Renewable and Sustainable Energy Reviews 15 (2011) 3980–4001

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Renewable and Sustainable Energy Reviews

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

Sodium borohydride as a fuel for the future

D.M.F. Santos ∗ , C.A.C. Sequeira
Institute of Materials and Surfaces Science and Engineering, Department of Chemical and Biological Engineering, Instituto Superior Técnico, TU Lisbon, 1049-001 Lisboa, Portugal

a r t i c l e i n f o a b s t r a c t

Article history: In a time of unprecedented change in environmental, geopolitical and socio-economic world affairs, the
Received 2 January 2011 search for new energy materials has become a topic of great relevance. Sodium borohydride, NaBH4 ,
Accepted 5 July 2011 seems to be a promising fuel in the context of the future hydrogen economy. NaBH4 belongs to a class
Available online 21 August 2011
of materials with the highest gravimetric hydrogen densities, which has been discovered in the 1940s
by Schlesinger and Brown. In the present paper, the most relevant issues concerning the use of NaBH4
Keywords:
are examined. Its basic properties are summarised and its synthesis methods are described. The general
Sodium borohydride
processes of NaBH4 oxidation, hydrolysis, and monitoring are reviewed. A comprehensive bibliometric
Electrosynthesis
Oxidation
analysis of the NaBH4 publications in the energy field opens the discussion for current perspectives
Hydrolysis and future outlook of NaBH4 as an efficient energy/hydrogen carrier. Despite the observed exponential
Monitoring increase in the research on NaBH4 it is clear that further efforts are still necessary for achieving significant
Direct borohydride fuel cells overchanges.
Bibliometrics © 2011 Elsevier Ltd. All rights reserved.

Contents

1. The overall energy scene . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3980

2. Hydrogen storage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3982
3. Synthesis of sodium borohydride . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3983
4. Properties of sodium borohydride . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3984
4.1. General . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3984
4.2. Crystal structure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3985
4.3. Electronic structure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3985
5. Methods for sodium borohydride monitoring . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3986
6. Sodium borohydride hydrolysis and dehydriding . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3987
7. Oxidation of sodium borohydride . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3988
8. Sodium borohydride for fuel cells . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3989
8.1. PEMFC systems based on NaBH4 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3989
8.2. DBFC systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3990
9. Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3991
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3991

1. The overall energy scene is then converted to mechanical energy by a motor. The scien-
tific use of the term “energy” was introduced by Thomas Young
The mastery of energy has always been the key to a better world. (1773–1829) who provided the most astute definition to date, as
Energy can be defined as an abstract quantity that manifests itself in “energy is the ability to do work”. It is commonly understood that
many forms, e.g., chemical, electrical, mechanical, radiant, nuclear, “work” means the application of effort to accomplish a task, and the
and thermal energy. In an electric vehicle, for example, a battery rate at which work is performed is called “power”. Thus, machines
is used to convert chemical energy into electrical energy, which consume energy, perform work, and provide power [1].
Until the advent of the Industrial Revolution in the 18th century,
humankind derived its power mainly from its own exertions, from
∗ Corresponding author. Tel.: +351 218417765. animal muscle (horses, oxen, camels), from the wind (windmills
E-mail address: [email protected] (D.M.F. Santos). and sailing ships), and from water (watermills). Even with these

1364-0321/$ – see front matter © 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.rser.2011.07.018
 D.M.F. Santos, C.A.C. Sequeira / Renewable and Sustainable Energy Reviews 15 (2011) 3980–4001 3981

limited resources, however, some humankind’s achievements were Table 1

Primary energy supply by fuel (%) for world in 2001 and forecast for 2010 and 2020
remarkable.
[3,4].
Sources of power began to change with the development of the
“atmospheric” engine in the early 18th century by Thomas New- Year
comen (1663–1729), who was inspired by the earlier work of Denis 2001 2010 2020
Papin (1647–1712) and Thomas Savery (1650–1716).
Oil 35.0 35.3 37.0
James Watt (1736–1819) subsequently recognised that the Coal 23.3 22.3a 22.6a
“atmospheric” engine was very inefficient – energy was wasted by Gas 21.2 23.1 23.9
having to reheat the cylinder after each stroke of the piston. Watt Combustible renewables 10.9 – –
solved this problem using a separate condenser and driving the (biomass) and wastea
Nuclear 6.9 6.2 4.2
engine by the pressure of steam itself. Thus, in 1769, he patented Hydro 2.2 2.3 2.3
the first real “steam” engine, which offered superior performance Otherb 0.5 10.9 10.0
in terms of both energy efficiency and economy. By the early 19th Total (%)c 100.0 100.1 100.0
century, steam was also replacing water to power cotton mills and Total (Mtoe) 10,029 12,100 14,800
The Times newspaper was printed in London on a steam press as a
Includes combustible renewables and waste for OECD countries only.
b
early as 1814. Thus, such engines turned steam into a universal The 2001 data separate out combustible renewables (mostly wood and dung)
source of power and heralded the beginning of the fossil-fuel age. and waste from “coal”; the IEA predictions for 2010 and 2020 report this item for
OECD countries under “coal”, and for non-OECD countries under “other”; this some-
By the end of the 19th century, there were steam-driven cars in what curious procedure explains the apparent increases attributed to renewables,
London, Paris and New York as well as lorries and trams. These which is most illusionary.
competed with electric vehicles and petrol-driven vehicles. Even- c
IEA data have a rounding error of 0.1%.
tually, the internal-combustion engine proved superior, and steam
vehicles were mostly phased out, although their use in agriculture
continued for at least another 20 years.
Coal was the first fossil fuel to be exploited to produce power. In our civilisation have steadily progressed since the Industrial Revo-
the 19th century, the pyrolysis of coal yielded coal gas (“town gas”), lution. In the long term, this is obviously an unsustainable situation
which was distributed in cities for lighting lamps and cooking, and as fossil fuels are being extracted at a rate that grossly exceeds the
coal tar, which was the early raw material for the organic chem- rate at which they are laid down. Moreover, the atmosphere will no
icals industry (explosives, dyes, drugs, etc.). As recently as 1937, longer accept unlimited combustion of fossil fuels. Consequently, it
coal accounted for three-quarters of energy consumption world- will be necessary to move away from fossil fuels, towards sustain-
wide through its use as a fuel for space heating, cooking, industrial able energy supplies of a non-polluting nature, while maintaining
processes, and transportation (steam trains and ships) [1]. the standard of living of the developed world and dramatically
In 1876, the four-stroke internal-combustion engine was built improving that of developing nations.
by the German engineer, Nikolaus Otto (1832–1891), initiating the Fortunately, nature has bestowed upon us a bountiful supply
petroleum (“oil”) industry. Otto’s engines ran at slow speed and it of such benevolent energy, in the forms of hydro energy, wind
was not until 1885 that a suitable power unit for motor cars (auto- energy, wave energy, tidal energy, ocean thermal energy, solar
mobiles) became available – the high-speed engine invented by energy, geothermal energy, and biomass. The task, therefore, is to
Gottlieb Daimler (1834–1900). Shortly afterwards, in 1892, Rudolf capture and utilise greater amounts of these renewable energies in
Diesel (1858–1913) introduced the diesel engine. The success of an efficient and economical way so as to minimise the environmen-
internal-combustion engines operating on petroleum (“gasoline”) tal impact of energy consumption by the industry, transportation,
was such that they rapidly replaced the steam engine (an external agriculture, commerce and domestic sectors.
combustion engine) for almost all other applications although, of The European “World Energy, Technology and Climate Policy
course, steam turbines are still used in electricity generation. Outlook (WETO)” predicted an average annual growth rate of 1.8%
Just how far the motor car has come in a little more than for the period from 2000 to 2030, for primary energy worldwide
100 years is quite remarkable, although on the pollution front we [2]. The International Energy Agency (IEA)’s forecast of the world
have merely replaced one environmental problem (horse manure) demand for primary energy in 2010 [3] and 2020 [4] is shown in
with another (tailpipe emissions). The 20th century saw the Table 1. Compared with the situation in 2001, the IEA predicted
widespread adoption of the internal-combustion engine for trans- a 21% increase in 2010 (12,100 Mtoe) (1 Mtoe is 1 million tonne
port and power applications. The use of this engine has become oil equivalent) and a 48% increase in 2020 (14,800 Mtoe) [5]. Fossil
so extensive that a serious concern has arisen over the pollution fuels (oil, coal, natural gas) will continue to provide about 80–85%
it causes in cities, and also over its contribution to global warm- of the world’s primary energy right through 2020. Oil, in the form of
ing through enhancement of the “greenhouse effect”, which is petroleum, will be the dominant fuel and will meet 35–37% of global
attributable in part to the carbon dioxide (CO2 ) produced by com- energy needs. This will require an increase in production from
bustion [1]. around 110 Mb d−1 in 2020 (Mb d−1 stands for million barrels per
Another major change that took place towards the end of the day; 1 tonne of crude oil approximates to 7.4 barrels). This reflects
19th century was the growth of the electrical industry, initiated a substantial increase in the demand for transportation fuels. Shell
by the earlier research of Michael Faraday (1791–1867) on electro- company, for example, has predicted that oil consumption by road
magnetic induction. vehicles in 2020 will be 40% higher than today. But whether or
During the second half of the 20th century, there has been not such increased production will take place is, in part, a political
wholesale exploitation of natural gas – the third major fossil fuel. question. Nuclear power output will decline as a proportion of the
Over the past decade or so, there has been a marked swing towards total energy supply as older reactors in Europe and North Amer-
the combustion of gas for the centralised generation of electricity. ica are retired. The apparent increase in “renewables”, categorised
This may be explained by the abundance, accessibility and rela- under “Other” in Table 1, is misleading. If the estimated contri-
tively low cost of natural gas, its convenience of transport and use, bution from wood and dung in developing nations is deducted, the
and the high efficiency of the combined-cycle gas turbine. expected contribution from “new” renewable sources (geothermal,
Energy from the three great fossil fuels – coal, petroleum and solar, wind, tidal, etc.) will increase from 0.5% to between 1% and
natural gas – has provided the means by which our industry and 3% of the total primary energy supply [1].
3982 D.M.F. Santos, C.A.C. Sequeira / Renewable and Sustainable Energy Reviews 15 (2011) 3980–4001

