DOI: 10.1002/ente.
201700705
Recent Advances in Flexible Electrochromic Devices:
Prerequisites, Challenges, and Prospects
Alice Lee-Sie Eh,[a, c] Alvin Wei Ming Tan,[a, c] Xing Cheng,[a, c] Shlomo Magdassi,[b, c] and
Pooi See Lee*[a, c]
Electrochromic (EC) technology has progressed tremendous-
ly in recent years. Rigid EC devices have advanced to offer
additional attractive physical attributes such as flexibility,
stretchability, and foldability. These features are appealing
for wearable and futuristic technologies, and hence serve to
revolutionize EC applications toward deformable electronics.
In this review, the essential prerequisites of each component
of the flexible EC devices are delineated, such that each
component is mechanically flexible to maintain the structural
integrity of the device. The recent progress in flexible EC
1. Introduction
Electrochromic applications have found widespread success
in smart windows for architectural buildings (SageGlass,
View, Inc.), auto-dimming rear view mirrors (Gentex), ther-
mal control in space satellites, and camouflage applications.
Prominent successful commercialization of EC applications
is found in the Boeing 787 Dreamliner airplane[1] and Ferrari
575M Superamerica.[2] EC smart windows are highly valued
for their aesthetic glazing, low energy consumption, and a
good coloration memory effect, which can reduce glare and
incoming solar irradiation into the buildings, thereby lower-
ing the energy consumption of air conditioning in the build-
ing by 26 %.[3, 4] However, most of these EC technologies are
typically built on rigid substrates such as transparent con-
ducting oxides on glass. Currently there is an unmet need for
flexible EC devices that can provide energy savings by retro-
fitting of existing windows or sunroofs.
There has been tremendous interest in developing flexible
devices for various applications in wearable and other futur-
istic technologies, ranging from robotic skin, biometric devi-
ces, the human-machine interface, and energy devices, to soft
electronics and optoelectronic devices.[5] The development of
flexible, lightweight, low-power and inexpensive deformable
electronics is urgently needed to realize these applications.
The design and fabrication of these devices in their soft form
will make the next generation of electronics possible in
terms of flexibility, stretchability, foldability, wearability, and
implantability. Technically, imparting stretchability to rigid
EC devices is more challenging than attaining flexibility.[6]
By imparting flexibility, stretchability and foldability, diverse
wearable EC applications can be realized such as adaptive
camouflage, biomimicry, wearable displays, and fashion.[7]
Notably, fabrics integrated with EC function could revolu-
Energy Technol. 2018, 6, 33 – 45 T 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
performance is discussed, from flexible to stretchable and
the foldable device being the latest trend in deformable elec-
tronics. Next, we address the pertinent challenges often en-
countered in the fabrication of flexible EC devices and out-
line the adopted strategies from the literature to this point.
Finally, the concept of the multifunctional EC device is dis-
cussed for achieving versatile emerging applications. We en-
vision that this review will shed light on the properties of
flexible ECs and shape the new milestones to be set for real-
izing a more versatile multifunctional EC device.
tionize fashion with infinite designs that could set a pave the
way towards wearable displays or sensors, human advertising,
or expressive garments.
EC materials hold potential in flexible displays due to
their low power consumption and compatibility with flexible
substrates.[8] Typically, EC displays fulfil the prerequisites of
paper-based media such as switching speed, readability,
power consumption, and stability.[4, 9] EC displays offer reada-
bility under wide illumination angles, high angle-independent
contrast, highly diffusive reflective properties, high degree of
viewing angles, and good coloration memory effects.[4, 9] EC
has also positioned itself as one of the attractive candidates
for the next-generation displays, owing to features such as
excellent ink-on-paper optical qualities, fast switching times,
low-power consumption, the ability to use thin and flexible
materials.[4, 10–13] Such displays are expected to address diverse
needs such as advertising, information signage, point-of-sale
[a] A. L.-S. Eh, A. W. M. Tan, X. Cheng, Prof. P. S. Lee
School of Materials Science and Engineering
Nanyang Technological University
50 Nanyang Avenue, Singapore 639798 (Singapore)
E-mail: pslee@ntu.edu.sg
[b] Prof. S. Magdassi
Institute of Chemistry and the Center for Nanoscience and Nanotechnology
The Hebrew University of Jerusalem, Jerusalem 91904 (Israel)
[c] A. L.-S. Eh, A. W. M. Tan, X. Cheng, Prof. S. Magdassi, Prof. P. S. Lee
Singapore-HUJ Alliance for Research and Enterprise (SHARE)
Nanomaterials for Energy and Energy Water Nexus (NEW)
Campus for Research Excellence and Technological Enterprise (CREATE), Sin-
gapore 138602 (Singapore)
This publication is part of a special collection on the work of the
“CREATE Research Campus”. To view the collection’s Table of Contents,
please visit http://bit.ly/CREATE-10.
33
Figure 1. Progress of EC devices from rigid to deformable electronics.
systems, switchable displays, e-readers, and mobile communi-
cations.[4]
In brief, a typical flexible EC device consists of a soft sub-
strate, transparent conductive electrode (TCE), EC layer, ion
storage layer, and electrolyte. The performances of conven-
tional EC devices are evaluated based on the coloration effi-
ciency (CE), optical modulation, switching speed, lifetime,
and cycling stability.[14] CE is defined as the ratio between
optical modulation and the consumed charge density. The
higher the CE, the larger optical modulation that is achieved
with minimal charge consumption. Switching speed is defined
as the time needed for the EC system to reach 90 % of its
full modulation between the bleached and colored states. For
Pooi See Lee is a full Professor in the
School of Materials Science and Engineer-
ing, Nanyang Technological University
(NTU), Singapore. She obtained her
B.Sc. (Hons) and Ph.D. at the National
University of Singapore. Her research
work focuses on the theme of electro-
chemical- and electrical-inspired devices
based on nanostructures and nanocompo-
sites, and the human machine interface.
Her works have demonstrated applica-
tions in electrochromics, energy storage,
stretchable devices, electrical memory devices, light-emission devices,
nanowire transistors, photodetectors, and sensors. She currently serves
as the Associate Dean in the College of Engineering, NTU.
Energy Technol. 2018, 6, 33 – 45 T 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
long-term cycling stability, the deterioration in EC devices
performance should be minimized.
This Review focuses on the prerequisites of flexible EC
devices that are required for the substrate, TCE, EC layers,
and ion storage layer, as well as the electrolytes. Next, we
review the progress made to this point on EC device per-
formances that are aimed for flexible, stretchable, and folda-
ble devices (Figure 1). This Review also illustrates the cur-
rent challenges in the fabrication of flexible EC devices, as
well as delineates the proposed solutions to bottleneck
issues. In the final part of the Review, the future prospects of
the multifunctional EC devices are discussed.
2. Prerequisites
2.1. Substrate
An ideal flexible TCE substrate for EC applications should
simultaneously possess high optical transparency and electri-
cal conductivity, good chemical durability, excellent thermal
stability, a low coefficient of thermal expansion, high trans-
parency, and mechanically durability. Conventional flexible
TCE substrates have been dominated by plastics such as
poly(ethylene), poly(ethylene terephthalate) (PET), polyeth-
yleneimine (PEI), polyimide (PI), polypropylene (PP), poly-
carbonate (PC), polyurethane (PU), and poly(dimethylsil-
oxane) (PDMS).[15–17] Recently, nanocellulose-based sub-
strates have stirred excitement in anticipation of sustainable
electronics. Its availability, recyclability, biocompatibility, and
degradability have been well-received. We have recently
demonstrated the use of nanocellulose substrates for electro-
34
chromics.[16, 17] Compared to inert plastic substrates, cellulose
fibers can provide strong hydrogen bonding with the active
material to ensure mechanical reliability under repeated
bending cycles.[18] Paper is considered the most extensively
used and cheapest soft substrate material in our everyday
life. The major advantage of the paper substrate is that it
does not deform as much as plastics upon heating.[19] Nano-
cellulose paper has good optical transparency, excellent ther-
mal stability (> 180 8C), chemical durability, and a low ther-
mal expansion coefficient of 5–10 ppm K@1 (close to metals
and glass), which ensures an excellent processability and
compatibility with a wide range of processing tech-
niques.[16, 19–20] On the contrary, poly(ethylene terephthalate),
polypropylene, and poly(ethylene) have higher thermal ex-
pansion coefficients between 60 and 200 ppm K@1. Moreover,
poly(ethylene) and polypropylene have low melting tempera-
tures of 105–130 8C and 130–170 8C, respectively, whereas the
glass transition temperature of poly(ethylene terephthalate)
is approximately 70 8C.[19] The bending radius of transparent
conducting oxides on plastics is limited (typically & 5 mm) if
the conductivity and transparency are to be maintained.[21–23]
These constraints are posing challenges in realizing flexible
and deformable electrochromics, which has attracted atten-
tion towards emerging flexible transparent conductors, for
which some of the approaches will be illustrated below.

