Synthesis of P‐Doped and NiCo‐Hybridized Graphene‐Based Fibers for Flexible Asymmetrical Solid‐State Micro‐Energy Storage Device

Fiber supercapacitors (FSCs) are promising energy storage devices in portable and wearable smart electronics. Currently, a major challenge for FSCs is simultaneously achieving high volumetric energy and power densities. Herein, the microscale fiber electrode is designed by using carbon fibers as substrates and capillary channels as microreactors to space‐confined hydrothermal assembling. As P‐doped graphene oxide/carbon fiber (PGO/CF) and NiCo₂O₄‐based graphene oxide/carbon fiber (NCGO/CF) electrodes are successfully prepared, their unique hybrid structures exhibit a satisfactory electrochemical performance. An all‐solid‐state PGO/CF//NCGO/CF flexible asymmetric fiber supercapacitor (AFSC) based on the PGO/CF as the negative electrode, NCGO/CF hybrid electrode as the positive electrode, and poly(vinyl alcohol)/potassium hydroxide as the electrolyte is successfully assembled. The AFSC device delivers a higher volumetric energy density of 36.77 mW h cm^?3 at a power density of 142.5 mW cm^?3. In addition, a double reference electrode system is adopted to analyze and reduce the IR drop, as well as effectively matching negative and positive electrodes, which is conducive for the optimization and improvement of energy density. For the AFSC device, its better flexibility and electrochemical properties create a promising potential for high‐performance micro‐supercapacitors. Furthermore, the introduction of the double reference electrode system provides an interesting method for the study on the electrochemical performances of two‐electrode systems.     

Vertically Oriented Graphene Nanoribbon Fibers for High‐Volumetric Energy Density All‐Solid‐State Asymmetric Supercapacitors

Graphene fiber based micro‐supercapacitors (GF micro‐SCs) have attracted great attention for their potential applications in portable and wearable electronics. However, due to strong π–π stacking of nanosheets for graphene fibers, the limited ion accessible surface area and slow ion diffusion rate leads to low specific capacitance and poor rate performance. Here, the authors report a strategy for the synthesis of a vertically oriented graphene nanoribbon fiber with highly exposed surface area through confined‐hydrothermal treatment of interconnected graphene oxide nanoribbons and consequent laser irradiation process. As a result, the as‐obtained fiber shows high length specific capacitance of 3.2 mF cm^?1 and volumetric capacitance of 234.8 F cm^?3 at 2 mV s^?1, as well as excellent rate capability and outstanding cycling performance (96% capacitance retention after 10 000 cycles). Moreover, an all‐solid‐state asymmetric supercapacitor based on graphene nanoribbon fiber as negative electrode and MnO₂ coated graphene ribbon fiber as positive electrode, shows high volumetric capacitance and energy density of 12.8 F cm^?3 and 5.7 mWh cm^?3 (normalized to the device volume), respectively, much higher than those of previously reported GF micro‐SCs, as well as a long cycle life with 88% of capacitance retention after 10 000 cycles.     

Self‐Assembled Nickel Pyrophosphate‐Decorated Amorphous Bimetal Hydroxides 2D‐on‐2D Nanostructure for High‐Energy Solid‐State Asymmetric Supercapacitor

To obtain a supercapacitor with a remarkable specific capacitance and rate performance, a cogent design and synthesis of the electrode material containing abundant active sites is necessary. In present work, a scalable strategy is developed for preparing 2D‐on‐2D nanostructures for high‐energy solid‐state asymmetric supercapacitors (ASCs). The self‐assembled vertically aligned microsheet‐structured 2D nickel pyrophosphate (Ni₂P₂O₇) is decorated with amorphous bimetallic nickel cobalt hydroxide (NiCo‐OH) to form a 2D‐on‐2D nanostructure arrays electrode. The resulting Ni₂P₂O₇/NiCo‐OH 2D‐on‐2D array electrode exhibits peak specific capacity of 281 mA hg^?1 (4.3 F cm^?2), excellent rate capacity, and cycling stability over 10 000 charge–discharge cycles in the positive potential range. The excellent electrochemical features can be attributed to the high electrical conductivity and 2D layered structure of Ni₂P₂O₇ along with the Faradic capacitance of the amorphous NiCo‐OH nanosheets. The constructed Ni₂P₂O₇/NiCo‐OH//activated carbon based solid‐state ASC cell operates in a high voltage window of 1.8 V with an energy density of 78 Wh kg^?1 (1.065 mWh cm^?3) and extraordinary cyclic stability over 10 000 charge–discharge cycles with excellent energy efficiency (75%–80%) over all current densities. The excellent electrochemical performance of the prepared electrode and solid‐state ASC device offers a favorable and scalable pathway for developing advanced electrodes.     

