Author's Accepted Manuscript: Journal of Membrane Science
Author's Accepted Manuscript: Journal of Membrane Science
Author's Accepted Manuscript: Journal of Membrane Science
www.elsevier.com/locate/memsci
PII: S0376-7388(18)31727-7
DOI: https://doi.org/10.1016/j.memsci.2018.08.011
Reference: MEMSCI16385
To appear in: Journal of Membrane Science
Received date: 23 June 2018
Revised date: 10 August 2018
Accepted date: 10 August 2018
Cite this article as: Dan Li, Huamin Zhang and Xianfeng Li, Porous
polyetherimide membranes with tunable morphology for lithium-ion battery,
Journal of Membrane Science, https://doi.org/10.1016/j.memsci.2018.08.011
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Porous polyetherimide membranes with tunable morphology for lithium-ion
battery
a
Division of energy storage, Dalian Institute of Chemical Physics, Chinese Academy
b
University of Chinese Academy of Sciences, Beijing 100039, China
c
Collaborative Innovation Center of Chemistry for Energy Materials (iChEM), Dalian
116023, China
E-mail: [email protected]
Abstract
Polyetherimide (PEI) porous membranes with tunable morphology are constructed via
a typical phase inversion method and applied in lithium-ion batteries (LIBs). The
polyvinyl pyrrolidone (PVP), in the cast solution. The obtained PEI porous
membranes show typical sponge-like microstructure and more connected and bigger
pores are formed in the membranes with the increase amount of PVP. Under LIBs test
condition, batteries with PEI membranes show superior thermal stability, good
electrolyte wettability, and tunable ion conductivity and rate performance. As a result,
1
a battery with a PEI-2 membrane exhibited comparable electrochemical performance
to that of commercial separators. A 96.4% capacity retention rate was obtained after
cycling for 100 cycles for a battery with a PEI-2 membrane. Thus, the membranes
with controlled performance in LIBs can be realized via adjusting their morphologies.
Graphical abstract
2
Keywords: Lithium-ion battery, polyetherimide, porous membrane, pore morphology
3
List of Symbols
PEI Polyetherimide
EV Electric vehicles
PE Polyethylene
PP Polypropylene
EC Ethylene carbonate
4
ρ2 Density of n-butanol (g/cm3)
SS Stainless steel
5
1. Introduction
Nowadays, lithium-ion batteries (LIBs) have attracted great interest for the most
competitive power sources [1-5] for electric vehicles (EV) and hybrid electric
vehicles (HEV) due to the advantage of high energy density, no memory effect,
excellent cycle life and environmental friendliness [6-9]. Commonly, a LIB mainly
LIBs, a separator plays the role of preventing the direct contact of anodes and
cathodes and providing the channels for ions transport [10-12]. Commercial
separators used in the LIBs are porous polyolefin separators, such as polyethylene
(PE), polypropylene (PP) and their composite separator [13, 14]. However, the
polyolefin separators suffer from high dimensional shrinkage at high temperature due
to the intrinsic low melting point of polymers (PE/130oC, PP/160oC), which would
cause internal short circuit, then generate a lot of heat, and final burn and even
induced poor compatibility with the organic electrolyte and leads to poor electrolyte
wettability and low ionic conductivity [15, 16], which would make adverse effect on
Currently, many efforts have been taken to improve the thermal stability and
the currently used separators. This hinders its application because of the complex
porous membrane [24] with highly security and reliability, ultrastrong polyoxyzole
nanofiber membranes [25] and solvent stable polyimide membranes [16, 26] for LIBs.
Recently, we have first reported the use of polyetherimide (PEI) porous membranes
[27] for lithium battery application due to their attractive features of good chemical
stability, high thermal stability, excellent insulation performance and good electrolyte
wettability, which was induced by the strong interaction between the polar ether bond
and amide bond in the polymer chains and organic electrolyte. The obtained porous
poly(ethylene glycol (PEG) [31]) to the casting solution. The morphology of poly
(ether sulfone) (PES) membranes [29] was adjusted via introducing hydrophilic PVP
in PES casting solutions, with addition of PVP in the cast solutions, the cross-section
morphology tuned from asymmetric finger like pores to sponge like pores. As stated
by Young Moo Lee et. al. [9], the electrochemical performance of membranes in the
a serial of spongy-like PEI membranes with different pore size were constructed using
solution (Scheme 1), the PVP inside prepared membranes was removed by immersed
in water for 24 h. With the increase amount of PVP, the pores of obtained membranes
7
became bigger and more connected. Their membrane morphology and battery
limited study has been carried out to investigate the relation between morphology and
performance in lithium ion battery. In this work, the properties of PEI porous
membranes by phase inversion method have been systematic studied, and in addition,
2. Experimental
8
2.1 Fabrication of membranes
A serial of PEI (the chemical structure showed in Fig. S7) porous membranes were
fabricated by phase inversion method. First, a proper amount of PEI (General Electric
Company) and PVP (Aladdin, average molecular weight: 10000) was dissolved in
onto a clean glass plate after removing bubble and transferred to a constant
temperature and humidity chamber (BPS-100CL, Hangzhou Haxi), which was kept at
o
50 C and 100% relative humidity, for 10 minutes. Afterword, the prepared
membranes. Finally, the obtained membranes were dried completely at 50 oC. The
temperature for 1 h. Then the thermal shrinkage rate was determined by measuring the
dimensional change before and after heat-treatment and calculated according to the
where the S0 and S1 are the area of membranes before and after heat-treatment
respectively.
