Inherent Impurities in Graphene/Polylactic Acid Filament Strongly Influence on the Capacitive Performance of 3D-Printed Electrode

Additive manufacturing or 3D-printing have become promising fabrication techniques in the field of electrochemical energy storage applications such as supercapacitors, and batteries. Of late, a commercially available graphene/polylactic acid (PLA) filament has been commonly used for Fused Deposition Modeling (FDM) 3D-printing in the fabrication of electrodes for supercapacitors and Li-ion batteries. This graphene/PLA filament contains metal-based impurities such as titanium oxide and iron oxide. In this study, we show a strong influence of inherent impurities in the graphene/PLA filament for supercapacitor applications. A 3D-printed electrode is prepared and subsequently thermally activated for electrochemical measurement. A deep insight has been taken to look into the pseudocapacitive contribution from the metal-based impurities which significantly enhanced the overall capacitance of the 3D-printed graphene/PLA electrode. A systematic approach has been shown to remove the impurities from the printed electrodes. This has a broad implication on the interpretation of the capacitance of 3D-printed composites.     

Understanding Self-assembly,Colloidal Behavior and Rheological Properties of Graphene Derivatives for High-performance Supercapacitor Fabrication

Graphene derivatives, such as graphene oxide(GO) and reduced graphene oxide(RGO), have been widely used as promising twodimensional nanoscale building blocks due to their fascinating properties, cost-effective production, and good processability. Understanding the intrinsic self-assembling, colloidal, and rheological features of graphene derivatives is of critical importance to establish the formation-structureproperty relationship of graphene-based materials. This article reviews recent progresses in our studies of these interesting properties of graphene derivatives for developing high performance supercapacitors. The content is organized to include characteristics of the dispersions of graphene derivatives, self-assembly of nanosheets from liquid medium, colloidal behavior, rheological properties of the dispersions, processing methods based on the properties, and performance of the fabricated supercapacitors. GO and RGO nanosheets are proved to form different types of assembled structures with unique morphologies, such as ultrathin layer-by-layer films, porous aggregates, and nanoscrolls. The unique rheological properties of GO dispersions and hydrogels, feasible for both the traditional wet-processing and newly-developed technology like three-dimensional printing, are highlighted for their potential in structural manipulation and scalable fabrication of graphene-based devices. The research devoted to up-grading the performance of supercapacitors is presented in some details, which could be applicable for fabricating other graphene-based energy storage devices. Some challenges and perspectives in our point of view are given in the last part of this feature article.     

Nanoarchitectured Graphene‐Based Supercapacitors for Next‐Generation Energy‐Storage Applications

Tremendous development in the field of portable electronics and hybrid electric vehicles has led to urgent and increasing demand in the field of high‐energy storage devices. In recent years, many research efforts have been made for the development of more efficient energy‐storage devices such as supercapacitors, batteries, and fuel cells. In particular, supercapacitors have great potential to meet the demands of both high energy density and power density in many advanced technologies. For the last half decade, graphene has attracted intense research interest for electrical double‐layer capacitor (EDLC) applications. The unique electronic, thermal, mechanical, and chemical characteristics of graphene, along with the intrinsic benefits of a carbon material, make it a promising candidate for supercapacitor applications. This Review focuses on recent research developments in graphene‐based supercapacitors, including doped graphene, activated graphene, graphene/metal oxide composites, graphene/polymer composites, and graphene‐based asymmetric supercapacitors. The challenges and prospects of graphene‐based supercapacitors are also discussed.     

