Carbon Nanotube Supported Molybdenum Carbide as Robust Electrocatalyst for Efficient Hydrogen Evolution Reaction.

Molybdenum carbide is considered to be one of the most competitive catalysts for hydrogen evolution reaction (HER) regarding its high catalytic activity and superior corrosion resistance. But the low electrical conductivity and poor interfacial contact with the current collector greatly inhibit its practical application capability. Herein, carbon nanotube (CNT) supported molybdenum carbide was assembled via electrostatic adsorption combined with complex bonding. The N-doped molybdenum carbide nanocrystals were uniformly anchored on the surfaces of amino CNTs, which depressed the agglomeration of nanoparticles while strengthening the migration of electrons. The optimized catalyst (250-800-2h) showed exceptional electrocatalytic performance towards HER under both acidic and alkaline conditions. Especially in 0.5 M H2SO4 solution, the 250-800-2h catalyst exhibited a low overpotential of 136 mV at a current density of 10 mA/cm2 (η10) with the Tafel slope of 49.9 mV dec-1, and the overpotential only increased 8 mV after 20,000 cycles of stability test. The active corrosive experiment revealed that more exposure to high-activity γ-Mo2N promoted the specific mass activity of Mo, thus, maintaining the catalytic durability of the catalyst.

Unravelling the pseudocapacitive origin of graphene oxide-based aerogels by comparative insights.

We reveal the intrinsic pseudocapacitive center of graphene-oxide-based aerogels by investigating different modified graphene skeletons from various approaches. A high proportion of carbonyl groups in carbon networks is shown to optimize the construction of rational pseudocapacitive sites by triggering reversible proton-induced surface reactions, leading to satisfactory electrochemical performance.

Intrinsic Interfacial Dynamic Engineering of Zincophilic Microbrushes via Regulating Zn Deposition for Highly Reversible Aqueous Zinc Ion Battery.

Aqueous rechargeable zinc ion batteries are promising efficient energy storage systems due to remarkable safety and satisfactory capacity. However, zinc metal anode instability including dendrite growth and side reactions severely hinders widespread applications. Herein, zincophilic microbrushes have been in situ anchored on zinc plates through simple freeze-drying and mild reduction of graphene oxide, successfully overcoming these thorny issues. By introducing suitable oxygen-containing groups, the microbrushes exhibit a good affinity for zinc ions, thereby providing sufficient depositing sites, promoting zinc plating and stripping during cycling, and suppressing side reactions. The delicate zincophilic microbrushes can not only function as protective layer to guide the deposition of zinc ions, but also act as high-speed pathways to redistribute the zinc ion flux for rapid kinetics. Consequently, the microbrushes-covered zinc anode displays long lifespan and good durability, whenever in symmetric cell or full battery tests. This work paves a feasible bridge to design advanced aqueous anodes by architecting both structures and compositions of metal coverings.

Poly(ethylene oxide)-Based Composite Electrolyte with Lithium-Doped High-Entropy Oxide Ceramic Enabled Robust Solid-State Lithium-Metal Batteries.

Solid polymer electrolytes using poly(ethylene oxide) (PEO) as matrix are mostly applied due to the superior Li+ transfer ability of oxyethyl chain. However, the high crystallinity, low oxidation potential window, and insufficient mechanical strength hinder PEO deployment in solid-state batteries. Here, a novel composite solid electrolyte combined PEO with a lithium-doped high-entropy oxide (Li0.25 HEO) ceramic powder is presented, which exhibits excellent properties for solid-state lithium metal battery applications. On one hand, the rich oxygen vacancies of Li0.25 HEO surface are favorable to capturing anionic groups (e. g. TFSI- ), reinforcing the Li+ dissociation. On the other hand, Li0.25 HEO with abundant Lewis acid sites markedly promotes the PEO oxidation potential window. Additionally, the incorporation of Li0.25 HEO ceramic powder can effectively inhibit the PEO crystallization and enhance the mechanic strength of the composite electrolyte as well. The assembled solid-state lithium metal battery based on the composite solid electrolyte exhibits high rate capacity and durable cycle performance, showing potential development and application prospects.

Ultrasensitive and Wearable Carbon Hybrid Fiber Devices as Robust Intelligent Sensors.

