i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 7 ( 2 0 1 2 ) 1 4 8 2 e1 4 9 4

Available online at www.sciencedirect.com

journal homepage: www.elsevier.com/locate/he

Review

Ammonia and related chemicals as potential indirect

hydrogen storage materials
Rong Lan a, John T.S. Irvine b, Shanwen Tao a,*
a
b

Department of Chemical and Process Engineering, University of Strathclyde, Glasgow G1 1XJ, UK

School of Chemistry, University of St Andrews, St Andrews, Fife KY16 9ST, UK

article info

abstract

Article history:

Energy production and combating climate change are among some of the most significant

Received 5 August 2011

challenges we are facing today. Whilst the introduction of a hydrogen economy has its

Received in revised form

merits, the associated problems with on-board hydrogen storage are still a barrier to

28 September 2011

implementation. Ammonia and related chemicals may provide an alternative energy

Accepted 2 October 2011

vector. Besides ammonia and metal amine salts, some other ammonia related materials

Available online 27 October 2011

such as hydrazine, ammonia borane, ammonia carbonate and urea also have the potential
for use as alternative fuels. These materials conform to many of the US DOE targets for

Keywords:
Ammonia

hydrogen storage materials.

Similar to hydrogen, ammonia itself is carbon-free at the end users, although CO2

Ammonium carbonate

emission on production of ammonia is dependent on the source of energy. Both hydrogen

Urea

and ammonia utilised similar energy sources for production: fossil fuels, biomass,

Hydrazine

renewable electricity, nuclear and solar energy.

Hydrogen storage

While a number of papers have been published on the catalytic decomposition of

ammonia or related chemicals to produce hydrogen, the use of fuel cells directly fed by

Fuel cell

ammonia and related chemicals would have a higher efficiency. In recent years significant
progress has been made on direct ammonia, hydrazine and urea fuel cells to generate electricity from these materials for transport applications. With the development and application
in these technologies, reduction of CO2 emissions in transportation would be possible.
In this review, we propose the use of ammonia and related chemicals as potential
indirect hydrogen storage materials. The progress on fuel cells using these fuels is also
briefly reviewed.
Copyright 2011, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights
reserved.

1.

Introduction

Combating climate change, a result of the release of greenhouse gases such as CO2, is an significant challenge for
researchers and the introduction of a hydrogen economy has

been one of the main strategies to reduce harmful emissions.

Globally about 23% CO2 emission originates from vehicular
waste gases through the combustion of fossil fuels [1]. The use
of hydrogen fuel cells to power electrical vehicles is expected
to have zero emission at the end user; however, on-board

* Corresponding author. Tel.: 44 (0) 141 548 2361; fax: 44 (0) 141 548 2539.
E-mail address: shanwen.tao@strath.ac.uk (S.W. Tao).
0360-3199/$ e see front matter Copyright 2011, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.
doi:10.1016/j.ijhydene.2011.10.004

i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 7 ( 2 0 1 2 ) 1 4 8 2 e1 4 9 4

hydrogen storage remains a big challenge despite the enormous efforts concentrated on the problem worldwide. In
general hydrogen can be stored using both physical and
chemical methods [2]. As for physical storage, liquid hydrogen
or compressed hydrogen are commonly used but both
methods have their own problems for efficient on-board
hydrogen storage due the large volume of compressed
hydrogen or the significant boil-off leaking of liquid hydrogen
[2]. Other solid hydrogen storage materials such as metal
hydrides, complex hydrides, organic-inorganic framework
etc. have been extensively investigated as potential hydrogen
storage materials, with a number of reviews detailing the
significant work in this area [2e10], but so far an ideal
hydrogen storage material which can meet the US DOE
requirements [11] is yet to be identified.
Hydrogen can also be stored indirectly in light hydrogencontaining chemicals such as ammonia, methanol or
methane, out of which ammonia provides the only carbonfree chemical energy carrier solution for the transportation
sector [12]. As shown in Fig. 1, in terms of energy density, only
ammonia and hydrides exhibit an energy density close to
fossil fuels such as coal and oil, much higher than compressed
hydrogen [13]. Nuclear reactions, i.e. fission and fusion exhibit
the highest energy density; however, nuclear power station is
more suitable for stationary power generation. Therefore,
potentially ammonia and related chemicals can be used as
excellent energy storage vector for on-board power
generation.
To the best of our knowledge, L. Green Jr. first proposed to
use ammonia as energy vector in 1982 [14]. L. Green Jr. proposed
to use heat from nuclear reactors to produce hydrogen before
synthesising ammonia through the HabereBosch process. The
synthesised ammonia is an ideal energy vector for low carbon
economy. Other ammonia-based materials such as hydrazine,
ammonia borane, metal ammine salts are also carbon-free at

