Electrochimica Acta 48 (2003) 41194125

Water electrolysis under microgravity

Part 1. Experimental technique
H. Matsushima a , T. Nishida a , Y. Konishi b , Y. Fukunaka a, ,
Y. Ito a,1 , K. Kuribayashi c
aGraduate School of Energy Science, Kyoto University, Sakyo-ku, Kyoto 606-8501, Japan
b Department of Chemical and Biomolecular Engineering, University of Illinois, Urbana, IL 61801, USA
c Institute of Space and Astronautical Science, Sagamihara 229-8510, Japan

Received 13 March 2003; received in revised form 7 July 2003; accepted 9 July 2003

Abstract

Water electrolysis was conducted in both alkaline (25 wt.% KOH, 2 wt.% KOH) and acid (0.1N H2 SO4 ) solutions for 8 s under microgravity
environment realized in a drop shaft. The gas bubble formation of hydrogen and oxygen on platinum electrodes was observed by CCD
camera. In alkaline solutions, a bubble froth layer grew on the electrode surface. Hydrogen bubble size was smaller than that of oxygen.
The current density at constant potential decreased continually with time. In spite of the growth of a bubble froth layer on the electrode,
the electrolysis never stopped, apparently because fresh electrolyte is supplied to the electrode surface by microconvection induced by the
gas bubble evolution. In acid solution, hydrogen gas bubbles frequently coalesced on the cathode surface, yielding a larger average bubble
than that of oxygen. The current density did not vary at constant potentials from 0.4 to 0.8 V versus reversible hydrogen electrode (RHE),
because the effective electrode surface area was significantly reduced by the larger bubble size compared to alkaline electrolyte. The present
experiments indicate that, especially in a microgravity environment, the bubble evolution behavior and the resultant currentpotential curves
are significantly influenced by the wettability of the electrode in contact with the electrolyte.
2003 Elsevier Ltd. All rights reserved.

Keywords: Water electrolysis; Microgravity; Bubble evolution; Microconvection; Wettability

1. Introduction In addition to electrocatalytic rate limitations, the pres-

Gas bubble evolution in water electrolysis is a typical in-
terfacial phenomenon. Many studies have been conducted
under terrestrial gravity condition from the industrial point
of view [15]. In a water electrolysis plant, the typical
cell voltage of 1.82.0 V at an operating current density of
100300 mA cm2 is considerably higher than the equilib-
rium voltage of 1.23 V. This is due to high overpotentials
at both anode and cathode [2], which are characteristic for
gas evolution processes. Much research aimed at developing
lower-overpotential electrodes with higher electrocatalytic
capability is now in progress.
Corresponding author. Tel.: +81-75-753-5415;
fax: +81-75-753-4719.
E-mail address: fukunaka@energy.kyoto-u.ac.jp (Y. Fukunaka).
1 ISE Member.
ence of the gas bubble on the electrode causes an increase
in ohmic drops (IR drops, where I is current and R solution
resistance) and this results in higher energy consumption,
although micro- and macro-convection of electrolyte is ex-
pected in the vicinity of a gas-evolving electrode. The rate of
the electrochemical reaction is controlled by the interfacial
phenomena in the three-phase zone where gas bubble, elec-
trolyte and electrode surface contact each other. The macro-
scopic natural convection due to buoyancy complicates the
analysis of the ionic mass transfer rate due to the microcon-
vection caused by gas bubble formation and growth. The
microgravity environment thus provides an ideal environ-
ment to examine the effect of microconvection on the elec-
trochemical reaction in the three-phase zone in the absence
of macroscopic convection (pumping action). A deeper un-
derstanding of the electrochemical interfacial phenomena in
a three-phase zone may contribute to a rational design strat-
egy for the industrial water electrolysis cells.

0013-4686/$ see front matter 2003 Elsevier Ltd. All rights reserved.
doi:10.1016/S0013-4686(03)00579-6
4120 H. Matsushima et al. / Electrochimica Acta 48 (2003) 41194125

