绿-黄可逆电热致变色织物的制备及其性能

石墨烯因其优异的导电性、优越的柔韧性和环境稳定性, 在可穿戴电子纺织品领域发挥了重要作用。本工作通过丝网印刷技术分别将自制的石墨烯浆料和复合热致变色油墨印在聚酯织物的正反面, 构筑了一种石墨烯基绿-黄可逆电热致变色织物。采用SEM、XRD以及FTIR等分析了织物的结构性质和变色原理, 采用红外热成像仪及全色差色度仪研究了织物的热学以及变色性能。结果表明：石墨烯电热致变色织物厚度约为250 μm, 在12 V电压下逐渐加热超过45 ℃, 焦耳热主要通过热传导至变色层, 结晶紫内酯的闭开环实现绿-黄可逆变色, 其变色响应时间约为15 s, 褪色响应时间约为27 s。石墨烯电热致变色织物经历30°~180°的弯曲角度后, 电压-电流曲线保持稳定。经200次加热/冷却循环后, 性能未发生明显衰退。本研究成功制备了颜色在绿-黄之间变化、响应迅速、循环性能良好的可逆电热致变色织物：石墨烯膜‖聚酯织物‖热致变色膜, 在军事伪装和可穿戴显示领域有一定的应用前景。     

NiO/PB复合电致变色薄膜的制备及其性能研

采用水热法制备了垂直生长的氧化镍(NiO)纳米片薄膜, 并利用电沉积法将普鲁士蓝(PB)负载到NiO纳米片薄膜上, 制备了新型的NiO/PB复合电致变色薄膜。利用X射线衍射仪(XRD)、场发射扫描电镜(SEM)对样品的晶型以及微观形貌进行了表征, 采用紫外-可见光光度计以及电化学工作站对NiO/PB复合薄膜的电化学和电致变色性能进行了研究和表征。结果表明: NiO/PB复合电致变色薄膜具有多孔结构和较大的比表面积, 可以增大电解质与电极材料的接触面积。PB成功负载到NiO薄膜表面, 使NiO/PB复合薄膜表现出较大的电流密度。相比于单层NiO薄膜, NiO/PB复合薄膜表现出更好的电致变色性能, 其光调制范围可以达到46%, 着色效率为141 cm²/C, 并且其着色时间可以缩短到5 s, 褪色时间为6 s。     

热处理温度对电致变色玻璃用WO_3薄膜性能的影响研究

采用过氧化聚钨酸法制备WO_3溶胶,在ITO导电玻璃基体上采用旋涂法制备WO_3薄膜。主要探讨了退火温度对WO_3薄膜结构与电变色性能、响应时间和循环稳定性的影响。热重和X射线衍射分析结果表明:热处理温度应低于320℃时,WO_3薄膜为非晶态。在240~320℃范围内,随着热处理温度升高,光密度变化量降低即电致变色性能变差,着-褪色时间延长,而薄膜的循环稳定性越来越好。经320℃退火处理的WO_3薄膜形成晶态,稳定性好,此时该电致变色薄膜的着-褪色响应时间分别为2.76和1.30s。     

NiO/PB复合电致变色薄膜的制备及其性能研究

采用水热法制备了垂直生长的氧化镍(NiO)纳米片薄膜,并利用电沉积法将普鲁士蓝(PB)负载到NiO纳米片薄膜上,制备了新型的NiO/PB复合电致变色薄膜。利用X射线衍射仪(XRD)、场发射扫描电镜(SEM)对样品的晶型以及微观形貌进行了表征,采用紫外–可见光光度计以及电化学工作站对NiO/PB复合薄膜的电化学和电致变色性能进行了研究和表征。结果表明:NiO/PB复合电致变色薄膜具有多孔结构和较大的比表面积,可以增大电解质与电极材料的接触面积。PB成功负载到NiO薄膜表面,使NiO/PB复合薄膜表现出较大的电流密度。相比于单层NiO薄膜,NiO/PB复合薄膜表现出更好的电致变色性能,其光调制范围可以达到46%,着色效率为141 cm~2/C,并且其着色时间可以缩短到5 s,褪色时间为6 s。     

