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Effects of Molecular Weight on the Electrochemical Properties of

Poly(vinylidene difluoride)-Based Polymer Electrolytes
Ying Liang, Shundong Guan, Chengzhou Xin, Kaihua Wen, Chuanjiao Xue, Hetian Chen, Sijie Liu,
Xinbin Wu, Haocheng Yuan, Liangliang Li,* and Ce-Wen Nan*
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ABSTRACT: Polymer-based electrolytes have attracted ever-

increasing attention for solid-state batteries due to their excellent
flexibility and processability. Among them, poly(vinylidene
difluoride) (PVDF)-based electrolytes with high ionic conductiv-
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ity, wide electrochemical stability window, and good mechanical

properties show great potential and have been widely investigated
by using different Li salts, solvents, and inorganic fillers. Here, we
report the influence of the molecular weight of PVDF itself on the
electrochemical properties of the electrolytes by using two kinds of
common PVDF polymers, i.e., PVDF 761 and 5130. Our results
demonstrate that the electrolyte with a larger molecular weight
(PVDF 5130) has a denser structure and lower crystallinity, and
thus much better electrochemical performance, than one with a
smaller molecular weight (PVDF 761). With PVDF 5130, the LiFePO4-based solid-state cells present a steady cycling performance
with a capacity retention of 85% after 1000 cycles at 1 C and 30 °C. The cycle life of the LiCoO2-based solid-state cells is also
extended by using PVDF 5130.
KEYWORDS: poly(vinylidene difluoride), polymer electrolyte, solid-state battery, lithium metal, molecular weight

1. INTRODUCTION Recently, studies on PVDF-based electrolytes have been

Solid-state lithium (Li) metal batteries (SSLMBs) with a high
energy density and enhanced safety are considered as the next
generation of energy storage devices.1−5 Thus, solid-state
electrolytes that are critical to SSLMBs have drawn ever-
increasing attention in recent years.1,6 Various solid-state
electrolytes such as sulfides,7−9 oxides,10 halides,11,12 and
polymer electrolytes13,14 have been investigated. Compared
with inorganic electrolytes, solid polymer electrolytes with
excellent flexibility and processability not only exhibit intimate
interfacial contact with electrodes but also present good
compatibility with the manufacturing processes of commercial
Li ion batteries.15−17 Furthermore, polymer electrolytes could
also present high ionic conductivity, good mechanical
properties, wide electrochemical stability window, and good
thermal stability.6,18 Therefore, they are promising electrolytes
for SSLMBs. Several polymers have been used as the matrices
of polymer electrolytes, including poly(ethylene oxide),19−21
polyacrylonitrile, 22 poly(methyl methacrylate), 23 poly-
(propylene carbonate),24 and poly(vinylidene fluoride)
(PVDF) family.25−28 PVDF-based electrolytes have been
studied extensively because of the high dielectric constant,
good mechanical properties, and excellent thermal stability of
PVDF.15,17
mainly focused on the improvement of ionic conductivity and
interfacial stability against Li metal by controlling Li salts,
solvents, and inorganic fillers used in PVDF-based electro-
lytes.25,29−32 For example, Zhang et al. synthesized three kinds
of PVDF-based electrolytes with different Li salts and found
that the PVDF−LiN(SO2F)2 (lithium bis(fluorosulfonyl)-
imide, LiFSI) electrolyte possessed high ionic conductivity
(1.18 × 10−4 S cm−1 at 25 °C) and optimal interfacial stability
with Li metal.25 Liu et al. investigated the influence of the Li
salt concentration on ionic conductivity and found that a
PVDF-based polymer electrolyte with a polymer-to-salt mass
ratio of 1:1.1 exhibited a high room-temperature ionic
conductivity of 1.24 × 10−4 S cm−1.29 Zhou et al. investigated
the effects of different solvents and found that PVDF-based
electrolytes prepared with N,N-dimethylformamide (DMF)
showed the most compact morphology and the best cycling
performance in Li symmetric cells.30 Moreover, different
Received: April 29, 2022
Accepted: June 22, 2022
Published: July 5, 2022

© 2022 American Chemical Society https://doi.org/10.1021/acsami.2c07471

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Figure 1. Characterization of PVDF 761- and 5130-based polymer electrolytes. (a) Ionic conductivity, (b) electrochemical stability window, (c)
stress−strain curves, and (d) CCD of the electrolytes at 26 °C. (e) Galvanostatic cycling profiles of the Li||Li symmetric cell at 30 °C under 0.1 mA
cm−2 and 0.1 mAh cm−2. (f) Galvanostatic cycling profiles of the Li||Li symmetric cell at 30 °C under 0.2 mA cm−2 and 0.2 mAh cm−2. The insets
in (e) and (f) show the enlarged voltage−time curves.
