新型聚乙烯醇缩甲醛基凝胶聚合物电解质的热稳定性

doi:10.7503/cjcu20130822

摘要/Abstract

摘要：

采用原位热聚合法制备了聚乙烯醇缩甲醛(PVFM)基凝胶聚合物电解质, 通过差示扫描量热法(DSC)研究了PVFM基凝胶聚合物电解质的热稳定性, 并利用热重-红外/质谱(TGA-FTIR/MS)联用技术比较研究了液态电解质和PVFM基凝胶聚合物电解质升温过程中逸出气体的成分及变化. 结果表明, 相比于液态电解质, 凝胶聚合物电解质中PVFM热聚合产生的三维网络结构可以有效抑制有机溶剂的挥发, 降低体系中HF的含量, 从而改善电解质体系的热稳定性, 提高其应用于锂离子电池的安全性能.

关键词: 锂离子电池, 凝胶聚合物电解质, 聚乙烯醇缩甲醛, 热稳定性, 热重-红外/质谱联用技术

Abstract:

A novel polyvinyl formal(PVFM) based gel polymer electrolyte(GPE) was prepared by means of initiator free in-situ thermal polymerization technology. The thermal stability of electrolytes was studied using differential scanning calorimetry(DSC). And the components of evolved gases from GPE and liquid electrolyte were comparatively analyzed by thermogravimetry-infrared spectrum/mass spectrometry(TGA-FTIR/MS) technique during the heating process. The results show that the macroscopic physical network formed by PVFM after polymerization can prevent the organic solvents from evaporating and reduce HF content at high temperatures effectively. Overall, PVFM based GPE is a promising electrolyte to achieve the enhanced thermal stability and improved safety.

Key words: Lithium-ion battery, Gel polymer electrolyte, Polyvinyl formal, Thermal stability, Thermogravi-metry-Fourier transform infrared spectroscopy/Mass spectrometry combined technique

中图分类号:

TrendMD:

关红艳, 连芳, 文焱, 潘笑容, 孙加林. 新型聚乙烯醇缩甲醛基凝胶聚合物电解质的热稳定性. 高等学校化学学报, 2014, 35(1): 80.

GUAN Hongyan, LIAN Fang, WEN Yan, PAN Xiaorong, SUN Jialin. Thermal Stability of Novel Polyvinyl Formal Based Gel Polymer Electrolyte^†. Chem. J. Chinese Universities, 2014, 35(1): 80.

图/表 6

Fig.1 Molecular structure of PVFM

Fig.2 DSC curves of the PVFM(a), liquid electrolyte(b) and gel polymer electrolyte(c) with scanning rate 10 ℃/min under Ar flux

Fig.3 FTIR spectra of the evolved gas from liquid electrolyte(A) and PVFM based gel polymer electrolyte(B) by TGA-FTIR/MS technology

Fig.4 FTIR spectra of the evolved gas from liquid electrolyte(A) and PVFM basedgel polymer electrolyte(B) at 144 ℃ by TGA-FTIR/MS technology

Fig.5 Thermogravimetry-mass spectrum analysis of the evolved gas from liquid electrolyte(A) and GPE(B) by TGA-FTIR/MS technology

Table 1 Corresponding fragments and their assignments of the evolved gas from electrolytes detected by TGA-FTIR/MS technique*

m/z	LE	GPE	Corresponding fragment	Possible assignment
m/z	T_p/℃	T_p/℃	Corresponding fragment	Possible assignment
15	85	82—150	—CH₃	DMC, EC
18		151	H₂O, ·OH	H₂O, polymerization products
20			HF	Hydrolysis product of LiPF₆
28		82	CH₂CH₂, CO	CO₂/Decomposition products of EC
29	86	83—149	·C₂H₅, ·CHO	DMC, EC
30	87	81—149	CH₂O	EC
31	86	81—149	·CH₃O, ·CH₂OH	DMC
44	86	80	CO₂	Decomposition products of DMC/ring-opening polymerization product of EC
45	86	82—149	·COOH, ·C₂H₅O	DMC
59	84	81—147	·C₂H₃O₂	DMC

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