Journal of Physics and Chemistry of Solids 135 (2019) 109082

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Journal of Physics and Chemistry of Solids

journal homepage: www.elsevier.com/locate/jpcs

Novel synergistic in situ synthesis of lithium-ion poly(ethylene citrate)-TiO2 T

nanocomposites as promising fluorine-free solid polymer electrolytes for
lithium batteries
Fernando Pignanellia, Mariano Romeroa,∗, Jorge Castiglionib, Ricardo Faccioa,∗∗,
Alvaro W. Mombrúa
a
Centro NanoMat/CryssMat/Física – DETEMA, Facultad de Química – Universidad de la República, Montevideo, C.P. 11800, Uruguay
b
Laboratorio de Fisicoquímica de Superficies – DETEMA, Facultad de Química – Universidad de la República, Montevideo, C.P. 11800, Uruguay

A R T I C LE I N FO A B S T R A C T

Keywords: Here, we report a synergistic in situ synthesis of lithium-ion poly (ethylene citrate) with embedded titania na-
Titania noparticles in which the esterification process itself triggered the hydrolysis of the titanium alkoxide precursor to
Polyester form a promising fluorine-free lithium-ion solid polymer electrolyte. Structural characterization by means of X-
Nanocomposite ray diffraction, small angle X-ray scattering and also confocal Raman spectroscopy revealed the formation of the
Lithium-ion
polyester with embedded titania nanoparticles in agreement with our Raman spectra simulation by means of
Solid polymer electrolyte
DFT methodologies. Our theoretical modeling of the polyester also envisaged the interaction of lithium-ion via a
tridentate coordination with oxygen atoms of carboxylate (–COO-) and ester (–COO–) groups. There is a slight
increase in the degree of polymerization and thermal stability for our lithium-ion polyester with increasing
titania nanoparticles concentration. In consequence, a two-order magnitude increase in the ionic conductivity
was observed, yielding 1.74× 10−4 S cm−1 for a 20% weight fraction of titania nanoparticles. Thus, involving a
novel approach based in the synergistic in situ preparation of lithium-ion poly (ethylene citrate) with titania
nanoparticles, this procedure contributes to solve the many safety and environmental issues of the constitutive
materials of lithium-ion solid polymer electrolytes.

1. Introduction particularly; poly (ethylene succinate) [12], poly (ethylene malonate)

In the last years, solid polymer electrolytes have been extensively
studied as promising materials to substitute the liquid electrolytes in
lithium batteries mainly because of their flexibility, safety and light
weight. The solid polymer electrolytes are basically composed of an
electronic insulating polymer and a lithium salt with high degree of
ionic-pair dissociation to assure good ionic conductivity [1–11]. Among
all polymers tested, the most frequently used are poly (ethylene oxide)
(PEO) [1,2], poly (acrylonitrile) (PAN) [3,4] or poly (methyl metha-
crylate) (PMMA) [5,6] and the most common lithium salts are nitrate
(LiNO3), perchlorate (LiClO4), tetrafluoroborate (LiBF4) or tri-
fluoromethanesulfonate (LiCF3SO3) [7–11]. Typically, the ionic-pair
dissociation of lithium salts is increased by the lithium-ion affinity for
ether (–CO–), nitrile (–C^N) or carbonyl (–COO–) groups of PEO, PAN
or PMMA, respectively [1–11]. Moreover, there have been attempts to
study the use of other ecofriendly polymer hosts such as polyesters,
[13], poly (ethylene citrate) [14–16], poly (glycidyl ether carbonate)
[17] pursuing an enhancement of ionic conductivity. The strategy of
using these polyesters is also based on the increment of the ionic-pair
dissociation of lithium-ion due to the interaction with (–COO–) ester
groups. However, no relevant enhancement above ∼10−5 –
10−4 S cm−1 was obtained for the previously mentioned cases [12–18].
In the case of lithium-ion poly (ethylene citrate) electrolytes, the effect
of silica nanoparticles was also reported yielding ionic conductivities up
to ∼ 10−4 S cm−1 at room temperature [19–21]. There is also recent
experimental and theoretical research focusing in the ability of polye-
sters as promising lithium-ion solid polymer electrolytes by the inter-
action of different available oxygen atom groups such as (–COO–) ester,
carbonyl (–C]O), hydroxyl (–OH) and ether (–CO–) coexisting in the
same polymer structure [19,20]. In addition to the high degree of ionic-
pair dissociation, the increase in the ionic conductivity of these solid
polymer electrolytes is also related to a decrease on the crystallinity of

