Polymer Journal

https://doi.org/10.1038/s41428-020-00397-4

ORIGINAL ARTICLE

Effect of plasticizer on the ion-conductive and dielectric behavior of

poly(ethylene carbonate)-based Li electrolytes
Kaori Kobayashi1 Gioele Pagot2 Keti Vezzù2 Federico Bertasi2 Vito Di Noto2 Yoichi Tominaga
● ● ● ● ●
1

Received: 7 July 2020 / Revised: 30 July 2020 / Accepted: 30 July 2020

© The Society of Polymer Science, Japan 2020

Abstract
Solid polymer electrolytes consisting of CO2-derived poly(ethylene carbonate) (PEC), LiPF6, and plasticizers (glycerol or 1-
ethyl-3-methylimidazolium bis(trifluoromethane sulfonyl)imide, EMImTFSI) were prepared by a simple casting method,
and their dielectric relaxation behavior was evaluated using broadband electric spectroscopy (BES), which clarified the
correlation between the polymer motion and ionic conduction. From the DSC and BES results, it was revealed that the
addition of plasticizer decreased the glass transition temperature and increased the dc conductivity (σdc) of the PEC
electrolyte. The BES results also revealed that the plasticizer increased the segmental motion of PEC and improved σdc, and
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the plasticizing effect of EMImTFSI on the PEC electrolyte was larger than that of glycerol. From the results of the Walden
plot and fragility analysis, it was expected that the degree of decoupling ε and fragility m would increase with the addition of
plasticizer because these plasticizers weaken the interactions between the PEC chains and Li ions in the electrolyte.

Introduction ionic transport is strongly coupled with the segmental motion

In the recent development of energy storage devices such as Li-
ion secondary batteries, solid polymer electrolytes (SPEs) have
become increasingly studied because they are lightweight, safe,
and flexible compared to classical liquid electrolytes [1, 2].
Since Wright and Armand first reported their fundamental
study and proposed the possibility of applying SPEs as solid
electrolytes for batteries [3, 4], many studies regarding SPEs
have been carried out, with most of the studies having been
directed toward polyether-based SPEs. However, the practical
use of polyether-based electrolytes is hindered because of their
limited ionic conductivity at ambient temperature. This limited
conductivity is due to the ion-conductive mechanism, in which
Supplementary information The online version of this article (https://
doi.org/10.1038/s41428-020-00397-4) contains supplementary
material, which is available to authorized users.
* Yoichi Tominaga
ytominag@cc.tuat.ac.jp
1 as a plasticizer into poly(ethylene oxide) (PEO)-based Li
Graduate School of Bio-Applications and Systems Engineering,
Tokyo University of Agriculture and Technology, Koganei,
Tokyo 184-8588, Japan
2
Department of Chemical Sciences, University of Padova,
Via Marzolo 1, I-35131 Padova, Italy
of polymer chains [5–8]. To improve the ion-conductive
properties of SPEs, various approaches have been carried out,
such as the incorporation of ethers as side chains into the
polymer structure, design of new types of Li salts, addition of
inorganic fillers to the SPE and decoupling of the segmental
motion from ionic conduction [9].
An alternative approach is to add organic compounds
with low molecular weights, such as poly(ethylene glycol)
dimethyl ether, ethylene carbonate, or propylene carbonate,
into the SPE to increase the presence of its amorphous
phases and to promote the segmental motion and dissocia-
tion of ion pairs [10–13]. These methods have shown
relatively high ionic conductivity values but run into basic
problems when using volatile and flammable components in
the SPE, so other additives should be incorporated into the
SPE. Room-temperature ionic liquids (ILs) are novel molten
salts composed of organic-based cations and anions and
show good properties, such as nonvolatility, high thermal
stability, nonflammability, and high ionic conductivity;
thus, these ILs can be applied in batteries and other appli-
cations [14–16]. Passerini et al. first incorporated Pyr13TFSI
electrolytes, and the mixed electrolyte showed good ionic
conductivity [17]. Since many studies regarding the addi-
tion of IL into an SPE have been carried out, it is worth
noting that the IL-containing imidazolium cation shows

