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Thermally-stable dynamic windows based on

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reversible metal electrodeposition from aqueous

Cite this: J. Mater. Chem. C, 2018,
6, 2132 electrolytes†
Geoffrey Kirk A. Alcaraz, Jose S. Juarez-Rolon, Nicholas A. Burpee and
Christopher J. Barile *

Received 15th November 2017,
Accepted 5th February 2018
DOI: 10.1039/c7tc05222g
rsc.li/materials-c
Dynamic windows based on the reversible electrodeposition of metals are a promising alternative to those
utilizing electrochromic materials. In this manuscript, we develop 25 cm2 dynamic windows based on the
reversible electrodeposition of Cu and Bi from aqueous gel electrolytes that switch with a contrast ratio of
B80% in one minute. Although the aqueous electrolyte promotes rapid and uniform metal electrodeposition,
its narrow operable temperature range limits practical implementation of the devices. To overcome this
issue, we employ additives that prevent electrolyte freezing while still allowing for reversible metal
electrodeposition. With properly-selected antifreezes that do not bind strongly to metal ions, the
windows switch reversibly at temperatures down to 40 1C. The enhanced thermal stability of these
systems is necessary for the practical implementation of metal-based dynamic windows.

Introduction using low cost, solution-based manufacturing techniques.14 These

Dynamic windows change transparency through the application
of a voltage. This optoelectronic control has applications in
buildings, automobiles, and switchable sunglasses.1,2 Dynamic
windows have been researched for more than four decades, with
electrochromic materials being the most heavily investigated
strategy for modulating transmission towards both visible and
infrared light.3–8 However, commercialization of dynamic windows
utilizing electrochromic materials has not been widespread due
to problems associated with color, durability, cost, and switching
speed.9,10
The reversible electrodeposition of metals is a promising
alternative to electrochromic materials in dynamic windows.11–13
These dynamic windows function through the reversible electro-
chemical movement of metals between the frame of the window,
where the metals are hidden, and the center of the window to
turn the window dark. An electrolyte between the two window
panes contains colorless metal ions that facilitate ion transport
between the metal frame and the transparent conducting
substrate, which is commonly indium tin oxide (ITO) on glass.
We recently demonstrated metal-based dynamic windows that
possess excellent durability, superb contrast ratios in excess of 80%,
minute-order switching times, and likely could be constructed
Department of Chemistry, University of Nevada, 1664 North Virginia Street, Reno,
NV 89557, USA. E-mail: cbarile@unr.edu
† Electronic supplementary information (ESI) available. See DOI: 10.1039/
c7tc05222g
windows utilize a water-based gel containing Cu ions and a second
metal ion such as Pb2+ or Ag+, which yields a color neutral
electrodeposit. Uniform metal electrodeposition is made possible
by the use of a self-assembled monolayer (SAM) of Pt nanoparticles,
which acts as a spatially-distributed seed layer for metal nucleation
across the entire electrode area. The combination of this seed
layer and a carefully-selected electrolyte enables the construction
of 25 cm2 dynamic windows that exhibit uniform tinting, which
is substantially larger than previously reported metal-based
windows.15–17
The temperature range of the solvent–electrolyte system used
in dynamic windows is an important consideration for practical
window operation. We chose to use water-based gels in our
dynamic windows since water solvates ions very well and thus
promotes rapid and reversible electrodeposition.18 Nonaqueous
electrolytes, on the other hand, tend to favor ion pairing, which
impedes electron transfer to metal cations, thus reducing the
kinetics and reversibility of the electrodeposition process.19 The
large overpotentials needed to drive reversible nonaqueous
electrodeposition can also lead to undesired side reactions in
the solvent–electrolyte system. Although aqueous-based electrolytes
promote facile electrodeposition, these electrolytes have a tempera-
ture stability range of about 0 1C to 100 1C, which is unacceptably
narrow for many applications. For example, dynamic windows can
be used in the sky roofs or rear-view mirrors of automobiles,20 but
since the interior temperature of vehicles is often uncontrolled, they
must endure large temperature swings. The formation of ice crystals
not only eliminates the transparency of the window, but expansion

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of the electrolyte upon freezing would likely cause the window
glass to break. Even in buildings where the interior temperature
is normally kept within a normal range, the risk of irreversible
device failure from freezing is too risky for a product that must
last 20–30 years.
