电泳沉积耦合电化学还原法制备柔性石墨烯自支撑薄膜电极超级电容器(英文)

通过电泳沉积和电化学还原相耦合的方法制备柔性的石墨烯自支撑薄膜电极。首先,通过电沉积的方法在石墨基底上制备氧化石墨烯薄膜,然后通过对氧化石墨烯薄膜进行电化学还原,得到电容性能优异的石墨烯薄膜电极材料。通过SEM、XRD、FT-IR和电化学测试对石墨烯的表面形貌、结构和电容性能进行表征。结果表明:制备的石墨烯电容性能良好,在1 mol/L的硫酸电解液中,循环伏安扫速为10 mV/s时,比电容为254 F/g;当电流密度为83.3 A/g时,比电容能保持在132 F/g;最大功率密度可达39.1 kW/kg,能量密度为11.8 W·h/kg;充放电循环1000次后,电容能保持97.02%,表明该石墨烯薄膜电极材料具有优异的循环稳定性能。     

富氧多孔石墨烯薄膜制备及其超级电容器性能

目的 改善传统的激光诱导石墨烯薄膜电极本身储电能力差、应用范围有限的问题。方法 利用CO2激光扫描自制的高含氧酚醛树脂薄膜制备了一种富氧的多孔石墨烯薄膜电极,并对其进行电化学活化处理,用以增强内部含氧基团的活性和含量,对石墨烯薄膜的形貌、组成以及电化学性能进行了表征。结果 在激光的高温高压下,酚醛树脂分解释放的大量气体会使石墨烯薄膜内部形成丰富的纳米孔隙结构,氮气吸附解吸曲线的结果显示其比表面积达到了324 m²/g。此外,在酸性电解质下采用电化学激活的方式,能够使石墨烯薄膜内部碳原子上的含氧基团发生转化反应,并且它们与碳原子的键合也为电极提供了更稳定的结构。在电化学性能测试中,石墨烯薄膜上的氧官能团发生高效的可逆氧化还原反应,在0.5 mA/cm²的电流密度下具有高达342.8 mF/cm²的面积比容量,组装成超级电容器后也保持了优异的储能特性和循环稳定性,在0.058 9 mW/cm²的功率密度下具有5.93 μWh/cm²的能量密度。结论 利用该方法制备的富氧多孔石墨烯电极材料兼具高稳定性和高比电容的优势,有望在实际应用中为后续赝电容材料的可靠负载和异原子的高含量稳定掺杂提供一种更可靠的石墨烯骨架,为构筑新型高性能储能器件提供了设计思路。     

静电纺丝结合还原氮化法制备多孔TiN纤维及其电化学性能

采用静电纺丝结合还原氮化法制备多孔TiN纤维,利用XRD、SEM、TEM和N_2吸脱附等分析其结构,使用循环伏安和充放电测试其电化学性能。结果表明,纤维为立方TiN相,纤维连续,存在较为丰富的介孔结构,其比表面积为21.55 m~2/g。样品在不同扫率下的CV曲线均呈类矩形,由电流密度为20 mA/g时GCD曲线计算其比电容为24.03 F/g,在电流密度为50 mA/g时,经4500次充放电循环后样品的比电容仍能保持90%以上,当功率密度为20 W/kg时,样品的能量密度为3.3 Wh/kg。因此,采用本方法制备的多孔TiN纤维在超级电容器领域具有应用潜力。     

石墨烯/纳米金刚石复合电极性能研究

为开发具有高能量密度、高功率密度和长寿命的超级电容器复合电极,将纳米金刚石(nano diamond,ND)经真空热处理获得石墨化纳米金刚石(graphitized nano diamond,GND),再采用超声法将不同质量比的石墨烯与GND制备成复合电极,进行电化学性能测试并分析其结构。电化学性能测试结果表明:质量比为4∶1时制备的石墨烯/GND复合电极具有良好的双层电容特性,其循环伏安曲线近似呈矩形且形状几乎不随扫描速率变化而改变。在扫描速率为2 mV/s,电解液为0.5 mol/L的K₂SO₄溶液的条件下,其比电容高达103.3 F/g;经循环扫描1000圈后,比电容衰减幅度不到0.95%,具有优异的循环稳定性。经透射电镜分析可知:真空高温处理后ND表面形成石墨烯层;受金刚石结构的制约,石墨烯层间距由内向外逐渐增加,提高了复合电极的导电性。由扫描电镜形貌表征可知:GND均匀附着在石墨烯表面,在石墨烯的片层之间形成阻断,防止石墨烯的杂乱堆叠,有利于电解液的扩散,从而使复合材料的比电容增大、电化学性能提高。      

