纤维素基离子凝胶聚合物电解质的制备与性能

通过原位交联木浆纤维素/1-乙基-3-甲基咪唑醋酸盐溶液制备了纤维素基离子凝胶聚合物电解质,并采用扫描电子显微镜(SEM)、流变、力学拉伸及交流阻抗等测试,研究了纤维素基离子凝胶的形貌﹑力学性能和电化学性能。SEM结果表明,所得交联型离子凝胶具有纳米多孔网状结构。流变结果表明高温下离子凝胶具有很好的弹性,200℃时的弹性模量为1.7×105 Pa。电学性能测试结果表明室温下离子凝胶具有很高电导率,达到6.3×10-3 S/cm,且电导率随温度的升高而增大。力学性能测试结果显示离子凝胶具有良好的力学强度,其拉伸强度达9.6 MPa。     

聚氧化乙烯-聚硅氧烷基离子液体复合聚合物电解质的研究

通过对不同聚硅氧烷(PDMS)含量的聚氧化乙烯-聚硅氧烷(PEO-PDMS)聚合物电解质电化学性能的测试,确定出PDMS最佳添加量,并以此聚合物配比为基体,通过复合不同质量分数的离子液体1-丁基-3-甲基咪唑双三氟甲磺酰亚胺盐([BMIM]TF-SI)或N-甲基、丙基哌啶双三氟甲磺酰亚胺盐(PP13TFSI),制备得到不同体系的离子液体复合聚合物电解质膜。离子液体的加入可显著提高聚合物电解质的室温电导率,样品PPP-100%室温电导率达到5.6×10-4S/cm。同时,样品均具有良好的热学和电化学稳定性。通过两种体系聚合物电解质性能对比得知,PP13TFSI离子液体复合聚合物电解质具有更优性能,有望作为新型电解质材料应用在锂离子电池中。     

PAN-POSS接枝共聚物改性聚环氧乙烷/离子液体凝胶电解质的制备及性能

采用自由基聚合法成功合成了聚丙烯腈与笼型倍半硅氧烷的接枝共聚物(PAN-POSS),并将其引入聚环氧乙烷(PEO)/1-乙基-3-甲基咪唑双三氟甲磺酰亚胺盐([EMIM][TFSI])/双三氟甲磺酰亚胺锂(LiTFSI)体系,通过溶剂挥发法制备具有自支撑性的凝胶电解质(GPEs)。采用差示扫描量热分析、热分析、拉伸测试和电化学性能测试等进行表征,研究了PAN-POSS含量对PEO基电解质结晶性能、力学性能、热稳定性和电化学性能的影响。结果表明,在PEO/[EMIM][TFSI]/LiTFSI凝胶电解质体系中,随PAN-POSS含量增加,PEO的结晶度逐渐降低,当质量分数为9%时,结晶度从初始的25.7%降至11.6%。此时,GPEs的室温离子电导率为2.87×10~(-4) S/cm,在0.1 C充电速率下,电池的容量达到130 mAh/g。PAN-POSS的添加提高了GPEs的热稳定性,热降解温度可达到380.6℃,力学性能略有下降,但是仍然达到3.3 MPa,具有良好的自支撑特性。     

高离子电导率聚离子液体基自修复固态电解质的制备EI北大核心CSCD

采用可逆加成-断裂链转移(RAFT)聚合法成功合成了高分子量、窄分布的聚[1-(4-乙烯基苄基)-3-甲基咪唑双三氟甲烷磺酰亚胺](P[VBMIM][TFSI]),并将其与双三氟甲烷磺酰亚胺锂(LiTFSI)共混,通过溶液浇筑法制备了固态聚合物电解质(SPEs)。首先通过力学性能、流变学、热分析和电化学测试研究了P[VBMIM][TFSI]本体结构与性能的关系。随相对分子质量增加,P[VBMIM][TFSI]缠结程度逐渐加深,拉伸强度大幅度提升,而离子电导率与热降解温度变化不大。进一步对固态聚合物电解质进行更深入的电化学测试和分析。结果表明,SPEs在30℃时离子电导率最高可达到4.06×10^(-4) S/cm,锂离子迁移数为0.34,电化学窗口达到了4.5V。通过光学显微镜观察其自修复性,SPEs在室温时20min便可平复表面划痕,且具备良好的弹性,可以在5min内几乎完全回复拉伸长度。     