1483

the end users. The use of ammonia as energy vector has several
advantages [15] such as low cost and ease of storage. Massproduction of ammonia based on the HabereBosch process is
a mature technology with over 100 million tons of ammonia
produced per annum around the world. As a basic agricultural
and industrial chemical, ammonia is routinely transported in
large tonnage by truck, tank car, barge, ship and pipeline [15].
Transmission and storage of ammonia is already a mature
technology requiring no additional development and its use as
an energy vector for transmission from a centralised production facility [14]. Ammonia is also a flexible energy vector as
hydrogen can be produced from ammonia for use in hydrogen
fuel cells, whilst ammonia and related chemicals can also be
directly utilised as fuels.
There are some chemicals containing both ammonia and
carbon such as ammonia carbonate, ammonia bicarbonate
and urea containing a large percentage of hydrogen by weight
which can be potential hydrogen carriers too. The CO2 emission issue in these chemicals depends very much on the
sources of carbon. The CO2 saving would be significant if the
carbon for the synthesis of these materials is sourced from
biomass or CO2 capture
Previous reviews have focused on the use of ammonia and
metal amine salts as an energy vector for the hydrogen
economy [12] and the generation of hydrogen from liquid
fuels such as ammonia borane, hydrazine and formic acid
[16e19]; however, other ammonia related chemicals such as
ammonia carbonate and urea can also be used for hydrogen
storage. In recent years significant progress has been made
on direct ammonia, hydrazine and urea fuel cells for transport applications. In this review, we intend to cover these
ammonia related materials, focussing on ammonium
carbonate and urea as potential hydrogen storage materials.
The progress on fuel cells using these materials is also
presented.

Fig. 1 e Volumetric versus gravimetric energy density of the most important energy carriers [13].

1484

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2.
Ammonia and related chemicals as
a potential hydrogen carrier
The challenges facing the implementation of a hydrogen
economy are: (1) On-board hydrogen storage for transport has
a multitude of problems; (2) There is no existing infrastructure
for hydrogen delivery and development of a new hydrogen
distribution system will be expensive; (3) There is no direct
hydrogen resource as over 90% of hydrogen production is still
from reforming of fossil fuels such as natural gas, with the
accompanying CO2 emissions [20].
The main US DOE 2015 targets for hydrogen storage materials
[4] are:
(i) High storage capacity: minimum 9 wt% abundance of
hydrogen and at least 81 g/L of hydrogen available from
the material;
(ii) Low cost, less than US$67/kg H2;
(iii) Operating ambient temperature 40 and 60  C;
minimum/maximum delivery temperature 40 and
80  C; maximum delivery pressure 100 atm;
(iv) System filling time for 5 kg, less than 2.5 min; start time to
full flow rate at 20  C, less than 5 min;
(v) Loss of useable hydrogen 0.05 g/h/kg H2 storage or 0.12%
per day;
(vi) Low-toxicity of a non-explosive and possibly inert (to
water and oxygen) storage medium;
In 2009, US DOE hydrogen storage capacity target was
revised to 4.5 wt%, 5.5 wt% and 7.5 wt% hydrogen as 2010,
2015 and ultimate target on system basis [11]. Ammonia meets
the first of these targets as it contains 17.6 wt% hydrogen.
Ammonia is a low-cost basic chemical [21] with a boiling point
of 33.5  C and can be stored as a liquid under pressure of
8 bar in stainless steel containers [21,22]. Hydrogen, on the

other hand, has to be stored at a very high pressure or in its

liquid state. The low boiling point (252  C) of hydrogen and
the evaporation loss of 2e3% per day (much higher than the
US DOE target) [4] make it difficult to handle liquid hydrogen
on the small scale required for transport applications, while
there would be no such leakage for liquid ammonia [12].
Toxicity is the major problem for the utilisation of ammonia
as a hydrogen storage material; however, this can be solved if
ammonia is stored in a solid such as metal amine salts,
ammonium carbonates or urea. Urea is a non-toxic chemical,
normally found as a solid powder, which can meet almost all
the US DOE requirements for hydrogen storage materials.
Ammonium carbonate and urea are commonly used as
nitrogen fertilisers while (NH4)2CO3, or bakers ammonia, is
widely used in the food industry [23]. For all of these
compounds there are no associated on-board storage issues
for transport applications. To store solid ammonia-based
chemicals is much easier than that for gasoline.
Hydrazine contains 12.5 wt% hydrogen and is therefore
also proposed as an indirect hydrogen storage material,
although hydrazine is toxic and explosive and therefore it will
be difficult to meet the safety requirements on hydrogen
storage materials (Table 1). Hydrous hydrazine has less associated safety issues but the hydrogen content is lower. Much
of the work into hydrazine focuses on fuel cell research which
has been briefly reviewed previously [17,24].