2.2. Transparent Conductive Electrode (TCE)

Low resistivity, high transparency, good chemical and elec-
trochemical stability, wide potential window, high Figure of
Merit (FoM, the ratio of electrical conductivity sCV and opti-
cal conductivity sOP, sCV/sOP), and high endurance to physical
deformation (bending, stretching, and folding) are some of
the important features that influence the performance of the
TCE in flexible EC devices.[16, 24] The most extensively used
TCEs are indium tin oxide (ITO) and fluorine-doped tin
oxide (FTO) due to their low resistivity and high transparen-
cy. However, their brittle nature makes them unsuitable for
flexible device applications, and the high costs complicate
the economic commercialization of the EC devices.[25] To ac-
complish versatile emerging applications, there are various
ongoing efforts to impart attractive features such as mechani-
cal flexibility, stretchability, and foldability properties in EC
devices. This can be achieved by replacing the rigid ITO or
FTO glass with flexible TCEs such as ITO or FTO on PET
and silver (Ag) rings/grids on PET substrates. A variety of
flexible TCEs have been investigated, including conducting
polymers (Figure 2),[24, 26] carbon nanotubes,[27] graphene,[15, 28]
metal nanowires,[6, 15–17, 29] and metal grids.[30, 31]
Graphene is a viable candidate for flexible TCEs due to its
high electrical conductivity, good chemical stability, good op-
tical properties, and good flexibility.[15, 28] Polat et al. demon-
strated reflective/transmissive multipixel EC devices on
transparent PVC substrates using multilayer graphene as
both the EC material and electrode, achieving up to 55 % of
optical modulation in the visible and near-infrared range.[32]
Hwang et al. fabricated electrolyte-free flexible EC cells on
Figure 2. Intrinsically stretchable EC film based on PEDOT/PU. (a) Molecular
structures of PEDOT and digital images of the stretched EC film of the
PEDOT/PU composite in reduced and oxidized states. (b) Configuration of
EC film/hydrogel hybrid device. (c) EC film/hydrogel wrapped around a glass
rod. (d) Color change of the hybrid device upon placing on a human finger.
Reproduced with permission.[26] Copyright 2017, American Chemical Society.
ITO/PET using conductive graphene quantum dots (anions)
where the methyl viologen electrochromes (cations) interact
with the graphene quantum dots through electrostatic inter-
actions, p–p stacking interactions, and cation–p electron in-
teractions.[33] The conductive graphene quantum dots provid-
ed efficient electron transport, leading to better operational
stability even under mechanical stress.
Percolating nanowire networks were reported to exhibit
good tolerance towards stretching before the networks rup-
ture into patches due to intersliding of entangled silver nano-
wires (AgNWs).[6] To overcome this issue, we have fabricated
AgNWs/PDMS elastic conductors using lithographic filtra-
tion, which enabled patterning.[6] These unique embedded
structures have good stretchability without the issue of de-
lamination during repeated stretching and improved durabili-
ty against mechanical scratching. Metal grids or connected
rings on plastics can be formed using the well-investigated
coffee-ring effect coupled with a room-temperature chemical
sintering approach.[34–36]

Energy Technol. 2018, 6, 33 – 45 T 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim 35
2.3. Electrochromic layer and ion storage layer
The basic prerequisite of an EC material is the reversible
electrochemical redox behavior, with the ability to modulate
the optical properties (absorption, transmittance, and reflec-
tance) upon application of electrical bias.[37–43] In general, EC
materials can be classified into three different categories.
The first category comprises transition metal oxides, for ex-
ample, the most commonly adopted are tungsten oxide
(WO3),[37, 40] nickel oxide (NiO),[41] vanadium pentoxide
(V2O5),[44, 45] and the polymers, such as polyaniline,[46] 3,4-pro-
pylendioxythiophene (ProDOT),[11–13] and poly(3,4-ethylene-
dioxythiophene):poly(styrenesulfonate) (PEDOT:PSS).[47] .
Inorganic EC materials are rich in their structure–property
diversification and significant progress has been made in tai-
loring them into various nanostructures such as nanoparti-
cles,[48–50] nanorods,[51, 52] and nanosheets.[53] In our recent
Review, the current state-of-the-art strategies of nanostruc-
tured inorganic EC materials are discussed in detail for the
recent developments in zero-dimensional (0D), one-dimen-
sional (1D), two-dimensional (2D), three-dimensional (3D)
hierarchical nanostructured, and ordered macroporous EC
materials.[14] Polymeric electrochromics are attractive for EC
applications as they offer fast response time, high contrast
ratio, high coloration efficiency, mechanical flexibility, long-
term redox stability, solution processability, and a range of
colors spanning the full visible spectrum, along with color
tunability through structural control.[12, 13] Color switching
occurs through intercalation or de-intercalation of ions (H + ,
Na + , and Li + ) and electron injection or extraction with the
exertion of electrical bias.[54] Transition metal oxides and
polymeric electrochromics for EC applications have been re-
viewed extensively in earlier Reviews.[37, 38, 54–60]
Besides the much-celebrated smart windows application,
the EC display has also garnered tremendous attention in
recent years as it offers multicolor capability and fast switch-
ing times. Hereby, the progression from rigid EC displays to
flexible displays is summarized. Berridge et al. reported the
fast switching of dual color polythiophene, which is attribut-
ed to the bent conformation of the non-aromatic dithiin rings
that inhibit the strong p-interactions between polymer
chains.[61] This effectively promotes anion diffusion through
the polymer film during doping and dedoping. Bar et al.
demonstrated a multicolor EC using viologen derivatives, of-
fering red, green, and blue (RGB) colors upon electrochemi-
cal reduction.[62] Achieving fast switching kinetics is of
utmost importance in realizing ECs for display applications.
Jain et al. achieved millisecond switching in ionic self-assem-
bled solid-state EC polymer devices using a self-assembly
technique that allowed the fabrication of thin, homogeneous
EC films with large diffusion coefficient.[63] Xu et al. pre-
pared plasmonic Au and Al nanoslit arrays in which the EC
polymers were coated conformally to achieve high contrast
and fast switching due to the fast charge transport in the
ultra-thin film.[64]
The second category consists of rare-earth metals and mix-
tures of transition metals/rare-earth metals with magnesium,
Energy Technol. 2018, 6, 33 – 45 T 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
which involves hydrogen-induced phase transitions to realize
variable reflectivity.[65–69] This switchable mirror switches be-
tween transparent and reflective states through hydrogena-
tion and de-hydrogenation of the films. The third category
comprises reversible electrodeposition and dissolution of ma-
terials, for example metals (Bi, Ag, Cu, Al, Ni, and
Pb)[43, 70–79] and viologens[80–83] onto the TCE, hence changing
their optical properties. We have recently demonstrated tri-
state electrochromics with a Cu-based electrolyte in which
the transparent, colored, and reflective states can be activat-
ed by modulated potential.[43]
Beyond the primary EC layer, the secondary EC layer is
equally important to ensure enhanced stability of the EC
device. This ion storage layer acts as the complementary
counter electrode, preferably to remain optically passive or
add complementary coloration during the intercalation and
deintercalation process.[84] Ma et al. reported a flexible EC
device with poly(3,4-(2,2-dimethylpropylenedioxy)thiophene)
as the EC layer and a composite film of vanadium oxide/tita-
nium oxide as the ion storage layer.[85] The flexible device ex-
hibited long cycling stability of over 40 000 cycles with a fast
switching speed of & 0.5 s.
There are various ways to coat the EC layer and ion stor-
age layer such as inkjet-printing,[31, 41, 50] spray-coating,[11–13]
electrochemical polymerization,[86] electrochemical deposi-
tion,[6, 87, 88] spin-coating,[89] slot–die coating,[90] roll coat-
ing,[32, 91, 92] screen printing,[93] or layer-by-layer self-assembly,[94]
as well as hydrothermal,[51, 52] solvothermal,[95] and solution-cast-
ing polymerization.[96] Our group has reviewed the recent prog-
ress in EC fabrication using solution-processible techniques.[4]
2.4. Electrolyte
In EC applications, the electrolyte is used as the ionic con-
ductor between the two EC-coated electrodes. The electro-
lyte separates both cathodes and anodes to avoid direct elec-
trical contact, but permits mutual ionic exchanges. The fol-
lowing section discusses the prerequisites and advances on
polymer electrolytes (PEs), the single layer approach, and
solid electrolytes for EC applications.
