energy density gasoline 12.7 kWh/kg) for
an average car. This is equivalent with 0.84 kg of hydrogen
(energy density 33.3 kWh/kg)

To store this amount of hydrogen in for example LaNi 5(weight percentage of 1.4
wt.%), one needs 300 kg of metal-hydride material. Besides the weight problem
also the heat development during hydrogenation is important. For an enthalpy of
formation of ∆H = -35kJ/mol H2 , the heat release during a 3 minute refilling timeis
405 kW.
some important questions that need to be considered for practical applications are:
1) Does hydrogen physisorb or chemisorb?
2) Does it bind molecularly or dissociatively?
3) Where does the hydrogen reside?
4) What is the nature of its hydrogen diffusion mechanism?
5) What are the activation barriers for hydrogen desorption?

6) What adverse effect does hydrogen have on the structural and mechanical
stability of the host material?
7) What is the nature of bonding of hydrogen with host atoms — ionic, covalent, or
metallic?
8) What roles do surface morphology and defects play in hydrogen absorption and
de-sorption?
9) In what ways is it beneficial to store hydrogen in novel materials, such as nanos-
tructures and porous materials?
10) How do catalysts help in reducing the operating temperature and pressure for
hy-drogen uptake and release?
High pressure hydrogen storage

For gaseous hydrogen storage under high pressure there are some techniques like steel
tanks, composite tanks, glass spheres etc. The most matureand promising technique are
the carbon-fibre-wrapped hydrogen composite storage tanks. These tanks are available,
safety-tested, simple of construction and can contain pressures up to700 bar (6.7 wt.%).
There are already several pilot applications in the world today using this technique, but
high pressure storage has some disadvantages. The large physical volume required (does
not meet the volumetric target), high costs and safety issues are still under investigation
and discussion. Furthermore, as the storage capacity of a composite tank is limited by the
molecular interaction of the hydrogen, an increase in pressure is not proportional to an
increase in storage capacity at higher pressure
Another restriction is the considerable energyloss during pressurization of the hydrogen gas
which is typically in the order of 12 – 16 % for compression to 800 bar (depending on the
type of compression)
It might be the simplest way to store hydrogen in a cylinder of pressure up to 20
MPa,but the energy density is too low to satisfy the fuel demand of driving practice.

About four times higher pressure is needed to meet the driving purpose, however,
such industrial cylinders have not been commercially available.

Industry sets up a goal to manufacture cylinders capable of withstanding pressure up

to 70 MPa with a weight 110 kg to reach a gravimetric density 6%; and volumetric
density 30 kg/m3

The hydrogen density as such is remarkably lower than the cryo adsorption method,
and the high cost of compression and the cylinder might hinder the method to be
accepted commercially.
 Physisorption

The storage of hydrogen can rely on physisorption because the adsorbed gas can be
released reversibly. There are different mechanisms of adsorption depending on the
geometry of the adsorbent and the temperature of adsorption. Multilayer mechanism
functions if the adsorption happens on an open surface and volume filling would happen in
a pore narrower than 2 nm. Capillary condensation could happen in a pore larger than 2 but
smaller than 50 nm. Adsorption in a pore larger than 50 nm is the same as that on open
surfaces. However, all the mechanisms here mentioned assume the possibility of
condensation of the adsorbed adsorbates. Such possibility does not exist at above-critical
temperatures; therefore, a different mechanism of adsorption must assume. There is only
one mechanism for the adsorption of supercritical gases on any kind of adsorbents, that is
the monolayer surface coverage.
The single mechanism corresponds to the single type of isotherms of supercritical
adsorption. This argument can be proved on considering the well-known BET theory of
adsorptio. According to BET, the first molecular layer of adsorbate is fixed on the solid
surface due to the interaction between gas and solid.
When the surface was completely covered with a layer of adsorbate, more gas molecules
would be adsorbed above the first layer due to the interaction between the same species
of adsorbate molecules forming the second layer, and so on for the subsequent layers. The
interaction force received by the first layer molecules is, thus, different from that received
by the second and subsequent layers. This difference must be reflected in the heat of
adsorption of different layers. The experiment with nitrogen and carbon black[3]showed
that the heat of adsorption of the first layer is 11–12 kJ/mol (0.11–0.12 eV) and it drops to
the latent heat of condensation, 5.56 kJ/mol (0.058 eV) in the subsequent layers.

Obviously, the subsequent layers from the second cannot exist at above-critical
temperatures, otherwise a classical law of physics, i.e. gas cannot be liquefied at above-
critical temperatures no matter how high pressure applied, would be false.

The monolayer adsorbate is itself fixed by a weak interaction; therefore, significant

physisorption is only observed at relatively low temperatures.
 Metallic hydrides
Some metals and alloys absorb hydrogen and form hydrides. There are two classes of
hydrides: metallic hydrides and complex hydrides. The main difference between them is
the transition of metals to ionic or covalent compounds for the complex hydrides upon
absorbing hydrogen. Some of the metallic hydrides of interest for the storage purpose are
listed in table. The prototype metallic hydrides are composed of two elements. The
A element is usually a rare earth or an alkaline earth metal and tends to form a stable
hydride. The B element is often a transition metal and forms only unstable hydrides.
Nickel is often used as B element since it is an excellent catalyst for the hydrogen
dissociation.
Some metal hydrides absorb and desorb hydrogen at ambient temperature and near the
atmospheric pressure, and the volumetric density of the hydrogen atoms present in the host
lattice is extremely high. A volumetric density of 115 kg/m 3 was reached in LaNi5H6.

