Free‐Standing Conducting Polymer Films for High‐Performance Energy Devices

Thick, uniform, easily processed, highly conductive polymer films are desirable as electrodes for solar cells as well as polymer capacitors. Here, a novel scalable strategy is developed to prepare highly conductive thick poly(3,4‐ethylenedioxythiophene):polystyrene sulfonate (HCT‐PEDOT:PSS) films with layered structure that display a conductivity of 1400 S cm^?1 and a low sheet resistance of 0.59 ohm sq^?1. Organic solar cells with laminated HCT‐PEDOT:PSS exhibit a performance comparable to the reference devices with vacuum‐deposited Ag top electrodes. More importantly, the HCT‐PEDOT:PSS film delivers a specific capacitance of 120 F g^?1 at a current density of 0.4 A g^?1. All‐solid‐state flexible symmetric supercapacitors with the HCT‐PEDOT:PSS films display a high volumetric energy density of 6.80 mWh cm^?3 at a power density of 100 mW cm^?3 and 3.15 mWh cm^?3 at a very high power density of 16160 mW cm^?3 that outperforms previous reported solid‐state supercapacitors based on PEDOT materials.     

An Aqueous Conducting Redox‐Polymer‐Based Proton Battery that Can Withstand Rapid Constant‐Voltage Charging and Sub‐Zero Temperatures

Electrodes based on organic matter operating in aqueous electrolytes enable new approaches and technologies for assembling and utilizing batteries that are difficult to achieve with traditional electrode materials. Here, we report how thiophene‐based trimeric structures with naphthoquinone or hydroquinone redox‐active pendent groups can be processed in solution, deposited, dried and subsequently polymerized in solid state to form conductive (redox) polymer layers without any additives. Such post‐deposition polymerization offers efficient use of material, high mass loading (up to 10 mg cm^?2) and good flexibility in the choice of substrate and coating method. By employing these materials as anode and cathode in an acidic aqueous electrolyte a rocking‐chair proton battery is built. The battery shows good cycling stability (85 % after 500 cycles), withstands rapid charging, with full capacity (60 mAh g^?1) reached within 100 seconds, allows for direct integration with photovoltaics, and retains its favorable characteristics even at ?24 °C.     

Porous Organic Polymer Films with Tunable Work Functions and Selective Hole and Electron Flows for Energy Conversions

Organic optoelectronics are promising technologies for energy conversion. However, the electrode interlayer, a key material between active layers and conducting electrodes that controls the transport of charge carriers in and out of devices, is still a chemical challenge. Herein, we report a class of porous organic polymers with tunable work function as hole‐ and electron‐selective electrode interlayers. The network with organoborane and carbazole units exhibits extremely low work‐function‐selective electron flow; while upon ionic ligation and electro‐oxidation, the network significantly increases the work function and turns into hole conduction. We demonstrate their outstanding functions as anode and cathode interlayers in energy‐converting solar cells and light‐emitting diodes.     

Assorted Phenoxyl‐Radical Polymers and Their Application in Lithium‐Organic Batteries

The synthesis and electrochemical characterization of novel polymers bearing phenoxyl‐radicals as redox‐active side chains is described. The monomers are synthesized from the corresponding phenols and quinones, respectively. These compounds are subsequently poly­merized via ring‐opening metathesis polymerization. The electrochemical properties of the phenoxyl‐radical polymers are characterized using cyclic voltammetry and the most promising polymer is investigated as active material in a lithium coin‐cell, creating the first phenoxyl‐lithium battery. These phenoxyl‐containing polymers represent interesting anode materials for organic radical and lithium batteries due to their suitable redox‐potentials and possibility to create batteries with higher potentials as well as straightforward synthesis procedures.

