Engineering 2D Architectures toward High‐Performance Micro‐Supercapacitors

The rise of micro‐supercapacitors is satisfying the demand for power storage in portable devices and wireless gadgets. But the miniaturization of the energy‐storage components is significantly limited by their energy density. Electrode materials with adequate electrochemical active surfaces are therefore required for improving performance. 2D materials with ultralarge specific surface areas offer a broad portfolio of the development of high‐performance micro‐supercapacitors in spite of their several critical drawbacks. An architecture engineering strategy is therefore developed to break these natural limits and maximize the significant advantages of these materials. Based on the approaches of phase transformation, intercalation, surface modification, material hybridization, and hierarchical structuration, 2D architectures with improved conductivity, enlarged specific surface, enhanced redox activity, as well as the unique synergetic effect exhibit great promise in the application of miniaturized supercapacitors with highly enhanced performance. Herein, the architecture engineering of emerging 2D materials beyond graphene toward optimizing the performance of micro‐supercapacitors is discussed, in order to promote the application of 2D architectures in miniaturized energy‐storage devices.     

Design of Architectures and Materials in In‐Plane Micro‐supercapacitors: Current Status and Future Challenges

The rapid development of integrated electronics and the boom in miniaturized and portable devices have increased the demand for miniaturized and on‐chip energy storage units. Currently thin‐film batteries or microsized batteries are commercially available for miniaturized devices. However, they still suffer from several limitations, such as short lifetime, low power density, and complex architecture, which limit their integration. Supercapacitors can surmount all these limitations. Particularly for micro‐supercapacitors with planar architectures, due to their unique design of the in‐plane electrode finger arrays, they possess the merits of easy fabrication and integration into on‐chip miniaturized electronics. Here, the focus is on the different strategies to design electrode finger arrays and the material engineering of in‐plane micro‐supercapacitors. It is expected that the advances in micro‐supercapacitors with in‐plane architectures will offer new opportunities for the miniaturization and integration of energy‐storage units for portable devices and on‐chip electronics.     

Recent Advances in High‐Performance Microbatteries: Construction,Application, and Perspective

High‐performance miniaturized energy storage devices have developed rapidly in recent years. Different from conventional energy storage devices, microbatteries assume the main responsibility for micropower supply, functionalization, and characterization platforms. Evolving from the essential goals for battery design of high power density, high energy density, and long lifetime, further practical demands for microbatteries (MBs) have been raised for the microfabrication technique and device design. Numerous studies have generally focused on specific aspects of the microelectrode structures or certain microfabrication techniques, while the connection from techniques to functional applications is rarely involved. This Review generally fills such blanks from an application‐oriented perspective. First, some basic micromachining techniques with different compatible features are summarized. Afterward, device designs including diversified battery reaction types, configuration, and assembly are highlighted, as well as microbatteries serving powering resources or further complicated functional systems. Finally, through providing the overall design concept based on requirements in application, this Review offers innovative insights for further development of microbatteries.     

3D Interdigitated Microsupercapacitors with Record Areal Cell Capacitance

Due to their high‐power density and long lifetime, microsupercapacitors have been considered as an efficient energy supply/storage solution for the operation of small electronic devices. However, their fabrication remains confined to 2D thin‐film microdevices with limited areal energy. In this study, the integration of all‐solid‐state 3D interdigitated microsupercapacitors on 4 in. silicon wafers with record energy density is demonstrated. The device electrodes are composed of a pseudocapacitive hydrated ruthenium dioxide RuO₂ deposited onto highly porous current collectors. The encapsulated devices exhibit cell capacitance of 812 mF cm^?2 per footprint area at an energy density of 329 mJ cm^?2, which is the highest value ever reported for planar configuration. These components achieve one of the highest surface energy/power density trade‐offs and address the issue of electrical energy storage of modern electronics.     

Designing Heterogeneous 1D Nanostructure Arrays Based on AAO Templates for Energy Applications

In order to fulfill the multiple requirements for energy production, storage, and utilization in the future, the conventional planar configuration of current energy conversion/storage devices has to be reformed, since technological evolution has promoted the efficiency of the corresponding devices to be close to the theoretical values. One promising strategy is to construct multifunctional 1D nanostructure arrays to replace their planar counterparts for device fabrication, ascribing to the significant superiorities of such 1D nanostructure arrays. In the last three decades, technologies based on anodic aluminium oxide (AAO) templates have turned out to be valuable meaning for the realization of 1D nanostructures and have attracted tremendous interest. In this review, recent progress in energy‐related devices equipped with heterogeneous 1D nanostructure arrays that fabricated through the assistance of AAO templates is highlighted. Particular emphasis is given on how to develop efficient devices via optimizing the componential and morphological parameters of the 1D nanostructure arrays. Finally, aspects relevant to the further improvement of device performance are discussed.     

