Free-standing and flexible polyvinyl alcohol-sodium alginate-polypyrrole electrodes based on interpenetrating network hydrogels.

Flexible supercapacitors (FSCs) have attracted much attention due to their strong mechanical flexibility, wearability and portability, which greatly rely on the employed flexible electrodes. The conductive polymer hydrogels with excellent flexibility, processability and capacitive performance are one of the most promising candidates, which are still limited by their poor mechanical properties. Constructing robust interpenetrating polymer networks (IPN) is an effective approach to promote their mechanical properties. Herein, interpenetrating polyvinyl alcohol (PVA)-sodium alginate (SA)-polypyrrole (PPy) hydrogels are prepared by the freeze-thaw and in-situ polymerization method. The IPN structure composed of PVA and SA not only enhances the mechanical properties of hydrogels, but also provides substantial active sites for electrochemical reactions. Moreover, the hydrogen-bonding interaction between different components in the PVA-SA-PPy hydrogel boosts the charge/ion transfer. The optimal PVA-SA-PPy hydrogels show an elongation at break of 380 %, a tensile strength of 1.5 MPa, and a specific capacitance of 2646 mF cm-2 at 2 mA cm-2. The symmetric PVA-SA-PPy FSCs show an energy density of 96.7 µWh cm-2 at a power density of 999.9 µW cm-2, and the capacitance retention is 66.3 % after 10,000 cycles. These exceptional mechanical and electrochemical properties make the PVA-SA-PPy hydrogels a promising candidate for FSCs.

Biomimetic Mineralization Synthesis of Flower-Like Cobalt Selenide/Reduced Graphene Oxide for Improved Electrochemical Deionization.

Rationally and precisely tuning the composition and structure of materials is a viable strategy to improve electrochemical deionization (EDI) performances, which yet faces enormous challenges. Herein, an eco-friendly biomimetic mineralization synthetic strategy is developed to synthesize the flower-like cobalt selenide/reduced graphene oxide (Bio-CoSe2 /rGO) composites and used as advanced sodium ion adsorption electrodes. Benefiting from the slow and controllable reaction kinetics provided by the biomimetic mineralization process, the flower-like CoSe2 is uniformly constructed in the rGO, which is endowed with robust architecture, substantial adsorption sites and rapid charge/ion transport. The Bio-CoSe2 /rGO electrode yields the maximum salt adsorption capacity and salt adsorption rate of 56.3 mg g-1 and 5.6 mg g-1 min-1 respectively, and 92.5% capacity retention after 60 cycles. These results overmatch the pristine CoSe2 and irregular granular CoSe2 /rGO synthesized by a hydrothermal method, proving the structural superiority of the Bio-CoSe2 /rGO composites. Furthermore, the in-depth adsorption kinetics study indicates the chemisorption nature of sodium ion adsorption. The structures of the Bio-CoSe2 /rGO composites after long term EDI cycles are intensively studied to unveil the mechanism behind such superior EDI performances. This study offers one effective method for constructing advanced EDI electrodes, and enriches the application of the biomimetic mineralization synthetic strategy.

Stabilizing non-iridium active sites by non-stoichiometric oxide for acidic water oxidation at high current density.

Stabilizing active sites of non-iridium-based oxygen evolution reaction (OER) electrocatalysts is crucial, but remains a big challenge for hydrogen production by acidic water splitting. Here, we report that non-stoichiometric Ti oxides (TiOx) can safeguard the Ru sites through structural-confinement and charge-redistribution, thereby extending the catalyst lifetime in acid by 10 orders of magnitude longer compared to that of the stoichiometric one (Ru/TiO2). By exploiting the redox interaction-engaged strategy, the in situ growth of TiOx on Ti foam and the loading of Ru nanoparticles are realized in one step. The as-synthesized binder-free Ru/TiOx catalyst exhibits low OER overpotentials of 174 and 265 mV at 10 and 500 mA cm-2, respectively. Experimental characterizations and theoretical calculations confirm that TiOx stabilizes the Ru active center, enabling operation at 10 mA cm-2 for over 37 days. This work opens an avenue of using non-stoichiometric compounds as stable and active materials for energy technologies.

Robust double-network polyvinyl alcohol-polypyrrole hydrogels as high-performance electrodes for flexible supercapacitors.

