Binder-free manganese oxide/carbon nanomaterials thin film electrode for supercapacitors

A ternary thin film electrode was created by coating manganese oxide onto a network composed of single-walled carbon nanotubes and single-walled carbon nanohorns. The electrode exhibited a porous structure, which is a promising architecture for supercapacitors applications. The maximum specific capacitances of 357 F/g for total electrode at 1 A/g were achieved in 0.1 M Na(2)SO(4) aqueous solution.     

棉花基多孔碳材料的合成、微结构及超电性能研究

由于制备方法简单并且原料易得, 多孔碳合成广泛采用生物质材料, 并用于能源存储。以天然生物质棉花作为碳源, 通过简单的一步法制备得到氮掺杂多孔碳材料。这种多孔碳材料在碳化温度为750℃时具有480 m²/g的比表面积和6.84%的高含氮量。当用作超级电容器电极材料时, 这种碳材料显示出了良好的电容性能。在1 mol/L硫酸电解液中, 电流密度为1 mol/L时, 比电容可以达到252 F/g, 并且在循环10000圈之后仍能保留94%的原电容。这种低成本的棉花基碳材料为超级电容器应用提供了可能。     

Flexible CoAl LDH@PEDOT Core/Shell Nanoplatelet Array for High‐Performance Energy Storage

A CoAl‐layered double hydroxide (LDH)@poly(3,4‐ethylenedioxythiophene) (PEDOT) core/shell nanoplatelet array (NPA) is grown on a flexible Ni foil substrate as a high‐performance pseudocapacitor. The LDH@PEDOT core/shell NPA shows a maximum specific capacitance of 649 F/g (based on the total mass) by cyclic voltammetry (scan rate: 2 mV/s) and 672 F/g by galvanostatic discharge (current density: 1 A/g). Furthermore, the hybrid NPA electrode also exhibits excellent rate capability with a specific energy of 39.4 Wh/kg at a current density of 40 A/g, as well as good long‐term cycling stability (92.5% of its original capacitance is retained after 5000 cycles). These performances are superior to those of conventional supercapacitors and LDH NPA without the PEDOT coating. The largely enhanced pseudocapacitor behavior of the LDH@PEDOT NPA electrode is related to the synergistic effect of its individual components: the LDH nanoplatelet core provides abundant energy‐storage capacity, while the highly conductive PEDOT shell and porous architecture facilitate the electron/mass transport in the redox reaction.     

Growth of manganese oxide nanoflowers on vertically-aligned carbon nanotube arrays for high-rate electrochemical capacitive energy storage

Manganese oxide nanoflower/carbon nanotube array (CNTA) composite electrodes with hierarchical porous structure, large surface area, and superior conductivity was controllable prepared by combining electrodeposition technique and a vertically aligned CNTA framework. This binder-free manganese oxide/CNTA electrode presents excellent rate capability (50.8% capacity retention at 77 A/g), high capacitance (199 F/g and 305 F/cm (3)), and long cycle life (3% capacity loss after 20 000 charge/discharge cycles), with strong promise for high-rate electrochemical capacitive energy storage applications.     

Synthesis, characterization and capacitive performance of hydrous manganese dioxide nanostructures

Hydrous manganese dioxide nanostructures were synthesized via a catalytic oxidation reaction mechanism at mild temperatures. It was found that the morphology of the manganese dioxide nanostructures was significantly influenced by the pH of the reaction system. With increasing pH the morphology of manganese dioxide nanostructures changed from urchin-like structures to nanobelts. The capacitive performance was investigated by using cycle voltammetry and galvanostatic charge/discharge techniques. Hydrous manganese dioxide nanostructures obtained from a basic solution exhibited a capacitance of 262 F g(-1) at a current density of 250 mA g(-1) and a capacitive retention of 75% after 1200 cycles, suggesting that this is a promising electrode material for supercapacitors. The high specific capacitance is attributed to the hydrous nature coupled with a high surface area (181 m(2) g(-1)) of the manganese dioxide nanostructure.     

