聚(3,4-乙烯二氧噻吩)/MXene复合材料的制备及电容性能研究

MXene材料具有组分灵活可调、电容量较高等优势在超级电容器储能领域备受关注。采用电化学法制得聚3, 4-乙烯二氧噻吩/Nb₂CT_x MXene (PEDOT/MXene)复合电极材料。结果表明,在扫描速率为30 mV·s^-1时,PEDOT/MXene的面积比电容可达250.21 mF·cm^-2,当电流密度从0.1 mA·cm^-2增加到5 mA·cm^-2时,PEDOT/MXene的面积比电容保持率为83.5%,远优于PEDOT的64.1%,并且在100 mV·s^-1的扫描速率下循环测试1 000次后初始电容保持率可达84%,表现出良好的倍率性能和稳定性。工作为基于MXene基材料构筑高性能电化学储能界面提供了一定的借鉴。     

PEG改性氧化钨薄膜的电致变色特性

为改善WO₃薄膜的电致变色性能, 采用溶胶-凝胶法制备了聚乙二醇(PEG)改性的WO₃电致变色薄膜, 并对其着色态与漂白态的光学特性以及循环伏安特性进行了研究。研究表明: PEG改性的WO₃薄膜具有良好的电致变色性能, 循环5000次伏安曲线无明显衰减, 对可见光的最大透过率调制幅度可达71%。PEG的加入改变了WO₃薄膜的微结构, 形成了平均直径为9 nm的介孔, 提高了离子在其中的扩散速率, 因此改善了WO₃薄膜的电致变色性能。由于循环稳定性对于电致变色材料的实际应用至关重要, 因此这种低成本的湿化学法有望用于制备高性能的WO₃基电致变色器件。     

基于氧化钨和氧化镍的电致变色器件研究进展

电致变色器件(Electrochromic Devices, ECDs)是一种颜色变化受电压调控的智能装置, 具有工作温度范围宽、光学对比度高、可逆双稳态性能好、驱动电压低和能耗低等优点, 在智能动态调光窗、全彩色电子显示屏、防眩光护目镜、自适应双隐身伪装以及可视化储能等领域展现出了巨大的应用潜力。阴极着色材料氧化钨(WO₃)和阳极着色材料氧化镍(NiO)是两种被广泛研究的无机电致变色材料, 由WO₃和NiO薄膜组成的互补型电致变色器件在大规模智能窗的应用中具有极高的商业价值。改善电致变色器件的综合性能如光学调制范围、响应速度、循环寿命和耐候性等问题一直备受关注。本文围绕互补型电致变色器件的结构组成, 综述了基于WO₃和NiO的电致变色全器件的近期研究进展。首先分别阐述了WO₃和NiO薄膜的电致变色机理和衰退机制, 讨论了改进制备工艺、元素掺杂改性、设计纳米结构和引入复合材料这四种薄膜性能优化策略的作用和最新研究进展, 其次, 按照器件的组成成分和结构设计介绍了互补型电致变色全器件的分类体系, 总结了各组分材料的选择和器件结构对器件综合性能的影响, 最后对电致变色器件的应用前景和发展趋势进行了展望。     

石墨烯/MnO2纳米片复合薄膜的制备及其超级电容性能研究

采用两步界面组装法制备石墨烯/MnO₂纳米片(GMTF)三维复合薄膜电极，研究了复合薄膜的电化学性能。结果表明，MnO₂的赝电容和石墨烯的双电层电容相互协调，使得GMTF复合薄膜材料比单一的MnO₂纳米片或者石墨烯材料具有更佳的电化学性能。在三电极体系中，GMTF电极的比电容在5mV/s时达156.54mF/cm²,远高于石墨烯(40.24mF/cm²)和MnO₂纳米片(69.03mF/cm²)。此外，在两电极体系中，基于GMTF复合薄膜的固态超级电容器也显示出较高的面积比电容(120.49mF/cm²)和质量比电容(204.22F/g)、优良的循环性能。在功率密度为39mW/cm³时，能量密度能够达到1.735mWh/cm³。     