静电纺丝结合还原氮化法制备多孔TiN纤维及电化学研究

采用静电纺丝结合还原氮化法制备多孔TiN纤维,利用XRD、SEM、TEM和N₂吸脱附等分析其结构,采用循环伏安和充放电测试其电化学性能。结果表明,纤维为立方TiN相,纤维连续,存在较为丰富的介孔结构,其比表面积为21.55 m₂/g。电化学测试表明样品在不同扫率下的CV曲线均呈类矩形,由电流密度为20 mA/g时GCD曲线计算其比电容为24.03 F/g,在电流密度为50 mA/g时经4500次充放电循环后样品的比容量仍能保持90 %以上,当功率密度为0.02 kW/kg时样品的能量密度为3.3 Wh/kg。因此,采用本方法制备的多孔TiN纤维在超级电容器领域具有应用潜力。     

水热电沉积法生长Co9S8薄膜电极

采用水热电沉积法在泡沫镍基体上原位沉积Co_9S_8薄膜,并对其形貌、组成、结构和电化学性能进行表征和测试。结果表明,镍基Co_9S_8薄膜呈花瓣片状,并具有优异的电化学性能,其在电流密度为10mA/cm~2时,比电容可高达2538.7 F/g。即使电流密度扩大至50 mA/cm~2时,比电容依然可达1930.7 F/g。经过1000次循环(电流密度为20 mA/cm2),比电容仍可达为1825.2 F/g,电容保有率72.8%,经过1500次循环后,电容保有率61.4%。     

N掺杂石墨化纳米金刚石超级电容器电极材料性能

为探索制备高能量密度和高循环性能的超级电容器材料,将三聚氰胺与石墨化纳米金刚石(graphitized nano diamond,GND)混合物在N₂气氛中高温处理,制备表面N掺杂吸附的核壳纳米复合粒子(nitrogen doped GND,N-GND)。由拉曼光谱和X射线衍射分析可知:N原子掺入石墨层中,在一定程度上增加其缺陷, 且不改变其晶体结构。由透射电镜分析可知:N掺杂引起GND周围石墨层出现蜷曲形状。对N-GND粉末电极进行电化学性能测试,结果表明:在扫速为5 mV/s时,电极比电容高达206.7 F/g;在对称两电极体系下的恒流充放电测试中,在电流密度为0.4 A/g时,N-GND的比电容达到198.7 F/g;在50 mV/s的扫描速度下,经2 000圈循环伏安测试后,比电容仅衰减4.23%,表现出优异的循环稳定性。以N-GND作为新型超级电容器电极材料,掺杂吸附的石墨壳层赋予其良好的导电性,GND芯部具有高热稳定性及化学稳定性,可避免传统石墨烯叠聚问题并构造可控的介孔通道,同时N掺杂吸附可提高其电容性能。      

基于石墨烯透明导电薄膜的OLED研究进展

作为透明导电薄膜材料,石墨烯（Graphene）因具有十分优异的力学、光学和电学特性,在未来的柔性光电器件如触摸屏、有机发光二极管（OLED）和有机光伏电池（OPV）中表现出极大的发展潜力和广阔的应用前景。然而,受面电阻大、功函数不匹配以及表面粗糙度等关键因素的影响,基于本征石墨烯薄膜的光电器件的性能较低、稳定性较差,严重阻碍了石墨烯薄膜在柔性光电器件中的发展和应用。主要针对近年来石墨烯透明导电薄膜在OLED中应用的研究进展进行概述,并总结得出可以通过石墨烯薄膜掺杂、表面功函数修饰、清洁无损转移,以及器件结构优化等方法,进一步提高器件的性能。最后分析了石墨烯透明导电薄膜在OLED器件应用中的关键技术瓶颈,并对石墨烯透明导电薄膜在OLED中的应用前景进行了展望。     

常用碳基固体润滑薄膜的研究现状与展望

首先从碳基固体润滑薄膜的应用需求与成本效益出发,探讨了研究碳基固体润滑薄膜的迫切要求和重要意义,然后对类金刚石(DLC)薄膜、类富勒烯(FLC)薄膜及石墨烯薄膜三类最常用的碳基固体润滑薄膜的研究现状进行了较详细的介绍。其中,重点介绍了DLC薄膜的三种减摩抗磨机理,探讨了掺杂元素改性对DLC薄膜硬度、摩擦系数和磨损率等多个方面的影响,并指出外部因素(基体材料、过渡层和应用环境等)对DLC薄膜性能的重要作用。探讨了掺氢、掺氟和掺氮对FLC薄膜构性转变和摩擦学性能的影响。总体来说,氟掺杂导致FLC结构变化,并显著改变薄膜硬度;掺氮会诱导类富勒烯微结构的增加;掺氢FLC薄膜热处理后可达到超润滑状态。总结了石墨烯薄膜制备工艺的发展、石墨烯基复合薄膜的摩擦学性能和石墨烯薄膜在不同基体材料的应用。最后,指出了碳基润滑薄膜领域亟待解决的关键难题,并对未来的研究方向做出了预测。     