聚醚接枝丙烯酸树脂基凝胶聚合物电解质的制备及在电致变色器件中的应用

本工作以甲氧基聚乙二醇丙烯酸酯(PEGMEA)和聚氨酯丙烯酸树脂(PUA)为预聚体,离子液体1-丁基-3-甲基咪唑鎓双三氟甲磺酰亚胺盐(BMimTFSI)为添加剂,通过紫外光固化,构建了一种新型聚醚接枝丙烯酸树脂基凝胶聚合物电解质。通过傅里叶变换红外光谱(FTIR)、热重分析(TG)、紫外-可见吸收光谱(UV-Vis)和电化学测试(循环伏安)等方法对该凝胶聚合物电解质进行表征。结果表明,该类凝胶聚合物电解质不仅拥有优良的离子电导率,还具有高热稳定性、易封装和不易泄漏的优点。其中,BMimTFSI含量为59.5%(质量分数)、PUA/PEGMEA配比为4.96∶2.96(质量比)时凝胶聚合物的电解质综合性能最好,可见光透过率大于90%,热分解温度达到300℃,30℃时离子电导率达到2.17×10^-5 S/cm。基于该类凝胶聚合物电解质的电致变色器件展现出优良的性能,经36 000 s循环后,依然保持着稳定的蓝色态—透明态切换,且着色、褪色态的可见光透过率对比度仍高达48%,电解质质地柔软,热稳定性良好,可应用于电致变色器件。     

聚氨酯离子凝胶传感器的制备及性能

以聚氨酯为聚合物网络、离子液体（1-乙基-3-甲基咪唑二氰胺，EMIM:DCA）为导电介质，通过共混后干燥成膜的方式制备了具有不同EMIM:DCA含量的导电离子凝胶。采用万能试验机、电化学工作站和差示扫描量热仪对离子凝胶进行了表征。结果表明，随着EMIM:DCA含量的增加，离子凝胶的力学性能下降，离子电导率上升。其中EMIM:DCA质量分数为30%的离子凝胶(WPU/IL-30)的综合性能最佳，拉伸强度为0.85 MPa，断裂伸长率为264%，离子电导率为0.5 mS/cm，并且具有出色的抗冻性能(Tg=-27.6℃)。利用便携式传感测试仪研究了离子凝胶的应变传感性能，结果表明，WPU/IL-30传感器能够规律且稳定地将人体的运动状态转换为电信号传输到手机终端，且各项性能不会受到储存时间和环境温度的影响。此外，传感器在经过200次50%的循环拉伸后，传感性能依旧保持稳定，具有良好的耐疲劳性。     

纤维素基导电水凝胶的合成及其结构性能表征

以离子液体(氯化-1-丁基-三甲基咪唑,BMIMCl)溶解微晶纤维素(MCC),以N,N-亚甲基双丙烯酰胺作为交联剂形成的纤维素水凝胶为基体,同时吡咯(Py)作为导电聚合物单体,制备了纤维素基导电水凝胶。对MCC/PPy复合导电水凝胶的化学结构和表面形貌进行了表征,研究了该导电水凝胶的导电性、溶胀性能和热稳定性。结果表明,PPy与MCC水凝胶形成了具有半互穿网络结构的导电水凝胶,该水凝胶表面呈蜂窝状;其电导率数量级可达10-4~10-3,且对甲苯磺酸钠掺杂可大幅提高其电导率;随着MCC浓度的增加,纤维素水凝胶的平衡溶胀率呈下降趋势,所得导电水凝胶的溶胀率比纯纤维素水凝胶的溶胀率略有下降,但仍能维持500%的水平;此外,该导电水凝胶的热稳定性较纯MCC水凝胶有所下降。     

电致变色器件关键材料凝胶聚合物电解质研究进展

凝胶聚合物电解质是构成电致变色器件(ECD)的关键材料,其在器件中作为电极间的传导介质,为电致变色反应提供补偿离子。利用不同基体材料制备的凝胶聚合物电解质对提高电致变色器件性能具有重要影响。综述了聚环氧乙烷(PEO)、聚丙烯腈(PAN)、聚甲基丙烯酸甲酯(PMMA)、聚偏氟乙烯(PVDF)、聚偏氟乙烯-六氟丙烯(PVDF-HFP)、聚乙烯醇缩丁醛(PVB)及生物材料作为凝胶电解质聚合物基体的导电机理。阐述了它们作为电致变色器件电解质层对离子电导率、透光度、电致变色性能的影响。最后对凝胶聚合物电解质未来发展趋势进行了展望。     

