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。     

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。     

纳米木质素基多孔炭的制备及其电化学性能

基于绿色低共熔溶剂（DES）高效分离麦草生物质组分以制备纳米木质素（LNP）,本文采用化学活化法并进一步热解炭化制备纳米木质素基多孔炭（LNPC）。借助SEM、Raman、BET-物理吸附等分析手段研究了锌系活化剂及热解炭化温度（600℃、700℃、800℃）对LNPC的结构特征及电化学性能的影响。研究结果表明,相对于LNP直接热解炭化后纳米碳粒子的极易团聚,经锌化物活化后所制备的LNPC表现出更好的分散性和多级孔道形貌结构。尤其,以ZnCO₃活化后制备的LNPC-ZnCO₃-800具有更突出的性能,较高石墨化程度（I_D/I_G为0.68）、较高BET比表面积（679m²/g）、高介孔率（86.7%）、均匀纳米碳粒子构成的介孔结构。此外,以LNPC-ZnCO₃-800制备的工作电极,在0.5A/g时的比电容可达179F/g,与直接热解炭化的LNPC-800（64F/g）相比,其比电容的容量提高了180%。     

Electrical properties of MgO/p-diamond junction fabricated on homoepitaxial single-crystalline diamond

Sufficiently flat and hillock-free insulating homoepitaxial diamond films were successfully grown on high-pressure–high-temperature-synthesized diamond using a 5-kW microwave-plasma chemical-vapor-deposition system with a 20-ppm-nitrogen-included source gas of 4% CH₄ diluted with H₂. Then, layered MgO/boron-doped (p-type) diamond structures were fabricated on the homoepitaxial insulating diamond. Current (I)–voltage (V) characteristics of these device structures showed strong nonlinear behaviors for both current directions, or those for two electrically-parallel, reversed diodes, with conduction limited mainly by sheet resistance of the p-diamond layer in a temperature range from 300 to 600 K. This suggests that the carrier transport occurred through different current passes in the junction region at both biases. Low-frequency capacitances measured were mainly dominated by the depletion capacitance which was influenced by the bias voltage. At relatively high frequencies, however, the total capacitance measured (C) was determined not only by the depletion capacitance but also by the series resistance and the dispersion capacitance. Equivalent circuits of the MgO/p-diamond structure were deduced to explain the measured I–V and C–V results. A possible conduction mechanism is proposed in relation to the electronic structure of the MgO/p-diamond junction.     

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。     

NiCo2S4/N,S-rGO纳米复合材料的制备和电化学储钠性能

NiCo₂S₄是一种极具发展前景的钠离子电池(SIBs)负极材料。采用简单的一步法(混合和热处理)原位合成了锚定在N、S共掺杂还原氧化石墨烯上的纳米颗粒自组装的NiCo₂S₄亚微米球(NiCo₂S₄/N,S-rGO)。XPS表明了NiCo₂S₄与N,S-rGO之间存在电子转移,证实了NiCo₂S₄与N,S-rGO之间强的协同作用。纳米粒子自组装的NiCo₂S₄亚微米球有效地促进了离子的扩散,N,S-rGO优异的电学和力学性能不仅提高了电极的导电性,而且有效地缓冲了充/放电过程中NiCo₂S₄/N,S-rGO的体积变化。NiCo₂S₄/N,S-rGO作为SIBs的负极材料呈现出高可逆容量,优越的倍率性能和长期稳定性(在电流密度为0.5 A/g时循环130次后仍保持了396.7 mA·h/g的高比容量。即使在电流密度为2 A/g时,经过1000次循环后比容量仍保持在283.3 mA·h/g)。研究结果为高效负极材料的设计和合成提供了新的思路。     

