Battery‐like Supercapacitors from Vertically Aligned Carbon Nanofiber Coated Diamond: Design and Demonstrator

To fabricate battery‐like supercapacitors with high power and energy densities, big capacitances, as well as long‐term capacitance retention, vertically aligned carbon nanofibers (CNFs) grown on boron doped diamond (BDD) films are employed as the capacitor electrodes. They possess large surface areas, high conductivity, high stability, and importantly are free of binder. The large surface areas result from their porous structures. The containment of graphene layers and copper metal catalysts inside CNFs leads to their high conductivity. Both electrical double layer capacitors (EDLCs) in inert solutions and pseudocapacitors (PCs) using Fe(CN)₆^3?/4? redox‐active electrolytes are constructed with three‐ and two‐electrode systems. The assembled two‐electrode symmetrical supercapacitor devices exhibit capacitances of 30 and 48 mF cm^?2 at 10 mV s^?1 for EDLC and PC devices, respectively. They remain constant even after 10 000 charging/discharging cycles. The power densities are 27.3 and 25.3 kW kg^?1 for EDLC and PC devices, together with their energy densities of 22.9 and 44.1 W h kg^?1, respectively. The performance of these devices is superior to most of the reported supercapacitors and batteries. Vertically aligned CNF/BDD hybrid films are thus useful to construct high‐performance battery‐like and industry‐orientated supercapacitors for future power devices.     

All‐Manganese‐Based Binder‐Free Stretchable Lithium‐Ion Batteries

Advanced electrode materials with bendability and stretchability are critical for the rapid development of fully flexible/stretchable lithium‐ion batteries. However, the sufficiently stretchable lithium‐ion battery is still underdeveloped that is one of the biggest challenges preventing from realizing fully deformable power sources. Here, a low‐temperature hydrothermal synthesis of a cathode material for stretchable lithium‐ion battery is reported by the in situ growth of LiMn₂O₄ (LMO) nanocrystals inside 3D carbon nanotube (CNT) film networks. The LMO/CNT film composite has demonstrated the chemical bonding between the LMO active materials and CNT scaffolds, which is the most important characteristic of the stretchable electrodes. When coupled with a wrinkled MnO_x /CNT film anode, a binder‐free, all‐manganese‐based stretchable full battery cell is assembled which delivers a high average specific capacity of ≈97 mA h g^?1 and stabilizes after over 300 cycles with an enormous strain of 100%. Furthermore, combining with other merits such as low cost, natural abundance, and environmentally friendly, the all‐manganese design is expected to accelerate the practical applications of stretchable lithium‐ion batteries for fully flexible and biomedical electronics.     

Iron‐Based Supercapacitor Electrodes: Advances and Challenges

Supercapacitors (SCs) have great promise as the state‐of‐the‐art power source in portable electronics and hybrid vehicles. The performance of SCs is largely determined by the properties of the electrode material, and numerous efforts have been devoted to the explorations of novel electrode materials. Recently, iron‐based materials, including Fe₂O₃, Fe₃O₄, FeOOH, FeO_x, CoFe₂O₄, and MnFe₂O₄, have received considerable attention as very promising electrode materials for SCs due to their high theoretical specific capacitances, natural abundance, low cost, and non‐toxicity. However, most of these Fe‐based SC electrodes suffer from poor conductivity and/or electrochemical instability, which seriously impede their implementation as high‐performance electrodes for SCs. To settle these issues, substantial efforts have been made in improving their conductivity and cycling stability, and great processes have been achieved. Here, recent research advances in the rational design and synthesis of diverse Fe‐based nanostructured electrodes and their capacitive performance for SCs are presented. Besides, challenges and prospects of Fe‐based materials as advanced negative electrodes for SCs are also discussed.     

