Solid State Ionics 295 (2016) 65–71

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Solid State Ionics

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

A promising PEO/LAGP hybrid electrolyte prepared by a simple method

for all-solid-state lithium batteries
Yanran Zhao a,b,1, Zhen Huang a,1, Shaojie Chen a,⁎, Bo Chen a, Jing Yang a, Qiang Zhang a, Fei Ding b,
Yanhua Chen a,c, Xiaoxiong Xu a,⁎
a
Ningbo Institute of Materials Technology and Engineering, Chinese Academy of Sciences, Ningbo 315201, China
b
Tianjin Institute of Power Sources, Tianjin 300381, China
c
Zhejiang Fashion Institute of Technology, Ningbo 315211, China

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

Article history: Four types of Li1.5Al0.5Ge1.5(PO4)3 (LAGP) with different particle sizes are selected as active fillers incorporated
Received 24 May 2016 into polyethylene oxide (PEO) matrix to fabricate PEO/LAGP hybrid electrolytes at drying room. The results
Received in revised form 9 July 2016 show that LAGP particles have a positive effect on the ionic conductivity, lithium ion transference number, elec-
Accepted 30 July 2016
trochemical stabilities and mechanical properties. Among the PEO/LAGP hybrid electrolytes, the PEO-20%LAGP-I
Available online xxxx
hybrid electrolyte exhibits a maximum ionic conductivity of 6.76 × 10−4 S cm−1 and an electrochemical window
Keywords:
of 0–5.3 V at 60 °C. The possible reasons for conductivities improving are discussed through characterizing the
Hybrid electrolyte phase transition behaviors of electrolytes. All-solid-state battery LiFePO4/Li is fabricated and presents fascinating
Polyethylene oxide electrochemical performance with high capacity retention (close to 90% after 50 cycles at 60 °C) and attractive
LAGP capacities of 166, 155, 143 and 108 mAh g−1 at current rates of 0.1, 0.2, 0.5 and 1 C, respectively. This work pro-
Simple preparation vides a promising PEO/LAGP hybrid electrolyte prepared by a simple method which can be manufactured easily
All-solid-state lithium battery in industry scale.
© 2016 Elsevier B.V. All rights reserved.

1. Introduction
Solid polymer electrolytes (SPEs) with excellent properties such as
absence of leakage of organic solvents, mechanical properties, and flex-
ibility are now becoming increasingly attractive for lithium-ion batte-
ries (LIBs) [1,2]. However, LIBs with SPE could hardly reach the stage
of large-scale commercial production due to the low ionic conductivity,
bad interfacial contacts between electrodes and electrolytes, and nar-
row electrochemical window. Therefore, it is very urgent to develop
an electrolyte which has simultaneously high ionic conductivity, good
interfacial and mechanical properties, fine thermal and electrochemical
stabilities, and safety. Polymer electrolytes based on PEO, owing to its
ability to solvate a wide variety of salts through interaction of its ether
oxygens with cations, have been widely investigated as promising can-
didates to prepare thinner, lighter and safer LIBs. Moreover, it can be
used in all-solid-state lithium battery designs in a free standing form
without modifying current battery fabrication processes [3].
In fact, for the SPEs, polymers act as hosts for ions and the ionic
conductivity displays a diffusive liquid-like behavior in the SPEs.
The polymer molecules are free to move above the glass transition tem-
perature (Tg), thus, the ions can transport in the space provided by the
free volume of the polymer host. Whereas, PEO is a semi-crystalline
polymer, and the amorphous phase with activated chain segments
(above Tg) is beneficial for ion transport [4]. PEO crystallization is
detrimental to ion transport due to the slowed down polymer chain dy-
namics upon crystallization [5]. Therefore, a lot of efforts have been de-
voted to suppressing PEO crystallinity and increasing the percentage of
the amorphous phase of PEO for ion transport.
Various strategies and approaches such as the addition of a plasti-
cizer [6] or filler [7], polymer blends [8], grafting short PEO oligomers
onto polymer backbones or cross-linking PEO-based polymers [9], and
block copolymer [10] have been explored to improve the ionic conduc-
tivity of PEO-based electrolytes.
The addition of filler into the PEO-based electrolyte can improve the
ionic conductivity, mechanical properties and the interfacial properties
in contact with the electrode, which could ascribe to the increased
amorphous phase and the inhibited recrystallization of PEO.
Al2O3 [11], SiO2 [12], TiO2 [13], and other metal oxides [14,15] are
usually used in PEO-based SPEs. The inorganic particles can compensate
the deterioration of mechanical properties arising from the low crystal-
linity of PEO polymer. Most importantly, these particles can often form a
pathway in the interphase for the ion transportation, resulting in the
improvement of ionic conductivity [16]. Hu et al. [17] developed a
PEO-based SPE using mesoporous LiAlO2 nanosheets as the filler. The
ionic conductivity of SPE containing 15 wt% filler reached a maximum
of 2.24 × 10−5 S cm−1 at 25 °C, which was more than two orders higher
than that without the filler, and the SPE exhibited good electrochemical
stability up to 5.0 V. In our previous work [18], solid electrolyte

