Journal of Solid State Electrochemistry (2020) 24:2595–2602

https://doi.org/10.1007/s10008-020-04682-3

REVIEW PAPER

On the evolution and application of the concept

of electrochemical polarization
Dóra Zalka 1,2 & László Péter 1

Received: 29 April 2020 / Revised: 27 May 2020 / Accepted: 28 May 2020 / Published online: 8 June 2020
# The Author(s) 2020

Abstract
This paper yields an overview on the evolution of the concept of polarization applied to electrochemical systems, ranging from
electrodes to cells. The historical discussion starts at the early phase of the development of electrochemistry when current-
controlled measurements were possible only, and when the early definitions of polarization, depolarization and depolarizer were
created. A number of contemporary handbooks, recommendations and other reference resources are listed in which these
concepts are represented in various ways, from conservative definitions to attempts of redefining them. The traditional definitions
are confronted with the everyday use of professional language, drawing attention to the fact that the widespread application of
potential-controlled electrochemical measurements led to new meanings. Some suggestions are made that open room for the
application of the term of polarization in accord with the modern methodologies, without compromising the traditional intro-
duction of the term. Polarization-related phenomena in biological membranes are not dealt with in the present work.

Keywords Electrode polarization . Depolarization . Depolarizer . Current control . Potential control

The beginning: early measurements the deviation of the cell voltage from its initial value was taken
and definitions as the consequence (in other words, the cell voltage was the
dependent variable). This contemplation is well exemplified
During the early development of electrochemistry, the general in one of the earliest electrochemistry textbooks written by
method of the control of an electrochemical cell was based on Arrhenius [1]. In his book, polarization is the very first topic.
the current passed through this cell. While the current was The demonstration experiment for introducing polarization is
taken as the independent (technically variable)1 parameter, constructed from a solution (Na2SO4) into which two identical
inert metal pieces (Pt) are immersed. When current is passed
1
Throughout the paper, the expression “independent variable” shall refer to through the cell and then it is interrupted, a potential difference
the one that is controlled (regulated) during the experiment. The discussion can be measured between the electrodes, which is taken as a
will be constrained to electrodes (or cells) for which the potential and the
current density are in a mutually unambiguous relationship; therefore, the consequence of the polarization of both electrodes due to the
controlled and measured parameter can be technically exchanged without reaction products evolved thereof. Hence, electrode polariza-
modifying the j–E relationship. Concerning causality, the parameter whose tion was regarded as a potential difference due to the accumu-
variation results in a change of the other can be arbitrarily selected. It will be
shown that the authors believe that, as an analogy to the transport process, the lation of specific electroactive substances on the electrodes.
difference in the intensive parameters should be regarded as the driving force When the cell is short-circuited after passing the current, a
which causes the transport of the corresponding extensive quantity, which current of opposite sign as compared to the externally applied
means the potential difference is the cause of the current. However, the reverse
choice is equally possible and can lead to the same the j–E relationship, even one can be measured, which was called the polarization cur-
though the j–E function is never evaluated along this line. rent. Although it was not claimed explicitly, polarization was
elucidated as the deviation of either the electrode potential or
* László Péter the cell potential difference from their non-perturbed (yet not
[email protected] an equilibrium) value.
1
A step of fundamental importance was the discovery of the
Wigner Research Centre for Physics, Konkoly-Thege út 29-33,
Budapest 1121, Hungary
linear relationship between the overvoltage of a current-
2
loaded electrode and the current density applied, known as
Hevesy György PhD School of Chemistry, Eötvös Loránd
University, Pázmány Péter sétány 1/A, Budapest 1117, Hungary
the Tafel equation [2]:
2596 J Solid State Electrochem (2020) 24:2595–2602