∗
Corresponding authors.
∗∗
Corresponding authors.
E-mail addresses: mromero@fq.edu.uy (M. Romero), rfaccio@fq.edu.uy (R. Faccio).

https://doi.org/10.1016/j.jpcs.2019.109082
Received 30 April 2019; Received in revised form 27 June 2019; Accepted 29 June 2019
Available online 05 July 2019
0022-3697/ © 2019 Elsevier Ltd. All rights reserved.
F. Pignanelli, et al.
Fig. 1. Scheme of our synergistic in situ preparation of lithium-ion ethylene citrate polyester with TiO2 nanoparticles.
the polymer and to the increase in the dissociation of lithium-ion salt by
adding ceramic nanoparticles as fillers. In this sense, several studies
performed by adding ceramic nanoparticles such as alumina (Al2O3)
[21,22], silica (SiO2) [23] and titania (TiO2) [24,25] yielded to an
improve in the room temperature conductivity of lithium-ion up
to ∼ 10−4–10−3 S cm−1. In addition, there are significant contribu-
tions for the successful in situ sol-gel preparation of hybrid titania na-
nostructures embedded in polymer hosts such as polyaniline [26],
polypyrrole [27] and poly (ethylene oxide) [28]. Inspired by this pre-
vious works and also contributing to solve the many safety and en-
vironmental issues of the constitutive materials of solid polymer elec-
trolytes, our strategy involves a novel approach based in the synergistic
in situ preparation of a fluorine-free lithium-ion poly (ethylene citrate)
polyester with titania nanoparticles. In order to achieve this task, we
use lithium carbonate salt as a lithium-ion source and titanium alkoxide
as precursor, which in situ hydrolysis to form titania nanoparticles is
synergistically triggered by the polymer esterification process, as re-
presented in the scheme shown in Fig. 1. In addition, we provide a full
characterization and discussion of the synthesis mechanism, structure,
microstructure and ionic conductivity analysis for our samples.
2. Materials and methods
2.1. Preparation of Li–P-X samples
Citric acid monohydrate (CA) with Sigma-Aldrich ID: C1909
(1.7794 g) and lithium carbonate (LC) with Sigma-Aldrich ID: 255823
(0.0632 g) in a CA:LC ∼ 10:1 M ratio were dissolved in 40 mL of ethy-
lene glycol (anhydrous, 99.8%) under magnetic stirring at 80 °C.
Appropriate quantities of titanium (IV) propoxide (Sigma-Aldrich ID:
2
Journal of Physics and Chemistry of Solids 135 (2019) 109082
253081) were dissolved separately in ethylene glycol and slowly
poured to the previous solution; the volumes of titanium propoxide
were calculated to obtain TiO2/polyester nano-composites of theore-
tical compositions equal to: 0%, 15%, 20% and 25% by mass (named
Li–P-X with X = 0, 15, 20, 25 respectively).
The mixtures were maintained under magnetic stirring at 80 °C for
12 h and a pH close to neutrality (pH∼7) was observed. Then, the
temperature was set to 150 °C in order to slowly evaporate the excess of
solvent and favor the polyesterification process until a transparent
light-yellowish gel was obtained in each case. Finally, the samples were
dried for 6 h in a vacuum oven at 100 °C to remove the presence of
residual solvent from our samples.
2.2. Characterization of the Li–P-X samples
Confocal Raman microscopy imaging and spectroscopy was per-
formed using a WITec Alpha 300-RA confocal Raman spectrometer; the
laser excitation wavelength used in this experiment was 785 nm in
order to avoid sample fluorescence and power was set to < 10 mW to
diminish the risk of thermal decomposition by local heating. Raman
spectra were obtained by averaging a set of 150 measurements with
0.5 s as integration time. Raman spectra simulation was performed
using density functional theory (DFT) [29,30] using the hybrid ex-
change correlation potential B3LYP [31–34] for a 6–31 G (d,p)+ basis
set, as implemented in Gaussian 09 [35]. X-ray powder diffraction
(XRD) measurements were performed using a Rigaku Ultima IV dif-
fractometer, utilizing CuKα radiation, operating in the
