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Water Electrolysis with Inductive Voltage Pulses

Chapter · October 2012

DOI: 10.5772/52453

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 Chapter 2

Water Electrolysis with Inductive

Voltage Pulses

Martins Vanags, Janis Kleperis and Gunars Bajars

Additional information is available at the end of the chapter

http://dx.doi.org/10.5772/52453

1. Introduction
The main idea of Hydrogen Economy is to create a bridge between the energy resources,
energy producers and consumers. If hydrogen is produced from renewable energy sources
(wind, solar, hydro, biomass, etc.), and used for energy production in the catalytic
combustion process, then the energy life cycle does not pollute nature longer. With
transition to Hydrogen Economy the Society will live accordingly to the sustainable
development model, defined in the 1987 (Our Common Future, 1987).

Hydrogen is not available on Earth in free form; therefore the production process is
representing a major part of the final price of hydrogen (Hydrogen Pathway, 2011). This is
the main reason while research for effective electrolysis methods is very urgent. On our
Planet the hydrogen is mainly located in compounds such as hydrocarbons, water, etc. and
appropriate energy is needed to release hydrogen from them. In principle the amount of
consumed energy is always greater than that which can be extracted from the hydrogen,
and in the real operating conditions, the cycle efficiency does not exceed 50% (The
Hydrogen Economy, 2004). The current problem is motivated to seek improvements to
existing and discovering new technologies to produce hydrogen from the water – widely
available and renewable resource on the Earth.

Water electrolysis is known more than 130 years already, and different technologies are
developed giving power consumption around 3.6 kWh/m3 - high temperature electrolysis,
and 4.1 kWh/m3 - room temperature alkaline electrolysers and proton exchange membrane
electrolysers (The Hydrogen Economy, 2004). Lower hydrogen production costs is for
technologies using closed thermo-chemical cycles, but only in places where huge amount of
waste heat is available (for example, nuclear power stations (The Hydrogen Economy, 2004).
Nevertheless what will be the hydrogen price today, in future only hydrogen obtained from
renewable resources using electricity from renewable energy sources will save the World, as

© 2012 Vanags et al., licensee InTech. This is an open access chapter distributed under the terms of the
Creative Commons Attribution License (http://creativecommons.org/licenses/by/3.0), which permits
unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.
20 Electrolysis

it was stated in 2nd World’s Hydrogen Congress in Turkey (Selected Articles, 2009). For
Latvia the hydrogen obtained in electrolysis using electricity from renewables (wind, Sun,
water) also would be the best solution to move to Hydrogen Economics (Dimants et all,
2011). That is because all renewables available in Latvia’s geographical situation are giving
non- stable and interrupt power, for which the storage solutions are necessary. Usage of
hydrogen as energy carrier to be produced from electricity generated by renewables, stored
and after used in fuel cell stack to generate electricity is the best solution (Zoulias, 2002).
Efficient and stable electrolysers are required for such purposes. Smaller electrolysis units
are necessary also for technical solutions were hydrogen is produced and used directly on
demand, for example, hydrogen welding devices, hydrogen powered internal combustion
cars (Kreuter and Hofmann, 1998).

DC power typically is used for electrolysis, nevertheless pulse powering also is proposed (see,
for example, Gutmman and Murphy, 1983). Using a mechanically interrupted DC power
supply (Brockris and Potter, 1952; Bockris et all, 1957) next interesting phenomena was
noticed: immediately upon application of voltage to an electrochemical system, a high but
short-lived current spike was observed. When the applied voltage was disconnect, significant
current continues to flow for a short time. In 1984 Ghoroghchian and Bockris designed a
homopolar generator to drive an electrolyser on pulsed DC voltage. They concluded that the
rate of hydrogen production would be nearly twice as much as the rate for DC.
The Latvian Hydrogen Research Team is developing inductive pulse power circuits for
water electrolysis cell (Vanags et all, 2009, 2011a, 2011b). The studies revealed a few
significant differences compared to conventional DC electrolysis of water. New model is
established and described, as well as the hypothesis is set that water molecule can split into
hydrogen and oxygen on a single electrode (Vanags et all, 2011a). There has been found and
explained the principle of high efficiency electrolysis. A new type of power supply scheme
based on inductive voltage pulse generator is designed for water electrolysis. Gases released
in electrolysis process from electrodes for the first time are analyzed quantitatively and
qualitatively using microsensors (dissolved gases in electrolyte solution nearby electrode)
and masspectrometer (in atmosphere evolved gases). The hypothesis of hydrogen and
oxygen evolution on a cathode during the process of pulse electrolysis is original, as well as
interpretation of the process with relaxation mechanisms of electrons emitted by cathode
and solvated in electrolyte (Vanags, 2011b).

2. Literature review
2.1. A brief history of the electrolysis of water
Adriaan Paets van Troostwijk, 1752.–1837., and Johan Rudolph Deiman, 1743.–1808., while
using Leyden jar and a powerful electrostatic generator noticed a gas evolution on the
electrodes of water electrolysis cell as a result of spark over jumping in the electrostatic
generator. The evolved gases displaced water out of the Leyden jar during the experiment
and spark jumped into the collected gas mixture creating an explosion. The researchers
decided that they have decomposed water into hydrogen and oxygen in a stoichiometric
 Water Electrolysis with Inductive Voltage Pulses 21

proportion 2:1; they published the results in 1789, which is considered to be the year of
discovering the water electrolysis (Zoulias et all, 2002; De Levie, 1999). In more that hundred
years, in 1902 there were more than 400 industrial electrolysers used all over the world, but
in 1939 the first large water electrolysis plant was commissioned with the hydrogen
production capacity of 10000 Nm3/h (Zoulias et all, 2002). The high-pressure electrolysers were
produced in 1948 for the first time; in 1966 General Electric built the first electrolysis system
with solid electrolyte and in 1972 the first solid oxide high-temperature electrolyser was built.
However the development of electrolysis devices is in progress nowadays as well along with
the development of proton exchange membrane, which can be used in the water electrolysers
and fuel cells, along with the development of high-temperature solid oxide electrolysers
likewise the optimization of alkaline electrolysers (Kreuter W, and Hofmann H (1998).