http://dx.doi.org/10.1016/j.ssi.2016.07.013
0167-2738/© 2016 Elsevier B.V. All rights reserved.
66 Y. Zhao et al. / Solid State Ionics 295 (2016) 65–71
Table 1
Post-treatment condition from LAGP glass to glass-ceramic.
Sample Post-treatment
Annealing Ball milling
LAGP-I 900 °C, 12 h 24 h
LAGP-II 800 °C, 6 h 24 h
LAGP-III 900 °C, 12 h 12 h
LAGP-IV 900 °C, 12 h – bis(trifluoromethane)sulfonimide (LiTFSI, 99.9%, Aldrich) with molar
Li10GeP2S12 (LGPS) was incorporated into PEO matrix to fabricate
SPE. The optimal SPE exhibits a maximum ionic conductivity of
1.18 × 10− 5 S cm− 1 at 25 °C and an electrochemical window of 0–
5.7 V. The LGPS particles, acting as active fillers incorporation into the
PEO matrix, could improve ionic conductivity, lithium ion transference
number and electrochemical stabilities effectively. The LiFePO4/Li bat-
tery exhibited good electrochemical performance with high capacities
and retention. However, the LGPS is sensitive to the air, difficult process-
ability and high cost. Consequently, all the procedures of preparation of
LGPS composite SPE must be conducted in the glove box that is very dif-
ficult for large-scale commercial production.
Li1 + xAlyGe2 − y(PO4)3 (LAGP) solid electrolytes have relatively high
lithium ion conductivity over 10−4 S cm−1 and high atmospherical sta-
bility [19,20]. It has been reported that LAGP showed the electrochemi-
cal window as high as 6 V (vs. Li+/Li) [21]. Therefore, in this paper, LAGP
was selected to disperse in the PEO-matrix without any other additive
to prepare a promising PEO/LAGP hybrid electrolyte at drying room. It
is easy processability and suitable for the manufacture of the product
in industry scale. The conductivity and phase behavior of LAGP-filled
polymer electrolytes were systematically investigated. The optimal
PEO/LAGP hybrid electrolyte exhibited an applicable ionic conductivity
and a wide electrochemical window. The feasibility and performance
of all-solid-state lithium battery using this hybrid electrolyte were char-
acterized as well.
2. Experimental
Four types of Li1.5Al0.5Ge1.5(PO4)3 (marked as LAGP-I, LAGP-II, LAGP-
III and LAGP-IV) glass-ceramic particles were prepared by three proce-
dures. Firstly, the fine LAGP glass was prepared by controversial melt-
quench method according to the reports [19,21]. Then, the fine LAGP
glass precursor was annealed under different temperature in a furnace
to get different devitrification degrees. Finally, the LAGP glass-
Fig. 1. FESEM images of LAGP particles (a) LAGP-I, (b) LAGP-II, (c) LAGP-III, (d) (e) LAGP-IV.
ceramics were crushed and formed various particle sizes by different
ball milling conditions. Four different post-treatment conditions includ-
