Electrochimica Acta 320 (2019) 134560

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Electrochimica Acta
journal homepage: www.elsevier.com/locate/electacta

A nanowire-nanoparticle double composite polymer electrolyte for

high performance ambient temperature solid-state lithium batteies
Shi Wang a, c, 1, Lei Zhang b, 1, Jingyu Li d, Qinghui Zeng c, Xu Liu c, Pingping Chen c,
Wen-Yong Lai a, Tong Zhao d, **, Liaoyun Zhang c, *
a
Key Laboratory for Organic Electronics & Information Displays (KLOEID) & Institute of Advanced Materials (IAM), Jiangsu National Synergetic Innovation
Center for Advanced Materials (SICAM), Nanjing University of Posts & Telecommunications, Nanjing 210023, China
b
School of Materials and Chemical Engineering, Chuzhou University, Chuzhou 239000, China
c
School of Chemical Sciences, University of Chinese Academy of Sciences, Beijing 100049, China
d
Laboratory of Advanced Polymer Materials, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China

a r t i c l e i n f o a b s t r a c t

Article history: Development of solid-state electrolytes that can allow corresponding lithium-ion batteries (LIBs) to
Received 5 June 2019 perform excellent room temperature cell performance is very meaningful, and also is still a great chal-
Received in revised form lenge. One effective measure to solve the above problem is to reduce the interface resistance of the cells
17 July 2019
via special methods. In this study, a novel double composite polymer electrolyte using polyethylene
Accepted 17 July 2019
oxide-polypropylene oxide-polyethylene oxide (PEO-PPO-PEO)/LiTFSI, ceramic nanowires and nano-
Available online 18 July 2019
particles is designed and prepared (the composite electrolyte is named as CPE) for the first time, which
combines the advantages of polymer electrolyte, ceramic nanowires and nanoparticles (different from
Keywords:
Double composite polymer electrolyte
the related works about only using ceramic nanopartices or ceramic nanowires as fillers). Compared with
Ceramic nanowires the composite electrolyte without adding ceramic nanoparticles (named as CPE-0), CPE presents higher
Ceramic nanoparticles ionic conductivity (4.58
105 S cm1 at ambient temperature), much higher lithium-ion transference
Ambient-temperature solid-state lithium- number (0.28), which likely because nanoparticles can promote the formation of more continuous ion
ion batteries channels at the interface of polymer and ceramic fillers. In addition, the CPE shows much wider elec-
trochemical window (5.6 V) than that of the CPE-0 (4.2 V), which can be attributed to the extra nano-
particles can further scavenge trace impurities. Especially, the galvanostatic cycling experiments confirm
that CPE has much better stability against Li metal than that of CPE-0, while the Li/CPE/Li symmetric cell
also shows a low and stable interface resistance of ~800 U from day 1 to day 25. Therefore, the LiFePO4/Li
cell using the CPE shows good cycle performance at 28  C. Specifically, the cell exhibits a discharge ca-
pacity of 154 mAh g1 with coulombic efficiency of 100% at the 100 cycles. Our work indicates that the
interface resistance of the corresponding batteries can be significantly reduced by preparation of CPE
with specific polymer electrolytes and ceramic fillers. Thus, the solid-state cells can be well run at
ambient temperature.
© 2019 Elsevier Ltd. All rights reserved.

1. Introduction liquid electrolytes can be effectively solved when solid-state elec-

Solid-state electrolytes have been paid intensive attention in
recent years due to their flexibility, easy to process and especially
the high safety (compared with liquid electrolytes) [1e5]. The poor
chemical stability, leakage, flammability problems come from
* Corresponding author.
** Corresponding author.
E-mail addresses: tzhao@iccas.ac.cn (T. Zhao), zhangly@ucas.ac.cn (L. Zhang).
1
Shi Wang and Lei Zhang contributed equally to this work.
trolytes are used to replace organic liquid electrolytes in lithium-
ion batteries (LIBs) [6,7]. Typically, solid-state electrolytes can be
divided into inorganic solid-state electrolytes (ISEs), solid-state
polymer electrolytes (SPEs) and composite solid-state electrolytes
(CSE) [8].
Among them, ISEs present high room temperature ionic con-
ductivity, high pressure resistance and the ability to inhibit the
growth of lithium dendrites [9,10]. However, the large interface
resistance, space charge layer and air sensitivity of ISEs make it
hard to realize the large-scale applications of ISEs [11,12].

