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Organic Electronics for Electrochromic Materials and Devices
Organic Electronics for Electrochromic
Materials and Devices
Hong Meng
Author All books published by Wiley-VCH
are carefully produced. Nevertheless,
Prof. Hong Meng authors, editors, and publisher do not
Peking University warrant the information contained in
Shenzhen Graduate School these books, including this book, to
Building G 306 be free of errors. Readers are advised
Lishui Road, Nanshan Disctrict to keep in mind that statements, data,
518055 Shenzhen illustrations, procedural details or other
China items may inadvertently be inaccurate.
10 9 8 7 6 5 4 3 2 1
v
Contents
Preface xiii
About the Author xiv
1 Introduction 1
1.1 General Introduction 1
1.2 The History of Electrochromic Materials 3
1.3 The Key Parameters of Electrochromism 5
1.3.1 Electrochromic Contrast 5
1.3.2 Switching Time 8
1.3.3 Coloration Efficiency 9
1.3.4 Optical Memory 11
1.3.5 Stability 12
1.4 Conclusion 14
References 14
5 Metallohexacyanates 143
5.1 Background 143
5.2 Technology Development of PB 144
5.3 Crystal Structure 144
5.4 Electrochromic Mechanism 145
5.5 Synthesis 147
5.6 Electrochromic Devices (ECDs) 150
5.7 Nanocomposites 154
5.8 PB Analogs 160
5.9 Multifunctional Applications 170
References 175
Index 505
xiii
Preface
In recent years, with the development of artificial intelligence, more and more
industries strive to be “smart.” As a new generation of display technology, organic
electrochromic (OEC) devices offer numerous advantages such as flexibility, full
colors, wide origins of materials, fast switching time, low driving voltage, and
simple configuration. In addition, these devices possess “smart” characteristics of
multi-stimulation and multi-response. Therefore, the OEC industry is emerging as
a potential display competitor in the field of electronic information.
This book covers major topics related to the phenomenon of electrochromism,
including the history of organic electrochromism, fundamental principles, different
types of electrochromic materials, development of device structures, multifunctional
devices, their characterizations and applications, and future prospects of OEC tech-
nology. It also spotlights recent research progress reported by academic institutes
and enterprises, and discusses the existing challenges in further development of this
area.
This book provides a comprehensive review of OEC materials and devices, and
can be used as a teaching reference for undergraduate and graduate students as well
as teachers in the fields of organic chemistry and polymer science etc. Also, this
book can be adopted as a comprehensive reference for researchers engaged in the
development of OEC technology enterprise in the field of electrochromism.
Introduction
2.5
UV Visible Infrared
2
Irradiance W/(m2 nm)
1.5
5778 K blackbody
1
Sunlight at sea level
H2 O
Atmospheric
0.5 H2O
absorption bands
O2
H2O CO
O3 H2O 2 H2O
0
250 500 750 1000 1250 1500 1750 2000 2250 2500
Wavelength (nm)
Figure 1.1 Solar irradiance spectrum above atmosphere and at the surface of the Earth.
Source: Nick84: https://commons.wikimedia.org/wiki/File:Solar_spectrum_en.svg, Licensed
under CC BY-SA 3.0.
current, and ions are conducted by the electrolyte solution. Then the EC materials
undergo electrochemical oxidation and/or reduction, which results in changes in
the optical bandgap and colors. As shown in Figure 1.2, a typical ECD has five layers:
two transparent conducting oxide (TCO) layers, EC layer, ion-conducting layer
(electrolyte solution), ion storage layer. Particularly, the ion storage layer acts as the
“counter electrode” to store ions and keep electric charge balance. And according to
the exact state of EC materials, there are three types of ECD: film type (I), solution
type (II), and hybrid type (III). The Type I ECD is the most common; many kinds of
EC materials are suitable for this type including TMOs, conjugated/non-conjugated
polymers, metallo-supermolecular polymers, and MOF/covalent organic frame-
work (COF) materials, which using spin-coating, spray-coating, and dip-coating
processes to form uniform films; these films won’t dissolute in electrolyte solutions.