Graphene/activated carbon supercapacitors with sulfonated-polyetheretherketone as solid-state electrolyte and multifunctional binder

Sulfonated polyetheretherketone (SPEEK) has been synthesised by sulphonation process and used as the solid-state electrolyte, binder and surfactant for supercapacitors. Reduced graphene dispersed by SPEEK is used as a high-efficiency conducting additive in solid-state supercapacitors. It is found that SPEEK can improve the stability of the reduced graphene dispersion significantly, and therefore, the solid-state supercapacitors show a large decrease in IR drop and charge-transfer resistance (R_ct), resulting in a higher rate capability. The solid-state supercapacitors with the activated carbon/reduced graphene/SPEEK/electrode can be operated from 1 to 8 A/g and exhibit capacity retention of 93%. The noteworthy is more than twice higher value for capacity retention by comparison with the solid-state supercapacitors using activated carbon/reduced graphene/PVDF electrode (capacity retention is 36%). The cell of reduced graphene with SPEEK can be cycled over 5000 times at 5 A/g with no capacitance fading.     

Graphene electrochemical supercapacitors: the influence of oxygen functional groups

We have critically compared graphene and graphene oxide as materials for utilisation as supercapacitors indicating that the former exhibits a larger capacitance over the latter which has implications for those fabricating supercapacitors.     

石墨烯基纤维电容器的可控制备及应用

超级电容器又名电化学电容器,是一种绿色储能器件。 超级电容器的研究,从根本上讲是寻找比表面积大且可以被充分利用的电极材料。 石墨烯作为sp²杂化碳质材料的基元单位,具有独特的二维结构和优异的物化特性,使得其在超级电容器领域具有巨大的应用潜力,其中石墨烯纤维超级电容器受到了研究工作者越来越广泛的关注。 本文通过对一维石墨烯纤维的自组装以及与制备材料的共组装来作为超级电容器的电极材料,对其可控制备进行了系统的归纳和总结,可控构建独特的电极材料,使其性能得以优化,组装出高性能的超级电容器,并对相关领域的发展趋势做了展望。     

Hierarchical Mn3O4 Anchored on 3D Graphene Aerogels via C−O−Mn Linkage with Superior Electrochemical Performance for Flexible Asymmetric Supercapacitor

Flexible asymmetric supercapacitors are more appealing in flexible electronics because of high power density, wide cell voltage, and higher energy density than symmetric supercapacitors in aqueous electrolyte. In virtues of excellent conductivity, rich porous structure and interconnected honeycomb structure, three dimensional graphene aerogels show great potential as electrode in asymmetric supercapacitors. However, graphene aerogels are rarely used in flexible asymmetric supercapacitors because of easily re-stacking of graphene sheets, resulting in low electrochemical activity. Herein, flower-like hierarchical Mn₃O₄ and carbon nanohorns are incorporated into three dimensional graphene aerogels to restrain the stack of graphene sheets, and are applied as the positive and negative electrode for asymmetric supercapacitors devices, respectively. Besides, a strong chemical coupling between Mn₃O₄ and graphene via the C-O-Mn linkage is constructed and can provide a good electron-transport pathway during cycles. Consequently, the asymmetric supercapacitor device shows high rate cycle stability (87.8 % after 5000 cycles) and achieves a high energy density of 17.4 μWh cm⁻² with power density of 14.1 mW cm⁻² (156.7 mW cm⁻³) at 1.4 V.     

Aqueous Dispersions of Graphene from Electrochemically Exfoliated Graphite

A facile and environmentally friendly synthetic strategy for the production of stable and easily processable dispersions of graphene in water is presented. This strategy represents an alternative to classical chemical exfoliation methods (for example the Hummers method) that are more complex, harmful, and dangerous. The process is based on the electrochemical exfoliation of graphite and includes three simple steps: 1) the anodic exfoliation of graphite in (NH₄)₂SO₄, 2) sonication to separate the oxidized graphene sheets, and 3) reduction of oxidized graphene to graphene. The procedure makes it possible to convert around 30 wt % of the initial graphite into graphene with short processing times and high yields. The graphene sheets are well dispersed in water, have a carbon/oxygen atomic ratio of 11.7, a lateral size of about 0.5–1 μm, and contain only a few graphene layers, most of which are bilayer sheets. The processability of this type of aqueous dispersion has been demonstrated in the fabrication of macroscopic graphene structures, such as graphene aerogels and graphene films, which have been successfully employed as absorbents or as electrodes in supercapacitors, respectively.     