i n o r g a n i c fi l l e r s ( e . g . , L L Z O p a r t i c l e s 2 6 , 2 7 a n d
Li1.4Al0.4Ti1.6(PO4)3 nanowires32) were added in the PVDF
matrix to obtain composite electrolytes with further improved
electrochemical performance. Among these studies, PVDF
with a low molecular weight was usually used,33−35 while the
application of PVDF with a high molecular weight in polymer
electrolytes and the influence of the molecular weight of the
PVDF matrix on its electrochemical properties have not been
studied yet.
In this work, we prepared PVDF-based polymer electrolytes
with two kinds of matrices, that is, PVDF 761 (Kynar) and
PVDF 5130 (Solef). PVDF 761 with a smaller molecular
weight (∼300 kg mol−1) is often used to prepare PVDF-based
electrolytes, while PVDF 5130 with a larger molecular weight
(∼1100 kg mol−1) is widely used as a commercial electrode
binder due to its high viscosity and good electrochemical
performance.36 The electrochemical properties of the electro-
lytes with these two matrices were measured and compared.
The effects of the molecular weight on the electrochemical
properties were systematically studied. The results showed that
the electrolytes with PVDF 5130 presented larger ionic
conductivity, improved mechanical properties, and enhanced
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interfacial stability against Li metal and thus significantly
enhanced cycling performance of SSLMBs.
2. EXPERIMENTAL SECTION
2.1. Electrolyte Preparation. LiFSI (TCI), PVDF 761 (Arkema,
Kynar 761, Mn = ∼300 kg mol−1), and PVDF 5130 (Solvay, Solef
5130, Mn = ∼1100 kg mol−1) were dried under vacuum at 80 °C for
24 h before use. The PVDF-based polymer electrolytes were prepared
via a slurry casting-drying method.25,31,34 In a typical experiment,
PVDF (0.3 g) and LiFSI (0.2 g) powders were dissolved in 3.0 mL of
the DMF (Adamas)−tetrahydrofuran (Adamas) binary solvent with a
volume ratio of 3:7. Then, the mixture was stirred for 2 h at 55 °C to
obtain a homogeneous slurry. Next, the slurry was cast on a glass slide
by a doctor blade. An electrolyte membrane with a thickness of ∼80
μm was obtained after the slurry was dried in a vacuum oven at 80 °C
for 24 h.
2.2. Materials Characterization. Scanning electron microscopy
(SEM, Zeiss Merlin) was used to examine the morphology of the
electrolytes. The cross-sectional SEM images of the electrolytes were
obtained after the samples were cryo-fractured in liquid nitrogen.