Type II ECD requires that the EC materials have good solubility in electrolyte
1.2 The History of Electrochromic Materials 3
The word “electrochromism” was invented by John R. Platt in 1960 [6], in analogy
to “thermochromism” and “photochromism.” However, the EC phenomenon could
be traced to the nineteenth century, as early as 1815. Berzelius observed the color
change of pure tungsten trioxide (WO3 ) during the reduction when warmed under
a flow of dry hydrogen gas. Then from 1913 to 1957, some patents described the
earliest form of ECD based on WO3 [7, 8]. Therefore the origins of electrochromism
are the nineteenth and twentieth centuries. After then, electrochromism technology
began to undergo rapid development, especially the exploration of many classes of
EC materials. As showed in the technology roadmap (Figure 1.3), we summarized
several generations of EC materials during long-term development.
The first-generation EC material is TMOs (e.g. WO3 , NiO, and PB). Among them,
WO3 plays an important role in the electrochromism field; as the first founded EC
material, it has already realized commercialization in smart windows application.
PB was discovered as a dye by Diesbach in 1704, and then the electrochemical behav-
ior and EC performance of PB was firstly reported by Neff at 1978 [9]. Benefitted
from the structure stability and reversible redox process of those inorganic TMOs,
the electrochromism based on the thin-film TMOs are widely investigated, including
n
S n N n O n N
H H
Poly(thiophene) Poly(pyrrole) Poly(furan) Poly(anlline) N N
n n
n N M N
N n
N N
N
H
Poly(carbazole) Poly(fluorene) Poly(triphenylamine) M = Fe, Co, Ru, Cu, Zn, Eu
H HO O
N N C C
n
N
PTTBTTh0.30
1.0
0.8
0.6
0.4
0.2
0.0
400 600 800 1000 1200 1400 1600 1800
Wavelength (nm)
(a)
80
–0.2 V
70 1.4 V
Transmittance (%)
60
Reduction
Oxidation
50
40
30
20
10
400 500 600 700 800
(b) Wavelength (nm)
wavelength of blue color is ranging from 455 to 490 nm. Therefore, in most cases,
the contrast in the characteristic wavelength is chosen to evaluate the degrees of
color change. Usually the absorption of this characteristic wavelength also reaches
its maximum value (𝜆max ). Moreover, there is evidence that human eyes are most
sensitive to green light with a wavelength of 555 nm [25]. It’s also recommended to
calculate the contrast in 555 nm for comparison in different publications. Specif-
ically, a contrast test example is shown in Figure 1.5a, the TMb and TMc of 𝜆max
425 nm are 1% and 99%, respectively; therefore the Δ%T is calculated as 98%. For
applications such as smart windows, in which the difference between the bleached
and colored states is expected to be the highest, the Δ%T should be higher than
80%. Many inorganic EC materials, organic small molecules, and PEDOT series
polymers, which have a high transmittance in the bleached state, can achieve this
index. Especially, some reported small molecule EC materials even show Δ%T
exceed 95% [23].
1.3 The Key Parameters of Electrochromism 7
Transmittance (%)
Transmittance (%)
80 20
60 40
98%
40 60
20 80
0 100
100 683
555 nm CIE 1978 60 PTTPhBT0.35
10
–1 100 55
L* 50
10
10–2
45
1 40
10–3
Orange
Yellow
Green
Violet
35
Cyan
Blue
Red
–4
0.1
10 –0.2 0.0 0.2 0.4 0.6 0.8 1.0 1.2
300 400 500 600 700 800
Potential (V)
Wavelength λ (nm)
(b) (c)
Figure 1.5 (a) The electrochromic contrast of a small molecule EC material. Source: Jiang
et al. [23], (b) sensitivity function of the human eye V (𝜆) and luminous efficacy vs
wavelength. Source: Fred Schubert [24]. © 2006, Cambridge University Press. (c) The
change of the lightness values from the neutral to the oxidized states. Source: Li et al. [21].
© 2018, Royal Society of Chemistry.
is the normalized spectral response of the eye. 𝜆min and 𝜆max define the considered
range of wavelengths.