The growing applications of wearable electronics, electronic textiles, and biomedical devices have sparked explosive demand for high-performance flexible sensors. Herein, we report a facile approach for fabricating a highly sensitive carbon hybrid fiber, which is composed of a graphene fiber skeleton and carbon nanotube (CNT) branches. In this hierarchical fiber, in situ grown CNTs prohibit the stacking of graphene sheets and bridge graphene layers simultaneously, making the hybrid fiber fluffy and conductive. Due to the well-designed architecture, the assembled fiber sensor exhibits satisfactory performance with a high gauge factor (up to 1127), a fast response time (less than 70 ms), and excellent reliability and stability (>2000 cycles). This work provides a feasible and scalable pathway for the fabrication of ultrasensitive fiber-based sensors, achieving the full realization of monitoring human physiological signals and architecting a real-time human-machine controlling system. Moreover, these practical sensors are used to monitor the sitting posture to prevent cervical spondylosis and lumbar disc herniation.

Heavy Water Enables High-Voltage Aqueous Electrochemistry via the Deuterium Isotope Effect.

Aqueous electrolytes, which possess the advantages of nonflammability and high ionic conductivity for safe and sustainable energy storage systems, are restricted by their narrow potential windows due to water electrolysis. The recent study of high-voltage aqueous electrolytes has mainly focused on the molecular-level hydration structure of electrolyte salts, while the influence from subatomic-scale neutrons of the water solvent has never been considered. Here, for the first time, we report an electrochemical isotope effect in which the numerically increased neutrons in the water solvent extend the potential window of aqueous electrolytes. This effect is caused by the following factors: the lower zero-point energy of the deuterium compound, the smaller ion product, and the larger dehydration energy of heavy water. It is affected by ion species, electrolyte concentrations, and the ratio of deuterium to protium. Our finding provides the new insight into aqueous electrochemistry that the isotope in molecular water improves the performance of aqueous electrolytes.

Oxide Film Efficiently Suppresses Dendrite Growth in Aluminum-Ion Battery.

Aluminum metal foil is the optimal choice as an anode material for aluminum-ion batteries for its key advantages such as high theoretical capacity, safety, and low cost. However, the metallic nature of aluminum foil is very likely to induce severe dendrite growth with further electrode disintegration and cell failure, which is inconsistent with previous reports. Here, we discover that it is aluminum oxide film that efficiently restricts the growth of crystalline Al dendrite and thus improves the cycling stability of Al anode. The key role of surficial aluminum oxide film in protecting Al metal anode lies in decreasing the nucleation sites, controlling the metallic dendrite growth, and preventing the electrode disintegration. The defect sites in aluminum oxide film provide channels for electrolyte infiltration and further stripping/depositing. Attributed to such a protective aluminum oxide film, the Al-graphene full cells can attain up to 45 000 stable cycles.

A Defect-Free Principle for Advanced Graphene Cathode of Aluminum-Ion Battery.

A conceptually new defect-free principle is proposed for designing graphene cathode of aluminum-ion battery: the fewer the defects, the better the performances. Developed through scalable approach, defect-free graphene aerogel cathode affords high capacity of 100 mAh g-1 under an ultrahigh rate of 500 C, exceeding defective graphene and previous reports. This defect-free principle can guide us to fabricate better graphene-based electrodes.

Hydrothermally Activated Graphene Fiber Fabrics for Textile Electrodes of Supercapacitors.

Carbon textiles are promising electrode materials for wearable energy storage devices owing to their conductive, flexible, and lightweight features. However, there still lacks a perfect choice for high-performance carbon textile electrodes with sufficient electrochemical activity. Graphene fiber fabrics (GFFs) are newly discovered carbon textiles, exhibiting various attractive properties, especially a large variability on the microstructure. Here we report the fabrication of hierarchical GFFs with significantly enlarged specific surface area using a hydrothermal activation strategy. By carefully optimize the activation process, the hydrothermally activated graphene fiber fabrics (HAGFFs) could achieve an areal capacitance of 1060 mF cm-2 in a very thin thickness (150 µm) and the capacitance is easily magnified by overlaying several layers of HAGFFs, even up to a record value of 7398 mF cm-2. Meanwhile, a good rate capability and a long cycle life are also attained. As compared with other carbon textiles, including the commercial carbon fiber cloths, our HAGFFs present much better capacitive performance. Therefore, the mechanically stable, flexible, conductive, and highly active HAGFFs have provided an option for high-performance textile electrodes.