Fourier transform infrared spectroscopy (FTIR, VERTEX 70) and X-
ray diffractometry (XRD, Rigaku D/max-2500 with Cu Kα, 40 kV and
200 mA) were employed to investigate the phase structure of PVDF
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Figure 2. Morphology and phase structure of the electrolytes. (a, b) Top-view SEM images of the PVDF 761- and 5130-based electrolytes,
respectively. (c) XRD patterns of the electrolytes and LiFSI powder. (d) DSC curves of the PVDF 761- and 5130-based electrolytes.
in the electrolytes. The mechanical properties of the PVDF-based
membranes with a size of 25 mm × 76 mm were measured by a
universal testing machine (EZ-LX HS, Shimadzu) at a stretching
speed of 5 mm min−1 at room temperature in air. Thermogravimetric
analysis combined with differential scanning calorimetry (TGA/DSC,
Mettler Toledo TGA2 SF) was performed to investigate the thermal
stability of the electrolytes. The TGA measurement was performed
with a heating rate of 20 °C min−1 under an argon (Ar) atmosphere.
Dual-beam focused ion beam scanning electron microscopy (FIB-
SEM, Zeiss Merlin, Crossbeam 340) was used to observe the surface
and cross-sectional topography of the Li electrodes. X-ray photo-
electron spectroscopy (XPS, Ulvac-Phi, PHI Quantera II) and time-
of-flight secondary ion mass spectrometry (TOF-SIMS, ION-TOF
GmbH, TOF.SIMS 5) were used to analyze the chemical composition
and components in the interface layers between Li electrodes and
electrolytes. Cs+ sputtering was used in the depth profiling of TOF-
SIMS.
2.3. Electrochemical Measurements. All electrochemical tests
were performed with the CR2025-type coin cells without liquid
electrolyte that were assembled in an Ar-filled glovebox (MBRAUN,
O2 < 0.1 ppm, H2O < 0.1 ppm). The ionic conductivity σ of the
electrolytes was determined by using stainless steel (SS)||electrolyte||
SS cells through an impedance analyzer (Zahner-elecktrik IM6) with a
frequency range of 1 Hz−1 MHz. The activation energy Ea was
calculated according to the Arrhenius equation σ(T) = A exp(−Ea/
RT), where A is a pre-exponential factor, R is the molar gas constant,
and T is absolute temperature. Li||electrolyte||SS coin cells were used
to determine the electrochemical stability window of the electrolytes
via the linear sweep voltammetry (LSV, Bio-Logic SAS, VMP3) tests
at a scan rate of 0.1 mV s−1. Li||electrolyte||Li coin cells were
assembled and tested at 0.1, 0.2, 0.3, and 0.5 mA cm−2 to explore
interfacial stability between the PVDF-based electrolytes and Li metal.
The Li symmetric cells were also tested with a step-increased current
density and a cycle time of 1 h to determine the critical current
density (CCD) of the electrolytes.
SSLMBs with a LiFePO4 (LFP) or LiCoO2 (LCO) composite
cathode, a PVDF 761- or 5130-based electrolyte membrane, and a Li
anode were assembled. LFP or LCO powder (Citic Guoan MGL
Inc.), Super P carbon black (TeenSky Inc.), PVDF, and lithium
bis(trifluoromethanesulfonyl)imide (LiTFSI, Aladdin) with a weight
ratio of 76:9:9:6 were mixed and homogeneously dispersed in N-
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methylpyrrolidone (Adamas) solvent to form a composite cathode
slurry. The type of PVDF used in the composite cathode was the same
as that used in the electrolyte membrane for both cases of PVDF 761
and 5130. LiTFSI was used as the Li salt in the composite cathode
because the thermal stability and humidity resistance of LiTFSI are
better than those of LiFSI. The as-prepared slurry was coated on an
aluminum (Al) foil and dried in a vacuum oven at 110 °C for 12 h to
obtain a composite cathode sheet. A round cathode with a diameter of
12 mm was cut from the cathode sheet and used in the cell assembly.
The mass loading of active materials in the cathodes was ∼1.8 or 5.2
mg cm−2. The cycling performance of the Li symmetric cells and
SSLMBs was tested at 30 °C by using a battery test system (C2001A,
Land).