Preparation and sodium storage performance of NiCo2S4/N,S-rGO nanocomposites

NiCo₂S₄ is a promising anode material for sodium ion batteries (SIBs). In this paper, a simple one-step method (mixing and heat treatment) was used to synthesize in-situ synthesized NiCo₂S₄ submicron spheres (NiCo₂S₄/N,S-rGO) anchored on N, S co-doped reduced graphene oxide. XPS characterization demonstrated electron transfer between NiCo₂S₄ and N,S-rGO, which confirmed the strong synergistic effect between NiCo₂S₄ and N,S-rGO. The nanoparticles self-assembled NiCo₂S₄ spheres effectively promoted ion diffusion, and the excellent electrical and mechanical properties of N,S-rGO not only improved the conductivity of the electrode, but also effectively buffeted the large volume changes of NiCo₂S₄/N,S-rGO during the charge/discharge process. Benefiting from the unique nano-architecture and strong synergistic effect, NiCo₂S₄/N,S-rGO applied as anode materials for SIBs presented a high reversible capacity, impressive rate capability and superior long-term stability (396.7 mA·h/g at 0.5 A/g after 130 cycles, 283.3 mA·h/g at 2 A/g after 1000 cycles). Those results open an interesting strategy for rational design and preparation of efficient anode materials for SIBs.     

Pyrolyzing soft template-containing poly(ionic liquid) into hierarchical N-doped porous carbon for electroreduction of carbon dioxide

Heteroatom-doped carbon materials have demonstrated great potential in the electrochemical reduction reaction of CO₂ (CO₂RR) due to their versatile structure and function. However, rational structure control remains one challenge. In this work, we reported a unique carbon precursor of soft template-containing porous poly(ionic liquid) (PIL) that was directly synthesized via free-radical self-polymerization of ionic liquid monomer in a soft template route. Variation of the carbonization temperature in a direct pyrolysis process without any additive yielded a series of carbon materials with facile adjustable textural properties and N species. Significantly, the integration of soft-template in the PIL precursor led to the formation of hierarchical porous carbon material with a higher surface area and larger pore size than that from the template-free precursor. In CO₂RR to CO, the champion catalyst gave a Faraday efficiency of 83.0% and a current density of 1.79 mA·cm^-2 at -0.9 V vs. reversible hydrogen electrode (vs. RHE). The abundant graphite N species and hierarchical pore structure, especially the unique hierarchical small-/ultra-micropores were revealed to enable better CO₂RR performance.     

Oxygen transport in zeolite Y measured by quenching of encapsulated tris(bipyridyl)ruthenium

This study deals with emission quenching of zeolite encapsulated trisbipyridyl ruthenium (II) (Ru(bpy)₃²⁺) by oxygen. Oxygen saturated solutions of Ru(bpy)₃²⁺ typically show about 70% quenching (I₀/I=3.3), where I₀ and I are the peak intensities of the emission in N₂ and O₂, respectively. However, an aqueous suspension of Ru(bpy)₃²⁺-zeolite Na–Y (Si/Al = 2.5) (abbreviated as Ru–Na–Y) showed no quenching at all. This observation motivated us to analyze how the transport of O₂ is occurring in the zeolite. Upon exposure of solid Ru–Na–Y (99% of intrazeolitic water) to N₂/O₂ dry gases, quenching in oxygen was found to be 5% (I₀/I=1.07). Partial dehydration at room temperature with loss of 33% of the water molecules from the zeolite led to 66% (I₀/I=2.96) quenching. Dehydration of Ru–Na–Y at 250 °C under vacuum overnight led to complete loss of intrazeolitic water and increased quenching to 90% (I₀/I=10.7). Nanocrystalline Ru(bpy)₃²⁺-zeolite Y upon vacuum dehydration lost 55% of the intrazeolitic water and showed 96% (I₀/I=25.3) quenching. The extent of quenching of Ru(bpy)₃²⁺ in zeolites by O₂ is by far the largest as compared to previously studied matrices, and is being attributed to confinement of O₂ in the supercages, which leads to increase in number of collisions with Ru(bpy)₃²⁺ and enhanced quenching. However, these samples showed complete lack of sensitivity (I₀/I=1) to oxygen upon exposure to water saturated gas or dissolved gas. Dealumination of zeolite framework by treatment with (NH₄)₂SiF₆ produced a framework of Si/Al = 9.5, and with SiCl₄ a framework of Si/Al > 100. With increasing dealumination, the extent of quenching by dissolved O₂ increased.     

