L Yesappa, M Niranjana, P Ashokkumar S, H Vijeth, M Basappa, Dwivedi Jishnu, Petwal V C, S Ganesh, H Devendrappa
Department of Physics, Mangalore University Mangalagangothri-574199 India
Head, Industrial Accelerators Division RRCAT Indore-452013 India.
RSC Adv. 2018 Apr 23;8(28):15297-15309. doi: 10.1039/c8ra00970h.
The influence of 8 MeV energy electron beam (EB) irradiation on optical properties and ionic conductivity of PVDF-HFP/LiClO (90 : 10 PHL10) electrolyte film with 40, 80 and 120 kGy doses. The FT-IR results show that C[double bond, length as m-dash]O bond stretching at 1654 cm is due to the degradation of polymer chains and the CH bond wagging intensity at 1405 cm corresponds to C-H bond scissioning in the 120 kGy dose irradiated film. H and C NMR spectroscopy was performed and the C NMR spectra confirm the effect of EB irradiation of the PHL10 polymer electrolyte by sharpening and splitting the spectral lines with increasing EB dose and revealing a new spectral line at 162.80 ppm with a 120 kGy EB dose. The size and shape of the porous morphology was drastically changed, becoming deeply porous with a visible inner hollow shaped structure, suggesting increased amorphous character upon irradiation. The absorption band of the unirradiated film observed at 202 nm in the ultraviolet region is shifted to 274 nm after irradiation due to inter band transition of electrons from the valence band to the conduction band and the optical band gap decreasing from 3.49 eV in the unirradiated film to 2.64 eV with a 120 kGy EB dose. Segmental motion in the polymer matrix leads to a decrease in the local viscosity by increasing the mobility of ions upon irradiation. Nyquist plots show semicircles at high frequency due to Li-ion migration through the porous surface of the electrolyte film. A maximum ionic conductivity of 8.28 × 10 S cm was obtained with a 120 kGy EB dose and the observed cyclic voltammetry of the irradiated polymer electrolyte suggests it is electrochemically stable.
8兆电子伏特能量的电子束(EB)辐照对剂量为40、80和120千戈瑞的聚偏氟乙烯-六氟丙烯/高氯酸锂(90∶10质量比,PHL10)电解质薄膜光学性能和离子电导率的影响。傅里叶变换红外光谱(FT-IR)结果表明,1654厘米处的C=O键伸缩归因于聚合物链的降解,而1405厘米处的CH键摇摆强度对应于120千戈瑞剂量辐照薄膜中的C-H键断裂。进行了氢和碳核磁共振光谱分析,碳核磁共振光谱证实了EB辐照对PHL10聚合物电解质的影响,随着EB剂量增加,谱线变尖锐并分裂,且在120千戈瑞EB剂量下出现了一条位于162.80 ppm的新谱线。多孔形态的尺寸和形状发生了显著变化,变得具有深孔且内部有可见的中空结构,表明辐照后非晶特性增加。未辐照薄膜在紫外区域202纳米处观察到的吸收带在辐照后由于电子从价带向导带的带间跃迁而移至274纳米,并且光学带隙从未辐照薄膜中的3.49电子伏特降至120千戈瑞EB剂量下的2.64电子伏特。聚合物基体中的链段运动通过辐照时增加离子迁移率导致局部粘度降低。奈奎斯特图显示在高频处有半圆,这是由于锂离子通过电解质薄膜的多孔表面迁移所致。在120千戈瑞EB剂量下获得了8.28×10⁻⁵ S/cm的最大离子电导率,并且观察到的辐照聚合物电解质的循环伏安法表明它在电化学上是稳定的。