3. RESULTS AND DISCUSSION
3.1. Comparison of Electrochemical Properties. The
ionic conductivity σ of the PVDF 761- and 5130-based
polymer electrolytes was obtained via electrochemical
impedance spectroscopy (Figure S1, Supporting Information)
and compared in Figure 1a. With the same amount of LiFSI,
the PVDF 5130-based electrolyte has an ionic conductivity of
2.38 × 10−4 S cm−1 at 26 °C, which is higher than that of the
PVDF 761-based one (1.23 × 10−4 S cm−1). The values of the
activation energy Ea of the PVDF 761- and 5130-based
electrolytes calculated from the Arrhenius equation are 0.35
and 0.26 eV, respectively, indicating faster Li+ migration in the
PVDF 5130-based electrolyte. The TGA curves in Figure S2a
show that the residual DMF contents in the two electrolytes
are the same (∼14.4 wt %), and all the residual DMF
molecules exist in the bound state (Figure S2b). Therefore, the
difference between the electrochemical properties of the PVDF
761- and 5130-based electrolytes are not due to bound DMF
molecules31 but other factors such as crystallinity and phase
structure, which will be thoroughly analyzed in the next
section.
The electrochemical stability windows of the PVDF 5130-
and 761-based electrolytes are tested by LSV, as shown in
Figure 1b. For the PVDF 5130-based electrolyte, the current
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Figure 3. Characterization of the interface layers in the Li symmetric cells after 100 cycles. (a, b) Top-view SEM images of the Li electrodes peeled
off from the PVDF 761- and 5130-based electrolytes, respectively. (c, d) Cross-sectional SEM images of the Li electrode peeled off from the PVDF
761- and 5130-based electrolytes, respectively. (e) XPS spectra of Li 1s, F 1s, and S 2p of the interface layers on the Li electrodes. (f) XPS spectra
of C 1s and F 1s on the surface of the electrolytes. (g, h) TOF-SIMS two-dimensional distribution (200 × 200 μm2) and depth profiles of F− in the
interface layers.

arises at 4.22 V and slowly increases between 4.22 and 4.70 V,
yet it is less than 10 μA. After 4.70 V, the current rapidly
increases. Thus, the decomposition of the PVDF 5130-based
electrolyte starts at 4.22 V and accelerates above 4.70 V. In
contrast, the decomposition of the PVDF 761-based electrolyte
begins at 4.12 V and accelerates above 4.33 V. The current rise
at about 4.22 V is attributed to the decomposition of the
DMF−LiFSI complexes in the electrolytes at ∼4.2 V (Figure
S3). The difference in electrochemical stability window
indicates that the PVDF with a larger molecular weight can
stand at higher voltages.37 Figure 1c compares the stress−
strain curves of the electrolytes. PVDF 5130 with a larger
molecular weight has longer molecular chains, which leads to
more entanglement and stronger intermolecular interaction
between the molecular chains.38 As a result, the Young’s
modulus (∼36 MPa), tensile strength (∼7.6 MPa), and
elongation of the PVDF 5130-based electrolyte are all higher
than those of the PVDF 761-based one. These improved
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mechanical properties are helpful for preventing from the Li−
dendrite penetration.39−41
For testing the electrochemical stability against Li metal of
the two electrolytes, the CCD at 26 °C was measured with Li
symmetric cells containing the PVDF-based electrolytes under
a fixed Li plating/stripping time of 30 min and step-increased
current density. Figure 1d shows that the CCD of the PVDF
5130-based electrolyte is higher than that of the PVDF 761-
based one (1.3 mA cm−2 vs 0.8 mA cm−2). Moreover, the
cycling tests were performed at 30 °C. At a current density of
0.1 mA cm−2 and a capacity of 0.1 mAh cm−2, both the Li||Li
cells can be cycled stably for 6000 h with a low and steady Li
plating/stripping overpotential (Figure 1e). However, when
the current density increases to 0.2 mA cm−2, as shown in
Figure 1f, the Li||Li cell with the PVDF 5130-based electrolyte
is cycled stably for 1000 h, whereas the Li||Li cell with the
PVDF 761-based electrolyte experiences a short circuit after
235 h. Furthermore, the Li||Li cells with the PVDF 5130-based
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electrolyte also show better cycling performance at high
current densities of 0.3 and 0.5 mA cm−2 (Figure S4). Thus,
the PVDF 5130 polymer with a large molecular weight renders
significantly enhanced electrochemical and mechanical proper-
ties to the electrolyte.