2.4.1. Polymer electrolyte
Liquid electrolytes are known to possess high ionic conduc-
tivity but face several drawbacks, for instance low electro-
chemical stability, hydrostatic pressure concerns, possible
electrolyte leakage, and sealing issues that render them prac-
tically unsafe for large-scale processes.[97] Compared to liquid
electrolytes, PEs offer good chemical and electrochemical
stability, a wider potential window, and good separator func-
tionality.[39, 42] PEs incorporating ionic liquids are beneficial in
EC devices as they offer high ionic conductivity, low viscosi-
ty, and a wider electrochemical window.[39, 42, 90] The key chal-
lenges in formulating the ideal PE for EC applications are
the preservation of the high ionic conductivity, high optical
transparency, high stability, good chemical and electrochemi-
cal stabilities, wide potential window, wide range of working
36

Figure 3. Important considerations in the synthesis of versatile PEs. Reproduced with per-
[44]
mission. Copyright 2013, Wiley-VCH.
temperatures, while retaining the ease of processing with
good mechanical strength and robustness (Figure 3).[39, 42]
Tailoring the ideal PE is about finding the right combina-
tion of both chemical and physical properties. A brief sum-
mary of the requirements of PEs in EC applications is de-
scribed below:[39, 42]
Transference number: The transference number analysis of
Li + ions characterizes the dissolution behavior of Li salt in
the electrolytes.
High ionic conductivity: To facilitate ion transport, PEs
should have high ionic conductivity and remain electronically
insulating at the same time. Higher ionic conductivity facili-
tates faster coloration and bleaching of the EC states.
Functional separator: PE acts as a separator by providing
physical separation between the anode and cathode, and pro-
viding good adhesion to the adjoining EC layers, besides
serving as a reservoir of anions and cations to balance the
redox reactions.
Stability (chemical and electrochemical stability, thermal
stability, mechanical stability): PEs should be stable against
electrical, thermal, and mechanical stress.
Ease of processing: The facile processing of a PE is attrib-
uted to its flexible film-forming ability with controllable
thickness.
Wide range of operating temperatures: PEs should be able
to work over wide temperature range.
High transparency: Highly transparent PEs maximize the
transmittance of the EC device during the bleached state.
Low volatility: PEs must not be volatile to ensure durabili-
ty of the EC device as minor seepage will have adverse
effect of the EC performance.
Energy Technol. 2018, 6, 33 – 45 T 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Inexpensive and environmental neutrality: Low-
cost, environmental friendly PEs are highly desira-
ble for practical EC applications.
Recently, stretchable, solid PEs have attracted
immense attention as they offer enhanced safety,
thin-film manufacturability, and mechanical and
electrochemical stability. Kelly et al. conducted in-
vestigations on the effects of tensile strain on the
ionic conductivity of a stretchable polymer electro-
lyte based on polyethylene oxide (PEO) by in situ
impedance spectroscopy.[98] Both in-plane and
through-plane ionic conductivities showed a steady
and linear increase during the axial stretching of
the PE, which can be attributed to the disentangle-
ment of polymer chains due to the reduction of the
degree of tortuosity in the ion transport path. Pu-
thirath et al. demonstrated a flexible solid PE
based on PEO–PDMS which was mechanically
robust and flexible with a YoungQs modulus of ap-
proximately 1 MPa and transparency of 85 %.[99] In
their work, a polymer blend of high ion conductivi-
ty was realized through the addition of a polymer
of lower glass transition temperature, which result-
ed in polymer chain relaxation and improved ion
transport behavior. Whitten et al. reported on me-
chanically robust poly(methyl methacrylate)
(PMMA) ionogels with elasticity of 480 % strain, breaking
strength of 3.2 MPa, and tear energy as high as 2.8 kJ m@2 for
stretchable electronics applications.[100] In a separate work,
we have demonstrated the extremely stretchable alternating-
current electroluminescent (ACEL) devices employing a PE
as the ionic conductor.[29] This highly transparent, solid
PMMA-based electrolyte possessed excellent mechanical sta-
bility, which allowed it to retain its low resistance after being
repetitively stretched to 700 % for 1000 cycles.
2.4.2. Single layer approach
The single layer approach is a strategy of combining the EC
polymer with the electrolyte to simplify EC device configura-
tion.[101] The EC device configuration is rather simple, as it
only requires an EC electrolyte layer and two electrodes.
The aim is to optimize the manufacturing process through
the reduction of the number of coating steps, prevent leakage
of the electrolyte, reduce the waste of materials, and increase
device stability.[101] MoonQs group used EC ion gels for flexi-
ble displays on ITO/PET by adding an EC redox molecule
(methyl viologen) in the formulation of the ion gels.[102–104]
These solid-state ion gels possessed high ionic conductivity,
flexibility, and low volatility, and could be solution-processi-
ble. The well-tailored electrolyte also composed of 1-ethyl-3-
methylimidazolium bis(trifluoromethylsulfonyl)imide ([EMI]
[TFSI]) ionic liquid and block copolymer PS-b-PMMA-b-
PSS. The device showed excellent coloration efficiency of
105 cm2 C@1, good operational stability over 24 hours in
air, and a low power consumption of approximately
9 mW mm@2.[103]
37
2.4.3. Solid electrolyte
A semi-solid electrolyte is an attractive electrolyte candidate
for EC devices due to its high ionic conductivity. However,
the possible issue of electrolyte leakage would affect the du-
rability and lifespan of EC devices. It was postulated that the
solid electrolyte is the “holy grail” of tailoring the ideal elec-
trolyte for EC devices. The amorphous tantalum pentoxide
(Ta2O5) is a potential solid electrolyte candidate due to its
high proton conductivity. Its ability for reversible ion inser-
tion provides good cycling stability during the lithiation and
de-lithiation process of a WO3 EC device.[105] When tantalum
oxide is deposited in a thin layer, it provides good optical
transparency, and at the same time provides high ionic con-
ductivity that leads to fast switching. In addition, Ta2O5 is
known to be stable under a wide range of environmental and
chemical conditions. In view of large-scale production, Ta2O5
can be deposited by RF sputtering or wet synthesis.[106, 107]
Jensen et al. demonstrated a printable, cross-linked, solid
electrolyte in flexible EC display devices that were driven by
polymer solar cells. The flexible EC display devices were fab-
ricated using roll-coating onto ITO/PET and switched in less
than 10 s between a magenta state and bleached state with
low current density and 58 % transmittance contrast at the
visible wavelength of 550 nm.[91] The EC polymers were
crosslinked with the electrolyte matrix to increase the elec-
trochemical stability of the EC devices. The electrolyte solu-
tion was a mixture of PMMA, tetrabutylammonium-hexa-
fluorophosphate, and propylene carbonate with a UV cura-
ble binder mixture composed of EbecrylU 150, EbecrylU 116,
AdditolU BCPK, and Zonyl FSO.
In the glass industry, poly(vinyl butyral) (PVB) has been
used for laminated safety glass for about 70 years.[108, 109] PVB
offers unique features for EC applications such as excellent
adhesion to glass, high transparency, excellent toughness and
flexibility, and high impact strength. PVB allows good lami-
nation between the TCEs to produce a robust, solid-state EC
device. Hence, PVB has been used as a matrix to host the
electrolyte. The ionic conductivity of this ionic-conducting
PVB electrolyte ranges from approximately 10@5 to
10@7 S cm@1, which is within acceptable limits for typical EC
devices.[108, 110] Nevertheless, it is still a challenge to realize a
stable and flexible EC due to the limited availability of flexi-
ble polymeric electrolytes with high ionic conductivity.
3. Flexible EC Performance
The development of soft electronics, robotics, and wearable
technologies has catalyzed the development of EC devices in
different form factors.[6, 16, 17, 30] A series of flexible EC tech-
nologies has been developed to cater for diverse applications.
