δ-MnO2纳米片的制备、表征及电化学性能

分别采用醋酸锰和乙醇还原高锰酸钾,制备2种超薄δ-MnO_2纳米片电极材料(δ-MnO_2-A与δ-MnO_2-B)。通过XRD、XPS、SEM/TEM、比表面积分析等手段研究材料的晶体结构、化学成分、微观形貌和孔径分布特征。电化学性能测试表明:2种材料具有相似的比电容和倍率性能。但是相比于δ-MnO_2-A,电极材料δ-MnO_2-B具有更高的钾含量和锰空位含量,片层状结构更加清晰、稳定,因而充放电循环稳定性更好。在0.5mol/L Na_2SO_4电解液中,1mV·s^-1扫描速率下δ-MnO_2电极材料的比电容可达227F·g^-1。100mV·s^-1扫描速率、5000次循环后,电容保持率为87.6%。     

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。     

一步法制备三维还原氧化石墨烯/NiO超级电容器电极材料及其性能研究

本研究以氧化石墨烯分散液(GO)和硝酸镍(Ni(NO₃)₂·6H₂O)为前驱体, 通过一步水热法制备自支撑三维还原氧化石墨烯/NiO复合电极材料(3D rGO/NiO)。用XRD和SEM等分析结果表明, 纳米NiO颗粒均匀分散在三维多孔石墨烯表面。当GO与Ni(NO₃)₂·6H₂O质量比为1 : 4时, 3D rGO/NiO在电流密度为1 A·g^-1 下比电容可达1208.8 F·g^-1; 当电流密度从0.2 A·g^-1增加到10 A·g^-1时, 复合电极材料电容保持率高于72.6%; 在电流密度为10 A·g^-1下进行恒流充放电循环测试10000次后, 其比电容仍然保持为初始比电容的93%, 表明该复合电极材料具有良好的倍率性能和循环稳定性能。3D rGO/NiO复合电极材料具有比纯NiO或rGO更优异的电化学性能。     

氮掺杂碳纤维包覆石墨烯纳米片的构建及电容特性

以石墨烯纳米片为骨架,聚吡咯为碳源,设计构建氮掺杂碳纤维包覆石墨烯纳米片（NFGNs）复合材料。采用SEM,XRD,Raman,FTIR,XPS和BET对材料进行表征,结果表明：相互连通的氮掺杂碳纳米纤维均匀地包覆生长在石墨烯纳米片层表面;NFGNs-800复合材料的氮原子分数为11.53%,比表面积为477.65 m²·g^-1。电容特性测试结果表明：NFGNs-800电极材料的比电容为323.3 F·g^-1（1.0 A·g^-1）,且具有良好的倍率特性;NFGNs-800超级电容器在功率密度为10500 W·kg^-1时,能量密度为87.1 Wh·kg^-1;经过10000次恒流充放电循环后,比电容保持率95.9%,库仑效率保持在99%以上。     

NiCo-LDH/CNW/CC三维结构复合电极及其电化学性能研究

NiCo-LDH具有优异的电化学性能,但自身易团聚且导电性差,导致其作为电极使用时本征电化学性能无法体现,常见的解决办法是将其分散负载于导电性好、比表面积大的惰性基体表面来使用。本文首次利用微波等离子体化学气相沉积技术先在具有大比表面积、导电性好且惰性强的碳布(CC)表面制备具有三维多孔结构的碳纳米墙(CNW)以进一步提高其比表面积和对粒子的负载性,再将NiCo-LDH通过电沉积法分散负载于CNW表面形成NiCo-LDH/CNW/CC三维结构复合电极。采用SEM观察复合电极的微观结构,同时通过Raman和XRD技术分析复合电极的材料组成,最后进一步使用电化学技术研究复合电极在三电极体系下的电化学性能。结果表明,CNW涂覆于CC表面作为载体能有效抑制NiCo-LDH的团聚,增加NiCo-LDH的分散性和有效暴露面积,所形成的NiCo-LDH/CNW/CC三维结构复合电极在2 mV·s^-1扫速下比电容是NiCo-LDH/CC的1.4倍;在电流密度为2 mA·cm^-2时,比电容高达3.9 F·cm^-2,同时展现出优异的倍率性能...     