2.2. Direct current water electrolysis

When dissolving acid in the water (e.g. sulfuric acid), molecules of water and acid dissociate
into ions. The same happens if alkali (e.g. KOH) is dissolved in the water, the solution
dissociates into ions, creating ionic conductor or electrolyte. There has been formed an ionic
conductor, where a direct current will be passed through. The processes taking place on
electrodes are in the case of sulfuric acid - the positive hydroxonium ions H3O+ (cation)
move to the side of negative electrode. When cations reach the electrode, they receive
missing electrons (Zoulias et all, 2002):

2 H 3O + + 2 e  H 2 + 2 H 2O (1)

Hydrogen is produced as gas from the medium, in its turn, water dissociates into ions again.
The reaction on an anode or positive electrode in an alkaline medium is (Zoulias et all, 2002):

1
2OH − − 2 e  O2 + H 2O (2)
2

Oxygen evolves as gas, but water dissociates into ions again. There are produced three parts
of volume of gaseous substance in the process described - two parts of hydrogen and one -
oxygen. In the case of alkaline electrolyte there are polarized water molecules, which have
their hydrogen atoms oriented toward an electrode, near the cathode and dissociation
reaction takes place:

2 H 2O + e  2OH − + H 2 (3)

The first law of thermodynamics for the open system states that:

Q – Ws = ΔH (4)

where Q is the amount of heat supplied to the system, Ws the amount of appropriate work
performed by the system and ΔH is the change in system's enthalpy. The work done is
electricity used up in electrolyser, therefore Ws is:
22 Electrolysis

Ws = -nFE (5)

where:
n - The amount of transferred electrons;
F – Faraday constant: = 23,074 cal/volts.g-equivalent;
E - Electric potential of the cell in volts.

Using equation (5), transform the expression (4), resulting:

ΔH − Q
E= (6)
nF

In an isothermal reversible process (without loss) Q is:

Qatg = TΔS (7)

where T is absolute temperature and ΔS is system entropy change. From (6) and (7) the
value of reversible reaction potential is obtained, where it is impossible to decompose water
into hydrogen and oxygen in real time:

ΔH − T ΔS
Erev = (8)
nF

(ΔH – ΔS) is the change in Gibbs free energy ΔG. At normal temperature and pressure ((25
oC temperature and 1 atm pressure) ΔH equals 68 320 cal/gmol and ΔG equals 56 690

cal/gmol. Therefore the reversible potential of the cell is:

ΔG 56,690
Erev = = = 1,23V (9)
nF 2(23,074)

Potential where Q equals zero and supplied energy transforms into chemical energy, is
called thermo-neutral voltage (Oldham and Myland, 1993; Bockris and Potter, 1952):

ΔH
Ethermo = = 1,48V (10)
nF
The voltage to split water in practical electrolysis devices is higher than thermo-neutral cell
voltage due transformation into heat, which heats up the cell. Therefore industrial
electrolyser requires additional cooling and the value of DC voltage is defined:

E = Erev +loss (11)

where the

loss = Eanode + Ecathode + Emt + IR (12)

In equation (12) Eanode – activation overvoltage of the anode; Ecathode – activation overvoltage of
the cathode; Emt – overvoltage of the mass transfer and IR – ohmic overvoltage (includes
resistance in an electrolyte, on electrodes, leads). Current density must be higher than 100
 Water Electrolysis with Inductive Voltage Pulses 23

mA/cm2 in industrial electrolysers, therefore voltage applied to individual cell partly

transforms into the heat, becoming typical loss in DC water electrolysis.

It is possible to write an expression for the efficiency factor of the water electrolysis, calculated
versus the thermo-neutral voltage, using relations above (Bockris and Potter, (1952):

ΔH E
η= = thermo (13)
ΔG + loss E

When ΔG is negative, the reactions are spontaneous and work has been done by releasing
the energy. When ΔG is positive, for reaction to happen external work must be used. As for
ensuring the reaction, work must be done, water electrolysis cell does not operate
spontaneously. The reaction in fuel cells is spontaneous because of the catalyst and during
reaction the energy is released (Salem, 2004).
Hydrogen Evolution Reaction (HER) is one of the most widely researched reactions in the
electrochemistry. The studies of HER are carried out in different kind of systems and
following each other processes is divided (Salem, 2004; Heyrovsky, 2006; Murphy, 1983;
Bockris, 1957; El-Meligi, 2009; Sasaki and Matsuda, 1981; Noel and Vasu, 1990; Kristalik,
1965): Volmer electrochemical discharge step, Heyrovsky electrochemical desorption step,
Tafel catalytic recombination step. Each of steps can be a reaction limiting step in a certain
system during the whole reaction. This means, that each step can have different reaction
rate, and the slowest step will determine the speed of reaction. Charge transfer may begin
when the reagent is next to the electrode. Two most typical steps are charge transfer ending
with the adsorption of hydrogen atom, and recombination of the adsorbed atoms with next
desorption of H2 molecule.