衬底温度对柔性硫化锌薄膜结构与光学性能的影响北大核心CSCD

本文利用射频磁控溅射薄膜沉积技术在柔性聚酰亚胺(PI)、氧化铟锡(ITO)玻璃及石英玻璃衬底上制备了透明硫化锌(ZnS)薄膜。通过改变生长过程中的衬底温度,全面系统地研究了衬底温度对柔性和刚性ZnS薄膜的晶体结构、光透过率、光学常数以及表面性能影响的规律。研究表明升高衬底温度有利于形成ZnS薄膜(111)晶面的择优取向生长。不同衬底温度条件下制备的柔性和刚性ZnS薄膜在可见光波长范围内的平均光透过率均大于80%;在红外波长范围的平均光透过率达到85%。柔性ZnS薄膜在400 nm-890 nm波长范围内的光学折射率为2.21-2.56。刚性ZnS薄膜的光学折射率随着衬底温度的升高有所增加,当衬底温度为300℃时,刚性ZnS薄膜在890 nm波长处的折射率达到2.26。柔性ZnS薄膜厚度及表面粗糙度均随着衬底温度的升高而降低,当衬底温度为300℃时,柔性ZnS薄膜表面均方根粗糙度达到最小值2.99 nm。为实现高性能柔性ZnS光电器件,应控制生长柔性ZnS薄膜的衬底温度在200℃-300℃,以获得最优化的器件性能。     

辐射变色薄膜剂量计的退火效应

制备了一批辐射变色薄膜,利用紫外线辐照该薄膜,辐照后薄膜由无色变为蓝色,并在670nm处出现一吸收峰,吸收峰的吸光度对辐照剂量有良好的线性响应关系。对辐照后的薄膜进行了退火实验,当温度升高到45℃后,出现一新的吸收峰(545nm),随着温度进一步升高670nm峰逐渐消失,545nm峰逐渐升高。当温度达到110℃时,670nm峰完全消失,545nm峰达到稳定,薄膜也相应地由蓝色变为粉红色。薄膜颜色的变化主要是由于其内部分子结构发生了变化:由碳碳三键共轭(无色)变为辐照后的碳碳三键和碳碳双键不在一个平面内的共轭(蓝),最后变为退火后的碳碳三键和碳碳双键在一个平面内的共轭(粉红)。进一步的红外光谱分析也证实了对薄膜结构变化的解释。     

静电喷雾法/原位洗脱法结合制备电致变色薄膜EI北大核心CSCD

电致变色材料在提倡低碳节能的发展理念下有很好的发展前景,而探索一种高效简单且性能优异的制备工艺尤为重要。利用静电喷雾法结合原位洗脱法制备了聚合物电致变色薄膜。根据电解质盐的颜色适配性和溶解性,选择四丁基高氯酸铵(TBAP)作为模板剂,在易加工的TPA-OMe-PA溶液中添加不同比例的电解质盐,然后利用静电喷雾技术在ITO玻璃表面沉积制备薄膜,再通过原位洗脱法去除其中的模板剂-电解质盐,最终制备出含有多层级孔结构的聚合物薄膜。采用电子扫描显微镜对其形貌进行分析,利用电化学工作站结合紫外/可见/红外光谱仪研究了薄膜的电致变色性能。研究结果表明,利用静电喷雾技术与原位洗脱法制备的聚合物薄膜具备多层级孔结构和良好的电致变色性能。其中电解质含量为33.3%(质量分数)时,多层级孔隙率最高,且电致变色性能最为优异,漂白时间/着色时间缩减至0.6 s/1 s,着色效率达到608.2 cm^(2)·C^(-1),为已报道基于相同材料的电致变色薄膜的最快响应速度。     

