ChemTexts (2019) 5:1

https://doi.org/10.1007/s40828-018-0076-x

LECTURE TEXT

Electrochromism: a fascinating branch of electrochemistry

Alexander Kraft1 

Received: 31 October 2018 / Accepted: 21 November 2018 / Published online: 27 November 2018
© Springer Nature Switzerland AG 2018

Abstract
This lecture on electrochromism and electrochromic devices starts with a short introduction to the field. This is followed by
an overview of the different classes of electrochromic materials, in which each class is illustrated by some typical examples.
The third part deals with some basic parameters to assess electrochromic compounds and devices. After this, we discuss the
different types of electrochromic devices or elements, again always illustrated by some examples. Manufacturing consid-
erations and real-world practical application examples of electrochromics are the topics of the last two parts of this lecture.

Keywords  Electrochromism · Electrochromic devices · Smart windows · Transition metal oxides · Conducting polymers

Introduction to electrochromism information displays to electrochromic glass for smart win-

Electrochromism is the reversible color change of chemical
compounds induced by electrochemical oxidation and reduc-
tion [1]. This phenomenon1 can be used in modern technol-
ogy for designing objects with variable light transmittance
or reflection, such as smart windows or dimmable rear view
mirrors. The modern field of research in electrochromism or
electrochromics started after Satyen K. Deb had published
his seminal work on molybdenum and tungsten oxide thin
films in the 1960s [2]. He had observed that these uncolored
thin film materials can be reduced electrochemically to deep
blue-colored films and reoxidized back by anodic oxidation
to an uncolored state.
The use of electrochromism for information displays
was the research focus during the 1960s and 1970s. In this
time, a multitude of other compounds which showed pro-
nounced electrochromic properties were discovered, among
them other transition metal oxides, a group of bipyridinium
derivatives also called viologens [3], some electronically
conducting and redox polymers [4] and inorganic complex
coordination compounds such as Prussian blue [5]. These
efforts toward electrochromic displays became of less
interest during the 1970s as liquid crystal displays began
to dominate the market for small displays. Therefore, dur-
ing the early 1980s the research focus began to shift from
* Alexander Kraft
kraftalex@aol.com
1
Kraft Consult, Am Graben 48, 15732 Eichwalde, Germany
dows in buildings [6, 7]. This is still the most promising
application field for electrochromism [8, 9]. Other applica-
tion areas which were investigated because they seemed to
be of commercial interest were the use of electrochromics
for dimmable rear-view mirrors in motor vehicles [10], for
glazing in means of transportation such as cars, trains and
aircraft, for (sun)glasses [11], for tunable optical filters [12]
and, from time to time, again for some kind of advanced
information display [13].
Major classes of electrochromic substances
Although most electrochemical oxidation or reduction
reactions are accompanied by more or less intensive color
changes, a material is called electrochromic only if the color
change is clearly visible. For most applications, the change
between a completely uncolored state and one or more
deeply colored oxidation states is what scientists are looking
for. Substances which change from an uncolored oxidized
state to a colored reduced state by electrochemical reduc-
tion are called cathodic electrochromic, whereas compounds
which change from an uncolored reduced to a colored oxi-
dized state are called anodic electrochromic compounds. For
1
  Historically, electrochromism refered to changes in optical absorp-
tion of a material due to an external electrical field without any redox
reaction (Stark effect). What we now call electrochromism was some-
times termed electrochemichromism to distinguish it from the physi-
cal effect. However, today mostly the electrochemically induced opti-
cal absorption change is denoted with the term electrochromism.

13
Vol.:(0123456789)
1 
Page 2 of 18 ChemTexts (2019) 5:1

some possible applications, the switching between two dif-

ferent colors, e.g., from red to green and back, could also be
interesting. In such a case, the denominations cathodic and
anodic electrochromic are difficult to apply.
In the following paragraphs, the most important electro-
chromic material classes are shortly described. Electrochro-
mic materials are usually first studied at a single working
electrode, under potentiostatic or galvanostatic control, using
a three-electrode system with counter and reference elec-
trodes in a liquid electrolyte [14]. The working electrode is
usually a small glass plate coated with a transparent conduct-
ing layer. Well-established techniques such as cyclic voltam-
metry, coulometry and chronoamperometry, preferably in
combination with in situ spectroscopic measurements are
employed for characterization of the electrochromic material
under investigation.

Transition metal oxides Fig. 1  Cyclic voltammogram of tungsten oxide in 0.5  M ­ LiClO4

From the beginning of electrochromics research in the 1960s
until today, tungsten trioxide, ­WO3, is by far the most pop-
ular electrochromic material which has been investigated
intensively [15, 16]. Thin layers of the yellow compound
­WO3, with thickness below 1000 nm, are largely uncolored.
Such a thin film can be reduced by electrochemical means
to a deep blue reduced form of tungsten trioxide. Therefore,
tungsten oxide is a cathodic electrochromic compound. Dur-
ing this reduction, charge balancing cations ­(M+) such as ­H+,
­Li+ or ­K+ are intercalated in the tungsten oxide structure.
By electrochemical oxidation, this process can be reversed:
blue uncolored
Mx WO3 ⇄ WO3 + xe− + xM+ x ≤ 0.3
. (1)
To show what happens in more detail, Eq. (1) can also be
written as follows:
blue( ) ( uncolored
.
Mx WV x WVI 1−x O3 ⇄ WVI O3 + xe− + xM+
)
x ≤ 0.3
(1b)
As long as less than 30% of the available W­ VI of tungsten
trioxide is reduced to ­WV the reaction is reversible. Figure 1
shows a typical cyclic voltammogram of tungsten oxide in
an aqueous solution. The strong change of the coloration in
dependence on applied potential is also shown.
Molybdenum trioxide, ­MoO3, also a cathodically blue
coloring substance, is known as an electrochromic com-
pound nearly as long as tungsten trioxide. Its properties and
behavior resemble that of W ­ O3 in many aspects. Besides
­WO3 and ­MoO3, there are many other transition metal
oxides, which show pronounced electrochromic effects as
a thin film. Iridium oxide (­ IrO2), an anodically electrochro-
mic material, switches between a dark blue oxidized and
an uncolored reduced state [17]. Vanadium pentoxide [18]
(scan rate: 100 mV/s). The electrochromic color change between blue
in the more cathodic and uncolored in the anodic range is depicted
or titanium and niobium oxide (­ Nb2O3) are further exam-
ples for electrochromic transition metal oxides [19]. Nickel
oxide (NiO) can be colored anodically to a brown color and
decolorized by cathodic reduction according to the following
simplified equation:
uncolored brown
. (2)
LiNiO ⇄ NiO + Li+ + e−
We can also go again in more detail:
uncolored brown(
.
LiNiII O ⇄ Li(1−x) NiIII x NiII (1−x) O + xLi+ + xe−
)( )
(2b)
The combination of a cathodically blue-coloring elec-
trochromic film such as tungsten oxide with an anodically
brown-coloring film of nickel oxide can result in an elec-
trochromic device which switches from an uncolored state
to a color neutral dark grey [20]. For many applications,
such a color neutral darkening of an electrochromic element
is the best choice. For transition metal oxide electrochro-
mic devices, this can be achieved by the combination of
the properly selected complementary electrochromic films
or by tuning the color in which the switching of an electro-
chromic transition metal oxide occurs. A possibility for the
latter approach is the production of well-defined mixtures of
at least two metal oxides [21].
Despite the enormous amount of research on electro-
chromic transition metal oxides in the last 50 years, there is
still room for improvement and new findings. An example
is the discovery of the so-called plasmonic electrochromism
in nanocrystals of typical transparent conducting transition

13
ChemTexts (2019) 5:1 Page 3 of 18  1

Fig. 3  Simplified structures and electrochemical redox reactions of

Fig. 2  Electrochromism of viologen derivatives
­ − is an
the three differently colored oxidation states of polyaniline: X
anion