9
In order to investigate the wettability of membranes with electrolyte, static contact
angle and electrolyte spreading test were conducted. Static contact angle of the
Shanghai Zhongchen Digtal Technology Apparatus Co., Ltd.). And the electrolyte
spreading test was analyzed by dipping electrolyte onto the membrane surface and
The liquid electrolyte uptake (U) of membranes was measured by immersing the
carbonate (DMC) and ethyl methyl carbonate (EMC) (EC/DMC/EMC, 1:1:1 vol)) for
12 h. Then the liquid electrolyte uptake (U) was calculated based on the weight of the
membrane before and after saturated with the electrolyte, and according to following
Eq. (2):
where the M0 and M1 are the weight of membrane before and after immersing in the
electrolyte.
for12 h. Then the porosity was calculated based on the weight of the membrane
before and after immersing in the n-butanol, and according to following Eq. (3):
where the m1 and m2 are the weight of dry membrane and n-butanol saturated in the
membrane respectively. The ρ1 and ρ2 are the density of polymer and n-butanol
respectively.
10
Gurley value was examined by a home-made instrument by measuring the time for a
certain volume of air (100 mL) to pass through a fixed area (19.6 cm2) under 0.02
MPa pressure.
The solubility parameters difference (Δδs-p) was used to discussion the compatibility
between the polymer and the liquid electrolyte and further explain the electrolyte
wetting performance on the membranes. This value can be calculated according to the
where the δd, δp, δh are the dispersion, polar, and hydrogen bonding components of the
total Hansen solubility parameter (δt), respectively. The p and s represent the polymer
In order to evaluate the ionic conductivity (σ) of membranes, the bulk impedance (Rb)
electrolyte-soaked membrane between two stainless steel (SS) electrodes. And the
impedance data was recorded over a frequency range from 0.1 to 106 Hz. The ionic
σ = d/(Rb × S) (8)
11
where the d and S are the thickness and area of the membrane respectively.
(PARSTAT 2273, Princeton Applied Research, USA) with a voltage range from 2.5 V
to 5.5 V with sweep rate of 0.5 mV s-1. The membrane was assembled into a battery,
in which metallic lithium and SS were served as reference and counter electrode
respectively.
half batteries with different membranes were assembled and tested on a Land
automatic battery tester (Wuhan, China). The LiFePO4 cathode (The active mass
loading of the electrodes was about 1.7 mg cm-2), was made from 80 wt. % LiFePO4,
10 wt. % Super-p and 10 wt. % Poly (vinylidene fluoride) (PVDF). The voltage
method. The morphology of the prepared membranes has been presented in Fig. 1. As
can be seen from the cross-section images, the prepared PEI membranes showed
formed due to the relatively slow exchange rate between the solvent and nonsolvent.
Then the homogeneous system will be solidified at similar time throughout the whole
12
film, meanwhile, with the forming of two phase, polymer rich phase and polymer lean
other hand, when the casting solution is immersed in the nonsolvent, a liquid layer
will emerge on the top of the cast solution, the existence of this liquid layer brings
about a solvent gradient through the cast film, leading to a lower solvent
concentration near the bottom and a higher concentration at the surface. As a result,
the droplets were coarsened and a porous structure was formed at the top layer of a
membrane (Fig. 1), where the viscosity was relatively low and a relativity dense
surface skin was formed at the bottom [24] (Fig. S1). As can be seen in Fig.1, with the
increase amount of PVP polymer in casting solution, the pores, whether inside or on
the surface of the PEI membranes get bigger and more interconnected. Which can be
further illustrated by average pore size of prepared membranes, calculated from the
Poiseuille equation via pure water fluxes (Fig. S2). Which was because that the
soluble PVP was easily diffused out from the membrane, and thus the space occupied
13
Fig. 1. The morphologies of prepared a serial of PEI membranes. (a-d) The
d: PEI-3). (a1-d1) The surface morphology of a serial of PEI membranes faced to air
14
Fig. 2. The wettability of membranes with electrolyte. (a) The Photograph of wetting
behavior (Left: without electrolyte, Right: with electrolyte) and (b) electrolyte contact
surface was evaluated by electrolyte spreading test and electrolyte contact angle test.
