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Electrolyse Pulsee PDF
Electrolyse Pulsee PDF
DOI 10.1007/s10800-005-9090-y
Key words: hydrogen generation, inductive energy storage circuit, static induction thyristor, ultra-short pulse,
water electrolysis
Abstract
A novel method of hydrogen generation by water electrolysis using ultra-short-pulse power supply is demonstrated.
The ultra-short power supply consists of a static induction thyristor (SIThy) and a specic circuit which is called the
inductive energy storage (IES) circuit. It was found that by using an ultra-short pulse with the width of 300 ns,
electrolysis takes place with a mechanism dominated by electron transfer, which is dierent from the conventional
diusion limiting process in DC electrolysis.
Fig. 1. Ultra-short pulsed power supply circuit for water electrolysis based on the inductive energy storage (IES) circuit [6, 7] with a static
induction thyristor (SIThy).
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In the case of water electrolysis using the above ultra- explained mainly because an electron with high energy
short pulse power, the water bath electrodes are can only reduce one hydrogen ion so that the dierence
connected to the secondary reactance L2 as seen in between the applied voltage and the decomposition
Figure 1. The pulsed voltage Vp2 is induced in the voltage is dissipated as heat. Since the current itself
secondary reactance L2, synchronized with the pulsed is also increased by increasing the applied voltage,
voltage Vp1 as seen in Figure 2. In the rst stage, when electrons which are not used for hydrogen reduction are
this secondary pulsed voltage is applied to the electrodes also dissipated as heat.
in the water bath, the bath acts as a quasi-capacitor Contrary to the case of DC power electrolysis, ultra-
since the pulse width is too short for ions in the bath to short power electrolysis shows a quite different behav-
cause a current through the bath. This gives a very short iour. As seen in Figure 3(a), in the case of DC
pulsed current Ip2 in the circuit through the secondary electrolysis, the hydrogen generation rate was not
coil (L2). This current is too rapid to be seen in the proportional to the input power. It deviates from the
gure. The water bath is not a real capacitor since all ideal line. The hydrogen generation eciency is calcu-
electrons collected at the cathode are transferred to lated as the ratio of the real generation rate to the ideal
hydrogen ions and high voltage does not remain as in hydrogen generation rate and it can be seen in Fig-
the case of conventional capacitors. After this pulsed ure 3(b) that the eciency is largely decreased in the
voltage had been applied to the electrolysis bath, in the case of DC electrolysis. This decrease is mainly because
second stage, the current I2 ows through the circuit. the energy of most electrons is dissipated as heat.
This current ows very slowly as seen in the gure with In the case of pulse power, it is seen in Figure 3(a) that
several tens microseconds. Since the application of the the hydrogen generation rate is increased as the peak
pulsed voltage Vp2 was already terminated, this current voltage is decreased. It should be noted, however, that
ow I2 may not be due to electron transfer to hydrogen the hydrogen generation rate increases as a function
ions but ion transport in the bath, thus compensating of the input power. This behaviour is quite dierent from
the lack of hydrogen ions in the vicinity of the cathode the case of DC electrolysis. When the input power is
electrode. increased by increasing the pulse frequency, the eciency
was not decreased in the case of high peak voltages, and
was increased in the case of low peak voltages as seen in
4. Results and discussion Figure 3(b). This behaviour is contrary to the case of DC
power. This increase of the eciency for the case of low
The hydrogen generation rate and its efciency are peak voltage may be because the energy dissipation is
plotted as a function of the input power between the decreased since each electron has lower energy and the
electrodes in Figure 3. In the case of DC power pulse waveform is sharper for low peak voltages. For
electrolysis, when the applied voltage is increased, the these reasons, power can be eciently consumed for
current increases so that hydrogen generation rate electrolysis. This fact implies that the ultra-short power
increases, but the eciency compared with the ideal electrolysis is a promising method in which the power
generation rate decreases from 40% at 2.2 V to 8% at application can be increased even with an increase in
12.6 V. Here, the ideal generation rate was calculated electrolysis eciency.
from thermodynamical data [10], for the thermodynam- In the case of DC power, the electric eld is always
ical energy for hydrogen to be converted to room present. The electrical double layer is also present and
temperature water. The decrease in eciency can be the diffusion layer always exists. The current ow is
Fig. 2. A typical example of pulse waveforms for the rst and second stages. In the rst stage, an ultra-short pulse with the width of about
300 ns is applied. In the second stage, the current ows slowly.
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Fig. 3. Hydrogen generation rate (a) and its eciency (b) as a function of the input power. In the case of pulsed power, various circuits with
dierent voltage (Vp2), current (I max
2 ) and frequency ((i)(iv)) have been compared. The input power is the integration of the secondary volt-
age and current multiplied by the frequency. The ideal line was calculated from the thermodynamical energy for hydrogen to be converted to
room temperature water. Hydrogen generation eciencies in (b) were calculated as the hydrogen generation rate divided by the ideal hydro-
gen generation rate at the same input power.
therefore determined by the diffusion of ions with a hydrogen generation so that electrons do not remain in
driving force of ion concentration difference. When the the electrode as in a conventional capacitor. After this
applied voltage is increased, the efciency decreases. In electron transfer, the current I2 ows slowly as shown in
the case of DC power, the power applicable for a certain Figure 2, probably due to the ion diusion in the
volume of the electrolysis bath is therefore limited. electrolysis bath.
In the case of ultra-short pulsed power, the electric From the above considerations, it can be concluded
eld is applied for only a very short time less than that the electrolysis mechanism for ultra-short pulse
several microseconds which is much shorter than the power is very different from that of DC electrolysis. DC
time necessary for the formation of the constant electric electrolysis is based on electrical double layer formation
double layer. By the application of the ultra-short pulse, and is a diffusion-limited process, while ultra-short pulse
electrons are collected on the surface of the cathode power electrolysis is based on the strong electric eld
electrode as in a capacitor. The electrons gathered application and the electron transfer limited process.
however are quickly transferred to hydrogen ions for This difference seems to be very important for the
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practical and industrial application of ultra-short power and S. Tange for their helpful discussion, and Mr M.
electrolysis since the electrolysis power can be increased Imaeda for his experimental help.
without decreasing the efciency.
5. Conclusion References