Research progress on IPMC’s material compositions and actuation/sensing properties
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摘要: 离子交换聚合物/金属复合材料(IPMC)可作为柔性的驱动器与传感器，用于仿生机械、医疗器械等领域。驱动器是IPMC的主要应用，存在输出功率低、驱动不稳定等问题。传感器是IPMC的重要应用，存在感应电压低、干扰大等缺陷。优化电极、电解质膜、电解质溶液的材料组成有望解决上述问题。驱动器方面，本文梳理了不同聚合物电解质膜的改性技术及驱动特点，重点归纳了电解质膜的成分、结构制约其物理性能(如离子交换当量、含水量、力学性能)，进而制约其驱动性能(如位移、力输出)的规律。传感器方面，本文从电极形状、电解质膜结构、电解质离子尺寸三个方面，讨论了IPMC传感性能(如感应电压的幅值、稳定性)的优化技术。论文还展望了IPMC的未来发展方向。
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关键词:
- 电活性聚合物(EAP) /
- 离子交换聚合物/金属复合材料(IPMC) /
- 驱动器 /
- 传感器 /
- 力电耦合
Abstract: As flexible actuators and sensors, ion exchange polymer-metal composites (IPMCs) are widely used in bionic machinery, medical devices and other fields. Actuation is the main application of the IPMC, and IPMC actuators have bottlenecks such as low output power and unstable actuation. Sensing is another important application, and IPMC sensors endure some defects such as low induced voltage and large interference. For actuator, we discussed the modification techniques and driving characteristics of different polymer electrolytes, and focused on the structure-activity relationship of that, the compositions and structures the electrolytes determine their physical properties (e.g. ion exchange capacity, water uptake, mechanical property), subsequently determine their electromechanical properties (e.g. displacement, force outputs). For sensor, we discussed the optimization technologies of IPMC sensing properties (e.g. amplitude and stability of the induced voltage) from three aspects of electrode shape, electrolyte membrane structure and electrolyte ion size. We also discussed IPMC’s future research. -
图 1 离子交换聚合物/金属复合材料(IPMC)的驱动与传感机制
Figure 1. Driving and sensing mechanisms of ion exchange polymer-metal composites (IPMCs)
图 2 (a) 仿蝠鲼[20]；(b) 仿乌龟[21]；(c)仿毛毛虫[22]；(d) 仿蟑螂[23]；(e) 仿蝴蝶[24]；(f) 仿蜜蜂[26]；(g) 五指机构[28]；(h) 十指机构[29]；(i) 流体开关[30]；(j) 多自由度导管[31]；(k) 仿生水仙花[24]；(l) 仿连翘花[25]；(m) 喉部传感器[32]；(n) 智能手套[36]。中间为自制IPMC连续驱动截图
Figure 2. (a) bionic manta ray[20]; (b) bionic turtle[22; (c) bionic caterpillar[23]; (d) bionic cockroach[24]; (e) bionic butterfly[24]; (f) bionic bee[26]; (g) five-finger mechanism[28]; (h) ten-finger mechanism[29]; (i) fluid switch[30];(j) multi-freedom catheter[31]; (k) bionic daffodils[24]; (l) bionic forsythia flower[25]; (m) throat sensor[32]; (n) smart gloves[36]. Middle: continuous actuations of a self-made IPMC actuator
图 4 (a) MXene的结构示意图[24]；(b) 嵌入PEDOT的MXene[24]；(c) MXene夹心的电解质膜[24]；(d) 垂直排列CNT的SEM图[43]；(e) CNT/Nafion复合材料[43]；(f) 复合电极切片的SEM图[43]；(g) IPMC的热压组装图[43]
Figure 4. (a) MXene flakes[24]; (b) MXene electrode embedded with PEDOT[24]; (c) MXene electrodes sandwiched electrolyte film[24]; (d) SEM image of vertically aligned CNT[43]; (e) schematic diagram of CNT/Nafion composite[43]; (f) SEM image of CNT/Nafion slice[43]; (g) assembly drawing of IPMC by hot-press technique[43]
图 5 (a) AgNO3被还原为Ag(0)，外表面包覆PVP；(b) 利用Dip-coating将PVP@AgNPs涂覆在废IPMC(IPMC-old)表面，得IPMC-repair；(c) 电场下，IPMC-repair稳定驱动[45]
Figure 5. (a) AgNO3 was reduced into Ag(0) seed which was coated by the PVP; (b) the PVP@AgNPs was coated on both surfaces of the futile IPMC (IPMC-old), thus obtained IPMC-repair; (c) triggered by the electric field, IPMC-repair generated stable actuations[45]
