珊瑚状氮掺杂多孔碳的制备及其超电容性能

在三聚氰胺为氮源、碳酸钾为活化剂的条件下，由菜籽饼制得了珊瑚状氮掺杂分级多孔碳(CNPCs)。采用场发射扫描电子显微镜、透射电子显微镜、X射线光电子能谱、氮吸脱附等表征手段，研究了三聚氰胺的用量对CNPCs微观形貌、组成及孔隙结构的影响。结果表明，当三聚氰胺的用量为2 g时，所得CNPC₂的比表面积达2050 m²·g^-1。以6 mol·L^-1 KOH为电解液，在0.05 A·g^-1的电流密度下，CNPCs的比容可达274 F·g^-1；当电流密度为50 A·g^-1时，CNPCs的比容为169 F·g^-1，显示了优异的倍率性能。经过10000次充放电测试后，比容保持率达96%，展现了良好的循环稳定性。此工作为从生物质大规模生产高性能储能用多孔碳材料提供了一种简单、绿色的方法。     

Three-dimensional oxygen-doped porous graphene: Sodium chloride-template preparation,structural characterization and supercapacitor performances

Supercapacitor is a new type of energy storage device, which has the advantages of high-power property and long cycle life. In this study, three-dimensional graphene (3D-GN) with oxygen doping and porous structure was prepared from graphene oxide (GO) by an inexpensive sodium chloride (NaCl) template, as a promising electrode material for the supercapacitor. The structure, morphology, specific surface area, pore size, of the sample were characterized by XRD, SEM, TEM and BET techniques. The electrochemical performances of the sample were tested by CV and CDC techniques. The 3D-GE product is a three-dimensional nano material with hierarchical porous structures, its specific surface area is much larger than that of routine stacked graphene (GN), and it contains a large number of mesoporous and macropores, a small amount of micropores. The capacitance characteristics of the 3D-GN electrode material are excellent, showing high specific capacitance (173.5 F·g^-1 at 1 A·g^-1), good rate performance (109.2 F·g^-1 at 8 A·g^-1) and long cycle life (88% capacitance retention after 10,000 cycles at 8 A·g^-1)     

纤维素基生物质多孔炭的制备及其超级电容器性能研究

以棉纤维素为原料,采用硝酸盐、尿素、纤维素共混后热裂解的方法制备分级多孔炭HPC样品,通过改变煅烧温度和KOH活化处理对多孔炭比表面积及孔结构进行调控。对比三个不同温度煅烧活化处理后样品的循环伏安曲线、恒电流充放电曲线、比容量等电化学参数,结果表明,4AC@HPC800样品作为超级电容器工作电极具有优良的电化学性能,其比表面积高达2433.8 m²·g^-1,在1 A·g^-1的电流密度下比容量高达234.7 F·g^-1,在大电流密度10 A·g^-1时依然有207.6 F·g^-1的比容量,具有良好的倍率性能;电极在2 A·g^-1的电流密度下循环10000次后依然有196.1 F·g^-1的比容量,表明其具有长时工作的特性。     

纤维素基生物质多孔炭的制备及其超级电容器性能研究

以棉纤维素为原料,采用硝酸盐、尿素、纤维素共混后热裂解的方法制备分级多孔炭HPC样品,通过改变煅烧温度和KOH活化处理对多孔炭比表面积及孔结构进行调控。对比三个不同温度煅烧活化处理后样品的循环伏安曲线、恒电流充放电曲线、比容量等电化学参数,结果表明,4AC@HPC800样品作为超级电容器工作电极具有优良的电化学性能,其比表面积高达2433.8 m²·g^-1,在1 A·g^-1的电流密度下比容量高达234.7 F·g^-1,在大电流密度10 A·g^-1时依然有207.6 F·g^-1的比容量,具有良好的倍率性能;电极在2 A·g^-1的电流密度下循环10000次后依然有196.1 F·g^-1的比容量,表明其具有长时工作的特性。     

