离子液体凝胶聚合物电解质的三元组分相互作用研究

doi:10.13208/j.electrochem.191120

电化学（中英文） ›› 2020, Vol. 26 ›› Issue (3): 406-412. doi: 10.13208/j.electrochem.191120

离子液体凝胶聚合物电解质的三元组分相互作用研究

潘晓娜¹, 刘丽来², 王治璞¹, 王丹¹, 李云¹, 杨培霞¹^*(), 张锦秋¹, 安茂忠¹

1. 哈尔滨工业大学化工与化学学院,黑龙江哈尔滨 150001
2. 黑龙江科技大学环境与化工学院,黑龙江省哈尔滨 150001

收稿日期:2019-11-20 修回日期:2020-01-05 出版日期:2020-06-28 发布日期:2020-02-14
通讯作者: 杨培霞 E-mail:yangpeixia@hit.edu.com
基金资助:
国家自然基金项目（No. 21878061）和国家自然科学基金项目（No. 51604102）资助

The Interaction of Ternary Components of Ionic Liquid Gel Polymer Electrolytes for Lithium Metal Batteries

PAN Xiao-na¹, LIU Li-lai², WANG Zhi-pu¹, WANG Dan¹, LI Yun¹, YANG Pei-xia¹^*(), ZHANG Jin-qiu¹, AN Mao-zhong¹

1. School of Chemistry and Chemical Engineering, Harbin Institute of Technology, Harbin 150001,Heilongjiang
2. School of Environment and Chemical Engineering, Heilongjiang University of Science and Technology, Harbin 150001, Heilongjiang

Received:2019-11-20 Revised:2020-01-05 Published:2020-06-28 Online:2020-02-14
Contact: YANG Pei-xia E-mail:yangpeixia@hit.edu.com

摘要/Abstract

摘要：

采用Raman光谱、傅里叶转换红外光谱和X-射线衍射光谱研究N-甲基-N-丙基哌啶双三氟甲磺酸亚胺离子液体（PP13TFSI）和双三氟甲磺酸亚胺锂盐（LiTFSI）对PVDF-HFP聚合物聚合方式的影响,结果表明,PP13TFSI、LiTFSI和PVDF-HFP是共混存在的,同时加入PP13TFSI和LiTFSI会使聚合物的聚合方式由晶体结构转变为无定形结构. 通过对电解质及其各组分的线性扫描伏安曲线和热重曲线分析可知,溶剂N-甲基吡咯烷酮（NMP）容易残留在凝胶聚合物电解质（ILGPE）中,这会降低ILGPE的电化学稳定性和热稳定性. 作者对固态LiFePO₄|ILGPE|Li电池的倍率性能进行了研究,实验结果表明其具有较好的倍率性能,当电池倍率由C/10增大至2C,然后再回到C/10时,其容量可以恢复到原来的90.9%左右. 该研究结果对理解PP13TFSI和LiTFSI在ILGPE中的作用机理具有重要的意义.

关键词: 离子液体聚合物电解质, 电化学稳定性, 热稳定性

Abstract:

Ionically conductive gel polymer electrolyte is an excellent candidate due to its inflammable, nonvolatile and high thermal stability as compared to commercial liquid electrolytes which are usually flammable, volatile, and containing toxic organic solution as solvent, The synthesis and application of ionic gel polymer electrolytes in lithium ion/metal batteries have been previously reported. However, the interaction effects of N-methyl-N-propylpiperidinium bis(trifluoromethanesulfonyl)imide (PP13TFSI) ionic liquid (as plasticizer) and lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) on PVDF-HFP polymer remain unclear. In this work, the molecular structure of ionic liquid gel polymer electrolyte (ILGPE) composed of PP13TFSI, LiTFSI and PVDF-HFP was studied by Raman spectroscopy and Fourier-transform infrared spectroscopy (FTIR). Meanwhile, X-ray diffraction (XRD) analysis was performed to qualify the crystallization of PVDF-HFP polymer in the ILGPE with or without PP13TFSI or/and LiTFSI to investigate ionic liquid or/and LiTFSI impact on PVDF-HFP polymer. The results showed that PP13TFSI, LiTFSI and PVDF-HFP were physical-blending without chemical reaction, but with molecular coordination with PVDF-HFP polymer chain. In addition, the crystallization of PVDF-HFP could be changed by additions of PP13TFSI and LiTFSI at the same time, and the ionic conductivity could be improved with increasing amorphous phase in polymer matrix. The electrochemical stability window and thermal stability of ILGPE became worse with the N-methyl-2-pyrrolidone (NMP) residue inside the ILGPE. The LiFePO₄/Li battery with the optimized ILGPE (the weight ratio of ionic liquid, LiTFSI, and PVDF-HFP polymer was 3/1/1) showed a good C-rate capability at room temperature. In summary, PP13TFSI and LiTFSI could coordinate with PVDF-HFP polymer chain, and no chemical reaction took place among the three compounds during preparing ILGPE. Furthermore, it is necessary to remove NMP solvent from ILGPE during drying process to improve the electrochemical stability window and thermal stability of ILGPE.

