A New View of Supercapacitors: Integrated Supercapacitors

Charging times ranging from seconds to minutes with high power densities can be achieved by electrochemical capacitors in principle. Over the past few decades, the performance of supercapacitors has been greatly improved by the utilization of new materials, preparation of unique nanostructures, investigation of electrolytes, and so on. However, the discovery of the related basic theory is very limited. Herein, a new view of a supercapacitor called the “integrated supercapacitor” is proposed. The electrode of the integrated supercapacitor consists of certain positive and negative materials. With this design, a single integrated electrode can work in both the positive and negative potential windows simultaneously. Additionally, the integrated full supercapacitor device shows a much higher capacitance and wider potential window than traditional single symmetric and asymmetric supercapacitors, which results from its multiple mechanisms, including the traditional positive//positive symmetric, positive//negative asymmetric, and negative//negative symmetric full supercapacitor mechanisms.     

Supercapacitors Performance Evaluation

The performance of a supercapacitor can be characterized by a series of key parameters, including the cell capacitance, operating voltage, equivalent series resistance, power density, energy density, and time constant. To accurately measure these parameters, a variety of methods have been proposed and are used in academia and industry. As a result, some confusion has been caused due to the inconsistencies between different evaluation methods and practices. Such confusion hinders effective communication of new research findings, and creates a hurdle in transferring novel supercapacitor technologies from research labs to commercial applications. Based on public sources, this article is an attempt to inventory, critique and hopefully streamline the commonly used instruments, key performance metrics, calculation methods, and major affecting factors for supercapacitor performance evaluation. Thereafter the primary sources of inconsistencies are identified and possible solutions are suggested, with emphasis on device performance vs. material properties and the rate dependency of supercapacitors. We hope, by using reliable, intrinsic, and comparable parameters produced, the existing inconsistencies and confusion can be largely eliminated so as to facilitate further progress in the field.     

Miniaturized Supercapacitors: Focused Ion Beam Reduced Graphene Oxide Supercapacitors with Enhanced Performance Metrics

Miniaturization of energy storage devices with enhanced performance metrics can reduce the footprint of microdevices being used in our daily life. Micro‐­supercapacitor architectures with planar geometry provides several advantages, such as, the ability to control and reduce the distances ions travel between two electrodes, easy integration to microdevices, and offer the potential of being extended into 3D without compromising the interelectrode distances. Here, focused ion beam (FIB) technology is used to directly write miniaturized planar electrode systems of reduced graphene oxide (FIB‐rGO) on films of graphene oxide. Using optimized ion beam irradiation, interdigitated FIB‐rGO electrode designs with 40 μm long and 3.5 μm wide fingers with ultrasmall interelectrode spacing of 1 μm demonstrate a large capacitance (102 mF cm^?2), ultrasmall time response (0.03 ms), low equivalent series resistance (0.35 mΩ cm²), and retain 95% of the capacitance after 1000 cycles at an ultrahigh current density of 45 mA cm^?2. These performance metrics show remarkable improvements on several counts of supercapacitor performance over existing reports due to the miniaturized electrode dimensions and minimal damage to the graphene sheets. It is believed that these results can provide avenues for large‐scale fabrication of arrayed, planar, high‐performance micro‐supercapacitors with a small environmental footprint.     

Negative Capacitance for Electrostatic Supercapacitors

The increasing demand for efficient storage of electrical energy is one of the main challenges in the transformation toward a carbon neutral society. While electrostatic capacitors can achieve much higher power densities compared to other storage technologies like batteries, their energy densities are comparatively low. Here, it is proposed and demonstrated that negative capacitance, which is present in ferroelectric materials, can be used to improve the energy storage of capacitors beyond fundamental limits. While negative capacitance was previously mainly considered for low power electronics, it is shown that ferroelectric/dielectric capacitors using negative capacitance are promising for energy storage applications. Compared to earlier results using (anti)ferroelectric materials for electrostatic energy storage, much higher efficiencies of more than 95% even for ultrahigh energy densities beyond 100 J cm^?3 are demonstrated using nonepitaxial thin films suitable for integration on 3D substrates. Stable operation up to 150 °C and 10⁸ charging/discharging cycles is further demonstrated.     

Boron Element Nanowires Electrode for Supercapacitors

The pursuit of new categories of active materials as electrodes of supercapacitors remains a great challenge. Herein, for the first time, elemental boron as a superior electrode material of supercapacitors is reported, which exhibits significantly high capacitances and excellent rate performance in all alkaline, neutral, and acidic electrolytes. Notably, boron nanowire‐carbon fiber cloth (BNWs‐CFC) electrodes achieve a capacitance up to 42.8 mF cm^?2 at a scan rate of 5 mV s^?1 and 60.2 mF cm^?2 at a current density of 0.2 mA cm^?2 in the acidic electrolyte. Moreover, in all these three kinds of electrolytes, BNWs‐CFC electrodes demonstrate a decent cycling stability with >80% capacitance retention after 8000 charging/discharging cycles. The Dominating energy storage mechanism of BNWs in the different electrolytes is analyzed by looking into the kinetics of the electrochemical process. Subsequently, the BNWs‐CFC electrode is used to fabricate a flexible solid‐state supercapacitor, which reveals a specific capacitance up to 22.73 mF cm^?2 and good mechanical performance after 1000 bending cycles. This study opens a new avenue to explore elemental boron‐based new nanomaterials for the application of energy storage with superior electrochemical performance.     