3.2. Mechanism Analysis. To understand the difference
in the ionic conductivity of PVDF 761- and 5130-based
electrolytes, the electrolytes’ morphology, crystallinity, and
crystal phase were investigated. The top-view SEM images in
Figures 2a and S5a show that the PVDF 761-based electrolyte
contains many pores with a diameter ranging from 0.2 to 0.4
μm. In contrast, the PVDF 5130-based electrolyte has a
smooth surface and a dense structure (Figures 2b and S5b).
The thickness of the two electrolyte membranes is ∼80 μm
(Figure S5c,d). The cross-sectional SEM images also show that
the PVDF 5130-based electrolyte is denser (Figure S5e,f).
Such a dense structure ensures a continuous ionic conducting
path, which is advantageous for the improvement of ionic
conductivity.
Besides the morphology, the degree of crystallinity and
crystal phase of polymer matrix also affect the migration rate of
Li+ ions in polymer electrolytes.15,42 Thus, XRD was
performed on the electrolytes, and the results are shown in
Figure 2c. The peaks of LiFSI disappear in the XRD patterns of
the two electrolytes, indicating that the PVDF−DMF system
has an excellent Li salt dissolving ability, and the peak at 22.1°
ascribed to the solvated complex [Li(DMF)n]+FSI− appears,43
which is consistent with the Raman spectra in Figure S2b. It is
worth noting that the peak intensity ratio of the PVDF peak at
20.1° to the [Li(DMF)n]+FSI− one in the PVDF 5130-based
electrolyte is much lower than that in the case of PVDF 761,
while the full width at half-maximum (FWHM) of the PVDF
peak is wider for the case of PVDF 5130. Both the phenomena
demonstrate that the crystallinity of the PVDF 5130-based
electrolyte is lower.
The degree of crystallinity of the electrolytes Xc can be
quantified by DSC. The Xc value is calculated by the equation
Xc = ΔHm/ΔH0m, where ΔH0m is the fusion enthalpy of fully
crystallized PVDF (104.7 J g−1) and ΔHm is the fusion
enthalpy of the electrolyte obtained from the area of the peak
at the melting temperature Tm.44,45 As shown in Figure 2d, the
Xc values are 29.6 and 37.8 mol % for the PVDF 5130- and
761-based electrolytes, respectively. The molecular chains of
PVDF 5130 with a larger molecular weight are longer, making
crystallization more difficult. Thus, the PVDF 5130-based
electrolyte has a dense structure (Figure 2b), whereas the
presence of more crystalline regions in the PVDF 761-based
electrolyte results in a porous morphology (Figure 2a). It is
well-known that the increase of the amorphous region in
polymer electrolytes often assists with the enhancement of
ionic conduction.46 The lower crystallinity of the PVDF 5130-
based electrolyte also leads to its larger ionic conductivity.