Key words: ionic liquid gel polymer electrolyte, electrochemical stability, thermal stability

中图分类号:

O646

潘晓娜, 刘丽来, 王治璞, 王丹, 李云, 杨培霞, 张锦秋, 安茂忠. 离子液体凝胶聚合物电解质的三元组分相互作用研究[J]. 电化学（中英文）, 2020, 26(3): 406-412.

PAN Xiao-na, LIU Li-lai, WANG Zhi-pu, WANG Dan, LI Yun, YANG Pei-xia, ZHANG Jin-qiu, AN Mao-zhong. The Interaction of Ternary Components of Ionic Liquid Gel Polymer Electrolytes for Lithium Metal Batteries[J]. Journal of Electrochemistry, 2020, 26(3): 406-412.

导出引用管理器 EndNote|Ris|BibTeX

链接本文: https://electrochem.xmu.edu.cn/CN/10.13208/j.electrochem.191120

https://electrochem.xmu.edu.cn/CN/Y2020/V26/I3/406

图/表 5

图1

图2

图3

图4

图5

参考文献 21

[1]	Ai X P( 艾新平), Gao Y L( 曹余良), Yang H X( 杨汉西). Self-activating safety mechanisms for Li-ion batteries[J]. Journal of Electrochemistryl( 电化学), 2010,16(1):6-10.
[2]	Chen D Q( 陈丁琼), Yang Y( 杨阳), Li Q L( 李秋丽), et al. Research progresses in Si-based anode materials for lithium-ion batteries[J]. Journal of Electrochemistryl( 电化学), 2011,22(5):489-488.
[3]	Yang Y( 杨勇). 锂离子电池的发现与发展-兼谈电池材料与固态电化学[J]. Journal of Electrochemistryl( 电化学), 2019,25(5):614-615.
[4]	Gu Y R( 顾月茹), Zhao W M( 赵卫民), Su C H( 苏长虎), et al. Reaearch progress in improvement for low temperature performance of lithium-ion batteries[J]. Journal of Electrochemistryl( 电化学), 2018,24(5):488-496.
[5]	Sheng O W, Jin C B, Luo J M, et al. Mg₂B₂O₅ nanowire enabled multifunctional solid-state electrolytes with high ionic conductivity, excellent mechanical properties, and flame-retardant performance[J]. Nano Letters, 2018,18(5):3104-3122. URL pmid: 29692176
[6]	Park K, Yu B C, Goodenough J B. Electrochemical and chemical properties of Na₂NiO₂ as a cathode additive for a rechargeable sodium battery[J]. Chemistry of Materials, 2015,27(19):6682-6688.
[7]	Yi J, Liu X Z, Guo S H, et al. Novel stable gel polymer electrolyte?: toward a high safety and long life Li-air battery[J]. ACS Applied Materials and Interface. 2015,42(7):23798-23804.
[8]	Pan X N, Liu T Y, Kauz D J, et al. High-performance N-methyl-N-propylpiperidinium bis(trifluoromethanesulfonyl)imide/poly(vinylidene fluoride-hexafluoropropylene) gel polymer electrolytes for lithium metal batteries[J]. Journal of Power Sources, 2018,403:127-136. doi: 10.1016/j.jpowsour.2018.09.080 URL
[9]	Raji A R O, Salvatierra R V, Kim N D, et al. Lithium batteries with nearly maximum metal storage[J]. ACS Nano, 2017,11:6362-6369. URL pmid: 28511004
[10]	Stich M, Göttlinger M, Kurniawan M, et al. Hydrolysis of LiPF₆ in carbonate-based electrolytes for lithium-ion batteries and in aqueous media[J]. Journal of Physical Chemistry C, 2018,122(16):8836-8842.
[11]	Kawamura T, Kimura A, Egashira M, et al. Thermal stability of alkyl carbonate mixed-solvent electrolytes for lithium ion cells[J]. Journal of Power Sources, 2002,104(2):260-264.