锂离子电池用凝胶聚合物电解质研究进展

凝胶聚合物电解质既具有固态聚合物电解质良好的力学加工性能和安全性能,又具有传统液态电解质较高的室温离子电导率。但凝胶聚合物电解质由于室温离子电导率低、力学强度较差的缺点限制了其在锂离子电池上的应用。结合目前研究的最新进展,本文针对几种常用凝胶聚合物电解质体系聚氧化乙烯、聚丙烯腈、聚甲基丙烯酸甲酯、聚偏氟乙烯-六氟丙烯和聚乙烯醇缩醛进行了综述,对其制备方法以及通过聚合物调控、加入无机填料和复合离子液体进行改性处理做了较全面的介绍,并探讨了凝胶聚合物电解质的应用前景。     

离子液体1-丁基-3-甲基咪唑四氟硼酸复合聚氧化乙烯制备凝胶聚合物电解质及研究

以十六烷基聚乙二醇甲基丙烯酸酯(HPEGM)和甲氧基聚乙二醇甲基丙烯酸酯(MPEGM)为单体,离子液体1-丁基-3-甲基咪唑(BmimBF4)为增塑剂,高氯酸锂(LiClO4)作锂盐,采用自由基溶液聚合法制备凝胶聚合物电解质(PGE)。用红外光谱(FT-IR)、差热分析(DSC)和交流阻抗(AC)等方法对聚合物电解质的结构与性能进行了研究。测试结果表明:离子液体对聚合物基体起到了很好的增塑作用,促进了聚氧化乙烯(PEO)链段的运动,有利于离子传输;当m(HPEGM)∶m(MPEGM)∶m(BmimBF4)=1∶4∶10,n(Li+)∶n(EO)=1∶20时,30℃下,聚合物电解质的离子电导率可达1.10×10-3 S/cm;聚合物电解质膜显示出优良的热稳定性;电化学窗口达4.6V。     

Altering Mechanical Properties to Improve Electrode Contacts by Organic Modification of Silica-Based Ionogel Electrolytes for Sodium-Ion Batteries

Sodium-ion batteries (SIBs) are a possible candidate to create safe, sustainable, and cost-effective batteries. Solid sodium-ion conducting organically modified ionogel electrolytes are investigated. Silica-based ionogels typically consist of an ionic liquid electrolyte (ILE) confined within a silica matrix and possess high thermal stability, good ionic conductivity, safety, and good electrochemical stability. However, they readily deteriorate when stress is applied, decreasing the electrolyte's and battery's overall performance. The mechanical characteristics of silica can be improved using organic moieties, creating Ormosils®. Silica-based ionogels with phenyl-modified silanes improve the mechanical characteristics by a reduction of their Young's modulus (from 29 to 6 MPa). This is beneficial to the charge-transfer resistance, which decreases after implementing the electrolyte in half cells, demonstrating the improved interfacial contact. Most importantly, the phenyl groups change the interacting species at the silica interface. Cationic imidazolium species pi-stacked to the phenyl groups of the silica matrix, pushing the anions to the bulk of the ILE, which affects the ionic conductivity and electrochemical stability, and might affect the quality of the SEI in half cells. In essence, the work at hand can be used as a directory to improve mechanical characteristics and modify and control functional properties of ionogel electrolytes.     

Cross-Link-Dependent Ionogel-Based Triboelectric Nanogenerators with Slippery and Antireflective Properties

Given the ability to convert various ambient unused mechanical energies into useful electricity, triboelectric nanogenerators (TENGs) are gaining interest since their inception. Recently, ionogel-based TENGs (I-TENGs) have attracted increasing attention because of their excellent thermal stability and adjustable ionic conductivity. However, previous studies on ionogels mainly pursued the device performance or applications under harsh conditions, whereas few have investigated the structure–property relationships of components to performance. The results indicate that the ionogel formulation—composed of a crosslinking monomer with an ionic liquid—affects the conductivity of the ionogel by modulating the cross-link density. In addition, the ratio of cross-linker to ionic liquid is important to ensure the formation of efficient charge channels, yet increasing ionic liquid content delivers diminishing returns. The ionogels are then used in I-TENGs to harvest water droplet energy and the performance is correlated to the ionogels structure–property relationships. Improvement of the energy harvesting is further explored by the introduction of surface polymer brushes on I-TENGs via a facile and universal method, which enhances droplet sliding by means of ideal surface contact angle hysteresis and improves its anti-reflective properties by employing the I-TENG as a surface covering for solar cells.     

