Author’s Accepted Manuscript

Porous polyetherimide membranes with tunable

morphology for lithium-ion battery

Dan Li, Huamin Zhang, Xianfeng Li

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

Dan Lia,b, Huamin Zhanga,c, Xianfeng Lia,c*

a
Division of energy storage, Dalian Institute of Chemical Physics, Chinese Academy

of Sciences, Zhongshan Road 457, Dalian 116023, China

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: lixianfeng@dicp.ac.cn

Abstract

Polyetherimide (PEI) porous membranes with tunable morphology are constructed via

a typical phase inversion method and applied in lithium-ion batteries (LIBs). The

morphology of PEI membranes is adjusted by introducing hydrophilic additives,

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.

This paper provides an effective way to optimize fabrication parameters of porous

membranes for LIBs application.

Graphical abstract

Tunable morphology membranes with superior thermo-stability and wettability were

fabricated and expect to optimize fabrication parameters of membranes for LIBs.

2
Keywords: Lithium-ion battery, polyetherimide, porous membrane, pore morphology

3
 List of Symbols

PEI Polyetherimide

LIBs Lithium-ion batteries

PVP Polyvinyl pyrrolidone

EV Electric vehicles

HEV Hybrid electric vehicles

PE Polyethylene

PP Polypropylene

PEG Poly (ethylene glycol)

PES Poly (ether sulfone)

SEM Scanning electronic microscopy

S0 Area of the membrane before heat-treatment (cm2)

S1 Area of the membrane after heat-treatment (cm2)

U Electrolyte uptake (%)

M0 Weight of the membrane before immersing in the electrolyte (g)

M1 Weight of the membrane after immersing in the electrolyte (g)

EC Ethylene carbonate

DMC Dimethyl carbonate

EMC Ethyl methyl carbonate

m1 Weight of dry membrane (g)

m2 Weight of n-butanol (g)

ρ1 Density of polymer (g/cm3)

4
ρ2 Density of n-butanol (g/cm3)

σ Ionic conductivity (S cm-1)

Δδs-p Solubility parameters difference (MPa0.5)

δd Dispersion solubility parameter (MPa0.5)

δp Polar solubility parameter (MPa0.5)

δh Hydrogen bonding solubility parameter (MPa0.5)

δt Total Hansen solubility parameter (MPa0.5)

Rb Bulk impedance (Ω)

d Thickness of the membranes (μm)

S Effective area of the membranes (cm2)

EIS Electrochemical impedance spectroscopy

SS Stainless steel

PVDF Poly (vinylidene fluoride)

LSV Linear sweep voltammetry

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

consists of electrodes, electrolyte and a separator. As one of the key components of

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

explosion of batteries. In addition, the hydrophobicity of polyolefin separators

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

the electrochemical performance.

Currently, many efforts have been taken to improve the thermal stability and

electrolyte wettability. One effective strategy is surface modification, introducing

hydrophilic organic polymer [17-20] or inorganic nanoparticles [21-23] into or onto

the currently used separators. This hinders its application because of the complex

fabrication process and high cost. Another effective approach is constructing a

6
heat-resistance skeleton for novel separators, such as fabricating a polybenzimidazole

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

membranes fabricated by phase inversion method showed spongy-like porous

membrane morphology, the membrane morphology and performance can be

controlled by adding a third component (such as polyvinyl pyrrolidone (PVP) [28-30],

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

LIBs can be improved by morphology shape engineering.

To clarify the effect of additives on membrane morphology and battery performance,

a serial of spongy-like PEI membranes with different pore size were constructed using

phase inversion method by introducing different content of PVP in the casting

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

performance were studied in detail. The relationship between membranes morphology

and battery performance was established, which provided an effective way to

construct high-performance separators for LIBs. Compared to previous reported work

[32, 33], in which membranes morphologies (from sponge-like morphology to

finger-like morphology) were adjusted by controlled parameters when fabricating

PEI-related composite membranes via a phase inversion process, even though a

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,

the relationship between membranes morphology and battery performance was

established , which provided an effective and simple way to construct

high-performance separators for lithium-ion batteries. And a comparative study with

the reported work have been given in Table S1.

Scheme 1. Schematic principle of membranes with sponge-like structure.

