X-Ray Spectromicroscopy Investigation of Heterogeneous Sodiation in Hard Carbon Nanosheets with Vertically Oriented (002) Planes.

Hard carbon (HC) is a promising anode material for sodium-ion batteries, but the performance remains unsatisfactory and the sodiation mechanism in HC is one of the most debated topics. Here, from self-assembled cellulose nanocrystal sheets with crystallographic texture, unique HC nanosheets with vertically oriented (002) planes are fabricated and used as a model HC to investigate the sodiation mechanisms using synchrotron scanning transmission X-ray microscopy (STXM) coupled with analytical transmission electron microscopy (TEM). The model HC simplifies the 3D sodiation in a typical HC particle into a 2D sodiation, which facilitates the visualization of phase transformation at different states of charge. The results for the first time unveil that the sodiation in HC initiates heterogeneously, with multiple propagation fronts proceeding simultaneously, eventually merging into larger aggregates. The spatial correlation between the preferential adsorption and nucleation sites suggests that the heterogeneous nucleation is driven by the local Na-ion concentration, which is determined by defects or heteroatoms that have strong binding to Na ions. By identifying intercalation as the dominant sodium storage mechanism in the model HC, the findings highlight the importance of engineering the graphene layer orientation and the structural heterogeneity of edge sites to enhance the performances.

Nano-RuO2 -Decorated Holey Graphene Composite Fibers for Micro-Supercapacitors with Ultrahigh Energy Density.

Compactness and versatility of fiber-based micro-supercapacitors (FMSCs) make them promising for emerging wearable electronic devices as energy storage solutions. But, increasing the energy storage capacity of microscale fiber electrodes, while retaining their high power density, remains a significant challenge. Here, this issue is addressed by incorporating ultrahigh mass loading of ruthenium oxide (RuO2 ) nanoparticles (up to 42.5 wt%) uniformly on nanocarbon-based microfibers composed largely of holey reduced graphene oxide (HrGO) with a lower amount of single-walled carbon nanotubes as nanospacers. This facile approach involes (1) space-confined hydrothermal assembly of highly porous but 3D interconnected carbon structure, (2) impregnating wet carbon structures with aqueous Ru3+ ions, and (3) anchoring RuO2 nanoparticles on HrGO surfaces. Solid-state FMSCs assembled using those fibers demonstrate a specific volumetric capacitance of 199 F cm-3 at 2 mV s-1 . Fabricated FMSCs also deliver an ultrahigh energy density of 27.3 mWh cm-3 , the highest among those reported for FMSCs to date. Furthermore, integrating 20 pieces of FMSCs with two commercial flexible solar cells as a self-powering energy system, a light-emitting diode panel can be lit up stably. The current work highlights the excellent potential of nano-RuO2 -decorated HrGO composite fibers for constructing micro-supercapacitors with high energy density for wearable electronic devices.

Nickel hydroxide-carbon nanotube nanocomposites as supercapacitor electrodes: crystallinity dependent performances.

Nickel hydroxide (Ni(OH)2) is a promising pseudocapacitive material to increase the energy storage capacity of supercapacitors. Ni(OH)2 has three common crystalline structures: amorphous (amor-), α-, and ß-Ni(OH)2. There is a lack of good understanding on their pros and cons as supercapacitor electrodes. In this work, we synthesized three nanocomposites with thin layers (10-15 nm) of amor-, α-, and ß-Ni(OH)2 deposited on conductive multi-walled carbon nanotubes (MWCNTs). The mass loading of Ni(OH)2 is analogous in these nanocomposites, ranging from 49.1-52.2 wt% with a comparable narrow-pore size distribution centered around 4-5 nm. They were fabricated into supercapacitor electrodes at a mass loading of 6 mg cm(-2) with a thickness of ∼250 µm, similar to the electrodes used in commercial supercapacitors. Our results show that MWCNT/amor-Ni(OH)2 has the highest specific capacitance (1495 or 2984 F g(-1), based on the mass of total active materials or Ni(OH)2 only at the scan rate of 5 mV s(-1) in 1 M KOH electrolyte). It also has the best rate capability among the three nanocomposites. Better performances can be attributed to its disordered structure, which increases its effective surface area and reduces diffusion resistance for redox reactions. However, superior performances gradually deteriorate to the same level as that of MWCNT/ß-Ni(OH)2 over 3000 charge/discharge cycles, because amor- and α-Ni(OH)2 transform slowly to more ordered ß-Ni(OH)2. Our results highlight that the electrochemical performances of MWCNT/Ni(OH)2 nanocomposites depend on the crystallinity of Ni(OH)2, and the performances of electrodes change upon the crystalline structure transformation of Ni(OH)2 under repeated redox reactions. Future research should focus on improving the structure stability of amor-Ni(OH)2.

