SODIUM BOROHYDRIDE FOR HYDROGEN STORAGE

Ying Wu, Richard M. Mohring

Millennium Cell Inc.
1 Industrial Way West, Eatontown, NJ 07724, USA
Introduction
The hydrolysis of sodium borohydride (NaBH4) is an
exothermic reaction that releases hydrogen gas [1] as in Equation 1:
NaBH 4 (
aq) 2 H 2O 4 H 2 NaBO2 (aq) ~ 300 kJ
cat

(1)

Another important HOD application is in fuel cell vehicles.

DaimlerChryslers Natrium and Peugeot-Citrons H2O are two

examples. For automotive applications, system pressure can vary
from 0-13 bar (0-190 psi) and the rated power output reaches 75
kWe. These specifications demand much higher hydrogen flow rates,
up to ~1000 SLM of H2.
Figure 1 shows the results of a testing on an automotive-scale
HOD system, designed to operate a H2 powered internal combustion
engine vehicle (>50 kWe) at Millennium Cell [3].
900

Water from Fuel Cell

Gas/Liquid

Fuel
tank:
NaBH4
solution
Discharge
d fuel
area:
NaBO2

Fuel Hydrogen on DemandTM

Pump Separator
Catalyst Chamber

H2

Heat

400

100
Hydrogen + Steam

Pure Humidified
H2

Fuel
Cell

Oxygen
from
Air

The reaction of Equation 1 allows for storage of hydrogen in

aqueous solutions at high gravimetric density. In a stoichiometric
mixture of NaBH4 and H2O, the amount of H2 stored represents
10.8% of the mixture weight. The higher the NaBH4 concentration,
the more hydrogen is stored in a given volume. Table 1 compares
the volumetric storage efficiency of a 30wt% NaBH4 solution to
compressed and cryogenic hydrogen storage.
The advantage of
NaBH4 is obvious.

Table 1. Volumetric Storage Efficiency Comparisons.

Compressed H2

500

0 0

H2O

SCHEME 1. Integrated HOD and Fuel Cell System.

Storage
Method
NaBH4
Liquid H2

HOD Flow

600

200

Coolant
Loop

Exchanger

Flow Set
CmpH2 Flow

700

300

H2
borate

NaBO2

Aggressive Flow Profile

TM
Compressed H2 and Hydrogen on Demand

800
Hydrogen Flow Rate (SLM)

NaBH4 can be dissolved in water and stabilized via the addition

of base (NaOH). In order to have any appreciable reaction, a catalyst
is necessary for activation and control of the release of hydrogen gas.
Based on this concept, Millennium Cell has developed a technology
known commercially as Hydrogen on Demand fuel systems (HOD
system) [2]. Hydrogen generated in this manner is of high purity and
free of carbon, sulfur, or nitrogen containing impurities that poison
the fuel cell catalyst. Scheme 1 illustrates the HOD system integrated
with a PEM fuel cell, whose water is recycled back to the fuel
mixture.

fuel cell. The rate at which H2 is generated is directly proportional to

the rate at which NaBH4 solution is pumped into the catalyst
chamber.
This operational simplicity translates into relatively
straightforward control strategies [3]. When the fuel cell demand for
hydrogen gas increases, the system pressure begins to drop. The
control system detects the load signal and the drop in pressure and
responds by increasing the rate at which fuel is pumped into the
catalyst chamber. As fuel reaches the catalyst, H2 gas is generated
causing the pressure to increase, and the fuel pump is regulated
accordingly. Examples of load following data will be presented.

Storage
Specifications
30 wt% solution
cryogenic

Volumetric
Storage Efficiency
~ 63 g H2/L
~ 71 g H2/L

5,000 psi
10,000 psi

~ 23 g H2/L
~ 39 g H2/L

Results and Discussion

A number of functioning prototype systems have been
constructed and operated by Millennium Cell. One example is an 18
SLM system designed to be coupled to a Ballard Nexa 1.2 kWe

50

100

150

200

250

300

Time (sec)

Figure 1. Data taken on an automotive scale Hydrogen on

DemandTM system, compared to a baseline of compressed hydrogen.
The figure shows an aggressive flow profile where the
hydrogen flow (directly related to the engine output power) was
varied over a wide range of flows and steps to simulate a driving
cycle. The HOD system response is shown by the solid diamond
symbols. For comparison, a bank of manifolded 2200 psig
compressed hydrogen cylinders was also run through the same
profile, shown in open triangle symbols. The compressed hydrogen
and HOD system response curves are essentially identical; both are
clearly capable of supplying the required hydrogen for the
application.
Conclusion
In summary, NaBH4 has a high intrinsic gravimetric and
volumetric hydrogen storage density for practical hydrogen
generation. The Hydrogen on DemandTM technology has been
successfully demonstrated over a wide range of hydrogen delivery
flow rates and delivery pressures. Research progress is being made
on improving current NaBH4 synthesis technology so that markets
such as transportation can be accessed.
Reference
1.
2.
3.

Schlesinger, H. I.; Brown, H. C.; Finholt, A. E. et. al., J. Am. Chem. Soc.
1953, 75, 215.
Amendola, S., et al., System for Hydrogen Generation, WO
Publication WO 01/51410 A1. US patent pending.
Mohring, R. M.; Eason, I. A.; Fennimore, K. A. SAE World Congress,
SAE Technical Paper Number 2002-01-0098, 2002.

Prepr. Pap.-Am. Chem. Soc., Div. Fuel Chem. 2003, 48(2), 940