η ¼ A þ Blogj jj ð1Þ sufficiently suppressed. This makes it possible to give a quan-

titative meaning for the constants A and B in the Tafel equa-
where j is the current density and η is the overvoltage (which is tion. In spite of the kinetic description given by Eq. 2 in which
taken equivalent to the electrode polarization of an equilibri- the electrode potential (or the overvoltage) plays the role of the
um electrode; see below). For the elaboration of the relation- driving force, electrochemical kinetic measurements remained
ship depicted with Eq. 1, Tafel used a Hg/HgSO4 reference for a long time a current-regulated technique, which necessi-
electrode which made it possible to measure the potential tated different views for theoretical and practical approaches.
change of the working electrode with respect to a point of The book of Vetter on electrochemical kinetics [7] summa-
fixed potential in the system, even though current control rized the knowledge achieved in this field until about 1960.
was applied. The Tafel equation is valid for a simple electrode Vetter offers a definition for the overvoltage η of an equilib-
reaction with charge transfer in the case where the concentra- rium electrode that is still feasible nowadays (η = E–E0 where
tion of the reactant can be taken unchanged in the entire cur- E0 is the equilibrium potential). Then, he makes an attempt to
rent density/overvoltage range applied. It is obvious that at the define polarization as well, taking into account electrodes on
time of its discovery, the current density was the primary which several electrode reactions take place simultaneously
(independent, controlled) variable, while the overvoltage and hence, they exhibit a mixed potential (non-equilibrium
was the dependent (measured) one. case). The definition of the polarization is given for the mixed
As it is described in a fascinating way in the work of electrode only by an equation similar to that applied for the
Bockris and Reddy [3], the current–potential relationship as overvoltage and taking E0 as the “zero current potential” of the
the key of electrochemical kinetics just slowly coped with the electrode. By admitting that differentiation between overvolt-
equilibrium-based view of the electrochemical systems since age and polarization was not very explicit in the electrochem-
non-equilibrium electrochemical cells had long been regarded ical literature, Vetter indicates that the two concepts are essen-
as being “imperfect” and not worth of scientific studies. Due tially the same for an equilibrium electrode. It is just collater-
to the dominance of the thermodynamic approach to the field, ally mentioned that polarization can be a function of the cur-
largely influenced by the successful work of Nernst on the rent density, indicating that various reasons may stand behind
thermodynamic description of electrochemical equilibrium, the variation of E0 of a mixed electrode. The question remains
electrochemical kinetics was just seldom studied. if a zero-current state can be achieved for a mixed electrode at
Additionally, the unidirectional view on the electrode poten- different conditions, which of them may yield the “true” E0
tial as a variable depending on the current delayed the devel- value as compared to which polarization can be calculated.
opment in this field.
The kinetic description of the electrode reaction as formu-
lated by Erdey-Grúz and Volmer [4] opened a new era in the The change in methodology: transitions
study of electrode kinetics. From their study concerning the from current to potential control
overvoltage of the hydrogen evolution reaction on mercury in
aqueous solutions, they concluded the relationship that was Vetter’s book was the last comprehensive work whose concept
soon generalized for essentially all electrochemical processes was based on the impact of the current as a primary technical
in which charge transfer is a rate-determining step. With the variable and in which the overvoltage was taken as a result. At
terms applied nowadays, the Erdey-Grúz–Volmer equation [5] the same time, all kinetic equations were formulated in a man-
(often also cited as Butler–Volmer equation [6]) for a one-step ner by taking the electrode potential (or overvoltage) as the part
reaction involving a single electron transfer, Ox+ e− ⇆ Red is of the driving force of the reaction. However, in a contradictory
as follows: manner, the overvoltage of the electrode was carefully
   
αA F ðE−E0 Þ αC F ðE−E 0 Þ discussed concerning the origin of the difference as compared
j ¼ k A FcR exp −k C FcO exp −
RT RT to the equilibrium state. In this sense, Vetter’s monograph
ð2Þ crowned an era that declined with the widespread accessibility
of potential-controlled electrochemical techniques.
The k parameters are the rate coefficients, c is the concen- The far-reaching impact of the contemplation to regard the
tration of the species marked in the lower index, and the di- electrode potential as the real driving force could manifest
mensionless α parameters are the so-called charge transfer itself when potentiostatic (or potential-controlled) measure-
coefficients for each partial reaction. ment was made possible. The first potentiostat was described
In the light of the description of an electrode reaction with by Hickling [8]. Commercial potentiostats with analogue
the above equation, it is straightforward that the Tafel equation input/output and data acquisition were available only until
is a good approximation of the j(E) relationship if the about the late 1980s, and the 2000s brought the age when
electrode potential is far enough from the equilibrium value any possible operation of programmable conditions, per-
so that either the anodic or the cathodic partial reaction is formed with either current or potential control, could be made
J Solid State Electrochem (2020) 24:2595–2602 2597