The general equation of the electrochemical reaction links current with potential (Noel and
Vasu, 1990):

    βλη F   (1 − β )λη F  
ic = i − i = i0 exp  −  − exp   (14)
  RT   RT 

β is symmetry factor (0, ½, 1 for process without activation, normal process and barrier-free
process accordingly).

2.3. Interface between electrode and electrolyte: double layer

When two equal electrodes (conductors) are immersed in an electrolyte, initially there is no
measurable voltage between them. But when the current is caused to flow from one rod to
the other by a battery, charge separation is naturally created at each liquid/solid interface
and two electrochemical capacitors connected in series are created. Typical capacitors store
electrical charge physically, with no chemical or phase changes taking place, and this
process is highly reversible; the discharge-charge cycle can be repeated over and over again,
virtually without limit. In electrochemical capacitor at electrode/electrolyte interface
solvated ions in the electrolyte are attracted to the electrode surface by an equal but opposite
24 Electrolysis

charge in it. These two parallel regions of charges at interface form the “double layer” where
charge separation is measured in molecular dimensions (i.e., few angstroms), and the
surface area is measured in thousands of square meters per gram of electrode material
(Miller and Simon, 2008).

Double-layer phenomena and electro-kinetic processes are the main elements of

electrochemistry. It is considered that the behavior of the interface is and should be
described in terms of a capacitor. It is a consequence of the “free charge” approach that in
the case of a continuous current flow through the interface a strict distinction should be
made between the so-called non-Faraday and Faraday currents. The former is responsible
for charging of the double-layer capacitor, while the latter is the charge flow connected with
the charge transfer processes occurring at the interface (Horányi, Láng, 2006). The state of an
interface at constant pressure and temperature can be changed by changing the
concentration of the components in the bulk phases, and by constructing an electrical circuit
with the aid of a counter electrode and forcing an electric current through the circuit, which
can be expressed as:

i = i '+ i '', (15)

Were i` is charging current of double layer, and i`` – charge transfer or Faraday current.
Double layer charging current can be viewed as an ideal capacitor charging current equal to
∂η
C , were η is overvoltage and C – double layer capacitance. Rewriting equation (15), next
∂t
current equation is obtained:

∂η
i =C + i '' (16)
∂t

which has caused much debates. Paul Delahais wrote in 1966 that this equation permits the
decoupling of the non-Faraday from Faraday processes, but at the same time concludes that
Faraday charge transfer and charging processes cannot be separated a priori in non-steady-
state electrode processes because of the phenomenon of charge separation or recombination
at the electrode-electrolyte interface without flow of external current. Charging behaviors as
ideal polarized or reversible electrode represent only two limiting cases of a more general
case (Delahay, 1966). Nisancioglu and Newman (2012) in their article even without going
into the assumptions and basing only on the mass balance equation, obtained next current
equation: i=dq/dt + i’’ and showed that a priori separation of double-layer charging and
Faraday processes in electrode reactions is the component mass balance for the electrode
surface. Equation (1) is valid if the rate of change of concentration of the species, which take
part in the electrode reaction, can be neglected at the electrode surface.

2.4. Water splitting with the pulse electrolysis

There are different ways of water splitting first reviewed by Bockris et all (1985), that
sharply differs from conventional DC water electrolysis. The most common could be:
 Water Electrolysis with Inductive Voltage Pulses 25

thermo chemical, sonochemical, photocatalytic, biological water splitting; water splitting

under the magnetic field and centrifugal force of rotation; pulse electrolysis and plasma
electrolysis. Regarding pulse electrolysis, Ghoroghchian and Bockris in 1956 already defined
that the pulse electrolysis is more effective than conventional electrolysis. Many new patents
on pulse electrolysis appeared in 1970-1990 (Horvath, 1976; Spirig, 1978; Themu, 1980;
Puharich, 1983; Meyer, 1986; Meyer, 1989; Meyer, 1992a, 1992b; Santilli, 2001; Chambers,
2002) stating to be invented over-effective electrolysis (i.e. the current efficiency is higher
than 100%). The water splitting scheme described in these patents initiated a huge interest,
but nobody has succeeded in interpreting these schemes and their performance mechanisms
up to now, and what is more important, nobody has succeeded to repeated patented devices
experimentally as well.
In interrupted DC electrolysis the diffusion layer at the electrode can be divided into two
parts: one part, which is located at the electrode surface is characterized with pulsed
concentration of active ions, and another part is fixed, similar to the diffusion layer in case of
DC. The concentration of the active ions in pulsing diffusion layer changes from defined
initial value when the pulse is imposed, to a next value when it expired. The concentration
of active ions in pulse may fall or can not fall to zero. Time, which is necessary for active ion
concentration would fall to zero, is called the transition time τ. The transition time is
depending from pulse current ip and pulse duration T. If depletion in stationary diffusion
layer is small, i.e. c’e≈c0, were c’e is concentration of ions in pulsed-layer outer edge, and c0 is
bulk concentration, the transition time can be found from Sand equation (Bott, 2000):

