Materials and Design 142 (2018) 221–228

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Materials and Design

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

Polyethylene glycol-based waterborne polyurethane as solid polymer

electrolyte for all-solid-state lithium ion batteries
Bing Cong a, Youxin Song a, Naiqing Ren a, Gongshan Xie a, Can Tao a, Yiping Huang a,b,
Gewen Xu a,b, Junjie Bao a,b,⁎
a
School of Chemistry and Chemical Engineering, Anhui University, Hefei 230601, PR China
b
Key Labortory of Environment-friendly Polymer Materials of Anhui Province, Engineering Technology Research Center of Water-Borne Polymer Materials of Anhui Province, Hefei 230601, PR China

H I G H L I G H T S G R A P H I C A L A B S T R A C T

• A waterborne polyurethane (WPU)

dispersion was synthesized from
polyethylene glycol and hexamethylene
diisocyanate.
• Solid polymer electrolytes were pre-
pared by blending waterborne polyure-
thane and LiTFSI.
• All solid state battery based on WPU
showed attractive electrochemical
properties and discharge capacity.

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

Article history: An environmental friendly waterborne polyurethane (WPU) dispersion was synthesized from polyethylene gly-
Received 22 November 2017 col (PEG), hexamethylene diisocyanate (HDI), diethylene glycol (DEG) and dimethylol propionic acid (DMPA).
Received in revised form 17 January 2018 Solid polymer electrolytes based on WPU and LiTFSI were fabricated via an organic solvent free process. The
Accepted 18 January 2018
LiTFSI salts were found to be dissolved in WPU by the coordination of Li+ ion with carbonyl and ether group in
Available online 3 February 2018
WPU. The as-prepared WPU showed a semi-crystalline structure and became amorphous after adding lithium
Keywords:
salts. The ionic conductivities increased with the increase of salt concentration and followed the Arrhenius be-
Solid polymer electrolyte havior. The 20 wt% LiTFSI in WPU electrolyte showed a superior comprehensive performance with an ionic con-
Lithium ion batteries ductivity of 7.3 × 10−4 and 2.2 × 10−3 S cm−1 at 60 °C and 80 °C. All-solid-state LiFePO4/SPE/Li cell using this
Waterborne polyurethane electrolyte exhibited an initial discharge capacity of 151 mAh g−1 at 0.1C under 60 °C. All of these results demon-
Polyethylene glycol strate that this new WPU-based solid polymer electrolyte is a promising environmentally friendly candidate for
all-solid-state lithium ion batteries.
© 2018 Elsevier Ltd. All rights reserved.

1. Introduction

Lithium ion batteries (LIBs) have been successfully used as the effi-
cient energy storage equipment for the consumable electronic devices
⁎ Corresponding author at: School of Chemistry and Chemical Engineering, Anhui
and electric vehicles in the past decades [1,2]. However, the conventional
University, Hefei 230601, PR China. LIBs which use the organic flammable liquid electrolytes can cause some
E-mail address: baoahu@ahu.edu.cn (J. Bao). safety and environmental problems [3,4]. All-solid-state lithium ion