B掺杂MnO2的制备及其电化学性能

用一步水热法制备B³⁺掺杂Birnessite-MnO₂负极材料,使用XRD,Raman,SEM,TEM,XPS和恒电流充放电等手段表征了材料的结构和电化学性能。结果表明,B³⁺掺杂前后的MnO₂都是由二维纳米片组装而成的花球,B³⁺离子掺杂使纳米片的厚度减小,从而缩短了锂离子和电子在材料内部的传输路径;掺杂适量的B³⁺离子,使Birnessite-MnO₂的电荷转移电阻显著降低。B³⁺掺杂比例为9%的电极材料,具有最优的电化学性能。在电流密度为100 mA·g^-1和1000 mA·g^-1的条件下,首次充电比容量分别为855.1 mAh·g^-1和599 mAh·g^-1,循环100次后仍然保有805 mAh·g^-1和510.3 mAh·g^-1的可逆比容量,容量保持率分别为94.1%和85.2%。     

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。     

锂硫电池正极用钴掺杂空心多孔碳载体材料

锂硫电池被认为是新一代低成本、高能量密度的储能系统。但由于硫正极导电性差、穿梭效应严重以及氧化还原反应速率慢, 导致电池容量衰减严重, 倍率性能较差。本研究以柠檬酸钠为碳源制备了具有三维中空结构的多孔碳材料, 并在其骨架上负载钴纳米颗粒后作为硫正极的载体。引入的钴纳米颗粒可有效吸附多硫化物, 提升其转化反应的动力学, 进而明显改善电池的循环和倍率性能。所得的钴掺杂复合硫正极在0.5C (1C=1672 mAh·g^-1)的倍率下首圈放电比容量高达1280 mAh·g^-1, 在1C的倍率下稳定循环200圈后可保持770 mAh·g^-1, 并且具有优异的倍率性能, 即使在10C的大电流密度下仍可稳定循环。     

菲醌修饰多孔碳纳米管复合材料的制备及其在对称超级电容器中的应用

为获得具有优异电化学性能的超级电容器电极材料,首先依次对实验合成的聚吡咯(PPy)纳米管进行碳化处理和活化处理来制备层级多孔碳纳米管(PCNTs)。然后用一步溶剂热法将9,10-菲醌(PQ)分子通过π-π堆积作用进一步修饰到PCNTs表面得到PQ分子非共价修饰的PCNTs复合材料(PQ/PCNTs)。不仅对合成的复合材料进行了形貌表征,而且还通过循环伏安法(CV)、恒电流充放电(GCD)和电化学阻抗谱(EIS)研究了具有不同PQ分子负载率的复合材料(PQ/PCNTs)的超级电容性能。实验结果表明：PQ分子与PCNTs质量比为5∶5的复合材料的电化学性能最好,在1 A·g^-1的电流密度下的比容量可以达到407.7 C·g^-1。同时复合材料表现出优异的倍率性能(电流密度为50 A·g^-1时的比容量为307.3 C·g^-1)和循环稳定性能(在10 A·g^-1电流密度下循环10,000次后电容保持率为91.4%)。为了进一步研究复合材料的实际应用性能,以PQ与PCNTs质量比为5∶5作...     

立方相碳化钛在锂空电池中的电化学行为

采用直流电弧等离子体法在甲烷和氩气混合气氛下原位合成碳化钛(TiC)纳米颗粒。X射线衍射、透射电子显微镜等物理表征结果显示TiC纳米颗粒粒径约为40～90 nm的立方体结构。循环伏安(CV)测试表明,TiC纳米颗粒兼具高效的氧还原和氧析出双效催化活性,可有效弥补炭材料氧析出催化活性较弱的缺陷。恒流充放电测试结果表明,相对于普通炭材料(导电炭黑,Super-P),TiC纳米颗粒催化剂可将锂空电池充电过电势降低280mV;在电流密度(i_sp)为50mA·g^-1时,首次放电比容量达1267mAh·g^-1;即使在较高的电流密度150mA·g^-1下,比容量仍保持在778mAh·g^-1,体现了良好的倍率性能。在电流密度为100mA·g^-1、限定比容量为500mAh·g^-1下,稳定循环10次。通过XRD、红外、扫描电镜表征可知,在TiC纳米颗粒的双效催化作用下,Li_2O_2的生成与分解具有良好的可逆性,有效避免了大量反应副产物积累的问题,进而提高锂空电池的电化学性能。     