In this manuscript, in an attempt to overcome the issues
associated with the limited temperature range of aqueous-based
electrolytes, we explore the use of alcohol-based antifreezes to the
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aqueous gel electrolytes that increase the temperature stability of
dynamic windows based on reversible metal electrodeposition. We
systematically test how these additives affect the electrodeposition
kinetics and reversibility in a Cu–Bi electrolyte and derive pertinent
structure-rate relations.
Experimental section
Chemicals were received from commercial sources and used
without further purification. Electrochemical studies were con-
ducted using a VSP-300 Biologic potentiostat. For experiments
using three electrodes, electrochemical potentials were measured
and reported with respect to a ‘‘no-leak’’ Ag/AgCl (3 M KCl) reference
electrode (eDAQ). ITO on glass electrodes (Xinyan Technology,
15 O sq 1) were cleaned by successively sonicating in de-ionized
H2O with 5% Extran solution for 15 minutes, acetone for 15 minutes,
and isopropanol for 15 minutes. The electrodes were subsequently
dried under a stream of air. Pt nanoparticles used to modify the
working electrodes had average diameters of 3 nm and were
purchased from Sigma-Aldrich. The cleaned ITO on glass
electrodes were first immersed in an ethanolic solution of 10 mM
3-mercaptopropionic acid for 24 hours. Subsequently, the substrates
were rinsed with ethanol and water before immersing them for
24 hours in a Pt nanoparticle solution that was diluted 1 : 4 with
water. Finally, the substrates were annealed in air at 250 1C for
30 minutes before use.
Dynamic windows were constructed in three-electrode or
two-electrode configurations. Three-electrode experiments con-
sisted of a Pt-modified ITO on glass working electrode, a Pt wire
counter electrode, a Ag/AgCl reference electrode, and a liquid
Cu–Bi electrolyte. The immersed geometric surface area of the
working electrode was 3.0 cm2. The liquid Cu–Bi electrolyte
consisted of 5 mM BiCl3, 15 mM CuCl2, 10 mM HCl, and 1 M
LiBr unless otherwise stated. For two-electrode experiments, a
Fig. 1 Schematic of 25 cm2 dynamic window based on reversible metal electrodeposition (a). Structures of antifreezes used in this study (b).
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gel electrolyte was used that was made by adding 3.0% hydro-
xyethylcellulose by weight to the liquid electrolyte. Two-electrode
dynamic windows utilized a 25 cm2 Pt-modified ITO on glass
working electrode coupled with a Cu foil counter electrode. To
make uniform electrical contact to the working electrode, Cu
tape with conductive adhesive was applied across the electrode
perimeter. Butyl rubber sealant separated the two device electrodes
with an interelectrode spacing of B3 mm.
The temperature of the windows was controlled during
switching using a water bath for temperatures between 0 1C and
60 1C, a bath consisting of dry ice and 90 : 10 vol% ethylene glycol :
ethanol for 20 1C, and a bath consisting of dry ice and 55 : 45 vol%
methanol : H2O for 40 1C. Transmission spectra were measured
with an Ocean Optics FLAME-S-VIS-NIR spectrometer coupled with
an Ocean Optics halogen light source (HL-2000-FHSA). A Shimadzu
UV-2550 UV/VIS spectrophotometer was used to measure Cu2+
binding constants. Electrolyte viscosities were measured using a
NDJ-5S viscometer. Optical images were taken with a Nikon D5000
Digital Camera. To quantify window uniformity, we obtained
greyscale photographs during window switching, with the only
source of illumination coming from a uniform light source
behind each window.