Preparation of stable dispersion of graphene using copolymers: dispersity and aromaticity analysis

In this study, effectiveness of non-ionic block copolymers such as Lugalvan BNO12 and Triton X series (Triton X100 & Triton X405) has been reported for graphene dispersion in aqueous solutions. Stability of the aqueous graphene dispersions is investigated using UV–visible spectroscopy, Rheological, and Conductivity studies. Adsorption isotherms are constructed to determine the amount of polymers adsorbed on the surface of graphene by the spectroscopic analysis. Lugalvan BNO12 has been found to be adsorbed in higher amounts on the graphene surface compared to the Triton X series polymers. Thermogravimetric analysis (TGA) and Fourier Transform Infrared (FTIR) Spectroscopy investigations indicated grafting of polymers chains to the graphene surfaces. The dispersions prepared with optimum concentrations (as determined from adsorption isotherms) of polymers have shown lower viscosity and conductivity values. Lugalvan BNO12 has been found to be a better stabilizer for graphene than the Triton X series dispersants because the former contains two aromatic rings in its structure that acts as an anchoring group and helps in the stabilization of graphene dispersion in comparison to the single aromatic group in the Triton X series. The experimental results reported have shown that the aromaticity of polymeric dispersants plays significant role in the aqueous graphene dispersions. The non-ionic block copolymers that assisted dispersed graphene are potential candidates for the fabrication of various devices such as sensors, batteries, and supercapacitors applications.     

Investigation of microstructures of ZnCo_2O_4 on bare Ni foam and Ni foam coated with graphene and their supercapacitors performance

The graphene coating was deposited on the surface of Ni foam using the chemical vapor deposition process. A large amount of flower-like ZnCo_2O_4 microspheres with short nanowires were formed on bare Ni foam by hydrothermal method, while large-scale ZnCo_2O_4 nanowires arrays homogeneously aligned and separated adequately on Ni foam coated with graphene. This ZnCo_2O_4 nanowire structure exhibited superior supercapacitors properties. The excellent supercapacitors were mainly attributed to the large specific surface and the porosity on the nanowires which promoted the electrons and ions transportation. In addition, graphene improved conductivity of substrate for current collecting.     

Simultaneous Photoreduction and Nitrogen Doping of Graphene Oxide for Supercapacitors by Direct Laser Writing

Graphene-based supercapacitors have attracted tremendous attention owing to their outstanding electrochemical performance. In terms of material, nitrogen(N)-doped graphene(NDG) displays enhanced specific capaci-tance and rate performance compared with bare graphene used as a supercapacitor electrode. However, it still remains a challenge to develop a facile and simple method of NDG in cost-effective manner. Here, we used a simple direct laser writing technique to accomplish the simultaneous photoreduction and N-doping of graphene oxide(GO) using urea as a N source. The N content of the resultant reduced N-doped graphene oxide(NGO) reached a maximum value of 6.37%. All reduced NGO(NRGO)-based supercapacitors exhibited a higher specific capacitance than those based on pure reduced GO(RGO). Interestingly, the electrochemical performance of NRGO-based supercapacitors varied with different contents ofN species. Therefore, we can control the properties of the obtained NRGOs by adjusting the doping ratios, an important step in developing effective graphene-based energy storage devices.     