At the start of the Industrial Revolution, the world population depending on the storage means and assumptions on these
was only a few hundred million. Today, it stands at almost 6.9 billion associated variables.
people who collectively occupy around a billion dwellings, drive Compressed gas and liquid hydrogen storage technologies are
800 million motor vehicles, and expend much effort to produce a the current state-of-the art, but more compact means of stor-
wide variety of industrial products to further their well-being. Of ing hydrogen are needed for portable and mobile applications.
the two billion people living without electric power, about one bil- Solid-state hydrogen storage materials would appear to be a very
lion have no supplies of commercial energy in any form – not even promising solution. However, they have in general low gravimetric
petroleum or diesel oil. These people operate entirely on wood fuels capacity and, therefore, there has been a growing interest in the use
and other biomass resources. Moreover, the disparity will intensify. of complex hydrides of the type of Na+ [AHx ]− , where A represents
It is generally expected that the world population will grow to an boron or aluminium.
estimated 7.7 billion in 2020, and 90% of the growth will take place Sodium and lithium borohydrides are well-known reducing
in the developing nations. Thus, over the next few decades, it is clear agents that are used in organic chemistry. For hydrogen storage,
that global energy supply issues will move from the industrialised the aluminium salts NaAlH4 and Na3 AlH6 (the so-called “alanates”)
to the developing countries, many of which have serious social, are the preferred reagents. Thermal decomposition of NaAlH4 takes
economic, and environmental problems. Those that have coal will place in two steps, i.e.,
wish to burn it, despite the environmental consequences.
3NaAlH4 → Na3 AlH6 + 2Al + 3H2 (1)
Of equal concern are the destructive effects of the growing
levels of energy conversion and usage on the earth’s biosphere. Na3 AlH6 → 3NaH + Al + 3/2H2 (2)
In global terms, the energy sector is the single largest source of
anthropogenic greenhouse gases, with emissions of CO2 , methane, These reactions are reversible at elevated temperatures and
and nitrous oxide. At the local level, energy use in motor vehi- pressures. The first step (Eq. (1)) at 323–373 K, corresponds to
cles is a major contributor to the degradation of urban air quality. the release of 3.7 wt.% hydrogen and the second step (Eq. (2)), at
The exhaust pollutants include carbon monoxide, nitrogen oxides 403–453 K, to a further 1.9 wt.% hydrogen. Research has shown that,
(NOx ), and hydrocarbons. Energy use in large stationary applica- in the presence of a titanium catalyst, the temperature for discharge
tions such as power stations is also a serious source of both sulphur and recharge of hydrogen may be brought down to acceptable lev-
oxides (SOx ) and NOx , which are the major precursors to “acid rain”. els. Titanium-catalysed Na[AlH4 ] has thermodynamic properties
Fossil fuels are remarkable in the way that they are not just fuels, but that are comparable with those of classic low temperature hydrides
also energy stores. Finding an economic means for storing energy, (e.g., LaNi5 H6 and TiFeH). Moreover, even if only the first step (Eq.
particularly electricity, lies at the heart of the renewables problem. (1)) can be utilised, the gravimetric hydrogen storage of NaAlH4 is
One prime form of keeping energy is to store it as hydrogen, still more than that offered by AB, AB2 or AB5 hydrides. By contrast,
which may be used to produce electricity in a fuel cell. Aspects of Na3 AlH6 requires higher temperatures for hydrogen liberation and
hydrogen storage and an overview of the chemical hydride tech- might be useful to non-fuel applications such as pumping and heat
nologies available for storing hydrogen are considered in the next storage. There are also complex hydrides based on transition met-
section. als, e.g., Mg2 FeH6 . In most cases, they have low reversibility. The
possibility of overcoming this limitation through development of
2. Hydrogen storage efficient catalysts awaits further research.
Sodium borohydride, NaBH4 , is stable until about 673 K and is,
Hydrogen can be stored as a compressed gas, as a liquid, in a therefore, not suitable for providing hydrogen through a thermal
chemical compound (e.g., chemical hydrides or metal hydrides), or activation process. It does release hydrogen, however, on reaction
physically held within nanoporous structures. A major element of with water, as described by Eq. (3).
the cost of most of these storage modes (and a major consideration
NaBH4 + 2H2 O → NaBO2 + 4H2 (3)
in terms of their energy efficiency) is the energy required to get
the hydrogen in and out of the storage medium. Table 2 shows The borohydride hydrolysis reaction is irreversible, but has the
the cost of a number of storage means, including liquefaction, gas advantage that 50% of the hydrogen comes from the water – in
compression above the ground and underground, and chemical and effect, NaBH4 is a “water-splitting” agent. Based on the mass of
metal hydrides. NaBH4 , the hydrogen released corresponds to 21 wt.% – a remark-
In each case, the cost of the storage method is dependent ably high figure. Several of these so-called “chemical hydrides”, e.g.,
on the cost of the requisite energy to get the hydrogen into the CaH2 , LiAlH4 , LiH, LiBH4 , KH, MgH2 , NaH, are being evaluated for
required form for storage, as well as on the scale and throughput, their reactivity with water. One approach to preparing the stor-
and sometimes on the storage medium. The storage can add age medium is to mix the hydride with light mineral oil and a
anything from 0.1 D to 3.5 D kg−1 to the price of hydrogen (Table 2), dispersant to form an “organic slurry”. The oil coats the hydride

Table 2
Costs for various hydrogen storage technologies [6].

