高功率超级电容器用介孔炭电极材料

以纳米CaCO3为模板、蔗糖为前躯体制备超级电容器用介孔炭电极材料.材料的结构由氮吸附、TEM表征,借助恒流充放电、循环伏安和交流阻抗评价了其在6 mol.L-1KOH电解液中的电化学电容性能.结果表明,蔗糖基介孔炭的比表面积606 m2/g,富含10~30 nm的介孔.恒流放电法测得介孔炭在电流密度50 mA/g下的比电容为125 F/g,大电流倍率性能特别突出.电流密度增大到20 000 mA/g,比电容还保持有88F/g,远高于进口电容炭,该介孔炭是一种很有前景的高功率超级电容器炭电极材料.     

微孔-介孔多级孔炭材料的制备及电化学电容性能研究

采用有机-有机自组装法, 并结合后活化法制备了一类具有微孔-介孔复合孔结构的多级孔炭材料(HPC), 并研究了这类材料的电化学电容性能. 孔结构测试表明, 采用KOH后活化法可以在介孔炭的孔壁上控制性地生成微孔. 电化学测试表明, 与文献中报道的硬模板法制备的介孔炭相比, HPC具有更好的电化学电容性能. 在100 mV/s的快速电压扫描速率下, 它的比电容值能达到168.9 F/g. 更值得指出的是, HPC的高频电容性能非常优异, 在1 Hz时的比电容值高达180 F/g, 这一数值优于任何其它类的电极材料. HPC优异的电化学电容性能应当归功于它特殊的多级孔结构, 有助于电解质离子在孔道内的快速扩散.     

生物质巨菌草衍生炭的合成及在超级电容器中的应用

将巨菌草低温预碳化处理,得到粉末炭质材料(JPC),再用不同比例的KOH在不同温度下进行活化处理,得到了以微孔和介孔分布为主的无定形炭材料(JPCK1).所合成的炭材料JPCK1-900-4X的比表面积高达3368 m²/g,具有较大的孔隙体积和0.95%(原子分数)的氮含量.电化学测试结果表明,JPCK1-900-4X在超级电容器应用中表现出优异的储能潜力;在电流密度为0.5 A/g时其比电容为311.7 F/g,电流密度提高到10 A/g时比电容为230 F/g;在电流密度为10 A/g时经过5000次充放电循环后其电容保持率为97.5%;在两电极体系下,当功率密度为250 W/kg时,其能量密度可达17.7 W·h/kg.     

离子液体辅助条件下由稻壳合成超级电容器用多孔炭

本文以稻壳为碳源,以离子液体1-丁基-3-甲基咪唑六氟磷酸盐(BMIMPF₆)为模板和辅助活化剂制备了多孔炭材料（PCs）. 多孔炭的比表面积达1438 m²·g^-1,总孔容达0.75 cm³·g^-1. 以PCs为超级电容器电极材料,6 mol·L^-1的KOH溶液为电解液组装成扣式电池,在0.05 A·g^-1的电流密度下,比电容高达256 F·g^-1;当电流密度增大至10 A·g^-1,其比电容仍保持在211 F·g^-1,展现出好的倍率性能. 所得的多孔炭电极均表现出优异的循环稳定性. 这一工作以BMIMPF₆作为模板和辅助活化剂,为合成生物质基超级电容器用多孔炭提供了一种新方法.     