     

Synthesis of Sub‐nanometer Porous Carbon Film for Energy Storage

Carbon‐based supercapacitors are a kind of supercapacitors with very promising applications because of their low cost, good stability and adjustable properties. Simple and rapid syntheses of carbon materials with a high surface area and narrow pore size distribution are of great significance to practical applications of carbon‐based supercapacitors. Here we report a new strategy to synthesize sub‐nanometer porous carbon films (Snp‐CF) via a condensation reaction under mild conditions. Carbon films exhibit a narrow pore size distribution (6.6 Å) and high surface area (508 m² g^?1) after annealing at 700 °C. Snp‐CF‐700 displays a good specific capacity and excellent cycle performance (130 F g^?1 after 5000 cycles, 118 % of initial 110 F g^?1).     

Integrated Devices to Realize Energy Conversion and Storage Simultaneously

Other forms of energy are generally converted to electric energy and then transported to electrochemical devices, where the energy is stored, by external electric wires. To further improve total energy conversion and storage efficiency, interest in simultaneously realize the energy conversion and storage in a single device has increased. This Concept describes recent progress in developing such novel integrated energy devices. Both planar and wire architectures are carefully illustrated with an emphasis on the “energy wire” which has been the focus of past developments due to its unique and promising applications, such as being woven into clothes or other complex structures by conventional textile technology. The current challenges and future directions of the integrated devices, particularly in the wire architecture, are summarized.     

Responsive Gels with the Polymer Containing Alternating Naphthalene Diimide and Fluorinated Alkyl Chains: Gel Formation and Responsiveness as Well as Electrical Conductivity of Polymer Thin Films

A new electroactive polymer 1 with alternating NDI (naphthalene diimide) moieties and fluorinated alkyl chains was prepared and characterized. Gels of polymer 1 were formed in several solvents. Interestingly, gels of polymer 1 exhibited responsiveness toward N₂H₄, F^? and CN^?. Absorption and ESR spectroscopic studies revealed that such responsiveness is owing to the reduction of NDI moieties into the respective NDI^.?. In addition, thin films of polymer 1 were easily prepared with spin‐coating technique and the electrical conductivity of thin films reached 52.4 S/m after exposure to N₂H₄ vapor.     

Novel Two‐Dimensional Porous Materials for Electrochemical Energy Storage: A Minireview

Two dimensional (2D) porous materials have great potential in electrochemical energy conversion and storage. Over the past five years, our research group has focused on Simple, Mass, Homogeneous and Repeatable Synthesis of various 2D porous materials and their applications for electrochemical energy storage especially for supercapacitors (SCs). During the experimental process, through precisely controlling the experimental parameters, such as reaction species, molar ratio of different ions, concentration, pH value of reaction solution, heating temperature, and reaction time, we have successfully achieved the control of crystal structure, composition, crystallinity, morphology, and size of these 2D porous materials including transition metal oxides (TMOs), transition metal hydroxides (TMHOs), transition metal oxalates (TMOXs), transition metal coordination complexes (TMCCs) and carbon materials, as well as their derivatives and composites. We have also named some of them with CQU‐Chen (CQU is the initialism of Chongqing University, Chen is the last name of Lingyun Chen), such as CQU‐Chen‐Co?O‐1, CQU‐Chen‐Ni?O?H‐1, CQU‐Chen‐Zn?Co?O‐1, CQU‐Chen‐Zn?Co?O‐2, CQU‐Chen‐OA?Co‐2‐1, CQU‐Chen‐Co?OA‐1, CQU‐Chen‐Ni?OA‐1, CQU‐Chen‐Gly?Co‐3‐1, CQU‐Chen‐Gly?Ni‐2‐1, CQU‐Chen‐Gly?Co?Ni‐1, etc. The introduction of 2D porous materials as electrode materials for SCs improves the energy storage performances. These materials provide a large number of active sites for ion adsorption, supply plentiful channels for fast ion transport and boost electrical conductivity and facilitate electron transportation and ion penetration. The unique 2D porous structures review is mainly devoted to the introduction of our contribution in the 2D porous nanostructured materials for SC. Finally, the further directions about the preparation of 2D porous materials and electrochemical energy conversion and storage applications are also included.     