https://doi.org/10.1016/j.electacta.2019.134560
0013-4686/© 2019 Elsevier Ltd. All rights reserved.
2 S. Wang et al. / Electrochimica Acta 320 (2019) 134560
For SPEs, it usually exhibits the characteristic of mechanically
robust, good thermal and electrochemical stability, good interface
compatibility with electrodes and high safety, which is well suited
for large-scale processing [13,14]. Up to now, poly(ethylene oxide)
(PEO) is still the most famous material used as polymer electrolyte
matrix due to the very good complexing ability with Liþ and the
low Tg of the material [15]. Unfortunately, the room temperature
ionic conductivity of SPEs based on PEO is usually very low (107-
106 S cm1) due to the high crystallinity of PEO. Although dis-
rupting the crystallinity of PEO via crosslinking [16e18] and
copolymerization [2,19] can increase the room temperature ionic
conductivity of the SPEs, the cells using the SPEs usually present
high interface resistance, which causes the solid-state LIBs (SSLIBs)
cannot run at room temperature (usually have to run at tempera-
ture higher than 60  C). Of particular interest, it is found that
incorporation of ceramic nanofillers into SPEs can remarkably in-
crease the ionic conductivity, electrochemical stability and me-
chanical strength of the CSEs. This is because ceramic nanofillers
can reduce the crystallinity of polymers and facilitate the motion of
segments (it is also believed that highly conductive interface
pathways can be formed between ceramics and polymers) [20,21].
More intriguingly, the strong Lewis acid-base interaction between
the surface chemical groups of the nanofillers and electrolyte ion
species can increase the dissociation of lithium salts and also sta-
bilize the anions [22e24]. Specifically, the ceramic nanoparticles
with large specific surface area can enhance the ionic conductivity
of polymer electrolytes drastically [20,25]. However, the limited
continuous interface ion channels, easy agglomeration of ceramic
nanoparticles and relatively weak interaction between particles
and polymers make it difficult to further improve the performance
of the composite SPEs [21,26]. Recently, researchers found that
nanowire fillers with high length-diameter can construct much
longer continuous ionic transport layers compared with nano-
particle fillers [21]. Nevertheless, the interface ionic transport
pathways still not totally continuous, and the assembled SSLIBs still
needed to be worked at high temperature due to the high interface
resistance [27,28]. Therefore, it can be speculated that using
nanoparticle and nanowire to prepare a double composite polymer
electrolyte likely can construct much more continuous ion chan-
nels, then the performance of the composite polymer electrolytes
likely can be further improved.
Moreover, for practical application of SPEs, it is very necessary
that the corresponding SSLIBs can be well cycled at room temper-
ature. Obviously, to reach this goal, it has to further reduce the
interface resistance of the SSLIBs. One of the most effective mea-
sures is to incorporate suitable contents of plasticizers (such as
liquid organic electrolytes and ionic liquids) on the solid electrolyte
films [29e34]. Very recently, we also used such strategy to design
the special solid electrolytes that can make the SSLIBs well run at
ambient temperature [35e37].
In fact, through reducing the molecular weight of the polymers,
the interface resistance of the corresponding SSLIBs can also be
obviously reduced due to the increased infiltration capacity of
polymers (it can improve the interface contact of electrolytes and
electrodes). According to this conception, a novel topological
structure polymer with controlled molecular weight was designed
and synthesized via controlled free radical polymerization by our
group. It is found that the corresponding SSLIBs show very good
cycle performance and rate capacity at ambient temperature [38].
However, it is not easy to synthesize such a special polymer elec-
trolyte matrix. Not to mention scale production. If a kind of polymer
from commercially available components with a reasonable mo-
lecular weight can be used to conduct Liþ, it likely can solve the