https://doi.org/10.1016/j.matdes.2018.01.039
0264-1275/© 2018 Elsevier Ltd. All rights reserved.
222 B. Cong et al. / Materials and Design 142 (2018) 221–228
batteries which use non-flammable solid electrolytes have received in-
creasing attention recently for their performances are superior than the
conventional LIBs especially in the safety issues [5–7]. As the key compo-
nent of all-solid-state LIBs, solid electrolytes should possess high ionic
conductivity and ion transference number, good mechanical strength,
chemical compatibility with the electrodes and wide electrochemical
window [5,8]. Therefore, the main issue right now is to design solid elec-
trolytes with better comprehensive performance.
Currently, various of solid electrolytes include solid oxide-based
electrolytes (i.e. LLZO [9] and LAGP [10]), solid sulfide-based electro-
lytes (i.e. LGPS [11]) and solid polymer electrolytes (SPEs) have been
extensively developed and successfully applied to the all-solid-state
LIBs. However, the oxide-based electrolytes exhibit great stability in
air but show a large interfacial resistance between the electrode and
solid electrolyte [12]. Solid sulfide-based electrolytes possess high
ionic conductivity at room temperature but they are very unstable in
air and polar solvents [13]. Compared to inorganic solid electrolytes,
SPEs possess several advantages like flexibility, light weight, well
interface contact between electrode and electrolyte and easy to fabricate
on a large scale [5,14]. These features make SPEs the most promising can-
didate electrolytes for all-solid-state LIBs. SPEs are usually comprised of
polymer matrix and lithium salt. Various polymer materials such as poly
(ethylene oxide) (PEO)[15,16], polycarbonate [17], polyphosphazenes
[18], polymethacrylate [19], polysiloxane [20], single-ion polyelectrolyte
[21] and polyurethane [22] have been investigated as polymer matrix.
However, looking for new polymer matrix to improve comprehensive
performance of SPEs is still an important issue for all-solid-state LIBs. Fur-
thermore, the fabrication of SPEs is usually use solution casting method,
which requires the usage of toxic and volatile organic solvent such as di-
methyl formamide (DMF) and acetonitrile (ACN) to dissolve the polymer
[23]. This process will lead to a considerable release of volatile organic
compounds (VOCs) which is harmful to the environment.
Environmentally friendly waterborne polyurethane (WPU) has
attracted increasing attention recently and has been widely used as
binder, coating, ink and so on in the field of industrial applications
[24,25]. WPU is a colloidal system in which the polyurethane particles
are dispersed in water without any VOCs [26]. Polyurethane shows
rubbery behavior and their properties can be designed by adjusting
the interaction of soft and hard segments [27]. Benefit from these char-
acteristics, polyurethane has been considered to be used as binder [28],
separator [29] and polymer electrolyte [30] in lithium batteries. Li et al.
[31] reported a WPU-based gel polymer electrolyte which showed good
ionic conductivity at room temperature, however it contained organic
solvent in the electrolytes. As for SPEs, Liu et al. [32] reported series of
cationic PU-based SPEs and Mustapa et al. [33] reported a Jatropha oil-
based PU used as SPEs recently. Although these polyurethane based
SPEs possess excellent mechanical properties and high ionic conductiv-
ities, the organic solvent are inevitably involved in the preparation of
these SPEs, which may cause serious environmental problems. In addi-
tion, the performance of all-solid-state LIBs used these PU based SPEs
have not been tested.
In this work, a waterborne polyurethane (WPU) was synthesized as
polymer matrix for SPEs by polymerization of polyethylene glycol
(PEG), hexamethylene diisocyanate (HDI), diethylene glycol (DEG)
and dimethylol propionic acid (DMPA). The SPEs were prepared by
complexing the WPU with various concentration of LiTFSI and used
water as the solvent during the environmentally friendly fabrication. It
was demonstrated that such WPU-based SPEs achieved high ionic
conductivity around 10−4 and 10−3 S cm−1 at 60 and 80 °C. The
LiFePO4/SPE/Li all-solid-state batteries were assembled and character-
ized with the WPU-based SPEs. It's found that the WPU-based SPEs
exhibited better discharge capacity and cycle performance than the
pristine PEO electrolyte and other polymer electrolyte reported recently
(Table S1, Supporting Information). These WPU-based SPEs may be-
come a promising environmentally friendly candidate for all-solid-
