Bio‐Nanotechnology in High‐Performance Supercapacitors

The use of bio‐nanotechnology for the fabrication of diverse functional nanomaterials with precisely controlled morphologies and microstructures is attracting considerable attention due to its sustainability and renewability. As one of the key energy storage devices, supercapacitor (SC) requires the active electrode material to have high specific surface area, interconnected porous structure, excellent electronic conductivity, and appropriate heteroatom doping for promoting the transfer of electrons and electrolyte ions. The combination of bio‐technology and SC will open up a new avenue for the large‐scale fabrication of high performance functional energy storage devices. In this review, the most state‐of‐the‐art research progress in bio‐nanotechnological fabrication of different nanomaterials, including carbon materials, metal oxides, conducting polymers, and their corresponding composites are reviewed with the following three bio‐nanotechnical approaches covered: (1) biomass carbonization technologies; (2) bio‐template methods; and (3) bio‐complex technologies, while also highlighting their applications as functional SC electrodes.     

All‐Printed MnHCF‐MnOx‐Based High‐Performance Flexible Supercapacitors

Here, a simple active materials synthesis method is presented that boosts electrode performance and utilizes a facile screen‐printing technique to prepare scalable patterned flexible supercapacitors based on manganese hexacyanoferrate‐manganese oxide and electrochemically reduced graphene oxide electrode materials (MnHCF‐MnO_x/ErGO). A very simple in situ self‐reaction method is developed to introduce MnO_x pseudocapacitor material into the MnHCF system by using NH₄F. This MnHCF‐MnO_x electrode materials can deliver excellent capacitance of 467 F g^?1 at a current density of 1 A g^?1, which is a 2.4 times capacitance increase compared to MnHCF. In addition a printed, patterned, flexible MnHCF‐MnO_x/ErGO supercapacitor is fabricated, showing a remarkable areal capacitance of 16.8 mF cm^?2 and considerable energy and power density of 0.5 mWh cm^?2 and 0.0023 mW cm^?2, respectively. Furthermore, the printed patterned flexible supercapacitors also exhibit exceptional flexibility, and the capacitance remains stable, even while bending to various angles (60°, 90°, and 180°) and for 100 cycles. The flexible supercapacitor arrays integrated by multiple prepared single supercapacitors can power various LEDs even in the bent states. This approach offers promising opportunities for the development of printable energy storage materials and devices with high energy density, large scalability, and excellent flexibility.     

Graphitic Petal Electrodes for All‐Solid‐State Flexible Supercapacitors

The charge storage characteristics of a composite nanoarchitecture with a highly functional 3D morphology are reported. The electrodes are formed by the electropolymerization of aniline monomers into a nanometer‐thick polyaniline (PANI) film that conformally coats graphitic petals (GPs) grown by microwave plasma chemical vapor deposition (MPCVD) on conductive carbon cloth (CC). The hybrid CC/GPs/PANI electrodes yield results near the theoretical maximum capacitance for PANI of 2000 F g^?1 (based on PANI mass) and a large area‐normalized specific capacitance of ≈2.6 F cm^?2 (equivalent to a volumetric capacitance of ≈230 F cm^?3) at a low current density of 1 A g^?1 (based on PANI mass). The specific capacitances remain above 1200 F g^?1 (based on PANI mass) for currents up to 100 A g^?1 with correspondingly high area‐normalized values. The hybrid electrodes also exhibit a high rate capability with an energy density of 110 Wh kg^?1 and a maximum power density of 265 kW kg^?1 at a current density of 100 A g^?1. Long‐term cyclic stability is good (≈7% loss of initial capacitance after 2000 cycles), with coulombic efficiencies >99%. Moreover, prototype all‐solid‐state flexible supercapacitors fabricated from these hybrid electrodes exhibit excellent energy storage performance.     