above problems, especially the ambient temperature cycle problem
of the SSLIBs.
In this study, we try to use such a strategy to reduce the interface
resistance of the SSLIBs, so that the SSLIBs can be well cycled at
ambient temperature. Specifically, the polymer we selected is
polyethylene oxide-polypropylene oxide-polyethylene oxide (PEO-
PPO-PEO). PEO-PPO-PEO is chosen as polymer electrolyte matrix
because the copolymer structure can further reduce the crystal-
linity and glass transition temperature of PEO. More importantly,
PPO segments also have similar structure with PEO, which is also
beneficial to the transport of Liþ. In addition, given contents of
nano-silica (25 wt%) is added to further reduce the crystallization,
create interface ion channels and enhance the electrochemical
stability of PEO-PPO-PEO. Furthermore, ceramic film containing
ceramic nanowires is used to load PEO-PPO-PEO/LiTFSI/nano-SiO2.
Here, the ceramic film is also used to build long-range interfacial
ion channels and act as a mechanical support for the polymer
electrolyte.
To the best of our knowledge, this is the first report about
combining the advantages of ceramic nanoparticles and ceramic
nanowires, while the ceramic materials are composited with a
polymer electrolyte matrix (PEO-PPO-PEO) of suitable molecular
weight to prepare a special composite polymer electrolyte (CPE)
(although there are reports about electrolytes based on PEO-PPO-
PEO, the prepared electrolytes either do not present the corre-
sponding SSLIBs performance [39e41] or show unsatisfied cell
performance due to the increasing interface resistance as reflected
by the enlarged polarization (the cells only has a capacity of ~94
mAh/g at 30  C) [42]). The advantage of combination of nanowires
and nanoparticles is that more continuous ion channels at the
interface of polymer and ceramic fillers can be formed than only
using one kind of the filler, likely resulting in much better perfor-
mance using CPE. As predicted, compared with the composite
polymer electrolyte without adding nano-SiO2 (named as CPE-0), it
is found that the CPE shows much higher ionic conductivity in the
whole temperature range (30e80  C), obviously wider electro-
chemical window and much higher lithium-ion transference
number (tþ). As a result, the SSLIBs using the CPE exhibits strongly
better cell performance than that of the SSLIBs using CPE-0 at
ambient temperature. This work highlights a simple but very
effective method to prepare a special CPE with satisfactory per-
formance, which can be used for ambient-temperature SSLIBs.
2. Experimental
2.1. Materials
Polyethylene oxide-polypropylene oxide-polyethylene oxide
(PEO-PPO-PEO, Balinway technology co., LTD, Mw ¼ 5800 g mol1),
silicon dioxide (SiO2, 99.8%, BET ¼ 300 m2 g1, grain diam-
eter ¼ 7e40 nm, Macklin, China), absolute methanol (AR, Beijing
Chemical Works) and bis(trifluoromethane)sulfonimide lithium
(LiTFSI, 99%, Aladdin) were used as received. Ceramic film con-
taining the ceramic nanowires is prepared via electrostatic spin-
ning (the solid alumina precursor (it has a melting temperature of
60  C) was provided by Suzhou tuna new material technology co. LTD,
see the detailed preparation method in our previous report [38]).
2.2. Preparation of composite polymer electrolyte (CPE)
LiTFSI (0.6 g), SiO2 (0.5 g) and PEO-PPO-PEO (2 g) were dissolved
in absolute methanol (10 mL). The mixtures were dropped on the
surface of an aluminium oxide ceramic electrostatic spinning film
containing the ceramic nanowires. Whereafter, the composite film
was stayed at ambient temperature for 30 min to evaporate part of
methyl alcohol (aging at RT), and then dried at 60  C under vacuum
for 24 h to obtain the CPE. For comparison, a composite film
 S. Wang et al. / Electrochimica Acta 320 (2019) 134560
without SiO2 was also prepared under the same condition, which is
named as CPE-0. Specifically, for CPE, according to the weight
content of PEO-PPO-PEO, the weight percentage content of LiTFSI
and SiO2 nanoparticles are 30 wt% and 25 wt%, respectively. For
CPE-0, the weight percentage content of LiTFSI is also 30 wt% ac-