The growing demands of flexible and wearable electronic devices boost the rapid development of flexible supercapacitors (FSCs). Conductive hydrogels are considered to be one type of promising electrode materials for FSCs due to their good processability and electrochemical properties. However, the poor mechanical properties of conductive hydrogels hinder their practical applications. Building robust cross-linked network structures is a feasible way to enhance their mechanical properties. Herein, the double-network polyvinyl alcohol (PVA)-polypyrrole (PPy) conductive hydrogels are synthesized by the freeze-thaw and in-situ polymerization method. The double-network structure not only enhances mechanical properties of the hydrogels, but also promotes their electrolyte ion transport. The maximum elongation at break of the optimized PVA-PPy hydrogels can reach 156.4%, and the specific capacitance is 1718.7 mF cm-2 at 0.5 mA cm-2. Furthermore, the energy densities of the symmetrical PVA-PPy FSCs are 46.7 and 13.3 µWh cm-2 at power densities of 200.0 and 2000.0 µW cm-2. Such excellent electrochemical performances and mechanical properties make the synthesized PVA-PPy hydrogels a promising candidate for FSCs.

High mass loading and additive-free prussian blue analogue based flexible electrodes for Na-ion supercapacitors.

Supercapacitor electrodes often suffer from the low mass loading of active substances and the unsatisfactory ion/charge transport features due to the use of various additives. Exploring high mass loading and additive-free electrodes is of huge significance to develop advanced supercapacitors with commercial application prospects, which still remains challenging. Herein, high mass loading CoFe-prussian blue analogue (CoFe-PBA) electrodes are developed by a facile co-precipitation method using activated carbon cloth (ACC) as the flexible substrate. The homogeneous nanocube structure, large specific surface area (143.9 m2 g-1) and appropriate pore size distribution (3.4 nm) of the CoFe-PBA endow the as-prepared CoFe-PBA/ACC electrodes with low resistance and appealing ion diffusion characteristics. Typically, the high areal capacitance (1155.0 mF cm-2 at 0.5 mA cm-2) is obtained for high mass loading CoFe-PBA/ACC electrodes (9.7 mg cm-2). Furthermore, symmetrical flexible supercapacitors (FSCs) are constructed using CoFe-PBA/ACC electrodes and Na2SO4/polyving alcohol (Na2SO4/PVA) gel electrolyte, achieving superior stability (85.6% capacitance retention after 5,000 cycles), maximum energy density of 33.8 µWh cm-2 at 200.0 µW cm-2 and promising mechanical flexibility. This work is expected to offer inspirations for the development of high mass loading and additive-free electrodes for FSCs.

Ultrafast charge transfer in mixed-dimensional WO3-x nanowire/WSe2 heterostructures for attomolar-level molecular sensing.

Developing efficient noble-metal-free surface-enhanced Raman scattering (SERS) substrates and unveiling the underlying mechanism is crucial for ultrasensitive molecular sensing. Herein, we report a facile synthesis of mixed-dimensional heterostructures via oxygen plasma treatments of two-dimensional (2D) materials. As a proof-of-concept, 1D/2D WO3-x/WSe2 heterostructures with good controllability and reproducibility are synthesized, in which 1D WO3-x nanowire patterns are laterally arranged along the three-fold symmetric directions of 2D WSe2. The WO3-x/WSe2 heterostructures exhibited high molecular sensitivity, with a limit of detection of 5 × 10-18 M and an enhancement factor of 5.0 × 1011 for methylene blue molecules, even in mixed solutions. We associate the ultrasensitive performance to the efficient charge transfer induced by the unique structures of 1D WO3-x nanowires and the effective interlayer coupling of the heterostructures. We observed a charge transfer timescale of around 1.0 picosecond via ultrafast transient spectroscopy. Our work provides an alternative strategy for the synthesis of 1D nanostructures from 2D materials and offers insights on the role of ultrafast charge transfer mechanisms in plasmon-free SERS-based molecular sensing.

Simultaneous electrical and thermal rectification in a monolayer lateral heterojunction.

