纳米活性炭/锌锰复合电极材料的制备及性能

使用溶胶-凝胶法合成锌掺杂二氧化锰的纳米晶电极材料,将其与干式振动滚压法制备的纳米活性炭混合制成超级电容器所需的片状电极。纳米活性炭材料为类球状颗粒,粒径约为50 nm,且为微孔和中孔并存的狭缝结构;制备的锌掺杂二氧化锰纳米晶材料为中孔占优的孔隙结构,含有纳米锌和氧化锌的成分,经XRD测试和比表面分析,得到此纳米晶材料的平均粒径小于30 nm。分析显示,经滚压振动研磨改性的纳米活性炭与10%纳米晶锌锰材料混合的电极材料具有较好的电容性能,比电容达到299 F.g-1。     

活性炭/二氧化锰纳米复合材料的合成及超级电容性能

以商业活性炭为载体,通过硝酸表面改性活性炭,引入含氧官能团,为棒状二氧化锰(MnO2)和活性炭的结合提供桥梁。采用化学沉淀法在炭表面反应生成纳米结构的棒状二氧化锰,制备二氧化锰/改性活性炭(MnO2/OAC)复合电极材料。采用扫描电镜(SEM)、X射线衍射(XRD)对其结构进行表征;采用循环伏安法、恒流充放电对其电化学性能进行研究。结果表明,生成的MnO2均匀地负载在碳的表面,颗粒的直径在20⁵0nm;在1mol/L的Na2SO4电解液中,MnO2/OAC6复合电极材料体现了极佳的比电容,达到369.7F/g。材料优异的电化学性能归功于活性炭发达的孔隙结构和MnO2提供的法拉第电容。     

活性炭/二氧化锰纳米复合材料的合成及超级电容性能

以商业活性炭为载体,通过硝酸表面改性活性炭,引入含氧官能团,为棒状二氧化锰(MnO2)和活性炭的结合提供桥梁。采用化学沉淀法在炭表面反应生成纳米结构的棒状二氧化锰,制备二氧化锰/改性活性炭(MnO2/OAC)复合电极材料。采用扫描电镜(SEM)、X射线衍射(XRD)对其结构进行表征;采用循环伏安法、恒流充放电对其电化学性能进行研究。结果表明,生成的MnO2均匀地负载在碳的表面,颗粒的直径在20~50nm;在1mol/L的Na2SO4电解液中,MnO2/OAC6复合电极材料体现了极佳的比电容,达到369.7F/g。材料优异的电化学性能归功于活性炭发达的孔隙结构和MnO2提供的法拉第电容。     

(NH4)2S2O8/AC氧化改性电极材料的制备及性能表征

以煤质活性炭(AC)为研究对象,通过(NH₄)₂S₂O₈氧化改性提高其电吸附性能。将活性炭材料制备成电极并在电容去离子技术(EST)下进行实验,对改性前后活性炭的表面形貌、表面官能团、孔结构变化进行对比分析。结果表明,活性炭经过1.5 mol/L的(NH₄)₂S₂O₈改性后比电容最大;改性后的活性炭电极比电容增大,改性后相比改性前孔容、平均孔径均下降;改性后的材料表面光滑、杂质较少、孔隙结构发达、含氧官能团增多;利用单因素和Box-Behnken响应面法得到改性后材料制备的最佳工艺为：1.59 g的AC在54.22℃下氧化改性4.93 h,电极比电容为259.850 F/g,改性后电极的CV曲线证明由于其含有赝电容从而使电化学性能得到提高。     

橡胶木纤维素纳米纤丝/二氧化锰/碳纳米管柔性电极材料的制备及表征

以橡胶木为原料,通过化学处理得到橡胶木纯化纤维素(PCF),在此基础上通过高速剪切结合超声波处理制备得到纤维素纳米纤丝(CNF)。通过单相合成法制备二氧化锰(MnO₂)纳米片。以CNF为结构支撑体,MnO₂纳米片和碳纳米管(CNTs)作为活性电极物质,通过真空抽滤的方式制备CNF/MnO₂/CNTs柔性电极材料。采用多种手段对CNF、MnO₂以及电极材料的结构性能进行表征,并测试了电极材料的电化学性能。结构性能表征结果表明：CNF的直径为3~10 nm,具有大的长径比,是很好的结构支撑体,CNF为纤维素Ⅰ型结构;MnO₂纳米片为片层花瓣状结构,晶型为δ型。电化学性能测试结果表明：在扫描速率为50 mV/s时电极材料的比电容值为78.45 F/g,在电流密度为0.1 A/g时的电极材料比电容值为97.02 F/g,在低频区时,交流阻抗(EIS)曲线的直线部分斜率较大,表明电极材料具有良好的电容特性,在200次充放电循环测试过程中,电极材料的电容保留率始终维持在99%左右,表明该电极材料具有良好的电化学性能并且具有一定的柔性变形能力,可用作超级电容器的电极材料。     

