Electrochimica Acta 462 (2023) 142785

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Electrochimica Acta
journal homepage: www.journals.elsevier.com/electrochimica-acta

Ionic transport in solid-state composite poly(trimethylene carbonate)–

Li6.7Al0.3La3Zr2O12 electrolytes: The interplay between surface chemistry
and ceramic particle loading
Kenza Elbouazzaoui , Funeka Nkosi , Daniel Brandell , Jonas Mindemark *, Kristina Edström
Department of Chemistry – Ångström Laboratory, Uppsala University, Box 538, Uppsala SE-751 21, Sweden

A B S T R A C T

The ionic transport in solid-state composite electrolytes based on poly(trimethylene carbonate) (PTMC) with LiTFSI salt and garnet-type ion-conducting Li6.7Al0.3
La3Zr2O12 (LLZO) ceramic particles is here investigated for a range of different compositions. Positive effects on ionic conductivity have previously been reported for
LLZO incorporated into poly(ethylene oxide) (PEO), but the origin of these effects is unclear since the inclusion of particles also affects polymer crystallinity. PTMC is,
in contrast to PEO, a fully amorphous polymer, and therefore here chosen for the design of a more straight-forward composite electrolyte (CPE) system to study ionic
transport. With LLZO loadings ranging from 5 to 70 wt%, the CPE with 30 wt% of LLZO exhibits the highest ionic conductivity with a cationic transference number of
0.94 at 60 ◦ C. This is significantly higher than for the pristine PTMC polymer electrolyte. Generally, low to moderate LLZO loadings display a gradual increase of the
ionic conductivity, transference number and also of the polymer-cation coordination number. The combined contributions of ionic transport along polymer-ceramic
interfaces and Lewis acid-base interaction between the LLZO particles and the LiTFSI salt can explain this enhancement. With loadings of LLZO above 50 wt%, a
detrimental effect on the ionic conductivity was however observed. This could be explained by agglomeration of ceramic particles, and by a partial coverage of LLZO
particles with a Li2CO3 layer. Consequently, inner polymer-particle interfaces become more resistive, and Li+conduction is prevented along interfacial pathways. The
presence of Li2CO3 has more detrimental impact at higher LLZO loadings, since inter-particle connectivity will be hampered, and this is vital for efficient ionic
transport. This suggests that there is an interplay between the LLZO particle surface chemistry with its loading, which ultimately controls the Li-ion transport.

1. Introduction degree [2,11,12]. During the last decade, the research community has
devoted immense efforts to improve the performance and address the
Solid-state batteries, in which the common liquid electrolytes are challenges faced by both polymeric and ceramic electrolytes [13–15].
replaced with solid-state counterparts, are among the most promising Naturally, combining polymeric and ceramic materials into one
candidates for future battery technology [1,2]. These are considered key ”composite” or “hybrid” electrolyte system constitutes an appealing
components for the progress of next-generation batteries, granted that strategy, aiming to merge the merits and overcome the respective
the solid electrolytes can provide similar or improved electrochemical problems of polymers and ceramics. This could in principle render high
performance as the liquid systems used today [3]. Solid electrolytes can ionic conductivity (⁓10− 3 S cm− 1), large electrochemical stability
generally be categorized into polymeric and inorganic materials. Poly­ window, and good interfacial contact with the battery electrodes
mer electrolytes are promising candidates thanks to their facile pro­ [16–19]. Nevertheless, this class of solid-state electrolytes has in prac­
cessing, fair mechanical strength and good interfacial contact with tice not yet fulfilled this entire set of requirements [12,20,21]. In this
electrode materials, but their implementation in practical applications is context, intensive work has been centered around developing and
held back due to their low intrinsic ionic conductivity, especially at investigating numerous composite electrolytes, often based on salt so­
room temperature or below [4–6]. Inorganic electrolytes, including lutions in poly(ethylene oxide) (PEO) with various ceramic fillers. Two
oxides, sulfides, phosphates, and other alternatives, are better Li-ion different approaches can be discerned depending on the ceramic
conductors and many are also electrochemically and thermally stable, loading: polymer-rich and ceramic-rich materials, where the filler con­
but are suffering from brittleness and poor interfacial contact with the centration is below or above 50 wt%, respectively [22].
electrodes. This, in turn, can generate high resistances and poor capacity Since the mid-1970s, PEO has been a focal point in the field of solid
[7–10]. Because of these drawbacks, solid electrolytes are still not being polymer electrolytes (SPEs), emphasized after Armand showed Li+-ion
employed in commercial large-scale batteries to more than a limited conduction in a matrix of PEO and a lithium salt [23,24]. Despite its

* Corresponding author.
E-mail address: jonas.mindemark@kemi.uu.se (J. Mindemark).

https://doi.org/10.1016/j.electacta.2023.142785
Received 12 April 2023; Received in revised form 12 June 2023; Accepted 24 June 2023
Available online 25 June 2023
0013-4686/© 2023 The Author(s). Published by Elsevier Ltd. This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/4.0/).
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K. Elbouazzaoui et al. Electrochimica Acta 462 (2023) 142785