It is also noteworthy that water electrolysis may become et al. [15]. They sketched the evolving gas bubble behavior.
a key technology in the operation of a space station [6]. It However, it is difficult to analyze their results quantitatively.
is utilized as a regenerative life support system as well as In the research reported in this paper, water electrolysis
part of an energy conversion system. The latter combines was conducted with the objective to obtain optimum under
a solar-powered water electrolysis cell with a fuel cell to microgravity condition inside the largest available drop shaft
generate a constant supply of electricity in the space station. (Kamisunagawa). Hydrogen and oxygen gas bubbles were
This is termed a regenerative fuel cell system (RFCS) [7]. observed simultaneously by CCD cameras, in alkaline and
Water electrolysis is increasingly carried out using a in acid solutions.
proton exchange membrane (PEM) like Nafion or Flemion
[8] rather than the traditional microporous diaphragm. This
membrane acts not only as an ion-conducting membrane 2. Experimental
but also as a gas separator. The electrocatalyst layers of
the anode and cathode are supported by the porous cur- 2.1. Electrochemical system
rent collectors as bipolar plates, and are separated by the
proton-carrying polymer membrane. Water fed to the anode An electrolytic cell (10 mm 10 mm 40 mm) was em-
decomposes at the interface between the electrocatalyst and ployed as schematically illustrated in Fig. 1. It was made
the electrolyte by the reaction: of polystyrene resin. Two platinum sheets (7 mm 5 mm
H2 O 2H+ + 21 O2 + 2e (1) 0.1 mm) were used as, respectively, the working electrode
and the counter electrode. Both electrodes were mounted on
The evolving oxygen does not always form a gas bubble. The acrylic resin block (7 mm 5 mm 4 mm) with epoxy resin
characteristic of generating fewer gas bubbles is favorable bond. Electrical lead wires were connected by soldering to
for space application. both electrodes through a glass tube. The reference elec-
The thin membrane allows a high operating current den- trode was an Ag/AgCl electrode with saturated KCl solution
sity, e.g. 1.5 A cm2 , but it is necessary to remove the excess (3.33 mol l1 ). The electrode potential was controlled with
heat generated by its poor electrolyte conductivity. In a mi- respect to a reference electrode in liquid contact through
crogravity environment, the excess heat generated may be a salt bridge filled with saturated KCl agar. The tip of a
radiantly dissipated, however, this is not easy from the tech- glass Luggin probe was held about 1.5 mm from the working
nological point of view. Moreover, this electrolysis technique electrode.
using PEM is not completely free from gas bubble evolution,
even when a porous electrode is used. Thus, the feasibility of
conventional large area water electrolysis at higher current
density must be examined in parallel with PEM electrolysis.
This is the reason why the present authors are engaged in
research on the non-equilibrium electrochemical interfacial
aspects of water electrolysis using microgravity as a tool.
In the literature, a number of research reports are found
about the effect of microgravity environments. Most of
them are related to the life sciences [9,10] and various
materials processing areas [11,12]. Although the interfacial
phenomena in electrochemical processing in a microgravity
environment are important, they have not been studied
systematically from the viewpoint of energy science and
technology.
The literature contains a few reports on water electrolysis
under microgravity conditions [1315]. Kaneko et al. [13]
observed oxygen gas evolution in sulfuric acid solution dur-
ing the parabolic flight of an airplane, and pointed out that
the resultant microgravity level (0.01 G) was not sufficient to
prevent bubbles from vibrating and departing from the elec-
trode. Iwasaki et al. [14] reported hydrogen gas evolution in
sulfuric acid solution at a silver reference electrode in a drop
shaft. They reported an extraordinarily high hydrogen over-
potential (e.g. 2.5 V versus Ag at 100 mA cm2 ), which is
Fig. 1. Schematic experimental cellA: electrodes (Pt, 7 mm 5 mm
far larger than the value reported in terrestrial experiments. 0.1 mm); B: luggin probe; C: salt bridge; D: reference electrode
Both oxygen and hydrogen gas evolution in sodium hydrox- (Ag/AgCl); E: polystyrene cell (10 mm 10 mm 40 mm); F: CCD cam-
ide solution were observed in a Mir space station by Nefedov era; G: syringe.
 H. Matsushima et al. / Electrochimica Acta 48 (2003) 41194125
Electrodes and a Luggin probe were fixed to the upper
lid of the electrolytic cell. The distance between the elec-
trode and the inner wall was kept at 3 mm. The electrode
configuration of the assembled cell was expected to yield
good uniformity of current distribution, while the cell design
made it possible to observe in situ the gas evolution at both
electrode surfaces simultaneously. The gas bubble evolution
was observed using CCD cameras. The front view as well as
side view of the gas-evolving on the electrode surface was
recorded with 8 mm VTR at 30 frames per second.
A 25 wt.% KOH, 2 wt.% KOH and 0.1N H2 SO4 aque-
ous solutions were adjusted with G.R. reagents and dis-
tilled water. A syringe was connected to the cell in order to
compensate the electrolyte volume expansion caused by the
gas evolution at both electrodes enclosed in the electrolytic
cell.
2.2. Drop shaft experiments
The drop shaft at Kamisunagawa is designed so that the
electromagnetically sustained capsule starts to descend by
gradually reducing the electromagnetic current (Fig. 2). The
capsule is designed so that it has an inner and outer struc-
ture. It is evacuated around the inner structure (inner cap-
sule), and the outer structure (outer capsule) is accelerated
by injecting gas at an appropriate rate to compensate the
friction of air inside the drop shaft. The injection rate of
Fig. 2. Schematic illustration of the drop shaft facilityA: capsule; B:
free-fall zone (490 m); C: braking zone (200 m); D: emergency braking
zone (20 m).
4121
10 -1.0
ratio of acceleration force to normal gravity
8 applied potential
Acceleration / G
Potential / V
6
interrupt -0.5
start
4
2
0 0
0 5 10 15
Time / s
Fig. 3. Scheduling of electrolysis experiment and transient variation of
acceleration force measured in capsule.
air is controlled by monitoring the relative distance between
the inner and outer capsules. Thus, the gravitational level
becomes about 1 105 G within 0.2 s after the capsule be-
gins to fall. The electrolysis starts 1 s after the microgravity
level has been attained. It is then terminated after 9 s, so
that the electrolysis is conducted only under microgravity.
The capsule reaches the deceleration zone after 10 s, i.e. 9 s
after starting electrolysis. As it enters this zone, the acceler-
ation level suddenly rises to approximately 3 G. The max-
imum acceleration level attains 8 G, followed by a gradual
decrease of the gravitational level (Fig. 3).
The electrochemical control system developed specifi-
cally for the drop shaft experiment is schematically illus-
trated in Fig. 4 [16]. The potentiostat is switched perma-
nently to the electrolysis mode. All electric power is turned
off before installing the electrolytic experimental equipment
in the capsule. Power is turned on again 15 min before
free-fall. At first, the electric current is transmitted to a
dummy cell. A relay circuit operates to switch the electric
current from the dummy cell to the electrolytic cell as the
capsule falls. The microgravity level reaches <104 G at
0.2 s after disconnecting the capsule. Therefore, the timer
circuit starts electrolysis 1 s after receiving the start of falling
signal and monitors the transient electrochemical reaction
only under <104 G microgravity conditions.
A kind of electromagnetic noise in the signal line some-
times induces a malfunction of the switching devices during
capsule assembly and free-fall operation. Some of this noise
occasionally overlaps with monitoring of the electrolysis
data. Therefore, the electrical devices are sealed in stainless
steel or aluminum boxes. The signal lines are also sealed
with aluminum foil more carefully than those for terrestrial
gravity experiment. A Schmitt Trigger Circuit and relay
are effective in rejecting such noise from the signal. These
circuits are connected between the switching devices and
the signal interface at the inner rack of capsule in order to
receive signals as correctly as possible.
4122 H. Matsushima et al. / Electrochimica Acta 48 (2003) 41194125

