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An exact equivalent circuit including terminal parts, which takes account of electrical and chemical control
parameters in a uniÐed way, is derived for a cell with a mixed conductor (or electrolyte) without internal
sources or sinks. In one-dimensional problems electrochemical kinetics can be mapped by two-dimensional
circuits exhibiting the spatial and the thermodynamic displacement as two independent coordinates. One main
advantage of the exact circuits with respect to the underlying di†erential equations is the ability to simplify the
description according to speciÐc situations. As we show in several examples in the second part of the paper, it
is straightforward to select the elements relevant for the particular experimental conditions and so to make
appropriate approximations. This is most helpful for the description of electrochemical systems, such as fuel
cells, membranes, pumps and batteries.
C P ]
A
d/ dk* ~1 B A
P
1
]
1 ~1B. (7) j, i
j, i j, i B
(symbol ko denotes the standard concentration independent
term and N the density of available sites). Then the deriv-
j, i j, i
electrochem dQ dQ C C j, i
electro chem ative in eqn. (9c) can be explicitly evaluated yielding
However, as will be explicitly shown later, the ““ charges ÏÏ
stored in electrical and chemical capacitors are not necessarily (ez )2
Cd \ j c As. (10)
equal and therefore such a series representation only applies j, i k T j, i
B
in a few cases and is generally not adequate ; rather there may Since Cd is proportional to the volume, it can be very large
be additional branches connected to the node between both j, i
compared to Cq. If the relative carrier density is 0.01%, the
capacitors, as indicated in Fig. 1b. In steady state experiments area 1 cm2 and the thickness 1 mm, then the chemical capac-
(pure energy dissipation) the only relevant potential is k8 itance at ambient temperature amounts to about 0.1 F. This is
(splitting into electrical and chemical parts is meaningless).
This introductory discussion of circuit elements reveals
already an important observation : apart from interfacial Ò If the time domain variables are sinusoidal (usual case in impedance
spectroscopy) amplitude and phase of the Fourier transforms reÑect
relaxations two di†erent timescales may be associated with directly amplitude and phase of the sinusoidal time domain quantities.
the transport processes : typically a short timescale involving p These transition compartments/regions (not shown in Fig. 2a) are of
electrical capacitances and a long timescale involving chemical the same size as the carrier residence compartments but shifted by s/2
capacitances. along the x-coordinate (for details see ref. 31).
10 orders of magnitude more than the sampleÏs electrostatic gence of the carrier currents has to be balanced by storage of
capacitance (if e \ 10). the carriers in chemical capacitors. Thus, Cd will be attached
Expression (10) has already been used in the context of to the nodes within the carrier rails (Fig. 2c) and aligned
equivalent circuits. In ref. 17 it is termed ““ NernstÈPlanck orthogonally (no electric potential drop is allowed across Cd).
capacitance ÏÏ. Franceschetti16 wrote two expressions for the The remaining balance for the currents,
““ shunt ÏÏ capacitance, as he called it : in the special case in [* I [ * I \ * I , will be obeyed if we connect the free
i 1 i 2 i dis
which local electroneutrality applies, he used the shunt capac- terminals of Cd to the nodes of the displacement rail. The
itance equals to ours (eqn. (10)), while in the case of the circuit obtained is shown in Fig. 2d. Finally we verify
NernstÈPlanckÈPoisson model it surprisingly includes e. Kircho† Ïs law for the potentials. To do so, it is sufficient to
restrict ourselves to the elementary loop indicated by the
dashed line in Fig. 2e. Since the elementary loop refers to a
3.1.2 Construction of the circuit. After the three basic ele- single carrier we skip the subscript j. The potential drop along
ments, electrochemical resistances, electrostatic and chemical the loop equals dk* ] * k8* [ dk* [ * /. Taking into
i i i`1 i
capacitors have been deÐned, they just have to be connected account that * k8* 4 dk* [ dk* ] * /, the sum obviously
i i`1 i i
such, that eqn. (8) are fulÐlled. Since our system is relatively vanishes. Since any other loop can be composed of such ele-
simple we do not necessarily need a bond-graph approach.22 mentary loops, Kircho† Ïs law for the potentials (electrical,
Nevertheless, di†erent potentials (/, k ) will appear in the chemical and electrochemical) applies to any part of the
j
circuit, thus the simple scheme displayed in Fig. 2b will be circuit.