inferior ionic conductivity as compared to liquid electrolytes at con­ similar active fillers primarily comes from the addition of conduction
ventional battery operating temperatures, it is widely used as a polymer mode (ii), but in practice mode (iii) has often been ascribed as the main
host in SPEs. Correspondingly, PEO-based systems are those that have factor behind to the significant conductivity enhancement observed.
been most extensively studied when fabricating polymer-ceramic hybrid However, it has also been found that the interfacial resistance in the
electrolytes [25,26]. Several Li+-ion conducting (garnet, NASICON, well-studied PEO-LLZO system is even larger as compared to the resis­
perovskite, argyrodite) and non-conducting (Al2O3, SiO2, ZrO2, etc.) tance at the polymeric and ceramic phases, and should thus limit the
inorganic fillers have been incorporated into a salt-containing (often conductivity [50].
LiTFSI) PEO-based polymer matrix, and the resulting composite elec­ In the efforts of exploring the conduction mechanisms in this cate­
trolytes have been evaluated in terms of their ionic transport properties gory of materials, it is useful to include also other polymer hosts than
[27–34]. Generally, adding fillers to the PEO matrix reduces its degree of PEO, and evaluating the transport mechanisms in such systems could be
crystallinity, thereby maximizing the amorphous regions of the polymer a crucial step towards a better understanding of how composite elec­
matrix, in which the ionic transport occurs [26,29]. trolytes function in a battery cell. In this context, it is noteworthy that
The garnet-structured Li7La3Zr2O12 (LLZO) oxide material has been suppressing the polymer crystallinity after ceramic addition is not
given much consideration as compared to other inorganic fillers thanks attainable with fully-amorphous polymer matrices, and eliminating this
to its ability to conduct lithium ions. A special focus has been attributed effect can contribute to a better understanding of other transport-
to the cubic LLZO phase because of its high bulk ionic conductivity at controlling phenomena. One such interesting amorphous polymer host
room temperature, explained by the particles densification and sintering is poly(trimethylene carbonate) (PTMC) that, despite its limited con­
at high temperatures (above 1000 ◦ C). However, the brittleness of LLZO, ductivity, has been extensively studied as a battery electrolyte [4,30,
interfacial issues with Li-metal, and chemical instability when exposed 51]. As PTMC is a fully-amorphous polymer, the effect of lowering
to air, still restrain its practical use as a solid electrolyte. Therefore, crystallinity that is seen in PEO-based composite electrolytes would not
incorporating LLZO as a ceramic filler in solid or gel polymer electro­ be present, thereby isolating the intrinsic effects of the combination of
lytes appears as a promising approach to overcome these problems [35, LLZO with the polymer matrix.
36]. Hence, the effect of LLZO concentration on the conduction properties
Utilizing transport pathways through the LLZO bulk within a flexible of a series of composite electrolytes based on a PTMC-LiTFSI matrix and
polymer matrix constructs a primary motivation for incorporating such LLZO ceramic filler throughout a large range of ceramic filler contents
active fillers [10,37–40]. In this context, several papers have evaluated (from 5 until 70 wt%) is here investigated. The ionic conductivity is
the ionic conductivity of PEO-LLZO composite electrolytes, and reported correlated to the polymer-ion interactions as a function of the ceramic
an enhancement resulting from suggested synergetic effects between the LLZO loading. In contrast to much work in the solid-state electrolyte
polymer and ceramic components in this hybrid system [29,34,41–47]. field, this study does not focus primarily on improving the ionic con­
However, the specific ionic transport mechanisms in these composite ductivity of these PTMC-based electrolytes with ceramic incorporation,
electrolytes remain elusive, and it is unclear if the LLZO bulk contributes but rather to provide insights into what controls the ionic transport
with any conductivity [48]. It could be considered that this lack of un­ mechanisms in these hybrid electrolytes.
derstanding constitutes a restriction for this class of solid-state electro­
lytes from reaching a major break-through, since it becomes difficult to 2. Experimental
design and tailor them for optimal performance. Therefore, it is neces­
sary to better explore the fundamentals behind the ionic conduction 2.1. Materials
behavior in LLZO-based hybrid electrolytes.
It is noteworthy that while the theories of the ionic transport Trimethylene carbonate (TMC; Richman Chemicals), stannous 2-eth­
mechanism in both polymer and ceramic electrolytes are fairly well ylhexanoate (95%; Sigma-Aldrich) and dry toluene (99.8%; Acros Or­
established, only few insights on the potential mechanism have been ganics) were stored and handled in an argon-filled glovebox. Lithium bis
proposed for the widely explored PEO-LLZO composite electrolytes. In (trifluoromethylsulfonyl)imide (LiTFSI; BASF) was dried at 120 ◦ C
SPEs, the conduction mechanism conventionally takes place in amor­ under vacuum in a Buchi oven for 48 h prior to use. Li2CO3 (99.99%), La
phous regions by segmental motion of polymer chains according to a (OH)3 (99.99%), and ZrO2 (99%) purchased from Sigma-Aldrich, and
Vogel-Fulcher-Tammann (VFT) behavior above Tg [49]. When the Al2O3 (99.9%; VWR) were the main precursors for LLZO synthesis, and
chains undergo segmental motion into a free-volume space, the Li+ were used as received. Anhydrous acetonitrile (99.8%; Sigma-Aldrich),
cations coupled to the polymer coordinating groups migrate within the 1-propanol (>99.5%; Sigma-Aldrich), and lithium foil (125 µm;
polymer matrix. Li+ conduction in inorganic solid electrolytes, on the Cyprus Foote Mineral Co.) were also used as received.
other hand, occurs by ion-hopping through interconnected fixed sites in
the host structure and is dependent on connected percolating pathways, 2.2. Synthesis of Li6.7Al0.3La3Zr2O12 particles
and the ionic conductivity thereby follows an Arrhenius-type behavior
rather than VFT [10]. Abbreviated as “LLZO”, the cubic phase of the garnet-type ceramic
For solid polymer-ceramic composite electrolytes, there is no general was synthesized following a classic solid-state synthesis route [52].
consensus on the conduction mechanism, and it seems dependent on Stoichiometric amounts of raw materials (Li2CO3, La(OH)3, ZrO2 and
several factors: polymer hosts, nature and loading of the ceramic filler, Al2O3) were mixed, to which 1-propanol was added and placed inside a
Li-salt concentration, etc. In the studies of PEO-based composite elec­ zirconia jar for wet ball-milling using zirconia balls at a speed of 450
trolytes, it has then been demonstrated that the transport mechanisms rpm for 12 h in a planetary ball-mill instrument (Retsch PM100). 10%
are strongly dependent on phase changes occurring in the polymer phase excess of Li2CO3 was added to the previous mix to compensate for Li loss
of the system, thereby affecting the overall ionic conductivity. Three during sintering at high temperatures. The obtained white mixture was
distinctive conduction modes have been suggested: (i) in the polymeric placed in an Al-crucible and dried inside a ventilated oven at 80 ◦ C for
phase, where the dispersed ceramic particles decrease the polymer 4–6 h to remove any solvent residues prior to heat treatment. The sin­
crystallinity, contributing to an increase of the amorphous regions tering was conducted in a muffle furnace (MTI corporation, VBF1200X)
where the conduction generally occurs; (ii) in the inorganic phase, bulk from room temperature up to 1000 ◦ C for 12 h in air with a rate of
conduction can also contribute to the total conductivity of the hybrid 2 ◦ C/min applied during both heating and cooling. The resulting powder
system if the ceramic fillers are active and the particle loading is high; was thereafter ball-milled again following the same above-described
(iii) at the polymer-ceramic interfaces formed, which can provide an procedure and stored immediately inside an argon-filled glovebox
additional transport pathway. The motivation for using LLZO and before use.

