锂离子电池凝胶聚合物电解质的研究进展

由于凝胶聚合物电解质具有较好的机械加工性能和安全性能以及较高的室温离子电导率,因而得到广泛的研究与应用。综述了聚偏氟乙烯、聚丙烯腈、聚甲基丙烯酸甲酯和聚氧化乙烯等锂离子电池凝胶聚合物电解质近几年的研究进展,主要介绍了这些凝胶聚合物电解质体系性能的优缺点以及对其改性研究的各种探索。特别是对目前研究最广泛的聚偏氟乙烯体系的改性进行了较为详细的论述。其中,添加无机纳米粒子的改性是目前的研究热点,是凝胶聚合物电解质的发展趋势,并对凝胶聚合物电解质的未来发展作了展望。     

钛凝胶的光致变色和电致变色特性

Titania gel is very sensitive to change of color to blue-purple by UV irradiation and to brown color under extra electric field polarzation. The UV absorption spectra of the photochromic (PC) and electrochromic(EC) titania gel are different to that of the nanocrystalline TiO_2 which changes to blue color by UV irradiation or under extra electric field polarization. The steady-state ESR measurements at room temperature indicate that ESR signals of Ti3+ appeared in PC and EC titania gel with the g values corresponding to 1.9505 and 1.9512, respectively.     

钛凝胶的光致变色和电致变色特性

过渡金属氧化物光致变色［１,２］和电致变色［３－７］材料在图象显示、信息存储以及做为调节光线强弱的“灵巧窗”等方面有着潜在的应用．国内外广大的科研工作者,在新型光电变色材料的寻找和光电变色机理等方面开展了较广泛而深入的研究．目前普遍认为变色机理为双注...     

GelatinnZn(CF3SO3)2 Polymer Electrolytes for Electrochromic Devices

The present work is focused on gelatin‐based electrolytes doped with a range of concentration of zinc triflate (Zn(CF₃SO₃)₂). The transparent‐thin‐film samples have been represented by the notation Gelatin_nZn(CF₃SO₃)₂, where n represents the zinc triflate salt concentration in the electrolyte membranes from 0.00 wt% to 10.93 wt% . The samples have been characterized by conductivity measurements, thermal analysis, cyclic voltammetry, X‐ray diffraction (XRD), polarized optical microscopy (POM) and scanning electron microscopy (SEM). The gelatin‐based electrolytes were also tested as ionic conductors in electrochromic devices with the glass/ITO/WO₃/gelatin‐based electrolyte/CeO₂‐TiO₂/ITO/glass configuration.     

磷腈-紫精聚合物的合成与电致变色性能

以六氯环三磷腈作为核心、紫精为电致变色活性基,合成了一种新型有机-无机杂化电致变色材料六(1-乙基-4,4’-联吡啶-甲基苯氧基)环三磷腈(PHV²⁺).通过傅里叶变换红外光谱(FTIR)、X射线衍射(XRD)及核磁共振氢谱(1H NMR)表征了PHV²⁺的结构.优良的水溶性使得该化合物可以通过简单的方法构造一个以聚乙烯醇(PVA)为凝胶基质的电致变色水凝胶,具有成本低廉及无毒害的优点.以氟掺杂氧化锡(FTO)涂层玻璃作为电极材料,PHV²⁺作为电致变色材料制备了PHV²⁺/PVA/KCl电致变色器件(PHV²⁺/PVA/KCl ECD).该电致变色器件在2. 1 V电压下由淡黄色变为紫色,颜色变化明显,并且该颜色变化可以循环500次;器件在526 nm处的光学对比度达到62. 19%.良好的电致变色性质使该化合物在电致变色器件方面具有潜在应用价值.     

含聚氧化乙烯侧链的聚合物凝胶电解质的动态力学性能和离子导电性

红外测试结果表明：产物是含聚氧化乙烯侧链的聚合物。该聚合物电解质的室温电导率为10^-3S／cm数量级。并用动态力学方法,研究了分子链段活动性与聚合物凝胶电解质组成(增塑剂含量、含盐量和盐种类)的关系。     

Thermal‐Gated Polymer Electrolytes for Smart Zinc‐Ion Batteries

Smart self‐protection is essential for addressing safety issues of energy‐storage devices. However, conventional strategies based on sol‐gel transition electrolytes often suffer from unstable self‐recovery performance. Herein, smart separators based on thermal‐gated poly(N‐isopropylacrylamide) (PNIPAM) hydrogel electrolytes were developed for rechargeable zinc‐ion batteries (ZIBs). Such PNIPAM‐based separators not only display a pore structure evolution from opened to closed states, but also exhibit a surface wettability transition from hydrophilic to hydrophobic behaviors when the temperature rises. This behavior can suppress the migration of electrolyte ions across the separators, realizing the self‐protection of ZIBs at high temperatures. Furthermore, the thermal‐gated behavior is highly reversible, even after multiple heating/cooling cycles, because of the reversibility of temperature‐dependent structural evolution and hydrophilic/hydrophobic transition. This work will pave the way for designing thermal‐responsive energy‐storage devices with safe and controlled energy delivery.     