useful : the transport coordinate which is identical with the Since the chemical capacitors once built into the circuit are
spatial coordinate x describes the direction of transport : all treated as the electrical ones we use the same symbol (Fig. 2).
the circuit elements, which are assigned to transport steps (R , In contrast to R and Cq, the two terminals of the chemical
j
Cq) have to appear aligned along the transport coordinate. capacitor refer to the same locus yet to di†erent potentials
The coordinate orthogonal to it is reserved for internal reac- (states) : one terminal is held at zero potential (i.e. at equi-
tions. Since we assume local equilibrium we do not have to librium potential) and the other at variable potential dk* . In
j, i
consider any reaction resistances, just chemical capacitors. A contrast to an electrostatic capacitor there is no separation of
simple example of an internal reaction is the local dissolution electric charge in a chemical capacitor. While in an electro-
of oxygen in an oxide or intercalation of lithium in graphite. static capacitor the Gibbs energy *G \ 1 Cq*/2 is stored elec-
2
The corresponding ions and electrons are stored in chemical trostatically, in a chemical capacitor Gibbs energy *G \
capacitors. 1 Cddk*2 is stored as entropy changes (in non-dilute cases
2
Since we consider three transport mechanisms, we will have energy changes also). In general the ionic and electronic capa-
three rails aligned along the transport coordinate : the ionic, citors connected to the particular node in the displacement
electronic and displacement rails (Fig. 2c). These three map rail are not charged equally (with the negative sign). Referring
eqn. (8a) and (8b). The coupling among the rails is described to the circuit, the currents Ñowing through them are not
by eqn. (8c) (essentially part of Kircho† Ïs law for the currents equal. This di†erence is compensated by the current in the
and Ñux-potential relation for chemical capacitors). The diver- displacement rail in the middle. In this way the electrical cur-
3.2.1 Electrode boundary conditions. A situation very often between the metal and mixed conductor. The chemistry of the
encountered in the solid state refers to electrochemical reac- electrode compartments is often highly complicated : the elec-
tions in which the reaction product and/or educt is in the gas trodes may be porous, there may be adsorbed oxygen, reac-
phase. The morphological changes at such interfaces can, at tions may be complex, etc. In this paper we consider them on
least to a Ðrst approximation, be neglected. On the other a “ black box Ï level which does not require any particular
hand, the geometry of the reaction sites may be quite complex mechanistic model, but assumes a quasi-steady state approx-
and, on the microscopic level, far from being planar (purely imation (see remarks at the end of this section and also ref.
electronically conducting electrodes are usually porous). We 30). Under these conditions the construction of the terminal
consider here, as an example, a mixed conducting oxide in part of the circuit is as follows : transition of electrons between
contact with very thin electrodes which serve as current collec- the metal and core compartment is characterised by the
tors and are basically permeable for oxygen (Fig. 3a, top). The ““ electrochemical ÏÏ resistance RM (see Fig. 3a). The displace-
eon
sample must Ðrst be equilibrated in an atmosphere with the ment rail is connected to the electrode via the electrostatic
same oxygen partial pressure at both sides (x \ L and capacitance, Cq . Since, in the metal compartment, the density
M
x \ [L ). This procedure deÐnes the initial situation. Besides of electrons is very high, dk* is vanishing there. Consequent-
eon
the di†erence of electron electrochemical potential, *k8 , ly the terminals of the displacement and electronic rails have
eon to be at the same potential, which is satisÐed by short-
applied we also allow for external chemical driving forces, i.e.
for deviations of the oxygen chemical potential from the initial circuiting the two terminals as shown in Fig. 3a, bottom.