1D Carbon‐Based Nanocomposites for Electrochemical Energy Storage

Electrochemical energy storage (EES) devices have attracted immense research interests as an effective technology for utilizing renewable energy. 1D carbon‐based nanostructures are recognized as highly promising materials for EES application, combining the advantages of functional 1D nanostructures and carbon nanomaterials. Here, the recent advances of 1D carbon‐based nanomaterials for electrochemical storage devices are considered. First, the different categories of 1D carbon‐based nanocomposites, namely, 1D carbon‐embedded, carbon‐coated, carbon‐encapsulated, and carbon‐supported nanostructures, and the different synthesis methods are described. Next, the practical applications and optimization effects in electrochemical energy storage devices including Li‐ion batteries, Na‐ion batteries, Li–S batteries, and supercapacitors are presented. After that, the advanced in situ detection techniques that can be used to investigate the fundamental mechanisms and predict optimization of 1D carbon‐based nanocomposites are discussed. Finally, an outlook for the development trend of 1D carbon‐based nanocomposites for EES is provided.     

3D Interdigital Au/MnO2/Au Stacked Hybrid Electrodes for On‐Chip Microsupercapacitors

On‐chip microsupercapacitors (MSCs) have application in powering microelectronic devices. Most of previous MSCs are made from carbon materials, which have high power but low energy density. In this work, 3D interdigital Au/MnO₂/Au stacked MSCs have been fabricated based on laser printed flexible templates. This vertical‐stacked electrode configuration can effectively increase the contact area between MnO₂ active layer and Au conductive layer, and thus improve the electron transport and electrolyte ion diffusion, resulting in enhanced pseudocapacitive performance of MnO₂. The stacked electrode can achieve an areal capacitance up to 11.9 mF cm^?2. Flexible and all‐solid‐state MSCs are assembled based on the sandwich hybrid electrodes and PVA/LiClO₄ gel electrolyte and show outstanding high‐rate capacity and mechanical flexibility. The laser printing technique in this work combined with the physical sputtering and electrodeposition allows fabrication of MSC array with random sizes and patterns, making them promising power sources for small‐scale flexible microelectronic energy storage systems (e.g., next‐generation smart phones).     

Micro-Cup Architecture for Printing and Coating Asymmetric 2d-Material-Based Solid-State Supercapacitors

High energy density micro-supercapacitors (MSCs) are in high demand for miniaturized electronics and microsystems. Research efforts today focus on materials development, applied in the planar interdigitated, symmetric electrode architecture. A novel “cup & core” device architecture that allows for printing of asymmetric devices without the need of accurately positioning the second finger electrode here have been introduced. The bottom electrode is either produced by laser ablation of a blade-coated graphene layer or directly screen-printed with graphene inks to create grids with high aspect ratio walls forming an array of “micro-cups”. A quasi-solid-state ionic liquid electrolyte is spray-deposited on the walls; the top electrode material -MXene inks- is then spray-coated to fill the cup structure. The architecture combines the advantages of interdigitated electrodes for facilitated ion-diffusion, which is critical for 2D-material-based energy storage systems by providing vertical interfaces with the layer-by-layer processing of the sandwich geometry. Compared to flat reference devices, volumetric capacitance of printed “micro-cups” MSC increased considerably, while the time constant decreased (by 58%). Importantly, the high energy density (3.99 µWh cm⁻²) of the “micro-cups” MSC is also superior to other reported MXene and graphene-based MSCs.     

2D Metal Chalcogenides Incorporated into Carbon and their Assembly for Energy Storage Applications

2D metal chalcogenides have become a popular focus in the energy storage field because of their unique properties caused by their single‐atom thicknesses. However, their high surface energy and van der Waals attraction easily cause serious stacking and restacking, leading to the generation of more inaccessible active sites with rapid capacity fading. The hybridization of 2D metal chalcogenides with highly conductive materials, particularly, incorporating ultrasmall and few‐layered metal chalcogenides into carbon frameworks, can not only maximize the exposure of active sites but also effectively avoid their stacking and aggregation during the electrochemical reaction process. Therefore, a satisfactory specific capacity will be achieved with a long cycle life. In this Concept, the representative progress on such intriguing nanohybrids and their applications in energy storage devices are mainly summarized. Finally, an outlook of the future development and challenges of such nanohybrids for achieving an excellent energy storage capability is also provided.     

