A Novel High-Performance TiO2-x /TiO1-y Ny Coating Material for Silicon Anode in Lithium-Ion Batteries.

Protective surface coatings on Si anodes are promising for improving the electrochemical performance of lithium-ion batteries (LIBs). Nevertheless, most coating materials have severe issues, including low initial coulombic efficiency, structural fracture, morphology control, and complicated synthetic processing. In this study, a multifunctional TiO2- x /TiO1- y Ny (TTN) formed via a facile and scalable synthetic process is applied as a coating material for Si anodes. A thin layer of amorphous TiO2 is uniformly coated onto Si nanoparticles by a simple sol-gel method and then converted into a two phase TiO2- x /TiO1- y Ny via nitridation. The lithiated TiO2-x provides high ionic and electrical conductivity, while TiO1-y Ny can improve mechanical strength that alleviates volume change of Si to address capacity fading issue. Owing to these synergetic advantages, TiO2- x /TiO1- y Ny -coated Si (Si@TTN) exhibits excellent electrochemical properties, including a high charge capacity of 1650 mA h g-1 at 0.1 A g-1 and 84% capacity retention after 100 cycles at 1 A g-1 . Moreover, a significantly enhanced rate performance can be achieved at a high current density. This investigation presents a facile and effective coating material to use as the high-capacity silicon anode in the emerging Si anode technology in LIBs.

Achieving Cycling Stability in Anode of Lithium-Ion Batteries with Silicon-Embedded Titanium Oxynitride Microsphere.

Surface coating approaches for silicon (Si) have demonstrated potential for use as anodes in lithium-ion batteries (LIBs) to address the large volume change and low conductivity of Si. However, the practical application of these approaches remains a challenge because they do not effectively accommodate the pulverization of Si during cycling or require complex processes. Herein, Si-embedded titanium oxynitride (Si-TiON) was proposed and successfully fabricated using a spray-drying process. TiON can be uniformly coated on the Si surface via self-assembly, which can enhance the Si utilization and electrode stability. This is because TiON exhibits high mechanical strength and electrical conductivity, allowing it to act as a rigid and electrically conductive matrix. As a result, the Si-TiON electrodes delivered an initial reversible capacity of 1663 mA h g-1 with remarkably enhanced capacity retention and rate performance.

A Strategic Approach to Use Upcycled Si Nanomaterials for Stable Operation of Lithium-Ion Batteries.

Silicon, as a promising next-generation anode material, has drawn special attention from industries due to its high theoretical capacity (around 3600 mAh g-1) in comparison with conventional electrodes, e.g., graphite. However, the fast capacity fading resulted by a large volume change hinders the pragmatic use of Si anodes for lithium ion batteries. In this work, we propose an efficient strategy to improve the cyclability of upcycled Si nanomaterials through a simple battery operation protocol. When the utilization degree of Si electrodes was decreased, the electrode deformation was significantly alleviated. This directly led to an excellent electrochemical performance over 100 cycles. In addition, the average charge (delithation) voltage was shifted to a lower voltage, when the utilization degree of electrodes was controlled. These results demonstrated that our strategic approach would be an effective way to enhance the electrochemical performance of Si anodes and improve the cost-effectiveness of scaling-up the decent nanostructured Si material.

Microscopic evidence of strong interactions between chemical vapor deposited 2D MoS2 film and SiO2 growth template.

Two-dimensional MoS2 film can grow on oxide substrates including Al2O3 and SiO2. However, it cannot grow usually on non-oxide substrates such as a bare Si wafer using chemical vapor deposition. To address this issue, we prepared as-synthesized and transferred MoS2 (AS-MoS2 and TR-MoS2) films on SiO2/Si substrates and studied the effect of the SiO2 layer on the atomic and electronic structure of the MoS2 films using spherical aberration-corrected scanning transition electron microscopy (STEM) and electron energy loss spectroscopy (EELS). The interlayer distance between MoS2 layers film showed a change at the AS-MoS2/SiO2 interface, which is attributed to the formation of S-O chemical bonding at the interface, whereas the TR-MoS2/SiO2 interface showed only van der Waals interactions. Through STEM and EELS studies, we confirmed that there exists a bonding state in addition to the van der Waals force, which is the dominant interaction between MoS2 and SiO2. The formation of S-O bonding at the AS-MoS2/SiO2 interface layer suggests that the sulfur atoms at the termination layer in the MoS2 films are bonded to the oxygen atoms of the SiO2 layer during chemical vapor deposition. Our results indicate that the S-O bonding feature promotes the growth of MoS2 thin films on oxide growth templates.