cording to the weight content of PEO-PPO-PEO. In addition, the
ceramic film containing the nanowires was cut into a round sheet
with a diameter of 20 mm. Subsequently, ~0.25 ml PEO-PPO-PEO/
LiTFSI or PEO-PPO-PEO/SiO2/LiTFSI mixture was dropped on the
surface of the ceramic film to prepare the composite electrolyte.
2.3. Characterization
Thermo Nicolet AVATAR 360 infrared instrument with an
attenuated total reflectance (ATR) attachment was used to conduct
the FTIR spectra of the related samples (from 4000 to 500 cm1).
SEM images and EDX data were performed using a Field Emission
Scanning Electron Microscope (FESEM, Hitachi SU8010) with an
EDX detector. The composite electrolytes were sputtered with Au
for 30 s. The thermal stabilities of the composite electrolytes were
obtained according to the TGA curves (PerkineElmer TGA 1 series
instrument was used to obtain the curves and the heating rate was
20  C min1 from 50 to 600  C under N2 atmosphere). To further
evaluate the thermal properties of the samples, differential scan-
ning calorimetry (DSC) tests were recorded using TA Instrument
Q2000. Specifically, an empty reference aluminum pan and pans
containing samples (~4 mg) with lids were heated from 30 to 120  C
at the rate of 10  C min1 and then cooled to 90  C at the rate of
10  C min1 under nitrogen atmosphere. The DSC curves used were
the second heating traces. In addition, the XRD tests were per-
formed on an Automated Multipurpose X-ray Diffractometer
Smartlab 9 kW with a copper target (l ¼ 1.54 Å), while the operated
voltage and current were 45 kV and 200 mA, respectively.
2.4. Electrochemical measurements
To measure the ionic conductivities of the composite polymer
electrolytes, electrochemical impedance spectroscopies (using the
Zennium Electrochemical workstation (Zahner-Zennium)) of the
Scheme 1. Preparation route of CPE film.
3
samples were obtained using a stainless steel (SS)/CPE/SS sym-
metric cell via the two-probe method, then the ionic conductivity
can be calculated. Li-ion transport number (tþ) was calculated
through alternating current (AC) impedance and direct-current
(DC) polarization tests using a Li/CPE/Li symmetric cell. The elec-
trochemical stability of the CPE was conducted by linear sweep
voltammetry using a Li/CPE/SS coin cell. See the detailed informa-
tion in our previous reports [36,43].
Moreover, LiFePO4 ((LFP), LFP is kindly provided by Pulead
Technology Industry Co., Ltd.)-based cathode was used to evaluate
the cell performance of the CPE and CPE-0. The active substance
content was 1.5e2.5 mg cm2. In addition, the cathode consisted of
LFP (70 wt%), super P (20 wt%) and PVDF (10 wt%). The LFP/Li cells
using CPE and CPE-0 were assembled in an Ar-filled glovebox (MB-
Labstar 1200/780) with O2 and H2O contents lower than 0.5 ppm.
The cell performance of all the all-solid-state batteries was tested
on the LANHE CT2001A battery testing system. Specifically, the
discharge and charge ranges of the LFP/CPE/Li cells were carried out
between 2.5 and 4 V and the cells were run at 28 or 80  C.
3. Results and discussion
A facile and easy preparation method is very meaningful for an
electrolyte material to be widely applied in LIBs. Scheme 1 shows
the preparation route of the CPE. Specially, a mixture of PEO-PPO-
PEO, SiO2, LiTFSI and methanol with a certain ratio was dropped
on the ceramic film. Subsequently, a freestanding CPE was obtained
after drying. A composite electrolyte film without adding SiO2 was
also prepared under the same condition and used as a blank sample
(CPE-0).
First, the thermal stabilities of CPE and CPE-0 matrices were
evaluated because high thermal stability is crucial for the corre-
sponding electrolytes to be applied in LIBs. As shown in Fig. 1a, both
composite films without and with SiO2 nano-filler present thermal
decomposition temperatures (Tonset) higher than 330  C, which can
meet the basic requirement of a solid-state electrolyte material to
be used in LIBs. However, according to the TGA curves, it can be
seen that the Tonset of the composite polymer slightly reduces after
adding SiO2 nanofiller, which likely because the hydroxyl groups on
4 S. Wang et al. / Electrochimica Acta 320 (2019) 134560