metal oxides [22]. In plasmonic electrochromism, the charge

carrier concentration of nanocrystals of an appropriate mate-
colored state of the viologens is not irradiated by UV radia-
rial is changed by application of small voltages. This change
tion from the sun.
in charge carrier concentration changes the wavelength of
the plasma reflection edge of the plasmon oscillations in
the material. With this phenomenon, it is possible to switch
Electronically conducting polymers
the transmittance of the near-infrared spectral range without
Polymers which are π-conjugated, i.e., with alternating dou-
much affecting the visible spectral range. This is considered
ble- and single-bonds along their molecular backbone, are
to be the basis to design independently dual-band switching
electronically conducting polymers also called intrinsically
electrochromic devices. The visible range could be switched
conducting polymers [28]. In a multitude of electronically
by traditional electrochromic redox reactions, whereas the
conducting organic polymers, their reversible electrochemi-
transmittance in the NIR spectral range could be switched
cal oxidation and reduction are accompanied by a strong
by plasmonic electrochromism [23].
change in their optical properties in the visible spectral
range. Polypyrrole [29], polythiophene [30], polyaniline
[31], polycarbazole, polyindole and many of their deriva-
Dissolved organic compounds
tives belong to this large class of electrochromic materi-
als. The archetypical electrochromic polymer and the most
Many organic compounds dissolved in an appropriate
investigated one is the anodic electrochromic polyaniline.
solvent are electrochromic [24], among them some dyes,
It has a slightly yellow nearly uncolored reduced oxidation
such as indigo, which can be switched between a reduced
state, an intermediate green-colored and an oxidized blue-
uncolored so-called leuco state and a deep blue-colored
or violet-colored state [32] as displayed in Fig. 3. Figure 4
state. Organic redox indicators are also part of this class of
shows the corresponding cyclic voltammogram, again with
electrochromic compounds. The most important compounds
the different colors which appear at the polyaniline elec-
of this class are the viologens [25], a group of cathodic elec-
trode. The switching between the reduced almost uncolored
trochromic bipyridinium derivatives [26]. The redox reac-
and the green-colored state is highly reversible. The oxidized
tion of viologens which is accompanied by color changes is
blue or violet state cannot be used for reversible electrochro-
shown in Fig. 2.
mics because switching polyaniline to this state easily leads
Generally, it is (rightly) assumed that organic compounds
to over-oxidation and degradation [33].
are less stable under the influence of solar radiation and heat
However, the commercially most successful electro-
compared to inorganic substances. Nevertheless, viologens
chromic conducting polymer is poly(3,4-ethylenedioxy-
are the most important component in the first commercially
thiophene) or short PEDOT [34], developed by Bayer AG,
successful electrochromic product, autodimming rearview
Germany and sold under the trade name ­Baytron®, but
mirrors of Gentex Corporation (USA). In these mirrors,
meanwhile as Clevios™ a product of Heraeus, Germany.
cathodic electrochromic viologens are combined with an
PEDOT is cathodically electrochromic because it has a
anodically electrochromic phenazine derivative [27] in a
deep blue-colored reduced oxidation state and a slightly
solution-phase electrochromic device. Crucial for the sta-
blue-colored oxidized state. In PEDOT, a problem of almost
bility of these devices was the fact that coloring is induced
all electrochromic conducting polymers (with the excep-
only at night in the dark. Therefore, the more UV-sensitive
tion of polyaniline) can be seen, their uncolored state is
not really uncolored but has still a too high absorbance for

13
1 
Page 4 of 18
Fig. 4  Cyclic voltammogram of polyaniline in 0.1 M HCl (scan rate:
100  mV/s) showing the electrochromic behavior of this conducting
polymer
most practical applications [35]. This can be seen in Fig. 5
in which the colors of the reduced and oxidized state for
different PEDOT film thicknesses are displayed. In addi-
tion, with electrochromic conducting polymers often if the
transmittance in the visible spectral range is lowered, the
transmittance in the near-infrared spectral range is increased
and vice versa.
Therefore in practice, PEDOT is mainly used for transpar-
ent conducting films and antistatic coatings on polymers and
glass, not for electrochromics. But because of its commercial
availability and ease of handling, a lot of often redundant
research work is done on the electrochromism of PEDOT.
But electrochromic conducting polymers have one great
advantage compared to inorganic electrochromic com-
pounds: they often have a much higher coloration efficiency.
Therefore, with thinner films and lower electrical charge a
comparable optical switching can be achieved with elec-
tronically conducting polymers.
Following the commercial introduction of PEDOT, many
new conducting polymers based on a modified PEDOT
Fig. 5  Photographs of PEDOT films with different thickness in the
oxidized state (left) and reduced state (right). These PEDOT films
were prepared by electropolymerization from 0.02  M EDOT mono-
13
ChemTexts (2019) 5:1
structure but some with much higher coloration efficiency
than PEDOT and with a more bleached uncolored oxidation
state have been developed [36]. An overview of this group
of electrochromic conducting polymers and the colors that
can be switched can be found in reference [37]. In Fig. 6
which has been taken from this publication some different
electrochromic conducting polymers derived from PEDOT
and the colors between which they can be switched electro-
chemically are displayed. From this, it is obvious that it is
possible to choose from a wide variety of colors which can
be switched from the many electrochromic polymers which
have been investigated so far.
By solution co-processing of differently colored electro-
chromic polymers it is possible to adjust a required color
precisely [38]. But an ultimate goal for many researchers
is an uncolored to grey to black switching electrochromic
polymer or polymer mixture. Several approaches toward this
goal were tested more or less successfully. So it is possible to
mix two or more different monomers that would, electropo-
lymerized on their own, give distinctively colored electro-
chromic polymers. But mixed in the right proportion and
electropolymerized together to a mixed conducting polymer
can result in a black switching electrochromic thin film [39].
Alternatively, the use of three different solution-processable
electrochromic conducting polymers was proposed for this
purpose. They are mixed in the deposition solution and are
co-deposited together on the same substrate. If the right pro-
portion of the three dioxythiophene-based electrochromic
polymers is chosen, a highly transmissive to black switching
electrochromic electrode results [40].
Complex coordination compounds
In complex or coordination compounds a central metal atom
or ion is surrounded by several bound ions or molecules,
the so-called ligands. Usually, the metal ions or atoms in
the complex can be oxidized or reduced electrochemically.
If this is accompanied by a substantial change of the opti-
cal properties in the visible spectral range, this substance is
electrochromic.
mer solution with a different number of deposition cycles in a poten-
tiodynamic mode, i.e., by cyclic voltammetry (source: [35], reprinted
with permission from Synthetic Metals. Copyright 2005 Elsevier)
ChemTexts (2019) 5:1 Page 5 of 18  1

Fig. 6  Structures and switchable colors of some electrochromic conducting polymers based on the PEDOT structure (source: [37], reprinted
with permission from Chemistry of Materials. Copyright 2004 American Chemical Society)

A typical electrochromic inorganic complex compound 300 years ago [42], has three differently colored electrochemi-
is iron(III) hexacyanoferrate(II) also called Prussian blue, cally switchable oxidation states, changing between colorless,
­KFeIII[FeII(CN)6] [41]. Prussian blue, discovered more than blue and brown as displayed in Fig. 7:

13
1 
Page 6 of 18 ChemTexts (2019) 5:1

Fig. 7  Cyclic voltammogram of Prussian blue in 0.5  M KCl (scan
rate: 5  mV/s) displaying the electrochromic behavior of this com-
pound
Fig. 8  Absorbance of Prussian blue on glass/ITO in 0.2M KCl in
the visible and near-infrared spectral range: a blue oxidation state
at + 0.5 V vs. Ag/AgCl wire, b uncolored oxidation state at − 0.2 V
(source: reproduced from Ref. [43] with permission from The Royal
Society of Chemistry, the Prussian blue-coated glass was added to
this figure)

uncolored blue [ brown

. (3)
M2 FeII FeII (CN)6 ⇄ MFeIII FeII (CN)6 + M+ + e− ⇄ FeIII FeIII (CN)6 + 2M+ + 2e−
[ ] ] [ ]

The oxidation and reduction reactions are accompanied

Other electrochromic compounds
by the insertion or exsertion of charge compensating cati-
There are many other electrochromic compounds which do
ons ­(M+), preferably ­K+ or ­NH4+. The completely oxidized
not fall in one of the above-mentioned classes. In “Dissolved
brown state is not stable; therefore, it is only possible to
organic compounds”, dissolved organic compounds were
use the reversible switching between colorless and blue
discussed as electrochromic materials. But there exist also
for practical applications. A mixture of the blue and brown
many inorganic compounds which are distinctively electro-
oxidation states gives the color green. The huge differ-
chromic in solution. These are not only several inorganic
ence in absorbance in the visible and near-infrared spec-
redox indicators such as iron thiocyanate, but also the group
tral range for Prussian blue and its reduced form Prussian
of polyoxometalates of tungsten and molybdenum [48].
white is displayed in Fig. 8 [43]. Prussian blue electro-
Besides electronically conducting polymers, there are
chromism was also proposed as a simple but impressive
also other electrochromic polymers, the so-called redox
experiment for teaching purposes at schools and universi-
polymers. This is a group of electrochemically active poly-
ties [44].
mers containing localized sites or groups that can be revers-
Prussian blue is the parent compound of a large group of
ibly oxidized and reduced. These redox sites can be located
metal polycyanometalates, in which one or both of the iron
directly in the polymer chain or as a pendant group to the
atoms in Prussian blue are replaced by other metal ions.
chain. Examples are the coupling of tetracyanoquinodimeth-
Therefore, there exists a large variety of these metal polycy-
ane [49] or viologen units [50] to non-electronically con-
anometalates, many of them but not all, are electrochromic
ducting polymers such as polyethylene oxide. Electrochro-
[45].
mic metallo-supramolecular polymers also belong to the
Metallophthalocyanines (MPcs) are another group of
group of redox polymers [51]. Redox polymers do not have
electrochromic complex compounds. The electrochromism
to be electronically conducting.
of MPcs was first investigated on lutetium phthalocyanine
[46]. The color of this compound can be changed electro-
chemically from red over orange to green and further over
blue to violet but many other MPcs are also electrochromic
[47].