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2.3. Synthesis of poly(trimethylene carbonate) 2.6. SPE and CPE characterization

High-molecular-weight PTMC was synthesized through bulk ring- The total ionic conductivity of the SPE and different CPEs was
opening polymerization of trimethylene carbonate catalyzed by tin(II) determined by electrochemical impedance spectroscopy (EIS). The
2-ethylhexanoate according to a procedure previously described in assembled coin cells were firstly annealed at 90 ◦ C for 1 h and then left to
detail by Sun et al. [51]. Briefly, in a stainless steel reactor 0.2 mol of cool down to room temperature prior to measurement to ensure good
TMC was added to 0.04 mmol of Sn(Oct)2 (40 µL of 1 M solution) as contact between the electrolyte film and the blocking electrodes.
catalyst in dry toluene. The reactor was sealed under argon atmosphere, Thereafter, the experiments were carried out in the frequency range 7
then placed in an oven at 130 ◦ C for 72 h. The reactor was shaken MHz – 100 mHz with an amplitude of 50 mV at temperatures ranging
regularly every 30 min for the first 3 h to ensure a good mix of all from 30 to 90 ◦ C using a Schlumberger SI 1260 impedance/Gain-Phase
constituents. Once the polymerization was complete, the reactor was put analyzer. All cells were kept for 1 h at each temperature to equilibrate
back inside an argon-filled glovebox and the final product was removed before measurements. The impedance data were treated and fitted to a
and cut into small pieces. The obtained polymer was a transparent and Debye circuit for the SPE and CPEs with 5 and 10 wt% of LLZO particles,
rubbery solid, with an approximate molecular weight Mw of 380 000 – and to another equivalent circuit (described in Fig. S1) for composite
400 000 g mol− 1 (confirmed by GPC). electrolytes with a ceramic concentration above 10 wt%. The bulk and
polymer-ceramic interface resistances were determined after fitting in
Zview v.3.3b (Scribner Associates), and the total ionic conductivity σ
2.4. Solid polymer electrolyte and PTMC/LLZO composite electrolytes was calculated using the equation:
preparation
l
σ= (1)
RA
Self-standing polymer and composite electrolyte films were obtained
via a controlled solvent evaporation solution-casting method. Firstly, 72 where l is the thickness, R is the bulk resistance for the SPE, or the sum of
wt% PTMC and 28 wt% LiTFSI salt were mixed and dissolved in the bulk and internal interfacial resistances for the CPEs, and A is the
acetonitrile ([Polymer]/[Solvent] = 0.05 g/ml) and kept under mag­ cross-section geometrical area of the electrolyte film.
netic stirring at 40 ◦ C for 12 h inside the glovebox. The resulting solution The Li+ transference number was determined through the Bruce-
was poured into Teflon molds before being transferred inside a vacuum Vincent method. The assembled pouch cells were first kept under
oven at a temperature of 30 ◦ C and a pressure of 200 mbar for the first open-circuit voltage conditions at room temperature for 24 h before
20 h. Subsequently, the temperature increased up to 60 ◦ C while the setting the temperature at 60 ◦ C for the measurements. The experi­
oven was further pumped down to <2 mbar for the next 40 h. After mental procedure was conducted using a BioLogic SP-240 Potentiostat,
cooling, the obtained SPE films were punched using a 15 mm in diam­ and consisted of two steps: impedance spectroscopy and potentiostatic
eter punching tool. All process steps were performed inside an argon- polarization. The measurements were carried out between 7 MHz and 10
filled glovebox and the as-prepared electrolyte films were used as mHz with an amplitude of 10 mV and a bias of 0 and 10 mV before and
obtained. after polarization, respectively. Thereafter, the bulk and interface re­
Polymer-ceramic composite electrolytes with a nominal composition sistances were determined by fitting to an appropriate equivalent circuit
of (1-x) wt% [PTMC – 28 wt% LiTFSI] – x wt% LLZO (5<x<70) were illustrated in Fig. S2, using EC-lab software, while the initial current was
prepared via a two-step process. Firstly, both PTMC and LiTFSI were calculated from the applied polarization potential and the total resis­
dissolved in acetonitrile at 60 ◦ C for 12 h. The ratio of polymer to solvent tance in the cell. The cationic transference number was then calculated
was 0.1 g mL− 1. The obtained solution was relatively viscous to facilitate from the following equation:
the impregnation of ceramic particles into the polymer matrix and avoid
sedimentation . Subsequently, appropriate amounts of the polymer+salt ISS (ΔV − I0 R0 )
T+ = (2)
solution and LLZO powder were placed in a zirconia jar and ball-milled I0 (ΔV − ISS RSS )
at 25 Hz for 15 min under argon atmosphere. The homogeneous
where ΔV is the applied polarization voltage, I0 and R0 are the initial
polymer-salt-ceramic slurry was solution-cast in Teflon molds, and the
current and resistance, respectively, and ISS and Rss are the steady-state
solvent was evaporated using the same method as previously described
current and resistance, respectively.
above. Similarly, the composite polymer electrolyte (“CPE”) films were
To investigate the ion coordination properties, Fourier-transform
punched out with a 15 mm in diameter puncher, and their thicknesses
infrared spectroscopy (FT-IR) experiments were carried out using a
were measured with a Mitituyo digital indicator micrometer with typical
PerkinElmer Spectrum One FT-IR spectrometer equipped with a ZnSe
values ranging from 50 to 250 µm depending on the ceramic concen­
crystal attenuated total reflectance (ATR) setup at room temperature.
tration in the composite electrolyte samples. The entire procedure was
FT-IR spectra were recorded from 4000 to 650 cm− 1 with a 4 cm− 1
performed inside an argon-filled glovebox prior to cell assembly and
resolution and the peaks of interest were deconvoluted using the Voigt
characterization.
function after a linear baseline correction in the Origin software. The
measurements were performed at least three times for reproducibility
and accuracy. Each sample was kept inside a hermetically sealed argon-
2.5. Cell assembly
filled transfer box and taken out directly before starting the measure­
ments to minimize air exposure.
The as-synthesized SPE and CPE films were hermetically placed in
The crystal structures of LLZO and PTMC-LLZO CPEs were confirmed
CR2025 coin cells, sandwiched between two blocking stainless-steel
through X-ray diffraction using a Bruker D8 Advance diffractometer.
electrodes with a Teflon spacer ring and pressed inside an argon-filled
The XRD patterns were recorded over a 2θ range of 10–70◦ and
glovebox before being taken out for measurements. This configuration
employing Cu Kα radiation (λ = 1.54178 Å) as the main X-ray source.
was employed for ionic conductivity experiments.
The CPE morphology, the ceramic particle distribution in the polymer
Prior to transference number measurements, Li/electrolyte/Li
matrix, and elemental composition were evaluated by scanning electron
configuration-type pouch cells were fabricated. First, Li-metal disks
microscopy using a Zeiss Merlin SEM coupled to an energy-dispersive X-
were cut using 13 mm and 15 mm in diameter punchers. The cells were
ray spectroscopy (EDS) detector. Top SEM images were acquired with an
assembled by placing the CPE film between two Li-metal disks, and
applied acceleration voltage of 3 kV, a 100 pA probing current, a ⁓6.3
sealed afterwards using a vacuum sealer. All steps were carried out in an
mm working distance, and a secondary electron detector. The samples
argon atmosphere.