For example, Xiong et al. realized flexible electronic paper in
full color using a combination of conjugated polymers and
ultrathin nanostructured plasmonic metasurfaces which deliv-
ered switching time reduction (millisecond regime), good
contrast (30–50 %), and ultralow power consumption (<
0.5 mW cm@2).[111] These plasmonic nanostructures provided
Energy Technol. 2018, 6, 33 – 45 T 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
reflective colors that can be electrically modulated and al-
lowed the generation of a color palette by varying the alumi-
na thickness. The alumina layer plays the role of tuning the
reflective color through Fabry–P8rot interference. For this
part of the Review, we will capture the recent progress made
on flexible EC devices, including the efforts to push EC devi-
ces from flexible to stretchable and finally foldable.
3.1. Flexible EC devices
Although conventional rigid EC devices have achieved re-
markable cycling stability, which paves the technology to the
route of commercialization, the migration from rigid EC de-
vices to flexible devices would first require a change in the
substrate from the conventional ITO/FTO glass to other
forms of flexible TCEs.[112] One of the most popular choices
is the ITO/PET substrate, as PET is highly transparent and
flexible. Liang et al. demonstrated the use of ITO/PET sub-
strates for the construction of flexible EC devices with ultra-
thin WO3·2 H2O nanosheets as the active EC layer.[53] The
nanostructured WO3 improved the optical modulation with
48 % contrast, and, simultaneously improved the adhesion of
the EC layer to the plastic substrate. During the cycling test,
the device remained stable for the first 400 cycles before
showing signs of degradation under constant bend state.
Alternative substrates such as Ag/PET are also adopted as
TCEs for flexible EC applications. We have reported the
self-assembled Ag grids on PET as a flexible TCE for EC ap-
plications.[31] WO3 nanoparticles were inkjet-printed onto the
Ag conductive grid substrates, which enabled EC patterning
to be accomplished. The printed samples were tested in a 3-
electrode electrochemical cell configuration to obtain an op-
tical modulation of 72 % with 15 printed layers of WO3 nano-
particles. The EC TCE sustained 10 bending cycles at a bend-
ing angle of 1808 without substantial optical modulation
decay.[31]
Though the inferior mechanical properties are the
AchillesQ heel of ITO- or FTO-based TCEs, the vulnerabili-
ties of Ag-based TCEs for EC application attributed to their
electrochemical instabilities cannot be ignored. This could be
detrimental for the cycling stability as evident in a series of
studies conducted.[31, 113, 114] To improve the cycling stability in
both electrochemical and mechanical aspects, we have pro-
posed the incorporation of a passivation layer to encapsulate
the Ag grid and enhance the electrochemical stability.[30] PE-
DOT:PSS was spin-coated onto the self-assembled Ag grid–
PET substrates, leading to the formation of Ag grid/PE-
DOT:PSS film, followed by electrodeposition of nanostruc-
tured WO3. The electrode was subjected to 1200 cycles of
compressive bending with only 7.5 % optical modulation deg-
radation (Figure 4). Improved electrochemical cycling stabili-
ty was also demonstrated as the electrode was reported to
sustain 1000 cycles without significant change in its optical
modulation.[30]
38
Figure 4. (a–d) The transmittance and optical modulations of WO3 on the Ag grid/PEDOT:PSS film in both bleached and colored states under repetitive com-
pressive bending (a, b) or tensile bending (c, d) with a curvature radius of 20 mm. Reproduced with permission.[32] Copyright 2016, Wiley-VCH.
3.2. Stretchable EC device
The sophisticated and futuristic soft robotics in conjunction
with complex ergonomics considerations in wearable technol-
ogies have motivated researchers to venture and integrate
stretchability into EC applications.[115] The realm of stretcha-
ble devices is enabled by the development of incorporating
metallic nanostructures into elastomeric substrates such as
PDMS. These intrinsic stretchable TCEs encounter a signifi-
cant challenge to balance the conductivity, optical transpar-
ency, and mechanical stretchability. We have recently provid-
ed a Review and analyses on the development of stretchable
transparent conductors for energy and electronic devices.[5]
Our initial efforts on stretchable electrochromics started
with the use of the embedded structures of the AgNWs/
PDMS electrodes to ensure durability and robustness against
adhesive forces, surface scratching, and repeated stretching.[6]
The electrodeposited WO3 microstructures retained their
structural integrities upon stretching due to the non-continu-
ous film morphology, which was resistant towards stretching.
This mechanically robust EC device exhibited fast switching
speed (coloration time of 1 s and bleaching time of 4 s) while
retaining 81 % of the initial contrast after cycling stability for
100 cycles in the relaxed state (Figure 5). To demonstrate its
compatibility for wearable applications, the device was also
transferred to textile-based substrates for testing.
Kai et al. demonstrated stretchable EC films of a uniform
composite of poly(3,4-ethylenedioxythiophene):p-toluene
Energy Technol. 2018, 6, 33 – 45 T 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
sulfonic acid (PEDOT:PTS) and PEDOT/PU, and its integra-
tion with a hydrogel as a free-standing, stretchable EC dis-
play.[26] The PEDOT/PU composite film was prepared by
spin-coating a solution containing the EDOT monomer and
polyurethane (PU), followed by oxidative polymerization
using iron(III) tosylate at elevated temperature. PU is an
elastic polymer with excellent stretchability that can be used
for intrinsically stretchable devices. The reduced form of
PEDOT exhibits a deep blue color due to visible light ab-
sorption that accompanies the p–p* transition, whereas the
oxidized form is pale blue because of the depletion of low-
energy p–p* absorption bands. The double-network hydrogel
is a class of hydrogels that is made of two interpenetrating
cross-linked polymer networks, and it is mechanically tough-
er and more stretchable than conventional hydrogels. The
double-network hydrogel consisted of poly(acrylamide)
cross-linked with N,N’-methylenebis(acrylamide) and gellan
gum cross-linked with Ca2 + , and this gel functioned as a
stretchable electrolyte reservoir. The robust EC device was
stretchable and could be wrapped around a glass rod or
mounted on a human finger.
3.3. Foldable EC device
To realize foldable EC devices, we reported the preparation
of nanocellulose-based transparent conductors (or nanopaper
electrodes) using the approach of nanocellulose transfer to
39
 form an adhering layer of AgNWs to the transparent nano-
cellulose substrates. The nanopaper electrode can also be
crumpled with minimal loss in conductivity. The WO3 layer
was subsequently electrodeposited onto the AgNWs, forming
the EC electrode.[16] 50 cycles of folding test on the foldable
EC electrode were realized, and beyond 50 folding cycles
some delamination was observed (Figure 6). The nanopaper
electrode achieved optical modulation of 41 % and surpassed
500 cycles of EC testing without significant change in optical
modulation.
Li et al. realized a lightweight, bendable, and foldable EC
film that showed good optical contrast, a high coloration effi-
ciency of 118.1 cm2 C@1, and good electrochemical stability
for 100 cycles, and it maintained structural stability even
after 500 bending or 100 folding cycles.[116] This film was fab-
ricated by spray-coating bilayer nanowire networks of
AgNWs and W18O49 onto the PET substrates. The alginic
acid/poly(dopamine) complex was used as a binder to im-
prove the interfacial stability with the PEDOT:PSS layer as
charge-balancing layer to prevent electrochemical corrosion
of AgNWs.

4. Challenges and Possible Solutions

Figure 5. (a) Schematic diagram of the stretchable EC device. (b, c) Stretcha-
ble EC device in the twisted and crumpled states. (d, e) Patterned EC device
in colored and bleached states at 0 and 50 % strain. Reproduced with permis-
sion.[6] Copyright 2013, American Chemical Society.
4.1. Challenges to electrode stability
4.1.1. Alternative solutions to thermal annealing of metal-based
TCE
One of the key challenges in flexible EC devices is the fabri-
cation of stable electrodes. A typical issue is the formation of

Figure 6. Nanopaper electrode undergoing foldability test. a) Schematic diagram for the folding method; FESEM images of the folded AgNWs nanopaper,
b) @1808 and c) + 1808, d) sheet resistance versus cycling with 100 cycles to @1808 and + 1808 conducted sequentially; digital images of the foldability test of
AgNWs nanopaper connected in a circuit with light-emitting diode (LED) bulbs e) before crumpling and f) after crumpling. Reproduced with permission.[17]
Copyright 2015, Wiley-VCH.