13
ChemTexts (2019) 5:1 Page 7 of 18  1

Fig. 9  Three optical states of a Mg–Gd switchable mirror: reflecting (a), absorbing (b) and transmitting (c) states (source: [60])

Reversible metal electrodeposition and dissolution/ atoms are produced from water which are absorbed by the
switchable metal hydrides metal to form metal hydride:
(transparent) (reflective or absorbing)
A different approach to the change of light transmittance by . (5)
MH + OH− ⇄ M + H2 O + e−
electrochemical means is the use of metal films on trans-
parent substrates for electrochromic devices. Two ways to Pd prevents surface oxidation of the metal and the for-
change the light transmittance have been investigated. mation of molecular hydrogen. The counterelectrode can
This is first the cathodic electrodeposition of a metal film be nickel oxide on glass coated with a transparent conduct-
and its anodic dissolution to go into the solution as a metal ing electrode because nickel oxide shows excellent elec-
cation and, second, the switching between a highly reflective trochromic properties in aqueous alkaline electrolytes. By
or absorptive metal state and more light transmissive metal anodic oxidation, this reaction can be reversed. Figure 9
hydride state. Both ideas could be used for switchable mir- shows an electrochromic metal hydride mirror in action.
rors or totally blackening electrochromic devices.
The older idea is the use of reversible cathodic metal
electrodeposition and anodic metal dissolution for so- Some basic science for electrochromism
called reversible electrodeposition electrochromic devices
[52, 53]. Investigations have focused on metals such as Visible light, color, photopic light transmission
silver [52, 54], bismuth [53] and for applications as infor- and solar energy transmittance of windows
mation display or in smart windows [55]. Depending on
the deposition conditions, e.g., by changing the surface If we discuss electrochromism as a technology to change
roughness of the electrode, the metal M can be deposited light transmittance or reflectance, we should shortly
cathodically as a highly reflective metal film or as a rough
black metal film [56]. By anodic dissolution, the metal
film disappears from the surface of the transparent con-
ducting film and the electrode becomes transparent again:
(reflective or absorbing) (transparent)
. (4)
M ⇄ M+ + e−
The later developed version of a switchable mirror sys-
tem is based on the reversible insertion and exsertion of
hydrogen into thin metal films realized by electrochemi-
cal means [57]. This was first demonstrated on thin films
of yttrium [58] but later extended to much more common
metals such as nickel [59] or magnesium [60]. How does
such a system work? The switchable metal film, e.g., a
magnesium alloy, is capped with a very thin film of Pd.
This electrode is brought in contact with an aqueous alka- Fig. 10  Solar irradiance spectrum above atmosphere and at the sur-
line electrolyte. By electrochemical reduction, hydrogen face of the Earth (source: Wikimedia Commons)