π Dc02 ( zF )2
τ= (17)
4ip2

were F is Faraday’s constant, z – charge number and D is its diffusion coefficient. As can be
seen, transition time τ depends on the ion concentration in bulk volume c0 and pulse current
density ip. Thickness of pulsed layer δp at the end of the pulse depends only from the density
of pulse current:
1/ 2
 DT 
δp = 2  (18)
 π 
With very short pulses extremely thin pulsating layer can be reached. This thin layer would
allow temporary to impose a very high current densities during metal plating (more than
250A/cm2, which is 10,000 times higher than currents in conventional electrolysis), which
accelerates the process of metal electroplating (Ibl et all, 1978). The rough and porous surface is
formed during metal plating with direct current, when the current value reached the mass
transport limit. When plating is done with pulse current, pulsating diffusion layer always will
be much thinner than the surface roughness, what means that in case the mass transfer limit is
reached, the plated surface is homogeneous still and copy the roughness of substrate. This
feature gives preference to pulse current in metal plating processes, comparing with
conventional DC plating, because the highest possible power can used (current above mass
transfer limit) to obtain homogeneous coatings in shortest times (Ibl et all, 1978).
26 Electrolysis

Pulse electrolysis is widely investigated using various technologies (Hirato et all, 2003;
Kuroda et all, 2007; Chandrasekar et all, 2008). In all of these technologies rectangular pulses
are mostly used which have to be active in nature. Shimizu et all (2006) applied inductive
voltage pulses to water electrolysis and showed significant differences with conventional
DC electrolysis of water. The conclusion of this research is that this kind of water electrolysis
efficiency is not dependant on the electrolysis power, thus being in contradiction to the
conventional opinion of electrolysis.
We studied inductive voltage electrolysis and promoted the hypothesis that pulse process
separates the cell geometric capacitance and double layer charging current from the
electrochemical reaction current with charge transfer (Vanags (2009), Vanags (2011a, 2011b).
To prove this we have done plenty of experiments proving double layer charging process
separation from the electrochemical water splitting reaction. There are no studies about the
usage of reactive short voltage pulse in the aqueous solution electrolysis; also no
microelectrodes are used to determine the presence of the dissolved hydrogen and oxygen
near the cathode in electrolysis process.

3. Experimental
3.1. Materials and equipment
Materials, instruments and equipment used in this work are collected in Tables 1 and 2.

3.2. Inductive reverse voltage pulse generator

The inductive voltage pulses were generated in the electric circuit (Fig. 1) consisting of a
pulse generator, a DC power source, a field transistor BUZ350, and a blocking diode
(Shaaban, 1994; Smimizu et all, 2006). A special broad-band transformer was bifilarly
wound using two wires twisted together. Square pulses from the generator were applied to
the field transistor connected in series with the DC power source. The filling factor of pulses
was kept constant (50%). To obtain inductive reverse voltage pulses, the primary winding of
the transformer is powered with low amplitude square voltage pulses. In the secondary
winding (winding ratio1:1) due to collapse of the magnetic field induced in the coil very
sharp inductive pulse with high amplitude and opposite polarity with respect to applied
voltage appears. Pulse of induced reverse voltage is passed through the blocking diode, and
the resulting ~1 μs wide high-voltage pulse is applied to the electrolytic cell. A two-beam
oscilloscope GWinstek GDS-2204 was employed to record the voltage (i.e. its drop on a
reference resistance) and current in the circuit.
MOSFET (IRF840) is used as semiconductor switch between DC power supply and ground
circuit. Pulse transformer is a solenoid type with bifilar windings; length is 20 cm and a coil
diameter of 2.3 cm and ferrite rod core. Number of turns in both the primary and the
secondary winding is 75, so ratio is 1:1. Inductance of solenoid is approximately 250 μH.
Super-fast blocking diode with the closing time of 10 ns is included in the secondary circuit,
to pass on electrolysis cell only the pulses induced in transformer with opposite polarity.
Direct pulses are blocked by diode.
 Water Electrolysis with Inductive Voltage Pulses 27

No Name Parameters Producer

1. KOH 99% Aldrich
2. NaOH 99% Aldrich
3. LiOH 99.9% Aldrich
4. K2CO3 99.8% Aldrich
Chemicals

5. H2SO4 95% Aldrich

6. (NH2)2CO 98% Aldrich
7. H2O 0.1 μS Deionised
1. Stainless Steel (parameters Table 2) 316L
Metals

2. Tungsten 95% Aldrich

3. Platinum 99.9% Aldrich
1. DC power supply Agilent N5751A 300V; 2.5A Aligent
echnologies
2. Frequency Generator GFG-3015 0 – 150 MHz GW-Instek
3. Oscilloscope GDS-2204 4 beams, resolution GW-Instek
10 ns
Equipments and Instruments

4. Power Meter HM8115-2 16A, 300V Hameg

Instruments
5. Water Deionization Crystal – 5 Water - 0.1 μS Adrona
Lab.Systems
6. Masspectrometer RGAPro 100 0 – 100 m/z units Hy-Energy
7. X-ray fluorescence spectrometer Ametek
EDAX/Ametek, Eagle III
8. Microsensors for dissolved gases H2 Resolution 0.1 Unisense,
and O2 μmol/l Denmark
Table 1. Materials and equipment used in this work.

Element C Si P S Ti Cr Mn Fe Ni Cu
Quantity, wt% 0.12 0.83 0.04 0.02 0.67 17.88 2.02 68.36 9.77 0.29
Table 2. Composition of Stainless steel 316L used for electrodes (wt%).

Figure 1. Experimental circuit for generation of inductive reverse voltage pulses.