Self-repairing interphase reconstructed in each cycle for highly reversible aqueous zinc batteries.

Aqueous zinc (Zn) chemistry features intrinsic safety, but suffers from severe irreversibility, as exemplified by low Coulombic efficiency, sustained water consumption and dendrite growth, which hampers practical applications of rechargeable Zn batteries. Herein, we report a highly reversible aqueous Zn battery in which the graphitic carbon nitride quantum dots additive serves as fast colloid ion carriers and assists the construction of a dynamic & self-repairing protective interphase. This real-time assembled interphase enables an ion-sieving effect and is found actively regenerate in each battery cycle, in effect endowing the system with single Zn2+ conduction and constant conformal integrality, executing timely adaption of Zn deposition, thus retaining sustainable long-term protective effect. In consequence, dendrite-free Zn plating/stripping at ~99.6% Coulombic efficiency for 200 cycles, steady charge-discharge for 1200 h, and impressive cyclability (61.2% retention for 500 cycles in a Zn | |MnO2 full battery, 73.2% retention for 500 cycles in a Zn | |V2O5 full battery and 93.5% retention for 3000 cycles in a Zn | |VOPO4 full battery) are achieved, which defines a general pathway to challenge Lithium in all low-cost, large-scale applications.

Tremella-like Mo and N Codoped Graphitic Nanosheets by In Situ Carbonization of Phthalocyanine for Potassium-Ion Battery.

A tremella-like Mo and N codoped graphitic nanosheet array supported on activated carbon (Mo2C-MoC/AC-N) is prepared via in situ carbonization of nitrogen-rich cobalt phthalocyanine nanoparticulates anchored on activated carbon as a high-performance anode for potassium-ion batteries. The nanosheets about 5 nm thick are uniformly distributed on the surface of activated carbon for fast K-ion intercalation, and the abundant micropores in activated carbon provide additional adsorption sites of potassium ions, forming a three-dimensional architecture for potassium storage. The 3.9 atom % Mo in Mo2C-MoC/AC-N is in the form of Mo2C and MoC flakes (around 1:1) attached to the graphitic nanosheets. X-ray diffraction (XRD) analysis revealed that the reaction with Mo2C (forming K2C) happens mainly at 0.8-0.4 V, while the reaction with MoC (forming K2C) occurs primarily at 0.4-0.01 V. The N doping (9.6 atom %) causes an interlayer spacing expansion of 0.3 Å in the graphitic nanosheets, beneficial to the potassium-ion insertion reaction to form KC8 at 0.4-0.01 V. The Mo2C-MoC/AC-N anode exhibits a capacity of 457.5 mA h g-1 at a current density of 0.05 A g-1 and an excellent capacity of 144.4 mA h g-1 at a high current of 5 A g-1 with a capacity loss rate of 0.49‰ per cycle.

1D Supercapacitors for Emerging Electronics: Current Status and Future Directions.

1D supercapacitors (SCs) have emerged as promising candidates to power emerging electronics in recent years because of their unique advantages in energy storage and mechanical flexibility. There are four main research fronts in the development of 1D SCs: 1) enhancing mechanical characteristics, 2) achieving superior electrochemical performance, 3) enabling multiple device integration, and 4) demonstrating multifunctionality. Here, a brief history of 1D SCs is presented and significant research achievements regarding the four fronts identified as the main pillars of the development of 1D SCs are highlighted. The current challenges of the fabrication and utilization of 1D SCs are critically examined and potential solutions are analyzed. Plus, the performance inconsistencies arising from the improper use and extreme diversity of performance evaluation and reporting methods are highlighted. Beyond, perspectives on future efforts are provided and goals regarding the four research fronts are set, to further push 1D SCs toward practical applications. The development of 1D SCs is summarized here, with existing obstacles diagnosed, corresponding solutions proposed, and future directions indicated accordingly.

Biomass-derived nanocarbon materials for biological applications: challenges and prospects.