13
1 
Page 8 of 18
Fig. 11  Sensitivity function of the human eye V(λ) and luminous effi-
cacy versus wavelength (source: Wikimedia Commons)
mention what we understand under the term “light”. Usu-
ally, this relates to the visible light, i.e., electromagnetic
radiation with wavelengths between 380 and 780 nm which
can be seen by the human eye. But this understanding often
extends to ultraviolet light with shorter wavelengths than
visible light. Ultraviolet (UV) light is also more energetic
than visible light. In addition, also near-infrared radia-
tion (NIR) with longer wavelengths and lower energy than
visible light is often included in the term light. The solar
radiation consists of these three parts: UV, visible and
near-infrared radiation, as shown schematically in Fig. 10.
One important characteristic in this regard is the photopic
spectral response of the human eye to visible light. The eye
sensitivity function V(λ) is displayed in Fig. 11, from which
it is evident that some wavelengths are more effective than
others in stimulating the visual system of the eye. The maxi-
mum sensitivity of the human eye is to green light with a
wavelength of 555 nm. Therefore, if photopic values of vis-
ible light transmittance Tvis or reflectance Rvis are stated,
these are integrated transmission or reflection spectra of
an object over the whole visible spectrum, weighted by the
photopic spectral response of a typical human eye calculated
according to international standards such EN410.
Another important characteristic value for the compari-
son of window glazing, in general, is the total solar energy
transmittance of windows. The solar transmittance Tsolar
is the part of all incident electromagnetic radiation from
the sun which is directly transmitted through a glass pane.
However, such a glass pane can also absorb solar radiation
which can be re-radiated or convected indoors. This is the
part of the solar energy which is transmitted through the
glass indirectly. Because of slightly different computation-
ally regulations in Europe and the USA, the sum of directly
and indirectly transmitted solar energy is stated as g value in
Europe and as solar heat gain coefficient (SHGC) in North
13
ChemTexts (2019) 5:1
America. It is the ratio of all transmitted solar radiation to
incident solar radiation of a window and ranges from 0 to 1.
This is a static value for conventional glass and a dynamic
one for electrochromic glass.
If we define electrochromism as the reversible color
change of chemical compounds induced by electrochemical
redox reactions we come to the question how to define and
measure color. Color is how the human brain distinguishes
the different signals which are produced by the cone cells
in the eye due to incoming light of different wavelengths. A
scientific quantitative description of color as sensed by the
human eye can be done by colorimetry. Such a quantitative
description is usually executed using the methodology which
was formalized by the International Commission on Illumi-
nation (usually abbreviated CIE for its French name, Com-
mission internationale de l’éclairage) in 1931 and further
developed later. This includes CIE 1931 color spaces and
the resulting CIE chromaticity diagram. This methodology
can also be applied to electrochromic materials and devices
for a more scientific description of color change [61, 62].
Comparison parameters for electrochromics
In the study and application of the phenomenon of electro-
chromism, it is necessary to quantify the intensity change
between different colored oxidation states and to compare
the material or device performance of electrochromic com-
pounds and devices between different laboratories or compa-
nies. The following performance parameters are commonly
used for this purpose [63].
Coloration efficiency
An important way to assess the many electrochromic com-
pounds and devices which are known or possible to con-
struct is to compare their respective coloration efficiencies.
The coloration efficiency CE or sometimes η ­[cm2 C−1] is
defined as the ratio of the change in optical density, ΔOD,
at a specified wavelength, λ, to the injected or ejected charge
Q per unit electrode area [C cm−2]:
CE(𝜆) = ΔOD(𝜆)∕Q. (6)
The ideal electrochromic material or device would exhibit
a large transmittance change with a small amount of charge,
giving rise to a high CE. The optical density is calculated
from the light transmission TM in the bleached and colored
state ­TMb and ­TMc at the specified wavelength:
(7)
[ ]
ΔOD(𝜆) = log TMb (𝜆)∕TMc (𝜆) .
CE will usually vary greatly based on the selected wave-
length. Most often, the CE for an electrochromic compound
or device is given for the wavelength at which it reaches its
maximum value [64]. Other researchers state the CE of an
ChemTexts (2019) 5:1 Page 9 of 18  1
Fig. 12  Visible light transmission in the fully colored and bleached
states and coloration efficiency in dependence on wavelength in the
visible spectral range for a typical complementary electrochromic
device with tungsten oxide and Prussian blue as electrochromic lay-
ers. Also indicated are the maximum coloration efficiency, CE at
550 nm and photopic CE. Color rendering index, CRI, of the device
in bleached state is 95, in colored state 9, photopic contrast ratio, CR,
is 9.6 (source: from the laboratory of Gesimat GmbH, Berlin, Ger-
many)
electrochromic device for 550 nm, the approximate wave-
length with highest sensitivity of the human eye to light.
This alone makes comparison between published CE values
for different electrochromic systems difficult. In addition, it
is also possible to use the photopic transmission according
to international standards EN410, ISO 9050 and ISO 13837
for the determination of CE [65]. The photopic transmis-
sion is a calculated light transmission over the wavelength
range between 380 and 780 nm normalized with the spectral
sensitivity of the human eye. This CE based on photopic
transmission changes is very seldom used although it gives
the best data because it reports what the human eye is really
seeing.
To make maximum comparison between different electro-
chromic devices possible, it would be best always to provide
three values in a scientific article on a specific electrochro-
mic device, i.e., (1) coloration efficiency data for 550 nm,
(2) for the wavelength with maximum value of CE and (3)
the photopic data for visible light transmittance according
to international standards EN410, ISO 9050 and ISO 13837.
An example of this is shown in Fig. 12 for an electrochromic
device with tungsten oxide and Prussian blue as complemen-
tary electrochromic layers and an ion-conducting PVB-based
polymer electrolyte.
Contrast ratio
Besides the coloration efficiency, the contrast ratio is the
second important parameter for the rating and comparison of
electrochromics. The contrast ratio, CR, is defined as
CR(𝜆) = TMb (𝜆)∕TMc (𝜆). (8)
Again, similar to the coloration efficiency CE, the con-
trast ratio CR is usually calculated for a specified wavelength
λ. Often the wavelength at which CR reaches its maximum
is used. But for comparison purposes, the CR at 550 nm
and the CR for photopic visible transmittance between 380
and 780 nm should also be calculated and published in a
scientific report because these data are often more impor-
tant than the maximum value. Obviously, as with coloration
efficiency, a high value for contrast ratio is what scientists
are looking for.
Color rendering index, CRI
Electrochromic devices can be used to change the light
transmittance of window glass. By changing the light trans-
mittance usually the color of electrochromic devices also
changes. When such a window filters the natural daylight in
architectural applications, its spectral characteristic affects
the color rendering of interior objects [66]. Often electro-
chromic windows switch from a slightly brown or nearly
colorless bleached to a deep blue-colored state. It is clear
that objects illuminated by deep blue light will appear in a
much different color compared to the case where they are
illuminated by unfiltered sunlight [67]. The color rendering
index CRI is a quantitative measure of the color appear-
ance of an object illuminated by an unnatural light source
compared to its color with an ideal or natural light source.
The color rendering index, CRI, can be calculated from the
transmittance spectrum of an electrochromic device using
the CIE methodology [68] which can also be found in inter-
national standards such as EN410. A CRI of 100 is perfect,
i.e., no color change. CRIs below 100 become worse the
more they are away from the ideal value. Deep blue-colored
electrochromic windows can reach unacceptable CRIs of
below 10, whereas grey coloring electrochromic devices
with CRI above 90 in their completely colored state are
possible. Unfortunately, CRIs of electrochromic devices are
reported only very rarely in scientific articles.
Switching time
For practical applications not only a high contrast ratio, a
good coloration efficiency and a high color rendering index
are advantageous, but also a short switching time or high
switching speed is of high importance. Therefore, switching
time, also called response time of electrochromic materials
and devices, is often measured. Usually, this is the time to
switch between T ­ Mb and T ­ Mc (or vice versa) or between
two distinctly colored states. Also switching time is not
straightforward and convincing to define. At first, we can
again consider the switching time between ­TMb and ­TMc at
13
1 
Page 10 of 18
a certain wavelength, at 550 nm or at photopic transmittance.
In addition, switching time for coloring and bleaching are
very unlikely to be the same and, this also very important,
switching time strongly depends on the applied voltage and
often also on temperature.
But this is not all, what makes a statement of switching
times for electrochromic elements difficult and not easy to
compare with one another? Switching time cannot only be
influenced by the coloration efficiency of an electrochromic
material and the ease of intercalation and deintercalation of
ions, but also very strongly by the electrical resistances in
the system to be switched. High electrical resistances are
introduced into an electrochromic system by the electrolyte
and/or by the transparent conducting films. In general, a liq-
uid electrolyte has a low resistance but for practical applica-
tions gel or solid electrolytes are preferred. Solid electro-
lytes can add a high electrical resistance to a system. But the
transparent conducting layers can also contribute significant
additional electrical resistance. The larger an electrochromic
device area, the larger is the resistance due to the transparent
conductors. In large electrochromic windows in the square
meter range, it is the resistance of the transparent conductors
that dominates the overall resistance of an electrochromic
system. A specific electrochromic device which can switch
in milliseconds in a small laboratory sample will need many
minutes to do this in a large area square meter-sized real-
world smart window device.
Therefore, it is difficult to compare the multitude of
switching or response times reported in the scientific lit-
erature because of poor, if any, consistency with either the
method of calculation or the point at which the measurement
is made, e.g., percentage of transmittance change. Only very
recently, a proposal for a new standard method to calculate
electrochromic switching time has been published [69].
Many processes in chemistry and physics can be
described by first-order differential equations [70]. This is
also true for the switching of an electrochromic element, i.e.,
the visible light transmittance change ΔTM with time t after
application of a d.c. voltage [69]:
ΔTM(t) = ΔTMmax (1 − e−t∕𝜏 ), (9)
with
ΔTMmax = TMb − TMc , (10)
and time constant τ [s]. What can we learn from τ? If switch-
ing time t is equal to τ, 63.2% of the maximum transmittance
change is reached, at a time of 2.3τ we are at 90%, at 3τ at
95% and finally at 4.6τ 99% of ΔTMmax is switched.
Since ΔTMmax and τ provide all necessary information for
describing the time necessary to switch an electrochromic
material or element, these values should be measured, calcu-
lated and stated in research reports together with all relevant
13
ChemTexts (2019) 5:1
experimental data, such as switching voltage, temperature
and device construction and size.
Cycle life
One of the most important properties of an electrochromic
device is a high cycle life. This means it must be possible to
switch between the differently colored oxidation states sev-
eral thousand times without significant change in switching
range, switching speed, transmission level of the bleached
and colored (and intermediate) states, and without cosmetic
defects such as delaminations, uneven coloring or bleach-
ing, non-switching areas and others. This goal is not easy
to reach. If we consider the use of electrochromic elements
in glazing for building applications it is generally assumed
that about 40,000 switching cycles and 20 years lifetime are
necessary [71] and this under changing environmental con-
ditions such as temperatures below − 20 and above + 40 °C,
high solar irradiation levels, fast temperature changes and
uneven temperature distribution over the area of the elec-
trochromic device. It has to be mentioned that an electro-
chromic glass can, if colored at high temperature and under
high sun irradiation levels, reach temperatures of 70 °C and
higher, under certain circumstances even higher than 100 °C.
In such a case the temperature of electrochromic elements is
much higher than the ambient temperature.
To assess the durability and reliability of electrochromic
devices a number of accelerated aging tests have been devel-
oped during the last years [72]. Meanwhile, an international
standard, ISO18543 Glass in building: Electrochromic glaz-
ings—Accelerated aging test and requirements, is describing
such a test procedure.
Electrochromic devices
To be able to make practical use of electrochromic effects
of solid thin film materials or dissolved compounds it is
necessary to construct suitable electrochemical cells, which
are often called electrochromic devices or electrochromic
elements. There are four basic types of electrochromic cells
which are schematically shown in Fig. 13. All have in com-
mon that the electrochromic system has to be placed between
two conductive substrates or electrodes of which at least
one has to be optically transparent. For applications such as
switchable mirrors or information displays, this can be suffi-
cient. But for other applications such as for smart switchable
window glass, of course, two optically transparent substrates
are absolutely necessary. Even for some kind of switchable
mirrors or information displays, two transparent substrates
could be advantageous.
The most often used transparent substrate is of course