28 Electrolysis

3.3. Construction of electrolyses cells

Experiments in this chapter are divided into five parts. In the first part the gas evolution rate
is explained and performance efficiency coefficients defined (current efficiency and energy
efficiency). The second part examines kinetics of the inductive voltage pulse applied to
electrolysis cell were electrolyte concentration and the distance between electrodes are
changing. The third part describes the application of respiration microsensors to measure
concentration of dissolved hydrogen gas directly to the cathode surface in an electrolysis
cell, powered with inductive voltage pulses. The fourth experiment studied inductive
voltage pulse kinetics in very dilute electrolyte solutions. The fourth experiment also noticed
interesting feature in current pulse kinetics, therefore additional experiment is performed, to
measure concentration of evolved hydrogen at the cathode with oxygen microsensor. This
experiment devoted to fifth.

Amount of released gases during electrolysis was determined with volume displacement
method (Fig. 2).

Figure 2. Principal scheme to determine the volume of released gases.

Electrolysis cell is in a separate chamber closed with a sealing cap. Glass tube bent in 180
degrees is attached to the bottom of the electrolysis chamber. The tube is graduated in units
of volume above the level of the electrolyte. Gases arising in electrolysis process are pressing
on electrolyte and the level in calibrated tube is increasing giving approximate volume of
gases produced. In measured value of volume the 5% relative error is from different
reasons; the biggest uncertainty is determined by the pressured gas generated during
electrolysis - higher than atmospheric pressure. Gases are produced in electrolysis by
volume 2/3 hydrogen and 1/3 oxygen. Knowing the mass of hydrogen generated in period
texp, the charge necessary to produce such amount can be calculated and compared with
consumed energy – result is current efficiency of particular electrolysis cell. Energy
efficiency is calculated from consumed energy compared to what can be obtained from
burning the produced amount of hydrogen at highest calorific value - 140 MJ/kg.

Self-made water electrolysis cell with movable electrode was used in experiments. It consists
of a polyethylene shell with built in micro-screw from one side. Using stainless steel wire
the micro-screw is connected to the movable electrode, situated perpendicular to the
 Water Electrolysis with Inductive Voltage Pulses 29

electrolyte cavity (diameter 40 mm). Stainless steel stationary electrode with same area is
situated against a moving electrode. SUS316L stainless steel plate electrodes with equal area
(2 cm2) were used in experiments. Before experiments the electrodes were mechanically
polished and washed with acetone and deionized water. As an electrolyte KOH solution in
water was used in different concentrations. At each electrolyte concentration the distance
between electrodes was changed with micro-screw from 1 mm to 5 mm. During experiment
the appropriate concentration of the electrolyte solution was filled and cell attached to an
inductive voltage pulse generator. At each electrolyte concentration the current and voltage
oscillograms were taken for 1 to 5 mm distance between electrodes (step 1 mm).
Oscillograms were further analyzed calculating consumed charge, pulse energy, and in
some cases - energetic factors.

To measure the concentration of dissolved hydrogen at the cathode during electrolysis, self-
made cell was used (Fig. 3). Cell consists from three cameras connected with ion conducting
bridges.

Figure 3. Three-camera electrolysis cell to measure concentration of dissolved hydrogen.

The first camera is for nickel plate counter electrode, second – for working electrode -
smooth wires (diameter 0.5 mm, length 100 mm) of tungsten and platinum, but third camera
was used for reference electrode in some specific experiments. Pt and W electrodes were
cleaned before experiments, etching them 24 hours in concentrated alkali solution and
rinsing with deionized water. The concentration of dissolved hydrogen was determined
with respiration microsensor used typically in biological experiments (Unisense, 2011). The
Unisense hydrogen microsensor is a miniaturized Clark-type hydrogen sensor with an
internal reference electrode and a sensing anode. The sensor must be connected to a high-
sensitivity picoammeter where the anode is polarized against the internal reference. Driven
by the external partial pressure, hydrogen from the environment will pass through the
sensor tip membrane and will be oxidized at the platinum anode surface. The picoammeter
30 Electrolysis

converts the resulting oxidation current to a signal. In our experiments sensor H2100 having
the tip with diameter 110 μm was placed as closely as possible to cathode (<1 mm distance).
Before experiments the microsensor was graduated in two points – zero H2 concentration
(Ar gas is bubbled through deionized water) and 100% or 816 mmol/l at 20 oC (H2 gas is
bubbled through deionized water – from Unisense, 2011 user manual). The experiment was
carried out as follows: separate inductive voltage pulses was delivered to the cell and
voltage and current oscillograms recorded. At the same time the concentration of the
dissolved hydrogen was measured using microsensor.

Figure 4. Water electrolysis cell to measure the concentration of dissolved oxygen.

The oxygen microsensor (also from Unisence, 2011) was used to measure the concentration
of dissolved hydrogen close to cathode during inductive pulse electrolysis (Figure 4). The
oxygen micro-sensor is all Clark-type sensor based on diffusion of oxygen through a silicone
 Water Electrolysis with Inductive Voltage Pulses 31

membrane to an oxygen reducing cathode which is polarized versus an internal Ag/AgCl

anode. The flow of electrons from the anode to the oxygen reducing cathode reflects linearly
the oxygen partial pressure around the sensor tip (diameter 100 μ) and is in the pA range.
The current is measured by a picoammeter. To generate short inductive voltage pulses, the
same circuit (chapter 3.2) is used. Cell is filled with deionized water, and the generator set in
mode when expressed negative current peak is observed in oscillograms.

Concentration of oxygen is measured simultaneously with microsensor, previously

calibrated in deionized water bubbled with oxygen.