Direct Laser Writing of Graphene Made from Chemical Vapor Deposition for Flexible,Integratable Micro‐Supercapacitors with Ultrahigh Power Output

High‐performance yet flexible micro‐supercapacitors (MSCs) hold great promise as miniaturized power sources for increasing demand of integrated electronic devices. Herein, this study demonstrates a scalable fabrication of multilayered graphene‐based MSCs (MG‐MSCs), by direct laser writing (DLW) of stacked graphene films made from industry‐scale chemical vapor deposition (CVD). Combining the dry transfer of multilayered CVD graphene films, DLW allows a highly efficient fabrication of large‐areal MSCs with exceptional flexibility, diverse planar geometry, and capability of customer‐designed integration. The MG‐MSCs exhibit simultaneously ultrahigh energy density of 23 mWh cm^?3 and power density of 1860 W cm^?3 in an ionogel electrolyte. Notably, such MG‐MSCs demonstrate an outstanding flexible alternating current line‐filtering performance in poly(vinyl alcohol) (PVA)/H₂SO₄ hydrogel electrolyte, indicated by a phase angle of ?76.2° at 120 Hz and a resistance–capacitance constant of 0.54 ms, due to the efficient ion transport coupled with the excellent electric conductance of the planar MG microelectrodes. MG–polyaniline (MG‐PANI) hybrid MSCs fabricated by DLW of MG‐PANI hybrid films show an optimized capacitance of 3.8 mF cm^?2 in PVA/H₂SO₄ hydrogel electrolyte; an integrated device comprising MG‐MSCs line filtering, MG‐PANI MSCs, and pressure/gas sensors is demonstrated.     

1D/2D Carbon Nanomaterial‐Polymer Dielectric Composites with High Permittivity for Power Energy Storage Applications

With the development of flexible electronic devices and large‐scale energy storage technologies, functional polymer‐matrix nanocomposites with high permittivity (high‐k) are attracting more attention due to their ease of processing, flexibility, and low cost. The percolation effect is often used to explain the high‐k characteristic of polymer composites when the conducting functional fillers are dispersed into polymers, which gives the polymer composite excellent flexibility due to the very low loading of fillers. Carbon nanotubes (CNTs) and graphene nanosheets (GNs), as one‐dimensional (1D) and two‐dimensional (2D) carbon nanomaterials respectively, have great potential for realizing flexible high‐k dielectric nanocomposites. They are becoming more attractive for many fields, owing to their unique and excellent advantages. The progress in dielectric fields by using 1D/2D carbon nanomaterials as functional fillers in polymer composites is introduced, and the methods and mechanisms for improving dielectric properties, breakdown strength and energy storage density of their dielectric nanocomposites are examined. Achieving a uniform dispersion state of carbon nanomaterials and preventing the development of conductive networks in their polymer composites are the two main issues that still need to be solved in dielectric fields for power energy storage. Recent findings, current problems, and future perspectives are summarized.     

Graphene‐Based Linear Tandem Micro‐Supercapacitors with Metal‐Free Current Collectors and High‐Voltage Output

Printable supercapacitors are regarded as a promising class of microscale power source, but are facing challenges derived from conventional sandwich‐like geometry. Herein, the printable fabrication of new‐type planar graphene‐based linear tandem micro‐supercapacitors (LTMSs) on diverse substrates with symmetric and asymmetric configuration, high‐voltage output, tailored capacitance, and outstanding flexibility is demonstrated. The resulting graphene‐based LTMSs consisting of 10 micro‐supercapacitors (MSs) present efficient high‐voltage output of 8.0 V, suggestive of superior uniformity of the entire integrated device. Meanwhile, LTMSs possess remarkable flexibility without obvious capacitance degradation under different bending states. Moreover, areal capacitance of LTMSs can be sufficiently modulated by incorporating polyaniline‐based pseudocapacitive nanosheets into graphene electrodes, showing enhanced capacitance of 7.6 mF cm^?2. To further improve the voltage output and energy density, asymmetric LTMSs are fabricated through controlled printing of linear‐patterned graphene as negative electrodes and MnO₂ nanosheets as positive electrodes. Notably, the asymmetric LTMSs from three serially connected MSs are easily extended to 5.4 V, triple voltage output of the single cell (1.8 V), suggestive of the versatile applicability of this technique. Therefore, this work offers numerous opportunities of graphene and analogous nanosheets for one‐step scalable fabrication of flexible tandem energy storage devices integrating with printed electronics on same substrate.     