higher conductivity and lower viscosity than other systems
[18]. It has also been reported that glycerol can be used as a
plasticizer for a natural polymer-based SPE [19]. Glycerol
also has a plasticizing effect on an SPE because of its low
molecular weight and high dielectric constant, which can
assist the dissociation of ion pairs [20, 21].
On the other hand, it is known that poly(alkylene carbonate)
s can be synthesized by alternating the copolymerization of
epoxides with CO2, since the synthesis was first proposed by
Inoue et al. [22]. The resulting polycarbonates (CO2/epoxide
copolymers) are basically amorphous and have excellent
properties, such as biodegradability, high transparency, and
easy processing [23, 24]. This synthetic method is also pro-
mising for the environment and for the sustainable use of
carbon sources. Tominaga et al. have studied novel polymer
electrolytes based on poly(alkylene carbonate)s such as poly
(ethylene carbonate) (PEC) and recently found that PEC-based
Li electrolytes have good ionic conductivity with a low glass
transition temperature (Tg), an excellent Li-ion transference
number, and good battery performance at room temperature
[25–29]. This specific ion-conductive behavior comes from the
uncoordinated structure between the Li ions and PEC chains,
which is different from the stable solvation structure in
polyether-based electrolytes [29–31]. The addition of plastici-
zer to the PEC electrolyte is also expected to increase the
conductivity, and the plasticizing effects on the thermal prop-
erties, polymer/ion interactions, and ion-conductive and
dielectric relaxation behaviors should be investigated. In this
study, novel PEC/LiPF6 electrolytes were prepared by plasti-
cizing with either 1-ethyl-3-methylimidazolium bis(tri-
fluoromethane sulfonyl)imide (EMImTFSI) or glycerol, and
their structural and physicochemical properties are reported
here for the first time.
Experimental
Electrolyte preparation
PEC (Mw = 265,000, Empower Materials Ltd., USA) was
precipitated from acetonitrile into methanol for rinsing and
dried under vacuum at 60 °C for 24 h before use. Lithium
hexafluorophosphate (LiPF6, Sigma Aldrich Co., battery
grade), glycerol (Carlo Erba Co.) and EMImTFSI (Sigma
Aldrich Co.) were used as received. The structures of PEC,
glycerol and EMImTFSI are shown in Fig. 1. PEC, LiPF6, and
the plasticizer were mixed with acetonitrile and stirred at room
temperature for 24 h. The concentration of LiPF6 in PEC was
12 mol% to a monomer unit ([Li+]/[monomer] × 100), and the
plasticizer was added to PEC at 5% by weight. The resulting
mixture was cast onto a plastic dish and dried at 40 °C for 24 h
on a hotplate in a glovebox filled with Ar gas and then dried
at 60 °C for 72 h under vacuum to remove the solvent.
K. Kobayashi et al.
CH2 O O
CH2 C
O n
H3CH2C CH3
N N
PEC +
OH F3C N- CF3
S S
HO CH OH O O O O
H2C CH2
Glycerol EMImTFSI
Fig. 1 Structures of PEC, glycerol, and EMImTFSI
The abbreviation of all samples, PEC/LiPF6 with or without
plasticizers, EMImTFSI (IL), and glycerol (Gly), are PEC/Li or
PEC/Li + IL and PEC/Li + Gly, respectively.
Characterization
Differential scanning calorimetry (DSC) measurements were
performed using a modulated differential scanning calorimeter
(MDSC Q20, TA Instruments Co.) in a N2 (25 ml/min) and He
gas (25 ml/min) flow and a temperature range −160 to 210 °C
at a heating rate of 3 °C/min. Thermogravimetric analysis
(TGA) was also carried out for all samples using a TGA2950
(TA Instruments Co.) in a N2 gas (100 ml/min) flow and a
temperature range of 25–950 °C at different rates between
0.001 and 50 °C/min according to each weight change. X-ray
diffraction (XRD) measurements for all samples were carried
out with an eXplorer instrument (GNR Analytical Instruments
Co.), Bragg–Brentano geometry, and a Cu Kα radiation (λ =
1.5406 Å) source in a Bragg’s angle (2θ) range of 3–50° with a
constant step of 0.05°. Several pieces of sample membrane
were layered so that the sample thickness was approx. 600 µm
and sealed between Mylar sheets with silicon grease in dry Ar.
Broadband electric spectroscopy (BES) measurements were
performed using a Novocontrol Alpha-A analyzer. The com-
plex permittivity ε* (ω) and conductivity σ* (ω) were measured
in a frequency range of 10−2–107 Hz at temperatures from
−100 to 100 °C. Each sample was loaded in a cell hermetically
sealed by two Pt electrodes with a diameter of 13 mm; these
cells were assembled in a glovebox filled with dry Ar gas, and
kept in dry N2 during measurements. Fourier transfer-infrared
(FT-IR) spectra were acquired at room temperature using a
Nicolet FT-IR Nexus spectrometer (Thermo Scientific) with a
SPECAC Golden Gate single reflection diamond ATR setup at
a resolution of 1 cm−1.
Results and discussion
Thermal analysis
Thermal analysis data of pure PEC and all electrolytes are
summarized in Table 1. The original TGA and DSC curves