Technology Transition scenarioa Cost rangeb , D kg−1 H2 Comments

−1
Liquefaction (>45 kg h ) CHT, UH 0.8–1.2 Cost highly dependent on scale, efficiency, cost of electricity
Compressed gas (<1 week)c CHT, UH, ES 0.1–0.5d For stand-alone (i.e., not on-board) storage only; strong economies of scale
Bulk underground CHT, UH 0.1–0.2 Costs rise with increased storage time/reduced throughput
Chemical hydrides CHT, UH, ES 1.2–1.9e Large economies of scale, figures apply to 3.6 kto–9 Mto H2 ; on-board storage
Metal hydrides CHT, UH, ES 0.3–3.5 For storage times of 1–14 days; on-board storage
Methanolf SLF n/a Cost not calculated; methanol can be produced from sources other than H2
a
Four scenarios: synthetic liquid fuels (SLF); central hydrogen for transport (CHT); ubiquitous hydrogen (UH); electricity stores (ES).
b
Assuming that 1 D = 1.3 US$.
c
Storage times of less than 1 week; cost rises with storage because H2 throughput is reduced.
d
One estimate is as high as 1.2 D kg−1 H2 ; storage pressure not given in source.
e
INCLUDES some energy and costs which could be regarded as H2 production.
f
NOT included in source table, but elsewhere in source.
 D.M.F. Santos, C.A.C. Sequeira / Renewable and Sustainable Energy Reviews 15 (2011) 3980–4001 3983

particles and protects them from inadvertent contact with water,

and also moderates the reaction rate of the hydride with water
when desired.
The downside of using chemical hydrides is that the spent solu-
tion has to be returned to a processing plant for regeneration of the
hydride. From the standpoint of mass, volume and cost, however,
the system appears superficially to be attractive as a hydrogen-
storage scheme for fuel-cell vehicles (FCVs). For example, Daimler
AG has demonstrated that a NaBH4 system, developed by Mille-
nium Cell in the USA, can provide a minivan (the “Natrium”) with a
range of 480 km. Much will depend on the difficulty and cost of the
reprocessing operation. At the service station, instead of refuelling
with hydrogen gas, the vehicle would have its tank emptied and
refilled with fresh hydride slurry. This is similar to the procedure
proposed for the zinc-air traction battery.
Organic liquids, such as cyclohexane or methanol, and nanos-
tructured materials are other possible approaches to chemical
storage of hydrogen, but borohydrides, namely sodium borohy-
dride, with their enormous potentialities as hydrogen storage
materials and as fuels, are considered a topic requiring further
attention. This is the main subject of the present paper, to be
detailed in the following sections.

3. Synthesis of sodium borohydride

Borohydrides belong to a class of materials with the highest

gravimetric hydrogen densities. There are many types of borohy-
drides depending on the composition of M, B and H, e.g., M(BH4 )n ,
M(B3 H8 )n , M(B6 H6 )n , M(B9 H9 )n and M(B12 H12 )n [7].
Here, we focus on sodium borohydride, NaBH4 , which has a
hydrogen-rich anion, the borohydride, BH4 − , which is similar to
AlH4 − (alanate) in NaAlH4 . Moreover, NaBH4 has a higher gravi-
metric hydrogen density than NaAlH4 , due to B being lighter than
Al. On the other hand, NaBH4 does not release hydrogen by the
same reaction pathways of alanate, e.g., NaAlH4 to Na3 AlH6 . There- Fig. 1. Evolution of the number of publications regarding the synthesis of NaBH4 :
fore, confirmation of similarity and difference between NaBH4 and (a) journal papers and (b) patents.
NaAlH4 is important.
NaBH4 is not a new compound since it was discovered in the
1940s [8]. In fact, the first report of a pure alkali metal borohydride 21st century, caused by the recent demand for alternative energy
appeared in 1940 by Schlesinger and Brown who synthesised LiBH4 power sources (Fig. 1b).
by the reaction of ethyllithium with B2 H6 [9]. The direct reaction Industrial production of NaBH4 using the Brown–Schlesinger
of the corresponding metal/metal hydride with diborane in ethe- process is carried out by the reaction of extremely fine sodium
real solvents under suitable conditions produces high yields of the hydride with trimethyl borate in high boiling hydrocarbon oil at
borohydride compound [10–12]: about 523–553 K [14,15]:

4NaH + B(OCH3 )3 → NaBH4 + 3NaOCH3 (5)

2MH + B2 H6 → 2MBH4 (M = Li, Na, K) (4)
The other industrial NaBH4 synthesis process was developed
Schlesinger and Brown also discovered NaBH4 in 1940, while by Bayer and uses finely grounded borosilicate glass, sodium and
leading a team that developed metal borohydrides for wartime hydrogen [17]:
applications, but their work involving NaBH4 was classified and
published in a scientific journal only in 1953 [10,13,14], although a Na2 B4 O7 + 7SiO2 + 16Na + 8H2 → 4NaBH4 + 7Na2 SiO3 (6)
patent had been granted 3 years before [15].
Thus far, about 100 methods for preparation of NaBH4 have been The NaBH4 material is then extracted from the
suggested in the last 60 years. Fig. 1a shows that the number of borohydride–silicate mixture with liquid ammonia under pressure.
published papers concerning the synthesis of NaBH4 has seen a Different approaches to the synthesis of NaBH4 have recently
considerable increase in the last decade [10,13,14,16–51], mainly been reviewed by Santos and Sequeira [51]. They consider syn-
due to the recent wave of interest on NaBH4 for energy systems. thetic processes that are or have been in operation on an industrial
Besides the papers in scientific journals, and given the importance scale; potential routes based on direct use of carbon, hydrocar-
of achieving a cheap method for NaBH4 production, it seems natural bons, or hydrogen reducing agents; multi-step thermochemical
that many patents have also been published on this matter. Fig. 1b reaction pathways that were developed to address the inadequa-
shows that over 78 patents have been granted to processes that cies of the former direct reactions, and which take advantage
claim the NaBH4 synthesis [12,15,52–127]. It is interesting to notice of the characteristic disproportionation chemistry of boron com-
the occurrence of two separate time periods with high number of pounds; reaction pathways that use metals as reducing agents;
patents on the NaBH4 synthesis: the first one was in the sixties, and alternative energy sources such as microwaves and nuclear
following the NaBH4 discovery; the second peak was already in the radiation.
3984 D.M.F. Santos, C.A.C. Sequeira / Renewable and Sustainable Energy Reviews 15 (2011) 3980–4001

In essence, the Brown–Schlesinger and Bayer processes are both Table 3

Physical and chemical properties of sodium borohydride.
electrochemical in nature, given that the majority of the energy
needed to make NaBH4 is introduced into the system in the form Appearance White to grey-white microcrystalline
of electricity used to make sodium metal. powder or lumps
Odour Odourless
As done for the thermal reaction processes, it makes sense
Solubility Soluble in water; reacts with hot water
to discuss the most desirable electrochemical reactions for the Specific gravity 1.074
NaBH4 synthesis, and then examine their flexibility. Cooper [87], % Volatiles by volume at 294 K 0
Hale and Sharifian [89], Sharifian and Dutcher [90], Sun and Melting point 778 K (10 atm H2 )
Liang [100], and Guilbault et al. [106] are among those who have Vapour density (air = 1) 1.3