Results and discussion
Fig. 1a shows a schematic of the 25 cm2 dynamic windows
constructed. The windows consist of an ITO on glass working
electrode modified with a SAM of Pt nanoparticles. As
described previously, the SAM of Pt nanoparticles serves as a
nucleation layer that encourages rapid, reversible, and uniform
growth across the entire electrode.14 The counter electrode of
the device is a Cu metal frame placed on top of a non-
conducting glass back pane, and the two electrodes are sealed
together using butyl rubber. Between the two window panes, we
injected an aqueous-based gel containing Cu2+ and Bi3+ ions
and hydroxyethylcellulose as a gelling agent. This electrolyte
was modified to contain various alcohol-based antifreezes,
namely methanol, ethylene glycol, and glycerol, which contain
1, 2, and 3 carbons and alcohol groups, respectively (Fig. 1b). To
evaluate the electrochemical performance of these additives as
a function of temperature and composition, we first performed
cyclic voltammetry (CV) experiments.
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Fig. 2 Cyclic voltammograms in the Cu–Bi electrolyte in H2O using a
Pt-modified ITO on glass working electrode at a scan rate of 20 mV s 1.
Fig. 2 shows the first three cycles of Cu and Bi electrodeposi-
tion and dissolution in an electrolyte containing water without
an antifreeze. The cathodic going scan of the CV shows two
reductive peaks. The more positive of the two peaks, occurring
around 0.1 V vs. Ag/AgCl corresponds to Bi electrodeposition
while the second cathodic peak around 0.2 V corresponds to
Cu electrodeposition.21 The prominent anodic peak at B0.1 V
corresponds to the dissolution of both Bi and Cu metal. At
potentials more positive than this anodic peak, the current
rapidly decreases to zero because there is no more metal on the
electrode to be dissolved. The general shape of the CVs are
similar to what has been reported for other Cu–Bi reversible
metal electrodeposition systems.13 We note that the onset
potential for Bi electrodeposition shifts from about 0.1 V to
0.075 V when comparing cycle one versus cycles two and three.
This shift in potential is due the establishment of stable nuclei
after the first cycle of electrodeposition. Once these metal
nuclei are formed, it is more thermodynamically favorable for
metal deposition to occur on these established nuclei than to
occur on bare areas on the ITO surface, hence explaining the
positive shift in the onset potential.
We next evaluated the CVs as a function of various antifreezes
added to the electrolyte at a volume percentage of 60% with 40%
water. The presence of antifreezes produces important changes
in the voltammetric response of the system although the main
features of the voltammetry are still present. All four CVs in Fig. 3
contain two reductive peaks, corresponding to Bi and Cu elec-
trodeposition, and they also possess a metal stripping peak. The
shoulder in the metal stripping peak at B0 V is due to the more
negative onset of Cu oxidation as compared to Bi oxidation as
evidenced by voltammetry performed in electrolytes containing
only Cu or only Bi as the electroactive metal (Fig. S1, ESI†).
However, the onset of deposition for Bi systematically changes as
the number of alcohol groups increases on the antifreeze added.
In particular, the Bi deposition onset potential progressively
shifts from 79 mV to 105 mV when changing the electrolyte
from water to those containing methanol, ethylene glycol, or
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Fig. 3 Cyclic voltammograms in the Cu–Bi electrolyte in H2O (black),
60 : 40 vol% methanol : H2O (red), 60 : 40 vol% ethylene glycol : H2O (blue),
and 60 : 40 vol% glycerol : H2O (green) using a Pt-modified ITO on glass
working electrode at a scan rate of 20 mV s 1.
glycerol (Table 1). Furthermore the Tafel slopes corresponding to
the Cu and Bi electrodeposition also possess important trends.
Whereas the Bi electrodeposition Tafel slope does not change
with electrolyte composition and remains relatively constant at
about 40 mV decade 1, the Tafel slope for Cu deposition changes
dramatically and increases from B120 mV decade 1 when water
is used as a solvent to B470 mV decade 1 when glycerol is used
as a solvent. The increase of the Bi electrodeposition onset
potential with increasing number of alcohol groups suggests
that the metal nucleation becomes more impeded. Likewise, the
progressive increase in the Cu Tafel slope suggests that Cu
electrodeposition is progressively inhibited as the number of
alcohol groups in the antifreeze increases.