ing annealing temperature and milling time were listed in Table 1. It
should note that the LAGP-IV is obtained directly after annealing with-
out further ball milling.
The PEO/LAGP hybrid electrolytes were prepared by conventional
solution-casting technique. PEO (Mw = 6 × 105, Aladdin) and lithium
ratio of 18:1 (EO:Li) were added into anhydrous acetonitrile (ACN,
Aladdin) and stirred to homogeneous solution. Subsequently, four
types of LAGP particles with different weight ratio (10%, 15%, 20% or
25%) were added into the homogeneous solution respectively. The
final solution was casted onto a Teflon plate after ultrasonic dispersion
for 4 h and stirring for 12 h in sequence, and then dried for 48 h at
room temperature and 48 h at 50 °C under vacuum, successively. All
these procedures were conducted at drying room. Finally, the uniform
hybrid electrolyte membranes were punched to circles with diameters
19 mm and 10 mm for further measurements.
The morphologies of LAGP particles and hybrid electrolyte mem-
branes were analyzed by field emission scanning electron microscopy
(FESEM, Hatchi S-4800). The crystal structure of LAGP particles were
identified by X-ray diffraction (XRD) measurements (Bruker D8 Ad-
vance) with Cu Kα radiation (λ = 1.54178) in the range of 10°–80°.
Thermal properties of hybrid electrolytes were evaluated by differential
scanning calorimetry (DSC) analyses (Mettler Toledo TGA/DSC 1) at a
heating rate of 10 °C min−1 from − 60 °C to 100 °C. The stress-strain
traces of electrolyte membranes were measured using Instron Electro-
mechanical Testing System 3365.
All electrochemical measurements were carried out by using a
Solartron 1470E multi-channel potentiostat electrochemical worksta-
tion. The SS/electrolyte membrane/SS cells were assembled to investi-
gate ionic conductivities in the range of 25 °C–80 °C. And the ionic
conductivity (σ, S cm−1) was calculated from the σ = L/RS, where R
(Ω) is resistance value of the bulk electrolyte measured by electrochem-
ical impedance spectroscope (EIS) with AC amplitude of 10 mV from
106 Hz to 10−2 Hz, and L (cm) is the thickness of electrolyte membrane,
and S (cm2) is the area of electrode.
The Li/electrolyte membrane/Li cells were fabricated to measure the
lithium-ion transference number (tLi+) of electrolyte membranes with
a combination measurement of AC impedance and DC polarization at
60 °C. The tLi+ was calculated using tLi+ = Iss(ΔV − I0R0)/I0(ΔV − IssRss)
as proposed by Vincent and co-workers [22], where Δ V is DC voltage
of 10 mV, and I0 and Iss are initial and steady current flowing through
 Y. Zhao et al. / Solid State Ionics 295 (2016) 65–71 67