Efficient waste heat dissipation has become increasingly challenging as transistor size has decreased to nanometers. As governed by universal Umklapp phonon scattering, the thermal conductivity of semiconductors decreases at higher temperatures and causes heat transfer deterioration under high-power conditions. In this study, we realized simultaneous electrical and thermal rectification (TR) in a monolayer MoSe2-WSe2 lateral heterostructure. The atomically thin MoSe2-WSe2 heterojunction forms an electrical diode with a high ON/OFF ratio up to 104. Meanwhile, a preferred heat dissipation channel was formed from MoSe2 to WSe2 in the ON state of the heterojunction diode at high bias voltage with a TR factor as high as 96%. Higher thermal conductivity was achieved at higher temperatures owing to the TR effect caused by the local temperature gradient. Furthermore, the TR factor could be regulated from maximum to zero by rotating the angle of the monolayer heterojunction interface. This result opens a path for designing novel nanoelectronic devices with enhanced thermal dissipation.

Lateral layered semiconductor multijunctions for novel electronic devices.

Layered semiconductors, represented by transition metal dichalcogenides, have attached extensive attention due to their unique and tunable electrical and optical properties. In particular, lateral layered semiconductor multijunctions, including homojunctions, heterojunctions, hybrid junctions and superlattices, present a totally new degree of freedom in research on electronic devices beyond traditional materials and their structures, providing unique opportunities for the development of new structures and operation principle-based high performance devices. However, the advances in this field are limited by the precise synthesis of high-quality junctions and greatly hampered by ambiguous device performance limits. Herein, we review the recent key breakthroughs in the design, synthesis, electronic structure and property modulation of lateral semiconductor multijunctions and focus on their application-specific devices. Specifically, the synthesis methods based on different principles, such as chemical and external source-induced methods, are introduced stepwise for the controllable fabrication of semiconductor multijunctions as the basics of device application. Subsequently, their structure and property modulation are discussed, including control of their electronic structure, exciton dynamics and optical properties before the fabrication of lateral layered semiconductor multijunction devices. Precise property control will potentially result in outstanding device performances, including high-quality diodes and FETs, scalable logic and analog circuits, highly efficient optoelectronic devices, and unique electrochemical devices. Lastly, we focus on several of the most essential but unresolved debates in this field, such as the true advantages of few-layer vs. monolayer multijunctions, how sharp the interface should be for specific functional devices, and the superiority of lateral multijunctions over vertical multijunctions, highlighting the next-phase strategy to enhance the performance potential of lateral multijunction devices.

Atomic Fe-N4 /C in Flexible Carbon Fiber Membrane as Binder-Free Air Cathode for Zn-Air Batteries with Stable Cycling over 1000 h.

Noble-metal-free, durable, and high-efficiency electrocatalysts for oxygen reduction and evolution reaction (ORR/OER) are vital for rechargeable Zn-air batteries (ZABs). Herein, a flexible and free-standing carbon fiber membrane immobilized with atomically dispersed Fe-N4 /C catalysts (Fe/SNCFs-NH3 ) is synthesized and used as air cathode for ZABs. The intertwined fibers with hierarchical nanopores facilitate the gas transportation, electrolyte infiltration and electron transfer. The large specific surface area exposes a high concentration of Fe-N4 /C sites embedded in the carbon matrix. Modulation of local atomic configurations by sulfur doping in Fe/SNCFs-NH3 catalyst leads to excellent ORR and enhanced OER activities. The as-synthesized Fe/SNCFs-NH3 catalyst demonstrates a positive half-wave potential of 0.89 V and a small Tafel slope of 70.82 mV dec-1 , outperforming the commercial Pt/C (0.86 V/94.74 mV dec-1 ) and most reported M-Nx /C (M = Fe, Co, Ni) catalysts. Experimental characterizations and theoretical calculations uncover the crucial role of S doping in regulating ORR and OER activities. The liquid-state ZABs with Fe/SNCFs-NH3 catalyst as air cathode deliver a large peak power density of 255.84 mW cm-2 and long-term cycle durability over 1000 h. Solid-state ZAB shows stable cycling at various flat/bent/flat states, demonstrating great prospects in flexible electronic device applications.

Mo2C-MoO2 Heterostructure Quantum Dots for Enhanced Electrocatalytic Nitrogen Reduction to Ammonia.

