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Hydrogen Production

From Water
Via Electrolysis

Reference: Kai Zeng, Dongke Zhang, Recent progress in alkaline water


electrolysis for hydrogen production and applications , Progress in Energy and
Combustion Science 36 (2010) 307326 .

1
DC Power resistan
importa
Oxygen Receiver + Electron Flow Hydrogen Receiver thermod
principl
Fig. 3
water el
side R1
O2 H2 wiring a
Electrolyte Electrolyte overpote
the anod
anode b
OH- H+ anode a

- - + and me
Anode - - + +
+
Cathode Similarly
Diaphragm hydroge
potentia
resistan

Electrolysis Of Water
Fig. 2. A schematic illustration of a basic water electrolysis system.
resistan

RTotal
electrolyte solution to anode, at which the hydroxide ions give
away electrons and these electrons return to the positive terminal
of the DC source. In order to enhance
2 the conductivity of the
What Happens During
Electrolysis
In the electrolyte However, the required voltage is
2H2O 2H+ + 2OH always 1.82.0 V at the current
density of 1000300 A/m2 in
At the cathode
industry water electrolysis.
2H+ + 2e H2
Why?
At the anode
2OH 12 O2 + H2O + 2e
Overall reaction
H2O 12 O2 + H2
Hr = 285.6 kJ/mol
Eo=-1.23V at 25C, pH=7

Therefore, theoretically, we need


only a 1.5 V alkaline battery to 1.23 volts 2.0 volts

produce hydrogen.
3
2.2.2. Transport-related resistances
2H 2e/H2 (R1) These are the physical resistances experienced in the

1
Resistance In The Electrolysis process such as gas bubbles covering the electrode s
present in the electrolyte solution, resistances to the io
OH" / O2 H2 O 2e (R2) in the electrolyte and due to the membrane used for sep
2
Circuit
ll chemical reaction of the water electrolysis can be
H2 and O2 gases. Rbubble;O2 , Rions, Rmembrane and Rb
considered as transport resistances.
For thisBoth electrical resistances
electrochemical and
reaction transport resistances
process
generation
to proceed, according
a number to the have
of barriers Joulesto law [37] and
1
O (R3) be phenomena [40] and extra
overcome, requiring thus inefficiency
electrical of the electrol
2 2 The lost energy due to these resistances is also known a
energy supply.
loss [41].
circuit analogy of water electrolysis cells Therefore, the voltage required for

2.2.3. Electrochemical reaction resistances
generating hydrogen with sufficiently fast
ectrochemical reaction process to proceed, a number The reaction resistances
o are due to the overpotentials
rate is greater than E =1.23V.
ave to be overcome, requiring a sufficient electrical overcome the activation energies of the hydrogen
y. These barriers include electrical resistance of the formation reactions on the cathode and anode surf
Ecell = E + i R = E+Eloss
ation energies of the electrochemical reactions directly cause the increase in the overall cell potential. T
= E+E
inherent energy ohmic+E
barriers of the reactions, determining
the surfaces of the electrodes, availability of electrode
to partial coverage by gas bubbles formed and the of the electrochemical reactions [42].
E: actual voltage required only for reaction
o
at conditions different than 25 C and pH=7
e
+ -

R1 Ranode Rbubble,O2 Rmembrane Rions Rbubble,H2 Rcathode R 1

4
Fig. 3. An electrical circuit analogy of resistances in the water electrolysis system.
surfaces of the electrodes, availability of electrode inherent energy barriers of the reactions, determi
partial coverage by gas bubbles formed and the of the electrochemical reactions [42].

Resistance During Electrolysis e


+ -

R1 Ranode Rbubble,O2 Rmembrane Rions Rbubble,H2 Rcathode R 1

R1:3. An electrical circuit analogy of resistances in the water electrolysis system.


R1 and Fig.
electrical resistance of the circuit Ohmic resistance:
resulting in
Rbubble, O2 and Rbubble,H2:
resistance from availability of electrode surfaces due to partial
joule heating
coverage by gas bubbles formed
i(R1+R1+Rbubble, O2
Rions: +Rbubble,H2+Rions
resistances to the ionic transfer within the electrolyte solution +Rmembrane )= iRohmic
= ohmic loss = Eohmic
Rmembrane:
resistance to the ionic transfer cross the membrane
over-potential resistance:
Ranode, Rcathode: energy barrier of reaction
resistance from activation energies of the electrochemical
reactions occurring on the surfaces of the electrodes i(Ranode+Rcathode )
= over-potential = E
5
Improve Energy Efficiency
Clearly, the strategies in any effort to improve the energy efficiency of
water electrolysis and thus the performance of the system must involve
the understanding of these resistances so as to minimize them.