秸秆基碳材料在Li2SO4电解液中的电化学性能

以生物质秸秆为碳源,利用水热结合KOH活化法制备了多孔碳材料,对其结构与形貌进行了表征。采用三电极体系,在不同浓度的Li₂SO₄电解液中,对多孔碳电极进行循环伏安、恒电流充放电和交流阻抗测试。结果表明,在0.5 mol·L^-1的Li₂SO₄电解液中,秸秆基生物质碳材料呈现出较好的电化学性能。当电流密度为0.5 A·g^-1时,比电容可达224 F·g^-1;经1500次充放电测试后,比电容保持率高达94.1%,循环性能良好。     

多孔碳负载五氧化二铌及其在超级电容器中的应用

以间苯二酚、甲醛和草酸铌为原料,通过原位聚合和高温煅烧,制备出多孔碳负载的五氧化二铌（Nb₂O₅）材料。X射线粉末衍射和扫描电镜分析表明,负载在多孔碳表面上的五氧化二铌具有三维纳米凸起结构,属于正交晶型。循环伏安测试表明该复合材料的比电容达到290 F·g^-1,并具有良好的大电流放电能力,5 A·g^-1的放电电流下,容量可以达到108 F·g^-1。0.5 A·g^-1的首次放电容量为355 F·g^-1 （1.0~3.0 V vs. Li⁺/Li）,100次循环后容量保持率为82%。通过对交流阻抗图谱和等效电路的模拟分析,对其电化学赝电容特性进行了讨论。该复合材料降低了电解液中离子在充放电过程中的迁移路径和扩散阻力,实现Nb₂O₅活性材料的多维度接触,提高了Nb₂O₅的导电性,改善了其超级电容特性。     

混合盐模板法制备超级电容器用氮掺杂分级多孔碳纳米片

分级多孔碳在电化学储能方面展现了巨大的潜力。模板与活化法相耦合是制备分级多孔碳最有效的方法之一。然而,该方法使用强酸和强碱,对环境造成污染。因此,开发一种无酸无碱制备分级多孔碳的方法迫在眉睫。以氯化钠和碳酸钠混合盐为模板,煤沥青为碳前体,碳酸钾为活化剂,合成了氮掺杂分级多孔碳纳米片（NHCNs）。模板与活化剂可以通过水洗除去,无需使用强酸和强碱,该工作为合成分级多孔碳纳米片提供了一种无酸无碱的技术。合成的NHCNs具有大的比表面积（1597 m²·g^-1）、丰富的微/中孔、适量的氧和氮杂原子。这些独特结构赋予NHCNs电极优异的超级电容性能。在KOH电解液中,NHCNs电极显示了高的比电容和好的循环稳定性。     

晶须形中空多孔氮掺杂复合碳电极材料的制备及电化学性能研究

中空多孔碳因其低密度、大孔容、高比表面积以及优良的电导率,被视为一种理想的电负极材料。以纳米碳酸钙晶须为模板剂,负载聚多巴胺薄膜与氧化石墨烯,作为碳源与氮源,制备出晶须形中空多孔碳材料（Cw-GO）,应用于锂离子电池负极。碳化过程中,碳酸钙晶须经高温分解释放出大量二氧化碳,刺破碳前体壳层,具有高效扩孔功能。利用扫描电子显微镜（SEM）、透射电子显微镜（TEM）、氮气吸附-脱附仪对样品形貌和结构进行了表征,利用循环伏安（CV）、阻抗谱（EIS）、循环充放电（GCD）对样品进行电化学性能检测。结果表明,复合材料Cw-GO在500 mA·g^-1的电流密度下,其初始放电比容量可达到1185.9 mA·h·g^-1,在循环200次后,比容量为921.8 mA·h·g^-1,库仑效率基本保持在99.4%,表现出优异的电化学性能。     