超低温热致变色复合物的制备与微胶囊包封研究

为了拓宽低温可逆热致变色材料变色温度和变色时间的范围,以聚乙二醇400(PEG400)为辅剂,十二醇等为隐色剂,变色母料为显色剂,无水乙醇为溶剂制备了超低温热致变色复合物;采用原位聚合法制备了以阿拉伯树胶为壁材,热致变色复配物为芯材的微胶囊,并对其进行显微结构、粒径、变色温度和变色时间等方面的测试与分析。结果表明:使用十二醇时,变色温度为5~15℃,变色时间为210s,颜色按照深蓝-蓝色-浅蓝的顺序变化。聚氨酯的引入使变色膜变色温度下降,但降幅较小,可以起到保温隔热的作用。微胶囊化后材料具有优良的耐疲劳性能,还扩展了变色材料的应用领域。     

电致变色纳米氧化镍薄膜的溶胶-凝胶法制备与表征

以无水氯化镍、乙醇为前驱液,加入适量的丁醇和柠檬酸为稳定剂,通过回流、水解得到稳定的溶胶;采用浸渍-提拉的方法在ITO导电玻璃上形成均匀的膜层;分析了溶胶制备中加水量的影响;研究了热处理温度对制备膜层的结构、光透过率的影响;对经过不同处理的膜层进行X射线衍射、透射电子显微镜、扫描电子显微镜、热重分析等研究表明:在空气中加热到350℃、保温30min薄膜分解为稳定的具有立方结构的NiO纳米晶;以氢氧化钾水溶液为电解质的循环伏安、电致变色实验结果表明制备的纳米氧化镍薄膜具有良好的电致变色特性.     

热处理温度对TiO2薄膜结构及电色性能的影响

采用溶胶-凝胶法在镀有ITO透明电极的玻璃上制备了TiO2电致变色薄膜,用XRD、FT-IR、SEM、TG-DTA、分光光度计和电化学工作站等研究了热处理温度对其成分、结构和电致变色性能的影响.结果表明:350℃以下,薄膜呈非晶态;450℃时形成锐钛矿结构,同时出现网状分布的缝隙.薄膜具有较弱的阴极电致变色效应,对可见光的调制幅度随温度的升高而降低.当温度从120℃上升到450℃时,样品的K值由0.56升高到0.93,循环寿命由不足50次增加到10000次以上,注入电荷密度则由14.12 mC/cm2下降到6.79 mC/cm2.350℃处理的薄膜具有较好的综合性能,适于制备透射型电致变色器件的对电极.     

Nanomanufacturing of RGO‐CNT Hybrid Film for Flexible Aqueous Al‐Ion Batteries

A highly electrically conductive film‐type current collector is an essential part of batteries. Apart from the metal‐based current collectors, lightweight and highly conductive carbon materials such as reduced graphene oxide (RGO) and carbon nanotubes (CNTs) show great potential as current collectors. However, traditional RGO manufacturing usually requires a long time and high energy, which decreases the product yielding rate and manufacturing efficiency. Moreover, the performance of the manufactured RGO needs to be further improved. In this work, CNT and GO are evenly mixed into GO‐CNT, which can be directly reduced into RGO‐CNT by Joule heating at 2936 K within less than 1 min. The fabricated RGO‐CNT achieves a high electrical conductivity of 2750 S cm^?1, and realizes a 10⁶‐fold increase. The assembled flexible aqueous Al‐ion battery with RGO‐CNT as the current collector exhibits impressive electrochemical performance in terms of superior cycling stability and exceptional rate capability, and excellent mechanical ability regarding the tolerance to mechanical damage such as bending, folding, piercing, and cutting without detrimental consequences.     