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were prepared under argon atmosphere and transferred inertly to the casting for all compositions. The amorphicity of PTMC was also
SEM microscope through a vacuum-sealed transfer box, designed to confirmed through the gaussian-shape XRD pattern obtained for the
ensure transfer under inert conditions. PTMC-based SPE, as shown in Fig. 2a.
Surface analysis of the as-synthesized LLZO powder was performed To investigate the polymer stability and if the addition of ceramic
by X-ray photoelectron spectroscopy (XPS). Firstly, a small quantity of filler had any significant effect related to structural changes in the
the powder was placed and pressed on top of copper tape. The sample polymeric matrix, FTIR was employed. The characteristic vibrations of
was prepared under argon atmosphere and brought to the XPS loading PTMC could be observed both before and after adding the Li-salt and the
chamber through an airtight transfer shuttle without being exposed to LLZO ceramic filler. As illustrated in Fig. 2b, the symmetric carbonyl
ambient air. XPS characterization was carried out on a Kratos Axis stretching vibration of neat PTMC is usually seen at 1741 cm− 1, which is
Supra+ spectrometer with a monochromatized Al Kα (hν = 1487 eV) X- sensitive to Li+-cation coordination. Therefore, the carbonyl vibration
ray source, corresponding to a probing depth of ⁓10 nm. An electron shifts to lower wavenumbers upon addition of salt, resulting in two vi­
neutralizer was also involved during measurements to compensate for brations assigned to free and Li+-coordinated carbonyl groups (as dis­
over-charging. All spectra were collected with an emission current of 15 cussed in more detail below).
mA and the pressure in the analysis chamber was ⁓2.6 × 10− 8 mbar. When discussing the effect of ceramic particles loading on the ionic
The elemental peaks of interest (La3d, Zr3d, C1s) were measured before conduction behavior of these CPEs, we first categorize the entire series
and after surface etching, after obtaining a general survey spectrum. based on the particle content. Thereby, a polymer-rich series is here
Surface etching was performed by monoatomic Ar+sputtering, through defined when the LLZO content is below 50 wt%, where the ceramic
which Ar gas is directly fed into the ionization chamber producing an primarily would contribute to the creation of novel Li+-ion transport
Ar+-ion beam with an energy of 500 eV to 8 keV. The beam allowed pathways along polymer-ceramic interfaces. When the LLZO content is
sputtering thin layers off the sample surface. Sputtering sequences of 60 at and above 50 wt%, the polymer could instead act as binder that is
s were employed 5 times. Spectra were recorded after each sputtering filling the gaps between the ceramic particles, and contribute to the
step and comparisons were made between the pristine and etched formation of a continuous particle network; thus defining a ceramic-rich
surfaces. series of composite electrolytes. It should be noted that these definitions
are based on the filler loading by mass and not by volume, which is also
3. Results and discussion the case for most studies in literature [18]. The volume percentages of
the entire series of this study are listed in Table S1 and range from ca. 1.3
Poly(trimethylene carbonate) (Fig. 1) is a fully amorphous poly­ vol% to 37.5 vol% for the materials studied here.
carbonate, which can be used to fabricate solid polymer electrolytes The ionic conductivities of the as-synthesized CPEs and the SPE
thanks to its ability to coordinate cations by its carbonyl groups [51]. It reference were investigated by electrochemical impedance spectros­
has previously not been studied as a polymer matrix for solid composite copy, using 15 mm diameter electrolyte films of a thickness varying from
electrolytes with ceramic fillers. The fact that PTMC is amorphous ren­ 50 to 190 µm with increasing the ceramic content. The Nyquist plot of
ders it particularly useful to investigate fundamental transport mecha­ the SPE without ceramic particles displayed a typical behavior of an SPE
nisms, since the addition of fillers will not affect the polymer as shown in Fig. 3, with a regular semi-circle at high frequencies
crystallinity, as is the case for PEO and other semi-crystalline SPE hosts, attributed to the polymer bulk conduction, followed by a spike at me­
and which makes it more difficult to distinguish the causes for variations dium and low frequencies. A similar Nyquist plot was obtained for the
in ionic transport. This work thereby focuses on investigating the ionic CPE with 5 wt% of LLZO, indicating that the introduction of such a small
transport in hybrid electrolytes based on a PTMC-LiTFSI matrix with fraction of ceramic particles did not bring any noticeable effect on the
LLZO as a potentially active ceramic filler. To ensure mechanical sta­ main transport mechanism. Starting from CPEs with 10 wt% of LLZO, a
bility of the films before and after filler addition, high-molecular-weight novel feature appeared at medium frequency ranges. The shape of the
PTMC was synthesized and employed, with a number-average molecular Nyquist plots showed two depressed semi-circles at high and medium
weight ranging approximately between 368 000 and 400 000 g mol− 1. frequencies, followed by a straight line at low frequencies. With
The obtained polymer batch was a rubbery-like transparent solid, to increasing ceramic loading in the polymer matrix, this feature became
which 28 wt% LiTFSI was added to form a polymer-salt matrix. The more pronounced and its resistance appeared to be higher as compared
[Li+]:[Carbonate] ratio was kept constant for the entire study, and was to the bulk resistance as seen in Fig. S1. Through comparisons with the
chosen based on previous work reporting the optimal ionic conductivity SPE reference, it is suggested that the first semi-circle for the CPEs is
with LiTFSI content ranging between 25 and 30 wt% [53,54]. An SPE attributed to the polymer bulk conduction, while the second is assigned
reference consisting of only PTMC with 28 wt% LiTFSI was likewise to the polymer-ceramic interfaces in the system. The absolute value of
prepared. impedance as function of the frequency was plotted in a Bode-type plot
To the PTMC-LiTFSI matrix, LLZO particles were added to produce in Fig. S2, and confirmed the appearance of two distinctive phenomena
composite electrolyte films with different ceramic loadings in the range at high and medium frequency range for CPEs with a ceramic loading
of 5 to 70 wt% (denoted CPE5 – CPE70). Firstly, the crystal cubic equal or above 10 wt%. Therefore, both bulk and interfacial resistances
structure of LLZO was confirmed by X-ray diffraction, and only minor (Rb and Rint, respectively) were taken into consideration when calcu­
appearance of secondary phases (<5%) could be detected. Similar XRD lating the ionic conductivity in these samples, while only the bulk
patterns were obtained for the CPEs, well displaying the characteristic resistance Rb was used for SPE and CPE5 samples. To verify reproduc­
peaks of cubic LLZO and thereby verifying the chemical stability of LLZO ibility and report reliable data, we have performed the analysis on at
after being incorporated into the polymer matrix and ball-milled prior to least 3 cells for each composition from the entire series, and observed
minor differences in total resistance values between different samples
from the same composition.
Appropriate equivalent circuits were proposed and employed to fit
the data and determine the resistance values for each material. For SPE
and CPE5, a typical Debye circuit was used, while another circuit con­
sisting of two R/constant phase elements in series was suggested for the
best fit for the other samples, as illustrated in Fig. S3. To confirm that the
high and medium-frequency features observed in the Nyquist plots
correspond to bulk and interfacial responses respectively, the capaci­
Fig. 1. Structure of poly(trimethylene carbonate). tance values obtained after fitting were evaluated. For the SPE and CPE5