state LIBs.
2. Experimental sections
2.1. Chemical and materials
Polyethylene glycol (PEG, Mw = 2000, Aladdin, China) was dried
under reduced pressure at 80 °C for 3 h before using. Hexamethylene
diisocyanate (HDI, Bayer AG, Germany), diethylene glycol (DEG, Alad-
din, China), dimethylol propionic acid (DMPA, Aladdin, China), bismuth
acid catalyst (BiCAT 8108, The Shepherd Chmical Company, USA),
triethylamine (TEA, Aladdin, China), acetone (AC, Aladdin, China) and
lithium bis (trifluoromethane) sulfonilimide (LiTFSI, Aldrich, China)
were used as received.
2.2. Synthesis of waterborne polyurethane
Waterborne polyurethane was prepared by the prepolymer method
as shown in Fig. 1 based on HDI (0.15 mol), PEG (0.03 mol), DMPA
(0.02 mol), DEG (0.08 mol) and TEA (0.02 mol). The PEG and HDI
were added into a four-necked flask equipped with a thermometer, con-
denser, nitrogen inlet and mechanical stirrer and reacted at 80 °C under
nitrogen atmosphere. After 2 h of reaction, DMPA, EDG, BiCAT 8108 as
catalysts and acetone as solvent were added into the system, the mix-
ture was kept for about 5 h at 60 °C. Then, the mixture was cooled to
35 °C and neutralized by TEA for 5 min and dispersed in distilled
water at high shearing rates to produce the WPU dispersion. Finally,
the acetone was removed in a distillation equipment at 40 °C. The mo-
lecular weight and polydispersity index (PDI) of WPU are 11,827
(Mn), 20,286 (Mw) and 1.71, respectively, which were characterized
by GPC (see Fig. S1, Supporting Information).
2.3. Preparation of solid polymer electrolytes
Solid polymer electrolyte samples were prepared by mixing various
contents of LiTFSI range of 10–25 wt% with WPU in water and continu-
ously stirred for 2 h. SPE films were prepared by pouring the dispersions
into the Teflon mould and dry at room temperature for 5 days. Then the
films were dried in a vacuum oven at 80 °C for 24 h. Finally, the dry films
were obtained and placed in an Ar-filled glove-box for further testing.
The water content of the SPE films was determined below 10 ppm
using a Karl Fisher moisture titrator (MKC-210, Kyoto Electronics,
Japan) before use. These SPEs consisted of 10, 15, 20 and 25 wt% of
LiTFSI are marked as WPU-X% Li (X = 10, 15, 20 and 25), respectively.
2.4. Characterization
1
H NMR spectra were carried out on an Avance II 400 MHz spec-
trometer (Bmker, Schweizerische) using CDCl3 (Aladdin, China) as sol-
vent and tetramethylsilan (TMS, Aladdin, China) as a reference at
room temperature. The polydispersity indices (PDI) and molecular
Fig. 1. Synthesis of waterborne polyurethane.
 B. Cong et al. / Materials and Design 142 (2018) 221–228
weights (Mn, Mw) of the waterborne polyurethane were tested by
Hewlett-Packard 1100 gel permeation chromatography (GPC)
equipped with a 5 μm PLgel MIXED-C column and a 5 μm PLGel Guard
guard column. Nearly monodisperse polystyrenes (PS, Agilent, USA)
were used as standards. THF (Aladdin, China) was used as mobile
phase with the flow rate of 1 ml min−1 at 25 °C. WPU samples were dis-
solved in THF with a concentration of 0.15% g ml−1.
The scanning electron microscopy analysis (SEM) was carried out on
a S4800 field emission scanning electron microscope (Hitachi, Japan).
The composition of the SPEs was detected by Fourier transform infrared
spectroscopy (FTIR) using a Nexus 870 (Nicolet, USA) FTIR spectrometer
with the ATR setup, all the samples were examined in the form of films.
The X-ray diffraction patterns (XRD) of the SPEs were recorded in a D8-
Advance diffractometer (Bruker, Germany) using CuKα radiation in the
2θ range from 5° to 80° with the scan rate of 0.05° s−1. Differential
scanning calorimetry (DSC) measurements were executed in Q2000
(TA, USA) instrument at a temperature range from −70–130 °C under
nitrogen atmosphere with the heating rate of 10 °C min−1. Thermogra-
vimetric analysis (TGA) was examined by using STA449F3 simultaneous
thermal analysis instrument (Netzsch, Germany), the temperature
was ramped (20 °C min−1) from room temperature to 600 °C under a
nitrogen atmosphere. The tensile test of the SPE films was performed
on an XLM-500 tensile strength tester (MTS, USA) with the sensitiv-
ity of 0.01 N at room temperature. Dog-bone shaped samples were
stretched at a rate of 50 mm/min with the sample straps of about
0.8 cm wide and 6 cm long. The gauge length is 4 cm.
2.5. Electrochemical measurements
All of the electrochemical measurements were conducted on a
CHI660D electrochemical workstation. The ionic conductivities of the