–20
–25
165 170 175 180 185 190 195 200 205
(a) Time (s)
40 710 nm
Δ %T = 52%
50 Pulse time = 15 s
90%
Transmittance (%)
60
70
80 tbleaching
tcoloration
90%
90 tb = 1.06 s
tc = 4.23 s
100 On Off
–5 0 5 10 15 20 25 30 35
50
40
30
Current (mA)
20
10 Qd = 9.75 mC/cm2
–10
–20
0 5 10 15 20 25 30
Time (s)
100 200
CE
90
Coloration efficiency (CE) (cm2/C)
60
50 100
40
TMVIS, colored = 8% CEmax, at 767 nm = 188 cm2/C
30
CE at 550 nm = 66 cm2/C 50
20
Photopic CE = 75 cm2/C
10
0 0
400 450 500 550 600 650 700 750
Wavelength (nm)
Figure 1.8 Different types of CE value of the same EC materials. Source: Kraft [25].
1.3 The Key Parameters of Electrochromism 11
Qd = QF + QC + QP
where the parasitic current was a small component (approximately <2%) compared
with the other two and therefore can be ignored. Then the time–evolution total
current flow can be described as following:
nFAC0 D1∕2 −1∕2
Id (t) = IF (t) + IC (t) = t + I0 e−t∕RC = k t−1∕2 + I0 e−t∕RC
𝜋
where n is the number of electrons transferred per molecule, F is the Faraday con-
stant (96 500 C/mol), A is the electrode area (cm2 ), C0 is the concentration of species
in the bulk solution (mol/cm3 ), D is the apparent diffusion coefficient (cm2 /s), t is
time in seconds, I 0 is the maximum current flow at t = 0, R is the cell resistance, and
C is the double layer capacitance. Then fitting the experimental data to this equation
and substituting the constant k, at last, a plot of the time–evolution faradaic current
will be obtained, and the corresponding faradic-corrected CEs can be calculated.
Usually, the faradic-corrected CEs are larger than the uncorrected results, because
the total charge ingress/egress (i.e. Qd ) is larger than the faradic charge (i.e. QF).
30
20
10
0 100 200 300 400 500 600
Time (s)
(a)
70
1.0 V
60 –0.2 V
Transmittance (%)
50
40
23% 20%
30
20
10
0 600 1200 1800 2400 3000 3600
(b) Time (s)
1.3.5 Stability
In most cases of laboratory study, researchers record the number of redox cycles
that an EC material stand without significant loss in the performance as the
electrochemical stability, irreversible oxidation or reduction at extreme poten-
tials, side reactions with water or oxygen, and heat release in the system during
switches may cause the degradation of electrochemical stability. Usually, the
charge density Qd recorded under electrochemical cycling is up to 104 –106 , as
shown in Figure 1.10a. The charge density of a Ti-doped V2 O5 EC film haven’t
changed through 2 × 106 cycles; meanwhile the transmittance change at a certain
wavelength during continuous cycling is also important to describe the stability
1.3 The Key Parameters of Electrochromism 13
–8
–12
–16
0 40 80 120 160 200
(a) Cycle number (K)
80
70
60
Transmittance (%)
50
680 nm
40 900 nm
10
0
0 40 80 120 160 200
(b) Cycle number (K)
UVa stability Prolonged cycles (12 h colored, 12 h bleach) for a total exposure of
6000 MJ/m2, UV intensity integrated between 300 and 400 nm
Heat storage 500 h at 90 °C
Low temperature storage 1000 h at 20 °C to – 30 °C
Humidity/temperature storage 1000 h at 70 °C, 90% humidity
Thermal cycling 85 °C for 4 h, followed by – 40° C for 4 h and followed by 37 °C for 16 h
at 100% R.H. (4 h of ramp between each condition) (repeat
four times)
Thermal shock One hour colored and one hour bleached. Test in a UV chamber, with
UVa lamp on during coloration. Spray with 25 °C water in bleached
state (24 cycles)
a
Black panel temperature during the bright periods of 60 °C, and 25 °C in the dark periods.
b
Asahi has used up to 100 000 cycles.
Figure 1.11 Recommended testing guidelines for EC windows for exterior architectural
applications. Source: Lampert et al. [31].