2θ = 5.00–70.00° range using steps of 0.02° with a 12 s integration time
per step. Grazing incidence small angle X-ray scattering (GI-SAXS)
measurements were taken in parallel beam configuration in the range
F. Pignanelli, et al.
Fig. 2. Raman microscopy images of polyester-rich (blue) and TiO2-rich
(yellow) zones for Li–P-X with X = 0, 15, 20 and 25 samples.
q = 0.01–1.80 Ε−1 and the fixed incident angle at +0.2° above the
critical angle. Thermal decomposition of samples was analyzed by
thermogravimetric analysis (TGA) using Shimadzu TGA-50, with a
50 mL min−1 air flow and a heating rate of 5°Cmin-1 in the 25–900 °C
temperature range. Differential Scanning Calorimetry (DSC) analysis
was obtained using Shimadzu DSC-60 with a 10 °C/min ramp rate in the
25–300 °C temperature range using sealed aluminum crimps with static
air atmosphere. Electrochemical impedance spectroscopy (EIS) mea-
surements were performed for the pellets with 1.0 cm surface/thickness
ratio sputtered gold blocking electrodes. EIS data was obtained using a
10 mV AC voltage amplitude in the 0.1 Hz − 1.0 MHz frequency range
at 20 °C. DC polarization using a Gamry Reference 3000 impedance
analyzer and data was processed using Echem Analyst software.
3. Results and discussion
3.1. - Confocal Raman microscopy
Confocal Raman microscopy images for Li–P-X with X = 0, 15, 20
and 25 samples are shown in Fig. 2. The confocal Raman images were
obtained for a 10 × 10 μm2 area by collecting 40 × 40 Raman spectra
with ∼270 nm/pixel resolution totalizing 1600 Raman spectra. The
contrast between the two complementary zones shown in the images
were filtered by the relative intensity of a sharp peak at ∼150 cm−1
typically ascribed to the Ti–O stretching mode of TiO2 anatase poly-
morph [36] and on the other hand, a peak at ∼ 1460 cm−1 typically
associated to the C–H bending mode of aliphatic chains of polymers,
already observed for ethylene citrate polyester [37], defining a TiO2-
rich (yellow) and polymer-rich (blue) zones in the images, respectively.
The presence of TiO2 anatase nanoparticles is evidenced by the
presence of yellow spots in the confocal Raman images, showing rela-
tively good homogeneity in their distribution embedded in the polymer
matrix. It is also observed that the increasing concentration of TiO2
nanoparticles (X) also lead to an increment in the agglomeration of
TiO2 nanoparticles evidenced by the formation of larger sized clusters.
Raman spectra associated to each zone in the confocal Raman images
for Li–P-X with X = 0, 15, 20 and 25 samples together with the Raman
spectra of lithium carbonate salt (Li2CO3), citric acid (CA) and ethyle-
neglycol (EG) precursors are shown in Fig. 3. At first inspection, we
observe the broadening and splitting of some Raman peaks in our Li–P-
X samples, respect to the isolated precursors and no clear sign of the
sharp peak of carbonate anion stretching at ∼1100 cm−1 in the Li–P-X
samples. This could be suggesting the partial elimination of carbonate
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Journal of Physics and Chemistry of Solids 135 (2019) 109082
Fig. 3. Confocal Raman spectra of selected polyester-rich (blue) and TiO2-rich
(yellow) zones for Li–P-X with X = 0, 15, 20 and 25 samples. Raman spectra for
Li2CO3 (grey), CA (red) and EG (green) precursors are shown as references
(REFs) and theoretical Raman spectra calculation for CA (red), EG (green) and
EG-(AC/Li)-EG (blue) models using Density Functional Theory (DFT) are shown
with their corresponding assignation of vibrational modes. The dotted lines
indicate selected Raman peaks position of precursor references as a guide to the
eye to show the Raman shifting of peaks corresponding Li–P-X with X = 0, 15,
20 and 25 samples.
anions when reacting with the CA residual protons in aqueous media,
possibly as carbon dioxide (CO2) gas, as previously proposed in litera-
ture [14–16]. In order to assign the vibrational modes for our polyester