Heteroatom‐Doped and Oxygen‐Functionalized Nanocarbons for High‐Performance Supercapacitors

Electrochemical capacitors (best known as supercapacitors) are high‐performance energy storage devices featuring higher capacity than conventional capacitors and higher power densities than batteries, and are among the key enabling technologies of the clean energy future. This review focuses on performance enhancement of carbon‐based supercapacitors by doping other elements (heteroatoms) into the nanostructured carbon electrodes. The nanocarbon materials currently exist in all dimensionalities (from 0D quantum dots to 3D bulk materials) and show good stability and other properties in diverse electrode architectures. However, relatively low energy density and high manufacturing cost impede widespread commercial applications of nanocarbon‐based supercapacitors. Heteroatom doping into the carbon matrix is one of the most promising and versatile ways to enhance the device performance, yet the mechanisms of the doping effects still remain poorly understood. Here the effects of heteroatom doping by boron, nitrogen, sulfur, phosphorus, fluorine, chlorine, silicon, and functionalizing with oxygen on the elemental composition, structure, property, and performance relationships of nanocarbon electrodes are critically examined. The limitations of doping approaches are further discussed and guidelines for reporting the performance of heteroatom doped nanocarbon electrode‐based electrochemical capacitors are proposed. The current challenges and promising future directions for clean energy applications are discussed as well.     

Programmable Nanocarbon‐Based Architectures for Flexible Supercapacitors

Supercapacitors (SCs), also called electrochemical capacitors, often show high power density, excellent charge/discharge rates, and long cycle life. The recent development of flexible and wearable electronic devices requires that their power sources be sufficiently compact and flexible to match these electronic components. Therefore, flexible SCs have attracted much attention to power current advanced electronics that can be flexible and wearable. In the past several years, many different strategies have been developed to programmably construct different nanocarbon materials into bendable electrode architectures. Furthermore, flexible SC devices with simplified configurations have also been designed based on these nanocarbon‐based architectures. Here, recent developments in the programmable assembly of bendable architectures based on nanocarbon materials are presented. Additionally, the design of flexible nanocarbon‐based SC devices with various configurations is highlighted. The progress made recently paves the way for further development of nanocarbon architectures and corresponding flexible SC devices. Future development and prospects in this area are also analyzed.     

All Pseudocapacitive MXene‐RuO2 Asymmetric Supercapacitors

2D transition metal carbides and nitrides, known as MXenes, are an emerging class of 2D materials with a wide spectrum of potential applications, in particular in electrochemical energy storage. The hydrophilicity of MXenes combined with their metallic conductivity and surface redox reactions is the key for high‐rate pseudocapacitive energy storage in MXene electrodes. However, symmetric MXene supercapacitors have a limited voltage window of around 0.6 V due to possible oxidation at high anodic potentials. In this study, the fact that titanium carbide MXene (Ti₃C₂T_x) can operate at negative potentials in acidic electrolyte is exploited, to design an all‐pseudocapacitive asymmetric device by combining it with a ruthenium oxide (RuO₂) positive electrode. This asymmetric device operates at a voltage window of 1.5 V, which is about two times wider than the operating voltage window of symmetric MXene supercapacitors, and is the widest voltage window reported to date for MXene‐based supercapacitors. The complementary working potential windows of MXene and RuO₂, along with proton‐induced pseudocapacitance, significantly enhance the device performance. As a result, the asymmetric devices can deliver an energy density of 37 µW h cm^?2 at a power density of 40 mW cm^?2, with 86% capacitance retention after 20 000 charge–discharge cycles. These results show that pseudocapacitive negative MXene electrodes can potentially replace carbon‐based materials in asymmetric electrochemical capacitors, leading to an increased energy density.     

Cellulose‐based Supercapacitors: Material and Performance Considerations

One of the biggest challenges we will face over the next few decades is finding a way to power the future while maintaining strong socioeconomic growth and a clean environment. A transition from the use of fossil fuels to renewable energy sources is expected. Cellulose, the most abundant natural biopolymer on earth, is a unique, sustainable, functional material with exciting properties: it is low‐cost and has hierarchical fibrous structures, a high surface area, thermal stability, hydrophilicity, biocompatibility, and mechanical flexibility, which makes it ideal for use in sustainable, flexible energy storage devices. This review focuses on energy storage applications involving different forms of cellulose (i.e., cellulose microfibers, nanocellulose fibers, and cellulose nanocrystals) in supercapacitors, with particular emphasis on new trends and performance considerations relevant to these fields. Recent advances and approaches to obtaining high capacity devices are evaluated and the limitations of cellulose‐based systems are discussed. For the first time, a combination of device‐specific factors such as electrode structures, mass loadings, areal capacities, and volumetric properties are taken into account, so as to evaluate and compare the energy storage performance and to better assess the merits of cellulose‐based materials with respect to real applications.     

