Co3O4电极材料的制备及其电容性能研究

采用水热法,通过控制反应时间制备出不同形貌和尺寸的Co_3O_4材料。利用XRD和SEM对其结构和形貌进行表征,采用循环伏安、恒电流充放电和交流阻抗等方法测试了其电化学性能。结果表明,随着反应时间的延长, Co_3O_4材料的晶粒尺寸增大,形貌由不规则颗粒状变为正立方体,其比电容不断降低。在电流密度为0.2 A·g~(-1)时,反应5 h、 10 h和15 h所制备的Co_3O_4材料的比电容值分别为153.3 F·g~(-1)、 99.3F·g~(-1)和51.1 F·g~(-1)。当电流密度从0.2 A·g~(-1)增大到1.8 A·g~(-1)时,反应5 h、 10 h和15 h所制备的Co_3O_4材料的比电容值分别为96.3 F·g~(-1)、 91.3 F·g~(-1)和27.1 F·g~(-1),其比电容保持率分别为62.8%、 91.9%和53.0%。水热反应5 h所制备的Co_3O_4材料具有最好的比电容。     

Co3O4/碳纳米管复合膜的超级电容器性能

采用电泳沉积法在镍片上沉积Co3O4/碳纳米管(CNT)复合膜。利用XRD、SEM和TEM对Co3O4/CNT复合膜进行物性分析,利用循环伏安和恒流充放电测试表征电容性能。研究表明在CNT表面成功包覆了一层Co3O4壳层,形成独特的核/鞘纳米电缆结构。电化学测试表明,Co3O4/CNT复合膜电极具有较好的电容性能,在充放电电流密度为0.5 mA/cm^2时,比电容高达282 F/g;增加电流密度到15 mA/cm2时,比电容为209 F/g,并具有优异的循环稳定性。     

纳米Co3O4催化降解1,2,4-三氯苯

选取1,2,4-三氯苯作为氯代有机物的模型化合物,利用气相色谱、气相色谱-质谱联用仪等实验手段,研究了纳米Co3O4催化降解1,2,4-三氯苯的影响因素及效果。获得的主要研究结果有：纳米Co3O4对1,2,4-三氯苯具有较高的催化降解活性,200 mg纳米Co3O4与1.5μL 1,2,4-三氯苯在300℃下反应60 min,对1,2,4-三氯苯的降解效率可接近100%。1,2,4-三氯苯在纳米Co3O4表面上的降解主要是逐级加氢脱氯,其中,1,2,4-三氯苯经过一级脱氯得到对二氯苯,然后对二氯苯再经过二级脱氯得到一氯苯是加氢脱氯的主要途径。     

溶胶-凝胶自蔓延法制备纳米Co3O4的研究

采用溶胶-凝胶自蔓延燃烧法制备锂离子电池纳米Co3O4负极材料,利用XRD、SEM和充放电测试等手段表征了不同的原料比和热处理温度对材料的结构、颗粒形貌和电化学性能的影响。实验表明:硝酸钴和柠檬酸摩尔比为1∶2,400℃空气气氛下热处理制备的Co3O4材料表现出良好的电化学性能。首次可逆容量为1121.4 m Ahg-1,循环30次后可逆容量仍能高达865.3 m Ahg-1,容量保持率约为77.2%。     

富氧空位Co3O4纳米线的制备及其电解水性能研究

在室温下利用NaBH₄溶液还原Co₃O₄纳米线获得富含氧空位（V_O）的三维自支撑纳米线阵列用作全水解电催化剂,其中NaBH₄处理10 min的Co₃O₄/NF在碱性介质中对析氧反应（OER）和析氢反应（HER）表现出很高的活性,在10 mA·cm^-2电流密度下分别仅需240和132 mV的过电位。V_O-Co₃O₄/NF同时作为阴极和阳极电催化剂时,在10 mA·cm^-2下电解水槽电压仅为1.63 V,其耐久性可达60 h以上。该工作为富含氧空位结构的过渡金属氧化物双功能电催化剂的制备提供了新的方法和思路。     