Having established from the voltammetric results that the
windows still reversibly switch in the presence of the antifreezes,
we next constructed 25 cm2 dynamic windows with different
electrolyte compositions and evaluated their switching speeds as
a function of temperature. Fig. 4a shows the transmission profile
at 600 nm of a 25 cm2 dynamic window without antifreeze
containing the Cu–Bi electrolyte. The window was held at 0.6 V
for 60 s to induce metal electrodeposition to turn the window dark
with high optical contrast across the visible and near-infrared
portions of the electromagnetic spectrum (Fig. S2, ESI†). During
the tinting process, the transmission of the window decreases to
Table 1 List of the Bi electrodeposition onset potential (mV vs. Ag/AgCl)
and the Cu and Bi Tafel slopes as a function of solvent–electrolyte system
Electrolyte Bi deposition Cu Tafel Bi Tafel
solvent system onset (mV) (mV decade 1) (mV decade 1)
H2O 79 121 40
60 : 40 vol% 98 459 41
methanol : H2O
60 : 40 vol% ethylene 105 468 45
glycol : H2O
60 : 40 vol% 105 472 42
glycerol : H2O
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Fig. 4 Transmission at 600 nm of 25 cm2 dynamic windows during 60 s of metal electrodeposition at
+0.6 V using the Cu–Bi electrolyte in H2O (a) and in 60 : 40 vol% ethylene glycol : H2O (b).
about 1% with the exact minimum value after 60 s depending
upon the temperature of the window. A video of the window
darkening at room temperature demonstrates that the metal
electrodeposition process occurs uniformly across the 25 cm2
electrode (Video, ESI†) due to the uniform distribution of Pt
nanoparticles across the electrode, which serve as electrodeposi-
tion nuclei as discussed in previous work.14 Without the Pt
nucleation layer, electrodeposition occurs preferentially on the
window edges. After electrodeposition, reversing the polarity of
the voltage to +0.6 V for 120 s restores the window to its original
transmission of 80%. Notably, there are shoulders in the bleaching
transmission profiles in Fig. 4a, which are due to the formation
of CuBr precipitate in the electrolyte. The shoulders are less
pronounced at higher temperatures because the solubility of
CuBr increases with temperature. Experiments in an electrolyte
containing a high concentration of Cu2+ indicate that the formed
CuBr can lead to a temporary, but visible white haze that
obscures transmission during the stripping process (Fig. S3
and S4, ESI†). Increasing the temperature of the window from
0 1C to 60 1C leads to a progressively greater contrast ratio of the
window, indicating that the metal electrodeposition process
occurs more rapidly at higher temperatures. The window could
not be operated at temperatures below about 2 1C because the
unmodified aqueous electrolyte freezes at this temperature.
In contrast, a dynamic window containing 60% ethylene
glycol and 40% water can be switched without issue at tempera-
tures as low as 40 1C (Fig. 4b). The transmission of the window
is fully reversible at this temperature and at all temperatures
tested from 40 1C to 60 1C with larger contrast ratios occurring
at higher temperatures. Similar trends in the temperature
switching profile of the windows were also obtained in methanol
and glycerol with both antifreezes enabling the windows to
operate reversibly below 20 1C (Fig. S5, ESI†). The amount of
antifreeze added to the window dictates the freezing point of the
electrolyte and hence the lowest operating temperature of the
device (Fig. S6, ESI†).
Regardless of whether the devices contain antifreeze, the
windows are constructed with a Cu counter electrode and an
electrolyte possessing 5 mM Bi3+ and 15 mM Cu2+. During the
first cycle of metal electrodeposition, a mixture of Cu and Bi deposit
on the Pt-modified ITO working electrode while concomitant Cu
oxidation to Cu2+ occurs on the counter electrode. These two
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0.6 V followed by 120 s of metal stripping at
Fig. 5 Contrast ratio of a 25 cm2 dynamic window using the Cu–Bi
electrolyte with 60 : 40 vol% ethylene glycol : H2O during cycling at 5 1C
(blue), 20 1C (black), and 60 1C (red). Each cycle consists of 60 s at 0.6 V
to induce metal electrodeposition followed by 120 s at +0.8 V to induce
metal stripping.
processes slightly increase the Cu2+ concentration in the electrolyte.