values, dk@ and dkA , referring to the left- and right- Finally we are left with connecting the ionic rail to the elec-
O(gas) O(gas) trode. The overall reaction relevant to this reads
hand side of the sample, respectively. Note that dk 4
O(gas)
1 dk . All three independent driving forces, */, dk@ ,
2 O2(gas) O(gas) 1 O (gas) H O2~ [ 2e~ . (12)
dkA , are control parameters and may be time (frequency) 2 2 core electrode
O(gas)
dependent. Next, we have to clarify the discretisation of the Close to equilibrium the rate of reaction (12) will be pro-
terminal parts. As already mentioned the sample is divided portional to the di†erence of the (electro-) chemical potentials
into compartments of thickness s. To both sides we add an referring to the left- and right-hand side of the equation. Thus,
additional compartment which stands for the electrodes (Fig. the oxygen Ñux density J , reads
3a). The adjacent compartment refers to the core of the inter- O
faces, i.e. in our case to a transition region of varied structure J \ K Mk [ (k8 2~ [ 2k8 ~)N. (13)
O O O(gas) O e
1672 Phys. Chem. Chem. Phys., 2001, 3, 1668È1678
The proportionality constant, K , is, in our approximation, a In the simplest case the sample ends with the surface core
O
frequency-independent materials parameter referred to equi- (no electrode compartments) (see Fig. 3b) and the only driving
librium. Eqn. (13) is actually the boundary condition we had forces are dk@ and dkA . The overall reaction between
O(gas) O(gas)
been looking for, however, it is much easier to visualise it the gas phase and the carriers in the surface core, which
graphically, by introducing normalised quantities : We replace occurs in several steps, can be written as
J by the equivalent electrical current density I \ [2eJ ,
O ion O 1 O (gas) H O2~ [ 2e@ , (15)
deÐne resistance of reaction (12) 1/RM 4 4e2K and normalise 2 2 core core
ion O
the chemical potential of O according to which is quite similar to reaction (12). The only di†erence is
2(gas)
1 that here the electrons refer to the core, not to the electrode.
dk* 4 dk . Using almost the same procedure as in the previous section
O(gas) [2e O(gas)
(we denote the surface reaction resistance by R ) we derive
s
Then eqn. (13) may be rewritten
^I R \ dk [ (dk* [ dk * ) at x \ ^L . (16)
I RM \ dk* [ dk* [ */. (14) ion s O(gas)* ion eon
ion ion O(gas) ion The source of oxygen chemical potential, dk* , is connected
The electric potential di†erence, */ \ / [ / , O(gas)
core electrode to the terminals T and T (see Fig. 3b) through R , which, on
appears, since the ions and electrons in reaction (12) refer to 1 2 s
the level of the equivalent circuit, describes the internal resist-
di†erent loci. The boundary condition (14) is implemented ance of the source. The division of the external driving force
into the circuit as shown in Fig. 3a. The chemical potential of dk* into dk* and dk* is determined by the structure of
O , which corresponds to one of the externally applied O(gas) ion eon
2(gas) the circuit. Please note that the core chemical capacitors for
driving forces, is implemented as an ideal voltage source (its ions and electrons are in general not Ðlled evenly, thus storing
potential is independent of the current). The source is dis- an excess surface charge, which was mentioned above. This
played in Fig. 3a as an ellipse with two terminals. One can charge is needed in order to enable the existence of the drag
easily verify the terminal part of the circuit by applying eqn. electric Ðeld within the sample, which is characteristic for
(14) as Kirchho† Ïs voltage law to the loop indicated in Fig. 3a ambipolar di†usion. In the literature dealing with chemical
by a dashed line. Please note, that according to our rules, the di†usion the surface reaction is usually characterised by a
electrical potential changes only from one carrier com- phenomenological rate constant k6 . It is straightforward to
partment to the other (along the x-coordinate), while along s
show that k6 is related to R~1 through the component chemi-
branches in y-direction (reaction coordinate) it remains s s
cal capacitance of the whole sample,30,32 viz. :
invariant.
The circuit elements, RM and Cq , which appear as a conse- L
j M k6 \ . (17)
quence of the boundary conditions, deserve some comments. s R Cd
The oxygen exchange reaction (12) is a multi-step process, s
thus RM stands for the sum of resistances of all the individual From eqn. (17) we see immediately, that k6 /L plays the role of
ion s
steps. If just one step is rate determining, then RM can be a time constant which characterises the transient behaviour of
ion the surface controlled di†usion.
