In this critical review, metal oxides-based materials for electrochemical supercapacitor (ES) electrodes are reviewed in detail together with a brief review of carbon materials and conducting polymers. Their advantages, disadvantages, and performance in ES electrodes are discussed through extensive analysis of the literature, and new trends in material development are also reviewed. Two important future research directions are indicated and summarized, based on results published in the literature: the development of composite and nanostructured ES materials to overcome the major challenge posed by the low energy density of ES (476 references).

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A review of electrode materials for electrochemical supercapacitors

Supercapacitors, also called ultracapacitors or electrochemical capacitors, store electrical charge on high-surface-area conducting materials. Their widespread use is limited by their low energy storage density and relatively high effective series resistance. Using chemical activation of exfoliated graphite oxide, we synthesized a porous carbon with a Brunauer-Emmett-Teller surface area of up to 3100 square meters per gram, a high electrical conductivity, and a low oxygen and hydrogen content. This sp 2 -bonded carbon has a continuous three-dimensional network of highly curved, atom-thick walls that form primarily 0.6- to 5-nanometer-width pores. Two-electrode supercapacitor cells constructed with this carbon yielded high values of gravimetric capacitance and energy density with organic and ionic liquid electrolytes. The processes used to make this carbon are readily scalable to industrial levels.

/pdf/carbon-based-supercapacitors-produced-by-activation-of-1wqrpq3luo.pdf

Carbon-based Supercapacitors Produced by Activation of Graphene

Electrochemical energy storage technology is based on devices capable of exhibiting high energy density (batteries) or high power density (electrochemical capacitors). There is a growing need, for current and near-future applications, where both high energy and high power densities are required in the same material. Pseudocapacitance, a faradaic process involving surface or near surface redox reactions, offers a means of achieving high energy density at high charge–discharge rates. Here, we focus on the pseudocapacitive properties of transition metal oxides. First, we introduce pseudocapacitance and describe its electrochemical features. Then, we review the most relevant pseudocapacitive materials in aqueous and non-aqueous electrolytes. The major challenges for pseudocapacitive materials along with a future outlook are detailed at the end.

https://hal.archives-ouvertes.fr/hal-01171774/document

Pseudocapacitive oxide materials for high-rate electrochemical energy storage

Safe and powerful energy storage devices are becoming increasingly important. Charging times of seconds to minutes, with power densities exceeding those of batteries, can in principle be provided by electrochemical capacitors--in particular, pseudocapacitors. Recent research has focused mainly on improving the gravimetric performance of the electrodes of such systems, but for portable electronics and vehicles volume is at a premium. The best volumetric capacitances of carbon-based electrodes are around 300 farads per cubic centimetre; hydrated ruthenium oxide can reach capacitances of 1,000 to 1,500 farads per cubic centimetre with great cyclability, but only in thin films. Recently, electrodes made of two-dimensional titanium carbide (Ti3C2, a member of the 'MXene' family), produced by etching aluminium from titanium aluminium carbide (Ti3AlC2, a 'MAX' phase) in concentrated hydrofluoric acid, have been shown to have volumetric capacitances of over 300 farads per cubic centimetre. Here we report a method of producing this material using a solution of lithium fluoride and hydrochloric acid. The resulting hydrophilic material swells in volume when hydrated, and can be shaped like clay and dried into a highly conductive solid or rolled into films tens of micrometres thick. Additive-free films of this titanium carbide 'clay' have volumetric capacitances of up to 900 farads per cubic centimetre, with excellent cyclability and rate performances. This capacitance is almost twice that of our previous report, and our synthetic method also offers a much faster route to film production as well as the avoidance of handling hazardous concentrated hydrofluoric acid.

Conductive two-dimensional titanium carbide ‘clay’ with high volumetric capacitance

Since the discovery of mechanically exfoliated graphene in 2004, research on ultrathin two-dimensional (2D) nanomaterials has grown exponentially in the fields of condensed matter physics, material science, chemistry, and nanotechnology. Highlighting their compelling physical, chemical, electronic, and optical properties, as well as their various potential applications, in this Review, we summarize the state-of-art progress on the ultrathin 2D nanomaterials with a particular emphasis on their recent advances. First, we introduce the unique advances on ultrathin 2D nanomaterials, followed by the description of their composition and crystal structures. The assortments of their synthetic methods are then summarized, including insights on their advantages and limitations, alongside some recommendations on suitable characterization techniques. We also discuss in detail the utilization of these ultrathin 2D nanomaterials for wide ranges of potential applications among the electronics/optoelectronics, electrocat...

