Direct Borohydride Fuel Cell BH
4 , in an aqueous alkaline solution, is an attractive

liquid-type fuel source in a DBFC.

In this section, electrochemical principles of a
Borohydrides (BH
4 , tetrahydroborates) bonding DBFC in comparison with those of PEMFC are in-
with Li, K, or Na are classified as chemical complex troduced briefly.
hydrides with high hydrogen content. For instance,
sodium borohydride (NaBH4) contains 10.6 mass%
of hydrogen and readily liberates hydrogen by hy- 1. Fundamentals of DBFC
drolysis. It has been widely utilized as a convenient
source of hydrogen in various chemical industries. In principle, the electrochemical reaction of a DBFC
Recently, it has been developed as a source of hy- takes place in an aqueous alkaline solution diluted by
drogen in the polymer electrode membrane fuel cell NaOH in order to maintain the long-term stability to
(PEMFC; see Fuel Cells: Materials). The hydrolysis, hydrolysis. The electrode and cell reactions can be
expressed as follows:


BH

4 þ 2H2 O ¼ BO2 þ 4H2 ð1Þ


4 þ 8OH -BðOHÞ4 þ 4H2 O
Anode: BH

proceeds by applying such catalysts as Pt, Ru, þ 8e
Ea0 ¼
1:24 V ð4Þ
Mg2Ni, and Ni.
Based on the liberation of hydrogen by hydrolysis,
a direct electrochemical utilization of the borohydride Cathode: 2O2 þ 4H2 O þ 8e
-8OH
Ec0 ¼ 0:40 V
has been attracting interest for developing a new type ð5Þ
of fuel cell, which is called the ‘‘direct borohydride


fuel cell (DBFC).’’ It offers a theoretical potential of Over-all reaction: BH

4 þ 2O2 -BðOHÞ4 E 0 ¼ 1:64 V
1.64 V, which is 33% higher than that of PEMFC. ð6Þ
The negative electrode potential is
1.24 V and it is

0.412 V more negative than in conventional A sodium ion (Na þ ) plays an important role as a
PEMFC. charge carrier in a DBFC. It exists in an aqueous
In an aqueous NaOH solution: solution of NaBH4 and NaOH on the anode side, and



transfers from the anode to the cathode through a
4 þ 8OH -BO2 þ 6H2 O þ 8e
BH
E 0 ¼
1:24 V ð2Þ polymer electrolyte membrane as a charge carrier,
and then, in the NaOH solution, on the cathode side.
The principle of the DBFC is schematically illustrat-
H2 þ 2OH
-2H2 O þ 2e E 0 ¼
0:828 V ð3Þ ed in Fig. 1.
It should be noted that one BH
4 ion generates
In Eqn. (2), the BH
4 ion releases eight electrons, eight electrons, and the electromotive force (EMF)
offering a theoretical energy density of 9.3 Wh g
1- yields 1.64 V, which is 1.33 times higher than that of
NaBH4 in a DBFC. Due to the high energy density, PEMFC and 1.35 times higher than that of DMFC.

8e

BH4−in NaOH O2 or air

solution

−
BH4 + 8OH− 2O2 + 4H2O
+ 8e
Na+

B(OH)4− + 4H2O
8OH−
+ 8e

B(OH)4− NaOH

Anode Nafion Cathode

Figure 1
Schematic diagram of the DBFC.

1
Direct Borohydride Fuel Cell
Table 1
A comparison of thermodynamics for DBFC and PEMFC.
DBFC
Cell reaction


BH

4 ð1Þ þ 2O2 ðgÞ ¼ BðOHÞ4 ðlÞ
DH0 ¼
1392.26 kJ mol
1
DG0 ¼
1267.56 kJ mol
1
EMF: E0 ¼
DG0/nF ¼ 1.64 V
Theoretical energy conversion efficiency
Z ¼ DG0/DH0 ¼ 0.91
Table 1
Unlike other fuel cells, the DBFC is an electro-
chemical system that directly applies the ‘‘protide
(H
),’’ which exists in BH
4 as a state of hydrogen, to
release two electrons per protide and generates eight