Biomass-derived nanocarbons (BNCs) have attracted significant research interests due to their promising economic and environmental benefits. Following their extensive uses in physical and chemical research domains, BNCs are now growing in biological applications. However, their practical biological applications are still in their infancy, requiring critical evaluations and strategic directions, which are provided in this review. The carbonization of biomass sources and major types of BNCs are introduced, encompassing carbon nanodots, nanofibres, nanotubes, and graphenes. Next, essential biological uses of BNCs, antibacterial/antibiofilm materials (nanofibres and nanodots) and bioimaging agents (predominantly nanodots), are summarized. Furthermore, the future potential of BNCs, for designing wound dressing/healing materials, water and air disinfection platforms, and microbial electrochemical systems, is discussed. We reach the conclusion that a crucial challenge is the structural control of BNCs. Furthermore, a key knowledge gap for realizing practical biological applications is the lack of systematic comparisons of BNCs with nanocarbons of synthetic origin in the current literature. Although we did not attempt to perform an exhaustive literature survey, the evaluation of the existing results indicates that BNCs are promising as easily accessible materials for various biomedically and environmentally relevant applications.

Zinc-Air Battery-Based Desalination Device.

Efficiently storing electricity generated from renewable resources and desalinating brackish water are both critical for realizing a sustainable society. Previously reported desalination batteries need to work in alternate desalination/salination modes and also require external energy inputs during desalination. Here, we demonstrate a novel zinc-air battery-based desalination device (ZABD), which can desalinate brackish water and supply energy simultaneously. The ZABD consists of a zinc anode with a flowing ZnCl2 anolyte stream, a brackish water stream, and an air cathode with a flowing NaCl catholyte stream, separated by an anion-exchange membrane and a cation-exchange membrane, respectively. During the discharging, ions in brackish water move to the anolyte and catholyte, and they return to the feed steam during charging. The ZABD can desalt brackish water from 3000 ppm to the drinking water level at 120.1 ppm in one step and concurrently provide an energy output up to 80.1 kJ mol-1 under a discharge current density of 0.25 mA cm-2. Further, the ZABD can be charged/discharged over 20 cycles without significant performance deterioration, demonstrating its reversibility. Moreover, the desalination performances can be adjusted by varying current densities and are also influenced by the initial concentration of salt feeds. Besides, two ZABD devices were connected in series to drive 60 light-emitting diodes during the salt removal process without external power supply over 2000 min. Overall, this ZABD system demonstrates the potential for simultaneous water desalination and energy supply, which is suitable for many urgent situations.

A hierarchically porous nickel-copper phosphide nano-foam for efficient electrochemical splitting of water.

Electrochemical splitting of water to produce oxygen (O2) and hydrogen (H2) through a cathodic hydrogen evolution reaction (HER) and an anodic oxygen evolution reaction (OER) is a promising green approach for sustainable energy supply. Here we demonstrated a porous nickel-copper phosphide (NiCuP) nano-foam as a bifunctional electrocatalyst for highly efficient total water splitting. Prepared from a bubble-templated electrodeposition method and subsequent low-temperature phosphidization, NiCuP has a hierarchical pore structure with a large electrochemical active surface area. To reach a high current density of 50 mA cm-2, it requires merely 146 and 300 mV with small Tafel slopes of 47 and 49 mV dec-1 for HER and OER, respectively. The total water splitting test using NiCuP as both the anode and cathode showed nearly 100% Faradic efficiency and surpassed the performances of electrode pairs using commercial Pt/C and IrO2 catalysts under our test conditions. The high activity of NiCuP can be attributed to (1) the conductive NiCu substrates, (2) a large electrochemically active surface area together with a combination of pores of different sizes, and (3) the formation of active Ni/Cu oxides/hydroxides while keeping a portion of more conductive Ni/Cu phosphides in the nano-foam. We expect the current catalyst to enable the manufacturing of affordable water splitting systems.

Amorphous Bimetallic Oxide-Graphene Hybrids as Bifunctional Oxygen Electrocatalysts for Rechargeable Zn-Air Batteries.

Metal oxides of earth-abundant elements are promising electrocatalysts to overcome the sluggish oxygen evolution and oxygen reduction reaction (OER/ORR) in many electrochemical energy-conversion devices. However, it is difficult to control their catalytic activity precisely. Here, a general three-stage synthesis strategy is described to produce a family of hybrid materials comprising amorphous bimetallic oxide nanoparticles anchored on N-doped reduced graphene oxide with simultaneous control of nanoparticle elemental composition, size, and crystallinity. Amorphous Fe0.5 Co0.5 Ox is obtained from Prussian blue analog nanocrystals, showing excellent OER activity with a Tafel slope of 30.1 mV dec-1 and an overpotential of 257 mV for 10 mA cm-2 and superior ORR activity with a large limiting current density of -5.25 mA cm-2 at 0.6 V. A fabricated Zn-air battery delivers a specific capacity of 756 mA h gZn-1 (corresponding to an energy density of 904 W h kgZn-1 ), a peak power density of 86 mW cm-2 and can be cycled over 120 h at 10 mA cm-2 . Other two amorphous bimetallic, Ni0.4 Fe0.6 Ox and Ni0.33 Co0.67 Ox , are also produced to demonstrate the general applicability of this method for synthesizing binary metal oxides with controllable structures as electrocatalysts for energy conversion.