The electrocatalytic nitrogen reduction reaction (NRR) has been regarded as a promising strategy for producing ammonia (NH3) at ambient conditions. However, the development of the NRR is severely hindered by the difficult adsorption and activation of N2 on the catalyst surface and the competitive hydrogen evolution reaction (HER) due to the lack of efficient NRR electrocatalysts. Herein, Mo2C-MoO2 heterostructure quantum dots embedded in reduced graphene oxide (RGO) are proposed as efficient catalysts for the electrocatalytic NRR. The ultrasmall size of the quantum dot is beneficial for exposing the active sites for the NRR, and the synergetic effect of Mo2C and MoO2 can promote N2 adsorption and activation and suppress the competitive HER simultaneously. As a result, a well-balanced NRR performance is achieved with a high NH3 yield rate of 13.94 ± 0.39 µg h-1 mg-1 at -0.15 V vs RHE and a high Faradaic efficiency of 12.72 ± 0.58% at -0.1 V vs RHE. Density functional theory (DFT) calculations reveal that the Mo2C (001) surface has a strong N2 adsorption energy of -1.47 eV with the side-on configuration, and the N≡N bond length is elongated to 1.254 Å, indicating the enhanced N2 adsorption and activation on the Mo2C surface. On the other hand, the low ΔGH* for HER over the MoO2 (-111) surface demonstrates the impeded HER process for MoO2. This work may provide effective catalyst-design strategies for enhancing the electrocatalytic NRR performance of Mo-based materials.

A Highly Sensitive Electrochemical Glucose Sensor Based on Room Temperature Exfoliated Graphite-Derived Film Decorated with Dendritic Copper.

An ultrasensitive enzyme-free glucose sensor was facilely prepared by electrodepositing three-dimensional dendritic Cu on a room temperature exfoliated graphite-derived film (RTEG-F). An excellent electrocatalytic performance was demonstrated for glucose by using Cu/RTEG-F as an electrode. In terms of the high conductivity of RTEG-F and the good catalytic activity of the dendritic Cu structures, the sensor demonstrates high sensitivities of 23.237 mA/mM/cm2, R2 = 0.990, and 10.098 mA/mM/cm2, R2 = 0.999, corresponding to the concentration of glucose ranging from 0.025 mM to 1.0 mM and 1.0 mM to 2.7 mM, respectively, and the detection limit is 0.68 µM. In addition, the Cu/RTEG-F electrode demonstrates excellent anti-interference to interfering species and a high stability. Our work provides a new idea for the preparation of high-performance electrochemical enzyme-free glucose sensor.

Graphitic carbon nitride (g-C3N4) alleviates cadmium-induced phytotoxicity to rice (Oryza sativa L.).

In the present study, graphitic carbon nitride (g-C3N4) was synthesized in a tube furnace and characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), and Fourier transform infrared (FTIR). Different concentrations (0-200 mg/L) of g-C3N4 were prepared in nutrient solution amended with or without 20 mg/L CdCl2 for the greenhouse study. Rice seedlings were exposed to g-C3N4 and Cd for 20 days. Our results suggest that 200 mg/L g-C3N4 significantly increased the fresh weight and root and shoot length as compared with the control, and notably alleviated Cd-induced toxicity. The addition of 200 mg/L g-C3N4 significantly reduced the root and shoot Cd content by approximately 14% and 23%, respectively. In addition, 200 mg/L g-C3N4 significantly elevated the nitrogen content and decreased C/N ration in rice shoots; most importantly, it alleviated Cd-induced nitrogen reduction. Our findings demonstrated the potential of g-C3N4 in regulating plant growth and minimizing the Cd-induced phytotoxicity, and shed light on providing a new strategy to maintain heavy metal contamination in agriculture using a low-cost and environmental friendly NMs.

Ultralight Flexible Electrodes of Nitrogen-Doped Carbon Macrotube Sponges for High-Performance Supercapacitors.