Fig. 2. XRD patterns of LAGP particles (a) before and (b) after processed by ACN.

the cell measured by DC polarization. R0 and Rss, representing the resis-
tance values before and after the perturbation of the system respec-
tively, were obtained by AC impedance spectra of the cell in the
frequency from 106 Hz to 10−2 Hz with an oscillation voltage of 10 mV.
The electrochemical stability windows of the electrolyte membranes
were determined by linear sweep and cyclic voltammograms per-
formed on SS/electrolyte membrane/Li cells at 60 °C. The linear sweep
voltammograms (LSV) were measured from 2.5 V to 6 V (vs. Li+/Li) at
a scan rate of 5 mV s−1, and cyclic voltammograms (CV) were measured
between −0.5 V and 2.5 V (vs. Li+/Li) at a scan rate of 5 mV s−1.
The time evolution interfacial resistances of electrolyte membranes
against Li electrode were monitored by measuring the EIS of Li/electro-
lyte membrane/Li cells under 60 °C for various durations. The EIS were
measured in the frequency range from 106 Hz to 10−2 Hz with AC am-
plitude of 10 mV.
The charge-discharge cycles of solid-state cells were performed on a
Land charge/discharge instrument (Wuhan Rambo Testing Equipment
Co., Ltd.) The LiFePO4 cathode was composed of 70 wt% LiFePO4,
10 wt% Super-P and 20 wt% PEO-20%LAGP-I electrolyte. The LiFePO4/
electrolyte membrane/Li batteries were charged and discharged be-
tween 3.0 V–3.8 V at various currents.
3. Results and discussion
3.1. Characterization of LAGP particles
The microstructures and crystal structure of LAGP particles are iden-
tified by FESEM. Fig. 1 shows the submicron-sized morphologies of the
LAGP particles. Because of the different conditions of ball milling pro-
cess, four types of LAGP particles present different particle sizes.
LAGP-I sample exhibits the smallest grain (Fig.1(a)), and LAGP-II and
LAGP-III samples display similar grain (Fig.1(b) and Fig.1(c)), while
LAGP-IV sample without milling becomes caking (Fig.1(d)) and shows
the biggest grain. And the average grain size of LAGP-IV sample is
around 30 μm as presented in Fig.1(e).
To identify lattice structures and chemical stabilities against ACN of
the prepared LAGP particles, XRD patterns of LAGP particles before
and after processed by ACN are employed as shown in Fig. 2(a) and
(b). The diffraction peaks are similar for all samples, which could be
indexed as NASICON-type structure [19,21]. And the XRD patterns of
LAGP samples before and after processed by ACN exhibit consistency,
which indicates the LAGP is stable with ACN solvent. Among them, the
peak intensities of LAGP-II sample exhibit much weaker than those of
other samples owning to the different annealing conditions as described
in Table 1, which suggests that LAGP-II has lower crystal phase content
[23]. Whereas, the others present similar peak intensities of XRD pat-
tern, which can ascribe to the same annealing condition.