用于超级电容器的还原氧化石墨烯/NixMn1-x/2O2复合材料的电化学性能

MnO₂为有前景的超级电容器正极材料,具有较高的理论比电容及良好的循环稳定性,但电子电导性不佳限制了其应用。采用一步水热法制备了还原氧化石墨烯（RGO）/Ni_xMn_1-x/2O₂复合材料。通过XRD、SEM、TEM、FTIR、电化学分析等手段对制备的RGO/Ni_xMn_1-x/2O₂物相组成、微观形貌和电化学性能进行了表征和分析。电化学测试结果表明：Ni元素的引入提高了MnO₂的电容性能,以水热法制备的MnO₂的比电容为66 F/g （扫描速度10 mV/s）,而Ni元素掺杂量x=0.02时,Ni_0.02Mn_0.99O₂比电容为111 F/g;材料中引入RGO后,RGO/Ni_xMn_1-x/2O₂复合材料电容性能进一步提高,加入2wt%的RGO时,RGO/Ni_0.02Mn_0.99O₂的比电容为136 F/g。RGO的引入提高了活性材料的电子迁移速率,Ni元素的掺杂造成了MnO₂晶格中存在适量的点缺陷,提高了其导电性。以RGO/Ni_xMn_1-x/2O₂为正极的超级电容器可同时具备双电层电容器和赝电容器的优点,以Ni掺杂MnO₂和RGO的负载协同提高了该复合材料电化学性能。     

基于Cu3(HHTP)2薄膜的离子液体电致变色电极

室温离子液体具有宽电化学窗口和良好的环境稳定性, 是电致变色器件的理想电解质。然而传统电致变色材料的晶格间隙较窄, 限制了离子液体中大尺寸离子的扩散, 且大离子反复脱/嵌会破坏传统电致变色材料的结构, 导致性能衰减。金属有机框架材料(MOFs)是一种具有拓扑结构的多孔晶态材料, 有望为离子液体中大尺寸离子的传输提供通道。本工作在导电玻璃表面制备了三亚苯类Cu₃(HHTP)₂ (HHTP=2,3,6,7,10,11-六羟基三苯并菲) MOF薄膜, 并研究了Cu₃(HHTP)₂薄膜在离子液体电解质中电化学和电致变色行为和性能。结果表明, 相对于传统的LiClO₄/PC和NaClO₄/PC电解质, Cu₃(HHTP)₂薄膜在离子液体[EMIm]BF₄中表现出更低的接触电阻和更高的离子扩散效率, 电极的着色/褪色速度得到了显著提高(着色时间由10.3 s缩短至8.0 s, 褪色时间由23.6 s缩短至5.2 s)。同时, Cu₃(HHTP)₂薄膜在[EMIm]BF₄中也具有更高的光调制范围和着色效率。这项工作展现出MOFs/离子液体电化学体系在电致变色领域中的潜在应用价值。     

微晶形状对锐钛矿型TiO2材料超级电容器性能的影响

研究了晶粒各向异性对锐钛矿型TiO₂电化学性能的影响，这对超级电容器材料性能提升具有显著的意义。利用水热合成法，以HF和H₂SO₄为不同的酸性形貌诱导剂，钛酸四丁酯为钛源制备了片状和球状微晶的TiO₂,两者会暴露不同的晶面。经X射线衍射(XRD)、扫描电子显微镜(SEM)及透射电子显微镜(TEM)证实片状TiO₂暴露的晶面是高活性{001},而球状TiO₂暴露的晶面具有随机性。采用X射线光电子能谱(XPS)和比表面及孔隙度分析(BET)以及相应的电化学性能测试：结果表明片状TiO₂的比表面积(112.76 m²/g)是球状TiO₂比表面积(46.88 m²/g)的2.41倍，片状TiO₂超级电容器的比电容(174.0 F/g)是球状TiO₂超级电容器比电容(67.00 F/g)的2.59倍，同时片状TiO₂     