Aqueous Manganese Dioxide Ink for Paper‐Based Capacitive Energy Storage Devices

We report a simple approach based on a chemical reduction method to synthesize aqueous inorganic ink comprised of hexagonal MnO₂ nanosheets. The MnO₂ ink exhibits long‐term stability and continuous thin films can be formed on various substrates without using any binder. To obtain a flexible electrode for capacitive energy storage, the MnO₂ ink was printed onto commercially available A4 paper pretreated with multiwalled carbon nanotubes. The electrode exhibited a maximum specific capacitance of 1035 F g^?1 (91.7 mF cm^?2). Paper‐based symmetric and asymmetric capacitors were assembled, which gave a maximum specific energy density of 25.3 Wh kg^?1 and a power density of 81 kW kg^?1. The device could maintain a 98.9 % capacitance retention over 10 000 cycles at 4 A g^?1. The MnO₂ ink could be a versatile candidate for large‐scale production of flexible and printable electronic devices for energy storage and conversion.     

离子的胶体状态与其电化学储能极限

阳离子氧化还原化学是电化学储能技术中最核心的储能机理,如何高效快速利用氧化还原活性阳离子是发展兼具高功率密度与高能量密度储电技术的关键。 处于胶体状态的阳离子可形成热力学平衡态和非平衡态,具有高反应活性和低离子迁移势垒,展现出独特的电化学特性。 本文着重介绍氧化还原活性阳离子的胶体状态与其在电化学储能上的应用,并从热力学和动力学方面阐述其储能机理,以及活性胶体离子电极和超级电容电池的构筑。 利用胶体的高比表面积、高离子吸附能力和荷电离子梯度分布等特性,创造性地构筑胶体超级电容电池,解决了现有电化学储能电极材料体系中高容量与高功率不能兼具的问题,同时开拓了胶体体系新的应用方向。     

基于玉米秸秆合成的多孔生物质炭材料及其电化学储能

以玉米秸秆为原料,合成了高比表面积(2167 m²/g)的多孔生物质炭材料。 优化实验条件即可获得性能最佳的生物质炭电极材料,其在电流密度为1 A/g时的比电容高达390 F/g。 更重要的是,以所得最佳多孔生物质炭为电极材料,3 mol/L 的KOH溶液为电解质,组装了液相对称超级电容器。 该超级电容器在功率密度为818 W/kg时,其能量密度高达7 Wh/kg,在循环10000圈后的电容保持率为91.1%。 同时,将两个这种超级电容器串联充电之后,能够点亮15个LED灯并驱动小风扇正常工作。 这些结果表明,将基于玉米秸秆的多孔生物质炭作为先进电极材料应用于超级电容器具有较大的实际应用价值。     

Large‐Scale Fabrication of Pseudocapacitive Glass Windows that Combine Electrochromism and Energy Storage

Multifunctional glass windows that combine energy storage and electrochromism have been obtained by facile thermal evaporation and electrodeposition methods. For example, WO₃ films that had been deposited on fluorine‐doped tin oxide (FTO) glass exhibited a high specific capacitance of 639.8 F g^?1. Their color changed from transparent to deep blue with an abrupt decrease in optical transmittance from 91.3 % to 15.1 % at a wavelength of 633 nm when a voltage of ?0.6 V (vs. Ag/AgCl) was applied, demonstrating its excellent energy‐storage and electrochromism properties. As a second example, a polyaniline‐based pseudocapacitive glass was also developed, and its color can change from green to blue. A large‐scale pseudocapacitive WO₃‐based glass window (15×15 cm²) was fabricated as a prototype. Such smart pseudocapacitive glass windows show great potential in functioning as electrochromic windows and concurrently powering electronic devices, such as mobile phones or laptops.     