In addition, the XRD patterns in Figure 2c show that the
phases of PVDF in the electrolytes are the β and γ phases
represented by the peaks at 20.5° and 20.1°, respectively.47−50
In contrast, the dominant phase in the original PVDF powder
is the α phase (Figure S6a).51 The spectra of FTIR
spectroscopy in Figure S6b also confirm that the β and γ
phases exist in the electrolytes, while the α phase is dominant
in the powder. The β and γ phases with polarity and a similar
conformation are usually considered as the electroactive
phases.52−54 Thus, the nonpolar α phase was transformed to
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these electroactive phases that are favorable for the migration
of Li+ ions during the process of electrolyte preparation.17,48,54
To explore the interface between the Li electrode and the
electrolytes, the Li electrodes were peeled off from the
electrolytes and observed by dual-beam FIB-SEM, after the Li||
Li cells with the two electrolytes were cycled for 100 cycles at
0.1 mA cm−2 and 0.1 mAh cm−2. As seen from Figure 3a, the
surface of the Li electrode contacting with the PVDF 761-
based electrolyte is rough and cracks appear (Figure S7a),
indicating the growth of Li dendrites. In contrast, the electrode
surface for the case of PVDF 5130 is smooth (Figure 3b), and
no crack is observed (Figure S7b). The thickness of the
interface layer between the Li electrode and the PVDF 761-
based electrolyte varies a lot (∼187−425 nm, Figure 3c),
whereas the interface layer in the case of PVDF 5130 is thinner
(∼120 nm) and much more uniform (Figure 3d).
In addition, XPS was performed to measure the components
of the interface layers on the electrodes, and the results are
summarized in Figures 3e and S8. According to the XPS
spectra, the interface layers are mainly composed of LiF, Li2O,
LiOH, Li2CO3, LixN, Li2S, Li2Sx, and Li2SOx, which is
supported by the results of the TOF-SIMS depth profiling
(Figure S9). A peak of metallic Li appears in the Li 1s
spectrum for the case of PVDF 761, but it does not exist in the
case of PVDF 5130, indicating that the interface layer between
the PVDF 5130-based electrolyte and a Li electrode is uniform
and dense enough to fully cover the underlying metallic Li
(Figure 3e).34,55 This accords with the SEM results in Figure
3c,d. The signal of LiF in the F 1s spectrum for the case of
PVDF 5130 is much stronger than that for the case of PVDF
761; therefore, more LiF, which is beneficial for the interfacial
stability and battery performance, was produced due to the
reaction between the PVDF 5130-based electrolyte and a Li
electrode.56,57 LiF may be originated from the dehydrofluori-
nation of PVDF chains or the decomposition of LiFSI. The
signal of SO2F (169.4 eV) in the S 2p spectrum of the interface
layer forming with the PVDF 5130-based electrolyte is much
weaker than that with the PVDF 761-based electrolyte,
indicating that more LiFSI is decomposed and more F− is
released to form LiF.58 Furthermore, the peak intensity ratio of
the C�C peak (285.4 eV) to the C−C one (284.6 eV) of the
PVDF 5130-based electrolyte is much lower and the
corresponding C−F peak is stronger, both indicating that
less PVDF is dehydrofluorinated (Figure 3f).32,34,56
Next, the two-dimensional distribution of F− in the interface
layers was measured by TOF-SIMS. Figure 3g shows that the
signal intensity of F− is obviously higher on the surface of the
Li electrode contacting with the PVDF 5130-based electrolyte,
indicating the presence of more LiF, which is consistent with
the XPS results. Also, the TOF-SIMS depth profiles of F−
demonstrate that LiF is enriched in the deeper region for the
case of PVDF 5130 (Figure 3h). LiF not only is a good
electron insulator that can suppress continuous reactions
between electrolytes and Li43,56,59 but also has a low energy
barrier and high surface diffusion rate for Li+ transport.60 On
the basis of the analyses above, it can be concluded that the
existence of a uniform, dense, LiF-rich interface layer enhances
the electrochemical stability against Li metal of the PVDF
5130-based electrolyte.