Co3O4纳米阵列的制备及应用

Co_3O_4纳米阵列因其特有的性质、丰富的3D结构、多样的形貌、独特的表面界面效应和良好的稳定性等在能量转换与存储、光电催化、气体传感等诸多领域中具有广泛的应用前景而得到广泛研究。对近年来有关Co_3O_4纳米阵列的制备方法、及其阵列材料在电催化分解水、能量存储与转换、电催化氧还原、光电催化二氧化碳还原、气体传感、一氧化碳氧化、非酶电催化葡萄糖、电磁吸收、疏水分离及有机物降解等研究领域的应用进行了综述。最后,对Co_3O_4纳米阵列发展过程中尚待解决的问题进行了总结,并对其未来的发展方向进行了展望。     

ZnCo2O4纳米线的制备及其电容性能研究

ZnCo_2O_4(ZCO)由于其良好的电化学活性而被备受关注。采用水热法和热退火两步法成功地在镍泡沫上制备了ZnCo_2O_4纳米线。利用扫描电镜(SEM)和X射线衍射谱(XRD)对ZnCo2O4的形貌和结构进行了表征。这种独特的一维结构可以为电子和离子提供有效的传输途径。在三电极系统下,通过循环伏安测试和恒电流充放电测试表明,在120℃水热条件下所制得的ZCO-120的电容性能最佳,在0.5 A/g的电流密度下,其比电容达到511.3 F/g。在10.0 A/g的电流密度下经1 000次循环充放电后,其比电容仍然保持95.8%,表明其具有较好的循环稳定性。同时,将ZCO-120作为正极,活性炭作为负极组装成不对称超级电容器,其电势窗可达到1.6 V,在功率密度为400 W/kg时,能量密度可达14.4 Wh/kg。证明了ZnCo_2O_4可以作为先进的超级电容器材料。     

Co3O4-Bi2O2CO3催化剂的制备及其光催化性能

以Bi(NO₃)₃·5H₂O、Co(CH₃COO)₂·4H₂O为原料,采用化学沉淀-水热法制备了Co₃O₄-Bi₂O₂CO₃异质结构复合半导体光催化剂,并通过X射线衍射仪（XRD）、扫描电镜（SEM）、X射线光电子能谱（XPS）、紫外可见漫反射光谱（DRS）、荧光光谱（PL）等手段对所合成的复合型催化剂进行了理化性能表征。研究结果表明：引入Co₃O₄没有改变Bi₂O₂CO₃物相结构,但促进了Bi₂O₂CO₃ 对可见光的吸收能力,提高了Bi₂O₂CO₃表面吸附氧物种的数量,抑制了光生载流子复合。复合光催化剂对罗丹明B（RhB）的光催化脱色实验显示引入Co₃O₄能够明显提高Bi₂O₂CO₃催化剂的光催化脱色能力。尤其是Co₃O₄引入量为0.6%的Co₃O₄-Bi₂O₂CO₃样品对罗丹明B染料的光催化脱色率可达到97%（模拟日光照射30min）。本文为复合型光催化剂制备提供了简单易行的技术路线,制备的新型半导体复合光催化剂Co₃O₄-Bi₂O₂CO₃在环境净化方面表现出了较好的应用前景。     

Co_3O_4纳米颗粒的制备及其超级电容性能研究

采用简单化学沉淀法,以十六烷基三甲基溴化铵（CTAB）为模板,Co（NO3）2.6H2O和NaOH为原料,空气作为温和氧化剂,室温下合成了具有花状分级多孔结构的Co3O4纳米颗粒电极材料。X-射线衍射（XRD）表明,产物中主要成分为Co3O4;扫面电镜的结果显示,制备的材料具有菜花状分级多孔结构;电化学测试结果表明,最高比容量达250 F/g,且经过1 000次循环后,容量保持了84%,显示出良好的超级电容性能。     