Effect of plasticizer on the ion-conductive and dielectric behavior of poly(ethylene carbonate)-based. . .
Table 1 TGA (1% decomposition temperature, Td1 (1st) and Td2 (2nd),
from Fig. S1) and DSC (Tg from Fig. S2) data of the pure PEC and
PEC/LiPF6 electrolytes
Sample Td1/°C Td2/°C
Pure PEC 193 – 21
PEC/Li 143 239
PEC/Li + Gly 123 243
PEC/Li + IL 123 222
are shown in Figs. S1 and S2 in the Supplementary Infor-
mation. The thermal degradation of pure PEC occurs at 193
°C, and the PEC loses almost all its weight very rapidly due
to backbiting in which the nucleophilic attack of the term-
inal hydroxyl group produces the corresponding cyclic
carbonate [32]. The PEC/Li clearly shows a two-step
decomposition; the first is attributed to the PEC, and the
second is due to the Li salt (LiPF6). The 1% decomposition
temperature (Td1) during the first step with PEC/Li is 50 °C
lower than that with pure PEC. This result is due to the
same degradation behavior in PEO in which the ether bonds
easily undergo thermal scission at low temperatures in an
electrolyte environment with Li salt [33]. In the case of the
PEC electrolytes with plasticizers, the effect of the addition
of plasticizer to PEC/Li on the Td1 value is relatively small.
The two Td1 values of the plasticized electrolytes are 20 °C
lower than that of PEC/Li, and this small decrease may be
due to the thermal scission of C–O bonds in the carbonate
unit of PEC at low temperatures in the plasticized electro-
lyte, in which they have bond energies comparable to that of
a C–C bond [33]. The value of Tg for pure PEC is 21 °C,
and this value is slightly higher than that of the same PEC
reported previously (Tg: 12 °C, Mn = 38,000) [34] because
of the difference in molecular weight. The addition of LiPF6
to PEC increases the Tg by 15 °C due to the formation of
interactions between the Li ions and C=O groups of the
PEC chain, but the addition of plasticizer to PEC/Li
decreases the Tg because of the plasticizing effect, which
weakens the interactions between the PEC chains and Li
ions [19, 35]. The electrolyte with EMImTFSI has a much
lower Tg than that with glycerol, which is probably due to
the plasticizing effect of TFSI anions on the polymer elec-
trolyte [36]. In Fig. S2, there are some unknown peaks for
all samples above 150 °C, and these peaks seem to be
attributed to the thermal decomposition of PEC, as shown in
Fig. S1. Tiny endothermic peaks are also observed in the
plasticized electrolytes at 96 °C (for PEC/Li + Gly) and 82 °
C (for PEC/Li + IL), which may be due to a microphase
separation by the formation of unknown complexes or
unstable crystals. From the XRD patterns (Fig. S3 in
the Supplementary Information) of all samples, only two
broad diffractions appear at 22 and 44°, which means the
samples exist in an amorphous phase [37].
Tg/°C
36
21
−0.1
Fig. 2 Real conductivity component (σ′) of the broadband electric
spectra for PEC/Li, PEC/Li + IL and PEC/Li + Gly from −100 to a
max. of 130 °C at 10 °C intervals. The blue curves indicate data
measured at 20 °C
Dielectric and ion-conductive behavior
The frequency dependencies of real conductivity σ′ for PEC
electrolytes are shown in Fig. 2. The conductivity values of
all PEC electrolytes are very low, below 20 °C (data are
shown in a blue color), because of its Tg. The conductivity
increases when above 20 °C, and a clear plateau in the
medium frequencies gradually appears with increasing
temperature.
The characterization of the dielectric (a) and conductive
spectra (b) for PEC/Li+IL at 50 °C is shown in Fig. 3 as an
example. The complex conductivity σ* is basically obtained
from the measured complex permittivity ε* using Eq. (1):
σ
¼ iωε
ðσ 0 ¼ ωε00 ; σ 00 ¼ ωε0 Þ ð1Þ
where ω is the angular frequency (=2πf, f is frequency). The
ε* value exhibits two distinct relaxation processes. One
process, which appears on the low-frequency side, is
attributed to electrode polarization. This event is associated
with the charge accumulation at the interface between each
sample and the Pt blocking electrodes of the measurement
cell [38]. The other process is called dielectric relaxation
and is associated with polymer motion. A detailed analysis
shows that this process splits into two components that can
be assigned to α and β relaxation. In the conductivity
spectra in Fig. 3b, the plateau of σ′ in the intermediate
frequency range corresponds to the dc conductivity σdc
[38, 39]. The increase in σ′ on the high-frequency side is
due to the dielectric loss of the two dielectric relaxations,
and the decrease on the low-frequency side expresses a
suppression of conductivity due to electrode polarization.
The imaginary component σ″ increases with increasing
frequency on the high-frequency side due to the dielectric
contribution. On the other hand, σ″ exhibits a symmetrical
peak on the low-frequency side, implying that the electrode
polarization results in conductive relaxation rather than