with a single instrument completed with digital data Treatment of the notions: how do we speak
acquisition. and write about them?
In parallel with the above listed changes, “polarization”
with the ordinary meaning lost its importance since the elec- Polarization used with its traditional meaning
trode potential became the technically controlled parameter. In
some sense, the world was stood to feet from its upside-down The current-based definition of the polarization is useful with no
situation caused by the current control in which the widely doubt still nowadays when the passage of a fixed current is either
admitted driving force (i.e., the electrode potential) had to be a directly controlled or a measured parameter. This is the case
treated as a consequence. This led to that the setting of the when a reference electrode is rated for the application in three-
potential of the working electrode was also called shortly po- electrode cells [14]. Here, the potential response of the reference
larization, hence avoiding a complicated phrasing of the ac- electrode to a burden of current due to the imperfect cell construc-
tion of the experimenter. This is what necessitates the recon- tion and, more importantly, to the limited (i.e., not infinitely large)
sideration of the terminology. input impedance of the reference connection of the instrument is
the parameter of topmost interest. Since the reference electrode is
assumed to be one of a constant potential, its polarizability is to be
kept at the minimum. Although electrochemical polarizability has
Recommendations and definitions no definition in the sources available to the authors, it may be our
intuitive feeling that the polarization resistance is a candidate for
The primary source of the relevant definitions is the IUPAC its proper quantitative measure. At least, polarizability of an
recommendation which is a reference work comprising the con- electrode is to be distinguished from that applied for chemical
sensus of international scientific bodies. As it can be seen from substances and species in electric field (where polarizability is
[9], “Polarization is the difference of the electrode potential from the ratio of the induced dipole moment and the electric field
the corrosion potential”, which is very much in accord with causing it). Where electrode polarizability (as well as non-
Vetter’s definition. This is the only recommendation and the polarizability) is discussed, it is noted that no absolute meaning
single one mentioning the term of polarization in the IUPAC can be attributed to this term, whereas it is admitted to be time-
recommendations. For depolarizer, the IUPAC recommendation and load-dependent [14, 15] when a long-term application of an
is that “The term ‘electroactive substance’ should be used in electrode is discussed. While the long-term application of an elec-
preference to ‘depolarizer’” [10]. Since the corrosion potential trode is characterized with an integral (macroscopic) term refer-
is never an equilibrium one, it can be questioned whether this ring to polarizability, the polarization resistance as a differential
definition provides an exact reference for a quantity to be mea- quantity can characterize the actual state of an electrode.
sured since the reference conditions are ill-defined. Another field where the current-based definition of the polar-
Another reference work is the Dictionary of ization is useful is the study of batteries and other electrochemical
Electrochemistry [11] which is a very comprehensive collec- power sources (e.g., fuel cells). These devices contain two elec-
tion of definitions that strives to comply with both the official- trodes by default, without an internal potential reference that is
ly accepted definitions and the consensus of the electrochem- independent of the load. The electrical performance of these
ical community. For polarization, the definition [12] refers to devices is rated at various currents passing. For these devices, it
both electrodes and cells, telling that “for a cell or an electrode is particularly true that the current is the independent (regulated)
that has a defined equilibrium potential (…), a departure of the parameter, while the deviation of the cell voltage from its equi-
electrode (or cell) potential (E) from its equilibrium value librium value is the dependent one (i.e., a consequence of the
(Eeq) is called polarization”. Here, equilibrium of the cell ob- current flow). This is well indicated by the structure of the polar-
viously refers to the electrochemical equilibrium [13] which ization diagram of such devices in which the current (density) is
refers to the homogeneity of the phases, equality of the elec- displayed at the abscissa of the graph. The classical terms related
trochemical potential of all components across the interfaces to the origin of the polarization are highly relevant in this case.
that they are allowed to pass and hence, a zero net current, Namely, activation, ohmic and diffusion polarization are usually
while chemical equilibrium of the cell reaction would lead to distinguished as the cell load increases, identifying the phenom-
EMF = 0. enon related to the potential drop in various parts of the battery/
The conflict between Refs. [9, 12] is obvious. On the one fuel cell.
hand, the former has a rather restrictive approach by claiming
the necessity of the equilibrium, which obviously cannot be Polarization in experiments where the working
the case for a corroding electrode referred to in Ref [9]. On the electrode is under potential control
other hand, however, Ref. [12] extends the application of the
term polarization from electrodes to cells. In contrast to current-controlled measurements, polarization ap-
parently obtained a new meaning when potential-controlled
2598 J Solid State Electrochem (2020) 24:2595–2602