It is important that these barriers are analyzed in the contexts of


thermodynamics and kinetics as well as transport process principles.

over-potential, determined by the surface


Activation activities of the electrodes, related to
energy kinetics

H2, O2

G: Gibbs Free energy,


H2O related to thermodynamics

6
potential. Hence the electrolysis of water to hydrogen and oxygen is
thermodynamically unfavourable at room temperature and can [17,49].
only occur when sufficient electrical energy is supplied. In contrast,
E # Ecathode 100
when the electrolysis process is performed under adiabatic condi- %voltage efficiency anode (6)

Thermodynamics
tions, the total reaction enthalpy must be provided by electrical
current. Under this circumstance, the thermo-neutral voltage is
required to maintain the electrochemical reaction without heat
generation or adsorption [45].
Ecell
The physical meaning of this equation is the proportion of effective
voltage to split water in the total voltage applied to the whole

Thermodynamics
Therefore, even when the equilibrium determines
potential is if the
met, reaction
the 2.0
electrode reactions
canare placeslow and then an overpotential h,
inherently
take 1.8 Exothomic Reaction

Electrolyser Cell potenial (V)


above the equilibrium cell voltage is necessary in order to kick start Thermoneutral Voltage
the reaction due to the activation energy barrier, low reaction rate 1.6
The relationship between Gibbs free energy,
and the bubble formation [42,46]. According to the resistances 1.4
enthalpy, and entropy is:
mentioned above, input of additional energy is also essential to
1.2 Endothemic Reaction
drive the ionic migration process and overcome the resistance of
the membrane as well as the electrical circuit. This extra energy 1.0
requirement causes a potential drop, iRcell, (where i is the current 0.8
through the cell and Rcell is the sum of electrical resistance of the Equilibrium Voltage
0.6
cell, a function of electrolyte properties, the form of the electrodes
and cell design) within
The the cell. energy
The cell potential Ecell canisbe written 0.4 H2 Generation Impossible
o
minimal o
demanded
as Equation (4), which is always 1.82.0 V at the current density of
G =nFE
1000300 A m#2 in industry water electrolysis [47]. The total
0.2
0.0
overpotential isn:themolesumnumber of waterorelectrolyzed
of overpotentials barriers from the 0 200 400 600
F:o Faraday
hydrogen and oxygen constant
evolution reactions, electrolyte concentra- o
Temperature ( C)
tion difference Eand bubble formation.
: equilibrium If one(-1.23V
voltage has a mild at condition
25C, pH 7)
under which gas bubble and concentration differences can be Fig. 4. Cell potential for hydrogen production by water electrolysis as a function of
neglected, the The
sumthermo-neutral
of overpotential voltage (EH) is the
can be calculated actualtemperature.
using minimum voltage that has to be applied to
the electrolysis cell when the electrolysis process is performed under adiabatic conditions
(without heat generation or adsorption). > EH = E+E
Under this circumstance, the total reaction enthalpy is only provided by electrical energy.
If applied voltage is higher than EH, energy is released (exothermic reaction).
If applied voltage is lower than EH, heating is required for reaction to happen
(endothermic).
7
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Anodic reaction 1/2O2 + 2e O2 O2 2e + 1/2O2

Thermodynamics
Total reaction H2 + 1/2O2 H2O H2O H2 + 1/2O2

FIGURE 4.1
Principle of high-temperature electrolysis of steam (reverse reaction of SOFC).

(kWh/m3 H2) (MJ/kg H2)


We can also look at the thermodynamics in the 3.5 16

way depicted in the figure at the right hand side:


H (Total energy demand)
14
The total energy demand H is similar for 3.0
reactions at different temperatures.
12
The electrical energy demand, G, 2.5
decreases with increasing temperature as
10 G
shown in the figure; the ratio of G to H is
(Electrical energy demand)

Energy demand
about 93% at 100C and about 70% at 2.0
1000C. 8
Water
Thus, the high temperature electrolysis of 1.5
Steam
steam demands less electricity to produce 6
hydrogen than the conventional water
electrolysis. 1.0 Q = TS
4
(Heat demand)
However, we still need energy input to heat the 0.5 2
system.
0.1 MPa

Additionally, electrodes are easily corroded at 0


0 200 400 600 800 1000 1200
high temperature Temperature (C)

FIGURE 4.2
8
Energy demand for water and steam electrolysis.
(2) voltage.
voltage This
as EDphenomenon is due totakes
H. If water electrolysis thatplace
heat isin absorbed
the shaded from
areathe
in
The rate of the elect
environment.
Fig. 4, the reaction Whenwill thebe denominator
endothermic. in Equation (8) is 1.48 V, the
he Gibbs free energy DG of density, firstly depend
electrolysis operates at the efficiency of 100%. No heat will be
quilibrium cell voltage as electrode surfaces. Sec

Efficiency Of Electrolysis
absorbed from or released to the environment.