3D‐Printed Stretchable Micro‐Supercapacitor with Remarkable Areal Performance

While stretchable micro‐supercapacitors (MSCs) have been realized, they have suffered from limited areal electrochemical performance, thus greatly restricting their practical electronic application. Herein, a facile strategy of 3D printing and unidirectional freezing of a pseudoplastic nanocomposite gel composed of Ti₃C₂T_x MXene nanosheets, manganese dioxide nanowire, silver nanowires, and fullerene to construct intrinsically stretchable MSCs with thick and honeycomb‐like porous interdigitated electrodes is introduced. The unique architecture utilizes thick electrodes and a 3D porous conductive scaffold in conjunction with interacting material properties to achieve higher loading of active materials, larger interfacial area, and faster ion transport for significantly improved areal energy and power density. Moreover, the oriented cellular scaffold with fullerene‐induced slippage cell wall structure prompts the printed electrode to withstand large deformations without breaking or exhibiting obvious performance degradation. When imbued with a polymer gel electrolyte, the 3D‐printed MSC achieves an unprecedented areal capacitance of 216.2 mF cm^?2 at a scan rate of 10 mV s^?1, and remains stable when stretched up to 50% and after 1000 stretch/release cycles. This intrinsically stretchable MSC also exhibits high rate capability and outstanding areal energy density of 19.2 µWh cm^?2 and power density of 58.3 mW cm^?2, outperforming all reported stretchable MSCs.     

Optimization of Carbon‐ and Binder‐Free Au Nanoparticle‐Coated Ni Nanowire Electrodes for Lithium‐Oxygen Batteries

A Au nanoparticle‐coated Ni nanowire substrate without binder or carbon is used as the electrode (denoted as the Au/Ni electrode) for Li‐oxygen (Li‐O₂) batteries. A minimal amount of Au nanoparticles with sizes of <30 nm on a Ni nanowire substrate are coated using a simple electrodeposition method to the extent that maximum capacity can be utilized. This optimized, one body, Au/Ni electrode shows high capacities of 921 mAh g^?1_Au, 591 mAh g^?1_Au, and 359 mAh g^?1_Au, which are obtained at currents of 300 mAg^?1_Au, 500 mAg^?1_Au, and 1000 mAg^?1_Au respectively. More importantly, the Au/Ni electrode exhibits excellent cycle stability over 200 cycles.     

Vertically Aligned MoS2 Nanosheets Patterned on Electrochemically Exfoliated Graphene for High‐Performance Lithium and Sodium Storage

Molybdenum disulfide (MoS₂) has been recognized as a promising anode material for high‐energy Li‐ion (LIBs) and Na‐ion batteries (SIBs) due to its apparently high capacity and intriguing 2D‐layered structure. The low conductivity, unsatisfied mechanical stability, and limited active material utilization are three key challenges associated with MoS₂ electrodes especially at high current rates and mass active material loading. Here, vertical MoS₂ nanosheets are controllably patterned onto electrochemically exfoliated graphene (EG). Within the achieved hierarchical architecture, the intimate contact between EG and MoS₂ nanosheets, interconnected network, and effective exposure of active materials by vertical channels simultaneously overcomes the above three problems, enabling high mechanical integrity and fast charge transport kinetics. Serving as anode material for LIBs, EG‐MoS₂ with 95 wt% MoS₂ content delivered an ultrahigh‐specific capacity of 1250 mA h g^?1 after 150 stable cycles at 1 A g^?1, which is among the highest values in all reported MoS₂ electrodes, and excellent rate performance (970 mA h g^?1 at 5 A g^?1). Moreover, impressive cycling stability (509 mA h g^?1 at 1 A g^?1 after 250 cycles) and rate capability (423 mA h g^?1 at 2 A g^?1) were also achieved for SIBs. The area capacities reached 1.27 and 0.49 mA h cm^?2 at ≈1 mA cm^?2 for LIBs and SIBs, respectively. This work may inspire the development of new 2D hierarchical structures for high efficiency energy storage and conversion.     

Recent Advancement of p‐ and d‐Block Elements,Single Atoms,and Graphene‐Based Photoelectrochemical Electrodes for Water Splitting

Solar‐assisted photoelectrochemical (PEC) water splitting to produce hydrogen energy is considered the most promising solution for clean, green, and renewable sources of energy. For scaled production of hydrogen and oxygen, highly active, robust, and cost‐effective PEC electrodes are required. However, most of the available semiconductors as a PEC electrodes have poor light absorption, material degradation, charge separation, and transportability, which result in very low efficiency for photo‐water splitting. Generally, a promising photoelectrode is obtained when the surface of the semiconductor is modified/decorated with a suitable co‐catalyst because it increases the light absorbance spectrum and prevents electron–hole recombination during photoelectrode reactions. In this regard, numerous p‐ and d‐block elements, single atoms, and graphene‐based PEC electrodes have been widely used as semiconductor/co‐catalyst junctions to boost the performances of PEC overall water splitting. This review enumerates the recent progress and applications of p‐ and d‐block elements, single atoms, and graphene‐based PEC electrodes for water splitting. The focus is placed on fundamental mechanism, efficiency, cells design, and various aspects that contribute to the large‐scale prototype device. Finally, future perspectives, summary, challenges, and outlook for improving the activity of PEC photoelectrodes toward whole‐cell water splitting are addressed.     