磷酸根掺杂MnFe2O4及其赝电容特性

采用水热法先合成MnFe₂O₄(MFO), 然后通过与PH₃反应制备了磷酸根离子掺杂的MnFe₂O₄(PMFO), 以提高它的电化学性能。研究结果表明, 磷酸根掺杂不仅增大了MnFe₂O₄的比表面积, 也增加了材料的电导性。在1 A/g电流密度下, PMFO比容量为750 F/g, 与MFO相比, 比电容提高了近70%, 同时循环稳定性也得到了极大改善。以PMFO为正极、活性碳为负极的非对称超级电容器(ASCs), 在功率密度为2.7 kW/kg时, 能量密度达到168.8 Wh/kg。因此, PMFO是有极大应用前景的超级电容器电极材料。     

导电聚合物PEDOT:PSS纸基印刷成膜和变色器件的制备

目的 以导电聚合物PEDOT:PSS作为电极和电致变色材料,通过棒涂、丝网印刷和凹版印刷等3种方式,实现导电聚合物纸基电致变色器件的制备.方法 通过溶剂(二甲基亚砜、异丙醇、甲醇、乙二醇、聚乙烯醇)掺杂的方式对3种印刷成膜特性进行优化;使用丙三醇提高PEDOT:PSS薄膜的导电性,采用PEDOT:PSS制作器件的变色层和电极层,简化变色器件结构.分别对变色器件的启动电压、变色效果、紫外吸收和弯曲等性能进行评价.结果 3种印刷方式均能实现纸基变色器件的制备,其中以凹版印刷方式制备的变色器件具有最佳的变色性能,即启动电压低(U=0.18 V)、响应时间短(t=2 s)、色差变化大(ΔE*=25.54),变色前后吸光度变化大(0.27),弯曲循环1000次后色差变化为1.结论 电致变色器件可以通过印刷的方式在纸基材料上进行制备,将纸基电致变色器件与印刷包装产品相结合,不仅能提高产品包装的外观表现,还可以增加产品包装的技术水平.     

氮掺杂和SnO2纳米粒子负载对全固态对称型石墨烯超级电容器性能的影响

电极材料是影响超级电容器性能的主要因素。本研究采用溶剂热法合成石墨烯和氮掺杂石墨烯, 通过简单的化学法在其表面负载SnO₂纳米粒子。利用刮涂工艺在FTO玻璃表面制备石墨烯、SnO₂/石墨烯、氮掺杂石墨烯和SnO₂/氮掺杂石墨烯薄膜, 并经400℃热处理。分别以制备的石墨烯基薄膜和PVA/H₃PO₄为电极和电解质组装对称型全固态超级电容器。测试结果表明, 与石墨烯相比, 氮掺杂石墨烯具有较大的晶粒尺寸、较高的比表面积和较高的超电容性能; SnO₂纳米粒子负载可显著提高石墨烯和氮掺杂石墨烯的超电容性能。     

Towards the improvement of attenuation range and response time of electrochromic polymer-based variable optical attenuators

A solid–liquid electrochromic variable optical attenuator device consisting of a thin layer of LiClO₄-doped poly(3,4-ethylenedioxythiophene) (PEDOT) and ferrocene in propylene carbonate has been demonstrated to exhibit a large dynamic range of optical attenuation at the telecommunication wavelength of 1550 nm. Doping of PEDOT film with an electrolyte greatly improves the device performance in terms of optical attenuation or color efficiency at 1550 nm and response time. An optimized single-layer device consisting of LiClO₄-doped PEDOT film (440 nm) shows a 10-dB dynamic range of optical attenuation at 1550 nm, a low optical loss of 0.86 dB for the bleached state, and a response time of 5–7 s at the switching potential of 0–2 V.     

