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纸质出版日期:2008-5-20,
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王书会, 颜红侠, 马晓燕, 黄韵. MMA/MAh共聚物的合成及其凝胶聚合物电解质性能[J]. 高分子学报, 2008,(5):442-447.
WANG Shuhui, YAN Hongxia, MA Xiaoyan, HUANG Yun. The Synthesis of a MMA/MAh Copolymer and Properties of the CopolymerBased Gel Polymer Electrolytes[J]. Acta Polymerica Sinica, 2008,(5):442-447.
王书会, 颜红侠, 马晓燕, 黄韵. MMA/MAh共聚物的合成及其凝胶聚合物电解质性能[J]. 高分子学报, 2008,(5):442-447. DOI: 10.3724/SP.J.1105.2008.00442.
WANG Shuhui, YAN Hongxia, MA Xiaoyan, HUANG Yun. The Synthesis of a MMA/MAh Copolymer and Properties of the CopolymerBased Gel Polymer Electrolytes[J]. Acta Polymerica Sinica, 2008,(5):442-447. DOI: 10.3724/SP.J.1105.2008.00442.
从聚甲基丙烯酸甲酯型凝胶聚合物电解质存在的问题出发,设计制备一种甲基丙烯酸甲酯/共聚马来酸酐型凝胶聚合物电解质.采用溶液聚合法,以偶氮二异丁腈(AIBN)为引发剂,甲基丙烯酸甲酯(MMA)、顺丁烯二酸酐(MAh)为单体,其MMA与MAh单体摩尔配比为1∶1,合成了P(MMA-co-MAh)共聚物;采用凝胶色谱(GPC)、傅立叶红外光谱(FTIR)、核磁共振(MNR)、示差扫描量热法(DSC)、热失重分析(TGA)、X-射线衍射分析(XRD)对所合成共聚物的结构进行了表征.结果表明,合成的共聚物为无规非晶型聚合物,其数均分子量 Mn为6.40×104,共聚物中MMA与MAh链段摩尔比大约为8∶1,热分解温度为300℃,玻璃化转变温度(Tg)为121.3℃.以 P(MMA-co-MAh)共聚物为树脂基体,环状碳酸1,2-丙二酯(PC)为增塑剂,LiClO4为电解质盐,制备了凝胶聚合物电解质(GPE),当共聚物含量为45 wt%时,GPE具有好的成膜性,其室温离子电导率为3.0×10-5 S/cm.
Poly(methyl methacrylate) (PMMA) is one of the matrix polymers commonly used in gel polymer electrolytes
and has been proposed for lithium battery applications.PMMA-based gel polymer electrolytes (GPE) show high ionic conductivity at ambient temperatures.However
low thermal stability and mechanical properties with hard forming freestanding film in gel systems at high organic solvents will limit its application.In order to overcome these problems
methyl methacrylate (MMA)-maleic anhydride (MAh) (P(MMA-co-MAh) ) copolymer was prepared
in the copolymer the ring structure of MAh units can improve the thermal stability and mechanical properties
consequently
improving the thermal stability of P(MMA-co-MAh)-based gel polymer electrolytes.The copolymer of P(MMA-co-MAh) was synthesized through solution copolymerization with toluene as solvent
2
2′-azobisiobutyronitrile (AIBN) as the initiator
MMA and MAh as the monomers with the molar ratios of MMA∶MAh monomer is 1∶1 The reaction was carried out at 80℃ under nitrogen atmosphere for 8 h. The structure and properties of the copolymer were characterized by Fourier transform infrared spectroscopy (FTIR)
1H-nuclear magnetic resonance (1H-NMR)
X-ray diffraction (XRD)
gel permeation chromatography (GPC)
thermogravimetric analysis (TGA)
differential scanning calorimetry (DSC).It was found that the unsaturated bonds existed in both of MMA and MAh (1637 cm-1) disappeared in the copolymer
whereas a strong absorption peak at 950 cm-1 for O=C-O-C=O ring stretching vibration of a saturated cyclic five-membered anhydride and a peak at 1445 cm-1 for —CO—O—CH3 stretching vibration of MMA were observed in the FTIR spectrum
respectively.The 1H-NMR spectrum of P(MMA-co-MAh) copolymer showed four peaks
and the peaks at δ=2.65~3.20 and 3.5~3.8 represent the chemical shift of H for MAh groups and —COOCH3 groups
respectively
indicating the molecular structure of copolymer P(MMA-co-MAh).The molar ratios of MMA and MAh in the P(MMA-co-MAh) copolymer is 8∶1. XRD showed that the P(MMA-co-MAh) was a typical amorphous polymer
which is beneficial in improvement of ionic conductivity of its GPE.GPC resalts show that the number average molecular weight (Mn) of the copolymer is 6.40×104 and the mass average molecular weight (Mw) is 6.68×104; the molecular weight distribution (Mw/Mn) is 1.04 The TGA curves show that the thermal degradation temperature of P(MMA-co-MAh) is 300℃
which is higher than that of the pure PMMA polymer.The DSC results of the P(MMA-co-MAh) copolymer reveal that the glass transition temperature (Tg) is 121.3℃
which is higher than that of the pure PMMA.The gel polymer electrolyte was prepared from the P(MMA-co-MAh) copolymer
propylene carbonate (PC) and lithium perchlorate.It is found that the GPE can form free-standing films.The ionic conductivity is 3.0×10-5 S/cm at room temperature for 45 wt% P(MMA-co-MAh) gel copolymer enlectrolyte with 55 wt% 1 mol/L LiClO4-PC solution.The ionc conductivity for GPE of P(MMA-co-MAh) copolymer is lower than that of the gel polymer electrolytes of pure PMMA containing 50 wt% PMMA with 50 wt% 1 mol/L LiClO4-PC solution.
P(MMA-co-MAh)凝胶聚合物电解质离子电导率
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