reported the electrochemical conversion of borate to borohydride

in aqueous media, but studies by Gyenge and Oloman [18] and The NaBH4 electrosynthesis reaction has also been studied in
by Calabretta and Davis [28] failed to verify that any borohy- ionic liquids medium. Two ionic liquids (octamethylimidazolium
dride was synthesised in the electrochemical systems used by and 1-butyl-1-methylpyrrolidinium trifluoromethanosulphonate)
Cooper, Hale and Sharifian [87,89,90]. NaBH4 electrosynthesis were selected and characterised as possible electrolyte medium
attempts in aqueous media, molten salts, and ionic liquids have for the synthesis. However, both ionic liquids displayed low ionic
also been carried out in our laboratory [51], as briefly summarised conductivity. Moreover, the tested ionic liquids displayed good
hereinafter. solubility for NaOH and NaBH4 but high insolubility for NaBO2 .
The electrosynthesis of NaBH4 in aqueous media has been Experience gained with available ionic liquids does not make them
attempted in a two-compartment electrolytic cell using alkaline particularly attractive for bulk electrolysis. Nevertheless, our group
catholyte solutions containing sodium metaborate (NaBO2 ), or at TU Lisbon is developing ways to minimise present limitations,
sodium tetraborate (Na2 B4 O7 ), with and without hydrogen poisons namely by: (i) increasing the working temperature to decrease the
(e.g., thiourea), sodium hydroxide aqueous anolyte solutions, and ionic liquid viscosity; (ii) using ultrasonication to assist mass trans-
Nafion 117 and other permselective membranes to separate the port; (iii) bubbling nitrogen gas through the solution to enhance
two compartments. Platinum, palladium, cadmium, nickel, gold, mass transport; (iv) minimising the volume of bulk electrolysis
zinc, lead, mercury, graphite, stainless steel and other materials, cell; (v) using a high area working electrode to optimise the area to
were tested as cathodes. As for the anode material, nickel, platinum, ionic liquid volume ratio; (vi) using a flow cell or other hydrody-
graphite and stainless steel, were used. The polarisation behaviour namic methods (e.g., stirring) to enhance mass transport; and (vii)
of the electrodes was controlled to guarantee that cathode poten- employing a mixture of an ionic liquid and a low viscosity highly
tials more negative than the discharge potential required for the volatile organic solvent (e.g., dichloromethane) to lower the vis-
borohydride production (≤−1.46 V vs. SHE) were attained during cosity. The volatile organic solvent may then be removed under
the electrolytic operation [51]. vacuum conditions after completion of the bulk electrolysis exper-
The aqueous electrosynthesis of NaBH4 , starting from NaBO2 , is iment. It is believed that the recent advances in the chemistry of
described by the overall reaction shown in Eq. (7), ionic liquids will soon render an effective electrolytic medium for
NaBO2 conversion to NaBH4 [128].
NaBO2 + 2H2 O → NaBH4 + 2O2 (7) Based on the obtained results, it is anticipated that much work is
still required to fully understand how the electrochemical approach
with the cathodic and anodic partial reactions being given by can be used in the synthesis of NaBH4 .
Eqs. (8) and (9), respectively.
4. Properties of sodium borohydride
NaBO2 + 6H2 O + 8e− → NaBH4 + 8OH− (E 0 = −1.24 V vs. SHE)

(8) 4.1. General

8OH− → 2O2 + 4H2 O + 8e− (E 0 = 0.40 V vs. SHE) (9) Sodium borohydride, also known as sodium tetrahydridobo-
rate (or tetrahydroborate), has the chemical formula NaBH4 (CAS
Assuming that the applied cathodic overpotential is sufficient 16940-66-2). It is a white solid, usually available as a powder or
to achieve complete conversion of the NaBO2 into NaBH4 within confectioned in pellets, that melt at 778 K and 10 atm H2 . NaBH4
the test solution, and there are no side reactions (e.g., hydrogen is hygroscopic, decomposing slowly at temperatures above 673 K
evolution and/or borohydride hydrolysis), the integrated charge [129].
is expected to rise asymptotically with time towards a value of NaBH4 is a selective speciality reducing agent used in the man-
znF (z is the number of moles of transferred electrons – 8 – per ufacture of pharmaceuticals, intermediates and fine chemicals.
mole of NaBO2 , n is the number of moles of NaBO2 present and F NaBH4 converts aldehydes and ketones into alcohols but, unlike
is Faraday’s constant). LiAlH4 (also widely used as a reductant), NaBH4 does not react with
Regarding the NaBH4 electrosynthesis attempts in molten esters, amides, or carboxylic acids.
salts, the analysis of the most suitable electrolytes for the reac- Table 3 presents some general physical and chemical properties
tion medium revealed that NaOH should be part of the molten of NaBH4 , and Table 4 shows its stability conditions.
electrolyte. NaOH provides the OH− ions for the oxidation at the Fig. 2 gives an idea of the number of published journal papers
anode, the Na+ ions for the ionic conduction through the separator, devoted to the characterisation of NaBH4 [130–178]. The number
stabilises the produced NaBH4 in the catholyte, and enables of papers per decade has been relatively constant until the 21st
the preparation of low melting point eutectic compositions for century, with a natural increase in recent years.
the NaBO2 electrolysis. A eutectic mixture composed of NaOH Industrially, NaBH4 is an important starting material for the pro-
(51%) + KOH (49%) (in molar%), having a melting point of 443 K, was duction of other borohydrides. For example, KBH4 is produced on
used as the molten electrolyte medium for the NaBH4 synthesis. an industrial scale by the following metathesis reaction:
This system showed problems concerning the electrodes’ stability,
NaBH4 + KOH → KBH4 + NaOH (10)
need for controlled atmosphere, nature of the metal electrocata-
lyst, the type of the separator material, and water contamination, Alkaline-earth borohydrides, trivalent and tetravalent borohy-
among others. drides, M(BH4 )n (M = alkaline-earth, groups 3–14 in the periodic
 D.M.F. Santos, C.A.C. Sequeira / Renewable and Sustainable Energy Reviews 15 (2011) 3980–4001 3985

Table 4 Table 5
Stability of sodium borohydride. Solubility of sodium borohydride in various solvents (g/100 g solvent at 298 K).

Stability Hygroscopic; stable in dry air up to 573 K; Tb of solvent (K) NaBH4 solubility
decomposes slowly in moist air or vacuum
Water 373.0 55
above 673 K
Methanol 310.7 16.4a
Hazardous decomposition Sodium oxide and hydrogen gas
Ethanol 351.5 4.0a
products
Isopropylamine 307.0 6.0b
Incompatibilities Reacts with water to evolve hydrogen;
Diethyl ether 309.0 Insol.
excessive heat decomposes it to sodium
THF 338.0 0.1c
metaborate, releasing hydrogen gas; may react
Diglyme 435 5.5
slowly or vigorously with acids or certain
Toluene 384 Insol.
transition metal catalysts to liberate hydrogen;
Ammonia 239.7 104
incompatible with oxidising agents, sulphuric
DMF 426 18.0d
acid, ruthenium salt and metal salts
Conditions to avoid Moisture, heat, flame, ignition sources, air and Adapted from [129].
incompatibles a
293 K, decomposition.
b
301 K, decomposition.
c
293 K, decomposition.
d
Dangerous decomposition possible at higher temperature.
table, n = valence of M) are synthesised by the metathetical reaction,
as follows:
Here, ROH is, for example, methanol or ethanol. Because NaBH4
nNaBH4 + MXn → M(BH4 )n + nNaX (11) decomposes up to 80% after 1 h in methanol at 273 K (and 6% after
1 h in ethanol), excess NaBH4 is used for this synthesis reaction (Eq.
Here, X = halogen, such as F, Cl, Br, I. These metathetical reactions
(13)).
occur with certain elements of M, e.g., group 2 (magnesium, etc.)
[179–181], groups 4, 13, etc. For example, Konoplev and Bakulina
4.2. Crystal structure
[179] have synthesised Mg(BH4 )2 by reaction of NaBH4 and MgCl2
in molar ratio 2.7–3.8:1 in diethyl ether (2:1 stoichiometry). After
There have been many recent works devoted to the study of the
progression of the metathetical reaction (Eq. (11)), the precipitated
crystal structure of NaBH4 (and other borohydrides) [161,172,176].
NaCl is filtered, and then the Mg(BH4 )2 ether solution is evacuated
Some data on the crystal structure of NaBH4 [151] is summarised
at 453 K in order to remove diethyl ether.
in Table 6.
Multi-cation borohydrides, MM (BH4 )n (M = alkaline metals,
 NaBH4 shows NaCl-type structure at ambient conditions
M = other metals) have been synthesised by the reaction described
[130,151,184]. The lattice constants and distances between Na and
in Eq. (12) [182].
B depend, of course, on the Na atomic number. However, the dis-
mMBH4 + M Cln → Mm–n M (BH4 )m + nMCl (12) tances between B and H, i.e., the size of the BH4 − tetrahedra, are
almost the same, independent of the alkali metal (Na, Li, K, Rb,
There are many kinds of multi-cation borohydrides with coor- Cs). NaBH4 shows structure transition at low temperature; it crys-
dinated solvents. For example, multi-cation compounds, such as tallises in tetragonal P42 /nmc below 190 K [152]. At 6.3 GPa, NaBH4
Li3 (BH4 )(NH2 )2 have been reported [183]. Those borohydrides has a structure transition to tetragonal P421 C, with lattice constants
might be useful for controlling the thermodynamic stability, sim- a = 4.0864(1) Å, c = 5.5966(7) Å, and to orthorhombic Pnma, with
ilar to the conventional “alloying” method for hydrogen storage a = 7.33890(1) Å, c = 5.6334(5) Å, at a pressure of 6.3 and 8.9 GPa,
materials [182]. respectively [185].
The solubility of NaBH4 in various solvents is summarised in
Table 5. In protic solvents, solvolysis occurs for NaBH4 , and hydro- 4.3. Electronic structure
gen is released as follows:
The electronic structure of NaBH4 has been investigated by first-
NaBH4 + 4ROH → NaB(OR)4 + 4H2 (13)
principles calculations. The electronic structure is non-metallic
with the calculated energy gap of 6.8–7.0 eV [152]. Because there
is little contribution of Na orbitals to the occupied states, Na atoms
are thought to be ionised as Na+ cations. The occupied states split
into two peaks: the low energy states are composed of B-2s and
H-1s orbitals and the high-energy states consist of B-2p and H-1s
orbitals. A boron atom constructs sp3 hybrids and forms cova-
lent bonds with surrounding four H atoms. The charge from the
extra electron needed to form these bonds is compensated by a
Na+ cation. This character is also confirmed experimentally by syn-
chrotron X-ray diffraction measurement and maximum entropy
method (MEM) analysis [152]. The calculated total density of state
(DOS) for NaBH4 is displayed in Fig. 3 [152]. The compound has