Video recorder Dummy

in bus module cell

Relay
Video
Cell Potentiostat
camera Memory in
bus module
Video Timer start Timer Digital
timer Timer start oscillographic
recorder
Trigger

Pulse generator

Signal interface

Video movie Experimental data

Fall to signal
(Optical signal monitoring) (Optical signal monitoring)

Fig. 4. Schematic diagram of control system for drop shaft experiments.

3. Results In 2 wt.% KOH solution, the current density was much

3.1. Currentpotential curve
Water electrolysis was potentiostatically conducted in al-
kaline (25 wt.% KOH, 2 wt.% KOH) and acid (0.1N H2 SO4 )
solutions. Fig. 5 shows the currentpotential curves of the
hydrogen evolution reaction recorded at 8 s after water elec-
trolysis is started. The applied potential is indicated with
respect to reversible hydrogen electrode (RHE).
In 25 wt.% KOH solution, the current density increased
with decreasing cathodic potential regardless of gravitational
levels. It was lower under microgravity than under terrestrial
gravity throughout all experiments. Good reproducibility of
the measurements was observed even under G.
less than that in the 25 wt.% KOH solution. This is at-
tributed to the poor conductivity of the electrolyte. The cur-
rent density difference between both gravitational strengths
was small at 0.4 and 0.5 V, while it was considerably
larger at less than 0.6 V.
In 0.1N H2 SO4 solution, the current density was much
smaller than in KOH solutions irrespective of gravity dif-
ference. As expected, it was lower under G than that un-
der 1 G, but under G it was constant at about 30 mA cm2
over a wide range of the cathodic potential. A similar result
was reported earlier by Kaneko et al. [13]. They attributed
the virtually constant current density to the strong bubble
attachment to the electrode surface.
3.2. CCD images

