Electrospun PVdF–PVC nanofibrous polymer electrolytes for polymer lithium-ion batteries

doi:10.1016/j.mseb.2011.09.008

Materials Science and Engineering: B

Volume 177, Issue 1, 25 January 2012, Pages 86-91

https://doi.org/10.1016/j.mseb.2011.09.008 Get rights and content

Abstract

Nanofibrous membranes based on Poly (vinyl difluoride) (PVdF)-Poly (vinyl chloride) (PVC) (8:2, w/w) were prepared by electrospinning and then they were soaked in a liquid electrolyte to form polymer electrolytes (PEs). The morphology, thermal stability, function groups and crystallinity of the electrospun membranes were characterized by scanning electron microscope (SEM), thermal analysis (TG), Fourier transform infrared spectra (FT-IR) and differential scanning calorimetry (DSC), respectively. It was found that both electrolyte uptake and ionic conductivity of the composite PEs increased with the addition of PVC. The composite PVdF–PVC PEs had a high ionic conductivity up to 2.25 × 10⁻³ S cm⁻¹ at 25 °C. These results showed that nanofibrous PEs based on PVdF–PVC were of great potential application in polymer lithium-ion batteries.

Highlights

► The nanofibrous polymer electrolytes based on PVdF–PVC (8:2, w/w) prepared by electrospinning have an ionic conductivity of 2.25 × 10⁻³ S cm⁻¹ at 25 °C. ► The nanofibrous polymer electrolytes presented a good electrochemical stability up to 5.1 V (vs. Li/Li⁺). ► The nanofibrous polymer electrolytes showed a very good charge/discharge and cycling performance.

Introduction

Recently, polymer lithium-ion batteries prepared with PEs have received wide attention, since they are lighter, safer and more flexible in shape compared with their liquid counterparts [1], [2]. To enable the applications of polymer lithium-ion batteries, a polymer electrolyte should possess high ambient temperature conductivity (≥mS cm⁻¹), good dimensional and thermal stability, an electrochemical stability window (≥5.0 V), chemical compatibility with Li electrodes, ability to afford Li cycling at an efficiency of greater than 90% [3], [4]. Therefore, it is very crucial to develop PEs to meet the social needs in the sources of energy.

PVdF which possesses high electrochemical stability, relatively low dissipation factor and high dielectric constant (ɛ ≈ 8.4), has become a favorable polymer matrix for PEs [5], [6], [7]. These features are useful in dissociating the lithium salt to lithium ions while transforming into a polymer electrolyte [8].

One of the problems which restrict the use of PVdF-based PEs is that PVdF is a semi-crystalline material. The crystalline part of PVdF hinders the migration of lithium-ion and hence batteries with PVdF-based PEs have low ionic conductivity and charge/discharge capacities [9], [10].

PVC (ɛ ≈ 3) is a commercially available polymer, which acts as good mechanical stiffener and easy processibility. In the recent years PVC-based PEs got their popularity due to their inexpensive price and good compatibility with many polymers [11], [12], [13]. Many literatures [14], [15], [16] showed that PVdF and PVC can be blended as the PEs. The addition of PVC was used to suppress the crystallinity and enhance the ionic conductivity.

Electrospinning has received significant attention in recent years as a method to prepare nanofibrous membranes. The membrane prepared by electrospinning is composed of ultra-fine fibers with diameters in the range of several micrometers to tens of nanometers [17], [18], [19]. Electrospinning technology has been used in a variety of fields like porous filters, biomedical materials, multifunctional composites, electronic devices, etc. [20], [21], [22]. Reports [23], [24], [25], [26] on using electrospinning for preparation of PEs are very familiar. The PEs membranes which provide with large surface area fibers and fully interconnected porous structures are able to uptake large amounts of liquid electrolyte, so the PEs prepared by electrospinning can achieve high ionic conductivity at room temperature [27].

The PEs based on PVdF–PVC prepared by casting technology have been earlier reported by Rajendran et al. [14] and Muniyandi et al. [16]. Their results demonstrated that the PEs prepared by casting technology had a low ionic conductivity and poor cycling behavior. Thus, it is inferred that conventional mixing for the preparation of PEs based on PVdF–PVC could not apply to practice of lithium-ion batteries.

