Effect of succinonitrile on the structural, ion conductivity, and dielectric properties of PVDF-HFP based solid polymer electrolytes

IF 2.7 3区 化学 Q2 POLYMER SCIENCE
Iqra Rani, Sajal Arwish, Khizar Hayat Khan, Muddassir Zamurad, Syed Mujtaba Shah, Hazrat Hussain
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Abstract

A detailed account of the poly(vinylidene difluoride-co-hexafluoropropylene) (PVDF-HFP)/succinonitrile (SN)/lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) based solid polymer electrolytes (SPEs) of various compositions is reported. SN is incorporated as plasticizer, while LiTFSI is employed as the source of lithium ions. Fourier transfer infrared (FTIR) spectroscopy reveals the formation of polar and electroactive γ crystal phase by PVDF in pristine PVDF-HFP and the prepared SPE films. FTIR further confirms the interaction between the host polymer and the salt and between the salt and the plasticizer. The interaction between the salt and plasticizer suggests that SN not only offers the plasticization effect but also facilitates salt dissociation. The ion conductivity increases with increasing salt content up to 20 wt% but beyond that concentration a decline in ion conductivity is observed, which could be attributed to the ion pair association or cluster formation due to the excess salt concentration that reduces the availability of free ions and ultimately leads to the reduction in ion conductivity. After including SN in the SPE formulation, electrochemical impedance spectroscopy reveals a substantial increase in room temperature ion conductivity of the SPE from ~1.08 × 10−5 S cm−1 for pristine SPE with 20 wt% salt to ~2.7 × 10−4 S cm−1 for plasticized SPE with 40 wt% SN and 20 wt% salt. This is attributed to the plasticizing effect of SN that enhances ion mobility through the matrix and to the increased charge carrier concentration (SN facilities salt dissociation). The fabricated SPEs exhibit a significant enhancement in ion conductivity with increasing temperature and the maximum ion conductivity of 1.1 × 10−3 S cm−1 is attained at 393 K by plasticized SPE with 40 wt% SN content. The ion conductivity of all the prepared SPEs follows the temperature dependent Arrhenius behavior, suggesting the thermally activated ion hopping mechanism of ionic conduction. Further, the plasticized SPEs display near unity ion transference number indicating the predominance of the ionic mode of conduction. The dielectric and electric modulus analysis reveal a faster relaxation phenomenon and hence higher ion conductivity of the prepared SPEs with increasing salt and plasticizer content.

Abstract Image

丁二腈对PVDF-HFP基固体聚合物电解质结构、离子电导率和介电性能的影响
详细介绍了不同组成的聚偏二氟乙烯-共六氟丙烯(PVDF-HFP)/丁二腈(SN)/锂二(三氟甲磺酰基)亚胺(LiTFSI)基固体聚合物电解质(spe)。SN作为增塑剂,LiTFSI作为锂离子源。傅里叶转移红外光谱(FTIR)揭示了PVDF在原始PVDF- hfp和制备的SPE薄膜中形成极性和电活性γ晶体相。FTIR进一步证实了宿主聚合物与盐以及盐与增塑剂之间的相互作用。盐与增塑剂的相互作用表明,SN不仅具有增塑剂的作用,而且有利于盐的解离。离子电导率随着盐含量的增加而增加,最高可达20 wt%,但在此浓度之外,观察到离子电导率下降,这可能是由于过量盐浓度降低了自由离子的可用性,从而导致离子对结合或簇形成,最终导致离子电导率降低。在SPE配方中加入SN后,电化学阻抗谱显示,SPE的室温离子电导率从含20 wt%盐的原始SPE的~1.08 × 10−5 S cm−1大幅增加到含40 wt% SN和20 wt%盐的塑化SPE的~2.7 × 10−4 S cm−1。这是由于SN的塑化作用增强了离子在基体中的迁移率,并增加了载流子浓度(SN促进了盐的解离)。随着温度的升高,制备的SPE的离子电导率显著提高,在393 K时,SN含量为40 wt%的塑化SPE的离子电导率达到了1.1 × 10−3 S cm−1。所有制备的spe的离子电导率都遵循温度相关的Arrhenius行为,表明离子电导率存在热激活的离子跳变机制。此外,塑化的spe显示出接近1的离子转移数,表明离子传导模式的优势。电介质和电模量分析表明,随着盐和增塑剂含量的增加,制备的spe具有更快的弛豫现象和更高的离子电导率。
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来源期刊
Journal of Applied Polymer Science
Journal of Applied Polymer Science 化学-高分子科学
CiteScore
5.70
自引率
10.00%
发文量
1280
审稿时长
2.7 months
期刊介绍: The Journal of Applied Polymer Science is the largest peer-reviewed publication in polymers, #3 by total citations, and features results with real-world impact on membranes, polysaccharides, and much more.
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