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Fig. 2. (a) X-ray diffraction patterns of filler-free solid polymer electrolyte (SPE), composite electrolytes (CPEs), and pristine LLZO powder; (b) FTIR spectra of SPE,
CPEs, and pristine PTMC polymer.

samples, capacitance values in the order of 10− 9–10− 10 F cm− 2 were

obtained, considered as typical values of the bulk capacitance of the
sample. Therefore, the first semi-circle at high frequencies can indeed be
associated to the conduction phenomena occurring in the polymer bulk.
For CPEs with LLZO content above 5 wt%, fitting data displayed similar
capacitance values assigned to the high frequency semi-circle as for SPE,
and capacitance values in the order of 10− 8–10− 7 F cm− 2 were attained
for the following semi-circle, that can be assigned to conduction feature
along the interfaces between polymer and ceramic in the CPEs [55].
The obtained impedance spectra for the PTMC-based CPEs display
striking differences as compared to those for similar materials based on
PEO. Here, the additional feature of an incomplete depressed semi-circle
in the medium-frequency region can clearly be observed, while PEO-
LLZO composites generally exhibit one single semi-circle at high fre­
quencies. Samsinger et al. attributed this signal to the bulk resistivity,
claiming that there was no observed feature for the polymer-ceramic
interface [56]. On the other hand, Kato et al. suggested that the
Li+-conduction can possibly occur in the LLZO phase and near the in­
terfaces [57].
The total ionic conductivity as a function of temperature for different
Fig. 3. Electrochemical impedance spectroscopy measurements of SPE and CPE
electrolytes from 7 MHz to 100 mHz: Nyquist plot of SPE and CPEs at 60 ◦ C. composite electrolytes and the SPE reference is plotted in Fig. 4a. As can
be seen, all samples display a VFT behavior within the entire tested
temperature range, indicating that the ionic conduction occurs primarily
coupled to the segmental motion of the polymer chains. For the polymer-

Fig. 4. (a) Arrhenius-type plots of the total ionic conductivity of SPE and CPEs from 30 to 90 ◦ C within the entire range of LLZO concentration; (b) Li-ion conductivity
as function of the ceramic LLZO concentration at 60 ◦ C. Standard error of the mean is represented as error bars.