3.

Ammonia production

Nowadays most of the hydrogen produced is from steam

reforming of natural gas. Reduction of CO2 emissions cannot
be achieved via this process unless waste CO2 is captured and
stored through CO2 sequestration. Hydrogen can also be
produced from reforming of biomass, which is a nearly CO2

Table 1 e Vapour pressure of different energy carriers, their relative toxicities, flammability, explosion limits in air and cost
[12,141e144].
Carriers

Hydrogen in
weight (%)

Petrol

w15.8
(octane)
12.5
25
100
100
12.5
17.6
6.16

Vapour pressure,
pi,293 K/bar

IDLH
(ppm)

Apparent toxicity
pi,293 K/IDLH

Flammability
limits (in air)

Explosion
limits (in air)

Cost

0.047

750

63

1.0e7.6%

1.1e3.3%

low

0.13
e
e
e
1.4  102
8
1.24

6000
e
e
e
50
300
300

21.6
e
e
e
280
w2.7  104
w4133

6-36%
5.3-15%
4-75%
4-75%
4.7e100%
e
e

5.5e44%
5.7e14%
18.3e59%
18.3e59%
4.7e100%
16e25%
16e25%

low
low
high
high
high
low
low

19.6

Not available

Not available

Mg(NH3)6Cl2

9.1

1.4  103

300

4.65

NH4CO2NH2
NH4HCO3
(NH4)2CO3
Urea

7.7
6.3
8.3
10.07a

0.885
7.85  102
Not available
e

300
300
300
e

w2986
w265
e
e

e
e
e
No

Methanol
Natural gas
Hydrogen
Liquid hydrogen
Hydrazine
Liquid ammonia
35wt% ammonia
solution
Ammonia borane

a Including hydrogen from water for hydrolysis of urea.

Build-up
pressure
e
e
e
e
No

high
medium/
high
low
low
low
low

i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 7 ( 2 0 1 2 ) 1 4 8 2 e1 4 9 4

neutral process. The produced hydrogen always contains

a small amount of CO which may poison the Pt/C electrode of
a proton exchange membrane fuel cells (PEMFCs) [25]. The
removal of the trace amounts of CO, in order to produce
a suitable fuel for PEMFCs, is a costly process. Another option
is to produce hydrogen through electrolysis of water or steam.
There are no CO2 emissions if the electricity for the electrolysis is from nuclear or renewable resources such as wind,
solar, wave or tide etc. Hydrogen can also be produced from
photocatalytic water-splitting [26], solar thermochemical
process [27], steam reforming of other hydrocarbons such as
biomethanol [28], fermentation process [29], and biological
synthesis [30]. All these process are carbon-free, or carbonneutral, but the technologies need further development for
production of low-cost hydrogen.
Ammonia can also be produced by methods similar to
those for hydrogen production and from similar energy
sources such as fossil fuels, biomass, nuclear, biosynthesis
and photosynthesis. In 2002, 96% of the hydrogen was
produced from fossil fuels while only 4% was produced from
electrolysis (Fig. 2). 50% of the hydrogen produced was used
for production of ammonia, much of which was then used as
fertilisers [31].
The most common process for production of ammonia is
the HabereBosch process which synthesises ammonia from
its constituent elements, hydrogen and nitrogen. Haber won
the Nobel prize for its development in 1918 [32]. This synthesis
process is normally performed under 200e350 bar pressure
and 300e500  C in a reactor with two to four catalysts bed with
an ammonia conversion of 15% [12]. Nitrogen is normally
derived from the air while there are various resources of
hydrogen for ammonia synthesis.

N2( g) 3H2(g) / 2NH3(g)

DH 92 kJ/mol

(1)

Much of the ammonia produced worldwide is derived from

fossil fuels. The conversion of natural gas to ammonia is about
60e65% energy-efficient [21], which is just slightly lower than
that for hydrogen production from reforming of natural gas
(65e75%) [33,34]. The reduction of CO2 emissions remains a big
challenge when using fossil fuels [35].

Fig. 2 e World hydrogen production and consumption. Redrawing from Ref. [31].