KOH添加方式对煤基活性泡沫炭电化学性能的影响

以强黏性炼焦煤为原料,经常压自发泡法制得的煤基泡沫炭(NCF)为碳基底,KOH为活化剂,采用机械混合、水溶液浸渍、乙醇浸渍三种不同的方式制备煤基活性泡沫炭(HPCs),并将其用作双电层电容器的电极材料,研究了KOH添加方式对其微观结构和电化学性能的影响。结果表明,KOH分散度和附着性对煤基活性泡沫炭孔隙结构的生成、晶体结构、表面化学性质以及电化学性能有显著影响。煤基泡沫炭本身具有三维连通泡孔结构,有利于活化剂(KOH)深入材料的泡孔内部并为其提供大量附着位点,增大活化剂与碳基体的接触面积进而发生高效的活化。KOH水溶液的流动性较好,可以使K⁺更有效地穿插在NCF的泡孔结构中,在活化过程中作用于缺陷部位,在碳基体内部基质上产生更多的微孔以及介孔结构,有效地放大了活化效果。KOH水溶液浸渍泡沫炭材料制得的ACF-W样品拥有最高的比表面积(3098.35 m²/g)、总孔体积(1.68 cm³/g)、介孔体积比(59.13%),将其用作电极材料表现出优异的比电容(310 F/g)以及循环稳定性。     

基于玉米秸秆合成的多孔生物质炭材料及其电化学储能

以玉米秸秆为原料,合成了高比表面积(2167 m²/g)的多孔生物质炭材料。 优化实验条件即可获得性能最佳的生物质炭电极材料,其在电流密度为1 A/g时的比电容高达390 F/g。 更重要的是,以所得最佳多孔生物质炭为电极材料,3 mol/L 的KOH溶液为电解质,组装了液相对称超级电容器。 该超级电容器在功率密度为818 W/kg时,其能量密度高达7 Wh/kg,在循环10000圈后的电容保持率为91.1%。 同时,将两个这种超级电容器串联充电之后,能够点亮15个LED灯并驱动小风扇正常工作。 这些结果表明,将基于玉米秸秆的多孔生物质炭作为先进电极材料应用于超级电容器具有较大的实际应用价值。     

金属有机骨架衍生氮掺杂碳材料的制备及其电化学性能研究

金属有机框架材料（MOFs）因其高比表面积、高孔容以及结构可调控等特性，可用作自牺牲模板或者前驱体合成纳米多孔炭材料。本文选择以沸石咪唑酯基骨架材料8（ZIF-8）为前驱体，并结合KOH活化法，系统研究了活化剂用量对材料孔结构、比表面积以及电化学性能的影响。所得氮掺杂纳米多孔炭（ZDPC）材料具有超高的比表面积和丰富的介孔结构。以其为电极材料，在2 M KOH中构建了对称超级电容器，在50 W kg^-1功率输出时，可以提供6.4 W h kg^-1的最大能量密度。当最大功率输出为10 k W kg^-1，器件依然具有5.3 W h kg^-1的能量密度，以及良好的倍率性能。在2 A g^-1电流密度下循环1万次，未出现容量衰减。     

离子液体辅助条件下由稻壳合成超级电容器用多孔炭（英文）

本文以稻壳为碳源,以离子液体1-丁基-3-甲基咪唑六氟磷酸盐(BMIMPF_6)为模板和辅助活化剂制备了多孔炭材料(PCs).多孔炭的比表面积达1438 m~2·g~(-1),总孔容达0.75 cm~3·g~(-1).以PCs为超级电容器电极材料,6 mol·L~(-1)的KOH溶液为电解液组装成扣式电池,在0.05 A·g~(-1)的电流密度下,比电容高达256 F·g~(-1);当电流密度增大至10A·g~(-1),其比电容仍保持在211 F·g~(-1),展现出好的倍率性能.所得的多孔炭电极均表现出优异的循环稳定性.这一工作以BMIMPF_6作为模板和辅助活化剂,为合成生物质基超级电容器用多孔炭提供了一种新方法.     