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rich materials, it is clearly seen that the ionic conductivity is higher with coordinating groups [59,60]. For polycarbonate-based polymers, both
incorporation of active ceramic filler as compared to the electrolyte FTIR and Raman spectroscopy has been used to explore the coordination
without LLZO particles; i.e., all curves are above that of the SPE refer­ chemistry of both polyethylene carbonate (PEC) [61,62] and PTMC for
ence. The conductivity increases with increasing ceramic contents up to both Li-based [63] and Na-based systems [54].
30 wt% of LLZO, after which the conductivity is observed to drop In PTMC-based electrolytes, the Li cations coordinate to the C = O
significantly, especially for samples with LLZO loadings of 50 wt% and groups. The FTIR C = O symmetric stretching vibration in neat PTMC
above. This is also seen in Fig. 4b, which shows the trend specifically for can be observed at ⁓1740 cm− 1, but – as seen in Fig. 2b – is split and
60 ◦ C. This conductivity trend can be due to several factors. Firstly, the shifted to lower wavenumbers with the addition of lithium salt and LLZO
incorporation of a small LLZO fraction could increase the Li mobility particles. The coordinating carbonyl groups can be assigned to the peak
through enhancing the Li solvation in the system. This can be explained at ⁓1715 cm− 1. By deconvolution of the C = O doublet into two peaks,
by a Lewis acid-base interaction between the ceramic particles and the assigned to coordinating and non-coordinating groups (illustrated in
salt anions, leading to an increased supply of mobile lithium cations. Fig. 5a), the fraction of either C = O type can be quantified from the peak
Secondly, the ceramic particle concentration can significantly affect the area.
conductivity in CPEs negatively if agglomerates are formed in the The obtained ratio here of [C = O:Li+]:[C = O]= 58:41 for the PTMC-
conductive SPE matrix, corresponding to obstacles which can hinder Li- based SPE without fillers is in good agreement with what has previously
ion transport pathways through the polymer matrix. Finally, inner been reported for the same system, with some minor differences due to
polymer-ceramic interfaces are likely to play a key role for the con­ differences in salt concentration [63].
ductivity in CPEs. While such interfaces are often argued to provide The cation coordination number to the polymer was calculated as
useful transport paths for the mobile cations and promote conductivity, CN = χ × n, where χ is the obtained percentage of Li+-coordinating
it has also been reported that such interfaces can be quite resistive and carbonyl groups after deconvolution, and n is the [C = O]:[Li+] molar
thereby restrict lithium ion transport along them [58]. ratio (kept constant at n = 7.23, equivalent to a salt concentration of 28
It is not straight-forward to explain the conductivity trends seen in wt%). The calculation was made assuming equity between the extinc­
Fig. 4. As can be seen from the Nyquist plot (Fig. 3), the observation of a tion coefficients for non-coordinating and coordinating carbonyl groups
second semi-circle at the medium frequency range indicates a contri­ in the system. Fig. 5b shows the variation of the coordination number
bution of the polymer-ceramic interfaces to the total ionic conductivity with LLZO content with the corresponding data in Table S2, while all
for CPEs with LLZO contents at and above 10 wt%. When the ‘optimal’ deconvoluted FTIR peaks can be found in Fig. S6. It is apparent that the
LLZO content is exceeded (at ca. 30 wt% here), there is an increase in the polymer continues to complex the Li ions also in the presence of ceramic
bulk ionic resistance (Fig. S4). This is likely related to the increased particles, while there is no evidence on any interaction between the
tortuosity for ion transport through the polymeric phase as more polymer and the particles, as is seen in Fig. S7. Comparing the spectra of
pathway-blocking particles are added. Even more striking, however, is neat PTMC and the salt-free samples containing PTMC and LLZO only,
the drastic increase in interfacial resistance when the LLZO content we can observe the same single peak attributed to the free carbonyl
reaches 50 wt%, leading to a huge drop in overall conductivity. At this group vibration. The fraction of coordinating carbonyl groups in fact
point, it is not clear why this particular particle concentration gives such increases with increasing ceramic loadings, with some small exceptions
a huge interfacial resistance, but it is consistently observed in our (e.g. CPE20, which also is an outlier in terms of conductivity; see Fig. 4).
samples. Particle agglomeration could be one possible answer, and ag­ The Li+-carbonyl coordination number increases with the ceramic
glomerates are clearly seen in SEM imaging (see Fig. S5). Moreover, the concentration all the way up to 70 wt%. This suggests that the ceramic
agglomeration can lead to that the particle surface area that is exposed particles have an interaction with the lithium salt, primarily through an
to the polymer stops to increase with particle loading. This might also be interaction between the anions from the salt acting as a Lewis base and
correlated to that the surface chemistry of the LLZO particles plays a the ceramic particles acting as a Lewis acid that can accept electron pairs
role, since these can be partially covered by Li2CO3 (discussed below), via La3+ or Zr4+. As a result, Li-salt dissociation is promoted, which
which is more resistive than the bare LLZO substrate. If the LLZO-LLZO could also render a decrease in the anionic mobility. An increased
contacts are preferred during agglomeration, it would lead to an number of ‘free’ lithium charge carriers (not ion-paired) is thereby likely
increased fraction of the poorly conductive surfaces on behalf of the to be obtained, thus enhancing the polymer coordination number.
well-conducting bare LLZO, and can thus partly explain the observed Assuming that Li+ dissolution and coordination to the mobile polymeric
trends. solvent can contribute to enhance the ionic conductivity in polymer
An increase in the ionic conductivity of CPEs with high LLZO load­ electrolytes, this can explain the conductivity trends observed for lower
ings (above 50 wt%) could also be expected due to contributions from ceramic contents (up to CPE30). However, a drastic decrease in ionic
LLZO bulk conduction. However, our data display the opposite trend for conductivity can still be observed at and above 50 wt% loading, despite
these PTMC-LLZO CPEs, with a drastic decrease in conductivity starting an increase of the coordination number. This trend at higher loadings
from 50 wt% of LLZO. We also observe agglomerates at these loadings, cannot be explained by any ionic coordination-ionic conductivity rela­
which highlights the insulating nature of the bulk LLZO in our CPEs. tionship, but rather by the agglomeration of particles in the SPE matrix,
To better elucidate the effect of active ceramic filler content on the resulting in a blockage of ionic transport paths.
ionic conduction properties of PTMC-based electrolytes, it is vital to In addition to interactions between lithium cations and the polymer
investigate the coordination chemistry of the cations, and how this de­ functional groups, Li+ ions can also coordinate to the TFSI anions
pends on the electrolyte composition. There is plenty of evidence in leading to the formation of ion pairs and clusters. This can significantly
literature that the ion-polymer coordination strongly influences the affect the conduction properties of the overall PTMC-based system,
ionic transport properties in SPEs. The cation solvation structure, which either positively or negatively [64]. Despite sometimes leading to a
in SPEs is dominated by the interaction with the functional groups of the higher transference number, ion pairing generally remains detrimental
polymer, is likely to change when a third component (the ceramic par­ in SPEs and CPEs, limiting the fraction of available free cations to be
ticles) is introduced. It can be envisioned that this occurs either through coordinated to the polymer functional groups.
modifications of certain polymer-salt interactions as a result of the In the analysis of the ion paring of in these systems, we focused on
chemical interplay between the polymer and the particles, or that the the polymer-rich series up to 50 wt% of LLZO, due to the complexity of
particles are acting as anion immobilizers through Lewis acid-base in­ fitting these multi-components systems at higher loadings. As shown in
teractions with the salt. In polycarbonate-based polymers, the interac­ Fig. 2b, a broad peak appears in the region 740–750 cm− 1, assigned to
tion with lithium cations results in the observation of two bands in the the S-N-S vibration of the TFSI anions. This same feature was seen for all
vibrational spectra which correspond to free functional groups and Li+- CPEs, and was deconvoluted in order to quantify the ratio of free anions