Using “intercalation bridging” to effectively improve the electrothermal properties of sheet graphite / ultrafine carbon powder conductive paste for screen printing

Electrothermal materials can easily and controllably convert electric energy into heat energy, and are widely used in many electrothermal fields. In this paper, a series of conductive pastes were simply prepared by ball milling, and their rheological and electrothermal properties were studied. Phenolic resin was used as curing agent of epoxy resin and rheological modifier, which could make the paste have very good printing applicability. Ultrafine carbon(UC) powder has excellent dispersion effect. Sheet carbon materials such as graphite powder(GP), graphite nanosheet(GS) and graphene(GE) would improve the performance of paste using only UC as conductive filler. It was proved that GE with the smallest thickness has the most obvious lifting effect. UC was gathered around the graphene sheet, as a bridge between graphene sheets. GE could also be connected with each other to build a more effective and denser conductive path. The electrothermal film could reach 199°C under 30 V voltage, increasing by 254.7% compared with the electrothermal film with only UC as conductive filler. The electrothermal film had a short response time, good recyclability and excellent flexibility. The electrothermal film also had certain electromagnetic shielding efficiency. The electromagnetic shielding efficiency SE could reach about 20 dB at 30–1500 MHz, and the ratio of field strength before and after attenuation SE_% could reach 97%?+?. This electrothermal film has simple preparation process, good printing applicability, controllable film resistance, excellent flexibility, fast response speed and good recyclability. It is suitable for large-scale preparation and has broad application prospects in many scenarios.

     

FeS2/RGO纳米复合材料的制备及热电池放电性能

以氯化亚铁、硫代硫酸钠和氧化石墨烯(GO)为原料, 采用水热法制备FeS₂/还原氧化石墨烯(RGO)纳米复合材料, 并采用X射线衍射仪(XRD)、扫描电子显微镜(SEM)、激光粒度分布仪和差热分析仪(DTA)等对FeS₂/RGO复合材料进行了表征。结果表明, 在水热反应过程中加入GO可以防止FeS₂颗粒的团聚, 使FeS₂形成疏松的球状颗粒。采用LiCl-KCl电解质, 在450℃以100mA/cm²电流密度放电时, 截止1.5 V时, FeS₂/RGO比容量为314.9 mAh/g, 较FeS₂高65.6 mAh/g; 采用LiF-LiCl-LiBr电解质, 在500℃以100 mA/cm²电流密度放电, 截止1.5 V时, FeS₂/RGO放电比容量为302.3 mAh/g, 较FeS₂高29.8 mAh/g。与FeS₂相比, 加入石墨烯提高了正极材料的导电性, 单体电池在放电过程中极化电阻相对较小, 使得FeS₂/RGO复合材料表现出较高的放电比容量。     

大气等离子喷涂MoSi2-30Al2O3电热涂层的组织结构及性能

以MoSi₂-30Al₂O₃混合粉末为原料, 利用大气等离子喷涂技术制备MoSi₂-Al₂O₃体系电热涂层。采用XRD、SEM、通电测试、热重-差热分析等对涂层的相组成、组织形貌和热稳定性进行表征。结果表明：MoSi₂-30Al₂O₃电热涂层体系组织均匀致密, 添加Al₂O₃能改善MoSi₂的电阻率及低温抗氧化性; MoSi₂-30Al₂O₃涂层电热性能优异, 在循环加热测试中, 能稳定地加热到320 ℃并长时间保温, 辊面温度分布均匀, 中部温差控制在25 ℃之内; 循环加热过程中的氧化及热应力的弛豫会导致涂层产生裂纹及孔隙进而导致涂层电阻率升高。     

Impermeable Graphene Skin Increases the Heating Efficiency and Stability of an MXene Heating Element