双电层电容器活性炭电极的优化

通过物理方法对双电层电容器用活性炭电极进行改性实验,探讨了活性炭电极的结构（比表面积、孔径分布、孔容）和性能（比电容、充放电特性）的优化问题.改性后活性炭电极BET比表面积从1739.77 m²•g^-1增至2215.40 m²•g^-1,其中微孔比表面积增幅22％,中孔比表面积增幅35％,孔容积也有20%～30％的增幅量,孔径分布更为合理.优化的活性炭电极结构改善了电极材料的电化学特性,比电容量可达424 F•g^-1,增幅10％.     

纳米Co3O4-碳纳米管复合电极的超级电容性能研究

采用湿法制备纳米Co_2O_4,并与碳纳米管掺杂,制备出纳米CO_3O_4-碳纳米管复合电极。纳米Co_3O_4与碳纳米管质量比为90：5。制备的复合电极表现出了良好的超级电容性能,复合电极单电极比电容达233．32F·g~(-1),与纯Co_3O_4电极相比,单电极比电容容提高20%。     

高电容氮硫共掺杂多孔炭纳米片的制备

提供一种新型的超级电容器用高电容氮硫共掺杂多孔炭纳米片的制备方法,该方法操作简单、时间周期短、重复性好。以葡萄糖酸钙为碳源、氢氧化钾为活化剂、硫脲为氮硫源,通过直接碳化法制备出氮硫共掺杂多孔炭纳米片,并用于超级电容器的电极材料。通过扫描电子显微镜、X射线光电子能谱仪、X射线衍射仪、拉曼以及氮气吸脱附测试分析,氮硫共掺杂多孔炭纳米片具有高比表面积(491 m²·g^-1)、高氮掺杂量(8.1%)、高硫掺杂量(3.7%)以及分级孔道结构,并在6 mol·L^-1的KOH水溶液中表现出良好的电化学性能。当电流密度为0.2 A·g^-1时,其质量比电容高至221 F·g^-1,在20 A·g^-1时,其质量比电容可以达到144 F·g^-1,质量比电容保持率高达65%,而且经过5 000次充放电循环的电容保持率高达100%。该方法制备出的氮硫共掺杂多孔炭纳米片不仅表现出较大实际应用潜力,而且为寻找电化学性能优异的氮硫共掺杂电极材料奠定基础。     

MnO2基超级电容器电极材料

超级电容器作为一种新型的储能装置,具有长寿命、高功率等特点,在诸多领域内有广泛的应用前景。在影响超级电容器性能的所有因素中,电极材料的性能起着决定性的作用。二氧化锰(MnO₂)具有原料易得,价格低廉,来源广泛,环境友好等优点。综述了MnO₂超级电容器电极材料的储能机理,纳米MnO₂的微观结构与电化学特性之间的关系,并从纳米MnO₂的制备及其综合改性角度,综述其合成、掺杂改性、复合方法在MnO₂基电极材料的新进展,指出了MnO₂基超级电容器电极材料的主要研究方向。     

偏钒酸根掺杂的NiCo-LDH电极的制备及性能研究

超级电容器是近年来电化学储能器件研发的热点之一，其电极材料对其性能起决定性作用。为了合成具有优异超电容性能的NiCo基二维层状双氢氧化物(LDH)电极材料，首先通过一步水热法在泡沫镍网表面制备NiCo-LDH纳米阵列；然后在水-乙二醇体系下，通过二次溶剂热反应，制备偏钒酸根掺杂的NiCo-LDH纳米阵列；最后，通过碱转化得到性能优异的电极材料。用此电极与活性碳组装成全固态不对称超级电容器件，在电压为0～1.8 V、功率密度为9 mW/cm²时，器件的能量密度达0.416 mW·h/cm²，且具有良好的循环稳定性。     