1.4 Conclusion
In this chapter, a broad overview of electrochromism, EC materials, device struc-
ture, development history, and key parameters of electrochromism have been
introduced briefly. More detailed descriptions of each area will be discussed in
Chapters 2–15. In summary, research in EC technologies has achieved significant
breakthroughs over the decades. Many generations of EC materials have been
developed, ranging from traditional metal oxides to more recent organic polymers,
small molecules, and hybrid materials. Moreover, benefit from the ECD design and
structural optimization, flexible substrate-based devices were fabricated with the
low-price roll-to-roll process, which makes the EC technology have large scope
applications, such as smart windows for reducing building energy consumption,
self-powered EC window using organic photovoltaic cells as power supplement, car
rear-view mirrors for greater safety, and smart sunglasses for better UV-radiation
protection. Many of these technologies and applications have been commercialized
and are available on the market. With the concerted efforts of researchers and
engineers, we believe that the new EC materials and advanced technologies will
constantly develop and more advanced ECD with low manufacturing cost will be
exploited to realize practical applications.
References
4 Wu, W., Wang, M., Ma, J. et al. (2018). Electrochromic metal oxides: recent
progress and prospect. Advanced Electronic Materials 4 (8).
5 Mortimer, R.J. (2011). Electrochromic materials. Annual Review of Materials
Research 41 (1): 241–268.
6 Platt, J.R. (1961). Electrochromism, a possible change of color producible in dyes
by an electric field. The Journal of Chemical Physics 34 (3): 862–863.
7 Hutchison, M.R. (1913). Electrographic display apparatus and method. US Patent
1,068,774, filed 29 July 1913.
8 Lehovec K. (1957). Photon modulation in semiconductors. US Patent 2,776,367,
filed 1 January 1957.
9 Neff, V.D. (1978). Electrochemical oxidation and reduction of thin-films of
prussian blue. Journal of the Electrochemical Society 125 (6): 886–887.
10 Michaelis, L. and Hill, E.S. (1933). The viologen indicators. The Journal of
General Physiology 16 (6): 859–873.
11 Schoot, C.J., Ponjee, J.J., van Dam, H.T. et al. (1973). New electrochromic
memory display. Applied Physics Letters 23 (2): 64–65.
12 Garnier, F., Tourillon, G., Garzard, M., and Dubois, J.C. (1983). Organic conduct-
ing polymers derived from substituted thiophenes as electrochromic material.
Journal of Electroanalytical Chemistry 148: 299–303.
13 Mengoli, G., Musiani, M.M., Schreck, B., and Zecchin, S. (1988). Electrochemical
synthesis and properties of polycarbazole films in protic acid media. Journal of
Electroanalytical Chemistry and Interfacial Electrochemistry 246 (1): 73–86.
14 Zheng, H.B., Lu, W., and Wang, Z.Y. (2001). Electrochemical and electrochromic
properties of poly(ether naphthalimide)s and related model compounds. Polymer
42 (8): 3745–3750.
15 Oishi, Y., Takado, H., Yoneyama, M. et al. (1990). Preparation and properties
of new aromatic polyamides from 4,4′ -diaminotriphenylamine and aromatic
dicarboxylic acids. Journal of Polymer Science Part A: Polymer Chemistry 28 (7):
1763–1769.
16 Cheng, S.-H., Hsiao, S.-H., Su, T.-H., and Liou, G.-S. (2005). Novel aromatic
poly(amine-imide)s bearing a pendent triphenylamine group: synthesis, thermal,
photophysical, electrochemical, and electrochromic characteristics. Macro-
molecules 38 (2): 307–316.
17 Arimoto, F.S. and Haven, A.C. (1955). Derivatives of dicyclopentadienyliron.
Journal of the American Chemical Society 77 (23): 6295–6297.
18 Whittell, G.R. and Manners, I. (2007). Metallopolymers: new multifunctional
materials. Advanced Materials 19 (21): 3439–3468.
19 Wade, C.R., Li, M., and Dincă, M. (2013). Facile deposition of multicolored
electrochromic metal–organic framework thin films. Angewandte Chemie Interna-
tional Edition 52 (50): 13377–13381.
20 Hao, Q., Li, Z.-J., Lu, C. et al. (2019). Oriented two-dimensional covalent organic
framework films for near-infrared electrochromic application. Journal of the
American Chemical Society 141 (50): 19831–19838.
21 Li, W., Ning, J., Yin, Y. et al. (2018). Thieno[3,2-b]thiophene-based conjugated
copolymers for solution-processable neutral black electrochromism. Polymer
Chemistry 9 (47): 5608–5616.