samples with more accuracy, we performed simulations of Raman
spectra by means of DFT calculations. In Fig. 3, we showed the calcu-
lated Raman spectra for theoretical optimized structures of CA, EG and
a small oligomer based in the esterification of two molecules of EG with
one molecule of CA and a lithium-ion bonded to the free carboxylate
group of CA; named as EG (AC-Li)EG, as displayed in Fig. 4a.
The DFT optimized structure of EG (AC-Li)EG showed the interac-
tion of lithium-ion via a tridentate coordination with carbonyl (–C]O)
groups from (–COO-) carboxylate and (–COO–) ester groups. The most
relevant features of the theoretically simulated Raman spectra of EG
(AC-Li)EG are basically, the splitting of the C]O stretching mode of CA
from 1730 cm−1 to 1790, 1710 and 1630 cm−1 for EG (AC-Li)EG, the
slight shift of the CH2 scissoring modes of EG at ∼ 1500 cm−1 and CA
at 1480 cm−1 towards ∼ 1466 cm−1 for EG (AC-Li)EG, the splitting of
the CH2 wagging mode of EG at ∼ 1380 cm−1 and CA at ∼ 1240 cm−1
towards ∼ 1330, 1300, 1280 cm−1 for EG (AC-Li)EG, the splitting of
F. Pignanelli, et al.
Fig. 4. (a) Lithium-ion ethylene glycol citrate model, named as EG (AC-Li)EG,
after optimization using DFT calculations. (b) Pictorial scheme for the Li–P-X
samples depicting the interchain (dC) and interdomain (d) distances for the
polyester.
the C–C backbone stretching mode at 1080 cm−1 of CA and the C–O
stretching mode at 1000 cm−1 towards several peaks with high relative
intensity at ∼ 1000–1100 cm−1 for EG (AC-Li)EG, the shifting of the
C–C–C backbone bending at ∼ 920 cm−1 to 970 cm−1 for EG (AC-Li)
EG, the non-modification of HOC–C stretching mode of EG at
830 cm−1, the central C–COO stretching mode of CA from ∼750 to
840 cm−1 for EG (AC-Li)EG and finally the shift of the OCO–H mode of
CA from ∼550 towards 610 cm−1 for EG (AC-Li)EG. In general, the
predictions of the simplified EG (AC-Li)EG model are in quite good
agreement with the trend experimentally observed for Li–P-X samples.
It is interesting to remark that the increasing amounts of TiO2 nano-
particles lead to a more notorious shifting and splitting of the Raman
peaks ascribed to the polyester, in agreement with the trends envisaged
by our theoretical calculations for the EG (AC-Li)EG model. This could
be suggesting that the presence of increasing amounts of TiO2 nano-
particles lead to a higher degree of polymerization of the polyester and
can be basically explained by the higher consumption of water mole-
cules for the titanium alkoxide hydrolysis, displacing the equilibrium to
the esterification process.
3.2. - Small angle X-ray scattering (SAXS) and X-ray diffraction (XRD)
Small angle X-ray scattering (SAXS) patterns for Li–P-X with X = 0,
15, 20 and 25 samples are shown in Fig. 5a. The unloaded lithium-ion
ethylene glycol citrate polymer (X = 0) showed the presence of two
well-defined peaks at q1 ∼ 1.50, q2 ∼ 0.83 nm−1 and a broader peak at
q3 ∼ 0.54 nm−1.
These well-defined peaks are probably associated to correlation
distances (d) between polymer domains which can be roughly esti-
mated using the Bragg's law as d = 2π/qi, with qi being the q value of a
maximum peak in the SAXS pattern, as schematized in Fig. 4b. The
presence of a broad peak at q3 ∼ 0.54 nm−1 in the SAXS pattern, with
an associated d3 ∼ 11 nm average inter domain spacing was also ob-
served for other polyesters [38]. Moreover, the well-defined two peaks
at q1 and q2 are suggesting the presence of other shorter-range corre-
lation lengths d1 ∼ 4 and d2 ∼ 7 nm, respectively, that can be probably
associated to interdomain distances with some degree of coherence for
our titania unloaded lithium-ion polyester sample, as also observed for
other polymers [39]. The increasing concentration of TiO2 nano-
particles showed the progressive emergence of a bump at low q-region
which can be associated to the formation of TiO2 nanoparticles. The