Energy Technol. 2018, 6, 33 – 45 T 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim 40
cracks upon sintering the printed nanoparticle inks, which
can be detrimental to the conductivity.[19] This is caused by a
large volume reduction upon removing the organic surfac-
tants that leads to a denser structure. Allen et al. applied
electrical sintering to reduce the volume resistivity of the Ag
nanoparticles on photopaper to 2.7 mW cm@1 within a
minute.[117] Kim et al. used a xenon flash lamp to sinter
copper nanoparticles to form a micrometer thick film and ac-
complished a volume resistivity of 5 mW.[118] The short sinter-
ing time overcame the issues of oxidation of the copper
nanoparticles in ambient environment and prevented the de-
formation of the plastic substrate. The Magdassi group intro-
duced a room-temperature chemical sintering approach to
deliver metal grids or interconnected metallic rings on plas-
tics using the coffee ring effect.[34–36] The inkjet-printed TCEs
made up of transparent Ag rings have a high transparency of
95 % and resistivity of 4 : 0.5 W/&.[35]
4.1.2. Blooming effect
Jensen et al. addressed the issue of sluggish kinetics and in-
homogeneous switching of the flexo-printed Ag hexagonal
grid-based EC devices, which caused a blooming effect
during coloration.[89] This was caused by the variation in sur-
face resistance, resulting in faster switching response of areas
that were in close proximity to the Ag grid lines. To over-
come this issue, a conductive PEDOT:PSS layer was coated
onto the Ag grids to homogenize the electric field distribu-
tion in the EC devices, thereby leading to prevention of the
blooming effect and homogeneous coloration.
4.1.3. Passivation layer
For metal-based TCEs, it is imperative to have a passivation
layer on top of the metals to prevent metal oxidation and
corrosion. CuiQs group addressed this issue by encapsulating
large-area, monolayer graphene films on Ag and Cu nano-
wire-based TCEs using roll-to-roll technique.[119] The encap-
sulation reduced the resistance of wire-to-wire junctions and
graphene grain boundaries while strengthening the adhesion
of nanowires to the plastic substrate, thereby resulting in a
low sheet resistance of approximately 8 W/&, high transmit-
tance of 94 %, resistance to corrosion, and mechanical flexi-
bility with outstanding mechanical cycling stability of
10 000 cycles. Yun et al. also addressed the susceptibility of
Ag nanowires to oxidation upon exposure to oxygen and
moisture by using reduced graphene oxide to overcome the
increase in the electrode resistivity.[18]
Ag-based TCEs are known to show poor cycling stability
for EC applications because they undergo oxidation and cor-
rosion at positive potentials in the electrolyte, which results
in the degradation in the EC performance.[31, 89] Our group
has successfully fabricated highly stable Ag grid/PEDOT:PSS
TCEs for bifunctional flexible EC supercapacitors.[30] The Ag
grid/PEDOT:PSS TCE has a high conductivity of 0.62 W/&
and transparency of over 70 %. The Ag grid-PET/PE-
DOT:PSS/WO3 hybrid film exhibited a high coloration effi-
Energy Technol. 2018, 6, 33 – 45 T 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
ciency of 124 cm2 C@1, large optical modulation of 81.9 %,
fast switching, good electrochemical cycling stability (retain-
ing 79.1 % of the initial optical modulation after 1000 cycles),
and outstanding mechanical flexibility (7.5 % of the optical
modulation decay after 1200 compressive bending cycles).
Considering the severe operating conditions (strong acid,
H2SO4, and the application of positive potential during
device cycling), the Ag grid/PEDOT:PSS TCE demonstrated
excellent cycling stability, which indicates that PEDOT:PSS
is an effective passivation layer by successfully protecting the
Ag grid during the electrochemical testing.
4.2. Adhesion of EC layer
EC devices usually experience a drastic decrease in colora-
tion efficiency with repeated mechanical bending due to the
poor adhesion of the EC layer onto the flexible substrate.[18]
The adhesion of the EC layer onto the electrode must be
strong to ensure that the EC layer does not delaminate from
the electrode, especially after long-term device cycling test.
In rigid EC devices, thermal treatment is the common prac-
tice to ensure good adhesion of the EC film to the electro-
des. Thermal treatment is usually avoided during the coating
of the EC layer onto flexible substrates, as these soft sub-
strates cannot undergo high-temperature treatment. Hence,
the fabrication of stable EC films without the need of ther-
mal annealing is highly desirable. Our group introduced
linear polyethylenimine (LPEI) to improve the interfacial in-
teraction between the ITO substrate and the vanadium oxide
film.[47] Film stabilization was achieved by hydrogen-bonding
and electrostatic interactions between the secondary amine
groups (LPEI) and the V = O groups (vanadium oxide frame-
work). The modified EC film showed good cycling stability
for 1500 cycles with retention of 63.3 % of the initial contrast.
The adhesion of the EC layer to the underlying substrates
could be enhanced by surface functionalization, which may
also be applicable to stretchable devices.[6, 45] Optimization of
the EC layer thickness can also improve the adhesion stabili-
ty.[6] For instance, denser WO3 layers provide better contrasts
but tend to be more rigid and prone to delamination upon
mechanical deformation. It was concluded that mechanical
stability against repetitive stretching can be improved by sur-
face functionalization and optimization of the EC layer
thickness.[6]
4.3. Electrolyte
In the EC device, the interface properties between the elec-
trolyte and the two electrodes played key roles in the overall
performance.[39, 42] Both the TCEs and EC layers must retain
good chemical stability upon contact with the PEs to ensure
no degradation in the EC performance in terms of optical
modulation, switching speed, and long-term cycling. For in-
stance, both the TCEs and EC layers should not dissolve or
delaminate when exposed to the PEs. Typically, the device is
sealed using epoxy sealant to avoid electrolyte leakage and
promote facile handling of the device.[39]
41
 In the EC devices that use solid-state electrolyte, electro- times of 6 s for coloration at an applied voltage of @3 V and
lyte cracking and formation of blisters during the processing 5 s for bleaching at an applied voltage of + 3 V; the devices
are major issues. The Sotzing group reported on the impor- also tolerated a bending radius of 7.5 cm. After 8000 cycles
tance of the addition of poly(ethylene glycol) dimethacrylate of coloration and bleaching, irregular stains were observed
to the gel electrolyte composition, which allowed the EC on the EC device during the bleached state, and a drop in
device to flex without cracking the gel electrolyte and to the initial current density was observed during coloration
extend the lifetime of the device.[8] Jensen et al. noted the and bleaching.
differences in surface energies between the EC layer and the Eventually, lifetime and durability are the critical aspects
electrolyte which caused mechanical stress, resulting in blis- that determine the successful commercialization of EC appli-
ters in the electrolyte layer.[90] By introducing a wetting layer cations. Granqvist and colleagues discussed how the shelf-life
of poly[9,9-bis(3’-(dimethylethylammoniumbromido)propyl)- of EC foil was tested, the deterioration in EC properties, and
2,7-fluorene]-alt-2,7-(9,9-dioctylfluorene) onto the primary techniques used to assess the EC degradation in their book
EC layer, this ensured good wettability of the electrolyte on chapter.[122] Durability testing and the accelerated weathering
the EC film prior to UV-crosslinking in the curing chamber. test are typical tests conducted to investigate the durability
of EC devices against UV irradiation, high temperature, and
humidity.[123, 124]
4.4. Addressing cycling stability
Coloration efficiency is one of the most crucial characteris-
tics for describing the performance of EC devices. Higher
5. Summary and Outlook
coloration efficiency is preferred as less charge or energy is We have discussed the prerequisites of the flexible electro-
needed to reach larger optical modulations. Higher ions in- chromic (EC) device components, followed by the recent ad-
sertion/extraction causes deformation of the crystal structure, vances of the flexible EC devices, highlighting the challenges
which in turn affects the electrochemical cycling stability. that are often encountered in the flexible EC, and we out-
Thus, a higher coloration efficiency is desirable to improve lined possible solutions to address these challenges.
the device stability for practical applications.[6] Increased ap- The prospects of flexible EC devices are further enriched
plied potentials resulted in faster switching speed but the op- with the advancements in various device architectures, proc-
erational stability of the EC devices was compromised.[90] essing techniques, and novel materials. EC device fabrication
Remmele et al. reported that asymmetric switching caused that incorporates other smart multifunctionalities, while re-
rapid device failure compared to symmetrically switched de- taining configurational integrity against mechanical deforma-
vices.[120] The EC device stability could be greatly improved tion, has been pursued recently. Yun et al. demonstrated a
using narrower potential windows and slower
device switching speed.