Ionic Ingress and Charge‐Neutralization Phenomena of Conducting‐Polymer Films

Ionic ingress and diffusion through a conducting‐polymer (CP) film containing embedded charges under potential and concentration gradients is studied. Electroneutrality, a common assumption in modeling of similar systems, is not justified in this case or similar diffusion‐limited processes, as the timescale of ionic diffusion in the solid matrix is quite large. Counter ions therefore cannot move instantaneously for effective neutralization of excess charges. Poisson–Nernst–Planck (PNP) equations have to be solved for such cases without any simplifying assumption. Analytical solution shows the existence of a charge boundary layer, which limits and strongly influences the ionic flux. A general numerical method for solution is also developed for the dynamic modeling, analysis, and design of these types of systems. The numerical results are validated by comparison with analytical solutions as well as with some experimental results available in the literature. With this modeling framework, the basic features of controlled release of molecules across a CP film under an applied electrical potential can be explained quantitatively.     

Substituent effect on supercapacitive performances of conducting polymer‐based redox electrodes: Poly(3′,4′‐bis(alkyloxy) 2,2′:5′,2″‐terthiophene) derivatives

This work reports the synthesis of novel poly(3′,4′‐bis(alkyloxy)terthiophene) derivatives (PTTOBu, PTTOHex, and PTTOOct) and their supercapacitor applications as redox‐active electrodes. The terthiophene‐based conducting polymers have been derivatized with different alkyl pendant groups (butyl‐, hexyl‐, and octyl‐) to explore the effect of alkyl chain length on the surface morphologies and pseudocapacitive properties. The electrochemical performance tests have revealed that the length of alkyl substituent created a remarkable impact over the surface morphologies and charge storage properties of polymer electrodes. PTTOBu, PTTOHex, and PTTOOct‐based electrodes have reached up to specific capacitances of 94.3, 227.3, and 443 F g⁻¹ at 2.5 mA cm⁻² constant current density, respectively, in a three‐electrode configuration. Besides, these redox‐active electrodes have delivered satisfactory energy densities of 13.5, 29.3, and 60.7 W h kg⁻¹ and power densities of 0.98, 1, and 1.1 kW kg⁻¹ with good capacitance retentions after 10,000 charge/discharge cycles in symmetric solid‐state micro‐supercapacitor devices. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 480–495     

A High‐Voltage and Ultralong‐Life Sodium Full Cell for Stationary Energy Storage

Recently, there has been great interest in developing advanced sodium‐ion batteries for large‐scale application. Most efforts have concentrated on the search for high‐performance electrode materials only in sodium half‐cells. Research on sodium full cells for practical application has encountered many problems, such as insufficient cycles with rapid capacity decay, low safety, and low operating voltage. Herein, we present a layered P2‐Na_0.66Ni_0.17Co_0.17Ti_0.66O₂, as both an anode (ca. 0.69 V versus Na⁺/Na) and as a high‐voltage cathode (ca. 3.74 V versus Na⁺/Na). The full cell based on this bipolar electrode exhibits well‐defined voltage plateaus near 3.10 V, which is the highest average voltage in the symmetric cells. It also shows the longest cycle life (75.9 % capacity retention after 1000 cycles) in all sodium full cells, a usable capacity of 92 mAh g^?1, and superior rate capability (65 mAh g^?1 at a high rate of 2C).     

Exciton Diffusion in Polyfluorene Copolymer Thin Films: Kinetics,Energy Disorder and Thermally Assisted Hopping

