基于碳纳米管－聚苯胺纳米复合物的超级电容器研究

为了提高碳纳米管的比容, 采用化学原位聚合的方法在碳纳米管的表面包覆聚苯胺, 制备碳纳米管-聚苯胺纳米复合物. 运用TEM和IR对样品进行了表征. 通过循环伏安研究样品的电化学特性. 利用恒流充放电考察基于碳纳米管-聚苯胺复合物超级电容器的性能. 在相同实验条件下, 对碳纳米管进行了比较分析. 实验结果表明, 在电流密度为10 mA/cm²时, 碳纳米管和碳纳米管-聚苯胺复合物的比容分别为52和201 F/g. 基于碳纳米管-聚苯胺纳米复合物的超级电容器的能量密度达到6.97 Wh/kg, 并且具有良好的功率特性.     

Nitrogen-doped holey graphene nanoscrolls for high-energy and high-power supercapacitors

Porous structure and heteroatom doping are two key parameters for significantly boosting the capacitive performance of graphene-based materials.Herein,we report a facile approach to prepare onedimensional(ID) nitrogen-doped holey graphene nanoscrolls(NHGNSs) through cold quenching treatment of two-dimensional graphene oxide sheets,followed by thermal annealing in the successive atmosphere of NH_3 and air.Benefiting from the synergy of the unique 1D tubular morphology,abundant nanoholes and nitrogen doping,the NHGNSs exhibit a high specific capacitance of 126 F/g at 1 A/g in ionic liquid electrolyte and excellent rate capability with 81% of the capacitance retained at 20 A/g.Furthermore,the fabricated symmetric supercapacitors based on NHGNSs achieve both high energy density of 53.5 Wh/kg at 875 W/kg and high power density of 17.5 kW/kg at 43.4 Wh/kg.The simple synthetic process and superior electrochemical performance suggest the great potential of NHGNSs for supercapacitor application.     

Supercapacitors based on self-assembled graphene organogel

Self-assembled graphene organogel (SGO) with 3-dimensional (3D) macrostructure was prepared by solvothermal reduction of a graphene oxide (GO) dispersion in propylene carbonate (PC). This SGO was used as an electrode material for fabricating supercapacitors with a PC electrolyte. The supercapacitor can be operated in a wide voltage range of 0-3 V and exhibits a high specific capacitance of 140 F g(-1) at a discharge current density of 1 A g(-1). Furthermore, it can still keep a specific capacitance of 90 F g(-1) at a high current density of 30 A g(-1). The maximum energy density of the SGO based supercapacitor was tested to be 43.5 Wh kg(-1), and this value is higher than those of the graphene based supercapacitors with aqueous or PC electrolytes reported previously. Furthermore, at a high discharge current density of 30 A g(-1), the energy and power densities of the supercapacitor were measured to be 15.4 Wh kg(-1) and 16,300 W kg(-1), respectively. These results indicate that the supercapacitor has a high specific capacitance and power density, and excellent rate capability.     

Redox-active electrolyte supercapacitors using electroactive ionic liquids

Here we present redox ionic liquid supercapacitors (RILSCs) which use electrolytes made from ionic liquids modified with an electroactive function to increase the energy density of activated carbon electrodes via faradaic reactions. More specifically, two different ionic liquids were made by modifying either the imidazolium cation or the bis(trifluoromethanesulfonyl)imide anion with ferrocene in order to determine the importance of the electroactive ion's polarity. The functionalization of an ionic liquid with ferrocene led to high concentrations of redox moieties in the electrolyte (2.4 M) and a large maximum operating voltage (2.5 V). An energy density of up to 13.2 Wh per kg (both electrodes) was obtained which represents an 83% increase vs. the unmodified ionic liquid. When the ionic liquid's anion is modified with ferrocene, the self-discharge at the positive electrode is fully suppressed due to the deposition of a film on the electrode. The results presented herein demonstrate that electroactive ionic liquids constitute a promising alternative to conventional solute in solvent electrolytes found in energy storage devices, and are particularly well-suited for redox-active electrolyte supercapacitors.     