[12]	Hu G X( 胡广侠), Xie J Y( 解晶莹). Some consideration for lithium-ion cells safety[J]. Journal of Electrochemistryl( 电化学), 2002,8(3):245-251.
[13]	Chen Y H( 陈玉红), Tang Z Y( 唐致远), He Y B( 贺艳兵), et al. Research of explosion mechanism of lithium-ion battery[J]. Journal of Electrochemistryl( 电化学). 2006,12(3):266-270.
[14]	Yang N C( 杨纳川), Wang Y( 王玉), Shuai Y( 帅毅), Chen K H( 陈康华). Research on preparation and properties of low cost sulfide solid electrolytes Li₆-_xPS₅-_xCl_x[J]. Journal of Electrochemistryl( 电化学), DOI: 10.13208/j.electrochem.190715.
[15]	Cheng H( 程琥), Nie X Y( 聂晓燕), Shen Y D( 申叶丹). Performance of piperidine ionic liquid based mixed electrolyte in Li/LiCoO₂ cell[J]. Journal of Electrochemistryl( 电化学), 2017,23(1):59-63.
[16]	Jin Y D, Zhang J H, Song J Z, et al. Functionalized ionic liquids based on quaternary ammonium cations with two ether groups as new electrolytes for Li/LiFePO₄ secondary battery[J]. Journal of Power Sources, 2014,254:137-147. doi: 10.1016/j.jpowsour.2013.12.048 URL
[17]	Liu Z D, Feng Y, Li W L. High dielectric constant and low loss of polymeric dielectric composites filled by carbon nanotubes adhering BaTiO₃ hybrid particles[J]. RSC Advances, 2015,5(37):29017-29021. doi: 10.1039/C5RA00639B URL
[18]	Wang W, Alexandridis P. Composite polymer electrolytes: nanoparticles affect structure and properties[J]. Polymers, 2016, 8(11): UNSP 387. doi: 10.3390/polym8110387 URL pmid: 30974666
[19]	Zhang X Y, Yang L, Hao F, et al. Lithium-excess research of cathode material Li₂MnTiO₄ for lithium-ion batteries[J]. Nanomater, 2015,5(4):1985-1994. doi: 10.3390/nano5041985 URL
[20]	Wang C, Zhang H R, Li J D, et al. The interfacial evolution between polycarbonate-based polymer electrolyte and Li-metal anode[J]. Journal of Power Sources, 2018,397:157-161.
[21]	Song A M, Huang Y, Zhong X P, et al. Gel polymer electrolyte with high performances based on pure natural polymer matrix of potato starch composite lignocellulose[J]. Electrochimica Acta, 2017,245:981-992.

离子液体凝胶聚合物电解质的三元组分相互作用研究

The Interaction of Ternary Components of Ionic Liquid Gel Polymer Electrolytes for Lithium Metal Batteries

RichHTML

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

图/表 5

参考文献 21

相关文章 6

Metrics

[1]	韦冬萍, 胡荣宗, 潘丹梅, 黄维雄, 董瑞, . 碳钢在N-甲基二乙醇胺介质中的电化学阻抗谱研究[J]. 电化学（中英文）, 2007, 13(4): 387-391.
[2]	陈玉红;唐致远;贺艳兵;刘强;. 锂离子电池爆炸机理分析[J]. 电化学（中英文）, 2006, 12(3): 266-270.
[3]	王军红,刘建敏,杨化滨,周作祥. PVA碱性凝胶聚合物电解质薄膜电化学稳定性研究[J]. 电化学（中英文）, 2005, 11(2): 129-132.
[4]	刘汉三,李劼,龚正良,张忠如,杨勇. LiNi_(0.8-y)Ti_yCo_(0.2)O_2电极材料中钛离子掺杂作用机理的研究[J]. 电化学（中英文）, 2005, 11(1): 46-52.
[5]	王廷勇,许立坤,陈光章. 混合金属氧化物阳极在海水中的电化学性能[J]. 电化学（中英文）, 2002, 8(2): 172-176.
[6]	王廷勇, 许立坤, 陈光章. 铱钽钛金属氧化物阳极的电化学特性[J]. 电化学（中英文）, 2000, 6(1): 72-77.