Preparation of High‐Performance Ionogels with Excellent Transparency,Good Mechanical Strength,and High Conductivity

Ionogels offer great potential for diverse electric applications. However, it remains challenging to fabricate high‐performance ionogels with both good mechanical strength and high conductivity. Here, a new kind of transparent ionogel with both good mechanical strength and high conductivity is designed via locking a kind of free ionic liquid (IL), i.e., 1‐ethyl‐3‐methylimidazolium dicyanamide ([EMIm][DCA]), into charged poly(2‐acrylamido‐2‐methyl‐1‐propanesulfonic acid) (PAMPS)‐based double networks. On the one hand, the charged PAMPS double network provides good mechanical strength and excellent recovery property. On the other hand, the free [EMIm][DCA] locked in the charged double network through electrostatic interaction offers ionic conductivity as high as ≈1.7–2.4 S m^?1 at 25 °C. It is demonstrated that the designed ionogel can be successfully used for a flexible skin sensor even under harsh conditions. Considering the rationally designed chemical structures of ILs and the diversity of charged polymer networks, it is envisioned that this strategy can be extended to a broad range of polymer systems. Moreover, functional components such as conducting polymers, 0D nanoparticles, 1D nanowires, and 2D nanosheets can be introduced into the polymer systems to fabricate diverse novel ionogels with unique functions. It is believed that this design principle will provide a new opportunity to construct next‐generation multifunctional ionogels.     

Inkjet printing of nanoporous gold electrode arrays on cellulose membranes for high-sensitive paper-like electrochemical oxygen sensors using ionic liquid electrolytes

A simple approach to the mass production of nanoporous gold electrode arrays on cellulose membranes for electrochemical sensing of oxygen using ionic liquid (IL) electrolytes was established. The approach, combining the inkjet printing of gold nanoparticle (GNP) patterns with the self-catalytic growth of these patterns into conducting layers, can fabricate hundreds of self-designed gold arrays on cellulose membranes within several hours using an inexpensive inkjet printer. The resulting paper-based gold electrode arrays (PGEAs) had several unique properties as thin-film sensor platforms, including good conductivity, excellent flexibility, high integration, and low cost. The porous nature of PGEAs also allowed the addition of electrolytes from the back cellulose membrane side and controllably produced large three-phase electrolyte/electrode/gas interfaces at the front electrode side. A novel paper-based solid-state electrochemical oxygen (O(2)) sensor was therefore developed using an IL electrolyte, 1-butyl-3-methylimidazolium hexafluorophosphate (BMIMPF(6)). The sensor looked like a piece of paper but possessed high sensitivity for O(2) in a linear range from 0.054 to 0.177 v/v %, along with a low detection limit of 0.0075% and a short response time of less than 10 s, foreseeing its promising applications in developing cost-effective and environment-friendly paper-based electrochemical gas sensors.     

Influence of Finely Dispersed Carbon Nanotubes on the Performance Characteristics of Polymer Electrolytes for Lithium Batteries

Electrospun membranes of poly(vinylidene fluoride-co-hexafluoropropylene) (PVdF-HFP)/multiwall carbon nanotube (MWCNT) composite are prepared and loaded with lithium salts from electrolyte solution. Field emission transmission electron microscopy provides evidence for the uniform distribution of MWCNTs into the matrix of PVdF-HFP. The interconnected morphology as evident from field emission scanning electron micrograph forms the path for the lithium ion conduction. Results from electrochemical impedance spectroscopy inform that the presence of MWCNTs in PVdF-HFP matrix improves interfacial stability between lithium electrode and membrane and augment conduction path in the polymer electrolyte membrane. Further results from impedance measurement reveal the contribution of MWCNTs toward conductivity. A prototype cell is fabricated with PVdF-HFP/MWCNT as polymer electrolyte. The electrospun PVdF-HFP electrolyte membrane with 2% MWCNTs content shows an ionic conductivity of about 5.85 mSmiddotcm^-1 at 25 degC. Also, PVdF-HFP/MWCNT electrolyte membrane exhibits good electrochemical and interfacial stability and can be potentially suitable as electrolyte in lithium ion secondary battery     

Preparation of poly(vinyl alcohol)-based separator with pore-forming additive for lithium-ion batteries