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Journal of Physics and Chemistry of Solids 135 (2019) 109082
estimation of the mean TiO2 nanoparticles size using the Beaucage
equation and assuming a spherical morphology was D ∼50 nm and no
drastic variations were observed for any composition. At high-q region,
the presence of low amounts of TiO2 nanoparticles (X = 15) showed the
suppression of the peaks associated to the correlation distances of the
polyester, suggesting that the nanoparticles are probably filling the
polyester interdomain available free space. However, the increasing
amounts of TiO2 nanoparticles showed the emergence of broad peaks at
q ∼0.6 and 0.4 nm−1, with associated d ∼10 and 13 nm correlation
distances, for X = 20 and 25, respectively. These correlation distances
are probably associated to a modification of the average interdomain
spacing of the polyester but can also be related to the interspacing of
TiO2 nanoparticles when agglomerated to form large-sized clusters
embedded in the polyester.
X-ray powder diffraction patterns for Li–P-X with X = 0, 15, 20 and
25 samples are shown in Fig. 5b. The unloaded polyester (X = 0) pat-
tern showed the presence of a broad halo at 2θ ∼ 20.5° which can be
associated to a mean correlation distance (dC) between the polyester
backbone chains which can be estimated using the Bragg law yielding
dC ∼ 0.43 nm. The presence of increasing amounts of TiO2 nano-
particles lead to the emergence of peaks associated to the TiO2 anatase
polymorph, which are evident for X = 25. In addition, the broad halo
ascribed to the polyester backbone interchain distance showed a slight
decrease in intensity and a shift towards higher 2θ values with the in-
crease of TiO2 nanoparticles. The slight decrease in the relative in-
tensity of the broad halo could be suggesting a declining of the degree
of order of the polyester structure. In addition, the broad peak slight
shift towards 2θ ∼22.2°, with an associated dC ∼0.40 nm mean in-
terchain distance, is probably suggesting that the increasing amounts of
TiO2 nanoparticles could be yielding to a slight compression of the
polyester chains, as schematized in Fig. 4b.
3.3. – Thermogravimetric analysis (TGA) and differential scanning
calorimetry (DSC)
Thermogravimetric analysis (TGA) profiles for Li–P-X with X = 0,
15, 20 and 25 samples are shown in Fig. 6a. The unloaded lithium-ion
ethylene glycol citrate polymer (X = 0) showed a two-step thermal
decomposition profile with a first ∼ 75% weight loss at T = 200–250 °C
and a second 25% weight loss at T = 500–550 °C. The first weight loss
at T = 200–250 °C is possibly ascribed to the decarboxylation of the
polyester while the second weight loss at T = 500–550 °C is typically
associated to the decomposition of the polyester backbone [37,40].
However, in addition to the two-stage thermal decomposition observed
for the unloaded polyester, Li–P-X with X = 20 and 25 samples also
showed a ∼10% weight loss at T = 120–200 °C, typically ascribed to
the presence of residual ethylene glycol. The first thermal decomposi-
tion stage in the T = 220–450 °C temperature range showed an ap-
parent slight shift to higher temperatures with increasing TiO2 nano-
particles concentration, while the second thermal decomposition in the
T = 450–550 °C temperature range showed a slight shift to lower
temperatures. Differential scanning calorimetry (DSC) studies were also
performed to get better insight, especially on the first thermal decom-
position stage of Li–P-X samples, as depicted in Fig. 6b. DSC profiles for
all samples consist of an endothermic peak at T = 200–250 °C, at al-
most the same temperature range where the weight loss associated to
the first stage thermal decomposition was observed in the TGA analysis.
This is corroborating that the weight loss observed in this temperature
range can be associated to an endothermic process such as the dec-