interpreted as the inverse of the exchange current density in
the ButlerÈVolmer formalism or as the inverse of the corre-
sponding rate constant in the ChangÈJa†e description (see 4 Applications of the equivalent circuit
also ref. 30). The description of the overall reaction rate with a
resistance only assumes that the output Ñux instantaneously 4.1 A single carrier conductor polarised with blocking
follows the time-dependent driving forcesÈa quasi-steady- electrodes
state approximation. Under general conditions, a transfer
function o†ers a proper description. The frequency depen- One of the simplest situations, which is met in solid state elec-
dence stems from the inclusion of energy storage mechanisms, trochemistry, is a single carrier system contacted by electrodes
e.g. oxygen adsorption, surface di†usion, etc. As in the bulk, which do not allow for any carrier transfer across the interface
these storage processes can easily be taken into account by (completely blocking electrodes). Such a cell is approximately
chemical capacitances. A detailed treatment in this respect realised by Pt/AgCl/Pt or C/b-alumina/C (as long as we
which highlights the power of the proposed tool for handling neglect electronic carriers in the solid electrolyte, i.e. we do
electrode kinetics will be given elsewhere. not consider the low frequency part of the impedance spectra
As far as Cq is concerned, we should stress that the relative near the dc conditions). Another single carrier system with
M blocking electrodes is the MOS (metal-oxide-semiconductor)
permittivity of the corresponding transition-compartment
located between electrode and core certainly di†ers from the structure M/SiO /Si/SiO /M. Here, the material under focus
2 2
bulk values (see in-depth studies concerning liquid is Si doped such that only electrons or holes are of impor-
electrochemistry). In terms of liquid electrochemistry the inter- tance. If we neglect ions in SiO , the SiO /Si contacts per-
2 2
facial core refers to the inner Helmholtz plane (IHP), thus Cq fectly block the carriers in Si. The impedance of these systems
M has been treated in detail on the continuum level25 as well as
to the capacitance of the region between the electrode and the
IHP.14 The capacitance due to the di†use (GouyÈChapmann) on the level of intuitive33 and exact equivalent circuits.15 Our
layer is already included in the ““ bulk part ÏÏ of the transmis- aim here is to derive from the equivalent circuit some inter-
sion line (see Section 4.1, also ref. 13 and 15) ; thus, there is no esting properties of the electrode capacitance (Is it electro-
need to include it explicitly in the terminal part, as has been static and/or chemical by nature ?) and of MaxwellÈWagner
done in the literature.17 relaxation.34 Before doing so, let us reproduce the well-known
impedance relations.
3.2.2 Free surface boundary conditions. In the Ðeld of solid
state electrochemistry, samples are not necessarily electrically 4.1.1 Impedance. Since we have just one charge carrier to
contacted. An important example is a mixed conducting mem- consider, the general circuit simpliÐes (here we take for
brane separating two chambers with di†erent component example the ions as charge carriers, but the circuit would have
partial pressures. Here di†erent charge carriers move in an the same topology also for electrons) : The electronic rail as
ambipolar and e†ectively electroneutral fashion. If the mobi- well as the chemical capacitors due to electrons can be
lities of the carriers, e.g. O2~ and e~ in the case of oxygen omitted (see Fig. 4a). In the case of blocking electrodes the
permeation, di†er, the membrane surface will become charged interfacial resistance is inÐnitely large, thus the ionic rail is
albeit not contacted externally (see for example ref. 31). simply disconnected from the electrodes. First we assume arti-
JCdCq \ ee A
S e2z2c
\ ee
A
. (20)
0 ee kT 0L
0 D
The Debye length, L , i.e. the screening length, reveals a
D
further interesting meaning. The chemical capacitance of the
whole sample increases with the sampleÏs thickness, while its
electrostatic capacitance decreases. Therefore, there must be a
critical thickness at which Cq \ Cd. In single carrier systems
this thickness is exactly the Debye length : if the sample is
thinner than L , its electrostatic capacitance will be larger, if
D
the sample is thicker the chemical capacitance will predomi-
nate.
As we noted, C is a ““ mixture ÏÏ of an electrostatic and a
dl
chemical capacitance (Fig. 4b). Since the capacitors are
arranged in a transmission line, the term ““ di†use layer
capacitance ÏÏ is very meaningful. A straightforward calculation
Fig. 4 Single carrier material contacted with blocking electrodes. shows that one half of the free energy in such transmission
Equivalent circuits (a) for the whole cell, (b) for the di†use layer and line is stored electrostatically, and the other half chemically
(c) for the interfacial capacitance with core e†ects. (conÐgurational entropy term). Although C can thus be con-
dl
sidered as an element in which the energy is stored
““ electrochemically ÏÏ it is not an electrochemical capacitor in
Ðcially that the interfacial core exhibits the same structure as the sense of its deÐnition (see Fig. 1b). The chemical and elec-
the bulk. Then the carrier concentration in the core is the trostatic capacitors are connected in a transmission line rather
same as in the bulk and no equilibrium space charge layers than in series. Already this shows that the concept of an elec-
are present. Correspondingly, in the equivalent circuit all the trochemical capacitance is not general.
elements are spatially invariant (we can omit the subscript i).