S-enriched porous polymer derived N-doped porous carbons for electrochemical energy storage and conversion

Porous polymers have been recently recognized as one of the most important precursors for fabrication of heteroatom-doped porous carbons due to the intrinsic porous structure, easy available heteroatom-containing monomers and versatile polymerization methods. However, the heteroatom elements in as-produced porous carbons are quite relied on monomers. So far, the manipulating of heteroatom in porous polymer derived porous carbons are still very rare and challenge. In this work, a sulfur-enriched porous polymer, which was prepared from a diacetylene-linked porous polymer, was used as precursor to prepare S-doped and/or N-doped porous carbons under nitrogen and/or ammonia atmospheres. Remarkably, S content can sharply decrease from 36.3% to 0.05% after ammonia treatment. The N content and specific surface area of as-fabricated porous carbons can reach up to 1.32% and 1508 m²·g⁻¹, respectively. As the electrode materials for electrical double-layer capacitors, as-fabricated porous carbons exhibit high specific capacitance of up to 431.6 F·g⁻¹ at 5 mV·s⁻¹ and excellent cycling stability of 99.74% capacitance retention after 3000 cycles at 100 mV·s⁻¹. Furthermore, as the electrochemical catalysts for oxygen reduction reaction, as-fabricated porous carbons presented ultralow half-wave-potential of 0.78 V versus RHE. This work not only offers a new strategy for manipulating S and N doping features for the porous carbons derived from S-containing porous polymers, but also paves the way for the structure-performance interrelationship study of heteroatoms co-doped porous carbon for energy applications.     

Electrochemical intercalation into graphite seen as an electrocapillary process

The electrochemical intercalation of H₂SO₄ into graphite leads to the well known graphite salts C⁺_n HSO⁻₄. χH₂SO₄ (with n → 20), χ ≈ 2.5). The potential—charge relations observed during intercalation agree well with a model involving the extended graphene layer-intercalate interfacial capacitance. The components of this capacitance are studied, including the effect of Fermi level lowering. A computed electrocapillary curve is compared to the separation work of graphene layers.     

Environmentally friendly coloured materials: cellulose/titanium dioxide/inorganic pigment composite spherical microbeads prepared by viscose phase-separation method

In order to develop environmentally friendly coloured materials, cellulose composite spherical microbeads hybridised with titanium dioxide (TiO₂) particles and inorganic pigment were prepared by a phase-separation method using viscose and an aqueous solution containing sodium polyacrylate. Findings regarding the relationships between cellulose xanthate and the electronic characteristics of TiO₂ particles used in the cellulose/inorganic material composite sphering process are also reported. These findings suggest that the location of TiO₂ particles in cellulose microbeads is related to electrical repulsion between the xanthate (CSS⁻) group and TiO₂. The use of TiO₂ powder as colour pigment is limited, as its colour is white. The cellulose composite spherical microbeads covered with TiO₂ and Fe₂O₃ particles were developed by addition of iron oxide (Fe₂O₃). Their surfaces were viewed by laser microscope and using SEM images. These composite microbeads retained the photocatalytic property of TiO₂. Cellulose/TiO₂/Fe₂O₃ composite spherical microbeads with both colour function and photocatalytic properties were successfully prepared.     

介孔CoMn2O4/还原氧化石墨烯复合材料的制备及其超级电容性能

采用共沉淀法制备了CoMn₂O₄/还原氧化石墨烯(CoMn₂O₄/rGO)复合电极材料,并研究了石墨烯含量对CoMn₂O₄/rGO复合材料形貌、微观结构及电化学性能的影响。结果表明:CoMn₂O₄纳米颗粒沉积在石墨烯纳米片的表面,随着石墨烯含量的增加,CoMn₂O₄纳米颗粒在r GO表面的分布逐渐均匀,聚集现象消失。CoMn₂O₄/rGO具有高的比表面积及优良的电化学性能,其中CoMn₂O₄/rGO20 (rGO质量分数为20%)电容性能最好,在电流密度1 A/g时具有1 420 F/g的比电容。CoMn₂O₄/rGO30(rGO质量分数为30%)的倍率性能和循环稳定性能最好。2 000次充放电后,样品CoMn₂O₄/rGO30在5 A/g时的比电容保持率为94%,样品CoMn₂O₄的比电容保持率为78%。     

