用于聚合物镍氢电池的新型PVA/SiO2碱性微孔聚合物电解质

doi:10.6023/A12110871

化学学报 ›› 2013, Vol. 71 ›› Issue (03): 427-432.DOI: 10.6023/A12110871 上一篇下一篇

研究论文

用于聚合物镍氢电池的新型PVA/SiO₂碱性微孔聚合物电解质

陆霞, 吴仁香, 李波波, 朱云峰, 李李泉

南京工业大学材料科学与工程学院南京新模范马路5号 210009

投稿日期:2012-11-05 发布日期:2013-02-01
通讯作者: 李李泉 E-mail:lilq@njut.edu.cn
基金资助:
项目受国家自然科学基金(Nos.51171079,51071085),教育部高等学校博士学科点专项科研基金(No.20093221110008)和江苏高校优势学科建设工程项目(PAPD)资助.

Novel PVA/SiO₂ Alkaline Micro-porous Polymer Electrolytes for Polymer Ni—MH Batteries

Lu Xia, Wu Renxiang, Li Bobo, Zhu Yunfeng, Li Liquan

College of Materials Science and Technology, Nanjing University of Technology, Nanjing 210009

Received:2012-11-05 Published:2013-02-01
Supported by:
Project supported by National Natural Science Foundation of China (Nos. 51171079, 51071085), Specialized Research Fund for the Doctoral Program of High Education (No. 20093221110008) and Priority Academic Program Development of Jiangsu Higher Education Institutions (PAPD).

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摘要/Abstract

采用溶胶凝胶法, 结合相转移法和碱液活化法制备了PVA/SiO₂碱性微孔聚合物电解质, 通过SEM、XRD、交流阻抗法和循环伏安法表征了电解质的结构与电化学性能. 研究表明, PVA/5 ω SiO₂ (ω为质量分数)共混膜上的微孔大小合适, 聚合物电解质的离子电导率最大可达1.62×10^-2 S·cm^-1, 电化学稳定窗口2 V以上; 将PVA/SiO₂碱性微孔电解质组装成聚合物镁基镍氢电池, 与传统镍氢电池相比, 循环稳定性大大增加.

关键词: 聚乙烯醇, 碱性微孔聚合物电解质, 离子电导率, 循环稳定性, 聚合物Ni-MH电池

New poly(vinyl alcohol)/silica (designated as PVA/SiO₂) alkaline micro-porous polymer electrolytes (AMPEs) were prepared by soaking PVA/SiO₂ micro-porous composite membranes, obtained by solution casting of PVA/PEG/SiO₂ membrane in acetone solution, into an electrolyte solution of 6 mol/L KOH aqueous solution. The morphology and structure of PVA/SiO₂ composite polymer membranes were characterized by scanning electron microscopy (SEM) and X-Ray diffraction (XRD). The SEM photographs showed that the nano-SiO₂ filler content was a crucial issue for the well-dispersed and optimal-sized pores which could storage charge carrier durably. Meanwhile, the crystalline of PVA decreased effectively for a large number of crystal defects and free volume appeared in the interface of inorganic particles and polymer for the addition of nano-SiO₂ filler. The electrochemical properties of the AMPEs were measured by the alternating current impedance (AC impedance) and the cyclic voltammetry (CV) techniques. The results indicated that the PVA/SiO₂ AMPEs containing 5 ω nano-SiO₂ filler exhibited good performances at room temperature, such as 1.62×10^-2S·cm^-1for ionic conductivity and 2.20 V for electrochemical stability window. What's more, we used the gravimetric method to obtain the electrolyte uptake of various PVA/SiO₂ composite micro-porous polymer membranes. From the data, we learned that the maximum electrolyte uptake could reach to 102.7% and it had very relevance to the size of pores in PVA/SiO₂ composite polymer membranes, and then influenced the ionic conductivity. Each polymer Ni-MH battery was assembled by three parts: the new AMPE, Mg-based hydrogen storage alloy and the commercial sintered Ni(OH)₂/NiOOH electrode, in which each part did for electrolyte and diaphragm, negative electrode and positive electrode, respectively. The cycle experiments of the batteries exhibited a high first-cycle discharge capacity of 613 mAh·g^-1 and stable discharge capacities about 330 mAh·g^-1 for the following 5 cycles. The results encouraged that the novel AMPEs are prospective for the applications of polymer electrolyte in Ni-MH battery field.

Key words: PVA, alkaline micro-porous polymer electrolyte, ionic conductivity, cycling stability, polymer Ni-MH battery

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陆霞, 吴仁香, 李波波, 朱云峰, 李李泉. 用于聚合物镍氢电池的新型PVA/SiO₂碱性微孔聚合物电解质[J]. 化学学报, 2013, 71(03): 427-432.

Lu Xia, Wu Renxiang, Li Bobo, Zhu Yunfeng, Li Liquan. Novel PVA/SiO₂ Alkaline Micro-porous Polymer Electrolytes for Polymer Ni—MH Batteries[J]. Acta Chimica Sinica, 2013, 71(03): 427-432.

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用于聚合物镍氢电池的新型PVA/SiO₂碱性微孔聚合物电解质

Novel PVA/SiO₂ Alkaline Micro-porous Polymer Electrolytes for Polymer Ni—MH Batteries

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