arboxylation of the polyester, which involves the loss of mass, probably
in the form of carbon dioxide gas [37,40]. Although the endothermic
heat associated to the decarboxylation stage showed no drastic mod-
ifications for all cases, the decarboxylation temperature showed a shift
towards higher temperatures from 200 to 230 °C with the increase of
TiO2 nanoparticles concentration.
This could be suggesting that there is an apparent increase in the
F. Pignanelli, et al.
Fig. 5. (a) Small angle X-ray scattering (SAXS) patterns indicating with arrows a rough estimation of the mean correlation lengths and (b) X-ray diffraction (XRD)
patterns indicating with arrows the mean coherence lengths for polyester and Bragg reflections of TiO2 anatase polymorph for Li–P-X samples.
Fig. 6. (a) Thermogravimetric analysis (TGA) expressed as weight loss (straight
lines) and corresponding first derivative (dotted lines) versus temperature for
Li–P-X samples. (b) Differential scanning calorimetry analysis (DSC) for Li–P-X
samples.
degree of polymerization of the polyester with increasing TiO2 nano-
particles concentration, as also envisaged by the Raman spectroscopy
studies. The higher degree of polymerization in polyesters con-
comitantly leads to the decrease of carboxylate species at terminal lo-
cations, thus only allowing the decarboxylation of the more stable
carboxylate groups from the backbone structure with associated higher
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Journal of Physics and Chemistry of Solids 135 (2019) 109082
decarboxylation temperatures [38]. The presence of heavier TiO2 na-
noparticles loadings (X = 25%) lead to no further increase but a slight
decrease of the decarboxylation temperature that could be related to a
slight decrease of the polyester degree of order for 25% in comparison
with X = 20%. This could be inducing the presence of more accessible
carboxylate groups yielding a slight decrease of the decarboxylation
temperature for larger amounts of TiO2 nanoparticles [38].
3.4. – Electrochemical impedance spectroscopy (EIS)
The total impedance (Z) can be defined in terms of the real part (Z’)
and the imaginary part (Z”) of the impedance response by the following
equation:
Z = Z′ − jZ"
Impedance spectroscopy analysis displayed as Nyquist plots (-Z” vs.
Z’) collected for Li–P-X with X = 0, 15, 20 and 25 samples are shown in
Fig. 7a. In all cases, the Nyquist plots showed a single semicircle-like arc
at the intermediate frequency regime (f > 103 Hz) associated to the
ionic transport followed by a straight line at the low frequency regime
(f < 103 Hz) which is typically associated to a sample-electrode dif-
fusion process [41]. The circuit model used to fit our impedance data
consists on the parallel combination of a resistor (R) and a constant
phase element (CPE), connected in serie with an additional resistor (Rs)
to describe the wire connections contribution and an additional CPE
element to describe the low frequency capacitive processes (CPEd) at
the gold blocking electrode interphase, as depicted in Fig. 7a. The im-
pedance of a CPE element is defined by the following equation:
1
ZCPE =
A0 (ωi)n
where A0 and n are frequency independent parameters, with n = 1 re-
sembling an ideal capacitor [41]. The most relevant fitting parameters
using the previously described circuit model are shown in Table 1.
As observed, the increasing amounts of TiO2 nanoparticles lead to a
drastic decrease in the fitted ionic transport resistance (R) from
R ∼ 169 kohm down to a minimum value of R ∼ 5.8 kohm observed for
X = 20. The decrease in the resistance is directly related to the notor-
ious decrease of the semicircle-like arc observed in the Nyquist plots, as
depicted in Fig. 7a and 7a-inset.
The ionic conductivity (σ) was calculated using the following
equation:
t
σ=
R. A
F. Pignanelli, et al. Journal of Physics and Chemistry of Solids 135 (2019) 109082