Fig. 3. (a) A photo of prepared hybrid electrolyte membrane; (b) cross-section and (c) surface FESEM images of prepared hybrid electrolyte membrane.
68 Y. Zhao et al. / Solid State Ionics 295 (2016) 65–71
Fig. 4. (a) The LAGP content dependence of ionic conductivities at 60 °C and (b) the Arrhenius plots for the ionic conductivities of the membranes with various optimum LAGP contents.
3.2. Morphology of hybrid electrolyte membrane
Fig. 3(a) shows the prepared hybrid electrolyte membrane is semi-
transparent and flexible. And its thickness can be easily adjusted by
the concentration or the amount of precursor solution. LAGP particles
are embedded in the PEO polymer uniformly, and covered by PEO mem-
brane completely, as shown in Fig. 3(b) and (c). No bare particles can be
observed. The cross-section FESEM image of the hybrid electrolyte
shows the thickness is about ~ 200 μm and homogeneous structure
from the interior to the surface. No obvious porous structure can be ob-
served from the surface or the cross-section of the hybrid electrolyte
membrane.
3.3. Conductivity
Ionic conductivities measured at 60 °C and Arrhenius plots for the
ionic conductivities of the membranes compositing various LAGP con-
tents are presented in Fig. 4. It shows the additions of LAGP are benefi-
cial for the ionic conductivity enhancing. Fig. 4(a) shows the LAGP
content dependence of ionic conductivities for electrolytes with differ-
ent LAGP particles composition at 60 °C, and the optimum LAGP content
of PEO/LAGP hybrid electrolytes are 20% LAGP-I, 15% LAGP-II, 20% LAGP-
III and 20% LAGP-IV respectively. The electrolyte incorporating 20%
LAGP-I shows higher ionic conductivity than other electrolytes,
6.76 × 10−4 S cm−1 at 60 °C, while the ionic conductivity of PEO-only
membrane is only 4.29 × 10−4 S cm−1. Therefore, the conductivity of
PEO/LAGP hybrid electrolyte is improved 58% compared to that of
PEO-only. For the LAGP-I, LAGP-III and LAGP-IV which are annealed
Fig. 5. DSC results for the electrolyte membranes.
under the same conditions, the conductivities of PEO/LAGP hybrid elec-
trolytes are gradually decreased as the particle sizes increasing. Thus, for
the same LAGP content, the smaller particle sizes result in better con-
ductivities owning to the smaller particles providing more Li+ transport
pathways. And for the LAGP-II, it shows a maximum conductivity at 15%
which is might be due to the different crystal phase content. As de-
scribed in Table 1, LAGP-II particles and the other samples (LAGP-I,
LAGP-III and LAGP-IV) are annealed under different conditions, which
is result in relatively low crystallinity of LAGP-II comparing to those of
other LAGP samples. Thus, the LAGP-II and the other LAGP samples
are belong to two catalogues of active fillers according to its crystallinity.
And the crystallinity of LAGP particles has influence on its ionic conduc-
tivity [23]. Therefore, it is reasonable that the optimal content of LAGP-II
is different to that of other LAGP samples. In conclusion, the PEO/LAGP
hybrid electrolyte membrane incorporating with 20% LAGP-I particles,
with smallest size and high crystal phase, exhibits the highest ionic
conductivity.
The improved ionic conductivities of PEO/LAGP hybrid electrolytes
probably attribute to two reasons as illustrated below. Firstly, the inter-
action between LAGP particles and polymer chains may improve the
ionic conductivities. Some studies [6,12–16] have reported that the
ionic conductivities would be improved by reducing crystallization
and weakening the interactions between the lithium ions and the PEO
chains. The results of DSC measurements have verified that well, as
shown in Fig. 5 and Table 2. It shows that incorporating LAGP particles
into the PEO-matrix could lower both glass transition temperatures
(Tg) and melting temperatures (Tm) of PEO polymer. The PEO-only elec-
trolyte shows Tg at −39.6 °C and Tm at 66.5 °C, while the PEO/LAGP hy-
brid electrolytes display Tg below −42 °C and Tm at 52.8 °C. The results
indicate that LAGP particles dominate the plasticizing effect on PEO
polymer and suppress polymer crystallization, which would increase
the amorphous range in polymer and speed up dynamics. Generally,
smaller fillers, leading to larger interfacial regions with polymer,
would more efficiently prevent dense packing of the polymer segments
[7]. Therefore, LAGP-I particles, presenting the smallest grain, result in
highest ionic conductivity of PEO/LAGP hybrid electrolyte. Secondly,
LAGP is a single ionic conductor with high conductivity (N10−4 S cm
−1
), and it would provide more mobile lithium ions and extra lithium-
ion transport pathways at the particles inside and surface. Conse-
quently, the addition of LAGP in the PEO-matrix could improve the con-
ductivity as analyzed above.
In addition, the addition of LAGP in the PEO-matrix could improve t+ Li
as well. The results of t+ Li measurements at 60 °C are summarized in
Table 3. It illustrates that LAGP particles could improve the t+ Li from
0.208 to N 0.36 and suppress the anion transport. Fillers could improve
the t+Li of hybrid electrolytes owning to the Lewis acid-base interactions
between the salt and filler surface. Acidic surface sites of fillers are in
particular thought to attract anions. Furthermore, fillers could behave
 Y. Zhao et al. / Solid State Ionics 295 (2016) 65–71 69

Table 2
The summary of thermodynamics and electronic parameters for electrolyte membrane.