A Joule heater made of emerging 2D nanosheets, i.e., MXene, has the advantage of low-voltage operation with stable heat generation owing to its highly conductive and uniformly layered structure. However, the self-heated MXene sheets easily get oxidized in warm and moist environments, which limits their intrinsic heating efficiencies. Herein, an ultrathin graphene skin is introduced as a surface-regulative coating on MXene to enhance its oxidative stability and Joule heating efficiency. The skin layer is deposited on MXene using a scalable solution-phased layer-by-layer assembly process without deteriorating the excellent electrical conductivity of the MXene. The graphene skin comprises narrow and hydrophobic channels, which results in ≈70 times higher water impermeability of the hybrid film of graphene and MXene (GMX) than that of the pristine MXene. A complementary electrochemical analysis confirms that the graphene skin facilitates longer-lasting protection than conventional polymer coatings owing to its tortuous pathways. In addition, the sp² planar carbon surface with a low heat loss coefficient improves the heating efficiency of the GMX, indicating that this strategy is promising for developing adaptive heating materials with a tractable voltage range and high Joule heating efficiency.     

Memory switching in amorphous Ge---Se---Tl chalcogenide semiconductor films

The switching effects in amorphous GeSe₂, GeSe₄, GeSe₂Tl and GeSe₄Tl thin films have been investigated. The observed switching phenimenon for these compositions was of the memory type. The threshold switching voltage was found to increase linearly with increasing film thickness (80–740 nm), while it decreased exponentially with increasing temperature (T < T_g).

The effect of adding thallium to both amorphous GeSe₂ and amorphous GeSe₄ results in decreasing the values of the threshold electric field, the activation energy of switching, as well as the thermal activation energy of conduction. The results obtained are explained in accordance with the electrothermal model of breakdown.     

Arc-instability generated during the Joule heating induced crystallization of amorphous silicon films

Joule heating induced crystallization (JIC) was accomplished by applying an electric field to a conductive layer located beneath the amorphous silicon film. This study found that an intense arc is generated at the interface between the silicon and the electrode. The artificial modification of a JIC-sample structure led us to the finding that arc generation is caused by the dielectric breakdown of a SiO₂ layer that is sandwiched between the transformed polycrystalline silicon and a conductive layer at high temperatures during Joule heating.     

还原氧化石墨烯/MnO_2气凝胶对甲醛的去除

为制备新型高效去除甲醛材料,采用水热法制备了还原氧化石墨烯(RGO)/MnO_2气凝胶,通过SEM、TEM、TGA、XPS和BET对RGO/MnO_2气凝胶的形态结构及性能进行了表征,并研究了RGO/MnO_2气凝胶对甲醛的去除能力。结果表明:在RGO/MnO_2气凝胶的前驱体中,氧化石墨烯(GO)为单层二维纳米材料;MnO_2气凝胶由MnO_2纳米线组成,MnO_2纳米线的直径在40nm左右,长度达5μm以上,且属于隐钾锰矿型结构。RGO/MnO_2气凝胶是一种由片状材料组成的具有三维多孔结构的材料,该片状材料是由均匀分布的RGO纳米片和MnO_2纳米线组成的,RGO将MnO_2纳米线隔开,起到隔板的作用,使MnO_2纳米线在RGO中均匀分布。RGO/MnO_2气凝胶在100℃以下具有良好的热学稳定性。RGO/MnO_2气凝胶对低浓度甲醛具有较好的去除能力,去除率为62.5%,与MnO_2气凝胶相比,相同条件下RGO/MnO_2气凝胶对甲醛的去除率提高了30.0%,证实RGO有助于提高MnO_2对甲醛的去除能力。     

电应力对HfO2栅介质漏电流的影响

使用导电原子力显微镜（Conductive Atomic Force Microscopy,CAFM）对电压应力作用下HfO2栅介质薄膜局域漏电点的形成和产生机制进行了研究,结果表明,在电压应力作用下,HfO2介质层中的缺陷被驱动和聚集形成导电通道,产生漏电点。漏电点产生的数量、漏电流大小均受电压应力和作用时间的影响。HfO2栅介质层中晶界处的缺陷密度高于晶粒处,导致晶界处更容易产生漏电通道。在栅介质击穿过程中,电压应力在诱发漏电流产生的同时产生焦耳热,对HfO2介质表面造成热损伤,导致击穿后HfO2介质表面出现凹陷。