However, all the reversible hydrides working around ambient temperature and
atmospheric pressure consist of transition metals; therefore, the gravimetric hydrogen
density is limited to less than 3 wt%, for example, the gravimetric density of hydrogen in
LaNi5H6is only 1.4%. Recent attention turns to the hydrides formed by light metals, and
Mg becomes the focus.

The formation of metal hydrides is an exothermic reaction. Significant heat is released during
absorbing hydrogen and the same amount of heat is required in order for hydrogen released
from the hydrides. More stable the hydride is, more heat is needed to desorb hydrogen. An
amount of energy approximately 25% higher than the heating value of hydrogen is needed for
the release of hydrogen from MgH2.

Although many efforts have been contributed to the Mg-based hydrides in recent years, it is
still a challenge to find out an appropriate hydride of light metals.
 Complex hydrides

Group I, II, and III elements, e.g. Li, Mg, B, Al, build a large variety of metal–hydrogen
complexes. The number of hydrogen atoms per metal atom is 2 in many cases.

This kind of complexes shows the highest volumetric density, 150 kg/m 3 ,in
Mg2FeH6and Al(BH4)3,and the highest gravimetric density at room temperature known
today in LiBH4(18 wt%).

NaAlH4 can reversibly absorb/desorb hydrogen at moderate temperatures; therefore,

received more attention . LiBH4 and NaBH4 are also on the list of candidates
. Some researchers thought complex hydrides as the promising solution of the
hydrogen storage problem may be because this group of material has not been well
studied with respect to the behavior as a hydrogen carrier.

The low dynamics of the hydrogen releasing process is a major problem. Unlike the
metallic hydrides, hydrogen is released via cascade decompositions from the complex
hydrides, and the step reactions call for different conditions. Therefore, there is a large
difference between the theoretical and the practically attainable hydrogen capacities.
Besides, significant changes in the particle morphology and elemental distribution were
induced by hydrogen desorption
Liquefaction

This method faces two challenges: the efficiency of the liquefaction process and the
boil-off of the liquid. The theoretical work necessary to liquefy hydrogen gas of room
temperature is 3.23 kW h/kg, but the technical work is about 15.2 kW h/kg, which is
almost half of the lower heating value of hydrogen. Gasification of liquid hydrogen
inside the cryogenic (21.2 K) vessel is an inevitable loss even with a perfect insulation
technique. The exothermic reaction of the conversion from ortho- to para-hydrogen
provides a heat source of the gasification. The heat of conversion is 519 kJ/kg at 77 K, and
523 kJ/kg at temperatures lower than 77 K, which is greater than the latent heat of
vaporization (451.9 kJ/kg) of normal hydrogen at the normal boiling point. The critical
temperature of hydrogen is very low (33.2 K), above which liquid state cannot exist.
Therefore, liquid hydrogen can only be stored in an open system otherwise the pressure in
a closed system can be as high as 1000 MPa at room temperature. So, the boil-off of liquid
means the emission of H2 into the atmosphere. The relatively large amount of energy
necessary for liquefaction and the continuous boil-off of liquid limit this storage system to
utilizations where the cost of hydrogen is not an important issue and the hydrogen is
consumed in a rather short time, e.g. air and space applications.
An other aspect is the purity of the used hydrogen gas. Hydrogen can be produced by several
techniques:
electrolysis of water (nuclear, renewable, conventional electricity), reforming processes
(natural gas, coal, oil, diesel, and biomass)and some new/future techniques (photoelectrical,
photobiological, thermal dissociation).

The hydrogen produced by these techniques requires purification, which impacts the
economical feasibility. Therefore in practical applications the hydrogen is not expected to be of
very high purity (>5N) and thus the storage materials need to be insensitive to these
impurities.

The effect of gas impurities (H2O, CxHy, H2S, etc.) on the hydrogen storage capacity and the
catalyst is often not considered as most research is performed under laboratory-conditions.

This implies small scale experiments under idealized conditions, no contaminations, and
identical hydrogenation experiments, small amounts of materials, etc. Therefore it is
interesting to investigate the mechanical stability, chemical stability, thermal conductivity and
cycle life, because real life applications will operate under non-idealized conditions. Also the
tolerance to impurities and contaminations, the adsorption/desorption kinetics under these
conditions are properties that need to be considered
Hydrogen storage is a key issue in the success and realiza-tion of hydrogen technology
and economy.
According to US DOE, the hydrogen-storage capacity target for commercializa-tion is
6.5wt% at the decomposition temperature between 60 and 120◦ C with high cycle life.

Although pure water contains 11.1wt% of hydrogen, its decomposition requires much
thermal, electric, or chemical energy

pressurizedH2gas and cryogenic liquidH2pose safety and per-meation problems along

with high cost, they do not meet future on-board applications goals set for hydrogen
economy. Solid state hydrogen fuel storage either absorption in the interstices
of metals and metallic alloys or adsorption on high surface area materials such as
activated carbons gain the attention for pos-sible future hydrogen applications.