The impedance of the circuit is deÐned as Z(u) \ 4.1.3 Interfacial capacitance including core e†ects. The
*k8 (u)/I(u) (the symbol * denotes the di†erence between the di†use layer capacitance of cells with solid ionic conductors
eon has never been clearly measured. The values found were
electrodes). Since the density of electrons in macroscopic
metal electrodes is very high (mesoscopic e†ects are con- always much higher (orders of magnitude) than expected from
sidered later in this section), *k8 B */. The ratio, voltage L . Although di†erent interpretations have been given in the
eon D
drop along the displacement rail over the total current, can be literature35,36 we propose an explanation which follows
readily calculated15 directly from the circuit. In the treatment above we assumed
that the sample is completely homogeneous. In reality, the
R 1 1 tanh(iL ) carrier density in the interfacial core will be di†erent from the
Z\ ] . (18) bulk since there the underlying structure di†ers from the
1 ] iuq 1 ] iuq iuCq iL
regular structure in the bulk. Thus the core chemical capac-
The symbol q 4 R Cq denotes the dielectric relaxation time. itance should be distinguished from the chemical capacitances
ion
The decay length, i~1 4 2L JCq/Cd (1 ] iuq)~1@2, describes of the subsequent compartments. The equivalent circuit for
the decay of electrochemical perturbations (dk, +/) in the the interfacial capacitance, C, is then composed of Cq , Cd
M core
direction towards the bulk. If we replace the resistance, and and C , as shown in Fig. 4c and derived earlier from the
dl
electrostatic and chemical capacitances in eqn. (18) by the deÐ- steady state considerations.37 If the core carrier density is very
nitions (eqn. (9)), the obtained impedance will be identical to high, then Cd [ C and C will appear as a series com-
core dl
the well-known result derived on the continuum level.25 This bination of the electrostatic Cq and chemical Cd . Thus an
M core
is no surprise since the equivalent circuit is an exact represen- interpretation of C as an electrochemical capacitance is indeed
tation of the continuum level equations. possible in this case (see also Fig. 1b). If a partial charge trans-
The Ðrst term in eqn. (18) refers to the bulk response while fer between the metal and core takes place, Cq will e†ectively
M
the second one includes the electrode capacitance. The latter be very large and C B Cd . Such a situation is met in super-
core
statement becomes particularly obvious in the low frequency capacitors, in the case of underpotential deposition or the
approximation assuming in addition that L P 3L (the Debye electrosorption process of e.g. Pb on Au (see e.g. ref. 9). Our
D
length L 4 Jee k T /(e2z2c)). Then core defects in these cases refer to the electrosorbed species
D 0 B comprising a part of the monolayer on the top of the elec-
2 trode. To make this point clear let us calculate the core capac-
Z(u ] 0) B R(1 [ 3L /L ) ] . (19)
D iu JCdCq itance explicitly. According to eqn. (9c) the capacitance is
deÐned as P(dk /c )~1. Using the surface coverage, h 4
core core
Obviously, the resistance measured at low frequencies (Ðrst c /c , rather than the concentration, and taking into
core max
term in eqn. (19)) does not include the contributions from the account that the density of core defects is limited by c , their
max
interfacial regions with a thickness of B3/2L . There is no chemical potential reads : k \ k0 ] k T ln [h/(1 [ h)].
D core core B
1674 Phys. Chem. Chem. Phys., 2001, 3, 1668È1678
The capacitance obtained C \ (ez )2/K T )c V (1 [ h)h is (Fig. 5a). Then the chemical capacitance is not proportional to
j B max
identical to the pseudo-capacitance9 derived from the electro- the volume but to the length, L , of the wires, Cd \ e2L /(hv ), h
F
chemical Langmuir isotherm. being the Planck constant. Assuming L \ 1 lm and the
velocity of electrons at the Fermi energy v to be 108 cm s~1
F
4.1.4 Maxwell–Wagner relaxation. There is another point then the chemical capacitance Cd B 0.05 fF becomes compara-
worth mentioning in a single carrier system. Let us consider a ble to Cq.
material which exhibits a Schottky contact with the metal.