glass, but also transparent organic polymeric materials can
ChemTexts (2019) 5:1 Page 11 of 18  1
Fig. 13  The four basic types of electrochromic devices. EC1 is the
first electrochromic compound, EC2 is the second electrochromic
compound or an ion-storage layer, TCE is a transparent conducting
electrode, Ox and Red are the oxidized and reduced states of the elec-
troactive compounds, respectively, ­M+ are cations and M is a metal
­(H+) potassium ­(K+), sodium ­(Na+) and lithium ions ­(Li+)
be used such as polyethylene terephthalate (PET), polycar-
bonate (PC) or poly(methyl methacrylate) (PMMA).
Transparent conducting materials are most often thin
films of highly doped wide-bandgap semiconducting metal
oxides such as indium tin oxide (ITO), which is essentially
tin-doped indium oxide or fluorine-doped tin oxide (FTO)
[73]. Also conducting polymers such as PEDOT [74], very
thin films of noble metals [75] or noble-metal nanowires
[76], carbon nanotubes [77] or graphene layers [78] have
been proposed and tested as a transparent conducting elec-
trode for electrochromic devices. However, ITO, FTO and
other transparent conducting oxides are still the first choice.
Compared to bulk metal conductors, transparent conducting
films have an electrical resistance that is around two orders
of magnitude higher. In large-area electrochromic devices,
e.g., in the square meter range, this can lead to a significant
voltage drop over the device area resulting in an uneven col-
oring and bleaching that starts at the bus bars and progresses
toward the center of the device. This phenomenon is also
called curtain or terminal effect [79].
Electrochromic elements of type 1 are the most common
ones. Two electrically conductive substrates are coated
with electrochemically redox active films, at least one of
these has to be electrochromic. Between these two films a
transparent electrolyte, i.e., an ion-conducting medium, is
placed. Concerning the two electroactive films, there are
two general possibilities. First, if only one of these films is
electrochromic the other is usually called ion-storage film.
Of course, this film also has to be redox active, but the redox
reactions are not accompanied by strong changes in the opti-
cal properties but by insertion or exsertion of cations from
the electrolyte.
But, second, both films can be electrochromic. In this
case, a cathodically and an anodically coloring electro-
chromic film are paired. Such an electrochromic element is
also called a complementary electrochromic device. It can
provide a higher coloration efficiency and a higher contrast
ratio compared to a device with only one electrochromic
film, because with the same electric current always two
films are coloring or bleaching. In addition, the use of two
electrochromic films in one device gives the possibility to
design an electrochromic device with other colors as the
single electrochromic layers provide. The combination of
the blue-coloring tungsten oxide with the brown-coloring
nickel oxide can result in a grey, color-neutral darkening
electrochromic device.
The electrochromic films can, e.g., be from the classes
of transition metal oxides, conducting polymers, inorganic
complex compounds or others which have been mentioned
above. The electrolyte can be a liquid, a polymer electrolyte
or a thin inorganic ion conducting film. The ions should be
small to be easily transported in an electric field. Protons
are by far the most common alternatives.
In electrochromic devices with only one electrochromic
layer and an ion storage layer, tungsten oxide as cathodic
electrochromic film can be paired, e.g., with Ce or V oxide
or with mixed Ce/V, Nb/V, Ti/V or Ce/Ti oxide films [80]. In
complementary electrochromic devices, often the cathodic
electrochromic tungsten oxide is paired with anodic electro-
chromic films such as nickel oxide, Prussian blue or polyani-
line. We see tungsten oxide to be the dominating cathodic
electrochromic material.
However, the cathodic and anodic electrochromic films
cannot only consist of one single material but also of a mix-
ture of two or more electrochromic substances. This is an
opportunity to tune the color in which switching will be
performed. Examples are mixed films of nickel oxide and
13
1 
Page 12 of 18
Fig. 14  Six different coloration states of a complementary electrochromic device with tungsten oxide and Prussian blue as electrochromic layers
and an ion-conducting PVB polymer electrolyte (source: from the laboratory of Gesimat GmbH, Berlin, Germany)
polyaniline [81], Prussian blue and polyaniline [82], or tung-
sten oxide and PEDOT [83] to name a few. These films of
mixed transition metal oxides or of mixtures of several dif-
ferent conducting polymers that were investigated in this
regard have been described above.
An electrochromic device of type 1 has a battery-like
structure and behavior [84] and is, if a Li ion conducting
electrolyte is used, essentially a Li ion battery between
transparent electrodes. In such a device, any coloration state
which has been reached is permanent, even if the driving
voltage is switched off. Each coloration state has a typical
open circuit voltage which can be used for the electronic
control algorithm of the electrochromic device [85]. Six
differently colored oxidation states of such a type 1 com-
plementary electrochromic device are displayed in Fig. 14.
But there is one exception to the battery-like behavior of
type 1 electrochromic devices: in monolithic, all inorganic
solid state, electrochromic devices which consist of a stack
of five thin ceramic metal oxide coatings on a single piece of
glass, usually an extremely thin inorganic electrolyte is used
to compensate for the very low ionic conductivity of such a
material. These very thin ceramic electrolyte films can have
small pin holes. Through these pinholes, the two electro-
chromic films can have direct electrical contact. This leads
to small short circuits which in turn result in a self-bleaching
electrochromic element. These devices need a permanently
applied voltage to stay in a given coloration state.
In electrochromic devices of type 2, both redox active
components are dissolved in an electrolyte solution. Because
of all redox species are dissolved and can freely diffuse
through the solution volume, the reduced species from the
cathode and the oxidized species from anode can meet in
the solution and react with one another. Therefore, such a
solution-phase electrochromic combination [86] is always a
self-erasing system in contrast to typical devices of type 1.
The hybrid device type 3 of electrochromic systems has
one thin solid electrochromic film, whereas the second redox
system is dissolved in the electrolyte. This results of course
also in a self-bleaching electrochromic element. An example
13
ChemTexts (2019) 5:1
for hybrid devices is the combination of a solution phase
cathodic electrochromic methyl viologen compound with a
surface-confined anodic electrochromic Prussian blue thin
film [62].
A type 4 device is the reversible electrodeposition elec-
trochromic device. At the working electrode, the metal is
deposited from the solution of its metal ions or, during
bleaching, it is dissolved. A second redox system is active
at the counter electrode. As long as the oxidation potential
of the reaction product from the counter electrode is not high
enough to oxidize the metal film, this is a not self-bleaching
system.
Multiple variations and combinations of these four basic
types are of course possible.
Electrochromic devices are electrochemical systems.
Therefore, between the two electrodes, an electrolyte is nec-
essary. An electrolyte is an ion-conducting medium with
a very low electronic conductivity. Usually, liquid, gel,
polymer or inorganic solid electrolytes are distinguished.
For laboratory tests often liquid electrolytes are used. Liq-
uid electrolytes are based on water or polar organic liquids
such as propylene carbonate, N-methyl-2-pyrrolidone,
γ-butyrolactone or acetonitrile in which, e.g., Li salts are
dissolved. Ionic liquids can also be used. For practical real-
world applications, liquid electrolytes are no good candi-
dates because of the lack of mechanical stability and the
possibility of leakage. Gel electrolytes are liquid electrolytes
to which some suitable polymers are added which results in
a more viscous less fluid solution with lower ionic conduc-
tivity compared to the liquid electrolytes without polymer
additives. Polymer electrolytes usually consist of at least one
polymer, at least one liquid additive also called plasticizer
and at least one salt. Polymer electrolytes are often mechani-
cally stable but still flexible materials. There are also poly-
mer electrolytes without plasticizer consisting only of poly-
mer and salt. They are also called solid polymer electrolytes
(SPE). Solid inorganic electrolytes have the advantage that
they are intrinsically more stable against high temperature,
overvoltage and other stress than the above-mentioned other
ChemTexts (2019) 5:1 Page 13 of 18  1
types of electrolytes for electrochromic elements. However,
they have a very high specific resistance. Therefore, they
are usually applied as a very thin film only which can result
in short-circuit problems between the electrodes. The ionic
conductivity of these different types of electrolytes follows
the row: liquid electrolytes > gel electrolytes > polymer elec-
trolytes > solid polymer electrolytes > inorganic ceramic
electrolytes.
Electrochromic elements are switched by use of small dc
voltages in the range of about 0.5–3 V. If there are large elec-
trical resistances in the system as it is the case in large area
electrochromic devices, the switching voltage can also be
somewhat higher to compensate for the iR or voltage drop.
In most cases, the voltage to drive the color change of
electrochromic glazing for windows is supplied by the power
grid. This makes the wiring of the window necessary. But
there also exists a concept of electrochromic devices directly
coupled to solar cells positioned in the window frame. In
such a case, the window should not be connected to the
power grid. A similar but also somewhat different concept
is that of a so-called photoelectrochromic (PEC) device. In
such a device, one of the electrodes in the electrochromic
device is also a solar cell [87]. Usually, a dye-sensitized
solar cell (DSSC) electrode is coupled with an electrochro-
mic electrode. This produces a self-powered window that
spontaneously darkens when illuminated by sunlight. The
optical state can be stored at open circuit or changes due to
varying illumination at short circuit. The cells can function
as purely photochromic devices, as electrochromic devices,
or as a hybrid of the two. Multiple variations of the combi-
nation of solar cells with electrochromic devices have been
comprised [88].
Manufacturing considerations
The next topic of this lecture is about manufacturing elec-
trochromic devices [89]. This topic is very extensive and
we want to touch it only shortly but from both an academic
laboratory and an industrial perspective.
Usually, the substrates, which are necessary for producing
electrochromic devices are bought from respective suppliers.
These substrates are mostly glass plates or transparent plas-
tic materials coated with transparent conducting oxides such
as ITO (indium-doped tin oxide), AZO (aluminum-doped
zinc oxide) or FTO (fluorine-doped tin oxide). Industrial
producers of large-area electrochromic devices on glass use
FTO-coated glass because this is produced in large quanti-
ties and available at reasonable prices. Plastic substrates,
e.g., PET films coated with ITO films, are also commercially
available in large area.
PEDOT, carbon nanotubes, metal grids, metal nanowire
meshes or other exotic transparent conducting materials and
structures are only used in academic research and not in
industry. However, this may change. For producing switch-
able mirrors, one of the TCO-coated substrates has a highly
reflective mirror coating on one of the transparent substrates
on the outer surface.
For producing type 1 electrochromic devices the electro-
chromic and, if used in the device, ion-storage films have
to be deposited on top of the transparent conducting film.
These films can be deposited by several technologies often
leading to somewhat different properties of the electroactive
film. The most often used technologies are vacuum evapora-
tion, sputtering, electrodeposition, chemical vapor deposi-
tion, layer-by-layer (LBL) assembly [90], spray pyrolysis
and sol–gel coating [91]. The technologically most impor-
tant of these methods is sputtering, the usual vacuum deposi-
tion technology for large-area glass coating in general.
Electrolytes between the two electroactive films can be
liquid, gel-like or solid. If solid electrolytes are used two
different configurations are possible.
First, the electrochromic film stack can be coated on a
single substrate. This is usually done for all necessary layers
by vacuum deposition technologies, e.g., sputtering. Such a
thin film stack often consists of five oxide-based thin films:
a TCO, an electrochromic film such as tungsten oxide, a
ceramic thin film electrolyte (e.g., ­Ta2O5), a second elec-
trochromic film such as nickel oxide and finally a second
TCO layer. Because this device structure on a single piece of
glass can be produced by established large area glass coating
technologies, this approach is favored by investors from the
glass industry. But, as already mentioned, to produce a good
pore-free inorganic ceramic electrolyte with a not too high
electrical resistance is still a challenge.
Second, if the solid electrolyte is a polymer electrolyte, a
two-substrate device is typically produced. Such a polymer
electrolyte has a lower resistance than an inorganic ceramic
electrolyte and can, therefore, be produced as a thicker film.
A two-substrate device is produced by coating both TCO-
coated substrates with their respective electroactive films
(electrochromic and perhaps ion-storage). These two elec-
trochromic electrodes have to be joined afterwards by the
polymer electrolyte. This can be done by lamination with
a solid but flexible ion-conducting interlayer material [92,
93] in a process similar to the production of laminated safety
glass or using a liquid mixture of monomers and other addi-
tives, fill a defined gap between the two electrochromic elec-
trodes with this mixture and polymerize the monomers of
the electrolyte by UV and/or heat treatment so that a solid
electrolyte is formed in situ [94, 95]. The gap between the
two substrates can be defined by double-sided spacer tapes
which are placed on the edge of the glass substrates and fix
them together with the required distance.
Liquid electrolytes are often used in academic research
in general and in industrial research at the beginning of
13
1 
Page 14 of 18 ChemTexts (2019) 5:1