SPEs were tested by electrochemical impedance spectroscopy with
the frequency range from 100 kHz to 0.1 Hz (with an amplitude of
10 mV). The SPE films were sandwiched between stainless steel
blocking electrodes (SS, 16 cm in diameter) and assembled in CR2032
coin cells. The examining temperature was increased from 25 °C to
120 °C. The ionic conductivity (σ, S cm−1) of the SPE was calculated
from the following equation [34]:
L
σ¼
RS
where R (Ω) is the resistance of the bulk electrolyte, L (cm) is the thick-
ness of the film and S (cm2) is the area of electrode.
The electrochemical stability of the samples was evaluated by linear
sweep voltammetry (LSV), which was conducted on a SS/SPE/Li CR2032
coin cell under 60 °C.
The compatibility of the WPU-based SPEs with lithium metal elec-
trode was measured by AC Impedance in Li/SPE/Li cells which stored
for different aging time at room temperature. The EIS measurements
were examined with an amplitude of 10 mV from 10 MHz to 0.1 MHz
at 60 °C. The charge-discharge behavior and cycling performance of
the batteries were conducted on a Neware battery tester (BTS-51,
China). The LiFePO4/SPE/Li cells were tested with a voltage range
from 2.2–4.0 V. The cathode was prepared by mixing LiFePO4 (LT-5,
Elementec, China), Super P carbon (Timcal, Schweizerische) and
TPU/PEO binder in the ratio of 70:15:15 wt% and casted on the alumi-
num foil. The TPU/PEO binder was prepared by blending thermoplastic
polyurethane (TPU, Mw = 400,000 g mol−1, BASF, Germany), polyeth-
ylene oxide (PEO, Mw = 500,000 g mol−1, BASF, Germany) and LiTFSI
in N,N-dimethylformamide (DMF, 99.8%, Aldrich, China). The mass
ratio of TPU, PEO and LiTFSI is 17:53:30. The mass loading of the LiFePO4
is around 2.2 mg cm−2. The all-solid-state LiFePO4/SPE/Li coin cells
(2032 type) were assembled by placing WPU-based SPE film between
the LiFePO4 cathode and the lithium metal anode.
223
3. Results and discussion
3.1. Structural characterization of WPU and WPU-based SPEs
The structure of WPU was confirmed by 1H NMR and FTIR spectra.
Fig. 2 presents a 1H NMR spectrum for a typical WPU sample. The label-
ing of peaks in Fig. 2 indicate the existence of polyethylene glycol-based
waterborne polyurethane (1H NMR (δ, ppm, CDCl3): δ = 1.2 (3H, CH3),
1.3–1.5 (4H, CH2), 3.2 (2H, CH2N), 3.7 (2H, CH2O), 3.9 (2H, CH2CO), 4.6
(1H, COOH), 5.1 (1H, NH)).
FTIR spectroscopy was used to confirm the structure of the WPU
and probe the interaction of lithium salt with WPU in the SPEs [35].
As shown in Fig. 3 (a), the absorption peaks of WPU observed at
3327, 2937 and 2871, 1701 and 1109 cm−1 related to the \\NH,
\\CH2 and\\CH3,\\C_O, and\\COC\\groups, respectively. The ab-
sence of \\NCO peak at 2250 cm −1 and the presence of -NH and
\\C_O peaks indicate the polyurethane has been formed
completely [36,37]. Note that with the addition of LiTFSI from 10%
to 25% concentrations in the WPU, the absorption peaks of -NH func-
tional groups became broad and shifted to high wavenumbers
(Fig. S2 (a), Supporting Information) indicating an increase in the
free\\NH bond strength. This may ascribe to the Li+ ions coordinate
to the \\C_O and \\COC\\ groups and the hydrogen bond between
NH group and carbonyls or ether group is destroyed [32]. However,
the stretching of \\C_O and \\COC\\ bond shifted to lower fre-
quency with the increase of lithium salt concentration (see Fig. S2
(b) and (c), Supporting Information). This indicated the strong ion-
dipole complexation between Li+ ions and carbonyl group of WPU
and ether oxygen of PEG segments [38]. From the FTIR analysis, it
suggests that the lithium salt can be dissolved in polyurethane ma-
trix by the interaction of Li+ ions to carbonyl and ether groups in
the WPU.
To investigate the crystalline behavior of the SPEs, the XRD studies
were carried out and the XRD patterns of the samples are shown in
Fig. 3 (b). The diffraction pattern of WPU exhibited a stronger reflection
at 2θ = 21.3°, which indicated the semi-crystallinity nature of WPU
arising by the ordered structure of PEG and HDI. A weak and broad
shoulder peak is appeared around 2θ = 41° indicating some minor
oriented structure in hard segment [39]. With the addition of lithium
salts, the intensity of the crystalline peaks of WPU-based SPEs were
ð1Þ weaken and a broad hump was observed in Fig. 3 (b). This may ascribe
to the lithium salts prevent the crystallization of WPU and lead to
more amorphous phase in SPEs [33]. The amorphous structure will
Fig. 2. The 1H NMR spectrum of waterborne polyurethane.
224 B. Cong et al. / Materials and Design 142 (2018) 221–228