experiments are performed in three-electrode cells to study the appropriate conditions; therefore, it makes a two-phase elec-
working electrode (reaction) only. A search for the term trochemical system with ionic conductors at both sides of the
“potentiostatic polarization” yields hundreds of papers. One can interfaces. This is why ITIES is not an electrode, having no
often encounter phrasings such as the electrode is polarized to/at electron-conducting phase involved in the two-phase system.
a particular potential in recent papers (a few examples selected As compared to current-controlled two-electrode cells and
from various fields can be found in Refs [16–24]). In the descrip- three-electrode cells with potential-controlled working elec-
tion of experiments performed with the control of potential, trodes, the study of ITIES usually requires a near-symmetric
anodic/cathodic polarization is extensively mentioned as the in- four-electrode cell without a working electrode. The potential
dication of either the potential sweep direction, the potential difference across the interface is measured between two refer-
range studied as compared to the rest potential of the electrode ence electrodes that are connected to each side of the interface
or the sign of the current hence produced [25, 26]. It also occurs by using a Luggin capillary in order to minimize the ohmic
that a polarization regime is given for indicating the stability drop if current flows across the interface. The current can be
range of some electroactive substance, which clearly refers to a applied by using two auxiliary electrodes that are not close to
potential interval instead of any current [27]. These terminologies the interface of the two liquids. For micro-ITIES, the measure-
occur regardless of whether or not either the manipulation with ment can be performed in two-electrode configuration, pro-
the electrode potential results in the permanent flow of a partic- vided that the auxiliary electrodes are sufficiently large as
ular current or the source of the electrochemically active species compared to the ITIES surface area. This case is fully analo-
can maintain a constant current. gous to the potential-controlled experiments with a microelec-
When one has either an electrode with no substance electro- trode as working electrode and a macroscopic electrode as
chemically active in the potential window applied (this is often combined counter and reference electrode.
termed as the ideally polarizable electrode [28]) or an electrode Since the early age of the electrochemical studies of ITIES,
with fixed redox capacity, the potential setting operation can be the terminology used has been very much parallel to that ap-
achieved by passing a limited charge through the cell. In either of plied for electrodes [31]. The criteria for both “non-polarized”
the above cases, the deviation of the potential of the electrode of (i.e., non-polarizable or ideally depolarized) and “ideally po-
interest from its rest potential (that is not even necessarily an larized” (i.e., ideally polarizable) interfaces are similar to the
equilibrium potential) is not regarded as a result of a permanent electrodes concerning the commonality of the components of
current. For such systems, polarization is naturally elucidated as varying oxidation state.
either setting or sweeping the electrode potential in a suitable ITIES is generally considered as a polarizable interface in
interval [29, 30]. the scientific literature nowadays [32–40]. However, we can
For experiments with potential control, the current is taken find no traditional root of the ITIES polarization related to
as the consequence of the potential setting of the electrode. In current control but experiments are carried out with the control
such cases, the classification of the means of polarization (ac- of the potential difference of the reference electrodes quite
tivation, diffusion etc.) loses its significance. Rather, one can exclusively. This sounds very natural if we consider that the
speak about the means of control (or limitation) of the birth of the field is dated after the spread out of the
resulting reaction: activation or mixed control, diffusion- potentiostat.
limited process etc.
The change in terminology has another aspect, too. While Depolarization: the application range of a term not
polarization in a current-controlled experiment is the reaction recommended anymore
or the response of the electrode (or that of the cell) to the current
passed, it becomes a deliberate action of the experimenter when Similarly to the term of polarization, depolarization has also
conducting potential-controlled operations. This duality makes undergone some meaning change, though it is relatively mi-
polarization a Janus-faced term in modern electrochemical termi- nor. The recent terminology often speaks about oxygen
nology. The second definition of the polarization also leads to the depolarized cathodes in aqueous electrolysis cells [41–43].
loss of the meaning of depolarization since a potential setting This terminology simply means that the cathode reaction is
applied externally to an electrode presumably cannot be oxygen reduction instead of hydrogen evolution, which results
counteracted by a chemical reaction at the electrode, provided in a diminished cell voltage due to the difference in the poten-
that a power source of sufficiently large capacity is applied. tial regime of O2 and H+ reduction. For the reactant at the
anode, the term “anode depolarizer” also occurs [44]. In both
Polarization of electrified interfaces that are not cases, depolarizer is the synonym of the electroactive sub-
electrodes: the ITIES stance, which is much alike the identification of the species
to be reduced in a corrosion process [45] (nevertheless, the
Interface of two immiscible electrolyte solutions (ITIES) is an term of “hydrogen depolarization” can be heavily criticized
interface across which charge transfer is possible at since H+ is reduced and hydrogen /H2/ is the product of the
J Solid State Electrochem (2020) 24:2595–2602 2599