is
In practice, if the potential drop caused by electrical resistance
3.2.0.25
D. Zhang / Progress in Energy and Combustion
(3)
Cell
V efficiencies
and
Science 360.6 V
(2010) for the
307326 cathode and
at 25 $ C, respectively, the Faradic efficiency is (1.23 * 100%)/
anode overpotentials
composition of the elec
These ions in the solut
electrode, form layers,
for example, the charg
of the efficiency
lectrons transferred of in (1.23Energy
thethe where 0.25Uefficiency
the is0.6)
thecell is voltage,
59%, commonly isdefined
and thei thermal as thetpercentage
the current,
efficiency stands
is (1.48for share
time. V is
* 100%)/
of the energy output in the total energy input. sium ions according to
The overall water electrol- the
Energy efficiency (1.23 hydrogen
0.25 production
0.6) 71%. Therate at unit
electrolysis cell isHowever,
volume there
electrolysis
exothermic are
atcell.
cell The
is commonly
a number of ways defined
ofand as the percentage
expressing the efficiencyof the energy output in
of production
electrolysis, of the reaction depends
andbased
ed the Gibbs
on the free energy physical
energy potential above
meaning 1.48ofV,Equation endothermic
(11) is at
the cell potential
hydrogen below this rate
#1 total energy input. However,
depending on there
how are aelectrolysis
number of ways
the investigates system of is
expressing
assessed the
and efficiency of
the reaction overpoten
mol
known [44], which
as the is the per
Faradic value. unitThe Faradic
electrical efficiency
energy input. It is athe
wayelectrolysis
for directreaction while
comparison of
rgy required to
electrolysis,
produce
depending
compared. on how the electrolysis system is assessed and compared. establish the macroscop
e the Gibbs free energy the thermal
hydrogen production efficiency takes the whole
capacity thermalelectrolysis
of different balance into account.
cells, or
Generally, and the surface overpo
int is known as reversible
omposition reaction as Yet anotherin meansthe electrochemistry
to compare and sense, the voltage
evaluate the efficiency
efficacy of of
lytic solution adjacent
r to hydrogenand We introduce
oxygen is a3an
waterelectrolysis
commonly electrolysis
E
cell systems
used can always
efficiencies
283:8 is to be
kJfor calculated
discussion:
consider the using Equation
output of hydrogen (6)
and hThermal adopt the [17,49]. Useable
total electrical energy applied to the system,(12) The double layer is i
oom temperature and can hproduction
H 2 yield
against the
y losses as the energy 1. the voltage efficiency DEof an electrolysis Uit cell: form two mobile layers
ergy is supplied. In contrast, in both terms of hydrogen production rate and energy (the high
#E
Eanode heating 100 (HHV) of one mole The one nearer the ele
med under adiabatic condi- where %voltage
heating 283.8
value kJ
efficiencyis the high
of hydrogen) by thevalue
carried cathode hydrogen produced. (6) = E on p.4)
(Eanode-Ecathode
t be provided by electrical hydrogen and t is for the time cell E needed for one gram hydrogen the inner Helmholtz la
2. (7)efficiency called outer Helmholtz
thermo-neutral voltage Theofphysical
is produced. generating meaning hydrogen:
of this equation is the ! proportion"of effective
ical reaction without heat 3 m&3 h&1 the surface of the electr
An alternative
voltage to split water expression
in the of
rH2 production the
total
rate
V
energy
voltage m efficiency
applied to is
the to subtract
whole
h input as shown in Equation (11) in the vicinity of the e
the energy losses from the
H 2 production rate
DE total energy Uit kJ
ium potential is met, the 2.0 plotted against the dist
(13). (U is Ecell, i is the current, t stands for time)
and then an overpotential(8) h, Exothomic Reaction
3. net 1.8
energy efficiency:
ectrolyser Cell potenial (V)

cessary in order to kick start Thermoneutral Voltage


1.6 1 & i Eloss t (E loss is on p.4)
(13)
gy barrier, low
potential andreaction rate hnet efficiency
total cell Einput (Einput includes electrical energy and heating or any other
cording to the resistances 1.4
kind of energy input)
energy is also essential to where E Endothemic Reaction
Depending onloss 1.2can
the size,betype,
expressed in terms
and condition ofan
of the resistancesplant,
electrolysis discussed
the energy
overcome the resistance of in Equation (1). Those resistances
(9)
l circuit. This extra energy
requirement to produce
1.0 1 Nm of H2 lies in the range 46 kWh. With a By
3 cause respective energy losses. hydrogen
, (where i is the current HHV ofconsidering
3.5 kWh/Nm these
3
, theresistances anwater
efficiency of analogous electrical
electrolyzers unit,
lies each
in the of 58
range
cell 0.8
them can be calculated using the Joules Law. Therefore,
electrical resistance of 87%. the Equilibrium Voltage
X 0.6
, the form of the electrodes
(10) 9
Eloss 0.4Eloss;i Eloss;circuit Eloss;anode Eloss;O bubble
3. Thermodynamic consideration Electrolyte Electrolyte
h jhanode jj jhcathode jj (5

Downloaded by [National Tsing Hua University - TAEBC] at 04:19 1


Cathodic reaction H2 + O2 H2O + 2e H2O + 2e H2 + O2
3.1. Theoretical cell voltages Fig. 4 shows the relationship between the electrolyser ce

Anodic reaction 1/2Opotential
2 2e
+ 2
Oand operating temperature 2e + 1/2O
O2 [17,48]. The cell potentia

Thermodynamics
2

Water is one of the thermodynamically most stable substances temperature plane is divided into three zones by the so-calle
Total reaction H2 + 1/2O2 H2O H2O H2 + 1/2O2
in the nature and it is always an uphill battle to try to pull water equilibrium voltage line and thermo-neutral voltage line. Th
molecules apart to make its elements into hydrogenFIGURE and oxygen
4.1 equilibrium voltage is the theoretical minimum potential require
Principle of high-temperature electrolysis of steam (reverse reaction of SOFC).
molecules. No pain, no gain. If we want hydrogen (and oxygen) to dissociate water by electrolysis, below which the electrolysis
from water by electrolysis, we have to at least overcome an equi- water cannot proceed. The equilibrium voltage deceases wit
!
librium cell voltage, E , which is also called electromotive force. (kWh/m increasing temperature.
3 H ) (MJ/kg H )
2 2 The thermo-neutral voltage is the actu
minimum 16 voltage that has to be applied to the electrolysis ce
With established reversibility and absence of cell current between 3.5
From the discussions above, we can
the two different electrode reactions, the open cell potential is below which the electrolysis is endothermic and above whic
H (Total energy demand)
2
conclude
called that
the equilibrium there are
cell voltage, two broad
it is defined asways of
equilibrium exothermic.
K. Zeng, D. Zhang / Progress in Energy and Combustion 3.0
14 The thermo-neutral voltage naturally includes th
Science 36 electrodes,
(2010) 307326
potential difference between the respective anode and cathode [43] overpotentials of the which are only weakly dependen
electrical energy
and is described by Equation (2).
efficiency improvement: on temperature. Thus, the thermo-neutral voltage only exhibi
12
ectrolysis cell. It is a good approximation of the efficiency of the awhere
slight the
2.5 U is with
increase the cell voltage,We
temperature. i is denote
the current, t stan
thermo-neutr
E! Eanode
! !
# Ecathode (2) voltage as E . If water electrolysis takes place in the shaded area
ectrolysis system. one is to thermodynamically reduce the the hydrogen
10
DH production G rate at unit volume elect
Fig. 4, the reaction willenergy
(Electrical be endothermic.
demand)
There are two Equation
other efficiencies
(3) relates thecalculated
change in thebased
Gibbsonfreethe energy
energy DG of physical meaning of Equation (11) is the hydrogen