双离子液体基多孔炭的制备与电化学性能

以质子型离子液体1-氢-3-乙烯基咪唑硫酸氢盐(HVImHSO₄)为主炭源, 以1-丁基-3-甲基咪唑六氟磷酸盐(BMImPF₆)为助剂, 在氮气气氛、 1000 ℃下一步炭化得到氮、 磷、 硫共掺杂多孔炭. 通过N₂吸附-脱附、 扫描电子显微镜(SEM)、 透射电子显微镜(TEM)、 X射线衍射(XRD)、 拉曼光谱(Raman)、 热重分析(TGA)和X射线光电子能谱(XPS)等技术对多孔炭进行了分析表征. 结果表明, 多孔炭的孔结构以微孔为主, 最高比表面积可达1111 m²/g, 其微晶结构中无定形碳和石墨化碳并存; 多孔炭中的氮主要以季氮(N-Q)、 吡咯氮(N-5)和吡啶氮(N-6)的形式存在, 磷以磷-氧(N—O—P)键合形式为主, 硫主要以噻吩硫(C—S—C)为主. 在6 mol/L KOH溶液、 三电极体系中, 多孔炭在0.5 A/g电流密度下的比电容为138 F/g; 在10 A/g电流密度下的比电容为100 F/g; 在2 A/g电流密度下循环充放电10000次, 其比电容保持率为95.8%, 显示出良好的电化学性能.     

蟹壳基氮/氧共掺杂多孔炭的原位制备及其超级电容器性能

采用废弃蟹壳为碳源,KOH为活化剂原位制备了氮/氧共掺杂多孔炭,并研究其作为电极材料在超级电容器中的应用。 固定蟹壳与KOH的质量比为5:3,考察了煅烧温度对所得炭材料产率、孔结构和氮氧含量的影响。 结果表明,蟹壳基炭材料的孔结构和氮/氧含量可通过改变煅烧温度调变。 随着煅烧温度从500 ℃上升至700 ℃,多孔炭的比表面积和孔体积逐渐增大,而氮/氧含量随温度升高则降低。 采用循环伏安和恒流充放电对所得材料的电化学性能进行测试。 结果表明,所得多孔炭的电化学性能取决于其孔结构与氮/氧表面性质的协同作用,其中煅烧温度为600 ℃所得的多孔炭比表面积为612 m²/g,氮和氧含量分别为3.53%和32.8%,在50 mA/g的电流密度下比电容达到310 F/g,循环1000次比电容仍然保持95%以上,展现出良好的电化学性能。     

N-doped honeycomb-like porous carbon towards high-performance supercapacitor

Biomass-derived porous carbon with developed pore structure is critical to achieving high performance electrode materials. In this work, we report a grape-based honeycomb-like porous carbon (GHPC) prepared by KOH activation and carbonization, followed by N-doping (NGHPC). The obtained NGHPC exhibits a unique honeycomb-like structure with hierarchically interconnected micro/mesopores, and high specific surface area of 1268 m²/g. As a supercapacitor electrode, the NGPHC electrode exhibits a remarkable specific capacitance of 275 F/g at 0.5 A/g in a three-electrode cell. Moreover, the NGHPC//NGHPC symmetric supercapacitor displays a high energy density of 12.6 Wh/kg, and excellent cycling stability of approximately 95.2% capacitance retention after 5000 cycles at 5 A/g. The excellent electrochemical performance of NGHPC is ascribed to its high specific surface area, honeycomb-like structure and high-content of pyrodinic-N (36.29%). It is believed that grape-based carbon materials show great potential as advanced electrode materials for supercapacitors.     

Effect of surface area and heteroatom of porous carbon materials on electrochemical capacitance in aqueous and organic electrolytes

A series of porous carbon materials with wide range of specific surface areas and different heteroatom contents had been prepared using polyaniline as carbon precursor and KOH as an activating agent. Effect of surface area and heteroatom of porous carbon materials on specific capacitance was investigated thoroughly in two typical aqueous KOH and organic 1-butyl-3- methylimidazolium tetrafluoroborate/acetonitirle electrolytes. The different trends of capacitance performance were observed in these two electrolytes. Electrochemical analyses suggested that the presence of faradaic interactions on heteroatom-enriched carbon materials in organic environment is less significant than that observed in aqueous electrolytes. Thus, in aqueous electrolyte, a balance between surface area and heteroatom content of activated porous carbon would be found to develop a supercapacitor with high energy density. In organic electrolyte, the capacitance performance of porous carbon is strongly dependent on the surface area. The results may be useful for the design of porous carbon-based supercapacitor with the desired capacitive performance in aqueous and organic electrolytes.     

