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From Water
Via Electrolysis
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
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
+ -
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].
H2, O2
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
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).
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
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)
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.
H2, O2
11
dN
Rate (16
dt
tion
Reduce Over Potential
or electrochemical desorption
[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