Fig. 3. (a) FTIR spectra and (b) XRD patterns of WPU and WPU-based SPEs.

results in better conductivity by providing faster segmental motion in
amorphous phases.
3.2. Morphology of SPEs
The SEM images and photographs of WPU and WPU-based SPE
membranes are presented in Fig. 4. Fig. 4 (a) to (e) show the surface
SEM images of as-prepared WPU and SPEs with different content of
lithium salts. The sourface of the pristine WPU membrane was very
rough. After adding with LiTFSI, the sourface of the SPE membranes be-
came more smooth and homogenous. The same trend has been found in
the photographs of the free-standing SPE films as shown in Fig. 4 (g).
The pure WPU membrane is semitransparent and the SPE films became
more transparent and flexible with the increase of the added amount of
LiTFSI. The SEM images and photographs also suggest that the lithium
salts have been uniformly dispersed in the SPEs.

Fig. 4. Surface SEM images of (a) WPU, (b) WPU-10% Li, (c) WPU-15% Li, (d) WPU-20% Li, (e)WPU-25% Li and (f) cross-section SEM image of WPU-20% Li;(g) photographs of the free-
standing WPU and WPU-based SPE films.
 B. Cong et al. / Materials and Design 142 (2018) 221–228 225

Fig. 5. (a) DSC curves and (b) TGA thermograms of the WPU and WPU-based SPEs.