Synthesis and single crystal structure of an AFX-type magnesium aluminophosphate

SAPO-56 (framework type: AFX) has a framework topology slightly different from that of zeolite chabazite (framework type: CHA). While metal substituted aluminophosphate chabazite analogues can be prepared under a variety of experimental conditions with dozens of different amines, the synthesis of SAPO-56 type materials has been more difficult, particularly in non-SAPO compositions. Prior to this work, the growth of large crystals of the AFX-type materials suitable for single crystal diffraction has not been possible in any composition. Here we report the synthesis and single crystal structure of a magnesium aluminophosphate denoted as MAPO-AFX. This represents the first time that the AFX-type topology is made in a metal aluminophosphate composition. The synthesis was accomplished with a novel polyether diamine as the structure-directing agent. Crystal data for MAPO-AFX, (RH₂)_0.10(NH₄)_0.45[Mg_0.65Al_1.35(PO₄)₂](H₂O) where R=O[CH₂CH₂O(CH₂)₃NH₂]₂, space group P-31c (#163), Z=12, MoK radiation, 2θ_max=50°, a=13.8425(6) Å, c=20.204(1) Å, V=3352.7(3) ų, refinement on F², R(F)=7.94% for 131 parameters and 1218 unique reflections with I>2.0σ(I).     

氮掺杂石墨烯/碳纳米管/无定形炭复合材料制备及其电化学性能

碳基复合材料被认为是超级电容器广泛应用最有前景的电极材料之一。本文使用氧化石墨烯（GO）、硝酸钴［Co(NO₃)₂］、三聚氰胺为原料,利用钴对高温下热解碳源的催化作用,制备得到了氮掺杂石墨烯/碳纳米管/无定形炭（NC）复合材料,并测试了其电化学性能。探究了金属和三聚氰胺添加量对碳基复合材料结构和性能的影响,研究发现,在添加量分别为0.02mmol和0.3g时,制得的样品具有大比表面积（380.5m²/g）和高掺氮质量分数（6.29%）,并在三电极系统中体现出优异的电化学性能,电流密度为0.5A/g时样品的比电容为137.1F/g,5A/g时比电容为113.5F/g,保持率为88.5%,具有优异的倍率性能,在循环5000圈后样品的容量保持率为104%,具有良好的循环稳定性,这归因于三维结构可以加快充放电过程中的离子转移和氮掺杂可提高材料润湿性和贡献部分赝电容,为超级电容器电极材料的制备提供了理论借鉴。     

NiMn2O4/还原氧化石墨烯复合材料的制备及其超级电容性能

采用水热法制备了NiMn₂O₄/还原氧化石墨烯（NiMn₂O₄/rGO）复合电极材料,研究了石墨烯对NiMn₂O₄/rGO材料形貌、微观结构及电化学性能的影响。结果表明：NiMn₂O₄纳米片沉积在石墨烯片的表面,聚集现象消失。与纯NiMn₂O₄相比,NiMn₂O₄/rGO具有高的比表面积和优良的电化学性能。在1A/g时具有1375F/g的比电容,而纯NiMn₂O₄的比电容为924F/g。5000次充放电后,NiMn₂O₄/rGO在5A/g时的比电容保留率为90%,而NiMn₂O₄的比电容保留率为78%。NiMn₂O₄/rGO表现出良好的电容性能,作为超级电容器电极材料具有广泛的应用前景。     

