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《山东大学学报(理学版)》 ›› 2019, Vol. 54 ›› Issue (1): 1-18.doi: 10.6040/j.issn.1671-9352.9.2018

• 高端论坛 •    下一篇

离子液体凝胶

高娟1,王晓琳2,HOFFMANN Heinz3,郝京诚3,*   

  1. 1. 山东药品食品职业学院基础教学部，山东 淄博 255011
    2. 山东农业大学化学与材料科学学院，山东 泰安 271018
    3. 山东大学胶体与界面化学教育部重点实验室，山东 济南 250100
  • 收稿日期:2018-12-22 出版日期:2019-01-20 发布日期:2019-01-23
  • 通讯作者: 郝京诚
  • 作者简介:郝京诚，男，1964年11月生。山东大学教授、博士生导师。国家杰出青年基金获得者、长江学者特聘教授、山东省泰山学者攀登计划专家、山东省智库高端人才社会建设领域首席专家
    长期从事物理化学教学和胶体与界面化学应用基础研究，在表面活性剂物理化学与性能领域有较高的国际影响，研究成果在提高石油采收率和凝胶技术污水重金属离子吸附净化，以及国家基础材料技术的提升和产业化等方面做出贡献
    曾任第21届国际表面活性剂溶液科学大会主席、亚洲胶体与界面科学联合会主席，2017年增选欧洲科学院Member、2018年增选国际胶体与界面科学联合会Member，现任亚洲胶体与界面科学联合会委员、中国化学会理事。担任Langmuir Senior Editor，任《Adv. Colloid Interface Sci.》《J. Colloid Interface Sci.》《Colloids Surf. A》国际和《物理化学学报》《化学进展》国内期刊编委。山东大学物理化学学科和世界一流化学学科学术带头人之一
    主持国家“973”重大研究计划，国家自然科学基金重点、重大国际合作和面上项目18项。在《Chem. Rev.》《Acc. Chem. Res.》《Chem. Soc. Rev.》《Angew. Chem. Int. Ed.》《JACS》《Langmuir》等期刊发表论文400余篇，撰英文专著2部，其中在《Langmuir》论文超过100篇，所发表论文他引10 000余次。获邀各类国际会议Plenary Lecture和Invited Talk报告40余次。曾获中科院百人计划择优资助、国家杰出青年科学基金、长江学者特聘教授、日本材料技术研究会特别奖、亚洲胶体与界面科学联合会特别奖、CCS-BASF青年知识创新奖、教育部自然科学一等奖(排名1)、亚洲化学新星奖、CCS-AkzoNobel化学奖等
  • 基金资助:
    国家自然科学基金重点国际(地区)合作研究资助项目(2140102006)

Ionic liquid gels

Juan GAO1,Xiao-lin WANG2,Heinz HOFFMANN3,Jing-cheng HAO3,*   

  1. 1. Basic Teaching Department, Shandong Drug and Food Vocational College, Zibo 255011, Shandong, China
    2. School of Chemistry and Material Sciences, Shandong Agricultural University, Taian 271018, Shandong, China
    3. Key Laboratory of Colloid and Interface Chemistry, Jinan 250100, Shandong, China
  • Received:2018-12-22 Online:2019-01-20 Published:2019-01-23
  • Contact: Jing-cheng HAO
  • Supported by:
    国家自然科学基金重点国际(地区)合作研究资助项目(2140102006)

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摘要：

离子液体凝胶是以离子液体为分散介质形成的凝胶，作为一种新型的混合材料，离子液体凝胶不仅保持了离子液体原有的性质，而且解决了离子液体外溢的问题，其在形状上较高的可塑性满足了人们对特殊材料的需求，同时拓展了离子液体的应用范围。离子液体凝胶的种类较多，大致可分为物理型和化学型两大类。离子凝胶的结构、特性和应用目前成为胶体与界面科学家研究热点内容之一，也是近年来软物质科学研究中的主要内容。通过综述近年来离子液体凝胶的构筑、凝胶结构和性能与应用研究取得的进展，为未来离子液体凝胶的构筑及应用提供了重要的理论指导。

关键词: 表面活性剂, 聚集体, 离子液体凝胶, 响应性

Abstract:

Ionic liquid gels (Ionogels) are the kind of gels formed by using ionic liquids as dispersing media. As new mixed materials, ionogels not only keep the original properties of ionic liquids, but also solve the problems of ionic liquid spillover. The high plasticity in shape meets the needs of special materials and expands the application of ionic liquids. There are many kinds of ionogels, which can be divided into physical and chemical types. Recent years, the structures, properties and applications of ionogels have become one of the hot topics in colloid and interface sciences, as well as the main contents of soft matters. The progress in the construction, structures, properties and applications of ionogels in recent years is reviewed and summarized, which can provide an important theoretical guidance for the construction and applications of ionogels in the future.