NiS2/三维多孔石墨烯复合材料作为超级电容器电极材料的电化学性能

选用合适的软模板,通过简便的一步溶剂热法成功制备了NiS₂/三维多孔石墨烯（3D rGO）复合材料。利用FESEM、TEM、XPS和电化学工作站对样品的表面形貌、元素价态和电化学性能进行表征。结果表明:制备的NiS₂/3D rGO复合材料存在石墨烯三维堆叠的孔道结构,且具备较大的比表面积,为57.51 m2g-1。电化学测试表明,在1 Ag-1的电流密度下NiS₂/3D rGO复合材料的比电容高达1 116.7 Fg-1,而且当电流密度增加到5 Ag-1时NiS₂/3D rGO复合材料的比电容为832.2 Fg-1,比电容保持率为1 Ag-1时的74.5%。在4 Ag-1电流密度下,经过1 000次循环后,NiS₂/3D rGO复合材料的比电容仍能保持91.2%。因此,NiS₂/3D rGO复合材料可作为一种理想的超级电容器电极材料。      

超级电容器用CeO_2-MnO/3D石墨烯复合材料的制备

以西瓜瓜瓤为碳源,采用两步碳化法制备三维石墨烯(3D-Fiberbased Graphene,3D G)材料,并使用水热法制备了CeO_2-MnO/3DG复合材料,以期获得比电容高,循环寿命好的石墨烯超级电容器电极材料。结果表明:3DG材料具有较高比表面积,最高可达到332m~2·g~(-1)。CeO_2-MnO/3DG复合材料具有三维导电网络结构,金属氧化物颗粒在石墨烯片层间生长均匀,粒径在10nm左右。电化学测试结果显示:在0.5 mol·L~(-1)的Na_2SO_4溶液中,电流密度1A·g~(-1),当摩尔比MnO∶CeO_2=4∶1,复合负载量在80%时得到的CeO_2-MnO/3D G复合材料拥有最高比电容,达308.5F·g~(-1),经过1 000次循环充放电测试比电容保持率为95.5%。CeO_2-MnO/3DG复合材料电化学性能的提高主要是因为两种金属氧化物复合负载与石墨烯的协同作用。     

Flexible Zn2SnO4/MnO2 core/shell nanocable-carbon microfiber hybrid composites for high-performance supercapacitor electrodes

We demonstrate the design and fabrication of a novel flexible nanoarchitecture by facile coating ultrathin (several nanometers thick) films of MnO2 to highly electrical conductive Zn2SnO4 (ZTO) nanowires grown radially on carbon microfibers (CMFs) to achieve high specific capacitance, high-energy density, high-power density, and long-term life for supercapacitor electrode applications. The crystalline ZTO nanowires grown on CMFs were uniquely served as highly conductive cores to support a highly electrolytic accessible surface area of redox active MnO2 shells and also provide reliable electrical connections to the MnO2 shells. The maximum specific capacitances of 621.6 F/g (based on pristine MnO2) by cyclic voltammetry (CV) at a scan rate of 2 mV/s and 642.4 F/g by chronopotentiometry at a current density of 1 A/g were achieved in 1 M Na2SO4 aqueous solution. The hybrid MnO2/ZTO/CMF hybrid composite also exhibited excellent rate capability with specific energy of 36.8 Wh/kg and specific power of 32 kW/kg at current density of 40 A/g, respectively, and good long-term cycling stability (only 1.2% loss of its initial specific capacitance after 1000 cycles). These results suggest that such MnO2/ZTO/CF hybrid composite architecture is very promising for next generation high-performance supercapacitors.     