PEBA/氮硫共掺杂多孔碳球混合基质膜的制备及CO2分离性能研究

为了获得高性能的混合基质膜,有效捕集烟道气中的CO₂,设计了对CO₂有优异的扩散选择性和吸附选择性的氮硫共掺杂多孔碳球添加剂,实现了烟道气中CO₂/N₂的高效分离。选用表面含氧基团丰富的葡萄糖作为碳源,硫脲作为氮源和硫源,通过水热法制备了氮硫共掺杂碳球（NSC）,并用KOH活化,获得了具有多孔结构的氮硫共掺杂碳球（NSPC）,再加入聚醚嵌段酰胺（PEBA）中制备出PEBA/NSPC混合基质膜。采用FTIR、XRD和BET表征了材料的化学结构和孔结构,借助力学性能表征了膜的两相界面相容性。系统研究了PEBA/NSPC混合基质膜中葡萄糖与硫脲的质量比、NSC和KOH的质量比、NSPC的添加量、操作压力、操作温度,以及模拟烟道气条件对膜CO₂渗透性、CO₂/N₂选择性的影响。结果表明：NSPC材料成功实现了氮、硫元素的共掺杂,而且具有较好的孔结构。在操作温度25℃、操作压力0.2 MPa的条件下,混合基质膜中NSPC添加量为3%（质量）时气体分离性能最优,CO₂渗透系数和CO₂/N₂选择性分别为589 Barrer和64,相比纯PEBA膜分别提高了244%和139%。这是因为多孔碳球的微孔结构显著提高了CO₂的扩散选择性,同时氮、硫元素的掺杂因为酸碱相互作用和良好亲和性有效提高了CO₂的吸附选择性。稳定性实验表明,PEBA/NSPC混合基质膜在360 h连续运行过程中气体分离性能稳定,具有较好的工业应用前景。     

多孔竹炭负载SnO2的制备及其电化学性能研究

多孔竹炭为无定形碳,具有丰富的孔结构,孔径分布在1~6 nm之间,且具有较大的孔体积(1.21 cm³/g)。本文以多孔竹炭为载体,采用溶胶-凝胶法制得B₂O₃-SnO₂/C复合材料。SEM和TEM结果显示SnO₂和B₂O₃均匀分布在多孔竹炭表面。多孔竹炭和B₂O₃有效缓冲SnO₂可逆反应的体积变化,提高SnO₂的循环稳定性。将B₂O₃-SnO₂/C复合材料作为负极组装成锂离子半电池,进行电化学性能测试,在1 C(1 C=372 mA/g)倍率下充放电循环200次结束后仍然保留649.9 mAh/g的放电比容量,放电比容量保留率为58.6%。B₂O₃-SnO₂/C复合材料充放电过程受扩散和电容两种行为控制,电容控制的贡献率随着扫描速率的增大而增大。     

碳材料吸附脱除二氧化硫性能的影响因素

选用了7种不同物理化学特性的碳材料,分别为活性炭-1 (比表面积1779m²/g)、活性炭-2 (比表面积970m²/g)、多孔纳米炭-1 (平均孔径14nm)、多孔纳米炭-2 (平均孔径85nm)、多孔纳米炭-3 (平均孔径4.7nm,掺氮)、多孔纳米炭-4 (平均孔径4.1nm,不掺氮)和纳米碳纤维。在对比这7种不同的碳材料的物理化学特性与其脱硫性能的基础上,研究材料的物理化学特性、脱硫温度、反应空速等因素对碳材料吸附脱除SO₂性能的影响。结果表明,碳材料吸附脱除SO₂的性能受材料的比表面积、孔隙结构、表面官能团、脱硫温度和反应空速的综合影响。不同的碳材料中,材料的孔隙结构和表面官能团对材料的脱硫性能影响很大,以微孔结构为主的碳材料SO₂去除率较高,以介孔结构为主的碳材料脱硫容量较高;随着脱硫温度升高,碳材料的吸附脱硫性能降低;随着反应空速降低,碳材料的吸附脱硫性能升高。本研究中,多孔纳米炭NCP-10的吸附脱除SO₂性能最好,能在室温下保持100%的...