1485

Biomass is a good alternative carbon source for synthesis of

ammonia carbonate or urea. Gasification of biomass will
produce syngas (H2 and CO) [36] and ammonia can be synthesised from H2 and N2 separated from air through the HabereBosch process (Fig. 3). A US company, SynGest is building
a plant to produce 50,000 tons of bio-ammonia (150 ton per
day) from 130,000 tons of corn cobs per year to fertilise 500,000
acres of farmland [37]. Ammonium carbonate or urea can be
further synthesised from bio-ammonia and CO2 yielded from
biomass. Another US company, Freedom Fertiliser is seeking
investment to produce 136 tons of ammonia per day through
a combination of electrolysis then the HabereBosch process
with an input of 50 MW renewable electricity, typically derived
from wind power [38].
Another alternative carbon-free hydrogen source is
nuclear hydrogen [14,39,40]. Hydrogen can be produced by
high temperature electrolysis using electricity from nuclear
reactors. The H2 can then be used for synthesis of ammonia
and related chemicals such as ammonium carbonate and
urea. Electricity generated from nuclear power can also be
used for electrochemical ammonia synthesis. Safety issues
with nuclear waste and nuclear proliferation currently
restrain large scale application of nuclear energy for power
generation [41]. Other safety issues deriving from external
damage to the plant, due to natural disasters or terrorism,
must also be taken into account when considering nuclear
energy as a viable power source.
Ammonia can also be synthesised by an electrochemical
process. In 1985, for the first time, Pickett and Tlarmin reported the electrochemical synthesis of ammonia at room
temperature through protolysis of cis-[W(N2)2(PMe2Ph)4] [42].
Marnellos and Stoukides reported the electrochemical
synthesis of ammonia from N2 and H2 at 570  C based on
a solid proton-conducting oxide SrCe0.95Tb0.05O3-d [43]. The
authors also further reported the synthesis of ammonia
directly from N2 and H2O bypassing the process of H2
production [44,45].

2N2(g) 6H2O / 4NH3(g) 3O2(g)

(2)

There are other reports on electrochemical synthesis of

ammonia from N2 and H2O in molten salts at a temperature
w300  C or from N2 and H2 at 400  C under atmospheric
pressure [45e47]. Previously the authors reported electrochemical synthesis of ammonia at w500  C based on oxideecarbonate composite electrolyte [48,49]. Details on
electrochemical synthesis of ammonia based on solid electrolytes are presented in a recent review [50].
The level of CO2 emission from electrochemically synthesised ammonia depends very much on the sources of
electricity. Over time more and more renewable electricity
from solar, wind, marine and wave is being generated. As
these energy sources are intermittent, there is a pressing need
to store the electricity generated at off-peak times. The
production of hydrogen through electrolysis of water is
a state-of-art solution but will be limited to stationary applications as the problems associated with hydrogen storage
have not yet been solved [51,52]. Alternatively, ammonia can
also be produced from renewable electricity through

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Fig. 3 e Diagram of an energy system using ammonia and urea as energy vector.

electrochemical synthesis. Energy stored in ammonia can be

recovered through direct ammonia fuel cells for both
stationary and transport applications [53]. The challenge for
the utilisation of electrochemical synthesis methods is that
the ammonia yield is too low at this early stage.
It is well known that some bacteria and higher plants can
convert nitrogen in air into ammonia, called nitrogen fixation
[54,55]. Biological nitrogen fixation occurs when atmospheric
nitrogen is converted to ammonia by an enzyme called
nitrogenase [56]. The energy for bio-ammonia synthesis is
from sunlight therefore this is a type of photosynthetic
process. There are also reports on artificial photosynthesis of
ammonia from nitrogen and water. In 1977, Schrauzer and
Guth found that ammonia, with the co-generation of a small
amount of hydrazine, can be produced from photo-reduction
of nitrogen on TiO2 catalysts [57]. The reaction for artificial
photosynthesis of ammonia can be described as,

N2(g) 3H2O nhv / 2NH3(g) 1.5O2(g)

(3)

Following this work, researchers have attempted to synthesise ammonia through photosynthesis on different catalysts such as zeolite [58], tungsten oxide [59] etc. There is an
excellent review on artificial photosynthesis of ammonia
which discusses the problems associated with this process
[60]. The major challenge to the use of ammonia photosynthesis is the low yield of ammonia which renders the process
economically unfeasible. Due to the depletion of fossil fuels,
the existing industrial ammonia synthesis processes based on
fossil fuels (coal, natural gas) must be replaced by a renewable

energy source. As solar energy is renewable and clean the

authors believe that photosynthesis of ammonia will be the
future for ammonia production. Ammonia related chemicals
such as ammonium carbonate and urea can also be synthesised from the ammonia derived from photosynthesis.
Ammonia has been investigated as a CO2 scrubber from flue
gas, with the formation of either ammonium carbonate or
urea [61,62]. Ammonium carbonate can be produced through
this process according to the following reaction.