刚性骨架COS-NMC材料制备及其电化学性能研究

以壳寡糖(COS)为碳前驱体,三嵌段共聚物(F127)和正硅酸乙酯(TEOs)为模板剂,通过溶胶-凝胶法制备了一种用于超级电容器的原位氮掺杂介孔碳材料(COS-NMC-x)。借助质谱仪、TG-DTG、XRD、Raman光谱、N₂吸附/脱附、XPS、FT-IR、亲水性以及电化学评价等手段对材料进行了表征,以研究材料的物化性质和电化学性能。结果表明,COS-NMC-x材料的比表面积、孔容、氮原子数分数随超声时间的增加呈先增后减的趋势,当超声时间为15 min时,样品的比表面积、孔容、氮原子数分数到最大,接触角最小,分别为144.94 m²·g^-1、0.19 cm³·g^-1、7.59%和23.16°。同时对COS-NMC-x进行了电化学性能评价,在电流密度为0.5 A·g^-1时,样品的比电容为189 F·g^-1,远高于同组其他材料,说明较大的孔隙结构和氮原子数分数等有利于材料的电化学性能提升。在10 A·g^-1下经过5 000次循环之后,该材料的电容保持率达到114%,表现出良好的电化学性能,在超级电容器应用方面展现出巨大的应用潜力。     

Fabrication and characterization of hierarchical porous Ni2+ doped hydroxyapatite microspheres and their enhanced protein adsorption capacity

Hydroxyapatite (HAP) is a common bio-adsorbent, which performance depends heavily upon its morphology and microporous structure. In this study, a novel synthesis strategy was proposed for hierarchical porous HAP microspheres by a simple “one-pot” hydrothermal reaction. In the strategy, L-glutamic acid serves as soft template to modulate the morphology and inner crystalline of HAP. To evaluate the application potential, doping Ni²⁺ on hierarchical porous HAP microspheres gives metal chelated affinity adsorbents. The prepared adsorbents show a perfect spherical shape, particles size of 96.6 μm, relatively specific surface area of 48.5 m²·g^-1 and hierarchical pores (mesopores: 4 nm and macropores: 53 nm). By the adsorption evaluation, it reveals that the Ni²⁺-HAP adsorbents have high adsorption capacities of 275.11 and 97.55 m²·g^-1 for hemoglobin and bovine serum albumin, respectively, which is comparable to other similar adsorbent. Therefore, this work provides a promising method for high-efficiency hydroxyapatite microspheres for proteins purification.     

A high-performance biochar produced from bamboo pyrolysis with in-situ nitrogen doping and activation for adsorption of phenol and methylene blue

Nitrogen doping is a promising method for the preparation of functional carbon materials. In this study, a nitrogen-doped porous coral biochar was prepared by using bamboo as raw material, urea as nitrogen source, and KHCO³ as green activator through in-situ pyrolysis. The structure of the obtained biochar was characterized by various techniques including nitrogen adsorption and desorption, Raman spectroscopy, X-ray photoelectron spectrometer, and etc. The adsorption properties of nitrogen-doped biochar were evaluated with phenol and methylene blue probes. The results showed that the nitrogen source ratio had a significant effect on the evolution of pore structure of biochar. Low urea addition ratio was beneficial to the development of pore structures. The optimum specific surface area of nitrogen-doped biochar could be up to 1693 m²·g^-1. Nitrogen doping can effectively improve the adsorption capacity of biochar to phenol and methylene blue. Biochar prepared at 973.15 K with low urea addition ratio exhibited the highest adsorption capacity for phenol and methylene blue, and the equilibrium adsorption capacity was 169.0 mg·g^-1 and 499.3 mg·g^-1, respectively. By comparing the adsorption capacity of various adsorbents in related fields, it is proved that the nitrogen-doped biochar prepared in this study has a good adsorption effect.     

PANI/煤基石墨烯宏观体复合材料的制备及其电化学性能

以太西无烟煤为原料,采用催化热处理、改良Hummers氧化等方法,制备煤基氧化石墨烯（CGO）,进而以CGO和聚苯胺（PANI）为前驱体,采用水热自组装法,制备得到PANI/石墨烯宏观体复合材料（3D-PCG）。采用FT-IR、XRD、Raman、SEM和TEM等技术,研究了材料的组成、结构和形貌,考察了3D-PCG的电化学性能。结果表明,PANI以纳米棒状形态均匀镶嵌在煤基石墨烯宏观体（3D-CG）的网状结构中;当PANI与CGO质量比为1：2时,3D-PCG的电化学性能优于PANI和3D-CG,其比电容可达663 F·g^-1。     