Fig. 7. (a) Impedance spectroscopy data collected at room temperature (300 K) for Li–P-X samples displayed as Nyquist plots (-Z″ vs. Z′) and corresponding fittings
using the depicted circuit model. The inset shows a zoom in the low impedance region. (b) Lithium-ion conductivity at room temperature versus TiO2 nanoparticles
weight fractions for Li–P-X samples with the lines as a guide to the eye.

where t is the thickness and A is the electrode area of the solid polymer
electrolytes. As it was expected from the fitted resistance values, the
increasing amounts of TiO2 nanoparticles yielded an increment of al-
most two-order of magnitude from σ ∼10−6 up to a maximum value of
σ = 1,74 × 10−4 S cm−1 for X = 20. The drastic enhancement on the
ionic conductivity (or decrease of resistance) with increasing TiO2 na-
noparticles up to 20% could be due to the increment of the polyester
structure disorder promoted by the presence of TiO2, as already ob-
served for similar systems [21–25]. Since only a slight decrease in the
degree of order was evidenced by XRD analysis, another possible ex-
planation could be based in an enhancement of the ionic-pair dis-
sociation of lithium ion due interactions with TiO2 nanoparticles sur-
face. However, it also important to note that heavier TiO2 nanoparticles
loadings above X = 20 yielded a slight decrease in the conductivity,
suggesting an ionic percolation threshold at X = 20, as typically ob-
served for lithium-ion solid polymer electrolytes with other nano-
particles [42,43]. Arrhenius plots of ionic conductivity, displayed as ln Fig. 8. Arrhenius plots of lithium-ion conductivity for Li–P-X samples.
(σ) vs. 1000/T, for Li–P-X with X = 0, 15, 20 and 25 samples are shown
in Fig. 8. In all cases, a good linear behavior was observed for all cases,
suggesting no drastic deviations from a typical Arrhenius behavior, as monitored as a function of time on application of fixed DC voltage
expressed by the following equation: across the sample with blocking electrodes. The results of DC polar-
ization measurements on our Li–P-X samples by applying a 2.0 V DC
Ea bias voltage at 300 K are shown in Fig. 9, suggesting that the electronic
ln (σ ) = ln(σ0) −
kB T residual conductivity is negligible compared to the ionic transport for
all the Li–P-X electrolytes, as similarly observed in the literature
where σ0 is the pre-exponential factor, Ea is the activation energy and [45,46]. Finally, in order to estimate the ionic residual conductivity
kB is the Boltzmann constant. The activation energies obtained from the associated to other ionic species in our polyester samples; possibly re-
slope of Arrhenius plots were Ea = 0.36, 0.31, 0.24 and 0.27 eV for sidual protons, a lithium-ion unloaded sample was also prepared and
X = 0, 15, 20 and 25. This is suggesting that there is a decrease in the measured as a reference. For this purpose, we used another carbonate
activation energy with increasing TiO2 nanoparticles loadings yielding salt with the aim to preserve the pH close to neutrality and avoid extra
a minimum for X = 20; the same concentration for which the highest acidity of the medium if no carbonate is added.
lithium-ion conductivity was observed. Thus, to have a better comparison with our samples, the reference
We estimate the residual electronic conductivity by means of was prepared using barium carbonate instead of lithium carbonate but
Wagner's polarization technique [44]. Here, the DC current is in the same concentration to reproduce, as close as possible, the