碳纳米管/纳米TiO2-聚苯胺复合膜电极的制备及电容性能研究

用循环伏安法,在含有0．2mol／L苯胺的0．5mol／L硫酸溶液中,以50mv／s的扫描速度,在-0．1-0．9V的范围内实现了苯胺在Ti基碳纳米管／纳米TiO2电极上的电化学聚合,并用循环伏安（CV）法和电化学交流阻抗谱（EIS）对制备的碳纳米管／纳米TiO2-聚苯胺（CNT／nanoTiO2-PAn）复合膜电极的电化学性质进行了表征,同时进一步对该电极的充放电性能进行了研究。实验结果表明,此条件下得到的PAn膜电极具有良好的导电性,同时具有疏松、多孔的网络结构;充放电测试研究表明,基于CNT／TiO2基体上的PAn膜的面积比电容在放电电流密度为2．5mA／cm^2时达到了833mF／cm^2,说明有很好的电容性能,可以作为超级电容器的电极材料。     

Anchoring mesoporous Fe3O4 nanospheres onto N-doped carbon nanotubes toward high-performance composite electrodes for supercapacitors

Fe-based oxide electrodes for practical applications in supercapacitors (SCs) suffer from low conductivity and poor structural stability. To settle these issues, we report on the design and synthesis of Fe₃O₄/carbon nanocomposites via firmly anchoring mesoporous Fe₃O₄ nanospheres onto N-doped carbon nanotubes (N-CNTs) via C–O–Fe bonds. Mesoporous Fe₃O₄ nanospheres are featured by rich electroactive sites and short ion diffusion pathways. The N-CNTs, on the other hand, serve as the scaffolds, which not only provide conductive networks but also suppress the accumulation between mesoporous Fe₃O₄ nanospheres as well as alleviate volume changes during charge/discharge cycles. Accordingly, the constructed Fe₃O₄/N-CNTs nanocomposite electrode demonstrates improved specific capacity values of up to 314 C g⁻¹ at 1 A g⁻¹, with 92% retention of the initial capacity after 5000 cycles at 10 A g⁻¹. In addition, the assembled Fe₃O₄/N-CNTs//active carbon (AC) asymmetric supercapacitor (ASC) device possesses an energy density of 25.3 Wh kg⁻¹, suggesting that the prepared Fe₃O₄/N-CNTs nanocomposites are promising electrode materials for use in SCs.     

超级电容器碳基材料研究的进展

超级电容器是一种介于传统电容器和蓄电池之间的储能装置,其以功率密度大,充电速度快,工作温度范围宽,循环使用寿命长和绿色环保等优点,被世界各国广泛关注。通过对超级电容器新型碳电极材料的最新研究进展进行介绍,展望了超级电容器的发展前景,认为超级电容器将不仅对全球性能源问题有着重大突破,还将会带来巨大的经济效益。     

Fabrication of graphene/single wall carbon nanotubes/polyaniline composite gels as binder-free electrode materials

A three-dimensional (3D) graphene-based hydrogels system containing one-dimensional (1D) carbon material-single wall carbon nanotubes (SWCNTs) and pseudocapacitor material-polyaniline (PANI) was prepared by combination of cross-linking, reduced and in situ polymerization. The polyaniline nanoparticles were combined with the reduced graphene sheet by π-π conjugation. The as-perpared composite gels could be directly used as electrode materials without binders. Due to the synergistic effect between SWCNTs, graphene sheet and PANI, the graphene/single wall carbon nanotubes/polyaniline (GH/SWCNTs/PANI) composite gel shows the enhanced electrochemical performances. The resultant GH/SWCNTs/PANI gel electroactive material shows a gravimetric specific capacitance of 145.4 F/g at 0.5 A/g and has improved 45% compared with initial graphene hydrogel (GH) at the same current density. And it keeps high retention of 98.8% of the initial capacity after 10,00 charge/discharge cycles at high current density of 10 A/g. The great cycle stability achieved is fundamentally attributed to the support of graphene sheet and single wall carbon nanotubes, which favors stress distribution and charge transfer during the longtime charge/discharge process. The graphene-based hydrogels could be a potential applicant for high rate charge/discharge applications. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 46948.     