超级电容器用聚苯胺/有序介孔炭复合电极的性能

利用原位聚合法制备了聚苯胺/有序介孔炭复合材料.通过恒流充放电、循环伏安和交流阻抗测试考察了不同聚苯胺含量对聚苯胺/有序介孔炭复合材料电化学性能的影响.研究表明:与纯的有序介孔炭和聚苯胺相比,聚苯胺/有序介孔炭复合材料具有更高的比容量,良好的稳定性和充放电循环性能.当聚苯胺质量分数为60%,电流密度为0.1A·g-1时,比容量可以达到409F·g-1.     

Hydrogenated TiO2 nanotube arrays for supercapacitors

We report a new and general strategy for improving the capacitive properties of TiO(2) materials for supercapacitors, involving the synthesis of hydrogenated TiO(2) nanotube arrays (NTAs). The hydrogenated TiO(2) (denoted as H-TiO(2)) were obtained by calcination of anodized TiO(2) NTAs in hydrogen atmosphere in a range of temperatures between 300 to 600 °C. The H-TiO(2) NTAs prepared at 400 °C yields the largest specific capacitance of 3.24 mF cm(-2) at a scan rate of 100 mV s(-1), which is 40 times higher than the capacitance obtained from air-annealed TiO(2) NTAs at the same conditions. Importantly, H-TiO(2) NTAs also show remarkable rate capability with 68% areal capacitance retained when the scan rate increase from 10 to 1000 mV s(-1), as well as outstanding long-term cycling stability with only 3.1% reduction of initial specific capacitance after 10,000 cycles. The prominent electrochemical capacitive properties of H-TiO(2) are attributed to the enhanced carrier density and increased density of hydroxyl group on TiO(2) surface, as a result of hydrogenation. Furthermore, we demonstrate that H-TiO(2) NTAs is a good scaffold to support MnO(2) nanoparticles. The capacitor electrodes made by electrochemical deposition of MnO(2) nanoparticles on H-TiO(2) NTAs achieve a remarkable specific capacitance of 912 F g(-1) at a scan rate of 10 mV s(-1) (based on the mass of MnO(2)). The ability to improve the capacitive properties of TiO(2) electrode materials should open up new opportunities for high-performance supercapacitors.     

Three-dimensional heterostructured MnO2/graphene/carbon nanotube composite on Ni foam for binder-free supercapacitor electrode

In this article, three-dimensional (3D) heterostructured of MnO₂/graphene/carbon nanotube (CNT) composites were synthesized by electrochemical deposition (ELD)-electrophoretic deposition (EPD) and subsequently chemical vapour deposition (CVD) methods. MnO₂/graphene/CNT composites were directly used as binder-free electrodes to investigate the electrochemical performance. To design a novel electrode material with high specific area and excellent electrochemical property, the Ni foam was chosen as the substrate, which could provide a 3D skeleton extremely enhancing the specific surface area and limiting the huge volume change of the active materials. The experimental results indicated that the specific capacitance of MnO₂/graphene/CNT composite was up to 377.1 F g^?1 at the scan speed of 200 mV s^?1 with a measured energy density of 75.4 Wh kg^?1. The 3D hybrid structures also exhibited superior long cycling life with close to 90% specific capacitance retained after 500 cycles.     

PVA-assisted hydrated vanadium pentoxide/reduced graphene oxide films for excellent Li+and Zn2+storage properties