2NH3 H2O CO2 / (NH4)2CO3

(4)

4.
Storage and transportation of ammonia
and related chemicals
Besides ammonia, the typical ammonia storage materials are
ammonia borane [63e66], ammonia ammine salts [12,67e69],
inorganic ammonium salts such as ammonium hydrogen
carbonate, ammonium carbonate and ammonium carbamate.
The properties of these chemicals in terms of hydrogen
content, toxicity, safety and cost are listed in Table 1. The
hydrogen content of liquid ammonia, ammonia borane,
Mg(NH3)6Cl2, ammonium carbonate and urea can meet or get
close to the US DOE target (9 wt%) [4,11].
Ammonia can dissolve in water to form ammonia aqueous
solutions with a solubility limit of around 35 wt% [70].
Ammonia aqueous solution can be stored in normal glass
bottles; however, to reduce the toxicity and to facilitate

i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 7 ( 2 0 1 2 ) 1 4 8 2 e1 4 9 4

transportation, storage of ammonia in solids form is desirable.

In general, all solids releasing ammonia on heating, vacuum
or reaction can be used for ammonia storage. Hydrolysis of
urea can also generate ammonia therefore urea is regarded as
an ammonia storage material [71].
CO(NH2)2 H2O / 2NH3 CO2

(5)

Recently it has been reported that porous covalent organic

framework built on hexahydroxytriphenylene and biphenyldiboronic acid can store 15 mol kg1 (or 25.5 wt% NH3,
4.49 wt% H2) at 298 K and 1 bar [72]. This work indicates that it
may be promising to use porous materials for ammonia
storage. Ammonia can be released from this framework at
200  C under vacuum.
Metal amine salts are also proposed for ammonia storage
or indirect hydrogen storage [68,69,73]. Ammonia is released
by heating some metal amine salts [68]. In order to reduce the
cost, recycling the metal salts through regeneration would be
necessary which may result in additional costs.
Mg(NH3)6Cl2 / MgCl2 6NH3

(6)

From this point of view, ammonium carbonate might be

a more appropriate choice as the decomposing temperature is
much lower, as NH4HCO3 and (NH4)2CO3 begin to melt and
decompose at 107 and 58  C respectively [74]. Recycling of CO2
is not required; however, further reductions in CO2 emissionis
possible if an on-board CO2 absorbing system can be
developed.
(NH4)2CO3 / 2NH3 H2O CO2

(7)

Ammonia borane has also been proposed as a solid indirect

hydrogen carrier. Pure ammonia borane can be stored in
a sealed vessel at room temperature but it tends to decompose
and built up pressure when in solution or containing certain
impurities. This may cause explosions [75]. Thus ammonia
borane would be difficult to handle (Table 1). The high cost for
regeneration of ammonia borane could be additional barrier
for large scale application as an indirect hydrogen storage
material [63]. It should be noted that recently there has been
a breakthrough in there generation of ammonia borane,
which is now possible through direct reaction with hydrazine
and liquid ammonia [76].

5.
Hydrogen from ammonia or related
chemicals
Ammonia is thermodynamically unstable at high temperatures as it begins to decompose at w200  C. The equilibrium
conversion of ammonia to hydrogen and nitrogen is 98e99%
at 425  C [12] with the practical conversion of ammonia highly
dependent on both temperature and catalyst. At a temperature above 500  C, thermal decomposition of ammonia is
significant even without catalysts [77]. Decomposition of
ammonia is a mildly endothermic process, yielding hydrogen
and nitrogen,

2NH3(g) / N2(g) 3H2(g)

1487

(8)

The process operated as above produces no CO or CO2, but

rather nitrogen (essentially benign to the fuel cell) as the only
co-product. Commercial ammonia is prepared at 99.5% purity.
The impurity is mainly water and would not damage a fuel cell
[78].
Quite a few papers have been published on the catalytic
decomposition of ammonia for hydrogen production [21,79].
Related studies along with a discussion of catalytic ammonia
decomposition for applications in alkaline fuel cells has been
reviewed by both Choudhary [80] and Yin [81]. Various catalysts have been investigated such as WC [82], NieAl2O3 [79],
NieCeO2/Al2O3 [83], Cr2O3 [84], Ru/ZrO2 [85], Ru on carbon
nano-fibres [86]. Caesium-promoted ruthenium supported on
graphite was found as the best catalyst for ammonia decomposition [87]. For these catalysts, a minimum temperature of
300  C is required for efficient release of ammonia for
hydrogen production. Under the circumstances, some electricity generated by the hydrogen fuel cells would have to be
used to heat up the ammonia cracking material resulting in
lower overall efficiency. In a recent report, it was found
hydrogen is mechanochemically produced from ammonia at
room temperature on milling BaTiO3 and SrTiO3 catalysts [88].
This make it possible to decompose ammonia at or near room
temperature in the presence of catalysts although the
hydrogen production rate is quite low at this early stage [88].
Hydrogen can also be directly produced from ammonia
borane at room temperature on supported Ru, Rh, Pd, Pt and
Au nano-clusters [89,90]. It was found that coating ammonia
borane within the mesoporus silica SBA-15 leads to suppression of borazine release, modification of the enthalpy of the
decomposition and lowering of the activation barrier for the
loss of H2 [91].