Light-weight and flexible supercapacitors with outstanding electrochemical performances are strongly desired in portable and wearable electronics. Here, ultralight nitrogen-doped carbon macrotube (N-CMT) sponges with 3D interconnected macroporous structures are fabricated and used as substrate to grow nickel ferrite (NiFe2 O4 ) nanoparticles by vapor diffusion-precipitation and in situ growth. This process effectively suppresses the agglomeration of NiFe2 O4 , enabling good interfacial contact between N-CMT sponges and NiFe2 O4 . More remarkably, the as-synthesized NiFe2 O4 /N-CMT composite sponges can be directly used as electrodes without additional processing that could cause agglomeration and reduction of active sites. Benefiting from the tubular structure and the synergetic effect of NiFe2 O4 and N-CMT, the NiFe2 O4 /N-CMT-2 exhibits a high specific capacitance of 715.4 F g-1 at a current density of 1 A g-1 , and 508.3 F g-1 at 10 A g-1 , with 90.9% of capacitance retention after 50 000 cycles at 1 A g-1 in an alkaline electrolyte. Furthermore, flexible supercapacitors are fabricated, yielding areal specific capacitances of 1397.4 and 1041.2 mF cm-2 at 0.5 and 8 mA cm-2 , respectively. They also exhibit exceptional cycling performance with capacitance retention of 92.9% at 1 mA cm-2 after 10 000 cycles under bending. This work paves a new way to develop flexible, light-weight, and high-performance energy storage devices.

Defect Engineering of van der Waals Solids for Electrocatalytic Hydrogen Evolution.

Van der Waals solids with tunable band gaps and interfacial properties have been regarded as a class of promising active materials for electrocatalytic hydrogen evolution reaction (HER). However, due to the anisotropic features, their basal planes are usually electrochemically inert, only a few unsaturated edge atoms could serve as active centers to actuate H2 generation. Hence, material utilization and productivity efficiency are insufficient for practical applications. Recently, diverse defects have been confirmed to enable tailoring atomic configurations and electronic properties of van der Waals solids, thus triggering their superior catalytic activity of in-plane atoms while introducing high amount of new active sites. In this minireview, we summarize the state-of-the-art progress of defect engineering in van der Waals solids for HER, focusing in particular on their advantages in material modification and corresponding catalytic mechanisms. We also propose the challenges and perspectives of these catalytic materials in terms of both experimental synthesis and fundamental understanding of the defect structures.

2020 Roadmap on Carbon Materials for Energy Storage and Conversion.

Carbon is a simple, stable and popular element with many allotropes. The carbon family members include carbon dots, carbon nanotubes, carbon fibers, graphene, graphite, graphdiyne and hard carbon, etc. They can be divided into different dimensions, and their structures can be open and porous. Moreover, it is very interesting to dope them with other elements (metal or non-metal) or hybridize them with other materials to form composites. The elemental and structural characteristics offer us to explore their applications in energy, environment, bioscience, medicine, electronics and others. Among them, energy storage and conversion are extremely attractive, as advances in this area may improve our life quality and environment. Some energy devices will be included herein, such as lithium-ion batteries, lithium sulfur batteries, sodium-ion batteries, potassium-ion batteries, dual ion batteries, electrochemical capacitors, and others. Additionally, carbon-based electrocatalysts are also studied in hydrogen evolution reaction and carbon dioxide reduction reaction. However, there are still many challenges in the design and preparation of electrode and electrocatalytic materials. The research related to carbon materials for energy storage and conversion is extremely active, and this has motivated us to contribute with a roadmap on 'Carbon Materials in Energy Storage and Conversion'.

Pore structure regulation of hard carbon: Towards fast and high-capacity sodium-ion storage.

Hard carbon is regarded as one of the most promising anode material for sodium-ion batteries in virtue of the low cost and stable framework. However, the correlation between pore structures of hard carbon and sodium-ion storage is still ambiguous. In this work, based on precise control of pore-size distribution, the capacity, ion diffusion, and initial Coulombic efficiency were improved. Meanwhile, the relationship between pore structure and capacity was investigated. Our result indicates that the micropores hinder ion diffusion and hardly ever accommodate Na+ ions, while mesopores facilitate Na+ ion intercalation. Hard carbon with negligible micropores and abundant mesopores delivers a maximum capacity of 283.7 mAh g-1 at 20 mA g-1, which is 83% higher than that of micropore-rich one. Even after 320 cycles at 200 mA g-1, the capacity still remains 189.4 mAh g-1.

Na0.76V6O15/Activated Carbon Hybrid Cathode for High-Performance Lithium-Ion Capacitors.