纳米α-MnO2/活性炭混合超级电容器的性能

研究了以纳米α-MnO₂和活性炭（AC）为电极材料的超级电容器,分别对纳米α-MnO₂的制备、电解液浓度的影响进行了研究,组装了MnO₂/KOH/MnO₂、AC/KOH/AC、MnO₂/KOH/AC三种类型的模拟电容器,用循环伏安、恒流充放电、自放电以及时间常数法对电极和电容器进行性能测试,发现当电解液KOH浓度为7 mol•L^-1时,混合超级电容器性能最佳,α-MnO₂单电极比电容可达237 F•g^-1,混合电容器工作电压高达1.5 V,并且具有良好的大电流放电性能和较好的循环寿命,实验还表明混合超级电容器具有极低的自放电率.     

Electrochemical properties of MnO2/CNT nanocomposite in neutral aqueous electrolyte as cathode material for asymmetric supercapacitors

A MnO₂/carbon nanotube (CNT) nanocomposite was synthesised using a simple hydrothermal treatment. The nanocomposite exhibits a CNT core/MnO₂ porous sheath hierarchy architecture, which makes it promising as an electrode material for supercapacitors. An asymmetric supercapacitor based on activated carbon (AC) as anode, MnO₂/CNT nanocomposite as cathode and 1M Na₂SO₄ solution as electrolyte was assembled in a Swagelok cell. The full cell exhibits excellent power capability, cycling stability and a high energy density of 23 W h/kg at a power density of 330 W/kg based on the total mass of the active electrode materials. This AC//MnO₂/CNT asymmetric supercapacitor is promising for high-power applications due to its high energy density and power density.     

Tailoring carboxyl tubular carbon nanofibers/MnO2 composites for high-performance lithium-ion battery anodes

Three kinds of novel carboxyl modification tubular carbon nanofibers (CMTCFs) and MnO₂ composites materials (CMTCFs/MnO₂) are prepared by combining hyper-crosslinking, liquid phase oxidation and hydrothermal technology. The complex morphology and crystal phase of MnO₂ in CMTCFs/MnO₂ are effectively regulated by adjusting the hydrothermal reaction time. The δ-MnO₂ nanosheet-wrapped CMTCFs (CMTCFs@MNS) are used as anode and compared with the other two CMTCFs/MnO₂. Electrochemical analysis shows that CMTCFs@MNS electrode exhibits a large reversible capacity of 1497.1 mAh g⁻¹ after 300 cycles at 1000 mA g⁻¹ and a long cycling reversible capacity of 400.8 mAh g⁻¹ can be maintained after 1000 cycles at 10 000 mA g⁻¹. CMTCFs@MNS manifests an average reversible capacity of 256.32 mAh g⁻¹ at 10 000 mA g⁻¹ after twelve changes in current density. In addition, the structural superiority of CMTCFs@MNS electrode is clarified by characterizing the microscopic morphology and crystal phase of the electrode after electrochemical performance test.     

Fibrous MnO2 electrode electrodeposited on carbon fiber for a fuel cell/battery system

A novel fibrous MnO₂ electrode for a fuel cell/battery system is fabricated on carbon fiber by the electrodeposition method. The characteristics of the fibrous MnO₂ electrode are examined by electrochemical impedance spectra, galvanostatic performance and cyclic voltammetry. The experimental results indicate that the fibrous MnO₂ electrodes are superior to pasted electrodes because of the following: (i) better contact between MnO₂ and the electrical conducting material; (ii) high charge-transfer rate because of a smaller diameter than conventional electrodeposited MnO₂ particles (thus it is expected that the specific surface area would be higher); and (iii) a low overpotential. The morphology and the crystal structure of the fibrous MnO₂ electrode are investigated by scanning electron microscopy and X-ray diffraction, respectively. The entire surface of the carbon fiber is found to be coated with γ-MnO₂ after 2 h of electrodeposition at 0.01 A dm⁻² current density.     