Hierarchical Micro‐Mesoporous Carbon‐Framework‐Based Hybrid Nanofibres for High‐Density Capacitive Energy Storage

Advanced methods, allowing the controllable synthesis of ordered structural nanomaterials with favourable charges transfer and storage, are highly important to achieve ideal supercapacitors with high energy density. Herein, we report a microliter droplet‐based method to synthesize hierarchical‐structured metal–organic framework/graphene/carbon nanotubes hybrids. The confined ultra‐small‐volume reaction, give well‐defined hybrids with a large specific‐surface‐area (1206 m² g^?1), abundant ionic‐channels (narrow pore of 0.86 nm), and nitrogen active‐sites (10.63 %), resulting in high pore‐size utilization (97.9 %) and redox‐activity (32.3 %). We also propose a scalable microfluidic‐blow‐spinning method to consecutively generate nanofibre‐based flexible supercapacitor electrodes with striking flexibility and mechanical strength. The supercapacitors display large volumetric energy density (147.5 mWh cm^?3), high specific capacitance (472 F cm^?3) and stably deformable energy‐supply.     

Phenylenediamine-formaldehyde chemistry derived N-doped hollow carbon spheres for high-energy-density supercapacitors

Porous carbon spheres represent an ideal family of electrode materials forsupercapacitors because of the high surface area,ideal conductivity,negligible aggregation,and ability to achieve space efficient packing.However,the development of new synthetic methods towards porous carbon spheres still remains a great challenge.Herein,N-doped hollow carbon spheres with an ultrahigh surface area of2044 m²/g have been designed based on the phenylenediamine-formaldehyde chemistry.When applied in symmetric supercapacitors with ionic electrolyte(EMIBF_4),the obtained N-doped hollow carbon spheres demonstrate a high capacitance of 234 F/g,affording an ultrahigh energy density of 114.8 Wh/kg.Excellent cycling stability has also been achieved.The impressive capacitive performances make the phenylenediamine-formaldehyde resin derived N-doped carbon a promising candidate electrode material for supercapacitors.     

ZIF-67 derived hollow Ni-Co-Se nano-polyhedrons for flexible hybrid supercapacitors with remarkable electrochemical performances

Nano-polyhedral NiSe₂/CoSe₂ (Ni-Co-Se) with hollow architectures are synthesized by selenizing the precursors of Ni-Co bimetallic hydroxides that are directly derived from ZIF-67. The as-fabricated Ni-Co-Se electrodes exhibit high specific capacitance of 1668 F/g at 1 A/g accompanying with outstanding rate capability (about 82.8% retention of the initial capacity at 20 A/g). The corresponding Ni-Co-Se//AC all-solid-state hybrid supercapacitors are assembled by directly using the Ni-Co-Se on carbon fabric as the positive electrode, which deliver high energy density and power density (38.5 Wh/kg at 802.1 W/kg, 32.0 Wh/kg at 8008.8 W/kg), excellent cyclic stability (82.3% retention after 5000 cycle) and robust mechanical flexibility (no obvious attenuation at bending to different angles). This work will provide a new and smart route for constructing transition metal selenides for supercapacitor devices.     

One-pot synthesis of CoO–ZnO/rGO supported on Ni foam for high-performance hybrid supercapacitor with greatly enhanced cycling stability

The high specific capacitance along with good cycling stability are crucial for practical applications of supercapacitors,which always demands high-performance and stable electrode materials.In this work,we report a series of ternary composites of CoO-ZnO with different fractions of reduced graphene oxide(rGO) synthesized by in-situ growth on nickel foam,named as CZG-1,2 and 3,respectively.This sort of binder-free electrodes presents excellent electrochemical properties as well as large capacitance due to their low electrical resistance and high oxygen vacancies.Particularly,the sample of CZG-2(CoO-ZnO/rGO 20 mg) in a nanoreticular structure shows the best electrochemical performance with a maximum specific capacitance of 1951.8 F/g(216.9 mAh/g) at a current intensity of 1 A/g.The CZG-2-based hybrid supercapacitor delivers a high energy density up to 45.9 Wh/kg at a high power density of 800 W/kg,and kept the capacitance retention of 90.1% over 5000 charge-discharge cycles.     