AC+Li（NiCoMn）O2/Li4Ti5O12+MWCNTs混合型电容器EI北大核心CSCD

以钛酸锂(Li 4Ti 5O 12)/多壁碳纳米管(MWCNTs)复合材料为负极、活性炭(AC)/镍钴锰酸锂(Li(NiCoMn)O 2)复合材料为正极,组装成混合型电容器并研究其电化学性能。利用扫描电子显微镜(SEM),透射电子显微镜(TEM),X射线衍射仪(XRD),拉曼光谱仪(Raman),热重分析仪(TGA)对电极材料进行分析,通过恒流充放电(GCD)和交流阻抗谱(EIS)研究混合型电容器的电化学性能。结果表明:掺杂适量MWCNTs和镍钴锰酸锂可提高电容器的电化学性能。当MWCNTs质量分数为5%时,在电流密度为0.1 A/g下恒流充放电时比容量达161.5 mAh/g。在0.1~1 A/g时,最大功率密度和最大能量密度分别为993.2 W/kg和52.2 Wh/kg。5000周次恒流充放电循环后,容量保持率在92.2%左右,库仑效率仍有99.1%,展现出较高的能量密度和功率密度,并具有优异的循环性能。     

脱合金制备纳米多孔Co及其超级电容器和对偶氮染料的降解性能

在0.5%(质量分数,下同)NH₄F和1 mol/L (NH₄)₂SO₄混合溶液中进行电化学脱合金Zr₅₆Al₁₆Co₂₈非晶合金,制备出纳米多孔Co。这种纳米多孔Co具有良好的超级电容器性能,其比电容在2 A/g的电流密度下能达318 F/g;同时,纳米多孔Co在方波电位下对直接蓝6和酸性橙II等偶氮染料具有优异的降解能力,降解效率均高于96%,其单位质量纳米多孔Co电极材料的降解能力是等质量Zr₅₆Al₁₆Co₂₈非晶合金的3.5倍。     

用作双电层电容器电极材料的三维层次孔结构多孔炭的合成

以葡萄糖为碳源,由金属框架有机物( MOF)高效地合成出一种具有三维层次孔结构的多孔炭.当葡萄糖渗入到方形MOF的表面或内部空隙之后,逐步进行聚合和炭化.在此过程中,MOF分解出ZnO,ZnO进一步被基体炭或CO还原成Zn;而Zn又在炭化过程中逸出,以致形成连续的基体炭组织.当所合成的多孔炭用作双电层电容器电极材料时,在1 mo1/L NEt4 BF4/碳酸丙烯酯电解液体系中,其初始比电容达175F·g-1(电流强度0.6A·g-1),并在12A·g-1大电流密度下电容保持率高达94.2％.     

Anomalous pseudocapacitive behavior of a nanostructured, mixed-valent manganese oxide film for electrical energy storage

While pseudocapacitors represent a promising option for electrical energy storage, the performance of the existing ones must be dramatically enhanced to meet today's ever-increasing demands for many emerging applications. Here we report a nanostructured, mixed-valent manganese oxide film that exhibits anomalously high specific capacitance (～2530 F/g of manganese oxide, measured at 0.61 A/g in a two-electrode configuration with loading of active materials ～0.16 mg/cm(2)) while maintaining excellent power density and cycling life. The dramatic performance enhancement is attributed to its unique mixed-valence state with porous nanoarchitecture, which may facilitate rapid mass transport and enhance surface double-layer capacitance, while promoting facile redox reactions associated with charge storage by both Mn and O sites, as suggested by in situ X-ray absorption spectroscopy (XAS) and density functional theory calculations. The new charge storage mechanisms (in addition to redox reactions of cations) may offer critical insights to rational design of a new-generation energy storage devices.     

用于高性能超级电容器电极的栓皮栎基多孔活性炭的制备

本研究以空腔细胞组成的栓皮栎为原料, KOH为活化剂制备了具有多孔结构的栓皮栎软木基多孔活性炭。以此方法制得的活性炭呈薄片状外形, 最大比表面积达到2312 m ²/g, 具有特殊的微孔-介孔结构。在呈碱性的KOH三电极体系中, 0.1 A/g电流密度时比电容达296 F/g; 两电极体系中, 5 A/g时的比电容达到201 F/g, 循环5000次后电容保持率达99.5%。在呈中性的Na₂SO₄两电极体系中, 电流密度0.5 A/g (174 F/g)至50 A/g (140 F/g)时电容保持率达80.5%, 倍率性能良好, 能量密度高达19.62 Wh/kg。     

Carbon nanotube-polypyrrole core-shell sponge and its application as highly compressible supercapacitor electrode

A carbon nanotube （CNT） sponge contains a three-dimensional conductive nano- tube network, and can be used as a porous electrode for various energy devices. We present here a rational strategy to fabricate a unique CNT@polypyrrole （PPy） core-shell sponge, and demonstrate its application as a highly compressible supercapacitor electrode with high performance. A PPy layer with optimal thickness was coated uniformly on individual CNTs and inter-CNT contact points by electrochemical deposition and crosslinking of pyrrole monomers, resulting in a core-shell configuration. The PPy coating significantly improves specific capacitance of the CNT sponge to above 300 F/g, and simultaneously reinforces the porous structure to achieve better strength and fully elastic structural recovery after compression. The CNT@PPy sponge can sustain 1,000 compression cycles at a strain of 50% while maintaining a stable capacitance （〉 90% of initial value）. Our CNT@PPy core-shell sponges with a highly porous network structure may serve as compressible, robust electrodes for supercapacitors and many other energy devices.     