A Versatile Capacity Balancer for Asymmetric Supercapacitors

Asymmetric supercapacitors (ASCs) with high theoretical energy density have attracted extensive attention during the past years. However, the huge capacity gap between the two electrodes greatly limits high energy density. Regulating electrode mass can make the capacity balanced, while sacrificing weight and volume. Herein, a soluble bipolar molecule, 4‐hydroxy‐2,2,6,6‐tetramethylpiperidinyloxyl (4‐OH‐TEMPO), is proposed as a versatile mediator in the electrolyte to balance the capacity gap in different types of ASCs. 4‐OH‐TEMPO is able to quickly obtain or lose electrons at different potentials regardless of the pH values, thus can contribute large redox capacity at the interface of capacitive electrode in ASCs in both positive or negative electrodes, acidic or alkaline systems. A case study of two typical ACSs is presented, Zn//activated carbon (AC) system with 4‐OH‐TEMPO for positive electrode enhancement in a mildly acidic electrolyte and AC//Ni(OH)₂ system with 4‐OH‐TEMPO for negative electrode enhancement in an alkaline electrolyte. Both demonstrate that the addition of 4‐OH‐TEMPO can effectively balance the capacity mismatching between two electrodes, and its capacity contribution can be adjusted by concentration. The energy density of the two ACSs with 4‐OH‐TEMPO can be greatly promoted without significant sacrifice of the device's volume or mass.     

Quantifying the Volumetric Performance Metrics of Supercapacitors

Nanostructured materials have greatly improved the performance of electrochemical energy storage devices because of the increased activity and surface area. However, nanomaterials (e.g., nanocarbons) normally possess low packing density, and thus occupy more space which restricts their suitability for making electrochemical devices as compact as possible. This has resulted in their low volumetric performance (capacitance, energy density, and power density), which is a practical obstacle for the application of nanomaterials in mobile and on‐board energy storage devices. While rating electrode materials for supercapacitors, their volumetric performance is equally important as the gravimetric metrics and more reliable in particular for systems with limited space. However, the adopted criteria for measuring the volumetric performance of supercapacitors vary in the literature. Identifying the appropriate performance criteria for the volumetric values will set a universal ground for valid comparison. Here, the authors discuss the rationale for quantifying the volumetric performance metrics of supercapacitors from the three progressive levels of materials, electrodes, and devices. It is hoped that these thoughts will be of value for the general community in energy storage research.     

Graphene–Cellulose Paper Flexible Supercapacitors

A simple and scalable method to fabricate graphene‐cellulose paper (GCP) membranes is reported; these membranes exhibit great advantages as freestanding and binder‐free electrodes for flexible supercapacitors. The GCP electrode consists of a unique three‐dimensional interwoven structure of graphene nanosheets and cellulose fibers and has excellent mechanical flexibility, good specific capacitance and power performance, and excellent cyclic stability. The electrical conductivity of the GCP membrane shows high stability with a decrease of only 6% after being bent 1000 times. This flexible GCP electrode has a high capacitance per geometric area of 81 mF cm^?2, which is equivalent to a gravimetric capacitance of 120 F g^?1 of graphene, and retains >99% capacitance over 5000 cycles. Several types of flexible GCP‐based polymer supercapacitors with various architectures are assembled to meet the power‐energy requirements of typical flexible or printable electronics. Under highly flexible conditions, the supercapacitors show a high capacitance per geometric area of 46 mF cm^?2 for the complete devices. All the results demonstrate that polymer supercapacitors made using GCP membranes are versatile and may be used for flexible and portable micropower devices.     

Pore and Heteroatom Engineered Carbon Foams for Supercapacitors

Carbonaceous materials are attractive supercapacitor electrode materials due to their high electronic conductivity, large specific surface area, and low cost. Here, a unique hierarchical porous N,O,S‐enriched carbon foam (KNOSC) with high level of structural complexity for supercapacitors is reported. It is fabricated via a combination of a soft‐template method, freeze‐drying, and chemical etching. The carbon foam is a macroporous structure containing a network of mesoporous channels filled with micropores. It has an extremely large specific surface area of 2685 m² g^?1. The pore engineered carbon structure is also uniformly doped with N, O, and S. The KNOSC electrode achieves an outstanding capacitance of 402.5 F g^?1 at 1 A g^?1 and superior rate capability of 308.5 F g^?1 at 100 A g^?1. The KNOSC exhibits a Bode frequency at the phase angle of ?45° of 18.5 Hz, which corresponds to a time constant of 0.054 s only. A symmetric supercapacitor device using KNOSC as electrodes can be charged/discharged within 1.52 s to deliver a specific energy density of 15.2 W h kg^?1 at a power density of 36 kW kg^?1. These results suggest that the pore and heteroatom engineered structures are promising electrode materials for ultrafast charging.