3.3. Thermal properties
The thermal properties of the WPU and WPU-based SPEs were char-
acterized by DSC and TGA (Fig. 5). It is known that the DSC curves of
polyurethane consist of multiple peaks which are arised by the hard
and soft segments [40]. The values of the glass transition temperature
of hard segment (Tg,h) and soft segment (Tg,s), the crystallization tem-
perature (Tc) and the degradation temperature at a 5% weight loss (Td,
5%) of the SPEs according to the DSC and TGA measurements are listed
in Table 1. As shown in Fig. 5(a), the soft segment Tg,s increased from
−55 °C to −45 °C and the hard segment Tg,h increased from 61 °C to
68 °C with the salt concentration increased. This may caused by the in-
teraction of Li+ ion with the oxygen in the soft and hard segment
forming transient cross-links which restrict the mobility of the segment
[41]. The pure WPU has a weak exothermic peak around −24 °C (Tc)
and a strong endothermic peak around 32 °C (Tm), indicating the crys-
tallinity nature of WPU. The Tc and Tm of WPU-based SPEs disappear
when the content of LiTFSI is above 15 wt%, which suggest that the crys-
talline structure is destroyed by the lithium salts. The values of crystal-
linity (χC) were calculated by equation: χC = ΔHm/ΔHPEO, where ΔHm is
the melting enthalpy and ΔHPEO is the enthalpy of PEO perfect crystal
which is 196.4 J g−1 [11]. As shown in Table 1, the degree of crystallinity
of the SPEs decreased with the increase of lithium salt content, which
indicated more amorphous phases were formed. The phenomenon is
consistent to the XRD results and the amorphous phase will beneficial
to improve the ionic conductivity for the batteries.
Typical TGA curves of the WPU and WPU-based SPEs are presented
in Fig. 5(b). The curve demonstrated that pure WPU has two decompo-
sition stages. The initial thermal degradation of WPU started around
250 °C due to the decomposition of the urethane bonds in the hard seg-
ment, the second stage of degradation was observed around 350 °C may
caused by the decomposition of ether bonds in the soft segment [42]. In
the case of the WPU-10% Li SPE, the Td, 5% value increased with the ad-
dition of LiTFSI in the WPU. This may attribute to the cross-links
between the Li+ ion and segment improved the thermal stability of
SPE. However, the Td, 5% value decreased in the addition of LiTFSI into
the WPU system from 20 wt% to 25 wt%. This may due to the interaction
of lithium ions and oxygen atoms decreasing the electronic density of
the oxygen atoms which weakens the C\\O and C_O bond [32] and
this effect is predominant. The TGA result indicates the WPU-based
SPE possess sufficient thermal stability and is suitable for all-solid-
state lithium ion batteries under the operating temperature (usually
40–100 °C).
3.4. Mechanical properties
The stress-strain curves of the WPU and WPU-based SPE films are
shown in Fig. 6. The tensile strength of pure WPU was 0.9 MPa with
an elongation-at-break value of 140%. However,the value of tensile
strength decreased with the addition of LiTFSI. This may ascribe to
the crystalline structure is destroyed by the addition of lithium
salts, and the increase of amorphous phase leads to the deterioration
of mechanical properties. The stress of WPU-20% Li presented a ten-
sile strength of 0.5 MPa with an extend elongation-at-break value of
300%, which is higher than the PEO-based SPE (around 0.2 MPa) re-
ported by previous literatures [43,44]. Therefore, the WPU-based
SPE can be used in LIBs due to its free-standing behavior and proper
mechanical properties.

Table 1
Thermal properties of the WPU and WPU-based SPEs.

Samples Tg,s/°C Tg,h/°C Tc/°C Tm/°C Td,5%/°C ΔHm χC

(J g−1) (%)