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K. Elbouazzaoui et al. Electrochimica Acta 462 (2023) 142785

Fig. 5. (a) Deconvoluted FTIR spectra of an SPE without ceramic particles in the 1850–1600 cm− 1 region; (b) Coordination number vs. ceramic concentration; (c)
Deconvoluted FTIR spectra of an SPE in the 760–725 cm− 1 region. The peaks at 740 and 745 cm− 1 are assigned to free ions and ion clusters respectively, and the
continuous black and dashed lines represent the sum of the fitted peaks and the experimental data respectively; (d) Portion of free ions and ion pairs vs. LLZO
loadings for the polymer-rich series. Standard error of the mean is represented as error bars.

to ion pairs (Fig. S8). The “Li-TFSI” ion pair peak is shifted and seen at As seen in Fig. 5d, the fraction of free anions and ion pairs display the
⁓745 cm− 1, while the “free” anions peak remains at 740 cm− 1. reverse trend. Assuming that the number of free TFSI anions is corre­
Deconvoluting the FTIR spectra in this region is challenging because of lated to free Li cations in the system, this would correspond to an in­
interference from a third peak, attributed to C–H bending vibration in crease of the fraction of free lithium cations up to 30 wt% ceramic
the polymer (see Fig. S9). Therefore, this additional component was loading, while a slight decrease of this fraction is observed starting from
taken into consideration during deconvolution where equity between 40 wt% of LLZO. The observed increase in the portion of free charge
extinction coefficients was assumed prior to calculation of the fraction of carriers up to 30 wt% of LLZO is in good agreement with the increase
free anions and ion clusters (see Table S3 for more details). seen in the total ionic conductivity of CPEs up to 30 wt%. In addition, it

Fig. 6. (a) Chronoamperometric response of a Li/CPE30/Li symmetrical cell at 60 ◦ C. Inset: Nyquist plot before and after polarization; (b) Variation of the cationic
transference number as function of LLZO ceramic concentration. Inset: T+ variation from 35 to 45 wt% of LLZO. Standard error of the mean is represented as
error bars.

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K. Elbouazzaoui et al. Electrochimica Acta 462 (2023) 142785

seems that the free ions and ion pairs portions for CPES with 40 and 50 observed, while no carbon signal was detected.
wt% of LLZO are more or less similar to the initial amount detected for Owing to the high resistivity of Li2CO3, its presence on the surface of
the filler-free SPE. This could be due to an interaction between F− from LLZO particles could be one reason behind the increase of polymer-
TFSI anions with La3+ or Zr4+ upon addition of LLZO particles, which ceramic interfacial resistance, resulting in a lower overall ionic con­
explains the decrease of ion pairs portion for CPEs up to 30 wt%. ductivity of CPEs. On the other hand, the presence of lithium carbonate
However, this interaction seems to be less pronounced for CPEs with 40 on the surface of LLZO particles can also limit the ability of LLZO to act
and 50 wt% of LLZO, which can be speculated to be due to any changes as an anion immobilizer. In other words, the Lewis acid-base in­
for the LLZO surface chemistry (more details given below). teractions between TFSI anions and La3+ or Zr4+ from the ceramic filler
To further understand the transport properties, the cationic trans­ is limited by the partial coverage of Li2CO3 since this obstructs the
ference numbers for the entire series of composite electrolytes were ability of LLZO to complex anions.
measured at 60 ◦ C. Prior to the transference number calculation by the Li2CO3 is known to be spontaneously formed on the surface of LLZO
Bruce-Vincent equation, EIS data was fitted using an appropriate due to its air sensitivity [39]. To affirm the negative effect of Li2CO3 on
equivalent circuit, illustrated in Fig. S10. Fig. 6a displays the current the global ionic conductivity, a control experiment was performed by
fading until reaching a steady-state for CPE30, and the inset figure employing Li2CO3 as a ceramic filler instead of LLZO. Three
shows the variation of interfacial resistance before and after polariza­ PTMC-Li2CO3 composite electrolytes were fabricated within three
tion. The Nyquist plot for all electrolytes displays two semi-circles: the different ceramic concentrations of 10, 20 and 30 wt%. XRD patterns
first observed at high frequency range can be assigned to the bulk (Fig. S14) of the CPE with 30 wt% Li2CO3 confirmed the stable inclusion
response, while the second semi-circle at medium-to-low frequencies of Li2CO3 into the polymer, displaying the characteristic peaks of
can be attributed to the Li/electrolyte interfacial response, from which lithium carbonate.
the interfacial resistance is determined after fitting. Data for the filler- Considering that the CPE with 30 wt% of LLZO displayed the highest
free SPE and all remaining CPEs are displayed in Fig. S11. ionic conductivity, it is interesting to focus on the conduction behavior
For the polymer electrolyte without ceramic filler, a T+ value of 0.88 of the analogous composite with 30 wt% of Li2CO3 (Fig. 7). Based on the
was obtained at 60 ◦ C which is in good agreement with literature [64]. shape of the Nyquist plot, a Debye equivalent circuit was used to
The variation across the series of CPE materials is shown in Fig. 6b. It can determine the bulk resistance. The shape of the signal, displaying one
be seen that T+ increases as a function of ceramic concentration for LLZO obvious semi-circle (Fig. 7a), indicates that no conduction occurs at the
contents up to 30 wt%, followed by a dramatic decline at 40 wt%, and interfaces between PTMC and Li2CO3, unless the time constants of both
then increasing again for even higher loadings. It is also worth to bulk and interfaces are almost identical and the two resulting semi-
mention that the increase in the fraction of free charge carriers as circles merge, but this is unlikely. Variation of the ionic conductivity
determined by FTIR can lead to an increase of the transference number. as function of the temperature reveals that the composite with Li2CO3
This is seen for CPEs up to 30 wt% of LLZO, with an exception for CPE20 exhibited considerably lower conductivities as compared to its equiva­
which displayed the highest transference number and the lowest portion lent with LLZO ceramic filler, thereby confirming the detrimental effect
of free lithium cations. Starting from 40 wt% of ceramic particles and of lithium carbonate on the ionic conductivity in these hybrid electro­
above, the transference number values are still fairly high but inferior lytes. It is also noteworthy that when increasing the Li2CO3 loading up to
compared to the SPE without ceramic filler. 50 wt%, the bulk resistance similarly increases (see Fig. S15). It thus
It is apparent from Figs. 4b and 6b that similar trends can be seen for seems that the Li2CO3 restrains the access to the pure LLZO surface, and
both transference number and total ionic conductivity for the polymer- then limits the capability of the ceramic fillers to immobilize the anions
rich CPEs. However, T+ was observed to increase gradually with or to provide easily-accessible conduction pathways along the in­
increasing LLZO contents up to 30 wt%. The lowest transference number terfaces. Consequently, the LLZO surface coverage by Li2CO3 can be
was found at 40 wt% of LLZO. Therefore, to affirm the accuracy of the considered as a critical factor that suppresses ionic conduction along the
obtained T+ value at 40 wt% of LLZO, we narrowed the ceramic content inner interfaces in PTMC-LLZO CPEs.
window centered around 40 wt% and performed additional measure­ The composite electrolyte with 30 wt% of LLZO exhibited the highest
ments on CPEs with 35 and 45 wt% of LLZO. The obtained data at 35 and ionic conductivity, at which the interfacial transport was optimized. As a
45 wt% clearly follow the T+ trend and confirm the low T+ observed at result of these findings, it can be suggested that the main objective of
40 wt% of LLZO as displayed in the inset of Fig. 6b. Generally, published incorporating ceramic particles into an amorphous PTMC-based matrix
studies on composite electrolytes have not reported the Li-transference is the creation of new transport pathways along the interfaces, and a
number as function of the ceramic filler concentration, but rather possible increase of the number of free charge carriers in the system via a
focused on comparing the T+ between an SPE and a CPE only. In context special salt-ceramic interaction. As far as a relative increase in ionic
of the ceramic-rich CPEs, we believe that the T+ fluctuations observed conductivity of CPEs was noticed compared to the pristine SPE, this is
from 50 wt% and above can be due to several factors, e.g. the presence of considered as a promising starting point to understand how the ceramic
particles agglomerates that can be either fully or partially covered by content can influence the transport mechanism and design more
Li2CO3, resulting thus in a cluster of carbonate-covered particles which appropriate composite electrolytes with improved properties. Depend­
can restrict lithium mobility in the electrolyte. ing on ceramic loading, we here in Fig. 8 propose transport mechanisms
Considering that the nature of the ceramic-polymer interface is that also take previous observations and findings into consideration. For
crucial for understanding ion transport properties in CPEs, their surface the polymer-rich domains, lithium cations can be transported via the
chemistry is necessary to explore. To this end, the pristine LLZO powder polymeric phase as well as along inner interfaces. Upon transition to the
was examined by XPS; the results are displayed in Figs. S12b and S13. ceramic-rich domain, the same conduction pathways can be considered.
The data of the same samples show that the surface chemistry is not However, the conduction becomes problematic and obstructed because
uniform. There are points where there is clearly a presence of carbon of formation of ceramic agglomerates and the presence of more Li2CO3-
which originates from lithium carbonate, where also the intensity of containing interfaces.
characteristic peaks of both lanthanum and zirconium are very low.
However, La and Zr peaks intensities are high at other parts of the same 4. Conclusions
sample. This indicates a partial coverage of a surface layer of Li2CO3 on a
certain proportion of the ceramic particles. A similar observation has In this work, polycarbonate-based composite electrolytes with a Li+-
previously been reported by Huo et al. for a PEO-based system [65]. conducting ceramic filler were fabricated and their ionic conduction
Consequently, the first layers on the surface of LLZO were etched by properties as function of the filler concentration were investigated. It
argon sputtering, where after intense peaks of both La and Zr could be was observed that there is a dependence of the conductivity of