electrons through a reaction between BH
4 and OH
in an aqueous alkaline solution at the anode surface,
as shown in Eqn. (4). For a detailed description of the
protide state, see ‘‘Bibliography’’ (Suda et al. 2004).
Table 1 shows a brief comparison between a DBFC
and a PEMFC. It is noted that the theoretical energy
conversion efficiency of a DBFC is 0.91 and this is
higher than 0.83 of a PEMFC.
2. Practical Aspects of DBFC
2.1 Features of DBFC
A DBFC does not apply gaseous hydrogen as a PE-
MFC does, but it applies the protide (H
, hydride
ion) in the BH
4 ion to generate electrons directly at
the contact surface of the anode catalyst (Eqn. (2)).
The most significant feature of a DBFC is the ease
with which large amounts of hydrogen can be stored
in a liquid form under ambient conditions. Hydrogen
is carried as an aqueous solution in compact and
portable tanks, cartridges, and canisters. The elect-
rochemical reaction proceeds under low temperature
conditions and can occur even at ambient tempera-
tures. Na þ is the charge carrier in a DBFC whereas
protons (H þ ) act as the charge carrier in a PEMFC.
As a few molecules of water accompany the Na þ ion
through the membrane from the anode to the cath-
ode, it easily forms a boundary layer of aqueous
NaOH at the surface of the cathode which hinders an
effective contact with O2 in the air, thus reducing the
power density. The NaOH solution so generated
must be removed as quickly as possible and returned
to the anode for recycling.
2
PEMFC
Cell reaction
H2 ðgÞ þ 1=2 O2 ðgÞ ¼ H2 OðlÞ
DH0 ¼
285.83 kJ mol
1
DG0 ¼
237.13 kJ mol
1
EMF: E0 ¼
DG0/nF ¼ 1.23 V
Theoretical energy conversion efficiency
Z ¼ DG0/DH0 ¼ 0.83
In a PEMFC, H2 gas is first absorbed physically at
the Pt surface and then chemically absorbed at the
surface region. Second, the absorbed H2 is trans-
formed to monoatomic hydrogen (H0: protium).
Finally, H0 is transformed to proton and electron
(H0 - H þ þ e
) when the electrochemical reaction
is initiated.


The anode reaction ðBH
4 -BðOHÞ4 Þ occurs only
at the extreme surface of the electrode material, as
shown in Fig. 1. This should be clearly distinguished
from the proton (H þ ) as the charge carrier in a PE-
MFC. Noble metals and alloys conveniently applied
in a PEMFC for converting H2 to H þ are not re-
quired in a DBFC. In this sense, the anode material
in a DBFC does not necessitate the functions re-
quired for hydrogenation and dehydrogenation reac-
tions between hydrogen and metals/alloys.
2.2 Anode and Cathode Materials
Under practical experimental conditions, the ob-
served potential is less negative than the theoretical
standard (–1.24 V) given in Eqn. (2). For example,
1 M NaBH4 in 6 N NaOH solution shows a potential
of about –1.05 V versus SHE against a nickel elec-
trode and –0.95 V versus SHE against Pd or Pt elec-
trode (Liu et al. 2004). The lower potential is due to
the partial hydrolysis of BH
4 , to generate gaseous
hydrogen, as shown in Eqn. (1). The electronegative
characteristics of a DBFC are apparently reduced
according to the degree of hydrolysis. Because of the
competition between the hydrolysis and electrochem-
ical reaction, the ideal eight-electron reaction shown
in Eqn. (2) is hardly realized in practice during de-
velopment of DBFCs.
Noble metals, alloys, and their carbon composites
have been used conveniently as anode catalysts in
PEMFCs and DMFCs. On the other hand, in DBFCs
 Direct Borohydride Fuel Cell

some inexpensive materials can be employed when 1.2 350

they exhibit strong chemical and electrochemical du-

Power density (mW cm−2)

1.0 300
rability under long-term alkaline conditions. Various

Cell voltage (V)