镁热还原CO2气体制备介孔石墨烯及其电容特性研究

以CO_2为原料,采用金属镁热还原法,制备出富含介孔结构的石墨烯材料。分别利用X射线衍射、扫描电镜、透射电镜、拉曼光谱和N_2吸附-脱附等测试手段对材料的微观结构进行了表征。通过在镁粉中加入不同质量的MgO,可以实现对石墨烯形貌和孔结构的调控,当MgO/Mg质量比为8∶1时,产物(MRG-8)具有均一的介孔结构(4nm)。并对材料的电化学性能进行了测试,在1mol/L KOH的电解液中,MRG-8具有最高的比电容(171F/g),同时具有非常好的倍率特性,循环测试12000周,比电容保持率为94%。当采用[EMIM][BF4]离子液体作为电解液,以MRG-8为电极材料组装成的对称型超级电容器显示出超高功率密度(175k W/kg),对应的能量密度为28.1Wh/kg。因此,采用此方法制备的介孔石墨烯材料在高功率的超级电容器领域具有潜在的应用前景。     

High Performance Supercapacitors Based on Mesopore Structured Multiwalled Carbon Nanotubes

A 3D CNT/few layered graphene construct (CNT−FLG) with mesopore structure was fabricated and applied in supercapacitors. The structure was acquired through a two-step method. Firstly, commercial multiwalled carbon nanotubes (MCNTs) were oxidized in a mixed solution of concentrated acid and modified with a couple of long-chain organic ions. Second, the above resultant product was carbonized at a high temperature. The achieved structure offers a 3D interconnected electrically conductive network as well as mesopore structure. It also significantly improves the specific surface area of MCNTs. Result of BET tests showed that the specific surface area of CNT−FLG reached to 2235 m²/g. When acted as electrode materials in a supercapacitor structure, specific capacitance was approximately 531.2 F/g at a current density of 0.8 A/g. At current density of 50 A/g, specific capacitance remained 204.4 F/g. Besides, the capacitance retention was as high as 96.18 % after 10000 cycles at the current density of 5 A/g.     

Lignin derived porous carbon with favorable mesoporous contributions for highly efficient ionic liquid-based supercapacitors

Lignin and its derivatives hold great potential in developing high performance porous carbon materials for supercapacitors due to the versatile features of high carbon content, abundant multifunctional groups, low cost, and environmental benefits. Unfortunately, their derived porous carbon generally has the features of unfavorable microporous-dominated morphologies and low specific surface area (SSA) attributed from the highly-branched structure of lignin, which are hardly suitable for the supercapacitors with ionic liquid (IL) electrolyte, leading to poor energy density and rate capability. Herein, porous carbon materials with desirable mesoporous contributions from sodium lignosulphonate are designed via a facile template method. Such rich mesoporisity carbon materials not only possess with three-dimensional interconnected network, large SSA, as well as favorable pore size distribution for accelerated ion and electron mass transfer, but also feature low heteroatom content for high electrochemical stability. Consequently, the optimal electrode exhibits a high capacitance of 166 F/g at 0.5 A/g, superior rate performance (59 Wh/kg at 59 kW/kg), as well as impressive cycle life with good capacitance retention of 93.1% in EMIBF₄ electrolytes. The present work opens a new avenue to design porous carbon materials with high mesopore properties from lignin for effective compatibility with IL electrolyte in high-performance supercapacitors.     

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。     

Electrochemical supercapacitors based on novel hybrid materials made of carbon nanotubes and polyoxometalates

We have characterized symmetric solid-state supercapacitors in swagelok cells using film electrodes made of novel hybrid materials based on multiwalled carbon nanotubes (CNT) and phosphomolybdate polyanion (Cs-PMo12) with PVA as binder. These hybrid materials were carried out by Cs-PMo12 adhesion onto previously functionalized CNT, in order to disperse both components at a molecular level and use Cs-PMo12 as energy density enhancer in supercapacitor cells. Our results show high capacitance values (up to 285 F/g at I = 200 mA/g) due to the contribution of Cs-PMo12, which was revealed on the higher energy density values compared to pure CNT electrodes. Additionally, good stability was observed during 500 charge–discharge cycles for most hybrid electrodes. These preliminary results show a new approach to enhance energy density of double layer supercapacitor cells through the introduction of Cs-PMo12, whereas from a material science point of view these materials are innovative, and open the way to search for diverse applications aside from supercapacitors (sensors, catalysts, photovoltaic cells, etc.).     