reaction). Depolarization is also used as a term to indicate that that perturbation amplitude of a few millivolts is used. Hence,
by using a certain electron conducting metal for one of the a concept coming from current-controlled experiments is
electrodes, an electrolysis process requires lower cell voltage transferred to potential-controlled experiments without a prop-
than with another metal [46]. Similarly, depolarization is men- er explanation, and the two contemplations are applied in par-
tioned when an overvoltage-diminishing additive is applied to allel, which can be misleading for the reader.
facilitate a process [47, 48], even if it is not a reactant but In one of the most cited textbooks of electrochemistry and
rather a catalyst. For the literature of solar cells, depolarization electroanalysis, Bard and Faulkner [53] define polarization in
is used as a term indicating the decay of the potential of an accord with the definition given in Ref. [12], telling that: “If a
electrode, comparing illuminated and dark conditions [49]. cell has a defined equilibrium potential (…), that potential is
The latter example is an exception in the above list in the sense an important reference point of the system. The departure of
that it is not related to the application of external current for a the electrode potential (or cell potential) from the equilibrium
cell or for an electrode. Somewhat differently from the above value upon passage of faradaic current is termed polarization.
listed papers, “charge depolarization” was used to indicate that The extent of polarization is measured by the overpotential, η”
the surface charge of a semiconductor electrode could be re- (Page 22 of Ref. [53]). In other parts of the same work, how-
duced in the presence of a suitable adsorbate [50]. Some au- ever, the authors do not adhere very strictly to the definition
thors attempt to make their findings understood in terms of cited above. In many cases when the primary controlled ex-
depolarization and depolarizer, noting at the same time that perimental variable is the electrode potential, polarization is
these concepts are not only old but “obsolete” [51]. used as an equivalent expression for the setting of potential
(see, e.g., Chapter 13.3 of Ref. [53] on the double-layer struc-
ture). Also, the expression of concentration polarization is
Handbooks: what do we teach nowadays? used in many cases where the experiments are run exclusively
with potential control.
Handbooks that give a definition for electrode Polarization is by far not consequently used even in text-
polarization book where it appears at all. Bockris, Reddy and Gamboa-
Aldeco speak about polarization in a footnote only as a cloudy
Koryta, Dvořak and Kavan [52] offer a definition for electrode and ill-defined term used only at engineering fields for the
polarization that is much in accord with that given later in quantization of all overpotentials occurring in a cell (page
[12]. Their definition for electrode polarization is based on 1279 of Ref. [54]). In spite of the lack of a definition specified
an equilibrium cell, simply by telling that the electrode poten- for electrodes, they use various expressions with polarization
tial change due to the current passed as compared to the equi- (anodic polarization, concentration polarization, polarization
librium state is the electrode polarization. The definition of curve, constant current/potential polarization).
overvoltage for electrodes having a single equilibrium reac- The dual meaning of polarization in the everyday language
tion is the same as given earlier in Vetter’s monograph [7]. of electrochemists was sensitively observed by Bagotsky [55].
Although the concept of electrode polarization could be easily While he adheres to the ordinary definition of the electrode
extended for electrodes that are not in electrochemical equi- polarization based on the current flow and potential response
librium, it was not applied in the abovementioned work [52]. (Page 29 of [55]), later, he refines it. With a minor logical
In the discussion of the electrode kinetics, the j–η dependence rearrangement of his definitions (Page 80 of [55]), he says that
is termed the polarization curve, and the latter term is not the electrode polarization can be:
extended to a j–E relationship of an electrode not in electro-
chemical equilibrium at the rest potential, although it was 1. The phenomenon of change in electrode potential under
obviously used throughout the work. Interestingly, the authors current flow, and, as its quantitative measure, the change
also use the expression “polarization voltage” for potential- of the electrode potential relative to its equilibrium value
controlled experiment, indicating the extension of the term 2. An operation performed by the experimenter at obtaining
polarization to the set-up of the electrode potential instead of a potential change by passing current of a suitable strength
applying a certain current. Similar terms related to the poten- and direction
tial control, such as the polarization rate as the analogy of the
sweep rate, occur in various part of this work [52]. Even though the second definition of Bagotsky is very
The highly controversial application of the term polariza- close to the everyday terminology, it still bears the contem-
tion can be seen in Chapter 2.4.5 of Ref. [52] dealing with plation that the primary (i.e., controlled) variable is the current
conductometry. On the one hand, it is stated that alternating that causes a potential change, not vice versa.
current is applied for conductometric measurements and the The concept of Sato [56] is quite similar to that of
electrodes are covered with platinum black “to avoid electrode Bagotsky. He defines the term of polarization in electrochem-
polarization”. On the other hand, however, it is also indicated istry as the deviation in the electrode potential from a specific
2600 J Solid State Electrochem (2020) 24:2595–2602