16 1 Introduction
22 Beaujuge, P.M. and Reynolds, J.R. (2010). Color control in π-conjugated organic
polymers for use in electrochromic devices. Chemical Reviews 110 (1): 268–320.
23 Jiang, M., Sun, Y., Ning, J. et al. (2020). Diphenyl sulfone based multicolored
cathodically coloring electrochromic materials with high contrast. Organic
Electronics 83: 105741.
24 Fred Schubert, E., Chapter 16. Human Eye Sensitivity and Photometric Quantities
in Light-Emitting Diodes, 2e. Cambridge University Press.
25 Kraft, A. (2018). Electrochromism: a fascinating branch of electrochemistry.
ChemTexts 5 (1): 1–18.
26 Padilla, J., Seshadri, V., Filloramo, J. et al. (2007). High contrast solid-state elec-
trochromic devices from substituted 3,4-propylenedioxythiophenes using the dual
conjugated polymer approach. Synthetic Metals 157 (6–7): 261–268.
27 Hsiao, S.-H. and Lin, S.-W. (2016). Electrochemical synthesis of electrochromic
polycarbazole films from N-phenyl-3,6-bis(N-carbazolyl)carbazoles. Polymer
Chemistry 7 (1): 198–211.
28 Hassab, S., Shen, D.E., Österholm, A.M. et al. (2018). A new standard method to
calculate electrochromic switching time. Solar Energy Materials and Solar Cells
185: 54–60. https://doi.org/10.1016/j.solmat.2018.04.031.
29 Fabretto, M., Vaithianathan, T., Hall, C. et al. (2008). Faradaic charge corrected
colouration efficiency measurements for electrochromic devices. Electrochimica
Acta 53 (5): 2250–2257.
30 Wei, Y., Zhou, J., Zheng, J., and Xu, C. (2015). Improved stability of elec-
trochromic devices using Ti-doped V2 O5 film. Electrochimica Acta 166: 277–284.
31 Lampert, C.M., Agrawal, A., Baertlien, C., and Nagai, J. (1999). Durability evalu-
ation of electrochromic devices – an industry perspective. Solar Energy Materials
and Solar Cells 56 (3): 449–463.
17
2.1 Introduction
The ionic conduction medium between the electrodes and electrochromic (EC)
materials is an electrolyte, which is one of the most essential active components
in electrochromic device (ECD). Electrolyte provides an indispensable role as the
prime ionic conduction medium between the electrodes while preventing electron
conduction between the two electrodes during EC operation. The important
electrolyte properties greatly affecting the EC performance are the electrolyte ionic
conductivity, ion dissociation, transport rate of ion through bulk and interface,
and thermal stability [1]. Electrolytes were initially reported in the early 1970s,
including ceramic, glass, crystalline, and polymer electrolytes (PEs). PE was first
introduced by Fenton et al. in 1973 [2] and widely applied since 1980s [3]. In the
past decades, PEs attracted much attention from all over the world’s researchers
due to their promising applications in electrochemical storage/conversion devices.
In general, electrolytes can be classified into PEs, liquid electrolytes, ceramic elec-
trolytes, and solid inorganic electrolytes [4–6]. Briefly, PE is a membrane composed
of a dissolution of salts in a polymer matrix with high molecular weight [7]. PE is
widely applied in electrochemical devices such as solid-state batteries and recharge-
able batteries, ECDs, supercapacitors, fuel cells, dye-sensitized solar cells, and EC
windows. Technologically, PEs evolved from polymer, liquid ionic conductor and
solid-state ionic conductor. PEs can be prepared by dissolving metal salts in polar
polymer hosts, which could be used to replace the liquid ionic solution. Liquid elec-
trolytes possessing high ionic conductivity have several inevitable drawbacks such
as the possibility of electrolyte leakage, low chemical stability, hydrostatic pressure
considerations, and difficulty in assured sealing and are unsafe for practical applica-
tions especially in scaling-up processes [8]. Comparing with liquid electrolytes, PE
has several prominent advantages, such as high ionic conductivity, safety, flexibility,
wide electrochemical windows, and so on [9, 10].
Organic Electronics for Electrochromic Materials and Devices, First Edition. Hong Meng.