Electrolytes Tg/°C Tm/°C σ/S cm−1 (60 °C) σLi+/S cm−1 (60 °C) Ea/kJ mol−1

25–50 °C 50–80 °C

PEO −39.6 66.5 4.29 × 10−4 0.89 × 10−4 121.7 33.8

PEO-20% LAGP-I −43.5 52.8 6.76 × 10−4 2.56 × 10−4 98.3 32.6
PEO-15% LAGP-II −43.5 54.6 5.43 × 10−4 2.06 × 10−4 124.1 31.2
PEO-20% LAGP-III −42.4 56.8 5.72 × 10−4 2.11 × 10−4 112.0 27.3
PEO-20% LAGP-IV −43.5 53.1 6.52 × 10−4 2.51 × 10−4 116.7 33.0

as crosslinking sites for the EO-segments and anions, changing the poly-
mer chain structure at the interface and creating pathways for Li+ trans-
port independent of segmental motion [7]. It seems that LAGP shows
less effectiveness to enhance t+Li compared to that of SiO2 or Al2O3 nano-
particles [24,25]. As is well known, smaller particle size leads to larger
interfacial regions, where nanoparticles could create more pathways
for Li+ transport and attract more anions. Generally, the SiO2 or Al2O3
nanoparticles incorporated into polymer are dozens or even a few nano-
meters in size [24,25]. In this paper, the sizes of LAGP fillers are
submicron-to-micron, which are several orders of magnitude lager
than those of frequently-used nanoparticles. Thus, with the same
amount of fillers, SiO2 or Al2O3 nanoparticles could create much larger
interfacial regions than that of LAGP, leading to the higher value of t+
Li .
Fig. 4(b) demonstrates that the changes in the ionic conductivities in
the lower temperature region (25–50 °C) have different slopes to those
in the higher temperature region (50–80 °C). This difference could be
described as the recrystallization of PEO from the amorphous state
when it is cooled to the transition temperature at around 50 °C. It
could imply that lithium ion transports of electrolyte membranes are in-
fluenced by the recrystallization of PEO. And the activation energies of
the various membranes are calculated according to σ = A exp (− Ea/
kT), where σ is the ionic conductivity, and A is the pre-exponential fac-
tor, and k is the Boltzmann constant, and Ea is the activation energy for
lithium ion conduction. The calculated results are listed in Table 2. The
activation energies of PEO/LAGP hybrid electrolytes are in the range
98–124 kJ mol−1 in the temperature of 25–50 °C and 27–35 kJ mol−1
in the temperature of 50–80 °C, respectively. Consequently, the addi-
tions of LAGP particles could lower the activation energies of PEO/
LAGP hybrid electrolytes.
3.4. Mechanical properties
In addition to ionic conductivity, mechanical property is another im-
portant parameter. The hybrid electrolyte membrane should withstand
big stress during cell packaging and charge/discharge cycling. Therefore,
the hybrid electrolyte membrane containing 20% LAGP-I is selected for
mechanical measurement. As shown in Fig. 6, the tensile strength of
PEO-only electrolyte membrane is 0.32 MPa with a elongation-at-
break value at 140%. With the addition of 20% LAGP-I, the tensile
strength of hybrid electrolyte membrane increases to 0.58 MPa and
elongation-at-break is around 80%. These results indicate that the addi-
tion of LAGP particles could enhance the mechanical strength of
electrolyte membrane and this is good for the stability during cell pack-
aging and charge/discharge cycling.
3.5. Electrochemical stability
As is well known, electrochemical stability is a critical parameter to
determine the practical application performance in the LIBs. In order
to investigate the electrochemical stability of the PEO/LAGP hybrid elec-
trolyte, LSV and CV are carried out. As presented in Fig. 7, the PEO/LAGP
hybrid electrolyte incorporating 20% LAGP-I is found to be electrochem-
ically more stable than the PEO-only membrane. For the cathodic scan,
both membranes exhibit cathodically stable behavior up to 0 V (vs.
Li+/Li). These results indicate that the prepared PEO/LAGP hybrid elec-
trolytes perform electrochemically stable until 0 V without being
decomposed by the reduction reaction with lithium. In the anodic
scan, there is a small anodic peak around 4.2 V (vs. Li+/Li) for PEO-
only membrane, corresponding to the decomposition of PEO. And the
oxidative current subsequently increases around 5.1 V, corresponding
to the common decomposition of salt and polymer, which is limited
by irreversible oxidation of the salt anion. By contrast, the oxidative cur-
rent of the hybrid electrolyte incorporating 20% LAGP-I increases at
5.3 V. These results indicate that LAGP-I particles enhance the electro-
chemical stability for hybrid electrolyte, which can be ascribed to the
LAGP particles retarding the decomposition of PEO and lithium salt
anion. It is interesting that LAGP is unstable with Li, but PEO/LAGP hy-
brid electrolyte exhibits good electrochemical stability. As described
above, LAGP particles are embedded in the PEO polymer uniformly
and covered by PEO membrane completely, which avoids the direct
contact between LAGP and metal lithium. Moreover, although LAGP is
unstable with lithium metal, it has an excellent oxidative stability at po-
tentials (N6 V vs Li+/Li) [21]. Most importantly, LAGP particles could in-
teract with PEO and lithium salt anion to suspend their decomposition
in two ways. Firstly, LAGP particles would behave as crosslinking sites
for EO-segments, which could change polymer thermodynamics