组氨酸功能化碳点/石墨烯气凝胶的制备及超级电容器性能

通过一步水热法制备组氨酸功能化碳点/石墨烯气凝胶(His-CDs/GA)。该材料具有独特的三维多孔结构、丰富的含氮和含氧官能团, 有利于电解液离子的快速扩散和提供更多的活性位点。当GO与His-CDs的质量比为2 : 1时, His-CDs/GA-2在1 A·g ^-1电流密度下比电容达到304 F·g ^{- 1}, 比GA(172 F·g ^-1)提高了76.7%; 当电流密度从1 A·g ^-1增加到50 A·g ^-1, 其比电容保持率为71.4%; 在电流密度10 A·g ^-1下, 循环充放电30000次后, 比电容仍保留93.5%。由His-CDs/GA组装的对称超级电容器展现出高能量密度(在功率密度为250 W/kg时, 能量密度达到10.14 Wh/kg)和良好的循环性能(在5 A·g ^-1下循环充放电20000次后, 比电容保持率为88.4%)。结果表明, His-CDs/GA是一种应用前景广阔的超级电容器电极材料。     

Synthesis and electrochemical performance of a laminated hollow porous carbon

A laminated hollow porous carbon with high surface area of 2368 m²/g was synthesized using a nonporous metal organic coordinate polymer as template. When used as electrode materials for electric double layer capacitors, the synthesized porous carbon presents a high specific capacitance of 234 F/g at a current density of 10 mA/g in 6 M KOH electrolyte and the capacitance retention can obtain 87% at current density of 20,000 mA/g.     

MnOOH-石墨烯-泡沫镍自支撑复合电极的制备及其超级电容性能

采用气相沉积法和后续的电沉积法制备得到自支撑结构的MnOOH-石墨烯（graphene）-泡沫镍（NF）复合电极。使用XRD、SEM、XPS等方法对样品的物相、形貌和价态等进行表征,通过恒流充放电、循环伏安、交流阻抗等方法对电极的电化学性能进行研究。结果表明:该方法可以成功制备得到具有自支撑结构的MnOOH-graphene-NF复合电极,超薄的graphene层均匀覆盖在NF的表面,微米球状的MnOOH纳米片紧密覆盖在graphene的表面。该自支撑复合结构可以直接用作超级电容器电极进行测试,在5 mol/L KOH溶液中表现出了较大的赝电容储存能力。在0.5 A/g的电流密度下,最大比容量可达934 F/g。当电流密度提高为5 A/g时,比容量仍达771 F/g。当电流密度为2 A/g时,循环5000次后的容量保持率高达98%,库伦效率接近100%,表现出了良好的超级电容性能。本实验提供了一种制备自支撑MnOOH-graphene-NF复合电极的新方法,该复合电极有望成为一种潜在的新型超级电容器电极材料。      

Hierarchical network architectures of carbon fiber paper supported cobalt oxide nanonet for high-capacity pseudocapacitors

We present a high-capacity pseudocapacitor based on a hierarchical network architecture consisting of Co(3)O(4) nanowire network (nanonet) coated on a carbon fiber paper. With this tailored architecture, the electrode shows ideal capacitive behavior (rectangular shape of cyclic voltammograms) and large specific capacitance (1124 F/g) at high charge/discharge rate (25.34 A/g), still retaining ~94% of the capacitance at a much lower rate of 0.25 A/g. The much-improved capacity, rate capability, and cycling stability may be attributed to the unique hierarchical network structures, which improves electron/ion transport, enhances the kinetics of redox reactions, and facilitates facile stress relaxation during cycling.     