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

1-Methyl-2-pyrrolidinone to form a 20 wt% solution. Then the solution was casted

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 were immersed in deionized water 24 h to remove PVP from prepared

membranes. Finally, the obtained membranes were dried completely at 50 oC. The

detailed composition of the resulted membranes was shown in Table 1.

2.2 Physical characterization

The membranes morphologies, including surface and cross-section morphologies

were characterized by scanning electron microscope (SEM) (JSM-7800F).

The dimensional thermo-stability of prepared PEI membranes and commercial PE

separators at different temperature was characterized by storing them at a certain

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

following Eq. (1):

Shrinkage (%) = (S0 - S1)/S0 × 100% (1)

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

membranes was conducted on a drop shape analysis system (Powereach JC2000C1,

Shanghai Zhongchen Digtal Technology Apparatus Co., Ltd.). And the electrolyte

spreading test was analyzed by dipping electrolyte onto the membrane surface and

observed its diffusion phenomenon.

The liquid electrolyte uptake (U) of membranes was measured by immersing the

membrane in the liquid electrolyte (1 M LiPF6 in ethylene carbonate (EC), dimethyl

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):

U (%) = (M1 - M0)/M0 × 100% (2)

where the M0 and M1 are the weight of membrane before and after immersing in the

electrolyte.

The porosity of membranes was measured by immersing the membrane in n-butanol

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):

Porosity (%) = (m1/ρ1)/(m1/ρ1 + m2/ρ2) × 100% (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

following Eq. (4):

Δδs-p = [(δdp - δds)2 + (δpp – δps)2 + (δhp – δhs)2]1/2 (4)

δd, electrolyte = (δd, EC + δd, DMC + δd, EMC)/3 (5)

δp, electrolyte = (δp, EC + δp, DMC + δp, EMC)/3 (6)

δh, electrolyte = (δh, EC + δh, DMC + δh, EMC)/3 (7)

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

and the solvent.

2.3 Electrochemical characterization

In order to evaluate the ionic conductivity (σ) of membranes, the bulk impedance (Rb)

of a membrane was measured firstly on an electrochemical impedance spectroscopy

(EIS) (Solartron 1287 electrochemical work station) by sandwiching the

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

conductivity (σ) can be calculated according to the following Eq. (5):

σ = d/(Rb × S) (8)

11
where the d and S are the thickness and area of the membrane respectively.

Electrochemical stability of a membrane was measured on an electrochemical system

(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.

To investigate the battery performance of a battery with different membrane, LiFePO4

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

window during galvanostatic charge−discharge test was 2.0 - 4.2 V.

3. Results and discussion

A serial of PEI porous membranes were fabricated by a typical phase inversion

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

sponge-like microstructure, which were the typical morphologies of membranes

prepared by the phase version method. The sponge-like microstructure was

determined by the thermodynamic and kinetic factors. On one hand, an even

concentration system, which was composed of polymer, solvent and nonsolvent,

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

phase. Finally, leading to the formation of the sponge-like microstructure. On the

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

by PVP polymer became pores.

13
Fig. 1. The morphologies of prepared a serial of PEI membranes. (a-d) The

cross-section morphology of a serial of PEI membranes (a: PEI-0, b: PEI-1, c: PEI-2,

d: PEI-3). (a1-d1) The surface morphology of a serial of PEI membranes faced to air

(a1: PEI-0, b1: PEI-1, c1: PEI-2, d1: PEI-3).

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

angle of PE separators and PEI-2 membranes.

The electrolyte wetting performance of a membrane was an important factor that

affected the battery performance. The electrolyte wetting behavior on membranes

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

membranes exhibited superior electrolyte wettability compatibility than PE

separators.

Table 1 Physical properties of a serial of PEI membranes and PE separators.

Sample Mass ratio of Porosity Gurley value Electrolyte Ion conductivity

PVP/PEI [%] [sec. 100 mL-1] Uptake [%] [S cm-1, 25 oC]

PE — 40.4% 20 110.8% 6.52*10-4

PEI-0 0/1 68.6% 147 189.9% 5.08*10-4

PEI-1 1/4 76.2% 128 282.2% 5.95*10-4

PEI-2 1/3 78.2% 115 306.1% 6.35*10-4

PEI-3 1/2.33 80.0% 106 332.0% 6.53*10-4

16
Table 2 The Hansen solubility parameters of the solvent and polymer, and the

solubility parameter difference between solvent and polymer.