The presence of oxygen or moisture is another
pertinent issue that affects the device stability. This
can be overcome by having encapsulation or pro-
tective barrier foil to protect the EC device from
moisture or oxygen. The device fabrication can also
be conducted in an inert environment such as a
glove box or a clean room with low-humidity con-
trol measures. To enhance the operational stability,
Jensen et al. encapsulated the EC devices in
oxygen-protecting barrier foils. This extended the
operational device stability, with the device exhibit-
ing optical modulation of 16 % after 7500 double
potential steps.[90] The cause of the operational deg-
radation was attributed to the presence of oxygen
or moisture that reacted with the electrochemically
charged polymers. The unprotected devices were
susceptible to irreversible oxidation by oxygen in
the ambient environment. Tang et al. also ex-
plained that the degradation in their EC device
Figure 7. Demonstration of a photoresponsive EC supercapacitor device. (a) When inte-
performance was ascribed to the immobilized Li grated with solar cell, the device undergoes reversible photoresponsive coloration.
ions caused by the residual water molecules that (b) Demonstration of a solar-cell-integrated, photoresponsive, EC supercapacitor device
adsorbed onto the film during device fabrica- attached to a glass cylinder illuminated with a Xenon arc lamp. (c) The device can under-
go wide range of transmittance changes by varying Xenon-light intensity. (d) Demonstra-
tion.[121] Tang et al. fabricated all-solid-state mono-
tion of energy storage capability in which the EC supercapacitor can store the solar
lithic, flexible EC devices (24 cm X 18 cm) using energy, which is later used to power another photoresponsive, EC supercapacitor device.
magnetron sputter deposition with a good response Reproduced with permission.[18] Copyright 2017, Wiley-VCH.

Energy Technol. 2018, 6, 33 – 45 T 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim 42
photoresponsive smart EC supercapacitor based on a cellu-
lose-nanofiber/AgNW/reduced graphene oxide/WO3 elec-
trode that could undergo reversible coloration while simulta-
neously functioning as an energy-storage device (Figure 7).[18]
The EC supercapacitor exhibited a good coloration efficiency
(CE) of 64.8 cm2 C@1, specific capacitance of 406.0 F g@1,
energy/power densities of 40.6–47.8 Wh kg@1 and 6.8–
16.9 kW kg@1, with a long cycle life of 75.0 % and 94.1 % re-
tention of its CE and electrochemical performance over
10 000 charge–discharge cycles. The smart EC supercapacitor
was integrated with a solar sensor to enable photoresponsive
coloration, thereby enabling tunable energy saving capabili-
ties by heat control for insulation. A bio-inspired stretchable
electronic skin with tactile-sensing control by integrating a
stretchable pressure sensor and stretchable organic EC
device was demonstrated (Figure 8).[125] The highly sensitive
pressure sensor was fabricated using pyramidal-microstruc-
tured PDMS with a thin film of single-walled carbon nano-
tubes as transparent conducting electrode (TCE). The e-skin
was able to detect varying applied pressures by using real-
time visible color change using poly(3-hexylthiophene-2,5-
diyl) (P3HT) as EC layer due to its good stretchability.

Figure 8. (a) Illustration of chameleon-inspired e-skin concept. Bottom left: Structures of electrochromic polymer, poly(3-hexylthiophene-2,5-diyl, P3HT), in the
neutral and oxidized states. Bottom right: Schematic diagram of the circuit layout (ECD: EC device; PS: pressure sensor; SWNT: single-walled carbon nano-
tube). (b) The absorption spectra of the neutral and oxidized P3HT. (c) Clor switching behavior of the stretchable polymer-based EC device at 0 % strain. (d) Ab-
sorption spectra related to the various applied pressures. (e) Speed of color saturation for different pressures in which each pressure was applied until color
saturation. Reproduced with permission.[125] Copyright 2015, Nature Publishing Group.

Energy Technol. 2018, 6, 33 – 45 T 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim 43
 EC applications are likely to find promising prospects in
our sustainable future. Further efforts are required to ex-
plore versatile multifunctional and flexible EC devices with-
out affecting the EC performance. By imparting flexibility to
the EC devices, this paves the way for low-cost, lightweight,
energy-efficient EC devices as it removes the need for the
expensive, rigid conductive ITO or FTO glass substrates, and
it promotes the rapid progress of flexible EC devices for the
next generation of futuristic technologies.
Acknowledgements
This research was supported by the National Research Foun-
dation, the Prime MinisterQs Office, Singapore, under its
Campus for Research Excellence and Technological Enter-
prise (CREATE) program.
Conflict of interest
The authors declare no conflict of interest.
Keywords: electrochromic devices · flexible devices · smart
electronics · smart windows · wearable electronics
[1] http://www.gentex.com/aerospace/aerospace-overview, accessed 24
August 2017.
[2] https://en.wikipedia.org/wiki/Ferrari_575M_Maranello, accessed 27
August 2017.
[3] T. Bhuvana, B. Kim, X. Yang, H. Shin, E. Kim, Angew. Chem. Int.
Ed. 2013, 52, 1180 – 1184; Angew. Chem. 2013, 125, 1218 – 1222.
[4] P. S. Lee, G. F. Cai, A. L.-S. Eh, P. Darmawan, Nanomaterials for 2D
and 3D Printing (Eds.: S. Magdassi, A. Kamyshny), Wiley-VCH,
Weinheim, 2017, pp. 317 – 339.
[5] S. Park, K. Parida, P. S. Lee, Adv. Energy Mater. 2017, 1701369.
[6] C. Yan, W. Kang, J. Wang, M. Cui, X. Wang, C. Y. Foo, K. J. Chee,
P. S. Lee, ACS Nano 2014, 8, 316 – 322.
[7] M. T. Otley, M. A. Invernale, G. A. Sotzing, Electrochromic Materi-
als and Devices, Wiley-VCH, Weinheim, 2013, pp. 503 – 524.
[8] M. T. Otley, Y. Zhu, X. Zhang, M. Li, G. A. Sotzing, Adv. Mater.
2014, 26, 8004 – 8009.
[9] D. Corr, U. Bach, D. Fay, M. Kinsella, C. McAtamney, F. OQReilly,
S. N. Rao, N. Stobie, Solid State Ionics 2003, 165, 315 – 321.
[10] U. Bach, D. Corr, D. Lupo, F. Pichot, M. Ryan, Adv. Mater. 2002,
14, 845 – 848.
[11] C. M. Amb, P. M. Beaujuge, J. R. Reynolds, Adv. Mater. 2010, 22,
724 – 728.
[12] P. M. Beaujuge, C. M. Amb, J. R. Reynolds, Adv. Mater. 2010, 22,
5383 – 5387.
[13] P. M. Beaujuge, S. Ellinger, J. R. Reynolds, Nat. Mater. 2008, 7, 795 –
799.
[14] G. F. Cai, A. L.-S. Eh, L. Ji, P. S. Lee, Adv. Sustainable Syst.,
1700074, in press.
[15] H. Lee, M. Kim, I. Kim, H. Lee, Adv. Mater. 2016, 28, 4541 – 4548.
[16] W. Kang, C. Yan, C. Y. Foo, P. S. Lee, Adv. Funct. Mater. 2015, 25,
4203 – 4210.
[17] W. Kang, M. F. Lin, J. Chen, P. S. Lee, Small 2016, 12, 6370 – 6377.
[18] T. G. Yun, D. Kim, Y. H. Kim, M. Park, S. Hyun, S. M. Han, Adv.
Mater. 2017, 1606728.
[19] D. Tobjçrk, R. Osterbacka, Adv. Mater. 2011, 23, 1935 – 1961.
[20] Y. Fujisaki, H. Koga, Y. Nakajima, M. Nakata, H. Tsuji, T. Yama-
moto, T. Kurita, M. Nogi, N. Shimidzu, Adv. Funct. Mater. 2014, 24,
1657 – 1663.
Energy Technol. 2018, 6, 33 – 45 T 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
[21] H. Wang, S. Liao, X. Bai, Z. Liu, M. Fang, T. Liu, N. Wang, H. Wu,
ACS Appl. Mater. Interfaces 2016, 8, 32661 – 32666.
[22] J. Yun, Y. H. Park, T.-S. Bae, S. Lee, G.-H. Lee, ACS Appl. Mater.
Interfaces 2013, 5, 164 – 172.
[23] C.-C. Lee, P.-C. Huang, K.-S. Wang, Materials 2016, 9, 850.
[24] R. Singh, J. Tharion, S. Murugan, A. Kumar, ACS Appl. Mater. In-
terfaces 2017, 9, 19427 – 19435.
[25] K. Ellmer, Nat. Photonics 2012, 6, 809 – 817.
[26] H. Kai, W. Suda, Y. Ogawa, K. Nagamine, M. Nishizawa, ACS
Appl. Mater. Interfaces 2017, 9, 19513 – 19518.