Tubular 3D Resistive Random Access Memory Based on Rolled‐Up h‐BN Tube

Due to their advantages compared with planar structures, rolled‐up tubes have been applied in many fields, such as field‐effect transistors, compact capacitors, inductors, and integrative sensors. On the other hand, because of its perfect insulating nature, ultrahigh mechanical strength and atomic thickness property, 2D hexagonal boron nitride (h‐BN) is a very suitable material for rolled‐up memory applications. In this work, a tubular 3D resistive random access memory (RRAM) device based on rolled‐up h‐BN tube is realized, which is achieved by self‐rolled‐up technology. The tubular RRAM device exhibits bipolar resistive switching behavior, nonvolatile data storage ability, and satisfactorily low programming current compared with other 2D material‐based RRAM devices. Moreover, by releasing from the substrate, the footprint area of the tubular device is reduced by six times. This tubular RRAM device has great potential for increasing the data storage density, lowering the power consumption, and may be applied in the fields of rolled‐up systems and sensing‐storage integration.     

Extrusion‐Based 3D Printing of Hierarchically Porous Advanced Battery Electrodes

A highly porous 2D nanomaterial, holey graphene oxide (hGO), is synthesized directly from holey graphene powder and employed to create an aqueous 3D printable ink without the use of additives or binders. Stable dispersions of hydrophilic hGO sheets in water (≈100 mg mL^?1) can be readily achieved. The shear‐thinning behavior of the aqueous hGO ink enables extrusion‐based printing of fine filaments into complex 3D architectures, such as stacked mesh structures, on arbitrary substrates. The freestanding 3D printed hGO meshes exhibit trimodal porosity: nanoscale (4–25 nm through‐holes on hGO sheets), microscale (tens of micrometer‐sized pores introduced by lyophilization), and macroscale (<500 µm square pores of the mesh design), which are advantageous for high‐performance energy storage devices that rely on interfacial reactions to promote full active‐site utilization. To elucidate the benefit of (nano)porosity and structurally conscious designs, the additive‐free architectures are demonstrated as the first 3D printed lithium–oxygen (Li–O₂) cathodes and characterized alongside 3D printed GO‐based materials without nanoporosity as well as nanoporous 2D vacuum filtrated films. The results indicate the synergistic effect between 2D nanomaterials, hierarchical porosity, and overall structural design, as well as the promise of a freeform generation of high‐energy‐density battery systems.     

Small‐Scale Biological and Artificial Multidimensional Sensors for 3D Sensing

A vast majority of existing sub‐millimeter‐scale sensors have a planar, 2D geometry as a result of conventional top‐down lithographic procedures. However, 2D sensors often suffer from restricted sensing capability, allowing only partial measurements of 3D quantities. Here, nano/microscale sensors with different geometric (1D, 2D, and 3D) configurations are reviewed to introduce their advantages and limitations when sensing changes in quantities in 3D space. This Review categorizes sensors based on their geometric configuration and sensing capabilities. Among the sensors reviewed here, the 3D configuration sensors defined on polyhedral structures are especially advantageous when sensing spatially distributed 3D quantities. The nano‐ and microscale vertex configuration forming polyhedral structures enable full 3D spatial sensing due to orthogonally aligned sensing elements. Particularly, the cubic configuration leveraged in 3D sensors offers an array of diverse applications in the field of biosensing for micro‐organisms and proteins, optical metamaterials for invisibility cloaking, 3D imaging, and low‐power remote sensing of position and angular momentum for use in microbots. Here, various 3D sensors are compared to assess the advantages of their geometry and its impact on sensing mechanisms. 3D biosensors in nature are also explored to provide vital clues for the development of novel 3D sensors.     

Recent Advances in 3D Graphene Architectures and Their Composites for Energy Storage Applications

Graphene is widely applied as an electrode material in energy storage fields. However, the strong π–π interaction between graphene layers and the stacking issues lead to a great loss of electrochemically active surface area, damaging the performance of graphene electrodes. Developing 3D graphene architectures that are constructed of graphene sheet subunits is an effective strategy to solve this problem. The graphene architectures can be directly utilized as binder‐free electrodes for energy storage devices. Furthermore, they can be used as a matrix to support active materials and further improve their electrochemical performance. Here, recent advances in synthesizing 3D graphene architectures and their composites as well as their application in different energy storage devices, including various battery systems and supercapacitors are reviewed. In addition, their challenges for application at the current stage are discussed and future development prospects are indicated.     