Ultrafast all-climate aluminum-graphene battery with quarter-million cycle life.

Rechargeable aluminum-ion batteries are promising in high-power density but still face critical challenges of limited lifetime, rate capability, and cathodic capacity. We design a "trihigh tricontinuous" (3H3C) graphene film cathode with features of high quality, orientation, and channeling for local structures (3H) and continuous electron-conducting matrix, ion-diffusion highway, and electroactive mass for the whole electrode (3C). Such a cathode retains high specific capacity of around 120 mAh g-1 at ultrahigh current density of 400 A g-1 (charged in 1.1 s) with 91.7% retention after 250,000 cycles, surpassing all the previous batteries in terms of rate capability and cycle life. The assembled aluminum-graphene battery works well within a wide temperature range of -40 to 120°C with remarkable flexibility bearing 10,000 times of folding, promising for all-climate wearable energy devices. This design opens an avenue for a future super-batteries.

Graphene-based single fiber supercapacitor with a coaxial structure.

A novel all graphene coaxial fiber supercapacitor (GCS) was fabricated, consisting of a continuously wet-spun core graphene fiber and facilely dip-coated graphene sheath. GCS is flexible, lightweight and strong, and is also accompanied by a high specific capacitance of 205 mF cm(-2) (182 F g(-1)) and high energy density of 17.5 µW h cm(-2) (15.5 W h kg(-1)). The energy density was further improved to 104 µW h cm(-2), when an organic ion liquid electrolyte was used.

Wet-spun, porous, orientational graphene hydrogel films for high-performance supercapacitor electrodes.

Supercapacitors with porous electrodes of graphene macroscopic assembly are supposed to have high energy storage capacity. However, a great number of "close pores" in porous graphene electrodes are invalid because electrolyte ions cannot infiltrate. A quick method to prepare porous graphene electrodes with reduced "close pores" is essential for higher energy storage. Here we propose a wet-spinning assembly approach based on the liquid crystal behavior of graphene oxide to continuously spin orientational graphene hydrogel films with "open pores", which are used directly as binder-free supercapacitor electrodes. The resulting supercapacitor electrodes show better electrochemical performance than those with disordered graphene sheets. Furthermore, three reduction methods including hydrothermal treatment, hydrazine and hydroiodic acid reduction are used to evaluate the specific capacitances of the graphene hydrogel film. Hydrazine-reduced graphene hydrogel film shows the highest capacitance of 203 F g(-1) at 1 A g(-1) and maintains 67.1% specific capacitance (140 F g(-1)) at 50 A g(-1). The combination of scalable wet-spinning technology and orientational structure makes graphene hydrogel films an ideal electrode material for supercapacitors.

Coaxial wet-spun yarn supercapacitors for high-energy density and safe wearable electronics.

Yarn supercapacitors have great potential in future portable and wearable electronics because of their tiny volume, flexibility and weavability. However, low-energy density limits their development in the area of wearable high-energy density devices. How to enhance their energy densities while retaining their high-power densities is a critical challenge for yarn supercapacitor development. Here we propose a coaxial wet-spinning assembly approach to continuously spin polyelectrolyte-wrapped graphene/carbon nanotube core-sheath fibres, which are used directly as safe electrodes to assembly two-ply yarn supercapacitors. The yarn supercapacitors using liquid and solid electrolytes show ultra-high capacitances of 269 and 177 mF cm(-2) and energy densities of 5.91 and 3.84 µWh cm(-2), respectively. A cloth supercapacitor superior to commercial capacitor is further interwoven from two individual 40-cm-long coaxial fibres. The combination of scalable coaxial wet-spinning technology and excellent performance of yarn supercapacitors paves the way to wearable and safe electronics.

Bismuth oxide nanotubes-graphene fiber-based flexible supercapacitors.

Graphene-bismuth oxide nanotube fiber as electrode material for constituting flexible supercapacitors using a PVA/H3PO4 gel electrolyte is reported with a high specific capacitance (Ca) of 69.3 mF cm(-2) (for a single electrode) and 17.3 mF cm(-2) (for the whole device) at 0.1 mA cm(-2), respectively. Our approach opens the door to metal oxide-graphene hybrid fibers and high-performance flexible electronics.