石墨烯纤维：制备、性能与应用

石墨烯纤维是一种由石墨烯片层紧密有序排列而成的一维宏观组装材料。通过合理的结构设计和可控制备,石墨烯纤维能够将石墨烯在微观尺度的优异性能有效传递至宏观尺度,展现出优异的力学、电学、热学等性能,从而应用于功能织物、传感、能源等领域。目前,石墨烯纤维主要通过湿法纺丝、限域水热组装等方法制备得到,其性能可以通过对材料体系和制备工艺的优化而进一步提升。本文首先介绍了石墨烯纤维的制备方法,然后详细阐述了石墨烯纤维的性能,讨论了其性能提升策略,并总结了石墨烯纤维的应用,最后对石墨烯纤维的未来发展、挑战和前景进行了展望。     

超级电容器用石墨烯薄膜：制备、基元结构及表面调控

石墨烯薄膜是一种以石墨烯纳米片为基元结构的宏观体,通过合理的结构设计和表面修饰使其具有优异的电学、力学和热学性能,将在电化学储能、电子器件、健康和环保等领域具有潜在的应用。本文主要综述了从石墨烯基元调控到二维宏观膜组装以及石墨烯薄膜在超级电容器应用中的研究进展。主要介绍了石墨烯薄膜的简易制备方法,并详细介绍了通过对石墨烯基元的结构调控和表面修饰来优化石墨烯薄膜电化学性能的两大策略,最后对石墨烯薄膜应用所面临的挑战和未来的发展进行了总结与展望。     

新碳源制备活性炭和石墨烯及其非等电极电容水系超级电容器

Carbon materials can offer various micro- and nanostructures as well as bulk and surface functionalities; hence, they remain the most popular for manufacturing supercapacitors. This article critically reviews recent developments in the preparation of carbon materials from new precursors for supercapacitors. Typical examples are activated carbon (AC) and graphene, which can be prepared from various conventional and new precursors such as biomass, polymers, graphite oxide, CH₄, and even CO₂ via innovative processes to achieve low-cost and/or high specific capacitance. Specifically, when producing AC from natural biomasses or synthetic polymers, either new, spent, or waste, popular activation agents, such as KOH and ZnCl₂, are often used to process the ACs derived from these new precursors while the respective activation mechanisms always attract interest. The traditional two-step calcination process at high temperatures is widely employed to achieve high performance, with or without retaining the morphology of the precursors. The three-step calcination, including a post-vacuum treatment, is also the preferred choice in many cases, but it can increase the cost per capacity (kWh∙g⁻¹). More recently, one-step molecular activation promises a better and more economical approach to the commercial application of AC, although further increase of the yield is necessary. In addition to activation, graphitization, N doping, and template control can further improve ACs in terms of the charging and discharging rates, or pseudocapacitance, or both. Considerations are also given to material structure design, and carbon regeneration during activation. Metal-organic frameworks, which were initially used as templates, have been found to be good direct carbon precursors. Various graphene structures, including powders, films, aerogels, foams, and fibers, can be produced from graphite oxide, CO₂, and CH₄. Similar to AC, graphene can possess micropores by activation. Self-propagating high-temperature synthesis and molten salt processing are newly-reported methods for fabrication of mesoporous graphene. Macroporous graphene hydrogels can be produced by hydrothermal treatment of graphite oxide suspension, which can also be transferred into films. Hierarchically porous structures can be achieved by H₂O₂ etching or ZnCl₂ activation of the macroporous graphene precursor. Sponges as templates combined with KOH activation are applied to create both micro- and macropores in graphene foams. Graphene can grow on fibers and textiles by electrodeposition, dip-coating, or filtration, which can be woven into clothes with a large area or thick loading, illuminating the potential application in flexible and wearable supercapacitors. The key obstacles in AC and graphene production are high cost, low yield, low packing density, and low working potential range. Most Carbon materials derived from new precursors work very well with aqueous electrolytes. Charge storage occurs not only in the electric double layer (i.e., the "carbon | electrolyte" interface), but also via redox activity in association with the bulk and surface functionalities, and the resulting partial delocalization of valence electrons. The analysis of the capacitive electrode has shown a design defect that prevents the working voltage of a symmetrical supercapacitor from reaching the full potential window of the carbon material. This defect can be avoided in AC-based supercapacitors with unequal electrode capacitances, leading to higher cell voltages and hence higher specific energy than their symmetrical counterparts. There are also emerging ways to raise the energy capacity of AC supercapacitors, such as the use of redox electrolytes to enable the Nernstian charge storage mechanism, and of the three dimensional printing method for a desirable electrode structure. All these developments are promising carbon materials from various precursors of new and waste sources for a more affordable and sustainable supercapacitor technology.     