Table 6
Crystal structure of sodium borohydride at room temperature [151].

Structure Cubic
Space Fm−3m
Group No. 225
Lattice constants (Å) a = 6.1506 (6)
Na–B distance (Å) 3.0753 (3)
Fig. 2. Evolution of the number of publications regarding sodium borohydride prop- B–H distance (Å) 1.17078 (6) × 4
erties.
3986 D.M.F. Santos, C.A.C. Sequeira / Renewable and Sustainable Energy Reviews 15 (2011) 3980–4001

Fig. 3. Calculated ground-state total DOS for NaBH4 . Fermi level is set at zero energy
and marked by the vertical dotted line; occupied states are shaded.
Adapted from [152].

finite energy gap between the valence and conduction bands.

Hence it is a proper insulator with an estimated band gap of
∼5.5 eV.

5. Methods for sodium borohydride monitoring

Fig. 5. Experimental setup used for the gasometric measurements of the hydrogen
Most existing methods for borohydride determination are generated on product sample hydrolysis and example of calibration curve used for
NaBH4 determination.
neither easy nor fast [186]. These include hydrogen evolution
[132,187], acid–base titration [132], iodate [188], hypochlorite
[189], and voltammetric procedures [191]. Fig. 4 shows that the
by the decomposable borohydride product resulting from the
number of published papers devoted to methods for the NaBH4
electrosynthesis experiments (Section 3), being assisted by a
monitoring is not very large [132,188–210].
calibration curve for pure NaBH4 . This new method shows good
The development of simpler and faster methods for NaBH4
reproducibility but requires further design optimisation to reduce
determination, either from a quantitative or from a qualitative
its detection limit [51].
point of view, would be very helpful for the scientific community
The use of infrared (IR) spectroscopy analysis (Fig. 6) has shown
working in any applications involving NaBH4 , e.g., energy systems
that the three B–H bond stretching vibration bands observed in the
(direct borohydride fuel cells, NaBH4 for hydrogen production and
NaBH4 electrosynthesis reaction products [51] are in good agree-
storage), in NaBH4 synthesis, for electrodeposition purposes, as
ment to the ones obtained for pure NaBH4 and with the values
reducing agent in organic synthesis, etc. Our group has studied
found in the literature [146,160,191].
several typical analytical methods for NaBH4 monitoring, as well
Table 7 presents data taken from the IR spectra of the electrosyn-
as a quick and simple potentiometric technique for the in situ
thesis product and of a sample of NaBH4 p.a. The values obtained
monitoring of small NaBH4 concentrations. Most of these meth-
experimentally are compared to previous data available in the
ods were initially tested in our laboratory for application in NaBH4
open literature. Although this method is able to detect the presence
electrosynthesis studies (Section 3).
of borohydride in the electrosynthesis products, IR spectroscopy
The well known iodate method [189] is based on the reaction
analysis has the disadvantage of taking excessive time. In fact, it
of NaBH4 with KIO3 . Addition of KI and acid convert the excess
requires full drying of the reaction products and preparation of a
iodate into iodine, which is then titrated with thiosulphate. This
KBr/sample pellet suitable for the IR spectrophotometer [51].
volumetric method was proven to be extremely time-consuming
The experience gained on the monitoring of the NaBH4 elec-
and leading to erroneous results, being promptly abandoned.
trosynthesis indicated that electrochemical methods should be
A new “hydride hydrolysis” test (Fig. 5) was developed based
appropriate to follow the reaction process.
on the gasometric measurements of the hydrogen generated
In 1999, Amendola et al. [204] reported the non-destructive
in situ detection of relatively low NaBH4 concentrations by an
undemanding method that is in essence a potentiometric titra-
tion technique. The method was simply based on the change of
the open circuit potential (OCP) of a given metal with the NaBH4
concentration.
In the majority of potentiometric measurements, the potential
of one electrode is kept constant, with this electrode being referred
to as the reference electrode. The second electrode responds to the
activity or concentration of the species contained in the solution
under investigation and is referred to as the indicator electrode.
Amendola et al. [204] used platinum, rhodium, and cobalt as metal
indicator electrodes.

Table 7
B–H bond stretching vibrations for sodium borohydride.

 (B–H)/cm−1

Electrosynthesis product 2225, 2293, 2359

NaBH4 p.a. 2224, 2290, 2387
NaBH4 [191] 2229, 2305, 2400
NaBH4 [146] 2217, 2284, 2404
NaBH4 [160] 2216, 2282, 2396
Fig. 4. Evolution of the number of publications regarding the borohydride
NaBH4 ·2H2 O [160] 2221, 2268, 2380
monitoring.
 D.M.F. Santos, C.A.C. Sequeira / Renewable and Sustainable Energy Reviews 15 (2011) 3980–4001 3987

Fig. 6. Infrared spectra taken for NaBH4 p.a. (a), and for the electrosynthesis reaction
product obtained in aqueous medium (b). Fig. 8. Top materials displaying steeper OCP changes for specific borohydride con-
centrations [209].

In order to develop the method originally proposed by Amen-

dola et al. [204], several materials (e.g., Pt, Pd, Cd, Au, Cu, Ni, Fe,
AISI 304 stainless steel, Zn, Mo, Nb, graphite, and Si) were tested as room temperature. The reaction (Eq. (3)) could be accelerated by
indicator electrodes for NaBH4 monitoring [209]. It was shown that rising the temperature or by adding acids/catalysts. By then, the
the materials whose OCP is significantly different when immersed Schlesinger group had tested the catalytic effects of more than 20
in NaOH supporting electrolyte with or without NaBH4 may be acids and of certain metal salts (manganese (II), iron (II), cobalt
candidate indicator electrodes for application in a novel borohy- (II), nickel (II), and copper (II) chlorides) [214]. Historically, their
dride microelectrode sensor. The potentiometric procedure for a observations have been crucial because they have introduced two
gold (Au) indicator electrode led to the curve shown in Fig. 7. features that are central today: NaBH4 generates hydrogen; and
Fig. 7 shows that the Au OCP starts to decrease for NaBH4 con- this hydrogen generation can be catalytically accelerated.
centrations above 10−2 M, with an OCP response range of about Nowadays, many papers entirely devoted to the NaBH4 hydroly-
1 V. Similar curves were recorded for other tested indicator elec- sis have been published [38,214–426]. Fig. 9 shows that the focus on
trode materials [209] and available thermodynamic data [211–213] the borohydride hydrolysis suffered an almost exponential increase
helped in the analysis of the obtained OCP–[NaBH4 ] plots. Accord- in the beginning of the 21st century, showing a maximum of 47
ing to the NaBH4 concentration ranges where the OCP changes take publications during the year of 2008.
place, the six selected materials presented in Fig. 8 can be classi- Levy et al. [215] reported that the CoCl2 -catalysed hydrolysis is
fied as the top indicator electrode materials for each specific NaBH4 a first-order reaction with respect to the NaBH4 concentration and
concentration range. that an application of kinetic data should allow a precise selection
of the catalyst concentration required to give the desired hydrogen
generation rates. Brown and Brown [216] showed that many of the
6. Sodium borohydride hydrolysis and dehydriding
heavy metals exerted a powerful catalytic effect on the hydrolysis
of NaBH4 . The platinum family metals were unusually effective,
In 1954, Schlesinger et al. [10] reported that NaBH4 reacts
following the order Ru, Rh > Pt > Co > Ni > Os > Ir > Fe  Pd, at 298 K.
slowly with water to liberate four moles of hydrogen per mole
NaBH4 reduced the platinum metals to the elementary state, in
of NaBH4 , equivalent to 2.5 l of hydrogen per gram of NaBH4 , at
a form which exhibited high catalytic activity for the hydrolysis
reaction. Davis et al. [217] focused on the hydrolysis catalysed by
general acids (Eq. (14)).