萘基相互连接的多孔碳纳米囊的制备及超电容性能

以萘为碳源, 采用MgO模板诱导耦合KOH裁剪技术制备了相互连接的多孔碳纳米囊(ICNC). 结果表明所制备的ICNC₂具有大的比表面积(1811 m²/g)、 高的压实密度(1.38 g/cm³)和微孔孔容含量(58.93%). 在对称的超级电容器(SC)中, ICNC₂电极的体积比容在不同电流密度下分别高达420.8 F/cm³(0.069 A/cm³)和315 F/cm³(27.6 A/cm³), 容量保持率为74.82%. 在38 W/L功率密度下, ICNC₂基SC的体积能量密度为14.6 W?h/L. 经过20000次循环后, 其体积比容仅衰减1.4%, 库伦效率为99.1%, 为从萘基小分子制备储能用功能碳材料提供了一种可行的方法.     

基于聚多巴胺的氮掺杂碳材料的制备及其电化学性能

多孔碳材料由于高的比表面积、优异的电子传导率、良好的化学稳定性等优点在超级电容器电极材料领域被广泛研究。 碳材料的组成及表面孔结构直接影响其电化学性能,为进一步提高碳材料的电容性能,本文首次以聚多巴胺球为前体,KOH为活化剂,通过高温碳化成功制备了良好电化学性能的氮掺杂多孔碳材料。 通过扫描电子显微镜(SEM)、透射电子显微镜(TEM)、 X射线粉末衍射(XRD)、傅里叶变换红外光谱(FT-IR)、X射线光电子能谱(XPS)和Raman光谱等对所制备的氮掺杂多孔碳材料进行了形貌及结构组成的表征。 在6 mol/L KOH电解液中, 采用循环伏安、恒电流充放电对多孔碳材料的电化学性能进行了研究。 结果表明,由于双电层电容和赝电容的协同作用,在电流密度为1 A/g时,材料的比电容可达269 F/g,充放电循环1000圈后电容仍可保留初始值的93.5%。     

Construction of a hierarchical architecture in a wormhole-like mesostructure for enhanced mass transport

A unique hierarchical architecture is successfully constructed in a wormhole-like mesopore structure via a multiple nanocasting route. This novel type of hierarchical porous carbon (HPC) consists of three-dimensional ordered macropores (ca. 150 nm) with interconnecting pore windows, and the walls of these macropores are rich in wormhole-like mesopores (ca. 2.7 nm) and large spherical mesopores (ca. 10 nm), as well as a significant microporosity, presenting a macro-meso-microporous structure with a three-dimensional interconnectivity. Such a hierarchically porous structure may provide fine diffusion pathways for reaction species, which is demonstrated by the experimental result of an enhanced performance in a supercapacitor. For example, with the introduction of a hierarchical porous structure for fast transport and effective access of ions, the as-prepared HPC exhibits a specific capacitance as high as 247 F g(-1), whereas traditional wormhole-like mesoporous carbon has only a specific capacitance of 176 F g(-1).     

多孔碳材料的化学气相后处理及其超级电容性能

以廉价的椰壳为原料制备了高比表面积的多孔碳材料,然后在密闭的反应釜中以硝酸蒸汽对多孔碳材料进行了后处理,制备了亲水性更好的多孔碳材料。采用扫描透射电子显微镜(TEM)、物理吸附、X射线粉末衍射(XRD)、拉曼光谱(Raman)和接触角测试对材料的微观形貌、孔道结构、组成和亲水性进行了表征,探究了不同温度下硝酸蒸汽对多孔碳材料的形貌、结构的影响,并采用循环伏安法、恒电流充放电法和交流阻抗法考察了多孔碳材料的超级电容性能。结果表明,经过硝酸蒸汽处理后的多孔碳材料的比表面积和孔体积均有所降低,且随着处理温度的升高,降低得更加明显,而亲水性却越来越好。电化学测试结果表明,经过100℃硝酸蒸汽处理的多孔碳材料(CSC-100)具有最佳的超级电容性能。在以6 mol·L^-1 KOH为电解液的三电极体系中,当电流密度为0.5 A·g^-1时CSC-100的比电容可达452.9 F·g^-1,而未经硝酸蒸汽处理的多孔碳材料(CSC)的比电容仅为350.4 F·g^-1。电容贡献分析表明CSC-100良好的亲水性和表面官能团不仅提高了双电层电容,也提高了赝电容。     