In our study, we have made use of electrospinning to prepare PVdF–PVC (8:2, w/w) composite nanofibrous membranes. The characterization and electrochemical performances of the electrospun PVdF–PVC membranes were investigated. These results showed that PVdF–PVC (8:2, w/w) composite nanofibrous membrane prepared by electrospinning had a good prospect as PEs for lithium-ion batteries.

Section snippets

Materials

PVdF (Alfa, Aesar) and PVC (WS-1000S) were vacuum dried for 12 h at 60 °C before use. The solvent N,N-dimethylformamide (DMF, AR) was used as received. The anhydrous Tetrahydrofuran (THF, AR) was distilled before use. The salt LiClO₄ (AR, Sinopharm chemical Reagent co., Ltd) was dried at 80 °C and kept under vacuum for 72 h before use. The plasticizers ethylene carbonate (EC) and propylene carbonate (PC) with high purity (N 99%) were purchased from Shenzhen capchem technology co., Ltd. and used

Morphology

Fig. 1 shows the SEM images of nanofibrous membranes describing the morphological variations between PVdF and PVC membrane and pure PVdF film. Much important information can be obtained in the morphology of electrospun nanofibrous membranes. Firstly, the electrospun PVdF–PVC membrane and pure PVdF film show a fully interconnected porous structure composed of lots of ultra-fine fibers. Diameters of PVdF–PVC nanofibers are 385–875 nm and the average fiber diameter (AFD) is 624 nm (Fig. 1a).

Conclusions

PVdF–PVC (8:2, w/w) composite nanofibrous membranes were prepared by electrospinning. SEM micrograph showed that there were no bead-fibers in nanofibrous membranes. FT-IR spectroscopy confirms the miscibility of PVC with PVdF in the composite PVdF–PVC membrane. The addition of PVC not only decreased crystallinity, but also promoted electrolyte uptake and ionic conductivity. The maximum ionic conductivity of PEs based on PVdF–PVC (8:2, w/w) composite membranes reached 2.25 × 10⁻³ S cm⁻¹ at 25 °C. The

Acknowledgement

This work was financially supported by the Key Laboratory of Environmentally Friendly Chemistry and Applications of 355 Ministry of Education item (Grant No. 09B101), and the Youth Project of National Nature Science Foundation of China (Grant No. 51103124).

References (43)

T. Iwahori et al.
Electrochim. Acta
(2000)
A.I. Gopalan et al.
J. Membr. Sci.
(2008)
J.K. Kim et al.
J. Power Sources
(2008)
Z. Jiang et al.
Electrochim. Acta
(1997)
K. Gao et al.
Mater. Sci. Eng. B
(2006)
A.I. Gopalan et al.
J. Membr. Sci.
(2008)
S. Abbrent et al.
Polymer
(2001)
Y. Wang et al.
Solid State Ionics
(2002)
S. Ramesh et al.
Eur. Polym. J.
(2007)
H.J. Rhoo et al.
Electrochim. Acta
(1997)

S. Rajendran et al.

J. Membr. Sci.

(2008)

S. Rajendran et al.

J. Power Sources

(2007)

P. Vickraman et al.

Mater. Lett.

(2006)

N. Muniyandi et al.

J. Power Sources

(2001)

N. Bhardwaj et al.

Biotechnol Adv.

(2010)

K.M. Manesh et al.

Biosens. Bioelectron.

(2008)

X. Li et al.

J. Power Sources

(2007)

G. Cheruvally et al.

J. Power Sources

(2007)

D. Bansal et al.

J. Power Sources

(2008)

J.K. Kim et al.

Electrochim. Acta

(2010)

Q.Z. Xiao et al.

J. Membr. Sci.

(2009)

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Short communicationElectrospun PVdF–PVC nanofibrous polymer electrolytes for polymer lithium-ion batteries

Abstract

Highlights

Introduction

Section snippets

Materials

Morphology

Conclusions

Acknowledgement

Electrochim. Acta

J. Membr. Sci.

J. Power Sources

Electrochim. Acta

Mater. Sci. Eng. B

J. Membr. Sci.

Polymer

Solid State Ionics

Eur. Polym. J.

Electrochim. Acta

J. Membr. Sci.

J. Power Sources

Mater. Lett.

J. Power Sources

Biotechnol Adv.

Biosens. Bioelectron.

J. Power Sources

J. Power Sources

J. Power Sources

Electrochim. Acta

J. Membr. Sci.

Short communication
Electrospun PVdF–PVC nanofibrous polymer electrolytes for polymer lithium-ion batteries