Flexible Na/K‐Ion Full Batteries from the Renewable Cotton Cloth–Derived Stable,Low‐Cost,and Binder‐Free Anode and Cathode

Flexible Na/K‐ion batteries (NIBs/KIBs) exhibit great potential applications and have drawn much attention due to the continuous development of flexible electronics. However, there are still many huge challenges, mainly the design and construction of flexible electrodes (cathode and anode) with outstanding electrochemical properties. In this work, a unique approach to prepare flexible electrode is proposed by utilizing the commercially available cotton cloth–derived carbon cloth (CC) as a flexible anode and the substrate of a cathode. The binder‐free, self‐supporting, and flexible cathodes (FCC@N/KPB) are prepared by growing Prussian blue microcubes on the flexible CC (FCC). Na/K‐ion full batteries (FCC//FCC@N/KPB) are assembled by using FCC and FCC@N/KPB as anode and cathode, respectively. Electrochemical performance, mechanical flexibility, and practicability of FCC//FCC@N/KPB Na/K‐ion full batteries are evaluated in both coin cells and flexible pouch cells, demonstrating their superior energy‐storage properties (excellent rate performance and cycling stability) and remarkable flexibility (they can work under different bending states). This work provides a new and profound strategy to design flexible electrodes, promoting the development of flexible NIBs/KIBs to be practical and sustainable.     

Combining Nature‐Inspired,Graphene‐Wrapped Flexible Electrodes with Nanocomposite Polymer Electrolyte for Asymmetric Capacitive Energy Storage

Two kinds of free‐standing electrodes, reduced graphene oxide (rGO)‐wrapped Fe‐doped MnO₂ composite (G‐MFO) and rGO‐wrapped hierarchical porous carbon microspheres composite (G‐HPC) are fabricated using a frozen lake‐inspired, bubble‐assistance method. This configuration fully enables utilization of the synergistic effects from both components, endowing the materials to be excellent electrodes for flexible and lightweight electrochemical capacitors. Moreover, a nonaqueous HPC‐doped gel polymer electrolyte (GPE‐HPC) is employed to broad voltage window and improve heat resistance. A fabricated asymmetric supercapacitor based on G‐MFO cathode and G‐HPC anode with GPE‐HPC electrolyte achieves superior flexibility and reliability, enhanced energy/power density, and outstanding cycling stability. The ability to power light‐emitting diodes also indicates the feasibility for practical use. Therefore, it is believed that this novel design may hold great promise for future flexible electronic devices.     

Thick Binder‐Free Electrodes for Li–Ion Battery Fabricated Using Templating Approach and Spark Plasma Sintering Reveals High Areal Capacity

The templating approach is a powerful method for preparing porous electrodes with interconnected well‐controlled pore sizes and morphologies. The optimization of the pore architecture design facilitates electrolyte penetration and provides a rapid diffusion path for lithium ions, which becomes even more crucial for thick porous electrodes. Here, NaCl microsize particles are used as a templating agent for the fabrication of 1 mm thick porous LiFePO₄ and Li₄Ti₅O₁₂ composite electrodes using spark plasma sintering technique. These sintered binder‐free electrodes are self‐supported and present a large porosity (40%) with relatively uniform pores. The electrochemical performances of half and full batteries reveal a remarkable specific areal capacity (20 mA h cm^?2), which is 4 times higher than those of 100 µm thick electrodes present in conventional tape‐casted Li–ion batteries (5 mA h cm^?2). The 3D morphological study is carried out using full field transmission X‐ray microscopy in microcomputed tomography mode to obtain tortuosity values and pore size distributions leading to a strong correlation with their electrochemical properties. These results also demonstrate that the coupling between the salt templating method and the spark plasma sintering technique turns out to be a promising way to fabricate thick electrodes with high energy density.     