Energy demand
2.0
electrical energy needed to split water
anges of thethe electrochemical
water electrolysisreaction to the known
reaction, equilibrium cell voltage
as the Faradicas per unit 8 electrical energy input. It is a way for direc
follows. to yield hydrogen, such as by Water
ficiency and the thermal efficiency. They use the Gibbs free energy hydrogen
1.5 production capacity of different electroly
increasing the operating temperature 3.2. Cell efficiencies
reaction or
Steam
ange and enthalpy
DG nFE change
!
of water decomposition as
(3) 6

e energy input,
where
pressureBothof hmoles
respectively.
n is the number Faradicofand hThermal
electrons adoptinthe
transferred the Useable
Energy efficiency E 283:8 kJ
is commonly defined as the percentage sha
h 1.0
H 4
yield Q = TS
eoretical energy requirement
reaction, and F is
to avoidthe plus
Faraday energy
extra constant.losses
The
efforts as the energy
overall water
in heating, electrol- of the energy output
2
E indemand)
D(Heat Uit input. However, there a
the total energy
ysis cell reaction, E! (25 ! C) is 1.23 V and the Gibbs free energy a number of ways of expressing the efficiency of electrolysi
put. As shown in Equations heat(7) canand be(8).
recycled#1from nuclear where
0.5
depending2 283.8
on how kJ isthethe high heating
electrolysis system isvalue (HHV
assessed an
change of the reaction is 237.2 kJ mol [44], which is the
minimum amount power ofplant
electrical energy required to produce
or thermo-chemical hydrogen and t is for the time
compared. 0.1 MPa needed for one
D G
hydrogen. The ED G
cell voltage at this point is known as reversible Generally, in the electrochemistry sense, the voltage efficiency
aradic process (7) produced.
0
DG Losses
potential. Hence Ethe electrolysis of water to hydrogen and oxygen is an electrolysis200cell can
0 400 always
600 800 calculated
be 1000 1200
using Equation (
cell An alternative expression
Temperature (C) of the energy efficien
thermodynamically unfavourable at room temperature and can [17,49].
only occur when sufficient electrical energy is supplied. FIGURE 4.2
In contrast, the energy losses from the total energy input as sho
DH the
the EDHis
other to reduce theunder
energy losses
Energy demand for water and steam electrolysis. Eanode # Ecathode 100
when electrolysis process is performed adiabatic condi- (13).
%voltage efficiency (6
hermal (8) E
DGtions,
Losses
the
intotal E
thereaction enthalpycell,
electrolysis
cell
must which
be provided
can bybe electrical
2009 by Taylor & Francis Group, LLC
cell
current. Under this circumstance, the thermo-neutral voltage is
realized by minimizing the dominant The physical meaning of this Eloss
equation is the proportion of effectiv i t
oth equationsrequired
can be to maintain the
simplified electrochemical
using reaction
cell potential andwithout
total cell heat hnet efficiency
voltage 1&
to split water in the total voltage applied to the who
components
generation of (10)
or adsorption [45]. the resistances. Einput
ltage as shown in Equations (9) and 2.0
Therefore, even when the equilibrium CRC_4575x_CH004.indd
potential is met, 129 the 5/28/20

electrode reactions are inherently slow and then an overpotential 10 h, where E can be expressed
loss Exothomic Reaction in terms of the resist
1.8
1:23 V
)

Thermoneutral Voltage
Reaction Kinetics Of Electrolysis
However, a thermodynamically favorable reaction does not guarantee the
reaction rate will be sufficiently fast. Therefore, we need to study the
reaction kinetics of electrolysis.

Reaction kinetics determines how fast the reaction proceeds.

Current is only generated when reaction happens; therefore, current density


is the main parameter that we can measure to quantify the reaction rate.
over-potential, determined by the surface
Activation activities of the electrodes, related to
energy kinetics

H2, O2

G: Gibbs Free energy,


H2O related to thermodynamics

11
dN
Rate (16
dt

Electrode Kinetics dQ/dt can be noted as Faradic current i [42].