Specific electrolysis cell was made for study the kinetics of inductive pulse electrolysis in
diluted electrolytes (Figure 5). It was made from glass bowl with two separate electrode
holders equipped with screws for electrodes from stainless steel 316L wires (diameter 2 mm,
length 100 mm). Steel electrodes were cleaned before experiments, etching them 24 hours in
concentrated alkali solution and rinsing with deionized water together with glass bowl of
electrolysis cell. Very diluted electrolyte was prepared pouring in the cell 350 ml deionized
water and adding drops of 5 M electrolyte from calibrated volume dropper (0.05±10% ml).
Four electrolytes (KOH, NaOH, LiOH, H2SO4) were used in experiments and measurements
were registered after each drop.

Figure 5. Water electrolysis cell to measure the kinetics of pulse electrolysis.

4. Results and analysis

4.1. Current and energy efficiencies
Average values of voltage and current, as well as flow of generated hydrogen gas
depending on KOH concentrations are shown in table 3. Theoretically maximal current is
32 Electrolysis

calculated knowing the hydrogen gas flow by assumption that 2 electrons generate one
molecule of hydrogen. Using data from Table 3, current and energy efficiency coefficients
are calculated for pulse electrolysis process (see Table 4) on the assumption that the pulse
transformer primary side and secondary side are two separate systems, which are only bind
by average value of current flowing in the cell.

KOH Average value Average Current value Hydrogen

concentration for current voltage calculated from mass flow
[mol/kg] pulse [mA] value [V] of generated [cm3/min]
hydrogen [mA]
0.1 6.5 2.1 3.2 0.043
1 8 2.1 3.7 0.054
2 8.3 2.1 4 0.057
3 8.6 2.1 4.2 0.059
Table 3. Parameters of registered voltage and current pulses on an electrolysis cell.

This assumption is not entirely correct, but acceptable. When viewed from the primary
circuit side, the pulse generator is with a reactive element included in its scheme - an
induction coil (the primary winding of pulse transformer).

KOH concentration Current efficiency Energy efficiency coefficient

[mol/kg] coefficient [%] [%]
0.1 49 66
1 46 64
2 48 68
3 49 68
Table 4. Current and energy efficiency coefficients

By disconnecting secondary side, primary side does not consume anything (except the
power that is distributed on elements with active resistances included in the primary
circuit). When connecting the secondary side, the active 1 V amplitude of the voltage pulse
in the primary side is unable to consume more, because it is necessary to exceed electrolysis
overvoltage – at least 1.23 V (ratio of windings in coil is 1:1).
Therefore, the average current values in Table 3 are replaced with the current consumed in
the power supply system. Voltage value is read from the oscilloscope by measuring the
voltage pulse on primary coil. Thus, equipment errors associated with variations in voltage
values are excluded. Then, the resulting pulse is averaged over time and the resulting
voltage values are shown in second column of Table 5.
It should be mentioned that adjusted energy efficiency coefficients were calculated without
any reference to the circuit elements and the quantity of generated gas flow. As it is seen
from Table 4.3., it is necessary to determine current and voltage values with oscilloscope
within scheme of this experiment, which eliminates the pulse schemes for analogue
measuring errors.
 Water Electrolysis with Inductive Voltage Pulses 33

KOH Power Average current Hydrogen Energy efficiency

concentration supply value on the cell flow coefficient [%]
voltage [V] [mA] [cm3/min]
0.1 1.43 6.5 0.043 97
1 1.48 8 0.054 96
2 1.53 8.3 0.057 94
3 1.49 8.6 0.059 97
Table 5. Adjusted parameters of voltage, current and efficiency.

4.2. Pulse kinetics at different concentration solutions and electrode distances

In Figure 6 the voltage and current pulse oscillograms are shown for steel electrode plates in
0.1 M KOH solution, where the maximum voltage pulse value is approximately 5.5 V when
distance between the electrodes is 5 mm and it drops to about 3 V when the distance
between the electrodes is 1 mm. In 0.3 M KOH solution (curves similar to 0.1 M solution) the
maximum voltage pulse value is 3.5 V, when distance between the electrodes is 5 mm and it
drops to 2.6 V when distance between the electrodes is reduced to 1 mm. In even more
concentrated solution, ie., 0.5 M KOH, the maximum voltage pulse value at the electrode
distance of 5 mm is approximately 2.9 V and when the electrode distance is 1 mm, it drops to
2.4 V. Current peak value does not change significantly depending on the electrode distance,
or the concentration, but there are observed changes in the discharge tail length, suggesting
that higher charge in electrolysis cell flows at more concentrated electrolyte solution.

Figure 6. Current and voltage pulses registered with oscilloscope in 0.1 M KOH.

When looking at pulse generation scheme in the experimental method section (Figure 1), it
is clear that high-voltage pulse generated in the transformer is reactive in nature. Reactive
pulse amplitude will depend on the quality factor of capacitive element. Capacitor with a
large leak (concentrated electrolyte solution) will not be able to hold the reactive pulse with
large amplitude, though in the previous figures it is shown that the amplitude of those
achieved in the secondary circuit on the electrolysis cell is greater than the direct pulse
34 Electrolysis

amplitude. This means that at the first moment when short inductive pulse is applied, the
water electrolysis cell behaves as good capacitor, also at the voltage region, in which water
electrolysis can occur. But after starting the discharge tail, the energy stored in the capacity
transforms into the chemical energy in the process of water electrolysis.