BH4 − + H3 O+ + 2H2 O → H3 BO3 + 4H2 (14)

Fig. 7. OCP change as a function of the NaBH4 concentration for an Au electrode in Fig. 9. Evolution of the number of publications regarding the borohydride hydrol-
4 M NaOH solution at 298 K [209]. ysis.
3988 D.M.F. Santos, C.A.C. Sequeira / Renewable and Sustainable Energy Reviews 15 (2011) 3980–4001

The reaction order was unitary in relation to the NaBH4 concen-

tration and unitary to the concentration of the acid. Many studies
attempting to understand the NaBH4 hydrolysis reaction kinetics
and mechanisms were then published [217–220].
The hydrogen generation in other solvents, like alcohols
[403,427,428], was also assessed. Davis and Gottbrath [428] inves-
tigated the reaction of NaBH4 with methanol (methanolysis).
Hydrogen gas is produced according to Eq. (15), which is, as
expected, of the same type as Eq. (13).

NaBH4 + 4CH3 OH → NaB(OCH3 )4 + 4H2 (15)

The reaction order vs. the NaBH4 concentration was found to be

of one. It was besides reported that the addition of an acid increased
the rate of methanolysis while basic materials decreased it.
The generation of hydrogen by complete dehydriding of NaBH4
is described by Eq. (16) [156].

NaBH4 → NaH + B + 3/2H2 (16)

Fig. 10. Evolution of the number of publications regarding the borohydride oxida-
The dehydriding reaction of NaBH4 liberates 8 wt.% H2 at above tion.
the boiling temperature (838 K) and decomposes into NaH and
B. The enthalpy change of the dehydriding reactions, Hd , is starting material for the hydriding reaction, with simultaneous
66 kJ mol−1 H2 [156,429,430]. The heat of formation of NaBH4 , reduction of the reaction enthalpy in ∼10 kJ mol−1 H2 .
Hboro , may be estimated from the difference of the total energies
between the left and right-hand sides of Eq. (17). 7. Oxidation of sodium borohydride

Na + B + 2H2 → NaBH4 (17) The oxidation of NaBH4 was studied for the first time in 1953, by
The bonding character between Na+ and BH4 − in NaBH4 is Pecsok [426], who proposed the net reaction for the polarographic
ionic, and the charge transfer from Na+ to BH4 − is responsible oxidation of the borohydride ion, BH4 − , described by Eq. (20).
for the stability of NaBH4 . The ability of the charge transfer can BH4 − + 8OH− → BO2 − + 6H2 O + 8e− (20)
be measured by the electronegativity. There is a good correlation
between Hboro and the Pauling electronegativity of the metal The standard electromotive force, E0 , of this half reaction was
cation. This is 0.9 for Na, so the predicted heat of formation for calculated as being 1.21 V vs. the standard hydrogen electrode
NaBH4 is given by Eq. (18). (SHE) and it was observed that the BH4 − oxidation was irreversible.
Two years later, Stockmayer et al. [133] calculated an E0 value of
H boro = 253.6 × 0.9 − 398.0 = −169.8 kJ mol−1 (18) 1.24 V vs. SHE. In 1962 [432,433] and 1992 [434] three more pub-
lications dealt with the BH4 − oxidation, but it was only from 2003
The estimation of Hd for NaBH4 not only takes into account
onwards that a large number of papers were published on the sub-
the stability of NaBH4 but also the stability of the products. There-
ject (Fig. 10).
fore, Hd is estimated using predicted Hboro and known values
In fact, during the last 7 years more than 80 papers have been
of Hproduct [431] (Eq. (19)).
published on exploratory fundamental research on the NaBH4
Hd = Hboro − Hproduct (19) electrooxidation [133,165,426,432–514]. In our laboratory, we
have undertaken systematic studies on the BH4 − electrooxida-
So, as reported above, Hd for NaBH4 is 66 kJ mol−1 H2 and the tion in several catalytic and noncatalytic electrode materials,
decomposition temperature, Td , is 838 K, which is the boiling tem- using various concentrations of NaBH4 and NaOH, and at different
perature. A thermodynamic unstable borohydride is expected only working temperatures [495–497]. Well-established electrochem-
for metal cations for which the Pauling electronegativity is larger ical methods, namely chronopotentiometry, chronoamperometry,
than 1.5. chronocoulometry, and cyclic voltammetry, were used to better
In the hydriding and dehydriding reactions of NaBH4 , not only understand the BH4 − anodic process. As electrode material, Au was
hydrogen but also other elements should be diffused. This is not selected because of its high catalytic activity for the BH4 − oxidation
the same as conventional metal hydride alloys in which diffusion reaction (with a number of exchanged electrons, n, close to the the-
of hydrogen and expansion of lattice for the alloy is dominant. Gen- oretical value of 8) and because of its relatively low catalytic activity
erally, the fast diffusion of elements is very difficult in the solid for the concurrent detrimental BH4 − hydrolysis reaction.
state at much lower than the melting temperature. Therefore, the Potential step experiments [495] were carried out at tempera-
observed Td during heating process seems to become higher than tures ranging from 298 to 338 K and imposed potentials from 0.05
that predicted. Moreover, a hydrogen pressure (generally more to 0.45 V vs. SHE. The supporting electrolyte was 2 M NaOH and
than 10 MPa) higher than that predicted for Hd is required for the NaBH4 concentrations varied from 0.03 to 0.12 M. The Cottrell
hydriding of NaBH4 . This is why a high temperature is required equation was applied to the obtained chronoamperometric curves,
for diffusion of elements, at which high hydrogen pressure should where diffusion prevailed, to determine the diffusion coefficient, D.
be applied for hydriding. Therefore, solving the kinetic problem is Arrhenius plots of the D values led to diffusion activation energies,
an important area of research in the use of complex hydrides as Ed , of 16.6, 15.6 and 20.5 kJ mol−1 , and maximum diffusion coef-
hydrogen storage materials. ficients, D0 , of 1.55 × 10−2 , 9.56 × 10−3 , and 5.13 × 10−2 cm2 s−1 ,
In order to improve the reaction kinetics, ball milling and addi- respectively, for the tested NaBH4 concentrations of 0.03, 0.06 and
tion effects (doping) have been investigated. Barkhordarian et al. 0.09 M. Chronocoulometric experiments [495] led to Anson plots (q
[27] reported that the kinetic barriers for the formation of NaBH4 vs. t1/2 ), from which it was possible to calculate accurate apparent
are drastically reduced when MgB2 is used instead of B as the rate constants for electron transfer. Activation energies for charge
 D.M.F. Santos, C.A.C. Sequeira / Renewable and Sustainable Energy Reviews 15 (2011) 3980–4001 3989

CE or EC mechanism is actuating, where C denotes coupled chemical

reaction (e.g., adsorption). The ˛ coefficients for the purely electro-
chemical step (E) varied between 0.77 and 0.89, for temperatures
ranging from 298 to 338 K, and NaBH4 concentrations between 0.03
and 0.12 M. The number of exchanged electrons, n, for the E step
involved less than 8 electrons per BH4 − anion (n = 6.8 ± 0.7), which
is consistent with the proposed [497] overall oxidation process
(leading to n between 3 and 8).