Fig. 1. (a) TGA curves of composite films without and with SiO2 nano-filler. (b) DSC curves of PEO-PPO-PEO, PEO-PPO-PEO/30 wt% LiTFSI, CPE-0 and CPE.

the surface of SiO2 tends to thermal decomposition at high tem-
perature [44]. The DSC curves of the PEO-PPO-PEO, PEO-PPO-PEO/
30 wt% LiTFSI, CPE-0 and CPE are shown in Fig. 2b. Addition of
LiTFSI into PEO-PPO-PEO (Tg ¼ 65  C) causes the Tg increasing of
PEO-PPO-PEO/30 wt% LiTFSI due to coordination between LiTFSI
and ether groups [45], while the plasticizing effect of LiTFSI also
strongly reduces the crystallinity of PEO-PPO-PEO. Furthermore, it
is also seen that CPE-0 and CPE show very close Tg value to PEO-
PPO-PEO/LiTFSI, confirming that the flexibility of polymer seg-
ments is not disrupted via adding nanoparticles and nanowires.
Nevertheless, an obvious melting peak is observed at the DSC curve
of CPE-0 while no obvious melting peak is seen at the DSC curve of
CPE, demonstrating that addition of nano-SiO2 into the composite
polymer electrolyte can further reduce the crystallization of the
composite electrolyte.
SEM can be used to effectively observe the microstructure of
samples. The SEM image of the original ceramic film in Fig. 2a in-
dicates that the ceramic film is composited of uniformly distributed
ceramic nanowires, and the nanowire has a diameter of ~200 nm
(see the SEM image in the supporting information). The SEM image
of the surface morphology of CPE-0 is presented in Fig. 2b. It is seen
that the ceramic film is uniformly coated by the polymer electro-
lyte. Meanwhile, as shown in Fig. 2c, the original ceramic film is also
well coated by the SiO2/polymer electrolyte. At a higher magnifi-
cation, nano-SiO2 particles with a diameter of ~50 nm can be clearly
observed on the surface of the CPE (Fig. 2d). The cross section
morphologies of the CPE at different magnifications (Fig. 2e and f)
indicate that the film has a thickness of ~50 mm, and the SiO2/