[27] C. Feng, K. Liu, J.-S. Wu, L. Liu, J.-S. Cheng, Y. Zhang, Y. Sun, Q.
Li, S. Fan, K. Jiang, Adv. Funct. Mater. 2010, 20, 885 – 891.
[28] D. S. Choi, S. H. Han, H. Kim, S. H. Kang, Y. Kim, C. M. Yang,
T. Y. Kim, D. H. Yoon, W. S. Yang, Nanotechnology 2014, 25,
395702.
[29] J. Wang, C. Yan, G. F. Cai, M. Cui, A. L.-S. Eh, P. S. Lee, Adv.
Mater. 2016, 28, 4490 – 4496.
[30] G. F. Cai, P. Darmawan, M. Cui, J. Wang, J. Chen, S. Magdassi, P. S.
Lee, Adv. Energy Mater. 2016, 6, 1501882.
[31] M. Layani, P. Darmawan, W. L. Foo, L. Liu, A. Kamyshny, D. Man-
dler, S. Magdassi, P. S. Lee, Nanoscale 2014, 6, 4572 – 4576.
[32] E. O. Polat, O. Balci, C. Kocabas, Sci. Rep. 2014, 4, 6484.
[33] E. Hwang, S. Seo, S. Bak, H. Lee, M. Min, H. Lee, Adv. Mater.
2014, 26, 5129 – 5136.
[34] S. Magdassi, M. Grouchko, O. Berezin, A. Kamyshny, ACS Nano
2010, 4, 1943 – 1948.
[35] M. Layani, M. Gruchko, O. Milo, I. Balberg, D. Azulay, S. Magdassi,
ACS Nano 2009, 3, 3537 – 3542.
[36] M. Grouchko, A. Kamyshny, C. F. Mihailescu, D. F. Anghel, S. Mag-
dassi, ACS Nano 2011, 5, 3354 – 3359.
[37] C. G. Granqvist, Solar Energy Mater. Solar Cells 2000, 60, 201 – 262.
[38] C. G. Granqvist, E. AvendaÇo, A. Azens, Thin Solid Films 2003,
442, 201 – 211.
[39] V. K. Thakur, G. Ding, J. Ma, P. S. Lee, X. Lu, Adv. Mater. 2012, 24,
4071 – 4096.
[40] G. F. Cai, M. Cui, V. Kumar, P. Darmawan, J. Wang, X. Wang,
A. L.-S. Eh, K. Qian, P. S. Lee, Chem. Sci. 2016, 7, 1373 – 1382.
[41] G. F. Cai, P. Darmawan, M. Cui, J. Chen, X. Wang, A. L.-S. Eh, S.
Magdassi, P. S. Lee, Nanoscale 2016, 8, 348 – 357.
[42] A. L.-S. Eh, X. Lu, P. S. Lee, Electrochromic Materials and Devices
(Eds.: R. J. Mortimer, D. R. Rosseinsky, P. M. S. Monk), Wiley-
VCH, Weinheim, 2013, pp. 289 – 310.
[43] A. L.-S. Eh, M.-F. Lin, M. Cui, G. Cai, P. S. Lee, J. Mater. Chem. C
2017, 5, 6547 – 6554.
[44] W. B. Kang, C. Y. Yan, X. Wang, C. Y. Foo, A. W. M. Tan, K. J.
Chee, P. S. Lee, J. Mater. Chem. C 2014, 2, 4727.
[45] Y. Lu, L. Liu, W. Foo, S. Magdassi, D. Mandler, P. S. Lee, J. Mater.
Chem. C 2013, 1, 3651 – 3654.
[46] C. A. Nguyen, S. Xiong, J. Ma, X. Lu, P. S. Lee, Phys. Chem. Chem.
Phys. 2011, 13, 13319 – 13326.
[47] H. W. Heuer, R. Wehrmann, S. Kirchmeyer, Adv. Funct. Mater.
2002, 12, 89 – 94.
[48] Y.-Y. Song, Z.-D. Gao, J.-H. Wang, X.-H. Xia, R. Lynch, Adv.
Funct. Mater. 2011, 21, 1941 – 1946.
[49] S. H. Lee, R. Deshpande, P. A. Parilla, K. M. Jones, B. To, A. H.
Mahan, A. C. Dillon, Adv. Mater. 2006, 18, 763 – 766.
[50] C. Costa, C. Pinheiro, I. Henriques, C. A. T. Laia, ACS Appl. Mater.
Interfaces 2012, 4, 1330 – 1340.
[51] J. Wang, E. Khoo, P. S. Lee, J. Ma, J. Phys. Chem. C 2008, 112,
14306 – 14312.
[52] J. Wang, E. Khoo, P. S. Lee, J. Ma, J. Phys. Chem. C 2009, 113,
9655 – 9658.
[53] L. Liang, J. Zhang, Y. Zhou, J. Xie, X. Zhang, M. Guan, B. Pan, Y.
Xie, Sci. Rep. 2013, 3, 1936.
[54] R. J. Mortimer, Annu. Rev. Mater. Res. 2011, 41, 241 – 268.
[55] C. G. Granqvist, Thin Solid Films 2014, 564, 1 – 38.
[56] D. R. Rosseinsky, R. J. Mortimer, Adv. Mater. 2001, 13, 783 – 793.
[57] W. M. Kline, R. G. Lorenzini, G. A. Sotzing, Color. Technol. 2014,
130, 73 – 80.
[58] P. M. Beaujuge, J. R. Reynolds, Chem. Rev. 2010, 110, 268 – 320.
44
 [59] A. A. Argun, P.-H. Aubert, B. C. Thompson, I. Schwendeman, C. L.
Gaupp, J. Hwang, N. J. Pinto, D. B. Tanner, A. G. MacDiarmid, J. R.
Reynolds, Chem. Mater. 2004, 16, 4401 – 4412.
[60] C. M. Amb, A. L. Dyer, J. R. Reynolds, Chem. Mater. 2011, 23, 397 –
415.
[61] R. Berridge, S. P. Wright, P. J. Skabara, A. Dyer, T. Steckler, A. A.
Argun, J. R. Reynolds, R. W. Harrington, W. Clegg, J. Mater. Chem.
2007, 17, 225 – 231.
[62] G. Bar, N. Larina, L. Grinis, V. Lokshin, R. Gvishi, I. Kiryuschev,
A. Zaban, V. Khodorkovsky, Solar Energy Mater. Solar Cells 2012,
99, 123 – 128.
[63] V. Jain, H. M. Yochum, R. Montazami, J. R. Heflin, Appl. Phys.
Lett. 2008, 92, 033304.
[64] T. Xu, E. C. Walter, A. Agrawal, C. Bohn, J. Velmurugan, W. Zhu,
H. J. Lezec, A. A. Talin, Nat. Commun. 2016, 7, 10479.
[65] K. Tajima, H. Hotta, Y. Yamada, M. Okada, K. Yoshimura, Solar
Energy Mater. Solar Cells 2011, 95, 3370 – 3376.
[66] P. H. L. Molten, M. Kremers, R. Griessen, J. Electrochem. Soc. 1996,
143, 3348 – 3353.
[67] T. J. Richardson, J. L. Slack, B. Farangis, M. D. Rubin, Appl. Phys.
Lett. 2002, 80, 1349 – 1351.
[68] T. Kazuki, Y. Yasusei, O. Masahisa, Y. Kazuki, Appl. Phys. Express
2010, 3, 042201.
[69] T. J. Richardson, Solid State Ionics 2003, 165, 305 – 308.
[70] S. I. C. de Torresi, I. A. Carlos, J. Electroanal. Chem. 1996, 414, 11 –
16.
[71] B. M. Howard, J. P. Ziegler, Solar Energy Mater. Solar Cells 1995,
39, 309 – 316.
[72] J. P. Ziegler, Solar Energy Mater. Solar Cells 1999, 56, 477 – 493.
[73] J. P. Ziegler, B. M. Howard, Solar Energy Mater. Solar Cells 1995,
39, 317 – 331.
[74] S. Araki, K. Nakamura, K. Kobayashi, A. Tsuboi, N. Kobayashi,
Adv. Mater. 2012, 24, OP122 – OP126.
[75] C. Park, J. Na, M. Han, E. Kim, ACS Nano 2017, 11, 6977 – 6984.
[76] C. Park, S. Seo, H. Shin, B. D. Sarwade, J. Na, E. Kim, Chem. Sci.
2015, 6, 596 – 602.