Table 3
Measured values for the parameter and the corresponding calculated values of lithium ion
transference numbers (t+Li ) at 60 °C.

Electrolytes I0/mA ISS/mA R0/Ω RSS/Ω ΔV/mV t+

Li

PEO 0.116 0.058 66.45 77.39 10 0.208

PEO-20% LAGP-I 0.115 0. 063 42.17 40.12 10 0.378
PEO-15% LAGP-II 0.086 0.056 71.92 61.99 10 0.380
PEO-20% LAGP-III 0.081 0.047 71.27 71.51 10 0.369
PEO-20% LAGP-IV 0.133 0.077 40.35 39.30 10 0.385
Fig. 6. Stress-strain behavior of electrolyte membranes.
70 Y. Zhao et al. / Solid State Ionics 295 (2016) 65–71
Fig. 7. CV and LSV curves of polymer electrolytes at 60 °C.
behaviors as presented in Table 2. It could stabilize the polymer chain
structure at the interface between EO-segments and fillers that retards
the decomposition of PEO [7]. Secondly, it is well known that oxidation
stability window is limited by irreversible oxidation of the salt anion
[26]. LAGP particles addition could promote t+ Li by suppression of TFSI-
migration, because the acidic surface sites of LAGP are thought to attract
TFSI-anions. Lewis acid-base interaction centers with the electrolyte
ionic species, which lowers ionic coupling and promotes the salt disso-
ciation via a sort of ‘ion-ceramic complex’ formation [27]. It is demon-
strated well by the improved t+ Li as shown in Table 3. Consequently,
these interactions described above suspend the decomposition of hy-
brid electrolyte and improve its electrochemical stability.
3.6. Interfacial stability against lithium metal electrode
The interface stability between lithium metal electrode and electro-
lyte in solid state lithium battery plays a primary role in the cell's cycling
life and rate capability. Fig. 8(a) shows the time evolution of interfacial
resistance (Ri) of Li/electrolyte as a function of storage time at 60 °C. The
interface resistances between lithium metal and PEO-20% LAGP-I elec-
trolyte membrane exhibit more stable during 10 days than those be-
tween lithium metal and PEO-only electrolyte membrane. As shown
in Fig. 8(b), the values of Ri for PEO-20%LAGP-I electrolyte are remained
stable after a small amount of increasing (from 16 to 25 Ω cm2), sug-
gesting an excellent compatibility with lithium electrode. In contrast,
the initial value of Ri for PEO-only electrolyte is 142 Ω cm2 at 60 °C,
and continues to increase up to 276 Ω cm2 after 7 days. During the
10 days, the values of Ri become unstable and changed obviously.
These results illustrate that incorporation of 20% LAGP-I particles into
polymer electrolytes is good to alleviating growth of interface imped-
ance, which might be owing to Lewis acid-base reactions between the
LAGP surface states and the PEO segments [28–30]. The Lewis acid char-
acter of the added LAGP would compete with the Lewis character of the
Fig. 8. (a) Time evolution of interfacial resistance of Li/electrolyte membrane after various storage times at 60 °C; (b) Impedance spectra for cell of Li/electrolyte membrane/Li at 60 °C.
Li+ for the formation of complexes with the PEO chains, which could en-
hance the interfacial stability [28].
3.7. Cell performance
LiFePO4/Li cells using PEO-20% LAGP-I as electrolyte are assembled
and cycled at 0.1–1C rate at 60 °C, as shown in Fig. 9(a), the cell
LiFePO4/PEO-20% LAGP-I/Li could achieve capacities of 166, 155, 143
and 108 mAh g−1 at current rates of 0.1, 0.2, 0.5 and 1C, respectively.