Fig. 3 (a) Dielectric and (b) conductive spectra of PEC/Li-IL at 50 °C
dielectric relaxation.

Before the quantitative analysis, the
derivative spectra ε00der ¼ ðπ=2Þ∂ε0 =∂ðln f Þ based on the
Kramers–Kronig relations were used to determine the
number of relaxation processes and the number of fitting
terms in Eq. (2) [8, 40]. The spectra of ε* are fitted with
Eq. (2), in which the first term, which is related to the
material conductivity, is added to the empirical equations
[38, 39].
 σ γ 0 X σ  1
 the addition of Gly and IL plasticizers to PEC/Li; further-
ε
¼ i
0 j
þ 1 γj
ω j
iω 1 þ ðiωτj Þ
X Δεk
þ n o αk þ ε 1
k 1 þ ðiωτk Þβk
The first term of Eq. (2) accounts for the material con-
ductivity. In most cases, γ0 is equal to 1 and only affects ε″
and σ′. The second term expresses the conductive relaxation
with a symmetrical loss peak at a frequency of fi = 1/2ππj.
In the jth conductive relaxation process, σj, τj, and γj are the
conductivity, relaxation time and symmetric shape para-
meter of the relaxation peak, respectively. The third term
accounts for the dielectric relaxation described by the
Havriliak–Negami theory [38]. In the kth dielectric relaxa-
tion process, Δεk, τk, ak, and βk are the relaxation strength,
relaxation time, asymmetric and symmetric shape para-
meters, respectively. The ε∞ of the last term describes the
instantaneous permittivity. The observed dielectric spectra
can be well reproduced by Eq. (2), as shown by the solid
K. Kobayashi et al.
Fig. 4 Temperature dependence of (a) dc conductivity (σdc) and
(b) relaxation frequency (fR) for the PEC/Li, PEC/Li+Gly and PEC/Li
+IL electrolytes. Filled and open plots in (b) are based on fα and fβ,
which are the α and β relaxation, respectively
lines in Fig. 3. As a result of fitting, the quantitative char-
acterization of the dielectric and conductive features can be
obtained.
The temperature dependencies of dc conductivity (σdc)
and relaxation frequency (fR) for PEC electrolytes are
shown in Fig. 4. In Fig. 4a, the dependence is shown as a
VFT-type, which is typical of ion-conductive polymer
electrolytes [5, 6, 8, 38, 39]. The σdc values increase with
more, the plasticizing effect of EMImTFSI is larger than
that of glycerol. On the other hand, two types of dielectric
ð2Þ
relaxations are observed in the PEC electrolytes, as shown
in Fig. 4b. The relaxation frequencies fR represented by the
filled and open plots indicate VFT-type and Arrhenius-type
temperature dependencies, respectively, so we determined
them to be the α and β relaxation, which are attributed to the
segmental and local motions of the polymer [5, 6, 38, 39].
Local motion occurs due to the motion of some monomer
units in which the number of moving units is smaller than
the segment because this relaxation is also observed in pure
PEC [41, 42]. The PEC/LiPF6 electrolytes can therefore
show specific dielectric relaxation behavior [38] contrary to
polyether-based electrolytes, thereby showing two types of
relaxation, α and β [5, 6, 8, 39]. It is notable that the fα
values increase with the addition of plasticizers, whereas the