Preparation of a Star Network PEG-based Gel Polymer Electrolyte and Its Application to Electrochromic Devices

A star network polymer with a pentaerythritol core linking four PEG-block polymeric arms was synthesized, and its corresponding gel polymer electrolyte based on lithium perchlorate and plasticizers EC/PC with the character being colorless and highly transparent has been also prepared. The polymer host was characterized and confirmed to be of a star network and an amorphous structure by FTIR, ^1H NMR and XRD studies. The polymer host hold good mechanical properties for pentaerythritol cross-linking. Maximum ionic conductivity of the prepared polymer electrolyte has reached 8.83 × 10 ^-4 S·cm^-1 at room temperature. Thermogravimetry （TG） of the polymer electrolyte showed that the thermal stability was up to at least 150 ℃. The gel polymer electrolyte was further evaluated in electrochromic devices fabricated by transparent PET-ITO and electrochromically active viologen derivative films, and its excellent performance promised the usage of the gel polymer electrolyte as ionic conductor material in electrochrornic devices.     

Single Lithium‐Ion Conducting Polymer Electrolytes Based on a Super‐Delocalized Polyanion

A novel single lithium‐ion (Li‐ion) conducting polymer electrolyte is presented that is composed of the lithium salt of a polyanion, poly[(4‐styrenesulfonyl)(trifluoromethyl(S‐trifluoromethylsulfonylimino)sulfonyl)imide] (PSsTFSI^?), and high‐molecular‐weight poly(ethylene oxide) (PEO). The neat LiPSsTFSI ionomer displays a low glass‐transition temperature (44.3 °C; that is, strongly plasticizing effect). The complex of LiPSsTFSI/PEO exhibits a high Li‐ion transference number (t_Li⁺=0.91) and is thermally stable up to 300 °C. Meanwhile, it exhibits a Li‐ion conductivity as high as 1.35×10^?4 S cm^?1 at 90 °C, which is comparable to that for the classic ambipolar LiTFSI/PEO SPEs at the same temperature. These outstanding properties of the LiPSsTFSI/PEO blended polymer electrolyte would make it promising as solid polymer electrolytes for Li batteries.     

用于锂离子电池聚合物电解质的组成、结构和性能

聚合物电解质是全固态锂离子电池的重要组成部分, 其电导率对电池的性能有很重要的影响.本文综述了聚合物电解质的组成、结构和性能对锂 离子电池导电率影响的最新研究进展,特别是介绍了聚合物-碱金属盐复合电解质和聚离子体电解质两个体系的研究进展.     

Ionic Liquid Based Polymer Gel Electrolytes for Use with Germanium Thin Film Anodes in Lithium Ion Batteries

Thermally stable, flexible polymer gel electrolytes with high ionic conductivity are prepared by mixing the ionic liquid 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide (C₄mpyrTFSI), LiTFSI and poly(vinylidene difluoride-co-hexafluoropropylene (PVDF-HFP). FT-IR and Raman spectroscopy show that an amorphous film is obtained for high (60 %) C₄mpyrTFSI contents. Thermogravimetric analysis (TGA) confirms that the polymer gels are stable below ∼300 °C in both nitrogen and air environments. Ionic conductivity of 1.9×10⁻³ S cm⁻² at room temperature is achieved for the 60 % ionic liquid loaded gel. Germanium (Ge) anodes maintain a coulombic efficiency above 95 % after 90 cycles in potential cycling tests with the 60 % C₄mpyrTFSI polymer gel.     

Safe,Low‐Cost,Fast‐Kinetics and Low‐Strain Inorganic‐Open‐Framework Anode for Potassium‐Ion Batteries

A key challenge for potassium‐ion batteries is to explore low‐cost electrode materials that allow fast and reversible insertion of large‐ionic‐size K⁺. Here, we report an inorganic‐open‐framework anode (KTiOPO₄), which achieves a reversible capacity of up to 102 mAh g^?1 (307 mAh cm^?3), flat voltage plateaus at a safe average potential of 0.82 V (vs. K/K⁺), a long lifespan of over 200 cycles, and K⁺‐transport kinetics ≈10 times faster than those of Na‐superionic conductors. Combined experimental analysis and first‐principles calculations reveal a charge storage mechanism involving biphasic and solid solution reactions and a cell volume change (9.5 %) even smaller than that for Li⁺‐insertion into graphite (≈10 %). KTiOPO₄ exhibits quasi‐3D lattice expansion on K⁺ intercalation, enabling the disintegration of small lattice strain and thus high structural stability. The inorganic open‐frameworks may open a new avenue for exploring low‐cost, stable and fast‐kinetic battery chemistry.     