In electrolyte spreading test, a certain amount of electrolyte was dipped on the surface
of membranes and the photograph of the membranes before and after dipping
electrolyte was recorded and shown in Fig.2. The electrolyte quickly spread over the
whole PEI-2 membranes in ten seconds. In contrast, the electrolyte on PE surface kept
a small droplet for a long time,which indicates that it’s easier for electrolyte diffusing
through the PEI-2 membranes than the PE separators. This can also be observed in
electrolyte contact angle test, 52o and 20o for PE separators and PEI-2 membranes
respectively. This is due to the different polarity of polymer chains, which further
15
affects the affinity between the membrane with polar electrolyte. The affinity can be
estimated by value of the solubility parameters difference. The smaller the solubility
parameters difference value, the larger affinity between materials will be obtained
[34]. The Hansen solubility parameters of the polymer, solvent and their solubility
parameter difference were calculated and summarized in Table 2. As can be seen, the
PE showed 10.1 solubility parameter difference with the liquid electrolyte, which was
much higher than that of PEI, 4.74. This indicated that the PEI polymer was more
compatible with the electrolyte than PE polymer, and consequently the PEI
separators.
16
Table 2 The Hansen solubility parameters of the solvent and polymer, and the
In addition, the electrolyte uptake was also conducted to study the electrolyte wetting
performance. The electrolyte uptake was related with the wetting performance on
membranes surface and membranes porosity, which was determined by weight change
before and after test. As shown in Table 1, the porosity of PEI membranes increased
with the increase of PVP in cast solution. Consequently, the electrolyte uptake of PEI
membranes increased with the increase of porosity, that’s the electrolyte uptake of PEI
membranes, the porosity was increased to 78.2%, the electrolyte uptake was 306.1%,
which were much higher than that of PEI-0 separators, which will further contribute
to higher ionic conductivity (Table 1). In general, the ionic conductivity was related to
the content and the mobility of Li+. Here Gurley value is used to quantitatively
evaluate the pore structure. Since all the prepared membranes showed sponge-like
structure, low Gurley value corresponds to the larger pores (Fig. S2), which can be
17
used for reserving the electrolyte, further meant relativity lower diffusion resistance
for Li+. The Gurley value and the pore size of the PEI membranes showed no
significant difference among them, ionic conductivity of the prepared PEI membranes
might be mainly influenced by the pore structure rather than the electrolyte uptake,
which made the ionic conductivity change rarely. For PEI-2 and PEI-3 membranes,
although they had higher porosity and electrolyte uptake compared with that of PE
separators. The Gurley value was larger than that of PE separators, thus the ionic
conductivity was almost the same with that of the PE separator due to a synergy
between them. The ionic conductivity of PEI-2 membranes was almost the same with
membranes was comparable with PE separators. Thus, the PEI-2 membranes were
PEI membranes were shown in Fig. S3. The tensile strength of PEI membranes
decreased with the increase of PVP content in cast solution (16.09 MPa, 12.27 MPa,
11.52 MPa and 9.84 MPa for PEI-0, PEI-1, PEI-2 and PEI-3 membranes), which was
due to the increased porosity of PEI membranes. A lower mechanical stability will be
than that of PE separators (166.22 MPa), however, we try to assemble the prepared
membranes into soft package batteries, which were strong enough and the battery
showed very good cycle performance as well (Fig. S5 and Fig. S6).
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Fig. 3. The thermal stability of the PE separator and PEI-2 membrane. (a) The thermal
shrinkage and (b) the photographs of PE separator and PEI-2 membrane after
heat-treatment.
thermo-stability was determined by the area change of membranes before and after
temperature. After heat-treatment at 130 oC, the PE separator showed 41.8% thermal
shrinkage. As the temperature increasing to 140 oC (higher than the melting point of
PE, 135 oC), the PE separators melted completely. In contrast, the PEI-2 membranes
superior thermal stability and will provide excellent safety characteristic for LIBs. In
of nitrogen and the temperature range from 50 to 750 oC. As shown in Fig. 4, there is
no obvious weight loss below 510 oC for the PEI membranes. While the PE separators
decomposed sharply at about 460 oC. These results indicated the PEI membranes
20
Fig. 5. The linear sweep voltammetry curves of the SS/separator/SS battery with the
LIBs. The linear sweep voltammetry was conducted to study the electrochemical
stability window of electrolyte-soaked samples, and the results were shown in Fig. 5.
From PE LSV curve, the current increased sharply when the voltage increased to
membranes stability window was a little lower than that of PE separators, at about 4.4
V.