investigations with a new electrochromic material even in

type 1 electrochromic devices. On the other hand, more or
less liquid electrolytes are also used in all type 2 solution-
phase electrochromic devices. Such devices do not work
with solid electrolytes because the dissolved electrochro-
mic substances cannot diffuse fast enough even in a highly
plasticized polymer electrolyte. They need liquid or gel-type
electrolytes. Typically, electrochromic rearview mirrors are
type 2 electrochromic devices. Electrochromic devices with
liquid electrolytes are made by sealing the perimeter of two
conductive substrates, at least one of which is transparent.
The sealant can be a double-sided adhesive tape or a curable
mixture which has spacer beads to allow a fixed distance
between the two substrates forming a cavity. Generally, a
small gap is left in the sealant so that after it is applied,
cured or solidified, liquid electrolyte is introduced through
this hole by vacuum backfilling and thereafter it is sealed
by another resin.

Already realized and possible future

applications of electrochromism

Automatic-dimming rearview mirrors in vehicles which

detect and eliminate dangerous rear-view mirror glare and
provide safer driving at night were the first mass product
which used an electrochromic technology. They were devel-
oped by Harlan Byker [96] and introduced into the market by
Gentex Corp. (USA) as early as 1987. This type of mirror,
a type 2 solution-phase electrochromic system between a
mirror and a transparent substrate has the advantage that the
light that should be dimmed has to pass two times through
the electrochromic solution. In comparison to a single-trans-
mission-mode device, such a double-pass operation reduces
by half the charge that must be delivered to produce a given
absorbance change. Most electrochromic displays have a
similar advantage.
As mentioned at the beginning of this lecture, information
displays are another possible application that received much
attention in the 1970s but never reached the market until
today. This is also true for electrochromic sunglasses and
goggles, switchable light filters and other possible products
based on electrochromism.
By far, the largest application field and market of elec-
trochromism are smart windows for buildings. In 2016, the
world market for flat glass for buildings amounted to about
8.6 billion square meters per year [97]. This does not mean
that 8.6 billion square meters of glass could be electrochro-
mic because of, amongst other things, the widespread use
of double-pane or even triple-pane insulating glass. But still
the potential is huge.
Electrochromic and other smart window technologies
could be very beneficial if applied on large scale for building
Fig. 15  First 8-m × 17-m electrochromic glass facade in Dresden,
Germany with 80 EControl glazing installed in August 1999 by Pilk-
ington. This business is continued by today’s company EControl-Glas
Plauen, Germany (source: photo by the author, 2001)
glazing. Modern architecture is proud to design buildings
with large glass facades. In areas or times with high sun irra-
diation levels, this can lead to very high energy input into the
buildings which in turn would increase the energy consump-
tion for air conditioning systems to prevent overheating. The
use of electrochromic glass could solve this problem, and,
in addition, it could provide glare control but still guaran-
tee an unobstructed view out of building. External shading
devices are not necessary anymore. Model calculations show
that the high investment costs for electrochromic windows
could be returned due to cost savings for air conditioning
and lighting [98].
Therefore, a lot of research efforts have been directed
towards large-area electrochromic glazing for buildings.
But it is no easy task to develop electrochromic devices for
such an application; they must be upscaled from laboratory
devices in the square cm size to the square meter range and
they must be visually homogeneous over the whole area,
with very low thickness variations of the electrochromic
layers and without any cosmetic defects. Switching shall be
performed homogeneously too, with not too long switch-
ing times at outside air temperatures from around − 20 to