碳纳米管-聚(3',4'-亚乙基二氧-2,2':5',2"-三噻吩)复合材料的制备及其电化学性能研究

通过Stille反应合成了3',4'-亚乙基二氧-2,2':5',2"-三噻吩(TET),并以其作为单体,采用化学氧化原位聚合方法在碳纳米管(CNT)的表面包覆新型聚(3',4'-亚乙基二氧.2,2':5',2"-三噻吩)(FTET),制备了PTET-CNT纳米复合材料.通过TEM、SEM和IR对其进行了表征,并利用循环伏安、交流阻抗、恒电流充放电等电化学测试方法,比较研究了复合材料以及碳纳米管在0.1 mol/L四乙基四氟硼酸铵(Et_4NPF_4)的乙腈溶液中的电化学行为.实验结果表明,在电流密度为3 mA/cm~2时,PTET-CNT复合材料的比电容为86 F/g,比原碳纳米管比电容20 F/g提高了3.3倍.基于这种复合材料的电容器的能量密度达到2.02 Wh/kg.     

A wide potential window aqueous supercapacitor based on LiMn<Subscript>2</Subscript>O<Subscript>4</Subscript>–rGO nanocomposite

Aqueous supercapacitors based on neutral solutions have the advantages of high-ionic conductivity, being environmentally friendly, safe, and low cost. However, the operating potential window for most aqueous electrolytes is far lower than that of organic electrolytes that are commonly used in commercial supercapacitors. In this work, we report on the fabrication of a wide potential window, high-energy aqueous asymmetric supercapacitor, without sacrificing power, by using a nanostructured LiMn₂O₄/reduced graphene oxide (LMO–rGO) nanocomposite. We synthesized the uniformly distributed LMO in the LMO–rGO nanocomposite using a co-precipitation route followed by a low-temperature hydrothermal treatment. In a three-electrode cell setup, the specific capacitance of the LMO–rGO nanocomposite electrode at 1 A/g (1.2 mA/cm²) is 268.75 F/g (258 mF/cm²), which shows a dramatic improvement over the sum of the specific capacitances of pristine LMO (162.5 F/g) and pure rGO (29.94 F/g) electrodes in their relative ratios, when used alone. This finding suggests a synergistic coupling of LMO and rGO in the nanocomposite. We also assembled the LMO–rGO nanocomposite, as the positive electrode, with activated carbon, as the negative electrode, into an asymmetric cell configuration. The device shows an ultra-wide potential window of 2.0 V in a neutral aqueous Li₂SO₄ electrolyte, with a maximum energy density of 29.6 Wh/kg (which approaches the commercial lead-acid batteries), power density of up to 7408 W/kg, and an excellent cycle life (5% loss after 6000 cycles). These findings confirm that an LMO–rGO nanocomposite is a promising material to meet the demands of real world energy storage.     

Supercapacitor electrodes with especially high rate capability and cyclability based on a novel Pt nanosphere and cysteine-generated graphene

In the present work, supercapacitors based on graphene/Pt films show especially high rate capability (120 F g(-1) even at 50 A g(-1)) and cyclability (no attenuation over 10,000 cycles) and peculiar nanosphere morphology after electrochemical cycling. Furthermore, supercapacitors based on the graphene powder with a binder exhibit high specific capacitance (249 F g(-1) at 0.1 A g(-1)), long cycle life (no attenuation over 40,000 cycles) and high rate capability (150 F g(-1) even at 50 A g(-1)), which are much better than those of most graphene electrode materials. These indicate the great potential of the cysteine reduced graphene electrodes in energy storage.     

Temperature stable supercapacitors based on ionic liquid and mixed functionalized carbon nanomaterials

The ionic liquid 1-butyl-2,3-dimethylimidazolium bis(trifluoromethylsulfonyl)imide (BDMIM-TFSI) showed a conductivity of 1.65?mS cm^?1 and an electrochemical stability window of 4.4?V at room temperature. Two types of electrodes based on carbon nanomaterials were prepared: (1) with alternating layers of two oppositely charged functionalized double-walled carbon nanotubes (DWCNTs) and (2) with the functionalized DWCNTs and graphene oxide nanoplatelets. The electrodes presented a porous morphology and a connected pathway between the carbon nanotubes and graphene oxide platelets. Electrochemical capacitors based on the carbon nanomaterials and BDMIM-TFSI were produced in a stacking configuration and were characterized at 25?°C, 60?°C, and 100?°C. The supercapacitors with electrodes based on the three alternating layers of two oppositely charged DWCNTs and graphene oxide presented higher values of capacitance, which were attributed to a morphology favorable to providing ionic access to the carbonaceous surface. Box-like voltammetric curves were used to calculate the capacitance in a 4-V potential window at 100?°C.     