And the Fig. 9(b) indicates the specific capacity of cell using PEO-20%
LAGP-I as electrolyte increase over 20 mAh g−1 compared to that of
PEO-only at 1C. After 50 cycles, the specific capacity retention of cell
LiFePO4/PEO-20% LAGP-I/Li is close to 90% (100 mAh g−1). While the ca-
pacity of cell LiFePO4/PEO-only/Li is 40 mAh g−1, and the retention is
only 44% after 50 cycles. LiFePO4/Li batteries using PEO-20% LAGP-I as
electrolyte exhibit improved cycling stability and rate capability which
is ascribed to the positive influence from LAGP particles addition. Specif-
ically, LAGP particles could lower both Tg and Tm of polymer chain as
demonstrated by DSC. And the reducing of Tg and Tm lead to excellent
interfacial connects between electrodes and electrolyte. In addition,
the improvement of ionic conductivity on account of well-developed
ion-conductive network pathways gives rise to the ion transference at
the interface between electrodes and electrolyte. In consequence, incor-
porating LAGP-I particles into PEO electrolyte, leading to the superior
interfacial stability and compatibility against electrodes, could provide
a good cycling and rate performance.
4. Conclusion
Hybrid electrolytes composed of organic PEO and four types of glass-
ceramic LAGP in various ratios were prepared via a simple preparation,
respectively. The prepared PEO/LAGP hybrid electrolyte exhibited en-
hanced ionic conductivities compared to the PEO-only membranes.
For the same LAGP content, the smaller particle sizes result in better
conductivities. The hybrid electrolyte containing 20% LAGP-I exhibited
the highest ionic conductivity (6.76 × 10−4 S cm− 1 at 60 °C). The
phase transition behaviors were characterized by DSC, and the results
demonstrated that the improvement of lithium ion conductivity in the
PEO matrix was related to inhibiting crystallization and weakening the
interactions between the lithium ions and the PEO chains. The CV and
LSV results showed that the electrochemical stability of the PEO-20%
LAGP-I hybrid electrolyte was improved (0–5.3 V vs Li+/Li) in contrast
with that of PEO-only sample (0–4.2 V vs Li+/Li). Finally, LiFePO4/Li bat-
tery with such PEO-20% LAGP-I hybrid electrolyte exhibited fascinating
electrochemical performance for high capacity retention (close to 90%
after 50 cycles at 1C at 60 °C) and outstanding rate performance. It
was a feasible preparation method for the manufacture of the product
in industry scale with further improved conductivity.
 Y. Zhao et al. / Solid State Ionics 295 (2016) 65–71 71

Fig. 9. (a) Charge and discharge profiles of the batteries at different rates; (b) Capacity and columbic efficiency versus cycle number of cells LiFePO4/electrolyte membrane/Li at 1C.

Acknowledgment [12] M. Wetjen, M.A. Navarra, S. Panero, S. Passerini, B. Scrosati, J. Hassoun,

ChemSusChem 6 (2013) 1037–1043.
[13] N. Plylahan, M. Letiche, M.K.S. Barr, T. Djenizian, Electrochem. Commun. 43 (2014)
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ural Science Foundation of China (Grant No. 51502317), the Strategic [14] H.M. Xiong, Z.D. Wang, D.P. Liu, J.S. Chen, Y.G. Wang, Y.Y. Xia, Adv. Funct. Mater. 15
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[17] L.F. Hu, Z.L. Tang, Z.T. Zhang, J. Power Sources 166 (2007) 226–232.
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