The asymmetry between the composition of the electrolyte and
counter electrode causes the ratio of Cu2+ and Bi3+ concentrations
to change during cycling. Based on the amount of charge passed
during cycling and the volume of the electrolyte, the maximum
possible change in Cu2+ concentration in the electrolyte is a
few mM over the course of 1000 cycles. Transmission profiles
of windows switching in electrolytes containing 5 mM Bi3+ and
10 mM, 15 mM, or 20 mM Cu2+ switch with fairly similar speeds
(Fig. S7, ESI†). In other words, the windows can tolerate small
changes in the ratio of Cu2+ and Bi3+ concentrations that occur
during extended cycling. Importantly, the windows can cycle
1000 times at 5 1C, 20 1C, or 60 1C without any significant
degradation in contrast ratio (Fig. 5).
Fig. 6 plots the transmission of the various windows after
60 s of metal electrodeposition using the four different electro-
lytes studied. From this plot, it is clear that increasing the
number of alcohol groups in the antifreeze results in lower
minimum achievable transmissions after 60 s. With methanol,
however, the window possesses very similar contrast ratios
from 20 1C to 60 1C as the window without antifreeze, but the
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Fig. 6 25 cm2 dynamic window transmission values at 600 nm after 60 s
of metal electrodeposition in Cu–Bi electrolytes containing H2O (black),
60 : 40 vol% methanol : H2O (red), 60 : 40 vol% ethylene glycol : H2O (blue),
and 60 : 40 vol% glycerol : H2O (green).
presence of the additive enables the window to operate at
temperatures well below 0 1C. This finding indicates that the
addition of methanol to the electrolyte improves the thermal
stability of the dynamic windows without significantly altering
the contrast ratio of the device after 60 s of tinting at room
temperature. We also assess the switching speeds of the
windows in terms of the time they take to darken to 90% of
their dynamic range at 600 nm. These switching times are 22 s,
48 s, 133 s, and 185 s for devices with electrolytes containing no
antifreeze, methanol, ethylene glycol, and glycerol, respectively.
The switching speeds evaluated in this manner give the same
trend in which increasing the number of alcohol groups in the
antifreeze results in slower device switching.
Fig. 7 displays photographs of the dynamic window contain-
ing the Cu–Bi electrolyte with ethylene glycol switching outside
in subfreezing weather without issue. Importantly, the unifor-
mity of the metal electrodeposition process is not hampered at
low temperatures. We further demonstrate that temperature
cycling of these windows does not affect the subsequent uni-
formity of metal electrodeposition at room temperature as
measured by uniformity maps taken from greyscale photo-
graphs of the windows switching under controlled lighting
conditions (Fig. S8, ESI†).
We next analyze the degree to which the antifreezes affect
the switching speeds of the devices as a function of
Fig. 7 Photographs of Mount Rose, Nevada taken the morning of October 21, 2017 through a 25 cm2 window containing the Cu–Bi electrolyte with
60 : 40 vol% ethylene glycol : H2O after 0 s (a), 30 s (b), and 180 s (c) of metal electrodeposition at 0.6 V. The outside temperature was 5 1C.
2136 | J. Mater. Chem. C, 2018, 6, 2132--2138
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temperature. The change in switching speed with respect to
temperature and antifreeze is manifested in the chronoampero-
metric curves. In particular, lower temperatures give rise to
lower currents in the chronoamperometry (Fig. S9, ESI†). By
plotting the nucleation current densities of the various dynamic
windows with the different electrolytes as a function of tem-
perature, we elucidated an Arrhenius-type relationship between
these two parameters. An Arrhenius plot of both the dynamic
windows without antifreeze and with ethylene glycol gives a
good linear relationship (Fig. 8a), indicating that the metal
electrodeposition process is a thermally activated process. A
similar relationship in the Arrhenius plot was also obtained for
dynamic windows with electrolytes containing methanol and
glycerol (Fig. S10, ESI†). From the slope of the Arrhenius plots,
we calculated the activation energy of the metal nucleation
process for the Cu–Bi electrolyte containing water and the three
antifreezes (Fig. 8b).