© 2021 WILEY-VCH GmbH. Published 2021 by WILEY-VCH GmbH.
18 2 Advances in Polymer Electrolytes for Electrochromic Applications
Factors that lead to the use of PE in an EC devices are as follows (Figure 2.1).
High
stability,
reversible, High ionic
and conductivity
Wide operation
potential reliable
window
Easy to
synthesize with
Cation low cost
coordination Main
ability concerns in
electrolyte Highly optical
transparent
Wide range of
working
temperature
Flexible and
mechanically
Chemical, and stretchable
electrochemical
stability Multifunctional
separator
Polymers in electrolytes with benign cation coordination ability can better make
for coordination bonding interactions with the metal cations.
● Wide operation potential window
Stable electrochemical window is the range of working potential in an EC device
without breakdown of electrolyte itself. The maximum potential is determined
by the potential of the oxidation reaction. Meanwhile, the minimum potential is
determined by the potential of the reduction reaction. To ensure the long-time and
cycling stability of the ECD, the working potential window of a device should be
considered in the electrochemical operating range of the electrolyte.
● Thermal, photo, chemical, and electrochemical stability
An ideal PE should possess good thermal and photo stability. During electro
chromic processes, the device may release heat, which may result in degradation
of the EC devices. Similarly, an ideal electrolyte with photo stability prevents
device from being destroyed via prolonged exposure to air. It is necessary to
keep good electrochemical stability in the voltage range for ECDs. Undesired
interaction effects between the EC layer and electrolyte should not exist in the
ECD during EC processes so that devices can keep reversible and long lifetime
performance for practical application. This chemical stability must be ensured
both during the deposition and during the cycling processes. Currently, small
molecule EC materials-based ECDs have appeared in lots of researches. However,
this kind of ECD mostly can be operated under higher potential. Therefore, PEs
with wide potential window are demanded.
● High ionic conductivity (>10−4 S/cm) with low electronic conductivity
PEs should be a good ionic conductor and electronically insulating (𝜎 e
< 10−12 S/cm) so that ion transport could be facilitated to minimize self-discharge.
In EC process, the essence of color change is the transfer of ions into and out of an
EC film. The electrolyte should also maintain its high ionic conductivity even after
thousands of cycles. The flexibility of polymer matrix chains in the amorphous
phase allows ions to be transported frequently. This easy transport of ions is
hindered in the crystalline phase, where the material is densely packed and there
is not enough space to allow rapid transport of ions [11]. The ion transference
number is important in the characterization of PEs. A large transference number
can reduce concentration polarization of electrolytes during charge–discharge
steps [12].
● Easy to synthesize with low cost
The price of PE cannot be the factor of resulting in hindering practical application.
Inexpensive, easily available PEs are highly necessary for the successful commer-
cialization and implementation of EC devices. It is worth mentioning that the
thickness of PE film should be controlled and easy to operate.
● Safe and environmentally friendly
Safe and environmentally friendly are highly desirable for practical application
of the ECDs. So far, ECDs have been widely used in people’s daily lives, such as
EC glasses, car mirrors, and cockpit glasses. A nontoxic, environmental, and recy-
clable electrolyte is a top priority in an EC device, which cannot jeopardize our
health.
20 2 Advances in Polymer Electrolytes for Electrochromic Applications
and poly(2-ethoxyethyl methacrylate) (PEO EMA), [31] poly vinyl chloride (PVC),
poly(vinyl sulfones) (PVS), and PVDF [32].
prepared by using PVDF for studying the coloration efficiency [53]. P(VDF-TrFE) as
GPE was also studied as potential PE in ECD with polyaniline as EC materials [1].
The gel electrolyte device reached an average ionic conductivity of 2.84 × 10−5 S/cm
and shows stable and reversible light modulation up to 65% in gel state. It was found
that the gel-state device was affected by the number of free ions, while the movement
of ions in the electrolyte bulk and the modulation of light in the semisolid device are
indicated by the electrolyte/EC material interface.
The ionic conductivity of PVDF PEs can be enhanced by incorporating sub-
stantial amounts of plasticizers or combining with IL. Jia et al. have studied
1-butyl-3-methylimidazolium hexafluorophosphate-loaded SCCO2 -treated electro-
spun P(VDF-HFP) membrane as an electrolyte in EC device [54].