钇梯度掺杂Ba0.6Sr0.4TiO3薄膜的sol-gel法制备及介电性能

用改进的溶胶-凝胶法(sol-gel)在Pt/Ti/SiO2/Si(S)上制备了各层Y掺杂浓度分别为0.5%/0.6%/0.7%/0.8%/0.9%/1%的上梯度掺杂和1%/0.9%/0.8%/0.7%/0.6%/0.5%下梯度掺杂的Ba0.6Sr0.4TiO3薄膜。X射线衍射(XRD)表明,各薄膜主要沿(110)晶面生长,均为立方钙钛矿结构。相比均匀掺杂薄膜,梯度掺杂薄膜表现出较好的相结构衍射强度及晶化,上梯度薄膜更为显著。原子力显微镜(AFM)表明,梯度掺杂使薄膜的表面形貌得到极大改善,上梯度比下梯度薄膜具有更加光滑致密的表面相貌和更小的表面粗糙度。电压-电容曲线表明,上梯度薄膜介电性能得到明显提高,在零偏压下的电容为28.5pF(介电常数190)、介电损耗为1.63%及40V下的调谐率为52.3%,优质因子为32。     

Flexible free-standing graphene-like film electrode for supercapacitors by electrophoretic deposition and electrochemical reduction

Electrophoretic deposition in conjunction with electrochemical reduction was used to make flexible free-standing graphene-like films. Firstly, graphene oxide (GO) film was deposited on graphite substrate by electrophoretic deposition method, and then reduced by subsequent electrochemical reduction of GO to obtain reduced GO (ERGO) film with high electrochemical performance. The morphology, structure and electrochemical performance of the prepared graphene-like film were confirmed by SEM, XRD and FT-IR. These unique materials were found to provide high specific capacitance and good cycling stability. The high specific capacitance of 254 F/g was obtained from cyclic voltammetry measurement at a scan rate of 10 mV/s. When the current density increased to 83.3 A/g, the specific capacitance values still remained 132 F/g. Meanwhile, the high powder density of 39.1 kW/kg was measured at energy density of 11.8 W·h/kg in 1 mol/L H₂SO₄ solution. Furthermore, at a constant scan rate of 50 mV/s, 97.02% of its capacitance was retained for 1000 cycles. These promising results were attributed to the unique assembly structure of graphene film and low contact resistance, which indicated their potential application to electrochemical capacitors.     

层次孔结构双功能碳负极材料的制备及性能

在500～900℃的活化温度下,以酚醛树脂为碳源,采用模板-物理活化联合法制备系列超级电容电池用层次孔结构双功能碳负极材料。借助扫描电镜、透射电镜及比表面积测试仪分析材料的物理结构,组装模拟电容器和对锂半电池,利用恒流充放电法及循环伏安法考察其电化学行为。结果表明:制备的层次孔结构碳材料具有较大的中微孔结构和局域石墨微晶结构;在LiPF6/EC+DMC和Et4NBF4/AN两种电解液中均表现出良好的电化学性能;其中以活化温度为600℃时制备的碳材料性能最优,其锂离子半电池可逆容量达到611.2 mA.h/g(0.2C),50次循环效率为74%,6C倍率下稳定可逆容量仍高达223 mA.h/g,模拟电容器比电容高达143 F/g(0.1 A/g),且倍率性能优异。     

硼酸对7050铝合金硼酸-硫酸阳极氧化膜结构及耐蚀性的影响(英文)

通过 AFM、交流阻抗谱及扫描 Kelvin 探针技术,研究硼酸对 7050 铝合金硼酸?硫酸阳极氧化膜结构及耐蚀性的影响。结果表明,在硼酸-硫酸阳极氧化体系中,硼酸不会改变氧化膜阻挡层的结构,但会显著影响氧化膜多孔层的结构形式,进而影响氧化膜的耐蚀性。在 0～8 g/L 的范围内,随着电解液中硼酸含量的增加,氧化膜的多孔层电阻增大,电容减小,表面势正移,孔径缩小,耐蚀性变好。在高于 8 g/L 时,随着硼酸含量的增加,氧化膜的孔隙变大,阻抗变小,电子逸出功降低,耐蚀性变差。     

Pseudocapacitive performance of hybrid manganese oxide films with multiwalled-CNT additions