K. Zeng, D. Zhang / Progress in Energy an
Generally the surface area at which the reaction takes plac
needs to be taken into account. IHL
The rate
OHL of the electrolysis reactio
can be expressed as -
+ - +
i j -
Rate
The rate of the electrode reaction, characterized (17
nFA nF + -
by the current density, which depends on:
where j is the current density. + + -
+
The rate constant of a chemical reaction can be in genera
Firstly, the properties of the electrode
expressed
surfaces. (which affects activation by the E
energy, Arrhenius
A) equation.
+ -
+
- ERTA -
reaction rate constant k Ae + - (18
Secondly, the composition of the electrolytic - a
solution adjacent to the electrodes.
These ions in the solution near the
E Electrode
electrodes, under the effect of electrode,
E
form layers, known as double layer.
>double layer consumes voltage E Solution

Finally, the electrode potential, characterized x


by the reaction over-potential. b
current density higher than optimal Fig. 5. A (a) A schematic
schematic illustration
illustration of electrical double layer andof
theelectrical
potential distribution
near an electrode surface.
increases over-potential double layer and
It can be clearly
(b) Theseen that the interfacial
potential distribution potential an exists
difference
near
between the electrode surface and the solution due to the existence
of the double electrode
layer [43]. surface
12
The phenomenon of the double layer formation is a non-faradic
4.1. Hydrogen generation overpotential
The directly
reaction is also mechanism of the by
determined hydrogen evolution reaction is widely
the overpotential, OHOHads OH "
ads #O
#OH ads
ads e "
4.1. Hydrogen generation overpotential
ch depends accepted [17] toofbe
on a number a step
factors. One involving the formation
of the important 4.2. of adsorbed
Oxygen generation " "
overpotential
The mechanism of theis hydrogen evolution reaction is widely OH OH ads #O ads H2
ors is the activation
hydrogen energy, E , which strongly influenced by Oads O
" #O2 #O
"
A
OH adsOH
The
accepted
hydrogenReaction On Electrode
mechanism
activation

H e /Hads
hydrogen
ce the overpotential,
"
[17] to
energies
be
of
of
a the
step
the
hydrogen
involving
electrode material, thus a focus of continuing research effort.
educe theaccepted " [17] to be a step involving
electrode
evolution
the formation
the
reactions,
it is therefore necessary to consider how
or
reaction
formation
of is
adsorbed
compared to (R4)
widely
of adsorbed Oads
the pathways
dence
reaction. There are a numberOne
Oads
One of#O
suggested
Oads
ofofof
thefor
ads
The mechanism of oxygen evolution reaction i
2charge
Ocharge
transfer
theories
the
#O
ad
tra
the hyd
coeffi
adspresented
2
trans
H eto
which
are related is/H
followed by either
the adselectrode chemical
materials anddesorption
surface (R4) variations
the literature and the dence
most generally can be used
accepted mec
figurations. ofOnetransfer
of thecoefficie
charg
H e /H "
electrochemical adsorption the -
OHfollowing -
OH adssteps: adsorption
(R4) example, a slow electron
which is followed by either chemical desorption
ads
2H ads /H2 (R5) variations
at dence
low
canof be used to
transfer
temperatures, co
on
" example, a slow electron tr
which
2H
"
is followed by either chemical desorption OHads #OH(R5) ads e variations
controls can at be us
Hydrogen or ads /H2
generation overpotential
electrochemical desorptionreaction
chemical at(R9)
lowelectrochemical
temperatures, high
on t
example,
different Tafela slow elec
2H
orelectrochemical
/H desorption " " (R5) (R9) controls
" atslopes
high be
reaction te
he mechanism adsof"the2 hydrogen evolution reaction is widely OH OHads #Oads mechanisms
H2 at
O low
e temperature
[51,59].betw
H e Hads /H2 electrochemical (R6) different Tafel slopes
pted [17] to be a" step involving the formation of adsorbed (R9) controls
or
H electrochemical
e H /H desorption
2 reaction (R6) mechanisms [51,59]. at h
The overpotential o
ogen where the subscript ads represents the adsorbed status.
ads Oads Oads #O2 chemical
different
measured reaction
byTafel slope
the Tafel
The overpotential of eo
Thethe
where "overpotential
subscript ads ofrepresents
hydrogen the
is generally measured by the
adsorbed status. mechanisms [51,59]
"
e /Hads H e H ads /H 2 (R4) (R6) measured
One of the charge transfer steps
by istherate controll
Tafel equ
Tafel equation
The overpotential of hydrogen is generally measured by the
dence of transfer coefficients The ain2:3
Equation RT (19)
H h anode OH -overpotentia lo
Tafelbyequation
where
ch is followed the subscript
either ads represents the adsorbedvariations
chemical desorption status. can be used to measured
identify the 1 RT
rate
" determ
aF
RT i h-ads 2:3 by thelog Taf
The overpotential
hcathode 2:3 log of hydrogen is generally example, a slow
measured (22) OH
by the anode
electron transfer step (R7) determi
1 " aF
ds /H2 RT
aF i EA (R5) at low temperatures, on theEAcontrast, a slow RT reco
Tafel 2:3 log 0
equation
hcathode (22)
ectrochemical desorption aF i0 (R9) controls at highTable 1 O2 2:3
temperatures
hanode on nickel
In this equation, i0, the exchange current H2 density differentof the reaction, O
Tafel slopes Table
between the steps can 1be" usa
In this can
equation, RT i asHthe
i0, the exchange current density ofmechanisms
the reaction,
ads
Kinetics
1 parameters of hydrog
hwhich
e" Hads /H
cathode
2 be analogised
2:3 log ads rate constant (R6)of reaction, is a func- (22) Kinetics parameters of hydrogen
[51,59].
which can be a F
analogised
tion of the nature of the i as
0 heatthe rate
electrode
of
constant of reaction,
(cathode) material is a
The [50].func-The
overpotential of Metal
heat oxygen
of Heat of H2 reacti
evolution Elec
re the subscript
tion ofads
overpotentialrepresents
the nature
of the thethe
of adsorbed
hydrogen status.
electrode (cathode)means
production material [50].
extra The
- energy Metal adsorption
Heat of H2 Electro
In this of
H +
equation, i0,is the adsorption
exchange current densityextra
OH
measured
of the
by the Tafel equation
Table
reaction, adsorption 1
(kJ mol"1)
adsorption
he overpotential
overpotential hydrogen
of the generally
hydrogen measured
production by themeans energy
barrier in the process of hydrogen formation. Kinetics(kJ parameters
mol"1) of hy
equationwhich
barrier can be analogised as the rate constant of reaction, is a func-
RT Ni i[55] 105 1M
The in the process ofon
overpotential hydrogen formation.
the cathode is directlyhanoderelated 2:3to the log
tionThe of overpotential
the nature ofonthe theelectrode
cathode (cathode)
is directly material
related to[50].
the aF Ni Fe
The
1 " [55] 105109 Heat of
Metal
i0[56] 1MH22Na
M
formation
RT i of hydrogen in the vicinity of the electrode. The formation Fe Pb
[56] [57] 109N/A adsorption
2 M6 Na
N
ode 2:3overpotential
log
formation
ofaF hydrogen of of
hydrogen the inhydrogen
the vicinity production
of the (22) means
electrode.
13
is intrinsically determined by the bond between The extra
formation energy PbZn[57]
i0 [57] N/AN/A (kJ mol6"1N6Na
) N
(R4) One of the charge transfer steps is rate controlling. The depen-
dence of transfer coefficients a in Equation (19) and Tafel slope
esorption variations can be used to identify the rate determining step. For