The Road Towards Planar Microbatteries and Micro‐Supercapacitors: From 2D to 3D Device Geometries

The rapid development and further modularization of miniaturized and self‐powered electronic systems have substantially stimulated the urgent demand for microscale electrochemical energy storage devices, e.g., microbatteries (MBs) and micro‐supercapacitors (MSCs). Recently, planar MBs and MSCs, composed of isolated thin‐film microelectrodes with extremely short ionic diffusion path and free of separator on a single substrate, have become particularly attractive because they can be directly integrated with microelectronic devices on the same side of one single substrate to act as a standalone microsized power source or complement miniaturized energy‐harvesting units. The development of and recent advances in planar MBs and MSCs from the fundamentals and design principle to the fabrication methods of 2D and 3D planar microdevices in both in‐plane and stacked geometries are highlighted. Additonally, a comprehensive analysis of the primary aspects that eventually affect the performance metrics of microscale energy storage devices, such as electrode materials, electrolyte, device architecture, and microfabrication techniques are presented. The technical challenges and prospective solutions for high‐energy‐density planar MBs and MSCs with multifunctionalities are proposed.     

Voltage‐Control of Magnetism in All‐Solid‐State and Solid/Liquid Magnetoelectric Composites

The control of magnetism by means of low‐power electric fields, rather than dissipative flowing currents, has the potential to revolutionize conventional methods of data storage and processing, sensing, and actuation. A promising strategy relies on the utilization of magnetoelectric composites to finely tune the interplay between electric and magnetic degrees of freedom at the interface of two functional materials. Albeit early works predominantly focused on the magnetoelectric coupling at solid/solid interfaces; however, recently there has been an increased interest related to the opportunities offered by liquid‐gating techniques. Here, a comparative overview on voltage control of magnetism in all‐solid‐state and solid/liquid composites is presented within the context of the principal coupling mediators, i.e., strain, charge carrier doping, and ionic intercalation. Further, an exhaustive and critical discussion is carried out, concerning the suitability of using the common definition of coupling coefficient ${\alpha }_C=\frac{\mathrm{\Delta }M}{\mathrm{\Delta }E}$ to compare the strength of the interaction between electricity and magnetism among different magnetoelectric systems.     

One‐Step Synthesis of Monodispersed Mesoporous Carbon Nanospheres for High‐Performance Flexible Quasi‐Solid‐State Micro‐Supercapacitors

Cost‐effective synthesis of carbon nanospheres with a desirable mesoporous network for diversified energy storage applications remains a challenge. Herein, a direct templating strategy is developed to fabricate monodispersed N‐doped mesoporous carbon nanospheres (NMCSs) with an average particle size of 100 nm, a pore diameter of 4 nm, and a specific area of 1093 m² g^?1. Hexadecyl trimethyl ammonium bromide and tetraethyl orthosilicate not only play key roles in the evolution of mesopores but also guide the assembly of phenolic resins to generate carbon nanospheres. Benefiting from the high surface area and optimum mesopore structure, NMCSs deliver a large specific capacitance up to 433 F g^?1 in 1 m H₂SO₄. The NMCS electrodes–based symmetric sandwich supercapacitor has an output voltage of 1.4 V in polyvinyl alcohol/H₂SO₄ gel electrolyte and delivers an energy density of 10.9 Wh kg^?1 at a power density of 14014.5 W kg^?1. Notably, NMCSs can be directly applied through the mask‐assisted casting technique by a doctor blade to fabricate micro‐supercapacitors. The micro‐supercapacitors exhibit excellent mechanical flexibility, long‐term stability, and reliable power output.