Metal-organic framework derived hierarchical NiCo2O4 triangle nanosheet arrays@SiC nanowires network/carbon cloth for flexible hybrid supercapacitors

To overcome the disadvantages of traditional powder electrodes,such as the insufficient performance,the aggregation of active materials,and the complex fabrication process,rationally constructing free-standing electrode materials with hierarchical architecture is an effective and promising method,which could further improve the electrochemical properties.Herein,using metal-organic framework nanoar-rays (MOFNAs) as self-sacrificial templates and SiC nanowires (SiCNWs) network as nanoscale conductive skeletons,we successfully fabricated the hierarchical core-shell SiCNws@NiCo2O4NAs on carbon cloth (CC)substrate.Taking advantages of structural merits,such as hierarchical porous triangle-like NiCo2O4NAs,the interwoven SiCNWs network and conductive CC substrate,when evaluated as a binder-free superca-pacitor electrode,the CC/SiCNWs@NiCo2O4NAs shows a high specific capacitance of 1604.7 F g-1 (specific capacity of 222.9 mA h g-1) at 0.5 A g 1,good rate performance,and excellent cycling stability.Signifi-cantly,the hybrid supercapacitor assembled with CC/SiCNWs@NiCo2O4NAs as the cathode and MOF derived CC/SiCNWs@CNAs as the anode,could deliver a high specific density of 49.9 W h kg-1 at a specific power of 800 W kg-1,stable cycling performance,and good flexibility.Impressively,this feasible strategy for fabricating hierarchical structure displays great potential in the field of energy storage.     

原位氧化法制备Zn-Ni氢氧化物纳米片及其电荷存储特性研究

通过简单、低成本的化学浴沉积法在泡沫镍上原位生成了Zn-Ni 氢氧化物(Zn-Ni double hydroxides)纳米片。SEM观察结果表明, Zn-Ni 氢氧化物纳米片均匀附着在泡沫镍表面, 形成均一的多孔纳米片阵列层。此外, 还有大量的Zn-Ni 氢氧化物纳米片聚集成多孔团聚体, 分布于泡沫镍骨架的空隙处, 从而获得较高的活性物质负载量(4.27 mg/cm²)。CV、CP和电化学阻抗测试表明, Zn-Ni 氢氧化物纳米片在2 mol/L KOH电解液中充放电电流密度1 A/g时, 比电容为746.2 F/g(面积电容为3.18 F/cm²); 3000次充放电循环后, 仍保持70.9%的初始比电容。     

MnO2/SMWCNT/PANI三元复合材料的合成及其电化学电容性能

用液相沉淀法制备了二氧化锰/酸化多壁碳纳米管(MnO₂/SMWCNT)和二氧化锰/酸化多壁碳纳米管/聚苯胺(MnO₂/SMWCNT/PANI)电极材料。通过循环伏安、恒电流充放电等方法测试了样品的电化学性能。结果表明, 当MnO₂:SMWCNT:PANI的质量比为1:1:0.4时,它的电化学性能最好, 在0.1 A/g电流密度下的比电容为318.6 F/g, 氧化电流为6.02 A/g, 循环100次后电流保持率保持在92.7%。     

Nanosized Ni-Mn Oxides Prepared by the Citrate Gel Process and Performances for Electrochemical Capacitors

Nanosized Ni-Mn oxide powders have been successfully citrate gel precursors. The powder materials derived from prepared by thermal decomposition of the Ni-Mn calcination of the gel precursors with various molar ratios of nickel and manganese at different temperatures and time were characterized using thermal analysis （TG-DSC）, scanning electron microscopy （SEM）, X-ray diffraction （XRD） and Brunauer-Emmet-Teller （BET）. The optimized processing conditions of calcination at 400℃ for 1 h with Ni/Mn molar ratio 6 were proved to produce the nanosized Ni-Mn oxide powders with a high specific surface area of 109.62 m^2/g and nanometer particle sizes of 15-30 nm. The capacitance characteristics of the nanosized Ni-Mn oxide electrode in various concentrations of KOH solutions were studied by the cyclic voltammetry （CV） and exhibited both a doublelayer capacitance and a Faradaic capacitance which could be attributed to the electrode consisting of Ni-Mn oxides and residual carbons from the organic gel thermal decomposition. A specific capacitance of 194.8 F/g was obtained for the electrode at the sweep rate of 10 mV/s in 4 mol/L KOH electrolyte and the capacitor showed quite high cyclic stability and is promising for advanced electrochemical capacitors.     

磷掺杂中空碳球的制备及其电容性能EI北大核心CSCD

以酚醛预聚体和苯乙烯为原料通过水热法一步合成中空聚合物球(HPS),再以三氯化磷为反应剂通过傅-克反应对HPS处理得到含磷交联聚合物,经高温炭化和KOH活化制备磷掺杂中空碳球(AP-HCS)。采用FT-IR,TG,SEM,TEM,Raman,BET,XPS等手段对含磷聚合物和碳材料的组成、结构与形貌进行表征,测试碳材料在1 mol/L H2SO4介质中的电容性能。结果表明:AP-HCS的比表面积可达2177 m2/g,在1 A/g电流密度下,比电容为288 F/g,5 A/g电流密度下经循环充放电5000次后比电容值仍能保持88.9%,具备良好的电容性能。