图 6 (a) PFSA的分子结构[56]；(b) 内管道形成示意图[56]；(c) 簇模型[57]；(d) 3 D内管道，提取出的3 D离子相图像，显示了离子相的空间分布[58]
Figure 6. (a) comparison of molecular structures of Nafion, Aciplex, and Flemion[56]; (b) schematic diagram of formation of the inner channels[56]; (c) cluster model[57]; (d) 3 D inner channels, the extracted 3 D images displayed the spatial distribution of ion phase[58]
图 13 (a) WU；(b) IEC；(c) 杨氏模量(上为干膜，下为湿膜)；(d) 偏转角；(e) 力输出；A-H依次为Nafion，PVDF，SPS，SPSU，SBC，SCS，SPEEK，SPVA复合物膜。图c中实心数据来自拉伸模量，空心数据来自压缩模量。偏转角来自文献中数据，或驱动截图中的最大偏转部分。力输出为单位母体膜厚度的力输出
Figure 13. (a) WU; (b) IEC; (c) Young's modulus (top: dry; bottom: wet); (d) deflection angle; (e) force output. A-H is Nafion, PVDF, SPS, SPSU, SBC, SCS, SPEEK, SPVA composite matrixes, respectively. In Figure c, the solid data originated from the tensile moduli, while the dotted data were from the compression moduli. The deflection angle originated from the data in the literatures, or the maximum deflection sections in the actuation videos. The force outputs were the detected forces divided by the thickness, which were extracted from the data in the literatures
图 14 压力下的离子分布图。绿色为聚合物链网络，红色的为阳离子，蓝色的为阴离子[99]。工作(感应)电极被放置在凹痕部分下方，参比电极(接地)放置在凝胶的未形变区域
Figure 14. Schematic of ion distribution under pressure[99]. Polymer chain network was colored in green, cations in red and anions in blue. The working (induction) electrode was placed below the dent and the reference electrode (ground) in the undeformed area
表 1 EAP、PZ、SMA的驱动参数比较
Table 1. Comparison of driving parameters of EAP, PZ, and SMA
Property EAP PZ SMA DE PZP CP IPMC Strain/% 8-380 0.1-10 2-40 0.5-30 0.1-0.3 5-8 Stress/MPa 0.3-38 4.8-45 5-200 3-78 30-110 200-700 Response speed μs μs ms-s ms-s μs-s s-min Density/g/cm3 1.5 1.78-8 1.48 1-2.5 6-8 5-6 Driving voltage/V >1000 >1000 1-30 1-7 50-800 - Mechanical property elasticity elasticity Soft elasticity brittleness elasticity Reference [12-14] [12, 13, 15] [12, 15] [12, 15-17] [13, 16] [12, 13, 15] Notes: EAP-Electroactive polymer; DE-Dielectric elastomer; PZP-Piezoelectric polymer; CP-Conductive polymer; IPMC-ion exchange polymer-metal composites; PZ-Piezoelectric; SMA-Shape memory alloy 
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表 2 电解质膜的参数比较
Table 2. Parameter comparisons for different electrolyte films
IEM IEC/mmol/g IC/mS/cm WU/wt% Y's (Dry、Wet)/MPa Reference PFSA 0.62-1.66 10.5-130 6-41 160-450/39-320 [51, 61, 63, 73, 74, 77, 81, 93, 94] PFCA 1.44-1.8 110 24 170/- [66, 95, 96] PVDF 0.48-4.21 0-114 10-199 712-1400/24-720 [70, 71, 73, 74, 90, 92, 94] SPS 0.48-3.11 1.4-120 19-194 710-1360/31-210 [69, 70, 82, 93, 94] SPSU 1.32-2.62 3.6-49.6 29-54 800-1260/220-630 [50, 81] SBC 1.15-1.63 0-3.7 27-50 350-780/- [97] SCS 1.2-2.6 0-0.03 - 820-1960/- [84] SPEEK 1.58-2.30 6.2-62 28-40 870-1830/300-550 [74, 86, 94] SPVA 0.25-1.8 1.5-28 36-181 266/3.4-140 [88, 91, 94] Notes: IEM-Ion exchange membrane; IEC-Ion exchange capacity; IC-Ionic conductivity; WU-Water uptake; Y's -Young's modulus; PFSA-Perfluorosulfonic acid; PFCA-Perfluorocarbonic acid; PVDF-Polyvinylidene difluoride; SPS-Sulfonated polystyrene; SPSU-Sulfonated polysulfone; SBC-Sulfonated bacterial cellulose；SCS-Sulfonated chitosan; SPEEK-Sulfonated polyether ether ketone; SPVA-Sulfonated polyvinyl alcohol
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