Electrochromic thin films from a redox active diarylethene by electrochemical polymerization

A diarylethene substituted with 3,4-(propane-1,3-diyldioxy)thiophene (ProDOT) was synthesized to induce electrochemical deposition of diarylethenes. The ProDOT substituted diarylethene (BTFPP) showed reversible photochromism from colorless to purple upon exposure to a UV light and bleached to colorless by a visibly light. The oxidation potential of the new ProDOT substituted diarylethene was lower than that of the unsubstituted diarylethenes due to the electroactive ProDOT unit. Under an electrochemical condition, the solution of BTFPP gave soluble polymers but deposited insoluble film on a working electrode coated with a PEDOT layer. This result indicates that the PEDOT nano layer (68 nm thick) function as a seeding layer to induce polymerization and electrodeposition of BTFPP. Furthermore electro-copolymerization using a mixture of BTFPP and EDOT afforded electrodeposition of the copolymers on the PEDOT seeding layer. An electrochromic electrode was successfully fabricated by depositing the photochromic BTFPP on an ITO glass, which shows a reversible electrochromic change from violet to sky blue.     

Comparison of performance parameters of poly(3,4 ethylenedioxythiophene) (PEDOT) based electrochromic device on glass with and without counter electrode

Conjugated polymers are promising materials for electrochromic device technology. Aqueous dispersions of poly(3,4-ethylenedioxythiophene)-(PEDOT) were spin coated onto transparent conducting oxide (TCO) coated glass substrates. A seven-layer electrochromic device was fabricated with the following configuration: glass/transparent conducting oxide (TCO)/PEDOT (main electrochromic layer)/gel electrolyte/prussian blue (counter electrode)/TCO/glass. The device fabricated with counter electrode (Prussian blue) showed a contrast of 18% and without counter electrode showed visible contrast of 5% at 632 nm at a voltage of 1.9 V. The comparison of the device is done in terms of the colouration efficiency of the devices with and without counter electrode.     

Conductivity enhancement of PEDOT:PSS thin film using roll to plate technique and its characterization as a Schottky diode

The conductivity of poly(3,4-ethylene dioxythiophene):poly(styrene sulfonate) was improved by pressing the PEDOT:PSS thin film using roll to plate system. PEDOT:PSS thin film was deposited on polyethylene terephthalate using electrohydrodynamics atomization technique. The physico-chemical properties of the pressed thin film at different loads were compared with an un-pressed sample. The electrical properties show that the film conductivity has been increased by four times. An optimized pressing load was found to have good conductivity and transmittance of the thin film. A hybrid device (PEDOT:PSS/F8BT/ZnO/Ag) was fabricated using layer by layer method with PEDOT:PSS as anode. The I–V characterization showed that the device with pressed PEDOT:PSS showed higher current densities. The results give a promising future of PEDOT:PSS in electronics device applications using printed electronics techniques.     

一种新型的溶液型电致变色器件的研究

通过在紫罗精溶液中加入钛离子, 得到了一种新型互补型的电致变色溶液. 利用这种电致变色溶液设计成电致变色器件, 通过紫外-可见分光光度计表征, 这种溶液型电致变色器件透过率变化在600nm附近可由80%降低到20%; 通过电致变色器件和透射光强变化的关系, 测得其退色时间<2s, 并且具有自擦除效果.     

导电聚3,4-乙撑二氧噻吩的制备及性能

以水为溶剂,分别选用对甲苯磺酸钠、高氯酸锂、硫酸钠为支持电解质,用电化学法合成聚3,4-乙撑二氧噻吩(PEDOT)膜。采用线性扫描伏安法(LSV)确定了合适的聚合电位;采用循环伏安法(CV)、电化学交流阻抗谱(EIS)研究了PEDOT膜的电化学行为。结果表明,掺杂阴离子种类对膜的循环伏安特性、EIS曲线等有很大的影响;此外研究了掺杂不同阴离子的PEDOT膜对电极的粘接性能,发现粘接性能也与阴离子种类有关。     

Multiwall carbon nanotube and poly(3,4-ethylenedioxythiophene): polystyrene sulfonate (PEDOT:PSS) composite films for transistor and inverter devices