WPU −55 61 −24 32 246 73 37

WPU-10% Li −51 62 −5 24 257 41 21
WPU-15% Li −49 62 – – 253 – –
WPU-20% Li −48 64 – – 241 – –
WPU-25% Li −45 68 – – 215 – –
Fig. 6. The stress-strain curves of WPU and WPU-based SPEs.
226 B. Cong et al. / Materials and Design 142 (2018) 221–228
Fig. 7. The Arrhenius plots for the ionic conductivities of the WPU-based SPEs·(Insert:
activation energy values of the SPEs calculated by the slopes).
3.5. Ionic conductivity and Li+ ion transference number
The ionic conductivity of WPU-based SPEs with different content
of LiTFSI at temperatures from 25 to 120 °C is shown in Fig. 7. The
ionic conductivities increased with the increase of salt concentration
for the amount of charge carrier (Li+ ions) increased. The ionic con-
ductivities of WPU-15% Li to WPU-25% Li were very close at various
temperatures. Take WPU-20% Li SPE for example, the ionic conductivi-
ties was 4.1 × 10−5, 7.3 × 10−4 and 2.2 × 10−3 S cm−1 at 25, 60 and
80 °C, respectively. It was observed that the conductivity-temperature
dependence of WPU-based SPEs fit the Arrhenius law equation, δ =
δ0exp(−Ea/kT), where δ0 is conductivity at T = 0 K, Ea is the activation
energy, T is the tested temperature and k is the Boltzmann's constant
[41]. The Ea values of the SPEs are calculated range from 0.25 to 0.27
eV, the low Ea values suggest the transient dynamical coupling between
the Li+ ions and polymer chain segmental motion in the ion-dipolar SPE
matrix [45]. The activation energy values increased slightly as the salt
concentration increased. This is related to the increased interaction be-
tween the Li+ ions and WPU segments decreased the segment mobility
of SPEs, which indicated a higher temperature is required for the seg-
mental movement in the high Li+ ion concentration cases. It could be
found that the ionic conductivities of WPU-25% Li was lowest at 25 °C
but highest at 120 °C among the WPU-15% Li to WPU-25% Li SPEs. Al-
though the WPU-25% Li exhibited highest ionic conductivities at high
temperatures, it was not used on the batteries research for its poor
Fig. 8. (a) Linear sweep voltammogram of WPU-based SPEs and (b) interfacial resistance (Rint) of Li/SPE/Li cell at 60 °C.
mechanical property. The WPU-20% Li was choosing for the battery
properties studies due to its better comprehensive performance.
3.6. Electrochemical stability and interfacial stability against lithium metal
electrode
The electrochemical stability of WPU-based SPEs was evaluated by
linear sweep voltammetry (LSV) in the stainless steel/SPE/Li cells at
60 °C. As shown in Fig. 8(a), all the SPEs were stable up to 4.8 V (versus
Li+/Li), indicating that such WPU-based SPEs can be used as electrolyte
for the 4 V class conventional cathodes. Interfacial compatibility of
WPU-20% Li SPE with the lithium metal was investigated by measuring
the interfacial resistances (Rint) of Li/SPE/Li cells for 15 days. The time
evolution of the values of Rint is presented in Fig. 8(b). It can be found
that the value of Rint slightly increased from 412 Ω to 516 Ω after 4
days and maintained around 520 Ω within 15 days. The increasing of
Rint by the WPU-based electrolyte at the initial 4 days may ascribe to
the formation of solid electrolyte interface (SEI) layer by the reaction
between Li metal and WPU-based SPE [46,47]. The interfacial resistance
became stable with the storage time after the formation of SEI layer in-
dicating the WPU-based SPE possesses good interfacial compatibility
with lithium electrode.
3.7. Performance of LiFePO4/SPE/Li cells
In order to investigate the battery performance of the WPU-based
electrolyte, the WPU-20% Li electrolyte was chosen to assemble the
all-solid-state batteries. The pure PEO (Mw = 500,000) with 20 wt%
LiTFSI was used as the reference SPE. The olivine type LiFePO4 was se-
lected as the cathode material for its good electrochemical/thermal sta-
bility, non-toxicity and low cost [48]. Each cycling experiments were
tested by three cells using same kind of electrode and SPE to guarantee
the reproducibility of the experimental data. The standard deviations of
the discharge capacity of the cells with the electrolyte of WPU-20% Li
and PEO-20% Li were around 2.1% and 2.7%. Fig. 9(a) shows the
charge/discharge curves of the cell at different rates under 60 °C. It de-
livered initial discharge capacities of 151, 145, 114, 102 and 25 mAh
g−1 at 0.1, 0.2, 0.5, 1 and 2C, respectively. Fig. 9(b) presents the rate per-
formance of the cells with the rate from 0.1C to 2C. It shows that the cell
using WPU-based electrolyte can deliver a relatively high and compara-