In this work, poly(vinyl alcohol) (PVA)-based separators with microporous structure were prepared from a casting solution composed of PVA resin, water as solvent, and poly(vinyl pyrrolidone) (PVP) polymer as pore controlling additive by non-solvent induced phase separation (NIPS) wet-process and investigated in lithium-ion batteries. The effects of PVP on the morphology and properties of the separator, such as porosity, electrolyte wettability, thermal stability and battery performance (discharge capacity, C-rate capability and cycleability) were systematically analyzed. Results show that PVP induced more pores on the bottom surfaces and the electrolyte uptake, ionic conductivity was further improved. Finally, a 10 wt% PVA-based separator with PVP solid content of 6 wt% exhibited greatly improved porosity, electrolyte uptake, ion conductivity and thermal resistance, resulting in the cell with high safety performance and matched electrochemical performance. The results demonstrated that the PVA-based separator with PVP as pore controlling additive can be a successful candidate serving as an effective separator for lithium-ion battery. Additionally, the present method of producing the microporous separator for LIBs is simple, environmentally benign and economically viable.     

基于OMMT/PVDF-HFP的锂离子电池用复合聚合物电解质

对蒙脱石进行改性,并用直接挥发溶剂法制备有机蒙脱石/聚偏氟乙烯-六氟丙烯复合聚合物电解质。用扫描电子显微镜和X射线衍射等对所制电解质性能进行表征,用交流阻抗和充放电实验研究聚合物电池的电化学性质。结果表明：直接挥发溶剂法制得的复合聚合物膜呈蜂窝状,孔穴丰富,强度增加,浸取电解液后室温离子电导率为1.51 mS/cm,电化学稳定窗口为5.5V;以LiCoO₂为正极制得的聚合物电池0.1C充放电,50次循环后容量保持率达到95.3%,倍率放电能力较好,有机蒙脱石的加入可改善电池的电极界面性质,提高电池充放电循环性能。     

Effect of ionic liquids on the electroluminescence of yellowish-green light-emitting electrochemical cells using bis(2-(2,4-difluorophenyl)pyridine)4,7-diphenyl-1,10-phenanthroline-iridium(III) hexafluorophosphate

A cationic iridium complex [Ir(dfppy)₂(dpphen)]PF₆, where dfppy is 2-(2,4-difluorophenyl)pyridine, dpphen is 4,7-diphenyl-1,10-phenanthroline and PF₆⁻ is hexafluorophosphate, has been synthesized and its photophysical and electrochemical properties were investigated. Light-emitting electrochemical cells (LECs) based on this complex were fabricated using air stable electrodes and emits yellowish-green light (533 nm) with Commission Internationale de L’Eclairage (CIE) coordinates of (0.35, 0.59) at 4 V. Effect of two different imidazolium based ionic liquids (ILs) viz, 1-butyl-3-methylimidazolium hexafluorophosphate (BMIMPF₆) and 1-ethyl-3-methylimidazolium hexafluorophosphate (EMIMPF₆) on the active layer has been studied and the luminance and the current density of the devices were found to be enhanced with increasing ionic conductivities.     

聚硅氧烷对水性聚氨酯聚合物电解质结构形态及电化学性能的影响

将PDMS引入到WPU中,合成了PEO-PDMS混合软段WPU嵌段共聚物,通过改变PDMS的含量得到一系列固态聚合物电解质膜。测试结果表明,PDMS的加入会对聚合物电解质材料的力学性能、微观形态、电化学性能产生显著影响。PDMS的加入可有效地提高聚合物电解质的室温电导率及电化学稳定性,30℃时样品C17-10电导率为1.05×10-4S/cm,其电化学稳定窗口达到5.5V。     

聚乙烯醇/[Nbmd]OH碱性复合阴离子膜的制备及性能

以吗啡啉与溴代十二烷为原料,合成新型[Nbmd]OH碱性双核离子液体,并将[Nbmd]OH引入聚乙烯醇(PVA)的铸膜液中,通过浇铸法制备了掺杂碱性离子液体的复合阴离子膜PVA/[Nbmd]OH。采用热重分析及扫描电镜对所制备的复合阴离子膜的热稳定性及形貌进行表征。同时考察了离子液体含量对PVA/[Nbmd]OH复合膜的含水率、溶胀性能、力学性能及电导率的影响。结果表明,离子液体含量的增加可提高PVA/[Nbmd]OH复合膜的含水率、溶胀度、电导率等。其中,当碱性离子液体质量分数为20%时,复合膜的综合性能达到最优,此时,膜的含水率和拉伸强度分别达到161.6%和23 MPa,在70℃时,膜的电导率为2.11×10~(-3)S/cm,表明碱性离子液体的引入,能明显改善膜的导电性能,但是拉伸强度受到了一定的影响。