Safe,Low‐Cost,Fast‐Kinetics and Low‐Strain Inorganic‐Open‐Framework Anode for Potassium‐Ion Batteries

A key challenge for potassium‐ion batteries is to explore low‐cost electrode materials that allow fast and reversible insertion of large‐ionic‐size K⁺. Here, we report an inorganic‐open‐framework anode (KTiOPO₄), which achieves a reversible capacity of up to 102 mAh g^?1 (307 mAh cm^?3), flat voltage plateaus at a safe average potential of 0.82 V (vs. K/K⁺), a long lifespan of over 200 cycles, and K⁺‐transport kinetics ≈10 times faster than those of Na‐superionic conductors. Combined experimental analysis and first‐principles calculations reveal a charge storage mechanism involving biphasic and solid solution reactions and a cell volume change (9.5 %) even smaller than that for Li⁺‐insertion into graphite (≈10 %). KTiOPO₄ exhibits quasi‐3D lattice expansion on K⁺ intercalation, enabling the disintegration of small lattice strain and thus high structural stability. The inorganic open‐frameworks may open a new avenue for exploring low‐cost, stable and fast‐kinetic battery chemistry.     

Ionic‐Liquid‐Based Polymer Electrolytes for Battery Applications

The advent of solid‐state polymer electrolytes for application in lithium batteries took place more than four decades ago when the ability of polyethylene oxide (PEO) to dissolve suitable lithium salts was demonstrated. Since then, many modifications of this basic system have been proposed and tested, involving the addition of conventional, carbonate‐based electrolytes, low molecular weight polymers, ceramic fillers, and others. This Review focuses on ternary polymer electrolytes, that is, ion‐conducting systems consisting of a polymer incorporating two salts, one bearing the lithium cation and the other introducing additional anions capable of plasticizing the polymer chains. Assessing the state of the research field of solid‐state, ternary polymer electrolytes, while giving background on the whole field of polymer electrolytes, this Review is expected to stimulate new thoughts and ideas on the challenges and opportunities of lithium‐metal batteries.     

Ion Tunneling in Polymeric Solid Electrolytes for Batery and Electrochromic Display in the Dry State

Polymeric solid electrolytes which show bi-or single-ionic tunneling were prepared, and their unique ion conduction was applied for the design of some devices. Poly [(oligooxyethylene) methacrylatel] /MX hybrids and poly [(oligooxyethylene) methacrylate-co-methacrylic acid alkali metal salts] were prepared as typical models of those tunneling systems. These showed ionic conductivities above 10^?5 and 10^?7 S/cm at room temperature, respectively. An all-solid-state electrochromic display and a dry battery were prepared with these polymeric solid electrolytes. The all-solid-state electrochromic display showed excellent coloring and bleaching response by 1–3 V. The all-solid-state battery showed V _oc = 3.1 V stability for over 2 weeks. Their characteristics as well as their mechanism are also reported.     

Enhanced Lithium‐Ion Conductivity of Polymer Electrolytes by Selective Introduction of Hydrogen into the Anion

The anion chemistry of lithium salts plays a pivotal role in dictating the physicochemical and electrochemical performance of solid polymer electrolytes (SPEs), thus affecting the cyclability of all‐solid‐state lithium metal batteries (ASSLMBs). The bis(trifluoromethanesulfonyl)imide anion (TFSI^?) has long been studied as the most promising candidate for SPEs; however, the Li‐ion conductivities of the TFSI‐based SPEs still remain low (Li‐ion transference number: ca. 0.2). In this work, we report new hydrogen‐containing anions, conceived based on theoretical considerations, as an electrolyte salt for SPEs. SPEs comprising hydrogen‐containing anions achieve higher Li‐ion conductivities than TFSI‐based ones, and those anions are electrochemically stable for various kinds of ASSLMBs (Li–LiFePO₄, Li–S, and Li–O₂ batteries). This opens up a new avenue for designing safe and high‐performance ASSLMBs in the future.     

氧化铑电致变色薄膜的制备、结构及性能

采用溶胶_凝胶方法在ITO导电基底上制备氧化铑电致变色薄膜 .当在碱性溶液中对薄膜分别施加阴极和阳极电位时 ,薄膜即呈现由亮黄到深绿的可逆变化 .采用原位XRD、TG_DTA、IR、XPS等方法对薄膜的结晶态、热处理过程以及膜的化学组成进行分析 .应用交流阻抗法计算了薄膜变色过程的扩散系数 ,结果表明该膜基本可以用于变色器件     

Highly Flexible and Efficient All‐Polymer Solar Cells with High‐Viscosity Processing Polymer Additive toward Potential of Stretchable Devices

Considering the potential applications of all‐polymer solar cells (all‐PSCs) as wearable power generators, there is an urgent need to develop photoactive layers that possess intrinsic mechanical endurance, while maintaining a high power‐conversion efficiency (PCE).Herein a strategy is demonstrated to simultaneously control the intercalation behavior and nanocrystallite size in the polymer–polymer blend by using a newly developed, high‐viscosity polymeric additive, poly(dimethylsiloxane‐co‐methyl phenethylsiloxane) (PDPS), into the TQ‐F:N2200 all‐PSC matrix. A mechanically robust 10wt% PDPS blend film with a great toughness was obtained. Our results provide a feasible route for producing high‐performance ductile all‐PSCs, which can potentially be used to realize stretchable all‐PSCs as a linchpin of next‐generation electronics.