NH3BH3 2H2O / NH
4 BO2 3H2

(9)

It has been reported that Rh(0),Rh4Ni, Ni0.93Pt0.07, Ni0.95Ir0.05,

nanoparticles are highly active for catalytic decomposition of
hydrous hydrazine to generate H2 and N2 under aqueous and
ambient reaction conditions [92e96].
N2H4(l) / N2(g) 2H2(g)

(10)

However, the key to exploit effectively the hydrogen storage

properties of hydrazine is to avoid its incomplete decomposition by the following pathway.
3N2H4(l) / N2(g) 4NH3(g)

(11)

From the above equations, it can be seen that the products

of hydrazine decomposition are normally a mixture of N2, H2
and NH3. A H2 selectivity of 33% has been achieved at 50  C
[92].
Hydrogen can also be produced from urea aqueous solution or urine through electrolysis [97e99].

CO(NH2)2(aq) H2O(l) / N2(g) 3H2(g) CO2(g)

(12)

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The advantage to production of hydrogen from ammonia,

hydrazine or ammonia borane is that, it is CO-free [79]. A CO
concentration of 100 ppm in H2 may have significant negative
effects on the performance and durability of proton exchange
membrane fuel cells based on Pt/C electrodes [100e102];
however, there is still some residual ammonia in the yielded
hydrogen. For ammonia, hydrazine and ammonia borane, the
best method for power generation is to use direct fuel for fuel
cells rather than to produce hydrogen from these chemicals.
The residual ammonia has to be removed first before it can be
used as fuel for conventional PEMFCs based on proton
exchange membrane electrolytes. Conventional PEMFCs
based on an acidic membrane such as Nafion are not
compatible with ammonia (0.1 ppm) [103] and, hence, an onboard storage system based on ammonia would require
a cracking reactor with a significant energy input with a large
mass and volume plus extra costs making it less suitable for
on-board applications [21]. It can be concluded that the
production of hydrogen from ammonia is not an ideal solution. Fuel cells directly fed by ammonia and related chemicals
would be a much more efficient and elegant solution.

6.
Development on fuel cells using ammonia
and ammonia related chemicals as fuel
6.1.

Direct ammonia solid oxide fuel cells

Fuel cells are electrochemical devices to generate electricity

from fuels such as hydrogen, ammonia and hydrazine
[104,105]. When using ammonia as a fuel, the best platform for
efficient operation is high temperature solid oxide fuel cells
(SOFCs). Ammonia fuel cells based on both oxygen ion- and
proton-conducting electrolytes have been reported. Vayenas
and Farr reported the first direct ammonia SOFC in 1980 based
on yttria stabilised zirconia (YSZ) electrolyte and platinum
electrodes for co-generation of electric energy and nitric oxide
[106,107]. Two electrochemical reactions may happen on the
SOFC anode:
2NH3 5O2 / 2NO 3H2O 10e
k

2NH3 3NO/5=2N2 3H2 O

(13)
(14)

Reaction (13) is rate limiting because of the slow diffusion of

O2 through the electrolyte therefore a small amount of NO is
produced at the SOFC anode and the yield of nitric oxide can
exceed 60% with simultaneous electric energy production
[106]. On the other hand, the formation of toxic NO is undesirable if the ammonia fuel cell is solely used for power
generation. Later it was found that, formation of NO can be
suppressed if an iron-based catalyst was chosen for the SOFC
system because of its ability to directly decompose ammonia
to its constituent elements according to reaction (8). If this
reaction is fast relative to the NO formation reaction (13), then
the selectivity for NO may be reduced to zero [108,109]. A
power density of 315 mW cm2 has been achieved at 700  C
when a proton-conducting oxide BaCe0.9Nd0.1O3-dwas used as
electrolyte [110]. High performance direct ammonia SOFC

based on oxygen-conducting Ce0.8Sm0.2O1.9 electrolyte with

a working temperature 550e650  C was also reported by Meng
et al. [111]. The power density of direct ammonia fuel cell is
just slightly lower than that for hydrogen fuel cells [111]. To
avoid the formation of nitric oxide, another option is to use
a proton-conducting electrolyte based doped BaCeO3 and
BaZrO3 [112e116]. Under the circumstance the anode reaction
is then as following,
2NH3  6e / N2 6H

(15)

Research on ammonia SOFCs has been reviewed by Leung

et al. [117]. Recently it has been proposed to use direct
ammonia SOFC for portable applications [118]. A thermodynamic analysis has been performed to compare the theoretical performance of ammonia fed solid oxide fuel cells (SOFCs)
based on proton-conducting electrolyte (SOFC-H) and oxygen
ion-conducting electrolyte (SOFC-O). It is found that the
ammonia fed SOFC-H is superior to SOFC-O in terms of
theoretical maximum efficiency [119]. Due to the high operating temperatures, the start-up time would be too long to use
a direct ammonia SOFC to power an electric vehicle. However,
it may be used as auxiliary power unit (APU) for a lorry, coach,
plane or ship.