Scalable,Self‐Aligned Printing of Flexible Graphene Micro‐Supercapacitors

Graphene micro‐supercapacitors (MSCs) are an attractive energy storage technology for powering miniaturized portable electronics. Despite considerable advances in recent years, device fabrication typically requires conventional microfabrication techniques, limiting the translation to cost‐effective and high‐throughput production. To address this issue, we report here a self‐aligned printing process utilizing capillary action of liquid inks in microfluidic channels to realize scalable, high‐fidelity manufacturing of graphene MSCs. Microstructured ink receivers and capillary channels are imprinted on plastic substrates and filled by inkjet printing of functional materials into the receivers. The liquid inks move under capillary flow into the adjoining channels, allowing reliable patterning of electronic materials in complex structures with greatly relaxed printing tolerance. Leveraging this process with pristine graphene and ion gel inks, miniaturized all‐solid‐state graphene MSCs are demonstrated to concurrently achieve outstanding resolution (active footprint: <1 mm², minimum feature size: 20 µm) and yield (44/44 devices), while maintaining a high specific capacitance (268 µF cm^–2) and robust stability to extended cycling and bending, establishing an effective route to scale down device size while scaling up production throughput.     

Flash Converted Graphene for Ultra‐High Power Supercapacitors

Supercapacitors are known for their rapid energy charge–discharge properties, often ten to a hundred times faster than batteries. However, there is still a demand for supercapacitors with even faster charge–discharge characteristics to fulfill the requirements of emerging technologies. The power and rate capabilities of supercapacitors are highly dependent on the morphology of their electrode materials. An electrically conductive 3D porous structure possessing a high surface area for ions to access is ideal. Using a flash of light, a method to produce highly interconnected 3D graphene architectures with high surface area and good conductivity is developed. The flash converted graphene is synthesized by reducing freeze‐dried graphene oxide using an ordinary camera flash as a photothermal source. The flash converted graphene is used in coin cell supercapacitors to investigate its electrode materials properties. The electrodes are fabricated using either a precoating flash conversion or a postcoating flash conversion of graphene oxide. Both techniques produce supercapacitors possessing ultra‐high power (5–7 × 10⁵ W kg^?1). Furthermore, optimized supercapacitors retain >50% of their capacitance when operated at an ultrahigh current density up to 220 A g^?1.     

Facile and Scalable Preparation of Ruthenium Oxide‐Based Flexible Micro‐Supercapacitors

Tremendous efforts have been invested in the development of the internet of things during the past 10 years. Implantable sensors still need embedded miniaturized energy harvesting devices, since commercialized thin films and microbatteries do not provide sufficient power densities and suffer from limited lifetime. Therefore, micro‐supercapacitors are good candidates to store energy and deliver power pulses while providing non‐constant voltage output with time. However, multistep expensive protocols involving mask aligners and sophisticated cleanrooms are used to prepare these devices. Here, a simple and versatile laser‐writing procedure to integrate flexible micro‐supercapacitors and microbatteries on current‐collector‐free polyimide foils is reported, starting from commercial powders. Ruthenium oxide (RuO₂)‐based micro‐supercapacitors are prepared by laser irradiation of a bilayered tetrachloroauric acid (HAuCl₄ · 3H₂O)–cellulose acetate/RuO₂ film deposited by spin‐coating, which leads to adherent Au/RuO₂ electrodes with a unique pillar morphology. The as‐prepared microdevices deliver 27 mF cm^?2/540 F cm^?3 in 1 m H₂SO₄ and retain 80% of the initial capacitance after 10 000 cycles. This simple process is applied to make carbon‐based micro‐supercapacitors, as well as metal oxide based pseudocapacitors and battery electrodes, thus offering a straightforward solution to prepare low‐cost flexible microdevices at a large scale.     

Electromechanical Properties of Polymer Electrolyte‐Based Stretchable Supercapacitors

Aligned carbon nanotube (CNT) forests filled with a dehydrated polymer electrolyte are used to fabricate flexible solid state supercapacitors (SSCs) for multifunctional structural‐electronic applications. Local stiffness measurements on the composite electrodes determined through nano­indentation showed an 80% increase over the neat solid polymer electrolyte matrix. Electrochemical properties are monitored as a function of average tensile strain in the SSCs. Galvanostatic charge‐discharge tests with in situ microtensile testing on SSCs are used to show a 10% increase in the specific capacitance through the elastic region of the composite. The increase in capacitance is partly attributed to the enhanced double layer interaction that results from the partial alignment of the polymer electrolyte chains at the electrode‐electrolyte interface. When soaked in 1 m sulfuric acid, the specific capacitance of the CNT‐polymer electrolyte reached approximately 72 F g^–1 at 60 °C.