Then the equilibrium carrier density in the space charge layer 4.3 Warburg di†usion and stoichiometry polarisation :
will be signiÐcantly depleted and the Cd referring to the com- General
i
partments within the space charge layer will be much smaller
than in the bulk. To a Ðrst approximation, Cd can be omitted, In general, in solid materials ionic and electronic charge car-
i riers are mobile. Here we discuss such a mixed conductor with
and the equivalent circuit of the space charge layer will consist
of the layerÏs resistance in parallel with the layerÏs electrostatic one ionic and one electronic charge carrier sandwiched
capacitance. If, on the other hand, the carrier density changes between electrodes which are nearly reversible for electrons
signiÐcantly only on a scale large compared to L ,38 then the and nearly blocking for ions. We use the word ““ nearly ÏÏ since
D we discuss a realistic cell. Such cells are often used in solid
opposite limit is realised : The discretisation can be coarser
(s [ L ), and the Cd will be relatively large (when compared to state electrochemistry in order to investigate separately the
D i ionic and the electronic conductivity and to measure the com-
Cq). Thus, the Cd can, to a Ðrst approximation, be short-
i i ponent di†usion coefficient. The electrochemical cells men-
circuited, resulting in a series of RCq terms. This description,
which is known in the literature under the term MaxwellÈ tioned in the previous section but now observed over the
Wagner relaxation,34 does not assume local electroneutrality entire frequency range are appropriate examples. Others are
but rather neglects the relative changes of carrier density. As C/PbO/C, and also cells in which the electronic carriers are
we have shown, the MaxwellÈWagner approximation is very blocked. For this purpose pure ionic conductors are used as
good for single carrier systems on a scale much larger than electrode phases, e.g. Pt, O /yttria-stabilised-zirconia (YSZ),
2
L , but, although used in the literature,39 is not appropriate contacted to PbO,40 or BaTiO ,41 or YBa Cu O .42 We
D 3 2 3 6`x
within space charge layers. further assume, just for simplicity, that the mixed conductor is
a single crystal and that the component partial pressures at
both sides of the sample are kept equal and constant. At high
4.2 Quantum-conÐned capacitor frequencies of the applied voltage the electrode inÑuence is
negligible ; the dielectric relaxation in the bulk yields a semi-
So far we have neglected the changes in electron densities in
circle in the complex plane described by the ““ non-blocked
metal electrodes upon applied potential di†erence. Since the
bulk resistance ÏÏ R R /(R ] R ) and the dielectric
number of electrons in metal electrodes is very high when ion eon ion eon
capacitance of the sample. In this regime both carriers con-
compared to the number of carriers in an ionic conductor, the
tribute fully to the bulk conductivity. At lower frequencies,
relative changes in the metal are indeed negligible. The situ-
however, the selectively blocking electrodes prevent ions from
ation is di†erent, however, if the size of the electrodes becomes
crossing the interface : ions periodically accumulate at one
very small (Fig. 5a). Let us brieÑy consider such a mesoscopic
side of the sample while becoming depleted at the other. Of
parallel plate capacitor10 using our equivalent circuit. If we
course, this accumulation and depletion over larger distances
neglect, for simplicity, the spatial variations within the plates,
is only possible if the electron density changes accordingly,
the equivalent circuit shown in Fig. 5b results. Since the
such that the sample remains locally electroneutral. In this
chemical and electrostatic capacitors, unlike in the case con-
frequency range chemical di†usion (45¡ Warburg di†usion
sidered in Section 4.1, appear in series then the system capac-
turning over into a semicircle) takes place : in an oxide, the
itance in this case is a proper electrochemical one, as derived
““ oxygen ÏÏ e†ectively swings between both halves of the
earlier.10 At T \ 0, and to a good approximation also at Ðnite
sample, and thus the composition changes as well.1 In ref. 20
temperatures, the chemical capacitance of electrons Cd \
eon and 21 we introduced intuitively an approximate equivalent
(e2/k T )V (dk /dc )~1 is proportional to the density of
B eon eon circuit for such a cell and showed that it applies in a very-
states at Fermi energy multiplied by the electrode volume. As
broad materials parameter window. However, we could not
we already mentioned, due to the high number of states, Cd is
derive it directly from the basic equations. Here we show how
usually much greater than Cq and thus negligible in the
this is possible (we will use an exact equivalent circuit rather
overall expression. Interesting e†ects appear at mesoscopic
than di†erential equations as the starting point).