6.2.
Direct ammonia alkaline and alkaline membrane
fuel cells
Although ammonia is not compatible with the acidic protonconducting polymer electrolytes such as Nafion, it is
compatible with alkaline electrolytes such as those based
around KOH. Ammonia has been reported as a fuel for fuel
cells based on KOH solution electrolyte as early as 1960s
[120]. Recently Aronsson et al. reported that ammonia can be
mixed with H2 for use as fuel in an alkaline fuel cell [121]. A
test cell was constructed by Ganleyusing a KOHeNaOH
eutectic mixture and produced approximately 40 mW cm2 of
power at 450  C while operating on a stream of pure
ammonia fed to the anode and compressed ambient air fed to
the cathode [122]; however, similar to conventional alkaline
fuel cells, the durability of ammonia fuel cells operating with
KOH-based electrolytes would be a critical issue due to the
reaction between KOH and CO2 if free air is used as
oxidant [53].
Recently, alkaline membrane fuel cells have attracted the
attention of researchers in the fuel cell society [123e126].
Unlike conventional fuel cells based on acidic polymer electrolytes, inexpensive nonprecious catalysts such as nickel,
silver, MnO2 can be used in alkaline membrane fuel cells.
Presently available alkaline membranes are mainly based on
organic quaternary ammonium hydroxide linked to various
polymers. It has been reported that this type of alkaline
membrane are compatible with CO2 and the introduction of
CO2 at the cathode can improve the fuel cell performance
[127,128] therefore air can be directly used in a fuel cell. Direct
ammonia fuel cells based on alkaline membrane electrolytes
have been demonstrated [53]. Due to the lower operating
temperature and short start-up time, like hydrogen PEMFCs,
direct ammonia alkaline membrane fuel cells have the
potential to power electrical vehicles. The ammonia can be

Electrolyte

Charge
carrier

References

700

0.951

315

[110]

Air

650

0.768

1190

[111]

Air

450

0.811

40

[122]

Air

Room
temperature
(w25  C)
600

0.8

[53]

0.91

210

[133]

BCNO and
La0.5Sr0.5CoO3-d
Ba0.5Sr0.5Co0.8Fe0.2O3-d

NH3

Air

NH3

Nickel-400
(NiCuFeMn alloy)
MnO2/C

NH3

MotlenNaOH/KOH
(51:49)
Anion exchange
resin/PVA

OHOH-

BaCe0.9Nd0.1O3-d:NiO
w/o 35:65
Ce0.8Sm0.2O2-d: NiO
w/o 50:50
Nickel-400 (NiCuFeMn
alloy)
Cr-decorated Ni/C

BaZr0.1Ce0.7Y0.2O3-d
(BZCY)
Anion exchange
membrane from
Tokuyama Corp.
Anion exchange
membrane from
Tokuyama Corp.
Anion exchange
resin/PVA

BCZY/NiO

OH

Pt/C (Pt loading

2.8mg cm2)

CZCY/
Ba0.5Sr0.5Co0.8Fe0.2O3-d
Co -polypyrrole
(PPY) e C

OH

Pt/C

Pt/C

OH

Ni/C

MnO2/C

O2-

Power density
(mW cm2)

Cathode

BaCe0.9Nd0.1O3-d
(BCNO)
Ce0.8Sm0.2O2-d

Fuel

Open circuit
voltage (V)

Anode

35% aqueous
ammonia solution

Oxidant

Temperature
( C)

N2H4

Air

N2H4 in 1 M KOH

O2 humidified
at 50  C

80

0.8

617

[137]

0.5 M NH3BH3 in
2 M NaOH

Humidified O2

45

0.86

110

[139]

1 M CO(NH2)2
aqueous solution

Air

60

0.83

14

[129]

i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 7 ( 2 0 1 2 ) 1 4 8 2 e1 4 9 4

Table 2 e Comparison of reported typical fuel cell performances on using ammonia and ammonia related chemicals as the fuel.