4.3. The concentration of dissolved hydrogen at cathode

Current and voltage pulses registered with oscilloscope (Fig. 7) show that changing the
electrode material, the rising front and relaxation of voltage pulses does not change, while
voltage pulse amplitude decreases with increasing current pulse amplitude when solution
concentration increases. Current pulses also are not different on the platinum and tungsten
electrodes with identical concentration of KOH solutions (Fig. 7). To evaluate pulse energy
supplied to the cell, pulse voltage and current values were multiplied and resulting curves
was integrated with time (Table 6). Each row in the Table 6 shows electrode material and the
concentration of the solution, and in the next column – calculated supplied energy to the
system during the pulse.

Figure 8 presents each electrode’s voltage and current oscillograms in the same time scale in
order to better evaluate the phase shift angle between current and voltage. There are not
noticeably significant differences observable between the phase shift angles depending on
the electrode material.

Figure 7. Current and voltage pulse oscillograms of Pt and W electrodes (Pt – black and blue, W – green
and red accordingly).

Electrode material and solution concentration Energy, mJ

Pt in 0.1M KOH solution 8.5
Pt in 0.2M KOH solution 7.7
W in 0.1M KOH solution 8.2
W in 0.2M KOH solution 7.6
Table 6. Energy supplied to the cell during the pulse, calculated from voltage and current oscillograms.
 Water Electrolysis with Inductive Voltage Pulses 35

Figure 8. Current and voltage pulse oscillograms of Pt and W electrodes in 0.1 M and 0.2 M KOH

In each experiment with microsensor to measure the concentration of dissolved hydrogen, the
measuring time lasted 100 s (curves at Fig. 9). As it is seen, the curves with largest slope are an
electrolyte with a higher concentration, and the tungsten electrode, rather than platinum.

Figure 9. Changes in concentration of dissolved hydrogen gas during pulse electrolysis.

It means that on the tungsten electrodes the concentration of dissolved hydrogen increases
faster than on the platinum electrodes. As it is seen from cathodic region of voltamperic
curves (Fig. 10), for platinum electrode the characteristic hydrogen adsorption/absorption
peak at negative currents appears at potential -0.5 V, but not for tungsten electrode.
36 Electrolysis

Figure 10. Voltamperic characteristics for platinum and tungsten electrodes in 0.1 M KOH solution
measured in two electrode configuration at scan rate 10 mV/s.

The pulse energy of inductive reverse voltage pulses is limited. Voltage and current during
the pulse reacts in such way that their multiplication and next integration in time would be
equal in the same concentration of electrolyte without reference to the material of electrodes
that are used. Pulse energy decreases whilst solution concentration increases, suggesting
that reactive energy component has decreased. Therefore it is observable that phase shift
angle between current and voltage is smaller in a more concentrated solution. Since the
inductive voltage pulse energy is limited, on platinum electrode it is consumed in the
adsorption area, thus structuring hydrogen adsorption monolayer on the platinum
electrode. There is no hydrogen adsorption/absorption peak for tungsten electrode and
during a very short voltage pulse, electrons from the metal discharge directly on hydrogen
ions at interface electrode/electrolyte and hydrogen molecules are formed intensively which
are detected with dissolved hydrogen microsensor.

4.4. Pulse kinetic measurements in highly dilute solutions

Voltage pulse growth at various concentrations of KOH solution (Figure 11) is equal in all
concentrations, while the discharge tile after voltage pulse at various concentrations is
different. Amplitude of voltage pulse is maximal in deionized water, but pulse dynamics in
cell with slightly diluted electrolyte is exactly what is in the case of the open circuit, only the
amplitude is smaller. Continuing to increase the concentration of electrolyte in cell, the
value of voltage pulse amplitude continues decrease, while the discharge tail will increase.

Current changes the direction from negative to positive with increasing concentration of
electrolyte passing through the point where the current pulse has not descending a long tail
(Fig. 12). Current pulse in deionized water most of the momentum is negative. By increasing
the concentration of solution up to 1 mM, current pulse appears in both positive and
immediately following a negative pulse, while discharge tail almost disappears. Continuing
to increase the concentration of electrolyte, the negative values of current pulse disappear
and the discharge tail remains positive and increasing, which indicates that the charge
injected in the cell during pulse increases. More increase of concentration does not change
the view of current pulse and it remains like from the previous concentrations (Fig. 12).
 Water Electrolysis with Inductive Voltage Pulses 37

When electrolyte concentration increases, voltage peak drop is observed (Fig. 13). The
peak value of voltage pulse is decreasing exponentially, and it stabilizes around the value
of 9 V for solutions, while in deionized water that value is over 600 V. These curves
almost coincide in different alkali solutions, while in the sulfuric acid the peak values are
falling faster.

Figure 11. Inductive discharge voltage pulses with different concentrations of KOH.

Figure 12. Current pulses initiated by inductive voltage pulses on cell with different concentrations of
KOH solution

The pulse charge (integral of the current pulse) increases with increase of electrolyte
concentration and tend saturate at some value (Figure 14).
38 Electrolysis

Figure 13. Decrease of voltage pulse amplitude with increasing concentration of electrolyte.

Figure 14. Changes of pulse charge (integrated current pulse) in various solutions with increasing
concentration of electrolyte.