sizes. If the width and thickness of the electrodes are of the
The exact equivalent circuit of a mixed conductor is shown
order of a few nm, the electrodes behave as quantum wires
in Fig. 3a (we omit outer chemical driving forces here). On the
basis of the previous single carrier study the following simpliÐ-
cations of the circuit can be made : (i) the bulk of the sample is
electrically homogeneous which suggests that local elec-
troneutrality will be a good approximation there. Thus Cd
ion
and Cd will be charged evenly, and there will be no current
eon
leakage into the displacement rail ; consequently the bulk Cq
behave as truly connected in series. We replace the Cqs from
the bulk part of the displacement rail by a single geometrical
capacitance of the sample connected externally (see Fig. 6a).
This is an approximation since the interfacial Cqs are now
counted twice, but as long as L A L , the approximation is
D
good. Now the bulk ionic and electronic chemical capacitors
allocated to the same compartments also appear to be con-
nected in seriesÈthus they can be replaced by the chemical
capacitance of the component, Cd, as derived previously. This
Ðrst simpliÐcation step yields the circuit shown in Fig. 6a.
Fig. 5 (a) Mesoscopic capacitor composed of two parallel quantum In the interfacial regions local electroneutrality is clearly
wires. (b) Corresponding equivalent circuit. violated. In this region we neglect, besides RM, all other resist-
j
Phys. Chem. Chem. Phys., 2001, 3, 1668È1678 1675
4.4 Warburg di†usion and stoichiometry polarisation : SOFC
kinetics
In this section we apply the circuit just derived above to the
interesting example of the electrode kinetics of solid oxide fuel
cells.44,45 To be speciÐc, we consider the impedance of the cell
(see Fig. 7a) O /(La, Sr)CoO /YSZ/Pt, O . From the
2(gas) 3~d 2(gas)
point of view of the SOFC cathode this is the set-up of a
WagnerÈHebb polarisation cell in which the electronic con-
ductivity is blocked by YSZ electrolyte. Since (La, Sr)CoO
3~d
(LSC) is a mixed conductor with relatively high electronic
conductivity the circuit shown in Fig. 6c can be further simpli-
Ðed by short-circuiting the electronic resistors and by connect-
ing the external lead to LSC directly (RM is not necessary).
eon
We use highly permeable LSC instead of the manganate since
we can then consider quasi-one-dimensional transport. The
oxygen exchange reaction is taken into account by the resist-
ance RM in parallel with the interfacial capacitor Cion, as
s dl
derived previously (see Fig. 6c). The right-hand side terminal
part of the circuit refers to the interface between the mixed
and ionic conductor. Here the electrons are blocked, thus only
Ceon remains in the electronic rail. The ionic transfer is charac-
dl
terised by RM . Let us assume that a reference electrode is
ion
used, connected to YSZ close to the interface, such that
further transport steps are not of importance. The resulting
circuit is shown in Fig. 7b.
An interesting situation occurs, if the transport in LSC is
surface controlled, then the ionic resistance of the mixed con-
ductor vanishes and the chemical capacitors, which are now
all in parallel, can be replaced by a single Cd which refers to
the whole sample. The resulting circuit (Fig. 7c) becomes even
Fig. 6 Mixed conductor. The exact circuit (Fig. 3a) is reduced over more transparent when presented in a nested form (Fig. 7d) : it
the steps (a) and (b) resulting in the circuit (c) which is simple enough yields two impedance semicircles in the complex plane, the
to be used in routine analyses of experimental data but still general high frequency one referring to the interface LSC/YSZ while
enough to apply to a variety of materials (restriction : L A L ). the low frequency one is composed of the surface exchange
D
resistance RM and the chemical capacitance of LSC. Since Cd
s