Key words: surfactant, aggregate, ionic liquid gel, responsibility

中图分类号: 

  • O648

图1

凝胶的不同分类方式[6]"

图2

凝胶的不同刺激响应性质"

图3

不同聚集模式示意图[6]"

图4

分子凝胶自组装过程示意图[8]"

图5

根据液体分散介质对凝胶进行的分类"

图6

不同类型的离子液体凝胶[11]"

图7

体系所用离子液体及所合成的两亲分子化学结构式[12]"

图8

凝胶因子1-6的分子式[13]"

图9

凝胶因子结构式及其在3种溶剂中形成凝胶的微观结构[14]"

图10

ABA三嵌段共聚物的合成路线图[16]"

图11

离子液体凝胶的构筑[17] (a)用于制备微纤维素离子液体凝胶的离子液体结构式及纤维素重复单元；(b)由微纤维素和离子液体[EMIM][Me(EG)2(Me)PO3]构筑的能够自支撑的离子液体凝胶。"

表1

不同SiO2尺寸和离子液体含量下[BMIM][TFSI]/SiO2混合材料的状态[20]"

IL conc.(wt%)
10 20 30 40 50 60 70 80 90
SiO2 100 μm P G G G L L L L
SiO2 70 nm P P G G G VL VL VL VL
SiO2 14 nm P P P P P G G G G
SiO2 7 nm P P P P P P G G G

图12

离子液体凝胶光学显微镜照片[21] (a)凝胶被剪切前；(b)离子液体凝胶被剪切后内部定向排列结构示意图，其中S代表剪切；(c)离子液体和HNTs通过非共价键相互作用形成的液晶相。"

图13

离子液体凝胶的制备过程[23] (a)利用有机硅烷修饰的碳量子点在离子液体[Carb-Bim]Br中构筑碳量子点-离子液体凝胶；(b)透明且能够自支撑的碳量子点-离子液体凝胶薄片。"

图14

[75/25]/64离子液体凝胶[24] (a)照片; (b) AFM结果; (c)薄膜横截面的SEM结果(箭头代表厚度)。"

图15

基于离子液体纳米复合材料聚合物电解质的制备过程[25]"

图16

20 ℃浸泡过夜得到的凝胶照片及不同凝胶样品的G'和G"数据[27]"

图17

聚二甲基硅氧烷(PDMS)离子液体凝胶及纯离子液体1-乙基-3-甲基咪唑四氰合硼酸盐(EMI TCB)[26]"

图18

离子液体凝胶材料的电化学性能[18] (a)在10 mV·s-1下，柔性器件在不同弯曲角度(0°, 45°, 90°和135°)下的循环伏安曲线; (b)在50 mV·s-1下，柔性全固态超级电容器在不同弯曲循环次数下的循环伏安曲线。"

图19

HNT, BMIMBF4及BMIMBF4/HNT离子液体凝胶的TGA曲线(a)和DTG曲线(b)(加热速率为10 ℃·min-1)[21]"

图20

离子液体凝胶的各类应用[11]"

图21

微型超级电容器的构筑及特性[37] (a)在PET基底上利用图案化的固体电解质构筑柔性MSC的过程；(b)所构筑的柔性MSC实物照片；(c)离子液体[EMIM][TFSI]及聚合物PEGDA分子结构；(d)不同电解质图案光学显微镜照片。"

图22

离子液体凝胶的构筑[38]"

图23

LiFePO4/HI-2/Li电池的电化学性能[38] (a)不同温度及倍率下LiFePO4/HI-2/Li电池的放电容量；(b)在0.1C充电-0.1C放电状态下，LiFePO4/HI-2/Li在不同温度下的放电结果。"

图24

电化学发光器件的制备[39] (a)由发光离子液体凝胶层构筑的ECL器件，凝胶3种组分Ru(bpy)3Cl2/PS-b-PMMA-b-PS/[EMI][TFSI]的质量比为1: 4: 16; (b) ECL器件原始状态照片; (c) ECL器件开启状态照片，当对器件以60 Hz的频率施加3.6 V (-1.8~+1.8 V)的交流峰对峰电压时其发射的红橙光; (d)由含有不同浓度的Ru(bpy)3Cl2(质量分数为0.5%~12.5%)的离子液体凝胶构筑的ECL器件的发射光谱，λmax=610 nm (2.04 eV)处的峰对应于Ru(bpy)32+的激发态; (e)图(d)中610 nm处的峰值随Ru(bpy)3Cl2浓度的变化曲线。"

图25

晶体管的截面示意图及光学照片[41] (a)装有离子液体凝胶的顶注式有机薄膜晶体管(凝胶-OTFT)的截面示意图; (b)凝胶-OTFT光学照片; (c)侧注式晶体管的截面示意图; (d)侧注式凝胶-OTFT光学照片。"

图26

离子液体、离子液体凝胶及凝胶因子的腐蚀测试结果(为了加速腐蚀，缩短测试时间，腐蚀测试是将钢板浸泡在分别含有离子液体、离子液体凝胶及凝胶因子的饱和Ca(OH)2溶液中，室温下45 d)[30]"

图27

凝胶的触变性和摩擦学性能[30] (a)离子液体凝胶的触变行为；(b) 1-己基-3-甲基咪唑六氟磷酸盐([C1C6Im][PF6])及含有不同凝胶因子(质量分数均为5%)的离子液体凝胶的摩擦系数随时间的变化曲线(测试条件：往复摩擦磨损测试仪SRV-IV，外加负载：400 N；冲程：1 mm；频率：25 Hz；历时：30 min；温度：20~80 ℃)；(c)真空状态(1.0×10-6 Pa)及不同温度(-50~50 ℃)条件下，质量分数为5 %的凝胶因子2(LMWG2)在离子液体[C1C6Im][PF6]中构筑的离子液体凝胶在施以3 N外力下的摩擦系数随时间的变化曲线(摩擦磨损测试是由钢球在圆柱形钢块上完成，负载：3 N；转速: 300 r/min；历时：60 min)；(d)纯离子液体[C1C6Im][PF6]及添加不同质量分数(0.5%和2%)的凝胶因子3(LMWG3)构成的离子液体凝胶的摩擦系数随时间的变化曲线(摩擦磨损测试是由钢球在圆柱形钢块上完成，负载：3 N；转速: 300 r/min；历时：60 min；温度：20 ℃;真空度：3.0×10-4 Pa；历时：150 min；原子通量：7.0×1015cm-2·s-1)。"

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