“一锅法”水热制备CuS/C复合材料及其在超级电容器中的应用

采用三水合硝酸铜为铜源、硫脲为硫源、D-葡萄糖酸钠为络合剂,发展了简单的“一锅法”水热直接一步合成CuS/C复合材料。采用X射线衍射仪（XRD）、激光显微拉曼光谱仪（Raman）、扫描电子显微镜（SEM）和有机元素分析仪对复合材料组成、结构及形貌进行表征。研究发现,样品主要由花状CuS球组成,同时含有质量分数约为6%的光滑炭球,CuS球表面分布有花瓣状褶皱,形成的大量孔道有利于离子传输,并增大活性物质与电解液的接触面积。研究表明,在1 A·g^-1电流密度下,比电容高达719 F·g^-1,与不加络合剂制备得到的CuS（382 F·g^-1）相比,比电容显著提高,并且在充放电1000次后比电容保持在80%左右,显示出良好的循环稳定性。     

Three-dimensional strutted graphene loading manganese oxide for supercapacitor

Graphene has shown superiority for advanced carbon electrodes in supercapacitors, characterized by high power density but limited energy density. Combining pseudocapacitive materials with graphene can alleviate the problem. This work synthesized the three-dimensional strutted graphene (SG) via the ammonium-salt-assisted sugar-blowing method, and the self-supporting MnO₂/SG porous monolith was then constructed via growing manganese oxide (MnO₂) nanorod array on the SG support in hydrothermal process. When tested in supercapacitor, the MnO₂/SG hybrid electrode achieved a high specific capacitance of 343.6 F·g^-1 at a current density of 0.5 A·g^-1, exhibiting excellent cycling stability with 83.8% capacitance retention after 5000 cycles. The symmetric supercapacitor further showed a high energy density of 11.93 W·h·kg^-1 at a power density of 500 W·kg^-1. The impressive result indicates a promising prospect of the excellent MnO₂/SG hybrid to be applied to electrochemical energy storage.     

三维筋撑石墨烯负载氧化锰的超级电容器

石墨烯基超级电容器，其功率密度较高，但能量密度受限。开发以三维石墨烯材料为载体的复合型赝电容多孔电极，是解决方案之一。本文采用铵盐辅助化学发泡法，制备了三维筋撑石墨烯泡沫体（SG）；以SG为载体，采用水热还原法在其表面生长二氧化锰（MnO₂）纳米棒阵列，从而构建了MnO₂/SG自支撑多孔材料。利用MnO₂/SG复合电极，组装了超级电容器，在0.5 A·g^-1的电流密度下，比电容达343.6 F·g^-1；经5000次循环，其容量保持率为83.8%；在500 W·kg^-1的功率密度下，其能量密度达11.93 W·h·kg^-1。因此，MnO₂/SG复合电极是一种性能优异的赝电容材料，在电化学储能领域有良好的应用前景。     

氮掺杂微孔活性炭制备及其超级电容性能

以土豆为碳源,乙二胺为氮源,氢氧化钾为活化剂制备具有微孔结构高比表面积氮掺杂活性炭。通过N_2物理吸附、扫描电镜、透射电镜、拉曼光谱和元素分析研究活性炭比表面积、孔结构、形貌及元素组成,并测试其电化学性能。结果表明,当碱碳质量比为5∶1时(NC600-800-5),活性炭材料比表面积最高2 440 m~2·g~(-1)、孔容最大1.07 cm~3·g~(-1)、孔径最大0.82 nm和1.80 nm。电流密度1 A·g~(-1)时比电容可达370 F·g~(-1),经3 000次循环充放电后,比电容保持率为95.2%。     

Platanus orientalis leaves based hierarchical porous carbon microspheres as high efficiency adsorbents for organic dyes removal