Preparation of 3D MnO2/Polyaniline/Graphene Hybrid Material via Interfacial Polymerization as High‐Performance Supercapacitor Electrode

MnO₂/polyaniline/graphene composite as a supercapacitor electrode material was synthesized through an interfacial polymerization approach in the interface of oil/water phase. The as‐synthesized MPG is characterized by infrared spectroscopy, XRD, XPS, SEM and TEM, and its electrochemical performance is measured by cyclic voltammetry, galvanostatic charge/discharge, and electrochemical impedance spectroscopy. The 3D nanostructure of MPG and loose nanorod structure of polyaniline (PANI) coated with round MnO₂ pellets could be clearly observed. The maximum energy density of MPG is 45.4 Wh/kg (at a power density of 67.8 kW/kg) and the highest power density is 229.2 kW/kg (at an energy density of 25.7 Wh/kg). The capacitance retentions after 500 cycles at the scan rate of 5 mV/s for MGP composite and PANI/graphene are 70.4% and 59.1%, respectively, and the capacitance values after 500 cycles are 158.4 F/g and 114.8 F/g, respectively. The improved performance of MPG is due to the 3D nanostructure, loose nanorod structure of PANI and stable support of graphene, which prevent the mechanical deformation effectively during the fast charge/discharge process and facilitate the diffusion of the electrolyte ions into the inner region of active materials. The composite material is very promising for the next generation of high‐performance supercapacitors electrode.     

Highly active N,O-doped hierarchical porous carbons for high-energy supercapacitors

Highly active N, O-doped hierarchical porous carbons (NOCs) are fabricated through the in-situ polymerization and pyrolysis of o-tolidine and p-benzoquinone. As-prepared NOCs have a variety of faradaic-active species (N-6, N-5 and O-I), high ion-accessible platform (1799 m²/g) and hierarchically micro–meso–macro porous architecture. Consequently, the resultant NOC electrode delivers an advantageous specific capacitance (311 F/g), with a pseudocapacitive contribution of 37% in a three-electrode configuration, and an enhanced energy output of 18.0 Wh/kg @ 350 W/kg owing to the enlarged faradaic effect in an aqueous redox-active cell. Besides, a competitive energy density (74.9 Wh/kg) and high-potential durability (87.8%) are achieved in an ionic liquid (EMIMBF₄)-assembled device. This study sheds light on a straightforward avenue to optimize the faradaic activity and nanoarchitecture for advanced supercapacitors.     

Excellent Capacitive Performance of a Three‐Dimensional Hierarchical Porous Graphene/Carbon Composite with a Superhigh Surface Area

Three‐dimensional hierarchical porous graphene/carbon composite was successfully synthesized from a solution of graphene oxide and a phenolic resin by using a facile and efficient method. The morphology, structure, and surface property of the composite were investigated intensively by a variety of means such as scanning electron microscopy (SEM), transmission electron microscopy (TEM), N₂ adsorption, Raman spectroscopy, and Fourier transform infrared spectroscopy (FTIR). It is found that graphene serves as a scaffold to form a hierarchical pore texture in the composite, resulting in its superhigh surface area of 2034 m²g^?1, thin macropore wall, and high conductivity (152 S m^?1). As evidenced by electrochemical measurements in both EMImBF₄ ionic liquid and KOH electrolyte, the composite exhibits ideal capacitive behavior, high capacitance, and excellent rate performance due to its unique structure. In EMImBF₄, the composite has a high energy density of up to 50.1 Wh kg^?1 and also possesses quite stable cycling stability at 100 °C, suggesting its promising application in high‐temperature supercapacitors. In KOH electrolyte, the specific capacitance of this composite can reach up to an unprecedented value of 186.5 F g^?1, even at a very high current density of 50 A g^?1, suggesting its prosperous application in high‐power applications.