Scalable Synthesis of 2D Si Nanosheets

2D Si nanomaterials have attracted tremendous attention due to their novel properties and a wide range of potential applications from electronic devices to energy storage and conversion. However, high‐quality and large‐scale fabrication of 2D Si remains challenging. This study reports a room‐temperature and one‐step synthesis technique that leads to large‐scale and low‐cost production of Si nanosheets (SiNSs) with thickness ≈4 nm and lateral size of several micrometers, based on the intrinsic delithiation process of chemically leaching lithium from the Li₁₃Si₄ alloy. Together with experimental results, a combination of theoretical modeling and atomistic simulations indicates that the formation of single SiNS arises from spontaneous delamination of nanosheets from their substrate due to delithiation‐induced mismatch. Subsequently, the synthesized Si nanosheets evolve from amorphous to nanocrystalline to crystalline structures during annealing at different temperatures. It is demonstrated that these SiNSs possess unique mechanical properties, in particular ultralow friction, in contrast to their bulk counterparts.     

Shape Memory Alloy (SMA)‐Based Microscale Actuators with 60% Deformation Rate and 1.6 kHz Actuation Speed

Shape memory alloys (SMAs) are widely utilized as an actuation source in microscale devices, since they have a simple actuation mechanism and high‐power density. However, they have limitations in terms of strain range and actuation speed. High‐speed microscale SMA actuators are developed having diamond‐shaped frame structures with a diameter of 25 µm. These structures allow for a large elongation range compared with bulk SMA materials, with the aid of spring‐like behavior under tensile deformation. These actuators are validated in terms of their applicability as an artificial muscle in microscale by investigating their behavior under mechanical deformation and changes in thermal conditions. The shape memory effect is triggered by delivering thermal energy with a laser. The fast heating and cooling phenomenon caused by the scale effect allows high‐speed actuation up to 1600 Hz. It is expected that the proposed actuators will contribute to the development of soft robots and biomedical devices.     

Design and integration of flexible planar micro-supercapacitors

As promising candidates for energy-storage devices,supercapacitors (SCs) have attracted considerable attention because of their unique features,such as their high power density,outstanding rate capability,excellent cycling performance,and safety.The recent boom in portable electronic devices requires high-performance SCs that are flexible,simplified,thin,and integrated.Tremendous efforts have been directed towards the design and integration of planar microSCs (MSCs) based on different active electrode materials by various methods.This review highlights the recent developments in the device design of flexible planar MSCs and their integration with other electronic devices.The current challenges and future prospects for the development of flexible MSCs are also discussed.     

3D knitted energy storage textiles using MXene-coated yarns

Textile-based energy storage devices offer an exciting replacement for bulky and uncomfortable batteries in commercial smart garments. Fiber and yarn-based supercapacitors, currently dominating research in this field, have demonstrated excellent performance below ∼4 cm in length, but suffer at longer lengths due to increased resistance. Herein, a new architecture of wearable energy storage devices, 3D knitted supercapacitors, is designed and prototyped with the intention of exploiting the architecture of a knit textile to improve the performance of long yarn electrodes. While Computer-Aided Design (CAD) knitting is a ubiquitous technology for producing textiles, knitted energy storage devices have been largely unexplored due to the need for meters of highly conductive yarn electrodes that meet the strenuous strength and flexibility requirements for CAD knitting. MXenes, a family of solution processable and conductive two-dimensional (2D) materials, have been realized as inks, slurries, pastes, and now dyes for the development of on-paper, on-plastic, and on-textile microsupercapacitor electrodes. In this work, Ti₃C₂T_x MXene was adopted as an active material for coating meters of commercial natural and synthetic yarns, enabling the production of knitted planar microsupercapacitors. The impact on electrochemical performance of knit structure and geometry was systematically studied in an attempt to produce energy storing textiles with power and energy densities that can be used for practical applications. The resulting energy storing textiles demonstrate high capacitance, up to 707 mF cm⁻² and 519 mF cm⁻² at 2 mV s⁻¹ in 1 M H₃PO₄ and PVA-H₃PO₄ gel electrolyte, respectively, and excellent cycling stability over 10,000 cycles. This work represents an important step towards the mass production of MXene-based conductive yarns and 3D knitted energy storage devices and demonstrates how knit structure plays a significant role on device performance.