The results demonstrate that the activation energy for metal
nucleation increases as the number of alcohol groups in the
antifreeze increases. The trend in activation energies along with
the change of the metal electrodeposition onset potential and
the switching speeds of the four different dynamic window
electrolytes suggest that the presence of alcohol groups some-
how impedes the metal electrodeposition process. One possible
explanation for this trend is that the viscosity of the alcohols
increases in the order of methanol, ethylene glycol, and gly-
cerol, and that increased electrolyte viscosity inhibits metal
electrodeposition. However, the viscosity of each electrolyte is
predominantly dictated by the 3 wt% hydroxyethylcellulose
gelling agent, not the antifreeze. Indeed, we measured the
viscosities of the various Cu–Bi electrolytes and found that all
of the electrolytes had comparable viscosities (9.0  1.6 Pa s 1,
Fig. S11, ESI†). The absence of a trend between the viscosity of
the electrolyte and metal electrodeposition kinetics indicates
that another effect is responsible for the decreased switching
speed of dynamic windows as the number of alcohol groups in
the antifreeze used increases.
The fact that the Tafel slope for Cu electrodeposition is
affected in the CVs suggests that the alcohol groups bind Cu
and that this binding inhibits the kinetics of metal electro-
deposition. We measured the binding constants of the alcohol
antifreezes to Cu2+ by tracking shifts in the position of the Cu
d–d transition in UV-Vis-NIR spectra as methanol, ethylene
glycol, or glycerol were added to solution. The calculated
binding constants of Cu2+ to methanol, ethylene glycol, and
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Fig. 8 Arrhenius plots of maximum nucleation current density of metal electrodeposition in 25 cm2 dynamic windows containing the Cu–Bi electrolyte
with H2O (a, black) and 60 : 40 vol% ethylene glycol : H2O (a, red). Calculated activation energies for metal nucleation from Arrhenius plots as a function of
different electrolyte compositions (b).
glycerol are (0.042  0.006), (0.063  0.008), and (0.10  0.02),
respectively (Fig. S12, ESI†), indicating that the presence of more
alcohol groups results in tighter metal binding. This result
suggests that the binding of the antifreezes to Cu results in
the decreased electrochemical kinetics of the dynamic window
and explains why methanol, with only one alcohol group, func-
tions as the antifreeze with the fastest switching speed.
Conclusions
In conclusion, we designed dynamic windows based on rever-
sible metal electrodeposition that have thermal stability at
temperatures as low as 40 1C and still switch reversibly. By
selecting the appropriate antifreeze that does not bind very
strongly to the metal ions in the electrolyte solution, we
developed electrolytes that have excellent temperature stability
and only slightly affect the switching speed of the window at
room temperature. We determined that the binding of the
metal ions by these antifreezes is a plausible mechanism by
which they can impede electrochemical performance, but these
additives do not affect electrochemical reversibility. These
results push the reversible metal electrodeposition system for
dynamic windows closer towards a commercial product.
We note that architecturally-relevant meter-sized windows
will not exhibit uniform electrodeposition using the device
architecture described in this work because current is collected
around the electrode perimeter. During device switching, series
resistance accumulates in the ITO causing a voltage drop
across the electrode, which will cause electrodeposition to
occur more rapidly on the edges compared to the center. To
enable larger dynamic windows based on reversible metal
electrodeposition, future research will explore using a working
electrode with a lower sheet resistance and a counter electrode
with a transparent metal grid to decrease the diffusion length
of metal ions.
Conflicts of interest
There are no conflicts to declare.
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Acknowledgements
This research was funded by Research and Innovation at the
University of Nevada, Reno. We acknowledge fruitful conversa-
tions with Prof. Michael McGehee and Michael Strand.
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