13
ChemTexts (2019) 5:1 Page 15 of 18  1
Fig. 16  Electrochromic window in a Boeing 787-8 Dreamliner air-
craft (source: Wikimedia Commons)
over 40 °C. In addition to that, lifetimes of 20–30 years are
expected, which translate to around 40,000–50,000 switch-
ing cycles. And last but not least, prices should be reason-
able for widespread adoption.
Therefore, it took more than 2 decades of research and
development until the first commercial installation of elec-
trochromic windows was finally realized. This facade of a
bank in Dresden, Germany, installed in 1999 is displayed
in Fig. 15 [99]. The product EControl was a development
of Pilkington, meanwhile part of NSG. The electrochromic
technology of this first installation is based on a tungsten
oxide cathodic electrochromic film combined with an ion
storage layer and a cast resin polymer electrolyte. This tech-
nology is today owned and still used by EControl-Glas,
Plauen, Germany [100]. Later other companies followed and
today electrochromic smart windows using tungsten oxide
are an established commercial product. However, because of
the high price compared to standard window glazing, it is
still only used for relatively few ambitious projects and did
not reach a large market penetration. This will not change if
costs do not come down.
Means of transportation, motor vehicles, trains, ships,
aircraft, are the second largest market for switchable
electrochromic glazing. In comparison to building applica-
tions, here the use of somehow bent and non-rectangular-
shaped glass is much more common. This is an additional
challenge for developing electrochromic products for this
field. But also in this application area, we find an already
well-established product: electrochromic windows in air-
craft. Figure 16 shows such a window. However, the high-
volume part of this market, automobiles, is still waiting for
an affordable electrochromic product.
Electrochromic poly(2,7-carbazole) derivatives which
switch between green and brown color have been proposed
for use in adaptive camouflage (chameleon effect) for mili-
tary assets [101]. Several other conducting polymers can be
used for this application too. “Dirty” colors and inhomoge-
neous switching could be advantageous for this kind of prod-
uct. Such an active camouflage equipment for military assets
should exhibit adaptive changes to the objects’ surroundings
by varying its patterns and colors, therefore, acting as a per-
fect concealment from visual and infrared detections [102].
Somewhat surprisingly, some research is also directed
towards electrochromic color changeable clothing [103]. It
is envisioned that electrochromic fibers should become the
basis for a new kind of wearable fashion and flexible dis-
plays. So your clothes or part of your clothes could change
color automatically or with the push of a button. Whether
this is an advance for humanity is an open question.
Another more unexpected application possibility of elec-
trochromics is control of satellites and spacecraft emissivity
by use of devices switching in the far-infrared spectral range.
This is again possible by use of tungsten oxide [104]. By
switching between high- or low -radiative surface state for
infrared wavelengths thermal control (heat conservation on
dark side, heat rejection on sun side and emittance of excess
heat) in satellites positioned in low earth orbit becomes
possible by balancing energy dissipated by heat against the
energy emitted as far-IR radiation [105].
Summary
The purpose of this paper was to give a tutorial overview of
the phenomenon of electrochromism and its use in technical
devices. Because of the impressive color changes that are
connected with the phenomenon of electrochromism, this
branch of electrochemistry is perhaps the most fascinating.
Therefore, it is much fun working in this field. Research
results can be easily presented also for an audience that does
not consist of electrochemists or even chemists. Every lay-
man can see and acknowledge your achievements, especially
if presented with films or even with switchable samples that
show the changing colors of electrochromic devices. But it is
also a challenging field because highly reversible, long-term
13
1 
Page 16 of 18
stable and visually homogeneous electrochromic devices are
difficult to produce.
Electrochromic products are more and more success-
ful in penetrating their respective markets. After the first
electrochromic mass product, the solution phase electro-
chromic rearview mirror of Gentex (USA), electrochromic
smart windows for buildings from several producers are now
commercial products. More and more buildings are equipped
with switchable electrochromic sun-protection glass from
companies such as ChromoGenics (Sweden), EControl-Glas
(Germany), Kinestral Technologies, Inc. (USA), SageGlass
(USA) and View, Inc. (USA). But there are also some draw-
backs or things that have to be improved to change electro-
chromic windows from an expensive curiosity to an every-
where-to-see commodity. Improvements are necessary for,
e.g., switching speed, contrast ratio, transmission level of the
bleached state, neutral color of dark state, and, last but not
least, price. Therefore, there is still much room for current
chemistry students to make their own impact in the field
electrochromism.
References
1. Rauh RD (1999) Electrochromic windows: an overview. Electro-
chim Acta 44:3165–3176
2. Deb SK (1995) Reminiscences on the discovery of electrochro-
mic phenomena in transition metal oxides. Sol Energy Mater Sol
Cells 39:191–201
3. Schoot CJ, Ponjee JJ, van Dam HT, van Doorn RA, Bolwijn
PT (1973) New electrochromic memory display. Appl Phys Lett
23:64–65
4. Kaufman FB, Schroeder AH, Engler EM, Patel VV (1980) Pol-
ymer-modified electrodes: a new class of electrochromic materi-
als. Appl Phys Lett 36:422–425
5. Neff VD (1978) Electrochemical oxidation and reduction of thin
films of Prussian Blue. J Electrochem Soc 125:886–887
6. Lampert CM (1984) Electrochromic materials and devices for
energy efficient windows. Sol Energy Mater 11:1–27
7. Svensson JSEM, Granqvist CG (1984) Electrochromic tung-
sten oxide films for energy efficient windows. Sol Energy Mater
11:29–34
8. Casini M (2018) Active dynamic windows for buildings: a
review. Renew Energy 119:923–934
9. Granqvist CG, Arvizu MA, Bayrak Pehlivan I, Qu H-Y, Wen
R-T, Niklasson GA (2018) Electrochromic materials and devices
for energy efficiency and human comfort in buildings: a critical
review. Electrochim Acta 259:1170–1182
10. Baucke FGK, Bange K, Gambke T (1988) Reflecting electrochro-
mic devices. Displays 9:179–187
11. Österholm AM, Shen DE, Kerszulis JA, Bulloch RH, Kuepfert
M, Dyer AL, Reynolds JR (2015) Four shades of brown: tuning
of electrochromic polymer blends toward high-contrast eyewear.
ACS Appl Mater Interfaces 7:1413–1421
12. Hein A, Kortz C, Oesterschulze E (2018) Electrochromic tun-
able filters based on nanotubes with viologen incorporation. In:
Proc SPIE 10679, optics, photonics, and digital technologies for
imaging applications V, 106791U
13
ChemTexts (2019) 5:1
13. Coleman JP, Lynch AT, Madhukar P, Wagenknecht JH (1999)
Printed, flexible electrochromic displays using interdigitated
electrodes. Sol Energy Mater Sol Cells 56:395–418
14. Saricayir H, Üce M, Koca A (2010) In situ techniques for moni-
toring electrochromism. An advanced laboratory experiment. J
Chem Educ 87:205–207
15. Bange K (1999) Colouration of tungsten oxide films: a model for
optically active coatings. Sol Energy Mater Sol Cells 58:1–131
16. Granqvist CG (2000) Electrochromic tungsten oxide films:
review of progress 1993–1998. Sol Energy Mater Sol Cells
60:201–262
17. Gottesfeld S, McIntyre JDE, Beni G, Shay JL (1978) Elec-
trochromism in anodic iridium oxide films. Appl Phys Lett
33:208–210
18. Gavrilyuk AI, Chudnovskii FA (1977) Electrochromism in
V2O5 films (in Russian). Pisma Zh Tekh Fiz 3:174–177
19. Dyer CK, Leach JSL (1978) Reversible optical changes within
anodic oxide films on titanium and niobium. J Electrochem Soc
125:23–29
20. Passerini S, Scrosati B, Gorenstein A (1990) The intercalation
of lithium in nickel oxide and its electrochromic properties. J
Electrochem Soc 137:3297–3300
21. Monk PMS, Akhtar SP, Boutevin J, Duffield JR (2001) Toward
the tailoring of electrochromic bands of metal-oxide mixtures.
Electrochim Acta 46:2091–2096
22. Runnerstrom EL, Llorde A, Lounisac SD, Milliron DJ (2014)
Nanostructured electrochromic smart windows: traditional
materials and NIR-selective plasmonic nanocrystals. Chem
Commun 50:10555–10572
23. Barawi M, De Trizio L, Giannuzzi R, Veramonti G, Manna
L, Manca M (2017) Dual band electrochromic devices based
on Nb-doped ­T iO 2 nanocrystalline electrodes. ACS Nano
11:3576–3584
24. Manos P (1969) Electrochromic device. US Patent US3451741
25. Bird CL, Kuhn AT (1981) Electrochemistry of the viologens.
Chem Soc Rev 10:49–82
26. Striepe L, Baumgartner T (2017) Viologens and their application
as functional materials. Chem Eur J 23:16924–16940
27. Byker HJ (1991) Bipyridinium salt solutions. US Patent
US5294376
28. Inzelt G (2012) Conducting polymers—a new era in electrochem-
istry, 2nd edn. Springer Verlag, Berlin
29. Genies EM, Bidan G, Diaz AF (1983) Spectroelectrochemical
study of polypyrrole films. J Electroanal Chem 149:101–113
30. Yoshino K, Kaneto K, Inuishi Y (1983) Proposal of electro-
optical switching and memory devices utilizing doping and
undoping processes of conducting polymers. Jpn J Appl Phys
22:L157–L158
31. Kobayashi T, Yoneyama H, Tamura T (1984) Polyaniline film-
coated electrodes as electrochromic display devices. J Electroanal
Chem 161:419–423
32. Kitani A, Yano J, Sasaki K (1986) ECD materials for the three
primary colors developed by polyanilines. J Electroanal Chem
209:227–232
33. Dinh HN, Ding J, Xia SJ, Birss VI (1998) Multi-technique study
of the anodic degradation of polyaniline films. J Electroanal
Chem 459:45–56
34. Heuer HW, Wehrmann R, Kirchmeyer S (2002) Electrochromic
window based on conducting Poly(3,4-ethylenedioxythiophene)-
Poly(styrene sulfonate). Adv Funct Mater 12:89–94
35. Lim JY, Ko HC, Lee H (2005) Systematic prediction of maxi-
mum electrochromic contrast of an electrochromic material.
Synth Met 15:595–598
36. Thompson BC, Schottland P, Zong K, Reynolds JR (2000) In situ
colorimetric analysis of electrochromic polymers and devices.
Chem Mater 12:1563–1571
ChemTexts (2019) 5:1 Page 17 of 18  1
37. Argun AA, Aubert P-H, Thompson BC, Schwendeman I, Gaupp
CL, Hwang J, Pinto NJ, Tanner DB, MacDiarmid AG, Reynolds
JR (2004) Multicolored electrochromism in polymers: structures
and devices. Chem Mater 16:4401–4412
38. Bulloch RH, Kerszulis JA, Dyer AL, Reynolds JR (2015) An
electrochromic painter’s palette: color mixing via solution co-
processing. ACS Appl Mater Interfaces 7:1406–1412
39. Lee K-R, Sotzing GA (2013) Color tuning of black for elec-
trochromic polymers using precursor blends. Chem Commun
49:5192–5194
40. Savagian LR, Österholm AM, Shen DE, Christiansen DT, Kuep-
fert M, Reynolds JR (2018) Conjugated polymer blends for high