Correction: Suppression of metal-to-insulator transition using strong interfacial coupling at cubic and orthorhombic perovskite oxide heterointerfaces.

Correction for 'Suppression of metal-to-insulator transition using strong interfacial coupling at cubic and orthorhombic perovskite oxide heterointerfaces' by Woonbae Sohn et al., Nanoscale, 2021, 13, 708-715, DOI: 10.1039/D0NR07545K.

Suppression of metal-to-insulator transition using strong interfacial coupling at cubic and orthorhombic perovskite oxide heterointerfaces.

A quasi-two-dimensional electron gas (2DEG) evolved at the LaAlO3 (LAO)/SrTiO3 (STO) interface has attracted significant attention, because the insertion of perovskite titanates can tune the 2DEG conductivity. However, this depends on the Ti-O-Ti bonding angle and structural symmetry. In this study, we controlled the octahedral tilt of the LAO/CaTiO3 (CTO) interface by heterostructuring it with CTO grown on STO substrates of various thicknesses. The 2DEG was maintained when the thickness of CTO was below the critical thickness of 5 unit cells (uc); however, it was suppressed when the CTO thickness was above the critical thickness. High-angle annular dark-field (HAADF) scanning transmission electron microscopy (STEM) combined with integrated differential phase contrast (iDPC) STEM imaging was used to visualize the TiO6 octahedral tilt propagation and symmetry of the 5 uc and 24 uc CTO films. The symmetry of the 5 uc CTO film resembled that of the STO substrate, whereas the octahedral tilt propagated in the 24 uc CTO film due to the structural relaxation. These results show that the interface engineering of the octahedral tilt can enable or suppress the formation of the 2DEG in perovskite oxides.

Silver grass-derived activated carbon with coexisting micro-, meso- and macropores as excellent bioanodes for microbial colonization and power generation in sustainable microbial fuel cells.

In this study, highly biocompatible three-dimensional hierarchically porous activated carbon from the low-cost silver grass (Miscanthus sacchariflorus) has been fabricated through a facile carbonization approach and tested it as bioanode in microbial fuel cell (MFC) using Escherichia coli as biocatalyst. This silver grass-derived activated carbon (SGAC) exhibited an unprecedented specific surface area of 3027 m2 g-1 with the coexistence of several micro-, meso-, and macropores. The synergistic effect from pore structure (macropores - hosting E. coli to form biofilm and facilitates internal mass transfer; mesopores - favors fast electron transfer; and micropores - promotes nutrient transport to the biofilm) with very high surface area facilitates excellent extracellular electron transfer (EET) between the anode and biofilm which resulted in higher power output of 963 mW cm-2. Based on superior biocompatibility, low cost, environment-friendliness, and facile fabrication, the proposed SGAC bioanode could have a great potential for high-performance and cost-effective sustainable MFCs.

An ionic liquid incorporated in a quasi-solid-state electrolyte for high-temperature supercapacitor applications.

An ionic liquid (IL) incorporated in a quasi-solid-state electrolyte (ILQSE) is prepared using 1-ethyl-3-methylimidazolium tetrafluoroborate (EMIBF4) and poly (ethylene glycol dimethacrylayte) (PEGDMA) for high-temperature application of supercapacitors. The prepared ILQSE displays a thermal stability up to 150 °C and the supercapacitors exhibit a specific capacitance of 134 F g-1.