Novel mesoporous MnO2 for high-rate electrochemical capacitive energy storage

MnO₂ with novel mesoporous structure has been firstly synthesized via a simple in situ reduction process by using different carbon materials as sacrificed template and reducing agent. The morphology and microstructure of as-synthesized mesoporous MnO₂ were characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), nitrogen adsorption and desorption experiments. The results demonstrate that porous MnO₂ prepared using mesoporous carbon as template has very large specific surface area and uniform pore-size distribution. The electrochemical measurements showed that novel porous MnO₂ have higher capacity (221 F g⁻¹) with excellent rate and higher capacity retention as electrochemical capacitors (ECs) electrode materials, which may be attributed to the unique nanostrcture of porous MnO_2. These all imply that MnO₂ with novel mesoporous structure has been attractive for practical and large-scale applications in mobile equipment.     

Li2MgxZn1-xSiO4离子导体材料的合成与表征

引　言Li4 SiO4 具有有利于离子传导的结构 ,是锂离子导体理想的基质材料[1～ 5] 而用M2 +(M =Zn ,Mg等 )部分取代Li4 SiO4 中的Li+离子 ,在一定的范围内所形成的固溶体可大大提高材料的离子导电性 ,且其导电性随取代量的增加而增高[6 ] 文献报道的合成方法多为固相法 ,但固相法不易保证成分的准确性、均匀性 ,且合成温度较高 低温软化学合成法已经成为目前新型功能性固体材料制备的主要方法 ,利用该方法 ,在较缓和的条件下获得了如薄膜、纳米材料、陶瓷和磁性材料等多种形式的无机功能材料[7] 其中溶胶 凝胶法是近年来发展起来的…     

Rate of the MnO−4/MnO2−4 and MnO2−4/MnO3−4 electrode reactions in alkaline solutions at solid electrodes

The influence of the ionic strength, pH, nature of the background electrolyte and its concentration as well as the influence of the electrode material (Pt, glassy carbon, carbon paste) on the electrode kinetics of the MnO^?₄/MnO^?2₄ and MnO^2?₄/MnO^3?₄ systems has been investigated by means of cyclic voltammetry and the rotating disc electrode method. Rate constants determined with the use of the carbon paste electrode agreed well with those which were in some instances available in the literature. At the Pt. electrodes the rate could be only estimated.The rate constants obtained for both electrode reactions were considered in terms of the Marcus theory. Also the charge of rate constants and formal potentials with studied parameters was discussed.     

喷雾热解法制备超细MnO2及其电化学性能

采用喷雾热解法制备了超细MnO₂阴极材料,并利用XRD、SEM和电化学测试方法研究了MnO₂的相组成、形貌、电化学性能以及在碱性溶液中的阴极极化行为.实验结果表明,喷雾干燥后的样品呈球形,表面有裂纹,经热处理后产物为Mn₂O₃,此时颗粒表面碎裂,形成多孔材料,酸处理后得到γ-MnO₂,含量超过90％.与EMD（电解二氧化锰）相比,所制备样品的放电容量（截止电压1.0V vs Zn）为215mAh·g^-1,放电深度可达一电子理论容量的70％,比EMD提高了15％;结合稳态极化和电化学阻抗法,发现质子在MnO₂晶格中的扩散符合多孔电极的阻挡层扩散模型,由等效电路拟合得到的数据能够较好地解释实验现象,反映了质子固相扩散的真实情况.     

Electrodeposited MnO2/Au composite film with improved electrocatalytic activity for oxidation of glucose and hydrogen peroxide

The major drawback of currently used MnO₂ film sensor is the loss of electrical conductivity due to the formation of a poorly conductive MnO₂ layer. To overcome this problem, a coating in which the Au is alloyed with MnO₂ has been developed. The fabrication of the codeposited film electrode of Au and MnO₂ by using a cyclic voltammetric (CV) method was described, and systematic physical and electrochemical characterization was performed. This MnO₂/Au film electrode enhanced MnO₂ electrocatalytic activity. The oxidation process of glucose at the codeposited MnO₂/Au shows a well-defined peak at 0.27 V in alkaline aqueous solution. In contrast, the glucose oxidation at Au modified glassy carbon electrode (GCE) just shows a shoulder wave at 0.42 V. The experimental results indicate that the modification of MnO₂ on the surface of GCE significantly improved the electrocatalytic activity towards the oxidation of glucose. Further study shows that the MnO₂/Au could also effectively catalyze the oxidation of hydrogen peroxide in pH 7.0 phosphate buffer solution (PBS).