Cup-stacked carbon nanotubes hybridized Si3N4/Si3N4 composite ceramics for high-effciency microwave absorption with excellent thermal stability

Hybridization between carbon nanotubes (CNTs) and Si₃N₄ is a promising strategy for developing high-temperature microwave absorption (MA) materials for military application. Toward long-life services, it's important to achieve strong MA at a filler loading as low as possible on account of antioxidant protection against CNTs wastage. Herein, cup-stacked CNTs (CSCNTs) have been prepared in porous Si₃N₄ ceramics by chemical vapor deposition (CVD) and then CVD Si₃N₄ has been coated on them, forming CSCNT-Si₃N₄/Si₃N₄ composite ceramics. Results show that CSCNTs possess abundant exposed atomic edges on the outer surface and in the inner channel. Such unique defects not only benefit the impedance match but also cause considerable conductive loss, which helps CSCNT-Si₃N₄/Si₃N₄ with a filler content of only 0.79 wt% to achieve an effective absorption bandwidth (EAB) of 3.74 GHz in the X band at a thickness of 3.5 mm coupled with a minimum reflection loss of ?43.3 dB and an EAB covering the entire Ku band at a thickness of 2.25 mm. The ultralow filler loading generates a high efficiency of CVD Si₃N₄ in protecting CSCNTs against high-temperature oxidation, leading to a steady MA performance for CSCNT-Si₃N₄/Si₃N₄ during 23–1200 °C thermal shock tests in air.     

Construction of NiCo2O4 nanoflake arrays on cellulose-derived carbon nanofibers as a freestanding electrode for high-performance supercapacitors

Cellulose has a wide range of applications in many fields due to their naturally degradable and low-cost characteristics, but few studies can achieve cellulose-nanofibers by conventional electrospinning. Herein, we demonstrate that the freestanding cellulose-based carbon nanofibers are successfully obtained by a special design of electrospinning firstly, pre-oxidation and high-temperature carbonization (1600 °C), which display a superior electrical conductivity of 31.2 S·cm^–1 and larger specific surface area of 35.61 m²·g^–1 than that of the polyacrylonitrile-based carbon nanofibers (electrical conductivity of 18.5 S·cm^–1, specific surface area of 12 m²·g^–1). The NiCo₂O₄ nanoflake arrays are grown uniformly on the cellulose-based carbon nanofibers successfully by a facile one-step solvothermal and calcination method. The as-prepared cellulose-based carbon nanofibers/NiCo₂O₄ nanoflake arrays are directly used as electrodes to achieve a high specific capacitance of 1010 F·g^–1 at 1 A·g^–1 and a good cycling stability with 90.84% capacitance retention after 3000 times at 10 A·g^–1. Furthermore, the all-solid-state symmetric supercapacitors assembled from the cellulose-based carbon nanofibers/NiCo₂O₄ deliver a high energy density of 62 W·h·kg^–1 at a power density of 1200 W·kg^–1. Six all-solid-state symmetric supercapacitors in series can also power a ‘DHU’ logo consisted of 36 light emitting diodes, confirming that the cellulose-based carbon nanofiber is a promising carbon matrix material for energy storage devices.     

导电聚合物复合材料作为超级电容器电极材料

本文综述了基于导电聚合物的复合材料(导电聚合物/碳材料、导电聚合物/金属氧化物材料、导电聚合物/碳材料l金属氧化物材料)作为电极材料在超级电容器中的应用进展,指出将导电聚合物与碳材料或金属氧化物复合,双电层电容与法拉第准电容结合,有机材料与无机材料结合,是超级电容器电极材料研究的重要发展方向.     