Increase Overall Reaction Rate


(R5)
example, a slow electron transfer step (R7) determines the reaction
at low temperatures, on the contrast, a slow recombination step
(R9) controls at high temperatures on nickel electrode. The
We can see from last different Tafel
slide that slopes between
electrolysis the
reaction is steps can be
controlled byused
manytosteps
judge the
including (R6)
adsorptionmechanisms
and surface[51,59].
reaction (both chemical and electrochemical).
The overpotential of oxygen evolution reaction is generally

adsorbed status.If adsorption is slower than surface reaction, then overall reaction rate is
controlled measured by the Tafel equation
generally measured by theby adsorption
If reaction is slower than adsorption,
RT then overall
i reaction rate is controlled
hanode 2:3
by surface reaction log (23)
1 " aF i 0
+ -
Therefore,(22)
we should find material that can quickly adsorb H or OH to avoid
reduced reaction rate due to slow adsorption
ent density ofAdditionally,
the reaction, Table 1
we should also
Kinetics find catalysis
parameters thatproduction
of hydrogen decreases activation
on different energy
electrode of
metals.
nstant of reaction, is areaction.
surface func-
athode) material [50]. The Metal Heat of H2 Electrolyte Temperature [55] i0 means the data
Tafel were
slope
adsorption (% C) obtained
(A m"2 from(mV) ref 55
ction means extra energy in the paper: Kai Zeng,
(kJ mol"1)
mation. Dongke "2 Zhang, Recent
Ni [55] 105 1 M NaOH 20 1.1 ' 10 121
is directly related to the progress"2in alkaline water
Fe [56] 109 2 M NaOH 20 9.1 ' 10 133
he electrode. The formation electrolysis for hydrogen
Pb [57] N/A 6 N NaOH 25 4 ' 10"2 121
production and
ed by the bond between Zn [57] N/A 6 N NaOH 25 8.5 ' 10 "6
124
applications , Progress in
Pd has the lowest heat of
"3
Co [58] N/A 0.5 M NaOH 25 4.0 ' 10 118
Energy and Combustion
s compared to 105 kJ mol"1 Pt [17] 101 0.1 N NaOH 22 4.0 105
Science "2 36 (2010) 307
Au [17] N/A 0.1 N NaOH 25 4.0 ' 10 120
mation is also influenced by 326. [56] means ref 56, etc.
14
which is followed by either (R4) chemical One desorption
of the charge transfer steps is rate controlling.
variations can be Theused
depen- to identify the rate de
dence of transfer coefficients a in Equation example, (19)a slow
and Tafel
electronslopetransfer step (R7) dete
2Hads /H2
er chemical desorption variations can be used to identify the at (R5) ratelowdetermining
temperatures, step.on Forthe contrast, a slow

tion
Reduce Over Potential
or electrochemical desorption

H e" Hads /H2


(R5)

The reaction rate decreases with increasing


example, a slow electron transfer step (R7)
atK. low
Zeng, D.temperatures, on the
Zhang / Progress in Energy
(R9) controls at high temperatures
activation energy, so
contrast,
and Combustion

different Tafel slopes between the steps can


(R6)
(R9)determines
adifferent
Science slow
controls the
36 (2010) 307326
on nickel electrode.
mechanisms
at reaction
recombination
high temperatures on nic

[51,59]. The
Thebeoverpotential
used to judge of
step
Tafel slopes between the steps can

theoxygen evolution re
315 b

reducing the activation energy is always favoured for more efficient 1.8
where the subscript ads(R6) represents the adsorbed
mechanisms status.
[51,59]. measured
Oxygen Overpotential
by the Tafel equation
water electrolysis. Furthermore, the activation energy increases Hydrogen Overpotential
The overpotential
Theincreasing
overpotential of hydrogen
of cathode is
The generally
overpotentialmeasured of by
oxygen the evolution reaction is generally
with current density and can and anode
be lowered by areusing 1.6
epresents the adsorbed
Tafel equation status.