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.     

Electrochemical Preparation of Polypyrrole/Graphene Films on Titanium Mesh as Active Materials for Supercapacitors

Films of polypyrrole/graphene on titanium mesh were prepared by electrochemical reduction of the fresh dried foam films of graphene oxide followed by an electrochemical polymerization of pyrrole. The as-obtained composite had highly surface area, conductivity, and could be used as the electrode for supercapacitors, especially directly used as the active materials in free of binders while the Ti mesh worked as the collector. Plenty of polypyrrole nanoparticles formed on the surface of reduced graphene film, and some fiber-like aggregates could be formed during the polymerization, which worked as the material for pseudo-capacitance. The specific capacitance of the supercapacitor reached 400 F/g and showed high stability with retaining capacitance of 82% after 5000 cycles, indicating that the nanocomposite is a suitable active material for supercapacitors.     

High performance supercapacitors based on highly conductive nitrogen-doped graphene sheets

Thermal nitridation of reduced graphene oxide sheets yields highly conductive (～1000-3000 S m(-1)) N-doped graphene sheets, as a result of the restoration of the graphene network by the formation of C-N bonded groups and N-doping. Even without carbon additives, supercapacitors made of the N-doped graphene electrodes can deliver remarkable energy and power when operated at higher voltages, in the range of 0-4 V.     

Graphene and carbon nanotube composite electrodes for supercapacitors with ultra-high energy density

We describe a graphene and single-walled carbon nanotube (SWCNT) composite film prepared by a blending process for use as electrodes in high energy density supercapacitors. Specific capacitances of 290.6 F g(-1) and 201.0 F g(-1) have been obtained for a single electrode in aqueous and organic electrolytes, respectively, using a more practical two-electrode testing system. In the organic electrolyte the energy density reached 62.8 Wh kg(-1) and the power density reached 58.5 kW kg(-1). The addition of single-walled carbon nanotubes raised the energy density by 23% and power density by 31% more than the graphene electrodes. The graphene/CNT electrodes exhibited an ultra-high energy density of 155.6 Wh kg(-1) in ionic liquid at room temperature. In addition, the specific capacitance increased by 29% after 1000 cycles in ionic liquid, indicating their excellent cyclicity. The SWCNTs acted as a conductive additive, spacer, and binder in the graphene/CNT supercapacitors. This work suggests that our graphene/CNT supercapacitors can be comparable to NiMH batteries in performance and are promising for applications in hybrid vehicles and electric vehicles.     

Activated carbon felts with exfoliated graphene nanosheets for flexible all-solid-state supercapacitors

Porous activated carbon felts (ACFs) with exfoliated graphene nanosheets were prepared by a simple thermal treatment strategy. They exhibit high gravimetric and areal specific capacitances as well as long-term cycling stability. Impressively, the all-solid-state supercapacitors based on ACFs electrodes deliver stable electrochemical performance even under different bending states.     

3D braided yarns to create electrochemical cells

The demands for new configurations of electrochemical cells continue to grow and novel approaches are being enabled by the advent of new electromaterials and novel fabrication strategies. Wearable energy storage devices that can be seamlessly integrated into garments are a critical component of the wearable electronics genre. Recently, flexible yarn supercapacitors have attracted significant attention due to their ability to be integrated into fabrics, or stitched into existing textiles. Large-scale production of yarn supercapacitors using conventional manufacturing processes, however, is still a challenge. Here, we introduce the use of braiding technology to achieve a predetermined arrangement of fibre electrodes, the basis of a mass fabrication protocol to produce specific electrochemical cells: wearable supercapacitors. The resultant supercapacitors show a high capacitance of 1.71 mF cm^− 1. The structure is highly flexible with a 25% capacitance loss recorded after 1000 bending cycles.