Ion Transport in Solvent-Free, Crosslinked, Single-Ion Conducting Polymer Electrolytes for Post-Lithium Ion Batteries
Ion Transport in Solvent-Free, Crosslinked, Single-Ion Conducting Polymer Electrolytes for Post-Lithium Ion Batteries
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DOI：
10.3390/batteries4020028
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发表时间：
2018-06-01
期刊：
影响因子：
4
通讯作者：
Schaefer, Jennifer L.
中科院分区：
文献类型：
--
作者：
Elmore, Clay T.;Seidler, Morgan E.;Schaefer, Jennifer L.
无溶剂的单离子导电电解液在电化学储能装置中的应用受到追捧。在这里，我们研究了具有不同系留阴离子和反阳离子类型的交联型单离子导电聚醚基电解液中的离子电导率以及链段迁移率和导电离子数对离子电导率的影响。由聚乙二醇二丙烯酸酯(PEGDA)、聚乙二醇甲基醚丙烯酸酯和离子单体聚合而成的交联型电解质。在差示扫描量热法和拉曼光谱测量的背景下，测量和解释了电解质的离子电导率。用聚乙二醇(31)DA和(4-styrenesulfonyl)(trifluoromethanesulfonyl)imide(STFSI)单体制备的锂离子交联电解液在55℃和100℃时的锂离子电导率分别为3.2x10(-6)和1.8x10(-5)S/cm。经拉曼光谱测定，该电解液中未配对阴离子的比例约为23%。尽管密度泛函理论(DFT)预测的金属阳离子-STFSI结合能有很大差异，离子电导率也有很大变化，但具有相同电荷密度和不同阳离子(Li、Na、K、Mg和Ca)的STFSI基交联电解质估计都有19%到29%的未配对阴离子。
Solvent-free, single-ion conducting electrolytes are sought after for use in electrochemical energy storage devices. Here, we investigate the ionic conductivity and how this property is influenced by segmental mobility and conducting ion number in crosslinked single-ion conducting polyether-based electrolytes with varying tethered anion and counter-cation types. Crosslinked electrolytes are prepared by the polymerization of poly(ethylene glycol) diacrylate (PEGDA), poly(ethylene glycol) methyl ether acrylate, and ionic monomers. The ionic conductivity of the electrolytes is measured and interpreted in the context of differential scanning calorimetry and Raman spectroscopy measurements. A lithiated crosslinked electrolyte prepared with PEG(31) DA and (4-styrenesulfonyl)(trifluoromethanesulfonyl)imide (STFSI) monomers is found to have a lithium ion conductivity of 3.2 x 10(-6) and 1.8 x 10(-5) S/cm at 55 and 100 degrees C, respectively. The percentage of unpaired anions for this electrolyte was estimated at about 23% via Raman spectroscopy. Despite the large variances in metal cation-STFSI binding energies as predicted via density functional theory (DFT) and large variations in ionic conductivity, STFSI-based crosslinked electrolytes with the same charge density and varying cations (Li, Na, K, Mg, and Ca) were estimated to all have unpaired anion populations in the range of 19 to 29%.