Magnéli Phase Titanium Oxide as a Novel Anode Material for Potassium-Ion Batteries.

Recently, K-ion batteries (KIBs) have attracted attention for potential applications in next-generation energy storage devices principally on the account of their abundancy and lower cost. Herein, for the first time, we report an anatase TiO2-derived Magnéli phase Ti6O11 as a novel anode material for KIBs. We incorporate pristine carbon nanotube (CNT) on the TiO2 host materials due to the low electronic conductivity of the host materials. TiO2 transformed to Magnéli phase Ti6O11 after the first insertion/deinsertion of K ions. From the second cycle, Magnéli phase Ti6O11/CNT composite showed reversible charge/discharge profiles with ∼150 mA h g-1 at 0.05 A g-1. Ex situ X-ray diffraction and transmission electron microscopy analyses revealed that the charge storage process of Magnéli phase Ti6O11 proceeded via the conversion reaction during potassium ion insertion/deinsertion. The Magnéli phase Ti6O11/CNT composite electrode showed long-term cycling life over 500 cycles at 200 mA g-1, exhibiting a capacity retention of 76% and a high Coulombic efficiency of 99.9%. These salient results presented here provide a novel understanding of the K-ion storage mechanisms in the extensively investigated oxide-based material for Li-ion batteries and Na-ion batteries, shedding light on the development of promising electrode materials for next-generation batteries.

The effect of ILs as co-salts in electrolytes for high voltage supercapacitors.

Ionic liquids (ILs) which have electrical stability are attractive materials to enhance the potential window of electrolyte. According to the potential window is extended, available voltage for supercapacitor is broaden. In this study, the addition of ILs which is 1-ethyl-3-methylimidazolium tetrafluoroborate (EMIBF4) and 1-ethyl-3-methylimidazolium bis(trifluoromethylesulfonyl) imide (EMITFSI) as co-salts, to a supercapacitor electrolyte increases the ionic conductivity and stability of it due to inhibition of electrolyte decomposition. As a result, the electrochemical stability potential windows (ESPWs) of supercapacitor is improved and the supercapacitor exhibited increased cycling stability. The loss of specific capacitance upon addition of 7 wt% EMIBF4 or EMITFSI to the electrolyte was 2.5% and 8.7%, respectively, after 10,000 cycles at 3.5 V, compared to the specific capacitance of the initial discharge.

Improved pseudocapacitive charge storage in highly ordered mesoporous TiO2/carbon nanocomposites as high-performance Li-ion hybrid supercapacitor anodes.

A Li-ion hybrid supercapacitor (Li-HSCs), an integrated system of a Li-ion battery and a supercapacitor, is an important energy-storage device because of its outstanding energy and power as well as long-term cycle life. In this work, we propose an attractive material (a mesoporous anatase titanium dioxide/carbon hybrid material, m-TiO2-C) as a rapid and stable Li+ storage anode material for Li-HSCs. m-TiO2-C exhibits high specific capacity (∼198 mA h g-1 at 0.05 A g-1) and promising rate performance (∼90 mA h g-1 at 5 A g-1) with stable cyclability, resulting from the well-designed porous structure with nanocrystalline anatase TiO2 and conductive carbon. Thereby, it is demonstrated that a Li-HSC system using a m-TiO2-C anode provides high energy and power (∼63 W h kg-1, and ∼4044 W kg-1).

Lithium-Sulfur Capacitors.

Although many existing hybrid energy storage systems demonstrate promising electrochemical performances, imbalances between the energies and kinetics of the two electrodes must be resolved to allow their widespread commercialization. As such, the development of a new class of energy storage systems is a particular challenge, since future systems will require a single device to provide both a high gravimetric energy and a high power density. In this context, we herein report the design of novel lithium-sulfur capacitors. The resulting asymmetric systems exhibited energy densities of 23.9-236.4 Wh kg-1 and power densities of 72.2-4097.3 W kg-1, which are the highest reported values for an asymmetric system to date. This approach involved the use of a prelithiated anode and a hybrid cathode material exhibiting anion adsorption-desorption in addition to the electrochemical reduction and oxidation of sulfur at almost identical rates. This novel strategy yielded both high energy and power densities, and therefore establishes a new benchmark for hybrid systems.