Highly conductive multiwalled carbon nanotube (MWNT)/Poly(3,4-ethylenedioxythiophene) polymerized with poly(4-styrenesulfonate) (PEDOT:PSS) films were prepared by spin coating a mixture solution. The solution was prepared by dispersing MWNT in the PEDOT:PSS solution in water using ultrasonication without any oxidation process. The effect of the MWNT loading in the solution on the film properties such as surface roughness, work function, surface energy, optical transparency, and conductivity was studied. The conductivity of MWNT/PEDOT:PSS composite film was increased with higher MWNT loading and the high conductivity of MWNT/PEDOT:PSS films enabled them to be used as a source/drain electrode in organic thin film transistor (OTFT). The pentacene TFT with MWNT/PEDOT:PSS S/D electrode showed much higher performance with mobility about 0.2 cm2/(V s) and on/off ratio about 5 × 10? compared to that with PEDOT:PSS S/D electrode (～0.05 cm2/(V s), 1 × 10?). The complementary inverters exhibited excellent characteristics, including high gain value of about 30.     

Poly(3,4-ethylenedioxythiophene) nanotubes as electrode materials for a high-powered supercapacitor

We report the fast charging/discharging capability of poly(3,4-ethylenedioxythiophene) (PEDOT) nanotubes during the redox process and their potential application to a high-powered supercapacitor. PEDOT nanotubes were electrochemically synthesized in a porous alumina membrane, and their structures were characterized using electron microscopes. Cyclic voltammetry was used to characterize the specific capacitance of the PEDOT nanotubes at various scan rates. A type I supercapacitor (two symmetric electrodes) based on PEDOT nanotube electrodes was fabricated, and its energy density and power density were evaluated by galvanostatic charge/discharge cycles at various current densities. We show that the PEDOT-nanotube-based supercapacitor can achieve a high power density of 25?kW?kg(-1) while maintaining 80% energy density (5.6?W?h?kg(-1)). This high power capability is attributed to the fast charge/discharge of nanotubular structures: hollow nanotubes allow counter-ions to readily penetrate into the polymer and access their internal surfaces, while the thin wall provides a short diffusion distance to facilitate the ion transport. Impedance spectroscopy shows that nanotubes have much lower diffusional resistance to charging ions than solid nanowires shielded by an alumina template, providing supporting information for the high charging/discharging efficiency of nanotubular structures.     

溶剂交换制备高比表面超级电容器材料V2 O5

采用淬冷法制备V2O5溶胶,浸渍覆盖在泡沫镍上,并以低表面张力有机溶剂交换除去其自然吸附水。研究表明,所得凝胶比表面积可达36．67m^2／g。用制备的V2O5为正极,锂片为对电极,LiPF6有机溶液为电解液,组成模拟超级电容器。以电压2V计,比功率为10kW／kg,比能量达158Wh／kg,而不经过溶剂交换过程制备的电极相同比功率下比能量为106Wh／kg。     

Photoresponsive Smart Coloration Electrochromic Supercapacitor

Electrochromic devices have been widely adopted in energy saving applications by taking advantage of the electrode coloration, but it is critical to develop a new electrochromic device that can undergo smart coloration and can have a wide spectrum in transmittance in response to input light intensity while also functioning as a rechargeable energy storage system. In this study, a photoresponsive electrochromic supercapacitor based on cellulose‐nanofiber/Ag‐nanowire/reduced‐graphene‐oxide/WO₃‐composite electrode that is capable of undergoing “smart” reversible coloration while simultaneously functioning as a reliable energy‐storage device is developed. The fabricated device exhibits a high coloration efficiency of 64.8 cm² C^?1 and electrochemical performance with specific capacitance of 406.0 F g^?1, energy/power densities of 40.6–47.8 Wh kg^?1 and 6.8–16.9 kW kg^?1. The electrochromic supercapacitor exhibits excellent cycle reliability, where 75.0% and 94.1% of its coloration efficiency and electrochemical performance is retained, respectively, beyond 10 000 charge–discharge cycles. Cyclic fatigue tests show that the developed device is mechanically durable and suitable for wearable electronics applications. The smart electrochromic supercapacitor system is then integrated with a solar sensor to enable photoresponsive coloration where the transmittance changes in response to varying light intensity.