1400 Both hydrogen and oxygen gas bubble evolution were

recorded by CCD cameras. Evolution in alkaline and acid
1200 solution is shown in Figs. 6 and 7, respectively. The front
Current Density / mA cm-2

view shows hydrogen evolution at the cathode, while the

1000
side view shows hydrogen evolution at the cathode on the
800
left side and oxygen evolution at the anode on the right
side.
600
3.2.1. Alkaline solutions
400 Fig. 6 shows gas evolution in 25 wt.% KOH solution at
0.8 V versus RHE, under (a) terrestrial gravity and (b) mi-
200
crogravity conditions. Under terrestrial gravity (Fig. 6(a)),
0 the front view shows the cathode surface covered with fine
-0.4 -0.5 -0.6 -0.7 -0.8 hydrogen bubbles, while some of these have grown in size
Potential / V. vs. RHE and are attached around the cathode. The video image illus-
trates that a significant amount of hydrogen bubbles moves
Fig. 5. Currentpotential curves of hydrogen evolution reaction at 8 s
upward to induce a kind of macroscopic natural convection
after starting water electrolysis under microgravity (G) and terrestrial
(1 G) conditions: () 25 wt.% KOH under 1 G; () 25 wt.% KOH under or bubble layer curtain along the cathode. The side view
G; () 2 wt.% KOH under 1 G; () 2 wt.% KOH under G; () 0.1N shows the oxygen gas curtain on the right, as well as the hy-
H2 SO4 under 1 G; () 0.1N H2 SO4 under G. drogen bubble curtain on the left side of the picture. Oxygen
 H. Matsushima et al. / Electrochimica Acta 48 (2003) 41194125
Fig. 6. Comparison of gas bubble evolution in alkaline electrolyte under (a) terrestrial gravity and (b) microgravity conditions, at 8 s after starting water
electrolysis (0.8 V vs. RHE, 25 wt.% KOH).
bubble size was larger than hydrogen bubble size throughout
all experimental conditions. Moreover, oxygen bubble size
distribution was more uniform. These results agree well with
previous results by Janssen et al. [4] who measured both
oxygen and hydrogen gas bubbles evolving from a transpar-
ent electrode in 1.0 M KOH solution.
Under microgravity, bubble froth layers as sketched by
Nefedov et al. [15] appeared on both electrodes as seen in
Fig. 6(b). Newly generated hydrogen gas bubbles pushed
away the already existing bubbles to generate the bubble
froth layer as seen in the side view in Fig. 6(b). Oxygen
bubbles more frequently coalesced with each other than hy-
drogen bubbles. Their sizes were lager and more uniform
than those of hydrogen bubbles under G as well as under
1 G. The size difference between oxygen and hydrogen gas
bubbles became stronger with decreasing cathodic potential,
as will be further described [17]. Compared with terrestrial
gravity experimental results, the bubble sizes of both gases
under G were larger, as noted in other papers [1315]. This
is attributed to a longer residence time of gas bubbles on
electrodes.
Under G, the bubble froth layer was formed in 2 wt.%
KOH solution as well as in 25 wt.% KOH solution. More
4123
detailed descriptions will be given in a following paper
[17].
3.3. Acidic solutions
Fig. 7 shows the gas evolution phenomena in 0.1N
H2 SO4 solution at 0.8 V. Several hydrogen gas bubbles
attached to the cathode surface are seen in the front view
under 1 G (Fig. 7(a)). When the hydrogen gas bubbles
coalesced with neighboring fine bubbles to grow up to a
certain size, they started to roll over or occasionally to
depart from the cathode surface. Oxygen gas bubbles, on
the other hand, form a bubble curtain similar to that in
alkaline solution. Oxygen bubble size is slightly smaller
than hydrogen. The size distribution of oxygen bubble
is more uniform than that of hydrogen in the terrestrial
experiment.
Under the microgravity environment, some hydrogen
gas bubbles coalesced frequently on the cathode surface
to grow much larger gas bubbles with a few mm in di-
ameter clearly even in Fig. 7(b). The bubble froth layer
seen in Fig. 6 has never been observed due to the fre-
quent coalescence. The side view indicates smaller oxygen
4124 H. Matsushima et al. / Electrochimica Acta 48 (2003) 41194125
Fig. 7. Comparison of gas bubble evolution in acidic electrolyte under (a) terrestrial gravity and (b) microgravity conditions, at 8 s after starting water
electrolysis (0.8 V vs. RHE, 0.1N H2 SO4 ).
bubble size than hydrogen, irrespectively of the electrode
potential.
4. Discussion
There are significant differences in the bubble evolution