A new general approach to synthesizing filled and yolk-shell structured metal oxide microspheres by applying a carbonaceous template.

New mechanisms were found for the formation of metal oxide microspheres with yolk-shell and filled structures by applying carbonaceous template microspheres with high porosity. Repeated impregnation first adopted to achieve a high loading rate of metal precursor in the carbonaceous template provided the breakthrough. The carbonaceous template with an appropriate loading rate of the metal precursor produced metal oxide microspheres with filled and yolk-shell structure depending on the ramping rate and oxygen concentration during the post-treatment process. Combustion of the carbonaceous template-which occurs during the moderate post-treatment process in air with a high oxygen concentration-must occur to form yolk-shell structured microspheres. On the other hand, the decomposition of carbon by post-treatment at a slow ramping rate in an atmosphere with a low oxygen concentration without burning produced filled-structured metal oxide microspheres. The carbonaceous template with a high loading rate of the metal precursor produced metal oxide microspheres with filled structures even at a fast ramping rate and high oxygen concentration during the post-treatment process. The new strategy was applied to synthesize various metal oxide microspheres including SnO2, Fe2O3, NiO, and Mn2O3 microspheres.

Multimodal porous carbon derived from ionic liquids: correlation between pore sizes and ionic clusters.

In this proof of concept study on the synthesis of ionic liquid (IL)-derived multimodal porous carbon using ionic clusters of different sizes as porogens, the carbonization behaviors of binary IL mixtures of 1-ethyl-3-methylimidazolium dicyanamide (EMIM-dca) and 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (EMIM-Tf2N) were systematically investigated to demonstrate the formation of multimodal porous carbons with hierarchical structures originating from the ionic cluster porogens. The multimodal porous structures of the resulting IL-derived porous carbons were characterized based on the quenched solid density functional theory, and the role of the ionic clusters as porogens is discussed. From the viewpoint of green and sustainable chemistry, the IL-based synthesis using ionic clusters as porogens is a simple, effective, and sustainable technique for synthesizing multimodal porous carbons with hierarchical structures. To the best of our knowledge, this is the first study demonstrating that a multimodal porous structure of IL-derived porous carbons could be systematically manipulated with the aid of ionic clusters of different sizes as porogens.

Multi-functionalized herringbone carbon nanofiber for anodes of lithium ion batteries.

Herringbone carbon nanofibers (HCNFs) are prepared for use as anode materials in lithium-ion batteries (LIBs). HCNFs are prepared using a Ni-Fe catalyst and subsequently multi-functionalized with oxygen using the Hummers' method, and then with both oxygen and nitrogen-containing 2-ureido-4[1H]pyrimidinone (UHP) moieties, which endow the HCNFs with the ability to form quadruple hydrogen bonds (QHBs). The as-prepared HCNFs are, on average, 13 µm in length and 100 nm in diameter, with a highly graphitic structure. The oxidized HCNFs (Ox-HCNFs) obtained by Hummers' method are partially exfoliated, having double-bladed saw-like structures that extend in the direction of the graphite planes. QHBs are formed between the HCNFs after functionalization with the UHP moieties. The final surface-modified HCNFs (N-Ox-HCNFs) have more electrochemical sites, shorter Li+ diffusion lengths, and additional electron pathways compared with the as-prepared HCNF and Ox-HCNF. The introduction of oxygen- and nitrogen-containing functional groups improves the performance of LIBs: a high charge capacity of 763 mA h g-1 at 0.1 A g-1, excellent rate capability (a capacity of 402 mA h g-1 at 3 A g-1), and near 100% capacity retention after 300 cycles are reported.

A study of the effects of synthesis conditions on Li5FeO4/carbon nanotube composites.