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K. Elbouazzaoui et al. Electrochimica Acta 462 (2023) 142785

Fig. 7. (a) Nyquist plot of the composite electrolytes with 30 wt% of LLZO and Li2CO3 at 60 ◦ C; (b) temperature-dependent variation of the total ionic conductivity of
SPE, and CPEs with either 30 wt% of LLZO and Li2CO3.

Fig. 8. Schematic representation of different possible Li-ion transport pathways in PTMC-LLZO composite electrolytes for low and high ceramic concentration.
Straight and dashed lines represent the conductive and restricted ionic transport routes, respectively.

composite electrolytes with LLZO filler loadings, leading to an increase CRediT authorship contribution statement
in conductivity upon addition of low-to-moderate concentrations. This
increase is presumably due to the creation of an additional transport Kenza Elbouazzaoui: Conceptualization, Methodology, Investiga­
pathway along polymer-ceramic interfaces, and to an increase in the tion, Writing – original draft. Funeka Nkosi: Investigation, Writing –
number of charge carriers in the matrix explained by a Lewis acid-base review & editing. Daniel Brandell: Conceptualization, Methodology,
interaction between ceramic particles and lithium salt. For higher LLZO Supervision, Writing – original draft, Funding acquisition. Jonas
loadings, a build-up of ceramic particle agglomerates was observed, Mindemark: Conceptualization, Methodology, Supervision, Writing –
which is one factor constraining both ionic and polymer chain mobility. review & editing. Kristina Edström: Supervision, Writing – review &
Importantly, the surface chemistry of the ceramic particles is shown to editing, Funding acquisition.
be vital to explain the overall conductivity of CPEs, where Li2CO3
coverage has detrimental effect on the ionic transport. Thereby, the Declaration of Competing Interest
incorporation of LLZO particles can lead to two opposite effects: positive
for LLZO surfaces, but negative for Li2CO3 covered surfaces. For high The authors declare that they have no known competing financial
LLZO contents, the negative effect of lithium carbonate is macroscopic, interests or personal relationships that could have appeared to influence
thus reducing the overall conductivity. Additionally, we affirm that the work reported in this paper.
there is no LLZO bulk transport, despite this material being considered
an ion-conducting “active” ceramic filler. This study sheds light on the Data availability
importance of both surface chemistry and filler loadings for the ionic
conduction properties of polymer-ceramic composite electrolytes. Data will be made available on request.

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K. Elbouazzaoui et al. Electrochimica Acta 462 (2023) 142785

Acknowledgments [22] X. Yu, A. Manthiram, A review of composite polymer-ceramic electrolytes for

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