Sample δd δp δh δt Δδs-p Ref

EC 19.4 21.7 5.1 29.55 — [35]

DMC 15.5 3.9 9.7 18.7 — [35]

EMC 16.05 3.5 7.9 18.23 — [35]

Electrolyte 16.98 9.7 7.567 20.97 — [35]

PE 16.9 0.8 2.8 17.15 10.1 [36]

PEI 21.1 7.4 7.1 23.46 4.74 [34]

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 increased with increasing amount of PVP in solution. For PEI-2

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

that of a PE separator, which indicated the electrochemical performance of PEI-2

membranes was comparable with PE separators. Thus, the PEI-2 membranes were

chosen as a representative for further study. The mechanical properties of prepared

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

induced by a higher porosity of a membrane, . The mechanical strength is much lower

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).

18
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.

The dimensional thermo-stability test and thermogravimetry analysis were conducted

to evaluate the thermal stability of prepared membranes. The dimensional

thermo-stability was determined by the area change of membranes before and after

heat-treatment at a certain temperature. As shown in Fig. 3, the commercial PE

separators showed remarkably dimensional shrinkage with the increasing of

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

showed superior high dimensional thermo-stability, with no dimensional shrinkage

19
observed even at 180 oC. The results indicated that the PEI-2 membranes showed very

superior thermal stability and will provide excellent safety characteristic for LIBs. In

addition, the thermogravimetry analysis was further conducted under an atmosphere

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

showed much higher thermal stability than the commercial PE separators.

Fig. 4. The thermogravimetric curves of PE separators and PEI-2 membranes.

20
Fig. 5. The linear sweep voltammetry curves of the SS/separator/SS battery with the

PE separator and PEI-2membrane.

The electrochemical stability of separators in electrolyte determined its feasibility in

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

about 4.5 V versus Li+/Li, which indicated that electrochemical stability of

electrolyte-soaked PE separators was up to 4.5 V. The electrolyte-soaked PEI-2

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

of batteries with PEI-2 membranes and PE separators at 1 C. (d) The

charging-discharging curves of batteries with PEI-2 membranes and PE separators at

1 C.

The electrochemical performance of membranes was evaluated by LiFePO4/Li half

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

separators after the 30th and 100th cycle at 1 C.

The cycle performance of membranes was a significant factor to ensure possibility of

a long-term operation of the LIBs. As shown in Fig. 6, the cycle performance of

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

porous membranes exhibited a very promising prospect in LIBs.

4. Conclusions

In summary, a serial of PEI porous membranes with tunable morphology were

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

membranes with proper pore morphology show promising prospect in LIBs.

Acknowledgments

This research is supported by the financial support from the China Natural Science

Foundation (Grant Nos. 21476224), Key project of Frontier Science, Chinese

Academy of Sciences CAS (QYZDB-SSW-JSC032).

25
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Figure and Table Captions

Scheme 1. Schematic principle of membranes with sponge-like structure.

Fig. 1. The morphologies of prepared a serial of PEI membranes. (a-d) The

cross-section morphology of a serial of PEI membranes (a: PEI-0, b: PEI-1, c: PEI-2,

d: PEI-3). (a1-d1) The surface morphology of a serial of PEI membranes faced to air

(a1: PEI-0, b1: PEI-1, c1: PEI-2, d1: PEI-3)

Fig. 2. The wettability of membranes with electrolyte. (a) The Photograph of wetting

behavior (Left: without electrolyte, Right: with electrolyte) and (b) electrolyte contact

angle of PE separators and PEI-2 membranes.

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. 4. The thermogravimetric curves of PE separators and PEI-2 membranes.

Fig. 5. The linear sweep voltammetry curves of the SS/separator/SS battery with the

PE separator and PEI-2 membrane.

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

of batteries with PEI-2 membranes and PE separators at 1 C. (d)The

charging-discharging curves of batteries with PEI-2 membranes and PE separators at

1 C.

Fig. 7. Nyquist plots of LiFePO4/Li batteries containing PEI-2 membranes and PE

31
separators after the 30th and 100th cycle at 1 C.

Table 1. Physical properties of a serial of PEI membranes and PE separators.

Table 2. The Hansen solubility parameters of the solvent and polymer, and the

solubility parameter difference between solvent and polymer.

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.

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