Fig. 2. (a) SEM image of surface microstructure of the pristine ceramic fibers, which is obtained by electrostatic spinning. (b) SEM image of CPE-0. (c) and (d) show the SEM images
of CPE at different magnifications, respectively. (e) and (f) are the microscopic cross section morphologies of the CPE at different magnifications, respectively. EDS mappings of the
CPE of Al (g), Si (h) and N (i) elements, respectively. The inset of Fig. 2g shows the SEM image that is used to obtain the EDS mappings.
 S. Wang et al. / Electrochimica Acta 320 (2019) 134560
polymer electrolyte has sufficiently filled in the space of the
ceramic nanowires. The EDS mappings of Al (Fig. 2g), Si (Fig. 2h)
and N (Fig. 2i) further demonstrate that the ceramic film containing
the ceramic nanowires is well composited with SiO2/polymer
electrolyte.
Ionic conductivity evaluation indicates that CPE has higher ionic
conductivity than that of CPE-0 in the whole temperature range
(Fig. 3a). Specifically, the CPE has an ambient temperature ionic
conductivity of 4.58
105 S cm1 and the ionic conductivity rea-
ches 5.7
104 S cm1 at 80  C, while the ionic conductivities of
CPE-0 are 3.4
105 and 4.6
104 S cm1 at ambient temperature
and 80  C, respectively. It should be noticed that PEO-PPO-PEO is
the main matrix to transport carriers. More directly, the IR spectra
in Fig. 3b also confirms that -C-O-C- has strong coordination ability
with Liþ. Specifically, the adsorption peak belongs to eC-O-C-
shifting from 1081 to 1040 cm1 after adding LiTFSI. In addition, the
ceramic film containing the nanowires plays an important sup-
porting role for polymer electrolyte and nano-SiO2. As a result, the
composite film is very flexible (see Scheme 1). Furthermore, addi-
tion of the nano-SiO2 into the CPE-0 can obviously increase the
ionic conductivity of the composite electrolyte because nano-SiO2
can further reduce the crystallinity of PEO-PPO-PEO (see the DSC
curve in Fig. 1b). Such conclusion can be further demonstrated by
the XRD characterization (Fig. 3c). Compared with PEO-PPO-PEO,
the peak intensity of PEO-PPO-PEO/LiTFSI at 20 strongly de-
creases due to the plasticizing effect of LiTFSI (the peak at 20
corresponding to a diffraction peak comes form PEO-PPO-PEO, the
intensity of the peak can be used to evaluate the degree of crys-
tallinity (usually higher peak intensity means higher cystallinity)).
After casting PEO-PPO-PEO/LiTFSI on the ceramic film (corre-
sponding to CPE-0), the intensity of peak at 20 do not decrease
obviously (Fig. 3c), denoting that ceramic film has no significant
ability to inhibit the crystallization of PEO-PPO-PEO. Furthermore,
Fig. 3c also exhibits that CPE has lower peak intensity at 20 , which
strongly reveals that SiO2 has the ability to restrain the crystallinity
Fig. 3. (a) Ionic conductivities of CPE-0 and CPE at a given temperature (from 30 to 80  C). (b) IR spectra of PEO-PPO-PEO/ceramic nanowires and PEO-PPO-PEO/ceramic nanowires/
30% LiTFSI, which indicates that the eC-O-C- can complex with Liþ. (c) XRD patterns of PEO-PPO-PEO, PEO-PPO-PEO/LiTFSI, CPE-0 and CPE. (d) Linear sweep voltammetry (LSV) of
CPE-0 and CPE at ambient temperature. (e) Cyclic voltammetry (CV) of CPE (the scan rate is 5 mV s1) at ambient temperature. (f) EIS of Li/CPE/Li cell after different storage times at
ambient temperature.
5
of PEO-PPO-PEO.
The positive effect of nano-SiO2 can also be reflected by the
electrochemical stability test. As shown in Fig. 3d, CPE presents an
electrochemical window of 5.6 V while CPE-0 only shows an elec-
trochemical window of 4.2 V. The enlarged LSV curves is also pre-
sented inset of Fig. 3d, minor oxidation currents at about 4 V are
observed for CPE-0, while the LSV curve of CPE exhibits no oxida-
tion characteristics from 3 to ~5.6 V, indicating the positive effective
of SiO2 nanoparticles. Such a significant difference (greatly
increased electrochemical window of CPE) can be attributed to the
extra nano-SiO2 can further scavenge trace impurities [46,47]. The
CV curves of the CPE are presented at Fig. 3e. The scanning voltage
range was set from 0.5e6 V, during the first cycle, the reverse
cycle approaching 0 V shows a line almost parallel to the Y-axis
because the electric potential has an initialization process
("initialization process" represents that voltage drops from open
circuit voltage to 0.5 V when the CV stars form 0.5 V). After the
first cycling, the CV curves at ~0 V become normal (“normal” means
after the initialization process, the voltage does not mutate and the
current does not change rapidly). In addition, it shows that the CV
curves are almost coincident in 3 cycles of cycling, indicating the
good deposition reversibility of the cell using CPE.
Li/CPE/Li symmetric cell is used to further evaluate the interface
stability of the CPE with lithium metal. As shown in Fig. 3f, the
interface resistances of the cell at medium frequency in the real axis
keep at ~400 U from the 1st day to 25th day, indicating the very
good interface stability and compatibility of the CPE with lithium
metal. Furthermore, the galvanostatic cycling curves of the Li/CPE/
Li and Li/CPE-0/Li symmetric cells is presented in Fig. S2. The
overpotential of Li/CPE/Li cell reaches stable value (0.24 V) after
~60 h cycling (both charge and discharge times are 1 h), while the
overpotential of the Li/CPE-0/Li cell is much higher (~8 V) than that
of the Li/CPE/Li and short circuit occurs after ~60 h of circulation,
demonstrating much better stability of CPE against Li metal.
The DC polarization of the Li/CPE-0/Li and Li/CPE/Li cells at room
6 S. Wang et al. / Electrochimica Acta 320 (2019) 134560