Overpotential (V)
appropriate electrocatalysts. Table measured bykinetic
the Tafel equation RT i
hydrogen is generallygenerally measuredmeasured
by the by2the compares
Tafelthe equation param-
h anode 2:3 log
eters, again represented by the current density and Tafel slope, of 1 " aF i0
RT reactions
i on different metal electrode RT materials. i 1.4
E hcathode
oxygen evolution
2:3 log the overpotential
Generally speaking,
Ehanodeofoxygen 2:3 evolutionlog (22) (23)
i0
k=b
aF i0 1 " aF is i0
more difficult to reduce than that of hydrogen evolution, owing to
io, the exchange (22) current density of Feof the
In the
thiscomplex
equation, i0, theand
mechanism exchange current
irreversibility. Alloysdensity and of the reaction, -0.2 Table 1
Ni have
been can reaction
found (occurs
to be able to reduce atthe
the same
overpotential condition
to asis a func- Kinetics parameters of hydrogen production on different
which o be analogised as the rate Table
constant
1
ofsome extent
reaction,
xchange current density
[63]. of
E ),nature the reaction,
which
tion of the ofcanthe be analogized
electrodeKinetics (cathode) as the
parameters rate [50].
material
of hydrogen The -0.4
production Metal electrode
on different Heat of H2
metals. Electrolyte Temperature i
as the rate constant of reaction, is a func- adsorption (% C) (
overpotential
4.3. Cell constant of the
overpotential of reaction, isMetal
hydrogen production a function meansof theextra energy
electrode (cathode) material [50]. The Heat of H 2 Electrolyte Temperature i 0 (kJ mol Tafel
"1
) slope
barrier in the process
nature of the ofelectrode
hydrogen formation.material. adsorption 316 (% C)
1 [55](A m"2 10 (mV) K.100 Zeng, D. Zhang / Progress in Energy
1,000
drogen productionAsmeans extra energy Ni 105 1 M NaOH 20 1
The shownoverpotential on the and
above, the hydrogen cathode
oxygen is directly
mol ) related
overpotentials
(kJ "1 can be to the Current Density (A m -2 )
ydrogen formation. refers
expressed to the transfer (23). coefficient, plot inits value 3.0 Fe [56] 109 2 M NaOH 20 9
formation ofby Equations
hydrogen in(22)
theandvicinity A typical
Ni of
[55]the electrode.
105
Fig.
The7 is
1 M formation
NaOH 20 Pb [57] 1.1 ' 10 "2
121
N/Afor both hydrogen
6 N NaOH 25 4
the cathode isthedirectly lies
Tafel plotrelated
between to 0the
as a function and
of 1 for
Equation thein one-electron
(21) water electrolysis. Fig. 7. Typical Tafel plots "2 and oxygen evolution.
of hydrogen is intrinsically determined
Fe [56] by the bond
109 between
2 M NaOH 20 Zn [57] 9.1 'N/A10 133 6 N NaOH 25 8
he vicinity of theThe parameters
electrode. Theused to compare the electrode kinetics are the
formation 2.5
hydrogen and reaction of hydrogen,
the electrode
the Tafel surface.
indicates
Pb [57] N/A
Pd has how
the lowest6 N NaOH
current heat
25 4
of k is theCoelectrical
[58] N/A'Ohmic
10 "2 Loss(electrode)
121 0.5 M NaOH 25 tenti"1 al 4
ally determinedexchange by thecurrentbondi0 and
between slope. A higher
Zn [57]
exchange
N/A 6 N NaOH where
25 8.5 conductivity
10 "6
124 and has the
n Ounit
v e rpoof U m"1,
droge
'
densityefficient the electron is"1 used foractivity.
surface
adsorption oflower
hydrogen (83.5 kJa mol )electrode
as compared to0.5
105 kJ mol "1 Pt [17] 101 0.1 HNyNaOH 22 4
and slope indicate higher subscript
25 2.0g stands for'each
10"3 component
118 0.1 Nof the circuit, including
ode surface. Pd has the lowest heat of Co [58] N/A M NaOH Au [17] 4.0 N/A NaOH 25otentia l 4
"1 for NiSince reaction
[54]. the
Meanwhile, on cathode
cell potential thecontains
hydrogen both
Pt anode 101
formation
[17] and cathode reac-
is also influenced
0.1 N NaOH by
wires,
22 connectors and 4.0 the electrode.
105 This part nofO v e
therpresistance can

VCELL (V)
3.5 kJ mol ) astions,
compared to 105 "1
Oxyg e
identifying thekJ mol
contributions of each
Au [17]of anode
N/A and cathode to NaOHbe reduced
0.1 N 25 1.5 by reducing 4.0 'the length
10"2 120 of the wire, increasing the cross-
e hydrogen formation
the cellis voltage
also influenced
and factors by influencing them is necessary to section area and adopting more conductive Ohmicwire material.
Loss(electrolyte)
From Tafel
understand the equation,
overpotential we can see
resistance. that: effect of
The typical Ionic transfer within the electrolyte depends on the electrolyte
1.0 Eo
temperature on the overpotential is summarised by Kinoshita [47]. concentration and separation distance between the anodes and
overpotential increases when temperature
As shown in Fig. 8 an increase in temperature will result in cathodes, the diaphragm between the electrodes. Different from
increases
a decrease in the overpotential at the same current density. 0.5
the conductance rate in the metallic conductor, the Molar conduc-
The overpotential is not only a function of temperature but also tivity is adopted to replace the conductivity and can be expressed as
overpotential increases when actual
a function of current density [38]. As can be seen from Fig. 9, the follows:0.0
current
overpotentials increases
from hydrogen and oxygen evolutions are the main 0 1000 2000 3000 4000 5000
sources of the reaction resistances. The other obvious resistance at k Current density (A m )
-2
15 L (25)
high current densities is the Ohmic loss in the electrolyte, which C
Reduce Ohmic Loss
Recall that on p.5, we have ohmic loss as
i(R1+R1+Rbubble, O2+Rbubble,H2+Rion+Rmembrane)= iRohmic= Eohmic

These resistances are the direct reasons of heat generation which leads to the
wastage of electrical energy in the form of heat formation according to the Ohms law.