Table 1
Most relevant impedance spectroscopy fitting parameters for Li–P-X with X = 0, 15, 20 and 25.
X=0 X = 15 X = 20 X = 25

R (103 Ω) 169 ± 1 32.0 ± 0.2 5.76 ± 0.08 6.66 ± 0.07

A0 (10−11S.sn) 2.00 ± 0.02 34.2 ± 0.2 45.0 ± 0.7 52.0 ± 0.7
n 0.909 ± 0.008 0.904 ± 0.005 0.89 ± 0.01 0.88 ± 0.01
σ (10−4S.cm−1) 0.0592 ± 0.0004 0.313 ± 0.002 1.74 ± 0.02 1.50 ± 0.02

The thickness to electrode area ratio (t/A) for our electrolytes was normalized to t/A ∼ 1 cm−1. The circuit model used for fitting analysis is shown in Fig. 6a-inset
and for all cases, Rs showed values < 7 ohms

6
F. Pignanelli, et al.
Fig. 9. DC polarization current versus time for Li–P-X samples.
synthesis conditions of our samples. The use of barium carbonate is
mainly based in the expected low conductivities down to 10−11 S cm−1
observed for the heavy Ba2+ ion in a similar poly (ethylene oxide) host
[47]. In addition, it is important to remark that we did not observe
detectable differences on the crystallinity between this reference
sample and our Li–P-X samples that could induce indirect variations in
the conductivity [48,49]. Thus, with the use of barium carbonate in the
reference sample, apart from reproducing as close as possible the
synthesis conditions of our Li–P-X samples, it is possible to consider that
the major contribution to the ionic transport will be that ascribed to
ions with higher mobility such as residuals protons [50,51]. The ionic
conductivity of the lithium-ion unloaded polyester reference showed a
σ ∼10−8 S cm−1 conductivity, which is two orders of magnitude lower
than the lowest observed for lithium-ion conductivities in our samples
(σ ∼ 10−6 – 10−4 S cm−1). Finally, by making a rough extrapolation
with all the suppositions described above, this is suggesting that the
contribution of residual protons in our Li–P-X samples is considerably
lower than that associated to lithium-ions.
4. Conclusions
In the present manuscript, a synergistic in situ preparation of li-
thium-ion poly (ethylene citrate) with titania nanoparticles as pro-
mising fluorine-free lithium-ion solid polymer electrolyte is reported.
Confocal Raman spectroscopy analysis revealed the formation of the
polyester with embedded titania nanoparticles in agreement with our
Raman spectra simulation. Our DFT theoretical modeling of the
polyester envisaged the interaction of lithium-ion via a tridentate co-
ordination with carbonyl (–C]O) groups from (–COO-) carboxylate and
(–COO–) ester groups. The degree of polymerization slightly increases
and the thermal stability also improves for our lithium-ion polyester
with increasing titania nanoparticles concentration. In consequence, a
two-order magnitude increase in the ionic conductivity was observed
yielding 1.74× 10−4 S cm−1 for a 20% weight fraction of titania na-
noparticles.
Acknowledgements
The authors wish to thank the Uruguayan ANII, CSIC and PEDECIBA
funding institutions.
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