A Strategy for Synthesis of Carbon Nitride Induced Chemically Doped 2D MXene for High‐Performance Supercapacitor Electrodes

A step‐by‐step strategy is reported for improving capacitance of supercapacitor electrodes by synthesizing nitrogen‐doped 2D Ti₂CT_x induced by polymeric carbon nitride (p‐C₃N₄), which simultaneously acts as a nitrogen source and intercalant. The NH₂CN (cyanamide) can form p‐C₃N₄ on the surface of Ti₂CT_x nanosheets by a condensation reaction at 500–700 °C. The p‐C₃N₄ and Ti₂CT_x complexes are then heat‐treated to obtain nitrogen‐doped Ti₂CT_x nanosheets. The triazine‐based p‐C₃N₄ decomposes above 700 °C; thus, the nitrogen species can be surely doped into the internal carbon layer and/or defect site of Ti₂CT_x nanosheets at 900 °C. The extended interlayer distance and c‐lattice parameters (c‐LPs of 28.66 Å) of Ti₂CT_x prove that the p‐C₃N₄ grown between layers delaminate the nanosheets of Ti₂CT_x during the doping process. Moreover, 15.48% nitrogen doping in Ti₂CT_x improves the electrochemical performance and energy storage ability. Due to the synergetic effect of delaminated structures and heteroatom compositions, N‐doped Ti₂CT_x shows excellent characteristics as an electrochemical capacitor electrode, such as perfectly rectangular cyclic voltammetry results (CVs, R² = 0.9999), high capacitance (327 F g^?1 at 1 A g^?1, increased by ≈140% over pristine‐Ti₂CT_x), and stable long cyclic performance (96.2% capacitance retention after 5000 cycles) at high current density (5 A g^?1).     

High‐Performance Suspended Particle Devices Based on Copper‐Reduced Graphene Oxide Core–Shell Nanowire Electrodes

Smart windows are one of the key components of so‐called “green” buildings. These windows are based on an actively switchable electro‐optic material that is sandwiched between two transparent electrodes. Although great progress has been made in identifying the optimal materials for such active windows, there is still a great need to improve their key elements, especially the performance of the transparent electrodes. Here, a new suspended particle device (SPD), holding a great potential for smart window applications, which is built upon copper‐reduced graphene oxide (Cu‐rGO) core–shell nanowire (NW) films as a transparent conductive electrode is reported. With the wrapping of rGO, the Cu NW electrodes demonstrate both high optical transparency and electrical conductivity, as well as significantly improved stability under various testing conditions. The novel sandwich‐structured SPDs, based on these electrodes, show a large change in their optical transmittance (42%) between “on” and “off” states, impressively fast switching time and superior stability. These high performances are comparable to those of the SPDs based on indium tin oxide electrodes. These promising results pave the way for the electrodes to be an integral part of a variety of optoelectronic devices, including energy‐friendly and flexible electronics.     

ITO‐Free,Small‐Molecule Organic Solar Cells on Spray‐Coated Copper‐Nanowire‐Based Transparent Electrodes

The great potential of solution‐processed metal nanowire networks utilized as a transparent electrode has attracted much attention in the last years. Typically, silver nanowires are applied, although their replacement by more abundant and cheaper materials is of interest. Here, a hydrazine‐free synthesis route for high aspect ratio copper nanowires is used to prepare conductive networks showing an enhanced electrode performance. The network deposition is done with a scalable spray‐coating process on glass and on polymer foils. By a pressing or an annealing step, highly conductive transparent electrodes are obtained, and they reveal transmittance‐resistance values similar to indium tin oxide (ITO) and networks made of silver nanowires. The application potential of the copper nanowire electrodes is demonstrated by integrating them into an evaporated small‐molecule organic solar cell with 3% efficiency.     

All‐Solid‐State,Foldable, and Rechargeable Zn‐Air Batteries Based on Manganese Oxide Grown on Graphene‐Coated Carbon Cloth Air Cathode

Pliable, safe, and inexpensive energy storage devices are in demand to power modern flexible electronics. In this work, a foldable battery based on a solid‐state and rechargeable Zn‐air battery is introduced. The air cathode is prepared by coating graphene flakes on pretreated carbon cloth to form a dense, interconnected, and conducting carbon network. Manganese oxide hierarchical nanostructures are subsequently grown on the large surface area carbon network, leading to high loading of active catalyst per unit volume while maintaining the mechanical and electrical integrity of the air cathode. Solid‐state and rechargeable Zn‐air battery with such air cathode exhibits similar polarization curve and resistance at its flat and folded states. The folded battery is able to deliver a power density as high as ≈32 mW cm^?2 and good cycling stability of up to 110 cycles. In addition, the flat battery shows similar discharge/charge curve and stable cycling performance after 100 times of repeated folding and unfolding, indicating its high mechanical robustness.