Li5FeO4/carbon nanotube (LFO/CNT) composites composed of sub-micron sized LFO and a nanocarbon with high electrical conductivity were successfully synthesized for the use as lithium ion predoping source in lithium ion cells. The phase of LFO in the composite was found to be very sensitive to the synthesis conditions, such as the heat treatment temperature, type of lithium salt, and physical state of the precursors (powder or pellet), due to the carbothermic reduction of Fe3O4 by CNTs during high temperature solid state reaction. Under optimized synthesis conditions, LFO/CNT composites could be synthesized without the formation of impurities. To the best of our knowledge, this is the first report on the synthesis and characterization of a sub-micron sized LFO/CNT composites.

Graphene-Selenium Hybrid Microballs as Cathode Materials for High-performance Lithium-Selenium Secondary Battery Applications.

In this study, graphene-selenium hybrid microballs (G-SeHMs) are prepared in one step by aerosol microdroplet drying using a commercial spray dryer, which represents a simple, scalable continuous process, and the potential of the G-SeHMs thus prepared is investigated for use as cathode material in applications of lithium-selenium secondary batteries. These morphologically unique graphene microballs filled with Se particles exhibited good electrochemical properties, such as high initial specific capacity (642 mA h g(-1) at 0.1 C, corresponding to Se electrochemical utilisation as high as 95.1%), good cycling stability (544 mA h g(-1) after 100 cycles at 0.1 C; 84.5% retention) and high rate capability (specific capacity of 301 mA h g(-1) at 5 C). These electrochemical properties are attributed to the fact that the G-SeHM structure acts as a confinement matrix for suppressing the dissolution of polyselenides in the organic electrolyte, as well as an electron conduction path for increasing the transport rate of electrons for electrochemical reactions. Notably, based on the weight of hybrid materials, electrochemical performance is considerably better than that of previously reported Se-based cathode materials, attributed to the high Se loading content (80 wt%) in hybrid materials.

Synthesis of Reduced Graphene Oxide-Modified LiMn0.75Fe0.25PO4 Microspheres by Salt-Assisted Spray Drying for High-Performance Lithium-Ion Batteries.

Microsized, spherical, three-dimensional (3D) graphene-based composites as electrode materials exhibit improved tap density and electrochemical properties. In this study, we report 3D LiMn0.75Fe0.25PO4/reduced graphene oxide microspheres synthesized by one-step salt-assisted spray drying using a mixed solution containing a precursor salt and graphene oxide and a subsequent heat treatment. During this process, it was found that the type of metal salt used has significant effects on the morphology, phase purity, and electrochemical properties of the synthesized samples. Furthermore, the amount of the chelating agent used also affects the phase purity and electrochemical properties of the samples. The composite exhibited a high tap density (1.1 g cm(-3)) as well as a gravimetric capacity of 161 mA h g(-1) and volumetric capacity of 281 mA h cm(-3) at 0.05 C-rate. It also exhibited excellent rate capability, delivering a discharge capacity of 90 mA h g(-1) at 60 C-rate. Furthermore, the microspheres exhibited high energy efficiency and good cyclability, showing a capacity retention rate of 93% after 1000 cycles at 10 C-rate.

Hierarchically structured activated carbon for ultracapacitors.

To resolve the pore-associated bottleneck problem observed in the electrode materials used for ultracapacitors, which inhibits the transport of the electrolyte ions, we designed hierarchically structured activated carbon (HAC) by synthesizing a mesoporous silica template/carbon composite and chemically activating it to simultaneously remove the silica template and increase the pore volume. The resulting HAC had a well-designed, unique porous structure, which allowed for large interfaces for efficient electric double-layer formation. Given the unique characteristics of the HAC, we believe that the developed synthesis strategy provides important insights into the design and fabrication of hierarchical carbon nanostructures. The HAC, which had a specific surface area of 1,957 m(2) g(-1), exhibited an extremely high specific capacitance of 157 F g(-1) (95 F cc(-1)), as well as a high rate capability. This indicated that it had superior energy storage capability and was thus suitable for use in advanced ultracapacitors.