potential; namely, from the rest (zero-current) potential, to a potential perturbation, it is clear that the instinctive eluci-
whether or not it is a well-defined equilibrium one. In Sato’s dation of the polarizability is quite far from the current-based
definition, the potential deviation is not even connected to the definition of the potential change, not to mention the lack of
flow of current. The meaning of the verb “to polarize” is equilibrium on an electrode with non-reactive species only.
associated by Sato with the shift of the electrode potential, The term of ideally polarizable electrode as opposed to an
regardless of the source of the phenomenon (either internal ideally polarized electrode may appear as a very subtle and
to the system or external). Non-polarizable electrodes are clas- even negligible difference. However, it indicates that one
sified as those with the equilibrium of an electrochemical re- speaks about the feature of an electrode itself, regardless of
action, while the lack of any chemical reaction is given as an any external impact whose application makes the electrode
inherent feature of a polarizable electrode. indeed polarized in a particular way.
A treatment similar to that applied in Ref. [59] can be found
Works that do not deal with the definition of the in some older literature, too [60]. Here, electrodes permeable
polarization of either electrodes, cells or ITIES for at least one kind of species that maintain equilibrium are
called ideally reversible electrode, while those having no such
Apparently, the introduction to electrochemistry is well possi- species are termed as blocking or ideally polarizable elec-
ble without mentioning polarization itself but relying in a def- trodes. Polarization itself is not defined in the abovementioned
inition concerning the polarizability of an electrified interface. work, and the j(E) relationship is alternatingly called either
Although it is not known whether the lack of the definition of current–potential curve or polarization curve.
electrode polarization means that the authors find it either The polarizability of electrodes in the book of Schmickler
useless or unnecessary, it is worthwhile of summarizing the and Santos [61] is dealt with in relation to electrodes at which
examples found. no electrochemical reaction takes place in the potential win-
With such an approach, Gileadi [57] offers a rather quali- dow of the solvent. The notion of the ideally polarizable elec-
tative verbal definition to the polarizability of an electrochem- trode is introduced without either telling any definition of
ical interface and loosely connects this definition with the polarization or referring to what kind of current–potential (or
reversibility of the chemical reaction occurring at that inter- vice versa) relationship makes the polarizability ideal. The
face (Chapter 1.2.1 of [57]). In this definition, the interrelation definition of the electrode polarization is completely missing
of the current passed and the potential difference achieved are from the work of Brett and Oliveira Brett [62] who mention
taken as being independent of which of them was a controlled the term of polarization in relation with membrane processes
parameter by restricting the perturbation to a near-equilibrium only.
linear region. Throughout his work, Gileadi avoids the term As books written by either a single or at most a few authors
polarization but overpotential is used wherever needed and often rely on intuitive understanding of the reader on the elec-
even polarization resistance related to electrochemical imped- trode polarization, this is particularly true for edited books.
ance measurements is called faradaic resistance. Similarly to The introductory chapter of the book of Zoski [63] defines
Gileadi, Lasia [58] also avoided the definition of both polari- the ideal polarizable and ideal non-polarizable electrodes
zation itself and polarization curves, although he classified the without the definition of polarization itself (and, sadly, con-
electrodes as ideally polarized or non-polarized ones on the nects these definitions with the role of the electrodes in a
basis of their response to external perturbation. Unlike three-electrode cell as if the former were the consequence of
Gileadi, Lasia still called the j(E) function the polarization the latter). The authors of other chapters apply the term of
curve. electrochemical polarization as the analogy of electrochemical
A similar concept is offered in the work of Hamann, treatment by passing some currents through, or applying a
Hamnett and Vielstich [59]. They define neither polarization particular electrode potential for, the electrode of interest
nor do they call the j(E) dependence polarization curve but the (see Chapter 5 of [63]). Various other books edited by a few
term current–potential characteristics is applied throughout authors but written by a wider team (e.g., [64–66]) have a
their book. Electrode as a polarizable object is referred to at similar character in the sense that polarization remains and
the discussion of the behaviour of the electrical double layer undefined term while it is widely used by the authors of var-
(Page 115 of [59]). Electrodes with chemical equilibrium are ious chapters in accord with their own understanding.
distinguished from those at which the species are all non-
reactive in the sense of the current response to an external
potential perturbation, equilibrium electrodes exhibiting a cur- Do we have to refine traditional definitions?
rent response and non-reactive electrode characterized with a
double-layer rearrangement consuming a little charge only When speaking about polarization with general meaning, we
without developing a permanent current. Electrodes with often associate polarization with the generation of poles; i.e.,
non-reactive species are called polarizable. Since it is related with charge separation and increase of field strength, should
J Solid State Electrochem (2020) 24:2595–2602 2601