In alkali solutions, the charge behavior is nearly identical for alkali tested, while in the cell
with sulfuric acid solution, the increase of charge is more rapid. Concerning occurrence of
the negative currents following hypothesis is proposed. Voltage pulse kinetics demonstrates
that around the electrode spatial charge density appears, i.e., when voltage rapidly grows in
two-electrode system, electrons are emitted from the cathode environment. Since water ion
concentrations in deionized water is low (H3O+ molar concentration is in the order of 10-7 M),
then, most likely, the emitted electrons are solvated between polar water molecules and than
will attach a neutral water molecule, which is described by following hydration reaction:

H2O + e- ↔ H + OH- (19)

 Water Electrolysis with Inductive Voltage Pulses 39

If OH- ions and solvated electrons don’t manage to discharge at the cathode, then around
the cathode a spatial charge appears. In case of arising the spatial charge around electrode, it
is more likely of electrons to move back into the metal. If the electron donor is the OH- ion,
then oxygen evolution should appear at the cathode. In principle, according to the
experimental circuit, such electron returning back in metal in large amounts what results
from the negative current pulse value presented in Fig. 12, is not possible since this current
component is blocked by the diode incorporated in the circuit. Therefore behind the diode,
parasitic element with the inductive nature must exist in the measurement circuit (Fig. 1)
which becomes comparatively small and solvated electrons are discharged by ions in
electrolyte, therefore decreasing negative current. To confirm this hypothesis, it is necessary
to determine if oxygen does not appear near the cathode (the solvated electrons OH- form
allows a reverse reaction (19) on the cathode).

4.5. Measurement of dissolved oxygen near the cathode

The concentration of dissolved oxygen in a solution near the cathode during pulse
electrolysis in dependence of time is presented in Fig. 15. During the first 60 seconds current
pulses has an explicit negative peak in the cell. After 60 seconds, the generator is set to
manage the negative current peak disappeared. From Fig. 15 it is seen that when a negative
current peak occurs, the oxygen evolves at the cathode, but when the negative current
during voltage pulses is prevented, the oxygen at cathode is no longer released and
concentration decreases.

Figure 15. Dissolved oxygen concentration near the cathode in two regimes of pulse generator – when
current peak is negative (left, dissolved oxygen concentration is increasing) and positive (right,
dissolved oxygen concentration is decreasing).
40 Electrolysis

5. Conclusions
Reactive short voltage pulse generator is designed to power water electrolysis cells of
different constructions, both with spatially separated and with variable distance
electrodes. Required value of electrolysis voltage in the primary circuit of power supply
can be reduced by inserting the electrolysis cell in secondary circuit of power supply
together with inductive element and reverse diode. For example, in this work electrolysis
is provided with direct pulse amplitude 1 V, which induces a short high voltage pulse
(tens, hundreds of volts, depending on the conductivity of electrolyte) in the secondary
circuit. For studying the process of electrolysis the microelectrode sensors are used to
measure concentration of dissolved hydrogen and oxygen gas in the direct vicinity of
cathode for the first time.

By changing the distance between the electrodes and concentration of electrolyte, it is

experimentally proved that the electrolysis cell is capacitor with high Q factor when short
voltage pulse (width below 1 μs) is applied. During this short time the capacitor (electrolysis
cell) is charged, which can be interpreted as charging of double-layer on interface
cathode/electrolyte. After the interruption of short voltage pulse the energy accumulated in
double-layer capacitor slowly discharges (pulse discharge tail), thus activating the process
of electrolysis. Consequently, it is shown that with short voltage pulse electrolysis the
charging of cell can be separated from the electrochemical reactions in electrolysis process.
Kinetics of charging the electrolysis cell with reactive high voltage short pulses does not
depend on concentration of the electrolyte, whereas kinetics of the subsequent long-
discharge process depends on the electrolyte concentration (faster in dilute solutions, slower
in more concentrated solutions). If concentration of electrolyte in the electrolysis cell is
above 3 mM, reactive voltage pulse energy does not depend on concentration of the
solution. The current polarity switch from cathodic to anodic and back is observed in
oscillograms, when de-ionized water electrolysis is performed with short reactive voltage
pulses. Polarity changes only during short time when reactive voltage pulse is applied; at
the beginning of the discharge tail the current is cathodic again. Measurements of
dissolved oxygen concentration by microsensor in the immediate vicinity of the cathode
show that oxygen concentration increases (reverse process to hydrogen evolution) in the
presence of anodic current. The hypothesis is proposed that high-voltage pulse causes the
emission of electrons from the cathode metal into electrolyte, where at first the electrons
are solvated, then dissociating the water molecules forms H atoms and OH- ions; next
generated OH- ions can discharge on cathode at the moment when applied voltage pulse
reduces, giving the release of oxygen detected by microsensor. Current efficiency of 50%
is registered in high-voltage reactive short pulse electrolysis, while the energetic efficiency
is in range 70-100%.

Platinum and tungsten electrodes are studied to find the impact of electrode material on the
process of short reactive voltage pulse electrolysis. Experimental results show that the
voltage and current characteristics of inductive voltage short pulse electrolysis are the same
 Water Electrolysis with Inductive Voltage Pulses 41

for both metals, but the concentration of dissolved hydrogen grows faster at the tungsten
electrode. Delay in the release of hydrogen on a platinum electrode is explained by the
tendency of platinum to adsorb hydrogen on the surface.

Author details
Martins Vanags, Janis Kleperis and Gunars Bajars
Institute of Solid State Physics, University of Latvia, Riga, Latvia

Acknowledgements
The authors acknowledge laboratory colleagues Liga Grinberga and Andrejs Lusis for
stimulating discussions, and Vladimirs Nemcevs for technical assistance. Authors thank
Professor Robert Salem for helpful guidance and advices, and deep compassion to his family
on the death of Professor in 2009. Financial support from the European Social Fund project
"Support for doctoral studies at the University of Latvia" is acknowledged by M.Vanags. All
authors thank the National Research Program in Energy supporting the development of
hydrogen infrastructure in Latvia.

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