[77] T.-Y. Kim, S. M. Cho, C. S. Ah, K.-S. Suh, H. Ryu, H. Y. Chu, J. Inf.
Disp. 2014, 15, 13 – 17.
[78] A. Tsuboi, K. Nakamura, N. Kobayashi, Adv. Mater. 2013, 25, 3197 –
3201.
[79] A. Tsuboi, K. Nakamura, N. Kobayashi, Chem. Mater. 2014, 26,
6477 – 6485.
[80] R. M. Elofson, R. L. Edsberg, Can. J. Chem. 1957, 35, 646 – 650.
[81] G. G. Barna, J. G. Fish, J. Electrochem. Soc. 1981, 128, 1290 – 1292.
[82] P. M. S. Monk, F. Delage, S. M. Costa Vieira, Electrochim. Acta
2001, 46, 2195 – 2202.
[83] P. M. S. Monk, C. Turner, S. P. Akhtar, Electrochim. Acta 1999, 44,
4817 – 4826.
[84] A. K. Bhosale, S. R. Kulal, V. M. Gurame, P. S. Patil, Bull. Mater.
Sci. 2015, 38, 483 – 491.
[85] C. Ma, M. Taya, C. Xu, Electrochim. Acta 2008, 54, 598 – 605.
[86] G. E. Gunbas, A. Durmus, L. Toppare, Adv. Mater. 2008, 20, 691 –
695.
[87] L. M. N. Assis, L. Ponez, A. Januszko, K. Grudzinski, A. Pawlicka,
Electrochim. Acta 2013, 111, 299 – 304.
[88] L. Liu, M. Layani, S. Yellinek, A. Kamyshny, H. Ling, P. S. Lee, S.
Magdassi, D. Mandler, J. Mater. Chem. A 2014, 2, 16224 – 16229.
[89] J. Jensen, M. Hçsel, I. Kim, J.-S. Yu, J. Jo, F. C. Krebs, Adv. Funct.
Mater. 2014, 24, 1228 – 1233.
[90] J. Jensen, F. C. Krebs, Adv. Mater. 2014, 26, 7231 – 7234.
[91] J. Jensen, H. F. Dam, J. R. Reynolds, A. L. Dyer, F. C. Krebs, J.
Polym. Sci. Part B 2012, 50, 536 – 545.
[92] R. R. Søndergaard, M. Hçsel, F. C. Krebs, J. Polym. Sci. Part B
2013, 51, 16 – 34.
[93] P. A. Ersman, J. Kawahara, M. Berggren, Org. Electron. 2013, 14,
3371 – 3378.
[94] M. Cui, W. S. Ng, X. Wang, P. Darmawan, P. S. Lee, Adv. Funct.
Mater. 2015, 25, 401 – 408.
Energy Technol. 2018, 6, 33 – 45 T 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
[95] G. F. Cai, X. Wang, M. Cui, P. Darmawan, J. Wang, A. L.-S. Eh, P. S.
Lee, Nano Energy 2015, 12, 258 – 267.
[96] J. Kim, J. You, B. Kim, T. Park, E. Kim, Adv. Mater. 2011, 23, 4168 –
4173.
[97] T.-Y. Wu, W.-B. Li, C.-W. Kuo, C.-F. Chou, J.-W. Liao, H.-R. Chen,
C.-G. Tseng, Int. J. Electrochem. Sci. 2013, 8, 10720 – 10732.
[98] T. Kelly, B. M. Ghadi, S. Berg, H. Ardebili, Sci. Rep. 2016, 6, 20128.
[99] A. B. Puthirath, S. Patra, S. Pal, M. M, A. Puthirath Balan, J. S. N.
Tharangattu, J. Mater. Chem. A 2017, 5, 11152 – 11162.
[100] P. G. Whitten, D. Nealon, S. Z. Saricilar, G. G. Wallace, Poly.-Plast.
Technol. Eng. 2015, 54, 310 – 314.
[101] J. Jensen, M. Hçsel, A. L. Dyer, F. C. Krebs, Adv. Funct. Mater.
2015, 25, 2073 – 2090.
[102] H. C. Moon, C. H. Kim, T. P. Lodge, C. D. Frisbie, ACS Appl. Mater.
Interfaces 2016, 8, 6252 – 6260.
[103] H. C. Moon, T. P. Lodge, C. D. Frisbie, Chem. Mater. 2015, 27,
1420 – 1425.
[104] H. Oh, D. G. Seo, T. Y. Yun, C. Y. Kim, H. C. Moon, ACS Appl.
Mater. Interfaces 2017, 9, 7658 – 7665.
[105] M. Kitao, H. Akram, K. Urabe, S. Yamada, J. Electron. Mater. 1992,
21, 419 – 422.
[106] F. Z. Tepehan, F. E. Ghodsi, N. Ozer, G. G. Tepehan, Solar Energy
Mater. Solar Cells 1999, 59, 265 – 275.
[107] K.-S. Ahn, Y.-C. Nah, Y.-E. Sung, K.-Y. Cho, S.-S. Shin, J.-K. Park,
Appl. Phys. Lett. 2002, 81, 3930 – 3932.
[108] A. K. H. Stenzel, K.-H. Heckner, M. Rottmann, M. Steuer, B. Pa-
penfuhs, Glass Processing Days, Conference Proceedings Book,
2003, pp. 423 – 426.
[109] A. Kraft, M. Rottmann, K.-H. Heckner, Solar Energy Mater. Solar
Cells 2006, 90, 469 – 476.
[110] F. C. Sentanin, L. Ponez, A. Pawlicka, Mol. Cryst. Liq. Cryst. 2014,
604, 107 – 116.
[111] K. Xiong, G. Emilsson, A. Maziz, X. Yang, L. Shao, E. W. Jager,
A. B. Dahlin, Adv. Mater. 2016, 28, 9956 – 9960.
[112] D. Lamine, P. Letocart, J.-C. Giron, T. Bertin-Mourot, US Patent
9482921 B2, 2016.
[113] H. Wu, D. Kong, Z. Ruan, P.-C. Hsu, S. Wang, Z. Yu, T. J. Carney,
L. Hu, S. Fan, Y. Cui, Nat. Nanotechnol. 2013, 8, 421 – 425.
[114] Y. Yang, J. Liu, Z.-W. Fu, D. Qin, J. Am. Chem. Soc. 2014, 136,
8153 – 8156.
[115] J. A. Rogers, T. Someya, Y. Huang, Science 2010, 327, 1603 – 1607.
[116] K. Li, Q. Zhang, H. Wang, Y. Li, J. Mater. Chem. C 2016, 4, 5849 –
5857.
[117] L. A. Mark, A. Mikko, M. Tomi, A. Ari, O. Kimmo, S. Mika, S.
Heikki, Nanotechnology 2008, 19, 175201.
[118] H.-S. Kim, S. R. Dhage, D.-E. Shim, H. T. Hahn, Appl. Phys. A
2009, 97, 791.
[119] B. Deng, P.-C. Hsu, G. Chen, B. N. Chandrashekar, L. Liao, Z. Ayiti-
muda, J. Wu, Y. Guo, L. Lin, Y. Zhou, M. Aisijiang, Q. Xie, Y. Cui,
Z. Liu, H. Peng, Nano Lett. 2015, 15, 4206 – 4213.
[120] J. Remmele, D. E. Shen, T. Mustonen, N. Fruehauf, ACS Appl.
Mater. Interfaces 2015, 7, 12001 – 12008.
[121] C.-J. Tang, J.-M. Ye, Y.-T. Yang, J.-L. He, Opt. Mater. 2016, 55, 83 –
89.
[122] C.-G. Granqvist, Electrochromic Materials and Devices, Wiley-VCH,
Weinheim, 2013, pp. 525 – 544.
[123] C. E. Tracy, J. G. Zhang, D. K. Benson, A. W. Czanderna, S. K. Deb,
Electrochim. Acta 1999, 44, 3195 – 3202.
[124] P. B. F. Beteille, J.-C. Giron, SPIE Conference on Switchable Materi-
als and Flat Panel Displays 1999, 3788, 70 – 74.
[125] H.-H. Chou, A. Nguyen, A. Chortos, J. W. F. To, C. Lu, J. Mei, T.
Kurosawa, W.-G. Bae, J. B. H. Tok, Z. Bao, Nat. Commun. 2015, 6,
8011.
Manuscript received: September 24, 2017
Revised manuscript received: November 10, 2017
Accepted manuscript online: November 14, 2017
Version of record online: November 29, 2017
45