they originate from any specific interaction. The decrease in possible with the traditional definition. Version (ii) of the
the electric field strength can be understood as depolarization, above definition list allows the match of the electrode classi-
and the susceptibility of a system towards external impacts fication of electrode polarizability to the polarization curves,
affecting the field strength can be called polarizability. At regardless of the mode of electrode control (current or poten-
the same time, it is to be noted that no field of science defines tial control) since a constant current is not a requirement of
two terms for the positive and negative result of the same polarization. It is also to be recognized that there is no conve-
effect but gives the appropriate sign to a quantity (we speak nient way to use polarization as a current perturbation-related
about acceleration only and do not define deceleration sepa- term for non-equilibrium cells because of the lack of any well-
rately, we give sign to the magnetic susceptibility etc.). Hence, defined fixed point in the scale of the cell voltage.
speaking about polarization and depolarization in electro- When we strive for correct and easily applicable definitions
chemistry depending on the direction of a change seems to of the basic concepts of electrochemistry, we have to bear in
violate this rule. mind that this pursuit is not self-contained. Experienced
By refraining from extreme vulgarization which may sug- electrochemists would certainly adopt the attitude to under-
gest that in electrochemistry, polarization is what the stand the view of other researchers, but students can be much
potentiostat does, it is thought that polarization should be ac- discouraged if they encounter any controversy that impedes
knowledged as a term with multiple meanings, depending on their understanding.
the control mode of either a cell or an electrode. Potential-
controlled operations should no longer be called polarization Acknowledgements L. Péter wishes to express his sincere thank to
Professor Fritz Scholz for both his personal support to the author as well
merely in the lab slang but it could be recognized that it gained
as for his long-standing efforts to help the entire community of the
a new meaning as a result of the improvement of the available Hungarian electrochemists.
instrumentation. It is also thought that, for the sake of the
usage of the term polarization curve as the compact and Funding information Open access funding provided by Wigner
smooth description of the current–potential relationship of Research Centre for Physics.
the electrode behaviour as well as the application of polariz- Open Access This article is licensed under a Creative Commons
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Therefore, the following multiple definitions of polariza- you give appropriate credit to the original author(s) and the source, pro-
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1. For an equilibrium electrode, polarization is the deviation Creative Commons licence and your intended use is not permitted by
statutory regulation or exceeds the permitted use, you will need to obtain
of the potential of this electrode from its equilibrium value permission directly from the copyright holder. To view a copy of this
as current is passed through the electrode from an external licence, visit http://creativecommons.org/licenses/by/4.0/.
power source.
2. For any electrode, polarization is the manipulation of the
electrode during which a particular electrode potential or
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