ble capacities to the PEO one at low rates and the capacity faded rapidly
when the rate reached 2C. However, the capacity can be recovered
when the rate returns to 0.1C, which indicates the electrochemical sta-
bility of the WPU-based electrolyte. The poor rate performance may as-
cribe to the stiff hard segments in the polyurethane matrix. It is known
that polyurethane possesses both hard and soft segments. The soft
 B. Cong et al. / Materials and Design 142 (2018) 221–228
Fig. 9. (a) The charge and discharge curves of LiFePO4/SPE/Li battery using WPU-20%Li as electrolyte at different rates and (b) C-rate capability and (c) cycling performance of the batteries
at 60 °C, where the electrolytes were WPU-20%Li and PEO-20%Li; (d) The initial charge and discharge curves of the battery using WPU-20% Li SPE at 0.02C at 30 °C.
segments of as-prepared WPU were consisted of polyethylene glycol
which can provide a sub-host for fast lithium ion diffusion. The high seg-
mental motion of the soft segments at elevated temperature offered the
whole WPU system with good ionic conductivity. The hard segments,
which consisted of isocyanate units were difficult to move at this tem-
perature and will act as barriers to the ion movement. In addition, the
non-polar segments (\\(CH2)6\\) in the hexamethylene diisocyanate
molecular have a low compatibility with lithium metal may increase
the interfacial resistance between the SPE and electrode [49]. However,
the hard segments can afford high mechanical strength and dimen-
sional stability to the SPEs which will be favorable for the cycle perfor-
mance. Fig. 9(c) shows the cycling performance of the all-solid-state
lithium ion battery at 0.2C under 60 °C. The discharge capacity of the
battery based on the WPU-20% Li SPE was 141 mAh g−1 and the capac-
ity was 97% retained after 50th cycles. However, the capacity retention
of the cell based on PEO electrolyte was only 4% after 50 cycles. The dis-
charge capacity of the PEO one faded quickly after 25th cycles. This re-
sult is consistent to the previous literatures which also showed the
poor cycling performance of the pure PEO-based electrolyte [11,44].
The poor cycling performance of the PEO-based cell may ascribe to the
unrestrained lithium dendrites and the SEI films formed by the side re-
actions between lithium metal and solid polymer electrolyte [50–52].
The improved cycling performance of the WPU-based cells indicates
the WPU-20% Li electrolyte could afford enough mechanical strength
to restrain the Li dendrite and good electrochemical properties for the
battery. The all-solid-state battery has also been tested at ambient tem-
perature. As shown in Fig. 9(d), it can deliver a discharge capacity of
118 mAh g−1 at 0.02C at 30 °C. Compared with other all-solid-state
polymer electrolyte, the WPU-20% Li electrolyte had a competitive per-
formance at this operator temperature (see Table S1). The high dis-
charge capacity and excellent cycle performance may ascribe to the
unique structure of WPU. These results demonstrate that the all-solid-
227
state batteries with this WPU-based polymer electrolyte can work
at 60 °C and show a satisfactory capability and excellent cycling
performance.
4. Conclusions
In conclusion, polyethylene glycol-based waterborne polyurethane
(WPU) was synthesized and characterized by GPC, 1H NMR and FTIR
analysis. Various contents of LiTFSI were added to the as-prepared wa-
terborne polyurethane to form solid polymer electrolyte films via an or-
ganic solvent free process. The FTIR results showed the lithium salts
were dissolved and interacted with the oxygen and nitrogen atoms in
the polyurethane. The SEM and XRD results revealed the WPU became
amorphous with the addition of lithium salts. The 20 wt% LiTFSI in
WPU electrolyte possessed an ionic conductivity of 7.3 × 10−4 S cm−1
at 60 °C and electrochemical window exceeding 4.8 V (vs. Li+/Li). The
LiFePO4/SPE/Li cell with this solid state electrolyte showed an initial dis-
charge capacity of 151 mAh g−1 at 0.1C and 97% capacity retention after
50 cycles at 0.2C under 60 °C. This WPU-based solid polymer electrolyte
may become a promising environmentally friendly candidate for all-
solid-state lithium ion batteries.
Acknowledgements
This study was supported by Education Ministry of Anhui Province
(KJ2017A031), we are grateful to the engineering technology research
center of waterborne polymer materials of Anhui province.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.matdes.2018.01.039.
228 B. Cong et al. / Materials and Design 142 (2018) 221–228
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