Low-cost,high safety and environment-friendly aqueous energy storage systems(ESSs)are huge poten-tial for grid-level energy storage,but the(de)intercalation of metal ions in the electrode materials(e.g.vanadium oxides)to obtain superior long-term cycling stability is a significant challenge.Herein,we demonstrate that polyvinyl alcohol(PVA)-assisted hydrated vanadium pentoxide/reduced graphene oxide(V2O5·nH2O/rGO/PVA,denoted as the VGP)films enable long cycle stability and high capacity for the Li+and Zn2+storages in both the VGP//LiCl(aq)//VGP and the VGP//ZnSO4(aq)//Zn cells.The binder-free VGP films are synthesized by a one-step hydrothermal method combination with the filtration.The extensive hydrogen bonds are formed among PVA,GO and H2O,and they act as structural pillars and connect the adjacent layers as glue,which contributes to the ultrahigh specific capacitance and ultralong cyclic performance of Li+and Zn2+storage properties.As for Li+storage,the binder-free VGP4 film(4 mg PVA)electrode achieves the highest specific capacitance up to 1381 F g-1 at 1.0 A g-1 in the three-electrode system and 962 F g-1 at 1.0 A g-1 in the symmetric two-electrode system.It also behaves the outstanding cyclic performance with the capacitance retention of 96.5％after 15000 cycles in the three-electrode system and 99.7％after 25000 cycles in the symmetric two-electrode system.As for Zn2+storage,the binder-free VGP4 film electrode exhibits the high specific capacity of 184 mA h g-1 at 0.5 A g-1 in the VGP4//ZnSO4(aq)//Zn cell and the superb cycle performance of 98.5％after 25000 cycles.This work not only provides a new strategy for the construction of vanadium oxides composites and demonstrates the potential application of PVA-assisted binder-free film with excellent electrochemical properties,but also extends to construct other potential electrode materials for metal ion storage cells.     

Construction of hierarchical three-dimensional interspersed flower-like nickel hydroxide for asymmetric supercapacitors

Low-cost and easily obtainable electrode materials are crucial for the application of supercapacitors.Nickel hydroxides have recently attracted intensive attention owning to their high theoretical specific capacitance,high redox activity,low cost,and eco-friendliness.In this study,novel three-dimensional (3D) interspersed flower-like nickel hydroxide was assembled under mild conditions.When ammonia was used as the precipitant and inhibitor and CTAB was used as an exfoliation agent,the obtained exfoliated ultrathin Ni(OH)2 nanosheets were assembled into 3D interspersed flower-like nickel hydroxide.In this novel 3D structure,the ultrathin Ni(OH)2 nanosheets not only provided a large contact area with the electrolyte,reducing the polarization of the electrochemical reaction and providing more active sites,but also reduced the concentration polarization in the electrode solution interface.Consequently,the utilization efficiency of the active material was improved,yielding a high capacitance.The electrochemical performance was improved via promoting the electrical conductivity by mixing the as-synthesized Ni(OH)2 with carbon tubes (N-4-CNT electrode),yielding excellent specific capacitances of 2,225.1 F·g-1 at 0.5 A·g-1 in a three-electrode system and 722.0 F·g-1 at 0.2 A·g-1 in a two-electrode system.The N-4-CNT//active carbon (AC) device exhibited long-term cycling performance (capacitance-retention ratio of 111.4％ after 10,000 cycles at 5 A·g-1) and a high specific capacitance of 180.5 F·g-1 with a high energy density of 33.5 W·h·kg-1 and a power density of 2,251.6 W·kg-1.     

一步法合成具有优异循环性能的聚苯胺纳米线/自支撑石墨烯复合材料

研究采用一步电化学剥离和电沉积法,在含Na₂SO₄、HCl与苯胺(An)单体的混合溶液中,以柔性石墨纸为原料,利用电场条件下电解液离子定向迁移和苯胺单体的电聚合制备聚苯胺纳米线/自支撑石墨烯(PANI/SGr)复合材料。更具活性的新生SGr与PANI结合,显著提高了PANI/SGr复合材料的稳定性。PANI呈纳米线状均匀分布在SGr上,形成的三维网络结构所呈现出的孔隙促进了电解液离子扩散到复合材料的内部结构中。将PANI/SGr复合材料作为超级电容器电极材料进行电化学测试,2 mV·s?1的扫速下获得的比电容为453 F·g?1。在0.5~10 A·g?1的电流密度范围内,PANI/SGr复合材料倍率性能达73.1%。在1 A·g?1的电流密度下PANI/SGr复合材料经10000次充放电之后的循环稳定性仍高达87.3%。这表明PANI/SGr复合材料具有良好的电容性能和优异的循环稳定性,有望作为超级电容器电极材料。