Dual template method to prepare hierarchical porous carbon nanofibers for high-power supercapacitors

Hierarchical porous carbon nanofibers serving as electrode materials are prepared through carbonization and hydrofluoric acid treatment of polyacrylonitrile-based electrospinning involving dual templates. The hierarchical porous structures are synergistically tailored by varying template contents in the spinning solution. The carbon nanofibers prepared from the electrospinning of polyacrylonitrile containing 15/15 wt.% polymethylmethacrylate/tetraethyl orthosilicate exhibit the largest specific surface area (699 m² g^?1) and microporous volume (0.196 cm³ g^?1). In 6 M KOH electrolyte, a symmetrical supercapacitor equipped with the hierarchical porous carbon nanofibers demonstrates its high-end specific capacitance of 170 F g^?1, superior rate capability, and high-power density output up to 14.7 kW kg^?1. Cycling evolution indicates capacitance fading is only 5.8 % of initial capacitance at a current density of 1 A g^?1 even after 8,000 cycles. The excellent electrochemical performances of the carbon nanofiber are mainly ascribed to the optimized pore size distributions of both micropores and mesopores and the unique hierarchical pore structures possessed by abundant micropores.     

Preparation and performance of polyvinyl alcohol-based activated carbon as electrode material in both aqueous and organic electrolytes

Porous carbon materials with high surface area and different pore structure have been successfully prepared by phenolic resin combined with polyvinyl alcohol (PVA) and KOH as activation agents. The surface morphology, structure, and specific surface area of the carbon materials were studied by scanning electron microscopy, X-ray diffraction, and nitrogen sorption measurement, respectively. Furthermore, the effects of specific surface area, pore structure, and electrolyte on electrochemical properties were investigated by galvanostatic charge–discharge measurement. The results show that KOH–PVA-activated carbon materials display specific capacitance as high as 218 F?g^?1 in 30 wt.% KOH aqueous electrolyte, 147 F?g^?1 in 1 M LiPF₆/(ethylene carbonate (EC) + dimethyl carbonate) (1:1?v/v), and 115 F?g^?1 in 1 M Et₃MeNBF₄/propylene carbonate organic electrolyte, respectively. In addition, the carbon materials demonstrate long-term cycle stability, especially the AK3P-0.30 in aqueous electrolyte and the AK2P-0.30 with excellent rate capability in organic electrolyte. These reveal that the existence of a micro-mesoporous structure of activated carbon is beneficial to store energy in an aqueous supercapacitor and broad pore size distribution of activated carbon is favorable to energy storage in an organic supercapacitor. The carbon materials with pore size distribution in different ranges improve the electrochemical performance of supercapacitor in different electrolytes. A new pore-expand agent (PVA combining with KOH) was used to obtain porous carbons with enhanced properties for supercapacitor.     

Facile synthesis of nitrogen-doped graphene aerogels functionalized with chitosan for supercapacitors with excellent electrochemical performance

Three-dimensional porous nitrogen-doped graphene aerogels (NGAs) were synthesized by using graphene oxide (GO) and chitosan via a self-assembly process by a rapid method. The morphology and structure of the as-prepared aerogels were characterized. The results showed that NGAs possesed the hierarchical pores with the wide size distribution ranging from mesopores to macropores. The NGAs carbonized at different temperature all showed excellent electrochemical performance in 6 mol/L KOH electrolyte and the electrochemical performance of the NGA-900 was the best. When working as a supercapacitor electrode, NGA-900 exhibited a high specific capacitance (244.4 F/g at a current density of 0.2 A/g), superior rate capability (51.0% capacity retention) and excellent cycling life (96.2% capacitance retained after 5000 cycles).