Recently, Reynold’s group reported paper-based ECDs consisting of PEDOT:PSS
electrodes and [EMI][TFSI]/PVDF-HFP ion gel electrolyte layer (Figures 2.2 and
2.3) [55]. The ECDs incorporating an ion gel electrolyte were demonstrated where
a magenta-to-colorless device achieves a color contrast (ΔE*) of 56, attributing to
a highly color-neutral bleached state of the extracellular protein (ECP) (a* = −0.5,
b* = 2.9). It was found that the gel-state device was affected by the number of free
ions, while the movement of ions in the electrolyte bulk and the modulation of light
in the semisolid device were indicated by the electrolyte/EC material interface.
R R
O Conductive ink
R O er Electrochromic paper
O O
R pap
ted
O
O O
F-coa O O
O CN m
S S S n
(a) N N
S
n
R R –
SO3
O O
O O
(b) S n
V
R R
R O O R
O O
(c) S S
n
R R
R O O
O R
O
O O
O O
S x S y
(d) N N
S n
CNF coating Inkjet-printed PEDOT:PSS ECP magenta Ion gel electrolyte +0.8 V
CNF-coated paper Printed electrodes ECP spray casting Blade coating electrolyte Lateral paper ECD
1 2 3 4 5
Figure 2.3 A fabrication process for lateral paper ECDs showing inkjet-printed PEDOT:PSS
electrodes, deposition of ECPs, and [EMI][TFSI]/PVDF-HFP ion gel electrolyte layer. Devices
are operated by applying a 0.8 V bias across the two lateral pixels. Source: Lang et al. [55].
24 2 Advances in Polymer Electrolytes for Electrochromic Applications
S
C ran
y S S
S x
+
AIBN, 80 °C, 30 h
Cl
1 Cl
ran ran S
S y S
N N x y S x
NH4PF6
Figure 2.4 Synthetic routes for P[S-r-VBMI][PF6 ]. Source: Seo and Moon [75].
PS
Bromination ATRP ATRP
Bromoisobutyryl Styrene Methyl methacrylate
PS
bromide
: Cyclodextrin PMMA
Figure 2.5 Synthetic routes for (PS-b-PMMA)18 . Source: Jang et al. [77].
for self-healable EC have been reported in Leong’s group [82]. The interaction of
polymer blends or the inclusion of reaction sites and addition of ILs may induce
rapid healing at lower temperatures, attributing to the increased fluidity and
inhibition of the glass transition temperatures. Moreover, self-healing polymers
based on DA reaction [83] is another effective method for self-healing func-
tional materials. A polymer N-(4-aminophenyl)-N-phenylbenzene-1,4-diamine
maleimide (DATPFMA) was the first report on a bifunctional self-healing EC
polymer, which exhibited superior cyclic stability and colors variations [57]. The
N,N′ -bis(4-aminophenyl)-N,N 0 -diphenyl-1,4-phenylene diamine used as core and
electro-active unit for synthesizing the polymer poly(pentafluorophenyl methacry-
late) (PPFMA) provided more electrochemical active sites to enhance the EC
performance (Figure 2.6) [84]. This DA polymer can also repair cracks by retro-DA
and DA reaction for the self-repair capability [57].
However, developing a material that simultaneously exhibits excellent EC proper-
ties and good self-healing behavior at low temperature is still an unmet challenge,
such as large optical contrast, high coloration efficiency, and long-term, stability, and
fast healing process.
26 2 Advances in Polymer Electrolytes for Electrochromic Applications
O O
O N N O
O O O N
O O
Heating Cooling
Cooling Heating
0V 0.85 V 1.15 V
Faint yellow Grass green Dark blue
N
O
N O
OH
N
N O O
N N
N
O O
Electrochromic Self-healing
(a)
O O
HO
N N O O
O O
OH HO + N N
O O
N N O O
OH
O O
O PPF O N O
MA PPFMA
(b)
Figure 2.6 (a) The mechanism of self-healing process for electrochromic PPFMA film and
(b) the retro-DA and DA reaction for self-healing polymer PPFMA. Source: Zheng et al. [84].
(1) Non-volatility.
(2) No decomposition at the electrodes.
(3) No possibility of leaks.
