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)

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.
Water from Fuel Cell
Gas/Liquid Fuel Hydrogen on DemandTM Separator Catalyst Chamber Pump H
2

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. 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].
900 800
Hydrogen Flow Rate (SLM)

Aggressive Flow Profile TM Compressed H2 and Hydrogen on Demand

Flow Set CmpH2 Flow
HOD Flow

700 600 500 400 300 200 100

Fuel tank: NaBH4 solution Discharged fuel area: NaBO2

H2
NaBO2
borate

H2O
Hydrogen + Steam Coolant Loop Heat Exchanger

50

100

150
Time (sec)

200

250

300

Pure Humidified H2

Fuel Cell

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.

Oxygen from Air

SCHEME 1. Integrated HOD and Fuel Cell System. 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.

Storage Method NaBH4 Liquid H2 Compressed H2 Storage Specifications 30 wt% solution cryogenic 5,000 psi 10,000 psi Volumetric Storage Efficiency ~ 63 g H2/L ~ 71 g H2/L ~ 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

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