Figure 4. (a) and (b) present the DC polarization of the Li/CPE-0/Li and Li/CPE/Li cells at ambient temperature, respectively. The pre-/post-AC impedance spectra are shown as
insets. (c) Possible lithium ions conduction pathways in nanoparticle-filled and nanowire-filled composite electrolyte. It illustrates that better continuous fast conduction pathways
can be formed (the red line means ions can transport more efficient using the double composite electrolyte).

temperature is presented in Fig. 4a and b (the insets show the EIS
before and after polarization), respectively. It is also find that the
CPE exhibits a tþ (0.28) 14 times higher than that of the CPE-0 (0.02,
see the related parameters in Table S1) and also can compare with
some reported works (see Table S2), demonstrating that nano-SiO2
is crucial for improving the transport efficiency of Liþ. Although the
interface between ceramic nanowires and polymer electrolyte can
form ion channels [21,48], the interface ion channels are still very
limited, while suitable contents of SiO2 nanoparticles can further
increase the ion channels. As a result, more continuous ion chan-
nels likely can be constructed at the interface of polymer and
ceramic fillers, which might be the main reason for the higher tþ of
CPE than that of CPE-0. For clarity, the model of possible lithium
ions conduction pathways in nanoparticles-filled and nanowires-
filled composite electrolyte is presented in Fig. 4c, it illustrates
that better continuous fast conduction pathways can be formed.
To further confirm the CPE can be well used in LIBs at ambient
temperature. We assembled LFP/CPE/Li cell to assess the cell per-
formance. Meanwhile, LFP/CPE-0/Li cell was also assembled and
cycled at the same condition as a comparison. The charge/discharge
curves of LFP/CPE/Li and LFP/CPE-0/Li cells at different cycles are
exhibits in Figure 5a. It is seen the cell using CPE shows lower over
potential than that of the cell using CPE-0. Moreover, Figure 5a also
shows that the charge/discharge capacities of LFP/CPE/Li cell are
higher than the LFP/CPE-0/Li cell at the same cycle. In addition,
according to Figure 5b, both of the two cells present coulombic
efficiency close to 100% from cycle 1 to cycle 100. It is found that the
capacity of the cell using CPE almost shows monotone increasing
with the increase of cycle number (it reaches 154 mAh g1 with
coulombic efficiency of 100% at the 100 cycles, which is much
higher than recently reported LFP/Li cell using solid-state electro-
lytes (see Table S3)), while the cell using CPE-0 exhibits a mono-
tonic decreasing of discharge capacity with the increase of cycle
number (drops to 30 mAh g1 after 100 cycles). Generally, the cell

Fig. 5. (a) Charge and discharge curves of the LFP/CPE-0/Li and LFP/CPE/Li cells at ambient temperature. (b) Cycle performance and coulombic efficiency of the solid-state cells at
28  C.
 S. Wang et al. / Electrochimica Acta 320 (2019) 134560
with CPE increases capacity likely because the cell shows a
continuous self-activation, while the cell with CPE-0 decreases
capacity probably can be attributed to the high interface resistance
and the influence of trace impurity without adding nanoparticles.
Specifically, the capacity of LFP/CPE/Li cell is much higher than the
cell using CPE-0 after 25 cycles. The assembled LFP/CPE/Li cell also
exhibits very good cell performance at 80  C (see the cell perfor-
mance and discussion in the supporting information), confirming
the good thermal stability of the CPE and the CPE has the potential
to be used in a wide temperature range. In a word, addition of nano-
SiO2 into the CPE-0 can strongly improve the cycle performance of
the LIBs, which can be attributed to the higher ionic conductivity,
much higher tþ (origins from the formation of more continuous ion
channels using double composite strategy) and better interface of
the CPE than that of the CPE-0.
4. Conclusion
A free-standing composite polymer electrolyte was prepared
using PEO-PPO-PEO/LiTFSI and ceramic film containing the ceramic
nanowires. Specifically, the PEO-PPO-PEO/LiTFSI methanol solution
was casted onto the ceramic film to prepare the composite polymer
electrolyte (CPE-0). As a result, the CPE-0 had a ambient tempera-
ture ionic conductivity of 3.4
105 S cm1, tþ of 0.02 and elec-
trochemical window of 4.2 V. It was also found that addition of
nano-SiO2 particles (25 wt%) into the CPE-0 could increase the
room temperature ionic conductivity (4.58
105 S cm1) of the
prepared CPE. Especially, the CPE showed a strongly improved
electrochemical stability (the electrochemical window reached
5.2 V) because the extra SiO2 nanoparticles could further scavenge
trace impurities. More importantly, the CPE had a tþ of 0.28, which
was 14 times higher than the CPE-0. The superior electrochemical
performance of the CPE made the LFP/CPE/Li cell have significantly
better cycle performance than that of the LFP/CPE-0/Li cell. Spe-
cifically, the discharge capacity of the LFP/Li cell using CPE was
increased with cycle number until it reached a capacity of 154 mAh/
g after 100 cycles (with coulombic efficiency of 100%) at ambient
temperature, while the discharge capacity of the LFP/CPE-0/Li cell
dropped to 30 mAh g1 after 100 cycles at the same condition. This
work highlights a simple but effective method to prepare a special
double composite polymer electrolyte with good performance,
which can be used for ambient temperature solid-state LIBs.
Notes
The authors declare no competing financial interest.
Acknowledgements
We thanks for the help from the analysis and testing center at
the University of Chinese Academy of Sciences. The authors also
express thanks for the supports of the National Natural Science
Foundation of China (No.51073170) and Innovation Program of CAS
Combination of Molecular Science and Education.
Appendix A. Supplementary data
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.electacta.2019.134560.
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