fβ values are almost constant despite the existence of plas-
ticizers. This result implies that the plasticizer has an effect
on the segmental motion of the polymer but no effect on the
local motion.
Effect of plasticizer on the ion-conductive and dielectric behavior of poly(ethylene carbonate)-based. . .
Fig. 5 Walden plots of the PEC/Li, PEC/Li + Gly, and PEC/Li + IL
electrolytes
Relation between the ionic transport and segmental
motion of polymer
To further discuss the ion-conductive properties of these
PEC-based electrolytes with plasticizers, we used the
Walden plot analysis. According to the Walden rule, the
molar conductivity (Λ) is inversely proportional to the
0
viscosity (η) of the electrolyte (Ληα ¼ const:), which
implies that all ions completely dissociate and their diffu-
sion is controlled by the macroscopic viscosity. Sokolov
et al. substituted the viscosity (η) into the segmental
relaxation time (τα) of polymers to apply the Walden plot
analysis [8, 40, 43]. From the Walden plot analysis, two
useful pieces of information can be obtained. One is the ion-
conductive ability of the material relative to the “ideal”
aqueous solution. A dilute aqueous solution is used as a
reference (e.g., LiCl) and can be drawn as an “ideal”
Walden line on the plot [40, 43]. This “ideal” line divides
the regime into a superionic regime (top side) and a sub-
ionic regime (bottom side). The other is the degree of
coupling or decoupling between the segmental motion and
ionic conduction. Ionic conductors that couple completely,
namely, dilute aqueous salt solutions, show a straight line
with almost the same slope on the reference line. The
Walden plots of PEC/LiPF6 electrolytes are shown in Fig. 5.
All plots are on the reference line or in the superionic
regime, so these are good ion-conductive materials. It is
worth noting that plots are placed upward by the addition of
plasticizer, and the plasticizing effect of EMImTFSI on
PEC/Li is larger than that of glycerol. The slope values for
the Walden plots (a′) are listed in Table 2. It is obvious that
these PEC/LiPF6 electrolytes are incomplete coupling sys-
tems because these a′ values are smaller than 1 (the refer-
ence line slope). The degree of decoupling ε (=1 − a′)
increases with the addition of plasticizer, and PEC/Li + IL
shows the highest value of all electrolytes investigated.
From the Walden plot analysis, it is expected that these
plasticizers weaken the interactions between the polymer
chains and ions.
Table 2 Slope values in the Walden plot a′ and the fragility m for the
PEC/LiPF6 electrolytes
Sample a′ m
PEC/Li 0.84 79.0
PEC/Li + Gly 0.74 92.3
PEC/Li + IL 0.63 146.6
Fig. 6 FT-IR spectra of the pure PEC and PEC electrolytes in the C=O
stretching vibration region
Another approach to discuss the degree of decoupling is
the estimation of the fragility value [44], which was carried
out. The fragility (m) is the quantitative parameter that
characterizes the deviation of the temperature dependence
of τα from the Arrhenius behavior near Tg and is defined in
Eq. (3) [45–47].