21
Fig. 6. The LiFePO4/Li battery electrochemical performance with PEI membranes and
commercial PE separators. The rate performance of batteries with (a) a serial of PEI
membranes and (b) PEI-2 membranes and PE separators. (c) The cycle performance
1 C.
battery performance. The rate performance of LIBs with a serial of PEI membranes
and a PE separator was shown in Fig. 6. As shown from Fig. 6a, the rate performance
of PEI based batteries was better with the increase amount of PVP polymer, and
finally, kept at a steady state. When the membranes were pure PEI (PEI-0) membranes,
22
meaning that there was no PVP polymer in casting solution, the discharge capacity at
5 C was 105 mAh g-1. With the increase amount of PVP polymer in casting solution,
the discharge capacity at 5 C were 110 mAh g-1, 119 mAh g-1, 119.5 mAh g-1 for
PEI-1, PEI-2, PEI-3 respectively. Comparing with PEI-0, the PEI-2 membranes, with
addition of 25 wt% PVP, showed the highest rate performance at high rate, indicating
that the pore structure of PEI-2 membranes was proper for lithium ion battery
application. When the amount of PVP polymer was increased to 30%, the rate
performance for PEI-3 membranes was almost the same with PEI-2 membranes,
indicating that further increasing the pore size of PEI based membranes has no effect
on rate performance. Consequently, the PEI-2 membranes were the most suitable for
the LIBs, which was consistent with the results of ionic conductivity. Comparing with
commercial PE separators, the rate performance of PEI-2 membranes was almost the
same with that of PE separators. The excellent rate performance was related to the
superior wettability with electrolyte and fast ionic conduction in PEI membranes,
which will induce fast Li+ transport through PEI membranes and the interface
between electrode and membranes and further lead to high rate performance.
23
Fig. 7. Nyquist plots of LiFePO4/Li batteries containing PEI-2 membranes and PE
batteries with PEI-2 membranes and PE separators was very stable during the test, and
the discharge capacity showed first increasing then a steady trend, which was due to
the activation process of electrode. The batteries with PEI-2 membranes showed
143.6 mAh/g initial discharge capacity (in steady state), after 100 cycles, the 96.4%
capacity retention rate was attained, which was almost the same with PE separators.
During the cycle process, the battery was stable and showed a coulombic efficiency of
nearly 100% (Fig S4), the initial unstable part was caused by activation process. In
Nyquist plots (Fig. 7), semicircle mainly represents the interfacial resistance. While,
increase of the interfacial resistance usually means the formation of the undesirable
resistive film. The impedance change of batteries with PEI-2 membranes (~ -29.6 Ω)
was smaller than that of PE separators (~ 8.99 Ω) during the cycle process, which
24
indicated that the PEI-2 membranes was conducive to the interfacial stability of the
batteries. The result may be due to the better wettability of the PEI-2 membrane with
the liquid electrolyte, then resulting in more benign contact of the PEI-2 membranes
with the electrodes, and thus affected the formation of the solid electrolyte interface
film. In addition to the above results, a comparation with previously reported porous
membranes for lithium ion battery separators (Table S1) demonstrated that PEI-2
4. Conclusions
prepared via phase inversion method by introducing the third PVP component in the
PEI casting solution. The obtained porous PEI membranes showed superior thermal
stability, good electrolyte wettability and high ion conductivity. And batteries with
PEI membranes showed stable cycle performance, comparable with the commercial
separators. In addition, the batteries exhibited better rate performance with the
increasing content of PVP in solution. In this study, a membrane prepared from the
solution with 25% PVP amount showed the best performance. Therefore, PEI
Acknowledgments
This research is supported by the financial support from the China Natural Science
25
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Figure and Table Captions
d: PEI-3). (a1-d1) The surface morphology of a serial of PEI membranes faced to air
Fig. 2. The wettability of membranes with electrolyte. (a) The Photograph of wetting
behavior (Left: without electrolyte, Right: with electrolyte) and (b) electrolyte contact
Fig. 3. The thermal stability of the PE separator and PEI-2 membrane. (a) The thermal
shrinkage and (b) the photographs of PE separator and PEI-2 membrane after
heat-treatment.
Fig. 5. The linear sweep voltammetry curves of the SS/separator/SS battery with the
Fig. 6. The LiFePO4/Li battery electrochemical performance with PEI membranes and
commercial PE separators. The rate performance of batteries with (a) a serial of PEI
membranes and (b) PEI-2 membranes and PE separators. (c) The cycle performance
1 C.
31
separators after the 30th and 100th cycle at 1 C.
Table 2. The Hansen solubility parameters of the solvent and polymer, and the
Highlights
PEI porous membranes with tunable morphology were fabricated for lithium-ion battery.
The morphology of PEI membranes was tuned by introducing additives in cast solution.
The PEI membranes exhibited very promising performance for lithium-ion battery.
The PEI membranes showed superior thermal stability and wettability with electrolyte.
32