electrode materials used in Ni–MH batteries and al- 0.8
250
kaline fuel cells (AFCs) are available for DBFCs 200
when replacing noble metal catalysts such as Pt, Pd, 0.6
and Ru. Recent efforts to replace such noble materials 150
by low-cost materials have attempted to use surface- 0.4
100
treated Zr-based Laves phase alloys (Li et al. 2003a). 0.2
The major problem to be addressed in the DBFC 50
anode development is to suppress the generation of 0.0 0
gaseous hydrogen by hydrolysis that results in polar- 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7
ization loss. The Coulombic efficiency on a porous Ni Current density (mA cm−2)
electrode was reduced to 50%. Kim prepared the an-
ode using a Pt catalyst and Nafions, and found that Figure 2
the cell performance was significantly influenced by Performance of a single DBFC cell. Experimental
the anode composition (Kim et al. 2004). It is uncer- details: effective electrode area: 67 cm2; fuel: 10 wt.%
tain from the experimental standpoint to confirm the NaBH4 in 20 wt.% NaOH; fuel flow rate: 0.15 l min
1;
report that an efficiency of 90% was attained by an air flow rate: 5 l min
1 (60 1C humidification); and
Au electrode (Amendola et al. 1999). Studies showed operation temperature: 60 1C.
that the electrochemical efficiency of DBFCs depends
strongly on the anode performance and BH
4 con-
centration (Liu et al. 2004).
The anode material should have a larger specific
surface area at the contact site of the BH
4 ions to
enhance the reaction in Eqn. (4) and to minimize the
generation of gaseous hydrogen. Development of an-
ode materials is significantly important for avoiding
partial hydrolysis that leads to a loss of the high po-
tential capability of DBFCs.
Since the reaction at the DBFC and the AFC
cathodes is the same, catalysts used in AFCs may be
applicable in DBFCs as well. A carbon-supported Ag
electrode was reported to perform similarly as the Pt
electrode (Liu et al. 2005). MnO2 was also reported as
a cathode catalyst for DBFCs (Feng et al. 2005,
Verma et al. 2005).

2.3 Recent Achievements

In recent years, the DBFC has been attracting tech-
nological interest for the development of more prac-
tical and commercially more viable fuel cells,
especially for such applications as portable power
generators and battery chargers for mobile electronic
devices.
A series of extensive efforts in the development of
DBFCs has been reported (Li et al. 2003a, 2003b,
2004, Liu et al. 2003, 2004, 2005). In DBFCs, Zr-
based Laves phase alloys as the anode catalyst and a
carbon-supported Pt as the cathode catalyst have
been applied in combination with a conventional
cationic membrane to form a membrane electrode
assembly (MEA) that is considerably durable against
Na þ -based BH
4 solutions. A power density of
290 mW cm
2 at 60 1C was achieved in a single cell,
as shown in Fig. 2. A five-cell stack with an effective
area of 67 cm2 generated 110 W constantly at 60 1C
Figure 3
The photo showing a 200 W DBFC stack.
after starting from room temperature conditions
without air humidification at the cathode. Figure 3
shows a picture of an experimental model of a 200 W
DBFC stack composed of 10 cells.
3. Problems for DBFC
The cell performance of a DBFC, particularly of an
MEA, has been greatly improved in recent years.
However, there are still some technical difficulties
to be solved. First, it is imperative to find a solution
for suppressing the generation of H2 gas on the anode
surface. The Coulombic efficiency of DBFCs can be
increased only by an improvement of the surface
properties and characteristics of the anode materials.

3
Direct Borohydride Fuel Cell
The second problem is related to the BH
4 concen-
tration as the aqueous solution of NaBH4 and
NaOH. As the energy density of a DBFC is basical-
ly determined by the BH
4 concentration, it is desir-
able to increase its concentration as far as possible.
However, NaBO2  4H2O (sodium metaborate), the
oxidized product of BH
4 after releasing electrons,
has a relatively low solubility in such a solution. Pre-
cipitation of crystalline material in the DBFC system,
especially in anode structures, will lead to a fatal de-
crease of the electric capacity and loss of cell life. A


higher BH
4 concentration as a H source was also
found to impose negative effects on the cell perform-
ance. The optimum concentration is found in the
range between 5 wt.% and 15 wt.% NaBH4.
Another common but serious problem of such fuel
cells as DBFCs and DMFCs, which apply diluted
liquid fuel, is the volume occupied by the fuel tanks,
cartridges, or canisters. It has been pointed out that,
in practice, not only liquid-sourced fuel cells such as
DBFCs and DMFCs but also H2-sourced PEMFCs
can hardly replace secondary batteries such as the
Ni–MH battery and the Li ion battery because of
their overall volume-based energy density. DBFCs
and DMFCs are not suitable as alternative power
sources for these secondary batteries.
See also: Fuel Cells: Electrochemical Reactions; Fuel
Cells: Materials.
Bibliography
Amendola S, Onnerud P, Kelly M, Petillo P, Sharp-Goldman S,
Binder M 1999 A novel high power density borohydride-air
cell. J. Power Sources 84(1), 130–3
Copyright r 2006. S. Suda. Published by Elsevier Ltd. All Rights Reserved.
No part of this publication may be reproduced, stored in any retrieval system or transmitted in any form or by
any means: electronic, electrostatic, magnetic tape, mechanical, photocopying, recording or otherwise, without
permission in writing from the publishers.
Encyclopedia of Materials: Science and Technology
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S. Suda
ISBN: 0-08-043152-6
pp. 1–4