Recent Advances in Ultrathin Two-Dimensional Nanomaterials

This tutorial review provides a brief summary of recent research progress on carbon-based electrode materials for supercapacitors, as well as the importance of electrolytes in the development of supercapacitor technology. The basic principles of supercapacitors, the characteristics and performances of various nanostructured carbon-based electrode materials are discussed. Aqueous and non-aqueous electrolyte solutions used in supercapacitors are compared. The trend on future development of high-power and high-energy supercapacitors is analyzed.

Carbon-based materials as supercapacitor electrodes

Chemically modified graphene and polyaniline (PANI) nanofiber composites were prepared by in situ polymerization of aniline monomer in the presence of graphene oxide under acid conditions. The obtained graphene oxide/PANI composites with different mass ratios were reduced to graphene using hydrazine followed by reoxidation and reprotonation of the reduced PANI to give the graphene/PANI nanocomposites. The morphology, composition, and electronic structure of the composites together with pure polyaniline fibers (PANI-F), graphene oxide (GO), and graphene (GR) were characterized using X-ray diffraction (XRD), solid-state 13C NMR, FT-IR, scanning electron microscope (SEM), transmission electron microscope (TEM), thermogravimetric analysis (TGA), and X-ray photoelectron spectroscopy (XPS). It was found that the chemically modified graphene and the PANI nanofibers formed a uniform nanocomposite with the PANI fibers absorbed on the graphene surface and/or filled between the graphene sheets. Such uniform structur...

Graphene/Polyaniline Nanofiber Composites as Supercapacitor Electrodes

Graphene is an emerging carbon material that may soon find practical applications. With its unusual properties, graphene is a potential electrode material for electrochemical energy storage. This article highlights recent research progress in graphene-based materials as supercapacitor electrodes. With a brief description of the working principle of supercapacitors, research progress towards the synthesis and modification of graphene-based materials, including graphene oxide, fullerenes, and carbon nanotubes, is presented. Applications of such materials with desirable properties to meet the specific requirements for the design and configuration of advanced supercapacitor devices are summarized and discussed. Future research trends towards new approaches to the design and synthesis of graphene-based nanostructures and architectures for electrochemical energy storage are proposed.

Graphene-based materials as supercapacitor electrodes

Nanoporous nickel hydroxide (Ni(OH)2) thin film was grown on the surface of ultrathin-graphite foam (UGF) via a hydrothermal reaction. The resulting free-standing Ni(OH)2/UGF composite was used as the electrode in a supercapacitor without the need for addition of either binder or metal-based current collector. The highly conductive 3D UGF network facilitates electron transport and the porous Ni(OH)2 thin film structure shortens ion diffusion paths and facilitates the rapid migration of electrolyte ions. An asymmetric supercapacitor was also made and studied with Ni(OH)2/UGF as the positive electrode and activated microwave exfoliated graphite oxide (‘a-MEGO’) as the negative electrode. The highest power density of the fully packaged asymmetric cell (44.0 kW/kg) was much higher (2–27 times higher), while the energy density was comparable to or higher, than high-end commercially available supercapacitors. This asymmetric supercapacitor had a capacitance retention of 63.2% after 10 000 cycles.

Nanoporous Ni(OH)2 thin film on 3D Ultrathin-graphite foam for asymmetric supercapacitor.

Tremendous efforts have been dedicated into the development of high-performance energy storage devices with nanoscale design and hybrid approaches. The boundary between the electrochemical capacitors and batteries becomes less distinctive. The same material may display capacitive or battery-like behavior depending on the electrode design and the charge storage guest ions. Therefore, the underlying mechanisms and the electrochemical processes occurring upon charge storage may be confusing for researchers who are new to the field as well as some of the chemists and material scientists already in the field. This review provides fundamentals of the similarities and differences between electrochemical capacitors and batteries from kinetic and material point of view. Basic techniques and analysis methods to distinguish the capacitive and battery-like behavior are discussed. Furthermore, guidelines for material selection, the state-of-the-art materials, and the electrode design rules to advanced electrode are proposed.

https://onlinelibrary.wiley.com/doi/pdf/10.1002/advs.201700322

Lili Zhang

Papers

Carbon-based materials as supercapacitor electrodes

Graphene/Polyaniline Nanofiber Composites as Supercapacitor Electrodes

Graphene-based materials as supercapacitor electrodes

Nanoporous Ni(OH)2 thin film on 3D Ultrathin-graphite foam for asymmetric supercapacitor.

Advanced Energy Storage Devices: Basic Principles, Analytical Methods, and Rational Materials Design.