8. Sodium borohydride for fuel cells

There are two types of fuel cell systems using NaBH4 aque-
ous solution as the fuel: the proton exchange membrane fuel cell
(PEMFC), which uses H2 generated in situ in a NaBH4 hydrolysis
reactor connected to a conventional PEMFC; and the direct boro-
hydride fuel cell (DBFC) system, which also belongs to the PEMFC
class, but it is fed directly by a NaBH4 aqueous solution as an anodic
fuel.
Fig. 11. Typical CV obtained at 1 V s−1 on a Au electrode in 2 M NaOH + 0.09 M NaBH4
While the fuel for both these two systems is the same NaBH4
solution, at 298 K.
aqueous solution, they have one major difference. In the regular
PEMFC, it is necessary to maximise the H2 generation from the BH4 −
transfer could then be obtained. The analysis of the i − t transients in hydrolysis, whereas in the DBFC system, the production of H2 must
the mixed control region allowed extending the Tafel plots to deter- be suppressed as much as possible for adequate cell performance.
mine exchange current densities, j0 , anodic transfer coefficients, ˛, Accordingly, NaBH4 , which was previously known mostly for
and consequently, the standard heterogeneous rate constants, ks . being a specialty reducing agent in the manufacture of pharma-
From the ln ks vs. T−1 plots, it was found that the standard activa- ceuticals and a bleaching agent in the manufacture of paper, is now
tion energies for charge transfer, Ect 0 , in the Au/NaBH system were
4 acquiring increasing importance as an energy/hydrogen carrier. It
−1
10.8, 25.2, 37.2 and 43.3 kJ mol , for the NaBH4 concentrations of is an energy carrier when it directly powers a DBFC. It works as
0.03, 0.06, 0.09 and 0.12 M, respectively [495]. a hydrogen carrier when it stores and releases hydrogen that is
Using the same experimental conditions, applied current den- intended to power a regular PEMFC. In other words, NaBH4 can
sities in the range of 10–1000 mA cm−2 were carefully selected directly or indirectly power a PEMFC.
to guarantee that the chronopotentiometric data [496] are col-
lected in a domain where the Sand equation is valid. A single 8.1. PEMFC systems based on NaBH4
oxidation wave was always observed for concentration ratios
[NaOH]/[NaBH4 ] > 4.4. The concept behind this system is based on the PEMFC use of H2
From our chronopotentiometric results and complementary generated in situ via the NaBH4 hydrolysis reaction (Eq. (3)) [253].
chronoamperometric data [437], the overall BH4 − oxidation pro- As indicated by the stoichiometry of Eq. (3), half of the H2 produced
cess was shown to be irreversible involving a number of electrons in the hydrolysis reaction is derived from the solution water, which
close to the theoretically expected value of 8. Linear E vs. accounts for the large amount of H2 generated in this reaction.
log ( 1/2 − t1/2 ) plots, where  is the transition time, were obtained, NaBH4 solutions rendered basic with NaOH become chemically
and this well-known diagnostic criterion enabled concluding that stabilised and do not generate significant amounts of H2 under
for the studied potential and NaBH4 concentration ranges (i.e., ambient conditions. However, upon the addition of certain hetero-
−0.25 to +1.75 V vs. SHE; 0.03 to 0.12 M), the rate-determining step geneous catalysts, the NaBH4 hydrolysis rate can be dramatically
is an irreversible, diffusion-controlled, one-electron oxidation step accelerated. Many conventional catalysts have been proposed for
for which several key kinetic parameters (˛, ks , Ect 0 ) were calculated
the reaction, of which ruthenium-based catalysts are known to be
[496]. the most effective for promoting H2 generation [253].
Further studies of the BH4 − electrooxidation on a Au disc The H2 produced in the hydrolysis reactor is then used as the
macroelectrode in 2 M NaOH solutions were performed by cyclic gaseous fuel for the coupled PEMFC, to generate electricity via the
voltammetry [497]. Voltammograms were obtained for NaBH4 general reactions described by Eqs. (21)–(23).
solutions of various concentrations, working temperatures, and
H2 → 2H+ + 2e− (Anode) (21)
potential scan rates ranging from 0.02 to 20 V s−1 , over a wide
+ −
potential range (−0.7 to 1.0 V vs. SHE). A typical CV for the borohy- ½O2 + 2H + 2e → H2 O (Cathode) (22)
dride oxidation in a Au electrode is shown in Fig. 11.
H2 + ½O2 → H2 O (Overall) (23)
Basically, there is a well-defined anodic peak (a1 ) around 0.1 V
(vs. SHE), followed by a broad oxidation hump (a2 ) around 0.55 V, The development of the PEMFC system based on borohydride
which is visible in the region of the Au oxides [439]. The Au elec- can be divided into two steps [253]. The first is the development
trode deactivates positive to peak a2 above 0.65 V, which reveals of a hydrolysis mechanism of NaBH4 with a high reaction conver-
that Au oxides are relatively inactive towards the BH4 − oxidation sion and a H2 generation rate sufficient to provide enough fuel for
reaction. On the reverse scan, a well defined, sharp, anodic peak (c1 ), the PEMFC. The second is the establishment of an effective sys-
is observed around 0.3 V, a potential value where it is expected that tem design for connecting this H2 supply source to the PEMFC
the Au oxides are reduced and the electrode surface is reactivated. system. The former step is generally accepted as being the key
This peak tails off at about 0.15 V, as the potential is scanned into the issue. While much research has already been devoted to the H2
range where the conversion, BH4 − → BO2 − , is no longer favourable. generation via the NaBH4 hydrolysis, it is still somewhat doubtful
Peak a1 is characteristic of an irreversible electrochemical step (E). if the amount of produced H2 and the reaction rate are sufficiently
The other two peaks, a2 and c1 , correspond also to irreversible elec- high to provide the fuel for a PEMFC system. Recently, these tech-
trochemical steps, but deeper analysis of the results suggests that a nological issues have been partially overcome, both theoretically
3990 D.M.F. Santos, C.A.C. Sequeira / Renewable and Sustainable Energy Reviews 15 (2011) 3980–4001

and experimentally, by the development of various catalyst sys-

tems [232–239]. As a result, the conversion rate of the hydrolysis
reaction has been increased to almost 100% at room temperature
and the H2 generation rate has been raised to a level sufficient for a
PEMFC. Subsequently, PEMFCs based on borohydride are presently
being evaluated by many researchers.
Although most of the research confirms the technological avail-
ability of this PEMFC system, in order to NaBH4 be regarded as a
promising hydrogen storage material there are some issues that
must be solved first [166]. One is the high price of NaBH4 (ca.
50 D kg−1 ). Another issue is that the hydrolysis reaction does not
always follow the ideal route given by the general reaction shown
in Eq. (3), but it is rather described by Eq. (24).

NaBH4 + (2 + x)H2 O → NaBO2 ·xH2 O + 4H2 (24)

The reaction byproduct is hydrated with x molecules of water,

decreasing the gravimetric hydrogen storage capacity from about
11 wt.% to 4–7 wt.%. Attempts should be made to improve these low
Fig. 12. Evolution of the number of publications concerning the DBFC.
capacity values. The third issue is the catalyst efficiency, including
its reactivity and resistance to deactivation. The performance of the
catalysts has received much attention but although their reactiv- the use of reactants that are liquid at ambient temperature. The
ity has been largely studied, little research can be found regarding use of liquid reactants greatly simplifies the storage, thermal man-
their resistance. The last issue is the post treatment of the hydrolysis agement and internal processing. The minimum energy content of
byproducts (anhydrous and hydrated NaBO2 ). NaBH4 is currently a the NaBH4 /H2 O2 reactants is 2600 Wh kg−1 (based on total fuel
non-reversible chemical hydride. Hence, a way for recycling NaBO2 weight), which is comparable to that of H2 /O2 (3660 Wh kg−1 ),
into NaBH4 is being investigated, a task with great significance. If without the need for cryogenic storage. In addition, high power
NaBO2 cannot be recycled, NaBH4 cannot be regarded as a sustain- densities can be achieved in the DBPFC due to the ability of provid-
able or renewable (or rather recyclable) material what will then ing a high concentration of reactants to the fuel cell.
imply an inevitable problem of boron resources depletion. Further- In the DBPFC, the BH4 − anodic oxidation proceeds through Eq.
more, NaBO2 recycling would greatly contribute to the reduction (20) whereas at the cathode H2 O2 is decomposed into oxygen and
of the NaBH4 cost up to a projected price of 1 D kg−1 . Investigations water at the catalyst/electrode interface according to Eq. (27), with
are in progress [48–51], namely in our Laboratory [51]. the produced oxygen being subsequently reduced through Eq. (25).