contrast black-to-transmissive electrochromism. Adv Opt Mater
6:1800594
41. Itaya K, Uchida I, Neff VD (1986) Electrochemistry of poly-
nuclear transition metal cyanides: Prussian blue and its ana-
logues. Acc Chem Res 19:162–168
42. Kraft A (2018) What a chemistry student should know about
the history of Prussian blue. ChemTexts 4:16
43. Mortimer RJ, Reynolds JR (2005) In situ colorimetric and com-
posite coloration efficiency measurements for electrochromic
Prussian blue. J Mater Chem 15:2226–2233
44. Garcia-Jareno JJ, Benito D, Navarro-Laboulais J, Vicente F
(1998) Electrochemical behavior of electrodeposited Prussian
blue films on ITO electrode: an attractive laboratory experi-
ence. J Chem Educ 75:881–884
45. de Tacconi NR, Rajeshwar K, Lezna RO (2003) Metal hexa-
cyanoferrates: electrosynthesis, in situ characterization and
applications. Chem Mater 15:3046–3062
46. Moskalev PN, Kirin IS (1970) Effect of the electrode potential
on the absorption spectrum of a rare-earth diphthalocyanine
layer (in Russian). Opt i Spektrosk 29:414–415
47. Lin C-L, Lee C-C, Ho K-C (2002) Spectroelectrochemical stud-
ies of manganese phthalocyanine thin films for applications in
electrochromic devices. J Electroanal Chem 524–525:8–89
48. Yamase T (1998) Photo- and electrochromism of polyoxometa-
lates and related materials. Chem Rev 98:307–325
49. Inzelt G, Day RW, Kinstle JF, Chambers JQ (1984) Spectro-
electrochemistry of tetracyanoquinodimethane modified elec-
trodes. J Electroanal Chem 161:147–161
50. Percec S, Tilford SH (2012) Amorphous polymers with pen-
dant chromogenic groups. US Patent US8287767
51. Schott M, Lorrmann H, Szczerba W, Beck M, Kurth DG
(2014) State-of-the-art electrochromic materials based on
metallo-supramolecular polymers. Sol Energy Mater Sol Cells
126:68–73
52. Zaromb S (1962) Theory and design principles of the reversible
electroplating light modulator. J Electrochem Soc 109:903–912
53. Howard BM, Ziegler JP (1995) Optical properties of reversible
electrodeposition electrochromic materials. Sol Energy Mater
Sol Cells 39:309–316
54. Kim T-Y, Cho SM, Ah CS, Suh K-S, Ryu H, Chu HY (2014)
Electrochromic device for the reversible electrodeposition sys-
tem. J Inf Disp 15:13–17
55. Ziegler JP, Howard BM (1995) Applications of reversible elec-
trodeposition electrochromic devices. Sol Energy Mater Sol Cells
39:317–331
56. Ye T, Xiang Y, Ji H, Hu C, Wu G (2016) Electrodeposition-
based electrochromic devices with reversible three-state optical
transformation by using titanium dioxide nanoparticle modified
FTO electrode. RSC Adv 6:30769–30775
57. Notten PHL (1999) Electrochromic metal hydrides. Curr Opin
Solid State Mater Sci 4:5–10
58. Notten PHL, Kremers M, Griessen R (1996) Optical switching
of Y-hydride thin film electrodes. a remarkable electrochromic
phenomenon. J Electrochem Soc 143:3348–3353
59. Yoshimura K (2015) Metal hydrides for smart-window applica-
tions. In: Mortimer RJ, Rosseinsky DR, Monk PMS (eds) Elec-
trochromic materials and devices, 1st edn. Wiley-VCH Wein-
heim, New York, pp 241–248
60. Manivasagam TG, Kiraz K, Notten PHL (2012) Electrochemical
and optical properties of magnesium-alloy hydrides reviewed.
Crystals 2:1410–1433
61. Mortimer RJ, Sialvi MZ, Varley TS (2014) An in situ colori-
metric measurement study of electrochromism in the thin-film
nickel hydroxide/oxyhydroxide system. J Solid State Electrochem
18:3359–3367
62. Mortimer RJ, Varley TS (2012) In situ spectroelectrochemistry
and colour measurement of a complementary electrochromic
device based on surface-confined Prussian blue and aqueous
solution-phase methyl viologen. Sol Energy Mater Sol Cells
99:213–220
63. Mortimer RJ, Monk PMS, Rosseinsky DR (2015) Definitions of
electrochromic materials and device performance parameters.
In: Mortimer RJ, Rosseinsky DR, Monk PMS (eds) Electrochro-
mic materials and devices, 1st edn. Wiley-VCH Weinheim, New
York, pp 623–626
64. Gaupp CL, Welsh DM, Rauh RD, Reynolds JR (2002) Com-
posite coloration efficiency measurements of electrochromic
polymers based on 3,4-Alkylenedioxythiophenes. Chem Mater
14:3964–3970
65. Roldan R, Romanyuk YE (2014) Dynamics in electrochromic
windows interpreted with an extended logistic model. J Electro-
chem Soc 163:E235–E240
66. Gunde MK, Krasovec UO, Platzer WJ (2005) Color rendering
properties of interior lighting influenced by a switchable window.
J Opt Soc Am A22:416–423
67. Arbab S, Matusiak BS, Martinsen FA, Hauback BC (2017) The
impact of advanced glazing on colour perception. J Int Colour
Assoc 17:50–68
68. Aste N, Leonforte N, Piccolo A (2018) Color rendering perfor-
mance of smart glazings for building applications. Sol Energy
176:51–61
69. Hassab S, Shen DE, Österholm AM, Da Rocha M, Song G, Ale-
sanco Y, Vinuales A, Rougier A, Reynolds JR, Padilla J (2018)
A new standard method to calculate electrochromic switching
time. Sol Energy Mater Sol Cells 185:54–60
70. Scholz G, Scholz F (2014) First-order differential equations in
chemistry. ChemTexts 1:1
71. Czanderna AW, Benson DK, Jorgensen GJ, Zhang J-G, Tracy
CE, Deb SK (1999) Durability issues and service lifetime predic-
tion of electrochromic windows for buildings applications. Sol
Energy Mater Sol Cells 56:419–436
72. Lampert CM, Agrawal A, Baertlien C, Nagai J (1999) Durability
evaluation of electrochromic devices—an industry perspective.
Sol Energy Mater Sol Cells 56:449–463
73. Granqvist CG (1993) Transparent conductive electrodes for elec-
trochromic devices: a review. Appl Phys A 57:19–24
74. Singh R, Tharion J, Murugan S, Kumar A (2017) ITO-free
solution-processed flexible electrochromic devices based on
PEDOT:PSS as transparent conducting electrode. ACS Appl
Mater Interfaces 9:19427–19435
75. von Benken W, Kuwana T (1970) Preparation and properties of
thin gold and platinum films on glass or quartz for transparent
electrodes. Anal Chem 42:1114–1116
76. Yan C, Kang W, Wang J, Cui M, Wang X, Foo CY, Chee KJ, Lee
PS (2014) Stretchable and wearable electrochromic devices. ACS
Nano 8:316–322
77. Hu L, Gruner G, Li D, Kaner RB, Cech J (2007) Patternable
transparent carbon nanotube films for electrochromic devices. J
Appl Phys 101:016102
13
1 
Page 18 of 18
78. Zhao L, Zhao L, Xu Y, Qiu T, Zhi L, Shi G (2009) Polyaniline
electrochromic devices with transparent graphene electrodes.
Electrochim Acta 55:491–497
79. Ho K-C, Singleton DE, Greenberg CB (1990) The influence of
terminal effect on the performance of electrochromic windows.
J Electrochem Soc 137:3858–3864
80. Krasovec UO, Orel B, Reisfeld R (1998) Electrochromism of
CeVO4 and Ce/V-oxide ion-storage films prepared by the sol–gel
route. Electrochem Solid State Lett 1:104–106
81. Kadam A, Sonavane AC, Inamdar A, Deshmukh H, Patil PS
(2010) Multicoloured electrochromic thin films of NiO/PANI. J
Phys D Appl Phys 43:315102
82. DeLongchamp DM, Hammond PT (2004) Multiple-color elec-
trochromism from layer-by-layer-assembled polyaniline/Prussian
blue nanocomposite thin films. Chem Mater 16:4799–4805
83. Li H, McRae L, Elezabbi AY (2018) Solution-processed inter-
facial PEDOT:PSS assembly into porous tungsten molybdenum
oxide nanocomposite films for electrochromic applications. ACS
Appl Mater Interfaces 10:10520–10527
84. Heckner K-H, Kraft A (2002) Similarities between electro-
chromic windows and thin film batteries. Solid State Ionics
152–153:899–905
85. Kraft A, Franz S, Rottmann M, Heckner K-H (2004) Process for
the electric control of electrochromic elements. European Patent
EP1517293
86. Byker HJ (2015) Solution-phase electrochromic devices and
systems. In: Mortimer RJ, Rosseinsky DR, Monk PMS (eds)
Electrochromic materials and devices, 1st edn. Wiley-VCH
Weinheim, New York, pp 401–418
87. Bechinger C, Ferrere S, Zaban A, Spague J, Gregg BA (1997)
Photoelectrochromic windows and displays. Nature 383:608–610
88. Cannavale A, Cossari P, Eperon GE, Colella S, Fiorito F, Gigli
G, Snaith HJ, Listorti A (2016) Forthcoming perspectives of pho-
toelectrochromic devices: a critical review. Energy Environ Sci
9:2682–2719
89. Park S-I, Quan Y-J, Kim S-H, Kim H, Kim S, Chun D-M, Lee
CS, Taya M, Chu W-S, Ahn S-H (2016) A review on fabrica-
tion processes for electrochromic devices. Int J Pr Eng Man-GT
3:397–421
90. Schmidt DJ, Pridgen EM, Hammond PT, Love JC (2010) Layer-
by-layer assembly of a pH-responsive and electrochromic thin
film. J Chem Educ 87:208–211
91. Heusing S, Aegerter M (2018) Sol–gel coating for electrochromic
devices. In: Klein L et al (eds) Handbook of sol–gel science and
technology, Springer, New York, pp 2745–2784
92. Kraft A, Rottmann M, Heckner K-H (2006) Large area electro-
chromic glazing with ion conducting PVB interlayer and two
13
ChemTexts (2019) 5:1
complementary electrodeposited electrochromic layers. Sol
Energy Mater Sol Cells 90:469–476
93. Kraft A, Rottmann M (2009) Properties, performance and cur-
rent status of the laminated electrochromic glass of Gesimat. Sol
Energy Mater Sol Cells 93:2088–2092
94. Jödicke D, Marquardt R, Batchelor RA (1994) Cast resin mix-
ture for bonding substantially sheet-shaped elements. US Patent
US5859723
95. Georen P, Marsal Berenguel R (2008) Electrolytes for electro-
chromic devices. US Patent US8218225
96. Byker H (1986) Single-compartment, self-erasing, solution-phase
electrochromic devices, solution for use therein, and uses thereof.
US Patent US4902108
97. Vitkala J (2017) Summary of GPD 2017. GPD_2107_World-
wide_glass_trends.pdf. https:​ //www2.glasto​ n.net/gpd-2017-glass​
-trend​s-summa​ry. Accessed 16 Oct 2018
98. Sbar NL, Podbelski L, Yang HM, Pease B (2012) Electrochromic
dynamic windows for office buildings. Int J Sust Built Environ
1:125–139
99. Wittkopf H, Cardinal J, Gumprich V (1999) Pilkington E-con-
trol—the new electrochromic glazing for optimization of light-
ing, heating and air-conditioning. In: Proceedings of the glass
processing days, pp 264–266
100. Jödicke D, Wittkopf H (2007) The 2nd generation of an electro-
chromic solar control glazing—ready for projects. In: Proceed-
ings of the glass performance days, pp 394–395
101. Beaupré S, Breton A-C, Dumas J, Leclerc M (2009) Multicolored
electrochromic cells based on Poly(2,7-Carbazole) derivatives for
adaptive camouflage. Chem Mater 21:1504–1513
102. Yu H, Shao S, Yan L, Meng H, He Y, Yao C, Xu P, Zhang X,
Hu W, Huang W (2016) Side-chain engineering of green color
electrochromic polymer materials: toward adaptive camouflage
application. J Mater Chem C 4:2269–2273
103. Otley MT, Invernale M, Sotzing GA (2015) Fabric electrochro-
mic displays for adaptive camouflage, biomimicry, wearable dis-
plays and fashion. In: Mortimer RJ, Rosseinsky DR, Monk PMS
(eds) Electrochromic materials and devices, 1st edn. Wiley-VCH
Weinheim, New York, pp 503–524
104. Franke E, Trimble CL, Schubert M, Woollam JA, Hale JS (2000)
All-solid-state electrochromic reflectance device for emittance
modulation in the far-infrared spectral region. Appl Phys Lett
77:930–932
105. Demiryont H, Moorehead D (2009) Electrochromic emissivity
modulator for spacecraft thermal management. Sol Energy Mater
Sol Cells 93:2075–2078