(4) Decreased cell price (such as PEO, PMMA, etc.).
(5) Flexibility.
(6) Lowering the cell weight – solid-based cells do not need heavy steel casing.
(7) Safety.
Many studies have been addressed to incorporate inert oxide ceramics particles
into PE, in order to improve the mechanical properties, reduce polymer crys-
tallinity, and thus solve the problem of low ionic conductivity of solid polymeric
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III
I
A LA MUY MAGNÍFICA SEÑORA DOÑA JERÓNIMA PALOVA
DE ALMOGÁVAR, GARCILASO DE LA VEGA[399]
S. C. C. M.t[411]
S. C. C. M.t
Criado de V. S. M.t
Garcilaſso.[416]
III
GARSIAE LASSI DE LA VEGA AD FERDINANDUM DE ACUÑA[417]
EPIGRAMMA
Págs.
Págs.
Introducción. vii
Datos bibliográficos. xxi
ÉGLOGAS
I.—El dulce lamentar de dos pastores. 1
II.—En medio del invierno está templada. 27
III.—Aquella voluntad honesta y pura. 123
ELEGÍAS
I.—Aunque este grave caso haya tocado. 145
II.—Aquí, Boscán, donde del buen troyano. 159
EPÍSTOLA
Señor Boscán, quien tanto gusto tiene. 169
CANCIONES
I.—Si a la región desierta, inhabitable. 175
II.—La soledad siguiendo. 179
III.—Con un manso ruído. 183
IV.—El aspereza de mis males quiero. 187
V.—Si de mi baja lira. 197
SONETOS
I.—Cuando me paro a contemplar mi estado. 205
II.—En fin, a vuestras manos he venido. 207
III.—La mar en medio y tierras he dejado. 208
IV.—Un rato se levanta mi esperanza. 210
V.—Escrito está en mi alma vuestro gesto. 211
VI.—Por ásperos caminos he llegado. 212
VII.—No pierda más quien ha tanto perdido. 214
VIII.—De aquella vista pura y ecelente. 215
IX.—Señora mía, si de vos yo ausente. 216
X.—¡Oh dulces prendas, por mi mal halladas! 217
XI.—Hermosas ninfas, que en el río metidas. 218
XII.—Si para refrenar este deseo. 219
XIII.—A Dafne ya los brazos le crecían. 220
XIV.—Como la tierna madre que al doliente. 221
XV.—Si quejas y lamentos pueden tanto. 222
XVI.—No las francesas armas odiosas. 223
XVII.—Pensando que el camino iba derecho. 224
XVIII.—Si a vuestra voluntad yo soy de cera. 225
XIX.—Julio, después que me partí llorando. 226
XX.—Con tal fuerza y vigor van concertados. 227
XXI.—Clarísimo Marqués, en quien derrama. 228
XXII.—Con ansia estrema de mirar qué tiene. 229
XXIII.—En tanto que de rosa y azucena. 231
XXIV.—Ilustre honor del nombre de Cardona. 232
XXV.—¡Oh hado esecutivo en mis dolores! 234
XXVI.—Echado está por tierra el fundamento. 235
XXVII.—Amor, amor, un hábito vestí. 237
XXVIII.—Boscán, vengado estáis con mengua mía. 239
XXIX.—Pasando el mar Leandro el animoso. 240
XXX.—Sospechas que en mi triste fantasía. 242
XXXI.—Dentro en mi alma fue de mí engendrado. 243
XXXII.—Estoy contino en lágrimas bañado. 245
XXXIII.—Mario, el ingrato amor, como testigo. 246
XXXIV.—Gracias al cielo doy que ya del cuello. 248
XXXV.—Boscán, las armas y el furor de Marte. 250
XXXVI.—A la entrada de un valle, en un desierto. 252
XXXVII.—Mi lengua va por do el dolor la guía. 253
XXXVIII.—Siento el dolor menguarme poco a poco. 254
APÉNDICES
I.—A la muy magnífica señora doña Jerónima Palova de
Almogávar, Garcilaso de la Vega. 261
II.—Carta de Garcilaso al Emperador Carlos V. 269
III.—Garsiae Lassi de la Vega ad Ferdinandum de Acuña,
Epigramma. 271
IV.—Octava rima. 272
V.—Anécdota. 273