Water contamination caused by hazardous organic dyes has drawn considerable attention, among all of the techniques released, adsorption has been widely used, which however to a large degree is dependent on the development of high efficiency adsorbents. Waste biomass based porous carbon is becoming the new star class of adsorbents, and thus contribute more to the sustainable development of the society. In this work, for the first time to the best of our knowledge, abundant waste fallen Platanus orientalis leaves are employed as the raw material for hierarchical activated porous carbon(APC) microspheres via a mild hydrothermal carbonization(210 °C,12.0 h) followed by one-step calcination(750 °C, 1.0 h). The APC microspheres exhibit a specific surface area of1355.53 m~2·g~(-1) and abundant functional groups such as O—H and C=O. Furthermore, the APC microspheres are used as the adsorbents for removal of Rh B and MO, with the maximum adsorption capabilities of 557.06 mg·g~(-1) and 327.49 mg·g~(-1), respectively, higher than those of the most porous carbon originated from biomass. The adsorption rates rapidly approach to 98.2%(Rh B) and 95.4%(MO) within 10 min. The adsorption data can be well fitted by Langmuir isotherm model and the pseudo-second-order kinetic model, meanwhile the intra-particle diffusion and Boyd models simultaneously indicate that the diffusion within the pores is the main rate-limiting step. Besides, the APC microspheres also demonstrate good recyclability, and may also be applied to other areas such as heterogeneous catalysis and energy storage.     

三金属Mn-Ni-Co-O@Ni-Mn-S纳米针/纳米片核壳阵列用于超级电容器的研究

为满足超级电容器对于高性能电极材料的需求,本研究采用水热和电沉积结合的方法,在泡沫镍上合成了具有独特三维(3D)核壳结构的纳米针/纳米片核壳阵列(3D NDNSA)的过渡金属氧化物和硫化物复合赝电容电极材料Mn-Ni-Co-O@Ni-Mn-S(MNCO@NMS)。SEM和TEM分析结果表明,一维MNCO纳米针为核心和二维NMS纳米片为壳层,相互连接并交织形成分层的3D核壳纳米结构的MNCO@NMS。由于过渡金属氧化物和硫化物的协同作用和分层核壳结构带来的导电性和活性位点的增加,制得的3D MNCO@NMS表现出了优异的电化学性能。在3 mol·L^-1 KOH作为电解质的三电极电化学测试系统中,MNCO@NMS电极在电流密度1 A·g^-1下比电容为 2 574.2 F·g^-1;在电流密度 10 A·g^-1下循环5 000次后,表现出接近100%的库伦效率和83.4%的比电容保持率。此外,以制得的MNCO@NMS为正极,活性炭为负极组装的混合超级电容器器件(HSCs)在功率密度799 W·kg^-1下的能量密度为54.4 Wh·kg^-1,在 5 A·g^-1下进行4 000次循环后,库伦效率接近100%和保持初始比电容的81.7%。这些电化学特性表明,核壳MNCO@NMS可以成为超级电容器高性能电极的选择之一。     

MOF衍生的NiCoP/C@NiMn-LDH复合材料的制备与电化学性能研究

为提升超级电容器电极材料的电化学性能,在泡沫镍(NF)上以MOF为模板制备出NiCoP/C导电骨架,后将超薄NiMn-LDH纳米片沉积其上,制备得到核壳结构的NiCoP/C@NiMn-LDH复合材料。电化学测试结果表明,MOF模板的高比表面积、独特的核壳结构和NiCoP/C与NiMn-LDH之间的协同作用有利于电极材料性能的提升。制备得到的NiCoP/C@NiMn-LDH电极在1 A·g^-1下比电容可达2 278.0 F·g^-1;循环2 000圈后电容保留率为93.7%。     

用过期切片面包制备环保超级电容器活性炭电极材料

考虑到世界上每天产生大量的过期面包等过期食品,以过期切片面包为原材料,经碳化、1 mol·L^-1 KOH活化并用稀盐酸中和及去离子水和乙醇洗涤后,制备了过期切片面包活性炭(EBAC)。对过期切片面包活性炭的表面形貌、物相结构、表面官能团、比表面积和孔径分布分别通过扫描电子显微镜(SEM)、X射线衍射(XRD)、傅里叶变换红外光谱(FTIR)、氮气吸脱附(BET)进行了表征。在以3 mol·L^-1 KOH为电解液的三电极体系中,进行了活性炭电极材料的电化学性能测试。充放电曲线显示,在0.5 A·g^-1电流密度下,电极材料比电容达到352 F·g^-1;在5 A·g^-1的电流密度下循环1000次后,比电容保持在99.87%,展示出良好的循环稳定性。交流阻抗测试得到的Nyquist图和Bode图则近一步说明了过期切片面包活性炭具有良好的超级电容器性能。