behavior between alkaline and acid solutions as described
above. The differences may be understood in terms of wet-
tability, which is determined by the three-phase interaction
among electrolyte, gas and electrode. The side views of
Figs. 6 and 7 clearly demonstrate that the alkaline solution
has a better wettability than the acidic solution.
The wettability phenomenon also influences the current
potential curves. In alkaline solution, the current density is
much smaller under G than under terrestrial gravity. This
is explained by the growth of a bubble froth layer causing a
larger electrolytic resistance for water electrolysis [1820].
Although the thick bubble froth layer fully covers the elec-
trode surface, the current density never decreases to zero and
the electrolysis is not interrupted. The enhanced mass trans-
fer rate associated with gas bubble growing on the electrode
surface has been related to a microconvection mechanism
[21,22]. This is superimposed on the mass transfer rate as-
sociated with the macroscopic natural convection induced
by gas bubbles moving upward along the vertical electrode.
The latter effect appears only in the gravitational field, while
the microconvection mechanism caused by the growth and
detachment of bubbles on the electrode surface is present
even in a G environment.
In alkaline solution, evolving gas bubbles frequently
detach due to the better wettability. The gas bubble de-
tachment causes a kind of microconvection that supplies
fresh electrolyte to the electrode surface via the bubble
froth layer. On the other hand, the bubbles seldom detach
from the electrode surface due to poor wettability, as in
acidic solution. The active electrode area is significantly
decreased by attached bubble as seen in the side view in
Fig. 7. Therefore, under microgravity, the current density
does not increase regardless of applied potential.
5. Conclusion
Using the largest drop tower in the world, an in situ
measurement technique may be used to examine the
non-equilibrium interfacial phenomena occurring under mi-
crogravity in water electrolysis. The experimental technique
 H. Matsushima et al. / Electrochimica Acta 48 (2003) 41194125
is briefly described in the present paper. Water electrolysis
was selected since it clearly illustrates the capability of this
present experimental system to observe non-equilibrium
electrochemical phenomena under G conditions.
Water electrolysis in 25 wt.% KOH, 2 wt.% KOH and
0.1N H2 SO4 solutions was took place under constant poten-
tial difference between the electrodes for 8 s under micro-
gravity, and the resultant current density monitored while
bubble formation was recorded. Gas evolution in the absence
of gravity is strongly influenced by the electrolyte wettabil-
ity at the electrode material (Pt).
In both 25 wt.% and 2 wt.% KOH solution, bubble froth
layers were formed under G, while bubbles moving upward
induced a bubble curtain which superimposes a pumping ef-
fect on the ionic mass transfer rate observed under terrestrial
gravity condition due to macroscopic natural convection.
Although the bubble froth layer fully covered the electrode
surface, water electrolysis was not interrupted, due to the
microconvection mechanism induced by the growth of gas
bubbles on the electrode surface. Bubble size in the mi-
crogravity experiments was larger than in terrestrial gravity
experiments, due to longer residence time at the electrode.
Oxygen bubble size distribution showed a larger average
value and a smaller variance than that for hydrogen gas
bubbles.
In 0.1N H2 SO4 solution, in a G environment, bubbles
coalesced with each other frequently to grow large bubbles
of more than a few mm in diameter. The current density did
not increase regardless of applied potential. This is ascribed
to the active surface area reduction caused by gas bubbles
which remain attached on the electrode surface. Oxygen
bubble size is smaller than that of hydrogen, and the oxy-
gen bubble size distribution is more uniform. The effect of
gravitational level is not so significant in the case of H2 SO4
solution as it is in KOH solutions.
Acknowledgements
The authors wish to thank NASDA and JSUP for provid-
ing the drop shaft experiment opportunity. They would also
4125
like to acknowledge the highly appreciate supportby JAMIC
staff.
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