The resistances of connection circuits (R1, R1) are determined by the types and
dimensions of the materials, preparation methods, and the conductivities of the
individual components.
This part of the resistance can be reduced by reducing the length of the wire,
increasing the cross-section area and adopting more conductive wire material.

Ionic transfer (Rion) within the electrolyte depends on the electrolyte concentration and
separation distance between the anodes and cathodes
improvements can be made by increasing the conductivity of the electrolyte or
altering its concentration or adding appropriate additives.
we can also decrease the distance between electrodes

Membrane resistance (Rmembran)can be improved by using thinner membrane or


membrane that has larger permeability to ions
16
adds to the eters
electricalfor comparis
resistan
surface properties to make them less electrodes. attractive In to addition, controlling
the gas bubbles. flow pattern to force
leave electrodes mechanically is alsobetween
the contact a means. the elect
Understanding the dynamics of the bubble behaviour is Cell configura
Intensive studies have been given
electron to % the bubble
and behav
important in order to determine the conditions for the departure of transfer, incre

Reduce Ohmic Loss electrolysis systems [71,7376].


the bubbles from the electrodes. The general thermodynamic
condition for the three phase contact between the gas bubble,
electrode and the electrolyte is a finite contact angle at thesystems.
three
It is a
system. Understanding thekey
important element in the de
gap between
issue to
electrolytes.
% Operating con
Mechanically circula
be r

Resistance of bubble can be reduced by decrease the operating tem


phase boundary [68,69] as illustrated in Fig. 11. detachment of bubbles, prov
coverage of bubble on the electrode. electrolytes a
The Youngs equation defines the contact angle in termsresistance of the due to gas bubbles.
% External requ
three interfacialcondition
The general thermodynamic tensions for
[70],
the three phase appropriate sv additives to the
issues such a
contact between the gas bubble, electrode and the electrolyte surface tension of the electrol
gsv " gsl and safety iss
cos qangle
is a finite contact at the three phase boundary. surface
(30) Gas properties to make th
Solid
glv Understanding the dyna
The Youngs equation
where gsvat, gthe right had side defines the contact important in order to determ
lv and gsl are the surface tensions of the solid/vapour,
angle in terms of the threeand
solid/liquid interfacial tensionsinterfaces, respectively.
liquid/vapour The the
Gibbsbubbles6.1.from Cell the
configura
elect
Liquid
free energy change accompanying the replacement of the unit condition
area for the three pha
There are two
The Gibbs free of energy change accompanying
the solid/liquid the replacement
interface by a solid/vapour interface electrode and the electrolyte
lv the monopolar an
of the unit area of the solid/liquid interface by a solid/vapour phase boundary [68,69] as ill
olar arrangement
interface is DG glv cos q " 1 (31)
The Youngs slequation defi
nected to the o
three interfacial tensions [70
The detachment
When is smaller, it is harder ofto the
havebubbles depends
solid/vapour onAn
interface
Fig. 11. the replacement
illustration of the
of the contact angle at respectively, givin
the three phase bounda
electrolyte at the solid/solution interface,
treat the electrode surfaces to make them more hydrophilic
bubble,which
electrodeisand
known as wet- gsvanother.
the electrolyte. " gsl The total
cos q essentially the sa
(electrodetablity [71,72].
likes water better) glv
Two kinds of electrode surfaces can be defined according to the electrodes in the
use additives in the electrolyte solution to reduce surface
surface tension, namely, hydrophobic and hydrophilic.svThe , and
where
lv elec-g are
slsv, gtwo the
lv and surface
end are the
gslelectrod
trode which favours water is hydrophilic, and the onetensions notofisthe solid/vapour,
tension so that bubbles are easy to depart from electrodes.
doessolid/liquid and liquid/vapou
every two adjacen
hydrophobic. Appropriate surface coating can therefore solid/liquid
free energy
be applied and liquid/vapour
change
are accompan
electrically lin
Controlling flow pattern to force bubbles to leave electrodes interfaces,the respectively.
to make the electrode surfaces more hydrophilic in order to ofreduce solid/liquid interface b
mechanically is also a means. For example, rotate the electrode
the surface coverage by the gas bubbles.
quickly while electrolyze. DG the glv cos q " 1
Therefore there are some broad approaches to manage a O2
bubble phenomena. One is to17treat the electrode surfaces to make
The detachment of the bubbl
More To Think About
Where does the electricity come from?

Where do we get water?


the shortage or the uneven distributed water resource is
the next big issue globally

Inert metal, which is expensive, is commonly used in the


electrolysis and the cost is high
inert metal is not easily corroded
inert metal is good catalyst for hydrogen production

Can electrolysis generate as much hydrogen as thermo-


chemical treatments of carbon hydrates in the same time?
18

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