"Smart poisoning" of Co/SiO2 catalysts by sulfidation for chirality-selective synthesis of (9,8) single-walled carbon nanotubes.

The chirality-selective synthesis of relatively large (diameter > 1 nm) single-walled carbon nanotubes (SWCNTs) is of great interest for a variety of practical applications, but only a few catalysts are available so far. Previous studies suggested that S (compounds) can enhance the chirality-selectivity of Co catalysts in SWCNT synthesis, however, the mechanism behind is not fully understood, and no tailorable methodology has yet been developed. Here, we demonstrate a facile approach to achieve the chirality-selective synthesis of SWCNTs by the sulfidation-based poisoning of silica-supported Co catalysts using a mixture of H2S and H2. The UV-vis-NIR, photoluminescence, and Raman spectroscopy results together show that the resulting SWCNTs have a narrow diameter distribution of around 1.2 nm, and (9,8) nanotubes have an abundance of ∼38% among the semiconducting species. More importantly, the carbon yield achieved by the sulfided catalyst (2.5 wt%) is similar to that of the nonsulfided one (2.7 wt%). The characterization of the catalysts by X-ray diffraction, X-ray photoelectron spectroscopy, X-ray fluorescence, and H2 temperature-programmed reduction shows that the sulfidation leads to the formation of Co9S8 nanoparticles. However, Co9S8 nanoparticles are reduced back to regenerate metallic Co nanoparticles during the synthesis of SWCNTs, which maintain a high carbon yield. In this process, Co9S8 nanoparticles seemingly intermediate the production of Co nanoparticles with narrow size distribution. Due to the fact that the poisoning step improves the quality of the end-product rather than hampering the growth process, we have coined the process developed as "smart poisoning". This study not only reveals the mechanism behind the beneficial role of S in the selective synthesis of relatively large SWCNTs but also presents a promising method to create chirality-selective catalysts with high activity for scalable synthesis.

Sandwich-Architectured Poly(lactic acid)-Graphene Composite Food Packaging Films.

Biodegradable food packaging promises a more sustainable future. Among the many different biopolymers used, poly(lactic acid) (PLA) possesses the good mechanical property and cost-effectiveness necessary of a biodegradable food packaging. However, PLA food packaging suffers from poor water vapor and oxygen barrier properties compared to many petroleum-derived ones. A key challenge is, therefore, to simultaneously enhance both the water vapor and oxygen barrier properties of the PLA food packaging. To address this issue, we design a sandwich-architectured PLA-graphene composite film, which utilizes an impermeable reduced graphene oxide (rGO) as the core barrier and commercial PLA films as the outer protective encapsulation. The synergy between the barrier and the protective encapsulation results in a significant 87.6% reduction in the water vapor permeability. At the same time, the oxygen permeability is reduced by two orders of magnitude when evaluated under both dry and humid conditions. The excellent barrier properties can be attributed to the compact lamellar microstructure and the hydrophobicity of the rGO core barrier. Mechanistic analysis shows that the large rGO lateral dimension and the small interlayer spacing between the rGO sheets have created an extensive and tortuous diffusion pathway, which is up to 1450-times the thickness of the rGO barrier. In addition, the sandwiched architecture has imbued the PLA-rGO composite film with good processability, which increases the manageability of the film and its competency to be tailored. Simulations using the PLA-rGO composite food packaging film for edible oil and potato chips also exhibit at least eight-fold extension in the shelf life of these oxygen and moisture sensitive food products. Overall, these qualities have demonstrated the high potential of a sandwich-architectured PLA-graphene composite film for food packaging applications.

Transforming Pristine Carbon Fiber Tows into High Performance Solid-State Fiber Supercapacitors.

A facile activation strategy can transform pristine carbon fiber tows into high-performance fiber electrodes with a specific capacitance of 14.2 F cm(-3) . The knottable fiber supercapacitor shows an energy density of 0.35 mW h cm(-3) , an ultrahigh power density of 3000 mW cm(-3) , and a remarkable capacitance retention of 68%, when the scan rate increases from 10 to 1000 mV s(-1) .