1489

1490

i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 7 ( 2 0 1 2 ) 1 4 8 2 e1 4 9 4

derived from liquid ammonia, ammonia solution, decomposition of metal amine salts, ammonium salt such as ammonium carbonate. Ammonia can also be obtained from
hydrolysis of urea, but a better option is to develop direct urea
fuel cells. Direct urea fuel cells based on alkaline membrane
electrolyte have been demonstrated [71,129]. AdBlue, a 32.5%
urea solution is commercially available as a NOx reduction
additive for selective catalytic reduction (SCR) catalysed diesel
vehicles and is widely available across the world, providing an
existing fuel distribution infrastructure. The same as petrol, it
can be pumped to your car in a petrol station. There are
already 3609 AdBlue pumps in Europe [130]. The mechanism
of direct urea fuel cell has not been investigated in detail
although it is believed that some intermediate species such as
ammonia and hydrogen could be produced at the anode when
an appropriate catalyst is used.
Water generated from fuel cells can be used to dissolve
ammonium carbonates and urea to form aqueous solution to
be fed in a fuel cell as the solubility of ammonium carbonates
and urea in water is very high. Recycling of solvent water is
another option to dissolve the solid powders. Although there
are drawbacks to the use of liquid ammonia as a hydrogen
carrier, the use of ammonia-based solid chemicals for indirect
hydrogen storage appears to be very promising.

6.3.

Direct hydrazine and ammonia borane fuel cells

Similar to ammonia, hydrazine can also be directly used as

fuel in fuel cells. The progress in direct hydrazine fuel cell has
been extensively covered in recent reviews [17,131]. Hydrazine
can be directly fed into an SOFC for power generation,
however the safety issues need to be thoroughly considered
[132,133].
The performance of direct hydrazine fuel cells based on
proton-conducting membranes is not high due to parallel
N2H4 decomposition in acidic media and high fuel crossover
from the anode to the cathode [131,134]. This problem can be
solved by using anion exchange membranes [135]. It has been
reported that high performance direct hydrazine fuel cell,
with a power density of 617 mW cm2, based on alkaline
membrane electrolyte (with addition of KOH) and nonplatinum catalysts has been developed [136,137]. Similar to
alkaline fuel cells, the stability of KOH in CO2 from air could be
an issue. To develop efficient hydrazine fuel cells based on
alkaline membrane without addition of KOH provides a better
alternative.
Xu and coworkers reported the first direct NH3BH3 fuel cell
based NaOH electrolyte [138],while a direct ammonia borane
fuel cell based on alkaline membrane electrolyte has also been
demonstrated [139]. An alkaline fuel cell power supply using
ammonia borane as fuel was investigated with a power
density of 315 mW/cm2 achieved at ambient pressure and
near ambient temperature [140]. Unlike direct ammonia fuel
cells, the recycling of boron and regeneration of ammonia
borane is required which significantly increases the cost of the
process [63]. Due to the associated problems with ammonia
borane, the use of direct ammonia fuel cells have increased
commercial prospects, particularly when ammonia is stored
in solids, although the power density of direct ammonia and
urea fuel cells without addition of KOH is not ideal at this early

stage. The reported performance of fuel cells using ammonia

and related chemicals as the fuel is listed in Table 2.

7.

Conclusions

Reduction of carbon emission to combat climate change is one

of the biggest challenges we are facing in this century. Besides
hydrogen, ammonia and related chemicals may provide an
alternative energy vector.
Both hydrogen and ammonia are derived from the same
energy sources: fossil fuels, biomass, renewable electricity,
nuclear and solar energy (Fig. 3). To reduce carbon emissions
fossil fuels have to be avoided as the energy sources for both
hydrogen and ammonia production. There are existing alternative energy sources which can be utilised, such as biomass,
renewable electricity, nuclear, photosynthesis or biosynthesis. One significant advantage of the use of ammonia over
hydrogen is that the storage of ammonia, either in liquid or
solid form, is a mature technology and therefore has less
associated problems. An distribution network for transportation of ammonia is already in place, negating the need
for development of an entirely new network, as would be
necessary for hydrogen. Additionally, safety is not an issue if
ammonia is stored in solids such as ammonium carbonate
and urea. As an indirect hydrogen storage material, urea hits
almost all the US DOE targets listed in Section 2.2 [4].
The development of fuel cells directly fuelled with
ammonia and related chemicals is at an early stage and
further investment, in both time and money, is required to
provide a commercial product. For transport applications
a fuel cell with a relatively low operating temperature is vital
to reduce start-up times as is required. The key to the development of this technology is the identification of a low cost
and robust ionic conducting electrolyte together with low cost
non-noble catalysts for direct ammonia, hydrazine, ammonium carbonate and urea fuel cells.
With the development of fuel cells based on ammonia and
related chemicals, it is possible to alleviate the on-board
hydrogen storage issue and to have an ammonia economy
before or in parallel with a hydrogen economy.

Acknowledgements
The authors would like to thank the EPSRC for funding.

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