4H2 O2 → 4H2 O + 2O2 (27)

8.2. DBFC systems
H2 O2 may also be directly electrochemically reduced according
The direct borohydride fuel cell (DBFC) system uses a NaBH4 to Eq. (28).
aqueous solution as the fuel, which is continuously supplied to the
4H2 O2 + 8e− → 8OH− (E 0 = 0.87 V vs. SHE) (28)
anodic chamber of the fuel cell.
In a DBFC, borohydride, BH4 − , is oxidised in strong alkaline When the pH of the H2 O2 catholyte solution is low (pH <1), two
media (pH >12) to metaborate, BO2 − , and water, generating eight reactions may take place: decomposition of H2 O2 to O2 (Eq. (27))
electrons according to Eq. (20). With the BH4 − oxidation at the followed by O2 reduction to water (Eq. (29)); or the direct H2 O2
anode, humidified oxygen or air is electrochemically reduced at the electroreduction described by Eq. (30).
interface between the cathode catalyst and the aqueous electrolyte,
2O2 + 8H+ + 8e− → 4H2 O (E 0 = 1.23 V vs. SHE) (29)
and the eight electrons are consumed according to Eq. (25)
4H2 O2 + 8H+ + 8e− → 8H2 O (E 0 = 1.77 V vs. SHE) (30)
2O2 + 4H2 O + 8e− → 8OH− (E 0 = 0.40 V vs. SHE) (25)
Accordingly, the net cell reaction in such an alkaline DBPFC is
Coupling of Eqs. (20) and (25) leads to the overall cell reaction given by Eq. (31)
described by Eq. (26).
BH4 − + 4H2 O2 → BO2 − + 6H2 O (31)
BH4 − + 2O2 → BO2 − + 2H2 O (E 0 = 1.64 V) (26)
The cell voltages for this DBPFC are 1.64, 2.11, 2.47, and 3.01 V
The DBFC theoretical cell voltage of 1.64 V is about 0.4 V higher for cathode reactions described by Eqs. (25), (28), (29) and (30),
than that of the ordinary PEMFC. It is also very high when com- respectively. The cell voltage of 3.01 V is 0.9 V higher than that for
pared to the methanol, formic acid, and hydrazine systems, with H2 O2 reduction in alkaline solution and assumes the direct elec-
theoretical cell voltages of 1.19, 1.45 and 1.56 V, respectively. troreduction of H2 O2 at low pH. Therefore, an appropriate cathode
The performance of fuel cells that operate on NaBH4 as the material should promote the reaction shown in Eq. (30), avoiding
fuel and oxygen or hydrogen peroxide (H2 O2 ) as oxidants has heterogeneous reactions and surface decomposition to oxygen (Eq.
been investigated in several laboratories [253,433,486,515–619]. (27)).
Although the initial suggestion of using NaBH4 as an anodic fuel Recent studies at our Laboratory have suggested that zinc (Zn)
dates from 1962 [433], there was a hiatus of almost 40 years until may be a good anode for DBPFCs [209]. A single DBPFC, employ-
the idea deserved a renewed interest. Fig. 12 shows that over 100 ing a Zn anode and a Pt cathode, was then assembled and its
papers on the DBFC have been published since 2003. performance was evaluated [616]. The cell voltage of this DBPFC
The focus of research on the direct borohydride/peroxide fuel was lower (2.14 V) than the equilibrium cell voltage, and a sta-
cell (DBPFC) is in developing a high energy density power source bility test showed that the cell was able of stable operation for
for space applications, underwater vehicles, and specific terres- not more than 6 h. DBPFC discharge curves led to power densities,
trial applications. One of the major advantages of the DBPFC is specific capacities, and energy densities as high as 528 mW cm−2 ,
 D.M.F. Santos, C.A.C. Sequeira / Renewable and Sustainable Energy Reviews 15 (2011) 3980–4001 3991

critical parameter, it is required a drastic reduction in the volume

of the NaBH4 aqueous solution.

9. Conclusions

Apart from its established use for hydriding and reduction

processes in the chemical industry, NaBH4 is being, particularly
in the present decade, converted to electricity in fuel cells and
other energy systems. This is particularly evidenced by specialist
journals, like the International Journal of Hydrogen Energy, that
are devoting much attention to the subject of NaBH4 as a clean
fuel.
NaBH4 can be produced by many ways, as discussed in the
present paper, and has many attractive features to generate elec-
tricity directly. However, there are many practical engineering and
economic considerations that explain why NaBH4 does not already
Fig. 13. Sodium borohydride energy system with integrated recharging. find extensive use as a fuel. A different future in which NaBH4 is
produced by electrolytic means seems to be not too much away,
and this paper reports some steps towards this direction. Traces
of NaBH4 have been detected in the products resulting from elec-
trosynthesis tests in aqueous media and it is suggested that this
embryonic study should be pursued. Methods to analyse NaBH4
are described and a newly developed potentiometric technique is
suggested for in situ monitoring of small NaBH4 concentrations.
The successful utilisation of NaBH4 in energy systems is highly
dependent on the reduction of its present price. A substantial
decrease in the NaBH4 cost can only be achieved by finding an effec-
tive method of recycling NaBO2 back to NaBH4 . Of course, if it would
be possible to develop a fully reversible system as schematically
shown in Fig. 13, interest in NaBH4 would increase exponentially.
The present paper has focused several important aspects con-
cerning the use of NaBH4 for energy systems. Fig. 14 accounts
for the total number of papers published on borohydride topics
that are relevant for its application in energy systems. Over 300 of
these papers have been published very recently, that is, from 2008
Fig. 14. Division among the number of journal papers devoted to energy-related onwards, which testify the importance of borohydride as a clean
sodium borohydride research areas.
fuel.
Specifically, the uses of NaBH4 as energy carrier for DBFC sys-
1577 Ah kg−1 , and 2799 Wh kg−1 , respectively. A poor rate capabil- tems or as hydrogen carrier for conventional PEMFCs have been
ity of the cell was demonstrated, being shown that for cell voltages discussed in detail in this paper. If the problems related to the
lower than ∼1.4 V, the cell may no longer be useful. Polarisation extent of the NaBH4 crossover, the high cost of the membranes,
data showed anode limitations (for short-time operation) caused by and the reuse/regeneration of NaBH4 , can be overcome, the DBFC
ohmic losses, particularly at high cell currents. Cathode limitations option for the renewable energies scenario would be highly enthu-
were only observed for longer operation periods. siastic. But, as evidenced in Fig. 14, a more promising technology,
It was concluded that to achieve a functional system, several which may be soon commercialised, is based on the reaction of
problems need to be overcome. These include the need to alter water and NaBH4 releasing hydrogen that can fuel a fuel cell
the Zn anode material (by modification of its metal surface and/or or be fed into a combustion engine. Following this avenue, it
by alloying), to reduce the ohmic losses at the Nafion 117 cation would be possible to develop low cost PEMFCs, without the need
exchange membrane (or testing alternative membrane materials), for hydrogen storage, and other concerns which may be quickly
to chose a more effective electrocatalyst for the direct electrochem- squelched.
ical reduction of H2 O2 , to adjust the electrolyte compositions, and
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