A series of {(9,9‐dioctylfluorene)_0.7?x‐(dibenzothiophene‐S,S‐dioxide)_0.3‐[4,7‐bis(2‐thienyl)‐2,1,3‐benzothiadiazole]_x} (PFS₃₀‐TBTx), where x represents the minor percentage of the red emitter 4,7‐bis(2‐thienyl)‐2,1,3‐benzothiadiazole (TBT) randomly incorporated into the copolymer backbone, is investigated in order to follow the energy transfer from PFS₃₀ to TBT moieties. The emission of the donor poly[(9,9‐dioctylfluorene)_0.7‐(dibenzothiophene‐S,S‐dioxide)_0.3 identified by PFS₃₀ and peaking at 450 nm, is clearly quenched by the presence of the red TBT chromophore emitting at 612 nm, with an isoemissive point observed when the spectra are collected as a function of temperature. A plot of the ratio between the TBT and PFS₃₀ emissions as a function of the reciprocal of temperature gives a clear linear trend between 290 and 200 K, with an activation energy of 20 meV and showing a turn over to a non‐activated regime below 200 K. Picosecond time‐resolved fluorescence decays collected at the PFS₃₀ and TBT emission wavelengths, show a decay of the PFS₃₀ emission and a fast build‐in, followed by a decay, of the TBT emission, confirming that the population of the TBT excited state occurs during the PFS₃₀ lifetime(～600 ps). The population of the TBT excited state occurs on a time regime around 150 ps at 290 K, showing an energy barrier of 20 meV that turns over to a non‐activated regime below 200 K in clear agreement with the steady‐state data. The origin of the activation barrier is attributed to the presence of physical and energetic disorder, affected by fast thermal fluctuations that dynamically change the energy landscape and control the exciton migration through the polymer density of states.     

酸功能化碳纳米管对多孔碳材料储能活性及稳定性的增强作用

采用球磨法将酸功能化碳纳米管（AMWCNTs）与环糊精均匀混合。 酸功能化有利于增强碳管和环糊精间的相互作用,从而使二者形成均匀、有效的复合。 在N2气保护下碳化并经后续的ZnCl2活化处理,最终获得酸功能化碳纳米管/多孔碳(PC)复合体材料。 采用透射电子显微镜、X射线衍射和拉曼光谱等方法对材料结构进行了表征。 结果表明,碳纳米管在多孔碳骨架内均匀分布,并且复合体同时具有较高的比表面积和良好的导电性。 循环伏安及恒流充放电等电化学测试表明,由于二者的协同作用及碳纳米管在多孔碳骨架内均匀、有效的复合,材料具有较好的电化学储能性能和良好的电化学稳定性。 电流密度为0.5 A/g时,AMWCNTs/PC12-4（其中12代表β-环糊精和AMWCNTs的质量比,4代表酸化碳纳米管/β-环糊精碳与氯化锌的质量比）复合材料的质量比电容为156 F/g,远远高于AMWCNTs（43 F/g）和PC-4（87 F/g）。 经5000次循环后,电极比电容无明显衰减,而且每次恒流充放电的库仑效率均大于99.9%,说明复合材料具有良好的稳定性,是非常有前景的超级电容器电极材料。     

Polymer‐Induced Surface Modifications of Pd‐based Thin Films Leading to Improved Kinetics in Hydrogen Sensing and Energy Storage Applications

The catalytic properties of Pd alloy thin films are enhanced by a thin sputtered PTFE coating, resulting in profound improvements in hydrogen adsorption and desorption in Pd‐based and Pd‐catalyzed hydrogen sensors and hydrogen storage materials. The remarkably enhanced catalytic performance is attributed to chemical modifications of the catalyst surface by the sputtered PTFE leading to a possible change in the binding strength of the intermediate species involved in the hydrogen sorption process.     

Synthesis and Electronic Structure of Boron‐Graphdiyne with an sp‐Hybridized Carbon Skeleton and Its Application in Sodium Storage

Boron‐graphdiyne (BGDY), which has a unique π‐conjugated structure comprising an sp‐hybridized carbon skeleton and evenlydistributed boron heteroatoms in a well‐organized 2D molecular plane, is prepared through a bottom‐up synthetic strategy. Excellent conductivity, a relatively low band gap and a packing mode of the planar BGDY are observed. Notably, the unusual bonding environment of the all sp‐carbon framework and the electron‐deficient boron centers generates affinity to metal atoms, and thus provides extra binding sites. Furthermore, the expanded molecule pores of the BGDY molecular plane can also facilitate the transfer of metal ions in the perpendicular direction. The practical effect of the all sp‐carbon structure and boron heteroatoms on the properties of BGDY are demonstrated in its performance as the anode in sodium‐ion batteries.