3.3. Performance of SSLMBs. SSLMBs with a LFP- or
LCO-based composite cathode, a PVDF 761- or 5130-based
electrolyte, and a Li anode were assembled and tested. In
Figure 4a, the initial specific discharge capacity of the LFP||
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Figure 4. (a, b) Cycling performance of the LFP||Li and LCO||Li batteries at 1 C, respectively. (c) Charge−discharge curves of the LFP||PVDF
5130-based electrolyte||Li battery at 1 C. (d, e) Rate performance of the LFP||Li and LCO||Li batteries, respectively. The mass loading of active
materials was ∼1.8 mg cm−2.
PVDF 761-based electrolyte||Li cell with an LFP mass loading
of 1.8 mg cm−2 is 113.6 mAh g−1 at a current density of 0.306
mA cm−2, i.e., 1 C (1 C is equivalent to 170 mA g−1). The
discharge capacity and Coulombic efficiency (CE) of the cell
fluctuate after ∼222 cycles, which may be ascribed to the
formation of dead Li during the plating/stripping processes.61
In contrast, the LFP||PVDF 5130-based electrolyte||Li cell
exhibits an excellent long-term cycling performance with a
capacity retention of 85% after 1000 cycles (1st: 133.8 mAh
g−1; 1000th: 114.2 mAh g−1) and a relatively low polarization
(Figures 4c and S10a). Furthermore, at a high LFP mass
loading of 5.2 mg cm−2 (0.881 mAh cm−2), the cell with the
PVDF 5130-based electrolyte also shows a higher discharge
capacity and better cycling performance in comparison with
the case of PVDF 761 (Figure S10b).
The difference in the cycling performance of the LCO-based
SSLMBs is also obvious (Figure 4b). The LCO||PVDF 5130-
based electrolyte||Li cell with an LCO mass loading of ∼1.8 mg
cm−2 presents an initial specific discharge capacity of 108.8
mAh g−1 at a current density of 0.252 mA cm−2, i.e., 1 C (1 C
is equivalent to 140 mA g−1) and runs for 440 cycles, whereas
the LCO||PVDF 761-based electrolyte||Li battery exhibits a
much lower initial discharge capacity of 98.5 mAh g−1 and
suffers from a rapid capacity decay after ∼245 cycles. The
nonlinear decay is due to the thick and inhomogeneous
interface layer that degrades the ionic kinetics on the Li
anode.62 Furthermore, the polarization of the LCO battery
with a PVDF 5130-based electrolyte remains constant during
the cycling process, whereas that for the case of PVDF 761
increases continuously (Figure S10c,d).
As expected, the SSLMBs with the PVDF 5130-based
electrolyte show better rate performance. The LFP||PVDF
5130-based electrolyte||Li battery delivers high capacities of
152.7, 148.8, 140.6, 134.7, and 128.3 mAh g−1 at rates of 0.2,
0.3, 0.5, 0.8, and 1.0 C, respectively (Figure 4d), which are
higher than the corresponding ones of the battery with the
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PVDF 761-based electrolyte. Similarly, the LCO-based
SSLMSB with the PVDF 5130-based electrolyte shows higher
discharge capacities at different rates in comparison with the
case of PVDF 761 (Figure 4e).
4. CONCLUSIONS
Two kinds of polymer electrolytes with PVDF 5130 and 716
polymers as matrices have been synthesized, and a comparison
shows that the molecular weight affects the electrochemical
performance of the PVDF-based electrolytes. When the
molecular weight of PVDF increases, the electrolyte is denser
and the content of amorphous phase in the electrolyte
increases, leading to the increase of ionic conductivity. The
electrochemical stability window and mechanical properties of
the electrolyte are also greatly enhanced when PVDF 761 is
replaced with PVDF 5130 with a larger molecular weight. With
PVDF 5130, a stable, thin, and LiF-rich interface layer that
formed between the electrolyte and Li metal suppresses the
growth of Li dendrites; therefore, the electrochemical stability
against Li metal of the electrolyte is significantly improved.