Lithium-ion hybrid capacitors (LICs) are regarded as one of the most promising next generation energy storage devices. Commercial activated carbon materials with low cost and excellent cycling stability are widely used as cathode materials for LICs, however, their low energy density remains a significant challenge for the practical applications of LICs. Herein, Na0.76V6O15 nanobelts (NaVO) were prepared and combined with commercial activated carbon YP50D to form hybrid cathode materials. Credit to the synergism of its capacitive effect and diffusion-controlled faradaic effect, NaVO/C hybrid cathode displays both superior cyclability and enhanced capacity. LICs were assembled with the as-prepared NaVO/C hybrid cathode and artificial graphite anode which was pre-lithiated. Furthermore, 10-NaVO/C//AG LIC delivers a high energy density of 118.9 Wh kg-1 at a power density of 220.6 W kg-1 and retains 43.7 Wh kg-1 even at a high power density of 21,793.0 W kg-1. The LIC can also maintain long-term cycling stability with capacitance retention of approximately 70% after 5000 cycles at 1 A g-1. Accordingly, hybrid cathodes composed of commercial activated carbon and a small amount of high energy battery-type materials are expected to be a candidate for low-cost advanced LICs with both high energy density and power density.

Advanced Materials for Sodium-Ion Capacitors with Superior Energy-Power Properties: Progress and Perspectives.

Developing electrochemical energy storage devices with high energy-power densities, long cycling life, as well as low cost is of great significance. Sodium-ion capacitors (NICs), with Na+ as carriers, are composed of a high capacity battery-type electrode and a high rate capacitive electrode. However, unlike their lithium-ion analogues, the research on NICs is still in its infancy. Rational material designs still need to be developed to meet the increasing requirements for NICs with superior energy-power performance and low cost. In the past few years, various materials have been explored to develop NICs with the merits of superior electrochemical performance, low cost, good stability, and environmental friendliness. Here, the material design strategies for sodium-ion capacitors are summarized, with focus on cathode materials, anode materials, and electrolytes. The challenges and opportunities ahead for the future research on materials for NICs are also proposed.

Electrochemically triggered degradation of silicon membranes for smart on-demand transient electronic devices.

Transient electronics is an emerging technology that enables unique functional transformation or the physical disappearance of electronic devices, and is attracting increasing attention for potential applications in data secured hardware as an ultimate solution against data breaches. Developing smart triggered degradation modalities of silicon (Si) remain the key challenge to achieve advanced non-recoverable on-demand transient electronics. Here, we present a novel electrochemically triggered transience mechanism of Si by lithiation, allowing complete and controllable destruction of Si devices. The depth and microstructure of the lithiation-affected zone over time is investigated in detail and the results suggest a few hours of lithiation is sufficient to create microcracks and significantly promote lithium penetration. Finite element models are proposed to confirm the mechanism. Electrochemically triggered degradation of thin film Si ribbons and Si integrated circuit chips with metal-oxide-semiconductor field-effect transistors from a commercial 0.35 micrometer complementary metal-oxide-semiconductor technology node is performed to demonstrate the potential applications for commercial electronics. This work opens new opportunities for versatile triggered transience of Si-based devices for critical secured information systems and green consumer electronics.

Sulfur-Doped Reduced Graphene Oxide for Enhanced Sodium Ion Pseudocapacitance.

Sodium-ion capacitors (NICs) are considered an important candidate for large-scale energy storage in virtue of their superior energy-power properties, as well as availability of rich Na+ reserves. To fabricate high-performance NIC electrode material, a hydrothermal method was proposed to synthesize sulfur-doped reduced graphene oxide (SG), which exhibited unique layered structures and showed excellent electrochemical properties with 116 F/g capacitance at 1 A/g as the cathode of NICs from 1.6 V to 4.2 V. At the power-energy density over 5000 W/kg, the SG demonstrated over 100 Wh/kg energy density after 3500 cycles, which indicated its efficient durability and superior power-energy properties. The addition of a sulfur source in the hydrothermal process led to the higher specific surface area and more abundant micropores of SG when compared with those of reduced graphene oxide (rGO), thus SG exhibited much better electrochemical properties than those shown by rGO. Partially substituting surface oxygen-containing groups of rGO with sulfur-containing groups also facilitated the enhanced sodium-ion storage ability of SG by introducing sufficient pseudocapacitance.