In the present study, hybrid manganese oxide films with additions of multiwalled carbon nanotubes (MWCNTs) were prepared by sol-gel process. Manganese acetate was used as the precursors and MWCNTs were added during the process. The effects of MWCNT addition and post heat treatment on the material characteristics and pseudocapacitive performance of the hybrid MWCNT/MnO_x films were investigated. Experimental results showed that manganese oxide was composed of Mn₃O₄ (minor) and Mn₂O₃ (major) phases after heat treatment. MWCNTs served as the template for the growth of manganese oxide films. Among the hybrid films prepared in the present study, manganese oxide films with 0.05 wt.% MWCNT addition heat treated at 350 °C exhibited the best electrochemical performance. The maximum specific capacitance was 340.3 F/g and retained 280.8 F/g (82.5%) after 1000 CV tests. With the addition of MWCNTs, not only the specific capacitance increased but also the reliability improved.     

Microwave-assisted synthesis of graphene-ZnO nanocomposite for electrochemical supercapacitors

Graphene-ZnO nanocomposite was successfully synthesized via microwave-assisted reduction of zinc ions in aqueous solution with graphite oxide dispersion using a microwave synthesis system. The electrochemical performance of the nanocomposite was analyzed through cyclic voltammetry and chronopotentiometry tests. The results showed that as compared with pure graphene, graphene-ZnO composite exhibited an improved electrochemical capacitance of 146 F/g with good reversible charge/discharge behavior.     

烧结NdFeB表面铜-石墨烯复合膜的制备与表征

采用电沉积铜-石墨烯（Cu-GR）复合膜的方法对稀土永磁NdFeB材料进行包覆以提高其耐腐蚀性。对Cu-GR膜层的微观结构、水接触角和表面显微硬度等方面进行了分析。结果表明,随着电沉积液中石墨烯的添加量从0 g·L^-1增加到0.9 g·L^-1,膜层的疏水性和硬度随之提高。通过SEM/EDS和XPS表征,验证了石墨烯在Cu-GR膜层中的均匀分散以及Cu-GR复合材料的组成。利用动电位极化曲线和电化学阻抗谱（EIS）研究了Cu-GR复合镀层的电化学性能。结果表明,石墨烯的加入使膜层的电化学性能更加稳定、耐蚀性得到提高。当电沉积液中石墨烯添加浓度为0.3 g·L^-1时,获得的Cu-GR复合包覆层在NdFeB基体上表现出最优的综合保护效果。     

Design of best performing hexagonal shaped Ag@CoS/rGO nanocomposite electrode material for electrochemical supercapacitor application

The mixed metal/metal sulphide (Ag@CoS) with reduced graphene oxide (rGO) nanocomposite (Ag@CoS/rGO) was synthesized for the possible electrode in supercapacitors. Ag@CoS was successfully deposited on the rGO nanosheets by hydrothermal method, implying the growth of 2D Ag and CoS-based hexagonal-like structure on the rGO framework. The synthesized nanocomposite was subjected to structural, morphological and electrochemical studies. The XRD results show that the prepared nanocomposite material exhibits a combination of hexagonal and cubic phase due to the presence of CoS and Ag phases together. The band appearing at nearly 470.33 cm⁻¹ in FTIR spectra can be ascribed to the absorption of S–S bond in the Ag@CoS/rGO nanocomposite. The clear hexagonal structure was analysed by SEM and TEM with the grain sizes ranging from nanometer to micrometer. The electrode material exhibits excellent cyclic stability with a specific capacitance of 1580 F/g at a current density of 0.5 A/g without any loss of capacitive retention even after 1000 cycles. Based on the electrochemical performance, it can be inferred that the prepared novel nanocomposite material is very suitable for using as an electrode for electrochemical supercapacitor applications.     

氮掺杂及PEG包覆对CNT/S材料储锂性能的影响

以硫代氨基脲为氮源,用高温退火法对碳纳米管实现氮掺杂,利用PEG对掺氮复合材料(NCNT/S)进行外包覆。采用X射线衍射仪(XRD),扫描电子显微镜(SEM),X射线光电子能谱仪(XPS)对复合材料进行了表征。结果表明高温退火使氮有效地掺入碳纳米管中,而碳纳米管仍保持原本征形貌。电化学测试表明:掺氮后复合电极首次放电比容量明显提高,达到882.5 mAh·g~(-1),90次循环过后具有89.46%的容量保持量,而PEG包覆使掺氮复合电极首次放电比容量提高至1109.7 mAh·g~(-1),经过90次循环放电比容量仍保持在995.2 mAh·g~(-1)。这说明掺氮和PEG包覆均能很好地改善复合材料的电化学性能。