Because of the excellent electrochemical performance of the
PVDF 5130-based electrolyte, the Li symmetric cell is cycled
stably for 1000 and 6000 h at current densities of 0.2 and 0.1
mA cm−2, respectively. The LFP- and LCO-based SSLMBs
with the PVDF 5130-based electrolyte also exhibit better
cycling stability and a lower capacity decay in comparison with
those containing the PVDF 761-based electrolyte.
■
*
ASSOCIATED CONTENT
sı Supporting Information
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acsami.2c07471.
Nyquist plots, TGA curves and SEM images of the
PVDF-based electrolytes; Raman spectra of a DMF−1
M LiFSI solution and the PVDF-based electrolytes;
FTIR spectra of DMF, a DMF−LiFSI solution, and the
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PVDF-based electrolytes; LSV curves of DMF and the
DMF−LiFSI solution; galvanostatic cycling profiles of
the Li||Li symmetric cells; XRD patterns of the PVDF
powders; FTIR spectra of the PVDF powders and
PVDF-based electrolytes; SEM images of cycled Li
electrodes; XPS spectra and TOF-SIMS depth profiles of
the components on the cycled Li electrodes; charge−
discharge curves of the LFP- and LCO-based solid-state
batteries at 1 C; cycling performance of the LFP||Li cells
with a high LFP mass loading at 0.3 C (PDF)
■ AUTHOR INFORMATION
Corresponding Authors
Liangliang Li − State Key Laboratory of New Ceramics and
Fine Processing, School of Materials Science and Engineering,
Tsinghua University, Beijing 100084, China; orcid.org/
0000-0001-7808-7052; Phone: +86-10-62797162;
Email: liliangliang@mail.tsinghua.edu.cn; Fax: +86-10-
62771160
Ce-Wen Nan − State Key Laboratory of New Ceramics and
Fine Processing, School of Materials Science and Engineering,
Tsinghua University, Beijing 100084, China; Phone: +86-
10-62773587; Email: cwnan@mail.tsinghua.edu.cn;
Fax: +86-10-62771160
Authors
Ying Liang − State Key Laboratory of New Ceramics and Fine
Processing, School of Materials Science and Engineering,
Tsinghua University, Beijing 100084, China; orcid.org/
0000-0001-9630-3126
Shundong Guan − State Key Laboratory of New Ceramics
and Fine Processing, School of Materials Science and
Engineering, Tsinghua University, Beijing 100084, China
Chengzhou Xin − State Key Laboratory of New Ceramics and
Fine Processing, School of Materials Science and Engineering,
Tsinghua University, Beijing 100084, China
Kaihua Wen − State Key Laboratory of New Ceramics and
Fine Processing, School of Materials Science and Engineering,
Tsinghua University, Beijing 100084, China
Chuanjiao Xue − State Key Laboratory of New Ceramics and
Fine Processing, School of Materials Science and Engineering,
Tsinghua University, Beijing 100084, China
Hetian Chen − State Key Laboratory of New Ceramics and
Fine Processing, School of Materials Science and Engineering,
Tsinghua University, Beijing 100084, China
Sijie Liu − State Key Laboratory of New Ceramics and Fine
Processing, School of Materials Science and Engineering,
Tsinghua University, Beijing 100084, China
Xinbin Wu − State Key Laboratory of New Ceramics and Fine
Processing, School of Materials Science and Engineering,
Tsinghua University, Beijing 100084, China
Haocheng Yuan − State Key Laboratory of New Ceramics and
Fine Processing, School of Materials Science and Engineering,
Tsinghua University, Beijing 100084, China
Complete contact information is available at:
https://pubs.acs.org/10.1021/acsami.2c07471
Notes
The authors declare no competing financial interest.
32081
www.acsami.org Research Article
■ ACKNOWLEDGMENTS
This work was supported by the National Natural Science
Foundation of China under Grants 51788104 and U21A2080.
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32083 https://doi.org/10.1021/acsami.2c07471
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