Enhancing the performance of polypyrrole composites as electrode materials for supercapacitors by carbon nanotubes additives

In the framework of this study, a facile method to obtain polypyrrole (PPy)/carbon nanotubes composites is presented. Chemical polymerization of PPy directly on the carbon nanotubes allows to obtain a homogenous distribution of the polymer. A low amount of carbon additive, varying from 1.5 to 5.5 wt %, is applied in order to prevent the decrease of capacitance value due to the presence of a low-capacitance component and, at the same time, to protect the electrode material from mechanical changes during cycling electrical measurements. The electrochemical properties, such as capacitance, its retention at different current loads, cycling stability, or self-discharge, are discussed. Improvement of electrochemical performances of the synthesized materials is observed mostly during cyclic stability measurements and at high current regimes. The obtained results confirm that the addition of only 3% of carbon nanotubes provides the best electrochemical performances as electrode materials for supercapacitor application. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48867.     

木质素基材料在混合型超级电容器电极材料中的研究进展

木质素是一种多酚聚合物,具有丰富的芳香类官能团和含氧官能团,且在碳化后形成的多孔碳材料易于转化为石墨化碳层,从而形成局部高导电区域,是制备超级电容器的优质前体,故将木质素用于混合型超级电容器逐渐成为研究热点之一。本文综述了近年来木质素碳材料在混合型超级电容器电极材料中的应用,重点分析了木质素在其中的作用,将其总结为3类进行介绍,包括木质素/多孔炭（石墨烯、碳纳米管）型、木质素/金属化合物（金属氧化物、硫化物、氢氧化物）型和木质素/导电聚合物（聚苯胺、聚吡咯、聚噻吩）型。此外,还介绍了木质素基混合型超级电容器在柔性超级电容器中的应用。最后,总结了木质素基材料应用在混合超级电容器中的优势和挑战。     

Co3O4/g-C3N4复合光催化剂降解罗丹明B的研究

为提高石墨相氮化碳(g-C3N4)的光催化性能,采用3D花状ZIF-Co与g-C3N4混合热处理的方法制备了3D花状Co3O4/g-C3N4复合光催化剂,并将其用于光催化降解罗丹明B模拟染料废水。结果表明:当ZIF-Co与g-C3N4的质量比为5%时,制备的Co3O4/g-C3N4的光催化性能最佳,在可见光下照射30 min,其对罗丹明B的降解率可达90%以上,且该催化剂的重复稳定性好。在降解罗丹明B的过程中活性基团的作用顺序为·O2->h+>·OH。     

MWCNTs-GONRs/Co3O4 electrode with needle-like arrays for outstanding supercapacitors

Multiwalled carbon nanotubes-graphene oxide nanoribbons (MWCNTs-GONRs) exhibit high specific surface area and good electroconductivity because of their unique three-dimensional cross-linking structure with the properties of both CNTs and GONRs. In this study, a hydrothermal method was employed to anchor MWCNTs–GONRs onto a Ni foam (NF) to obtain a precursor substrate. Subsequently, Co₃O₄ arrays were grown on the NF substrate to synthesize a MWCNTs–GONR/Co₃O₄ electrode. The electrode showed a capacitance of 846.2 F g⁻¹ at 1 A g⁻¹ and a capacitance retention of 90.1% after 3000 cycles. Furthermore, MWCNTs–GONRs/Co₃O₄ and active carbon (AC) were used as the positive and negative electrodes, respectively, to assemble a supercapacitor, which delivered a maximum energy density of 38.23 W h kg⁻¹ and a high power density of 6.80 kW kg⁻¹. In addition, the specific capacitance of the device reached a maximum of 91.5% after 9000 cycles. Thus, the MWCNTs–GONRs/Co₃O₄ electrode showed huge potential for supercapacitor applications.