d log τα 
m¼
 ð3Þ
d Tg =T 
T¼Tg
The systems that have high m values are called “fragile,”
and the systems that have low m values are called “strong.”
In other words, a material that shows little change in phy-
sical properties with temperature is “strong,” while a
material that shows a very abrupt change in properties as it
approaches Tg is “fragile.” Sokolov et al. proposed that
polymers with relatively stiff backbones or relatively stiff
side groups showed high m values [45], and systems with
high m values showed high decoupling exponents [46, 47].
The results of estimation for all m values are listed in
Table 2. In our previous paper, we revealed that pure PEC
has a high m value of 120, and this value decreases with the
addition of LiTFSI [42]. In this study, the addition of LiPF6
to PEC also decreases the m value. However, the m value
increases with the addition of plasticizer, and PEC/Li + IL
shows the highest value of all electrolytes investigated. This
means that the electrolyte plasticized by EMImTFSI is the
most decoupled system, and this is consistent with the
results of the Walden plot analysis.

Table 3 Peak fraction of the FT-
Sample Peak fraction/%
IR bands for free C=O and
C=O that interacts with Li ions Free C=O (two bands)
(Li+) in the pure PEC and PEC/ 1735–1750 cm−1
LiPF6 electrolytes
Pure PEC 91.6
PEC/Li 53.0
PEC/Li + Gly 73.3
PEC/Li + IL 61.3
FT-IR studies
The characterization of interactions between PEC, Li, salt
and plasticizer was performed using the FT-IR results. The
FT-IR spectra at frequencies of 1650–1850 cm−1 with the
pure PEC and PEC/LiPF6 electrolytes are shown in Fig. 6.
The bands at 1735–1750 cm−1 can be attributed to the
stretching vibration mode of free C=O in the PEC chains
[35, 41]. These two peaks are assigned to free C=O without
a strong interaction, which implies that there are two C=O
in this region; one is free C=O without any interactions,
and the other is based on weak intramolecular interactions
between C=O and the hydrogen of the methylene unit [41].
When Li salt is incorporated into PEC, a new band appears
at lower wavenumbers of 1710–1720 cm−1, which is
attributed to the stretching vibration mode of the interacting
C=O peak with a Li ion (C=O…Li+) [35, 41]. Here, the
vibration region is divided into three peaks (free C=O,
C=O…Li+ and unknown, as a dotted line) for quantitative
analysis, and the fraction values of each peak are sum-
marized in Table 3. The peak fraction of the interacting
C=O for PEC/Li clearly decreases with the addition of
plasticizer, so it is expected that plasticizer may weaken the
interaction between the PEC chains and Li ions. The
addition of glycerol to PEC/Li decreases the fraction by
approx. 15% for the interacting C=O peak, which may be
due to the separation of Li ions from the PEC environment
because of the existence of three OH groups.
Conclusions
Novel ion-conductive polymer electrolytes based on PEC/
LiPF6 (PEC/Li), with and without glycerol (Gly) and
EMImTFSI (IL) plasticizers, were prepared, and their
structural and physicochemical properties were character-
ized using TGA, DSC, XRD, BES, and FT-IR techniques.
The DSC and BES studies revealed that the addition of
plasticizer decreased Tg and increased the ionic conductivity
of PEC/Li. The dc conductivity (σdc) values of PEC/Li
increased with the addition of plasticizers, and the plasti-
cizing effect of IL was larger than that of Gly. From the
results of the temperature dependencies of relaxation
K. Kobayashi et al.
C=O…Li+ Unassigned peak
1710–1720 cm−1 1680–1700 cm−1
0 8.4
40.3 6.7
25.0 1.7
36.7 2.0
frequency (fR), two types of dielectric relaxations were
observed: one was the VFT-type dependence of fα, which
was determined as the α relaxation of the segmental motion
of PEC, and the other was the Arrhenius-type dependence
of fβ, which was determined as the β relaxation of the local
motion. The fα values increased with the addition of plas-
ticizers, whereas the fβ values were almost constant despite
the existence of plasticizers, which implied that the plasti-
cizer increased the mobility of PEC segments but had no
effect on local motion.
From the Walden plot analysis, it was revealed that the
degree of decoupling ε (=1−a′) increased with the addition
of plasticizer, and the ε value of PEC/Li + IL was the
highest of all electrolytes. It was concluded that these
plasticizers weakened the interactions between the PEC
chains and Li ions in the electrolyte, which was supported
by the results of the fragility and FT-IR analysis.
Acknowledgements This work was supported financially by a Grant-
in-Aid for Scientific Research (B) of JSPS KAKENHI (No.
16H04199), Japan. One of the authors (KK) acknowledges financial
support from the Tobitate! Young Ambassador Program, Japan for her
study abroad.
Compliance with ethical standards
Conflict of interest The authors declare that they have no conflict of
interest.
Publisher’s note Springer Nature remains neutral with regard to
jurisdictional claims in published maps and institutional affiliations.
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