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Redox flow batteries (RFBs) are gaining significant attention due to the growing demand for sustainable energy storage solutions. In contrast to conventional aqueous vanadium RFBs, which have a restricted voltage range resulting from the use of water and vanadium, the utilization of redox-active organic molecules (ROMs) as active materials broadens the range of applicable liquid media to include non-aqueous electrolyte solutions. The extended voltage range of non-aqueous media, exceeding 2 V, facilitates the establishment of high-energy storage systems. Additionally, considering the higher cost of non-aqueous solvents compared to water, the objective in developing non-aqueous electrolyte solution-based organic RFBs (NRFBs) is to efficiently install these systems in a compact manner and explore unique applications distinct from those associated with aqueous RFBs, which are typically deployed for grid-scale energy storage systems. This review presents recent research progress in ROMs, electrolytes, and membranes in NRFBs. Furthermore, we address the prevailing challenges that require revolution, encompassing a narrow cell voltage range, insufficient solubility, chemical instability, and the crossover of ROMs. Through this exploration, the review contributes to the understanding of the current landscape and potential advancements in NRFB technology and encourages researchers and professionals in the energy field to explore this emerging technology as a potential solution to global environmental challenges.

Here, we aimed to demonstrate the efficacy of silver diamine fluoride (SDF) in halting dental erosion caused by dietary selection and offer a potential explanation for the underlying mechanism. We investigated the surface chemical and mechanical characteristics of human tooth enamel when exposed to Coca-Cola from 10 s to 1 h, with and without the topical treatment of SDF. We analyzed the mechanical properties by measuring the enamel surface roughness and elastic modulus using atomic force microscopy and the surface chemical composition through x-ray photoelectron spectroscopy and Fourier transform infrared spectroscopy analyses, with scanning electron microscopy as a supplementary characterization method. After 1 h of immersion in Coca-Cola, the roughness changed from 83 to 287 nm for enamel without SDF treatment and 64 to 70 nm for enamel with SDF treatment. Under the same conditions, the elastic modulus changed from 125 GPa to 13 GPa for enamel without SDF treatment and 215 GPa to 205 GPa for enamel with SDF treatment. Topical coating of SDF onto enamel formed a passivation layer composed of fluorapatite and created added fluorine flux in the system, which protected the teeth from demineralization under Coca-Cola etching, as shown by morphology and chemical composition analysis as well as roughness and modulus characterization. Applying SDF to enamel minimizes changes in chemical compositions and surface roughness while improving enamel elastic modulus., Competing Interests: Competing interests: The authors declare that they have no competing interests., (Copyright © 2024 Aditi Saha et al.)

A N-Co-N core is embedded within [Co(CNC) 2 ] 2+ (1) supported by two bis(4-methyl-2-(3-methyl-imidazolium)phenyl)amine (CNC) ligands. This species reveals a stable S = 1/2 state and its spin density is significantly delocalized within the N-Co-N core via parallel π-bonding interaction. Interestingly, it displays unusual stability towards O 2 and water, proving that the core is well protected. Upon reduction, compound 1 was converted to its reduced diamagnetic species [Co(CNC) 2 ] + (2) having two amide donors and a low-spin Co(III) ion, which can be oxidized by air to regenerate 1.

Lithium (Li) metal has been regarded as the ideal anode for rechargeable batteries due to its low reduction potential and high theoretical capacity. However, the formation of fatal Li dendrites during repeated cycling shortens the battery life and causes serious safety concerns. Functionalized separators with electrically conductive and lithiophilic coating layers potentially inhibit dendrite formation and growth on Li metal anodes by providing nucleation sites for reversible Li deposition/stripping. In this work, we propose functionalized separators incorporating heteroatom-doped (N or B) graphene interlayers to modulate the Li nucleation behavior. The electronegative N-doping and electropositive B-doping were investigated to understand their regulation of the Li deposition behavior. With the heteroatom-doped graphene-coated separators, we observe significantly improved cycling stability along with enhanced charge transfer kinetics and low Li nucleation overpotential. This is attributed to the heteroatom-doped graphene interlayer expanding the surface area of the Li metal anode while providing additional space for uniform Li deposition/stripping, thus preventing undesirable side reactions. As a result, the formation of dendrites and pits on the Li metal anode surface is suppressed, demonstrating the protective effect of the Li metal anode. Interestingly, N-doped graphene-coated separators exhibit lower Li nucleation overpotentials than B-doped graphene-coated separators but rather lower average Coulombic efficiencies and reduced cycling stability. This implies that adequate adsorption on B-based sites, as opposed to the strong adsorption on N-based sites, improves the reversibility. Notably, the Li adsorption strength of the lithiophilic functional groups critically affects the reversibility, as observed by Li nucleation barrier measurements and atomistic simulations. This work suggests that interface engineering using conductive and lithiophilic materials can be a promising strategy for controlling Li deposition in advanced Li metal batteries.

In redox flow batteries, a compelling strategy for enhancing the charge capacity of redox-active organic molecules involves storing multiple electrons within a single molecule. However, this approach poses unique challenges such as chemical instability by forming radicals, elevated energy requirements, and unsustainable charge concentration. Ion pairing is a possible solution to achieve charge neutrality and engineer redox potential shifts but has received limited attention. In this study, we demonstrate that Li + can stabilize naphthalene diimide (NDI) anions dissolved in acetonitrile and significantly shift the second cathodic potential close to the first. Our findings, supported by density functional theory calculations and Fourier transform infrared spectroscopy, indicate that dimeric NDI species form stable ion pairs with Li + . Conversely, K + ions exhibit weak interactions, and cyclic voltammograms confirm significant potential shifts when stronger Lewis acids and solvents with lower donor numbers are employed. Galvanostatic examinations reveal a single voltage plateau with Li + , which indicates a rapid redox process involving doubly charged NDI 2- with Li + . These aggregated ion pairs offer the additional benefits of hindering crossover events, contributing to excellent cyclability, and suppressing undesirable side reactions even after 1000 redox cycles.

Copper (Cu) is a widely used catalyst for the nitrate reduction reaction (NO 3 RR), but its susceptibility to surface oxidation and complex electrochemical conditions hinders the identification of active sites. Here, we employed electropolished metallic Cu with a predominant (100) surface and compared it to native oxide-covered Cu. The electropolished Cu surface rapidly oxidized after exposure to either air or electrolyte solutions. However, this oxide was reduced below 0.1 V vs. RHE, thus returning to the metallic Cu before NO 3 RR. It was distinguished from the native oxide on Cu, which remained during NO 3 RR. Fast NO 3 - and NO reduction on the metallic Cu delivered 91.5 ± 3.7% faradaic efficiency for NH 3 at -0.4 V vs. RHE. In contrast, the native oxide on Cu formed undesired products and low NH 3 yield. Operando shell-isolated nanoparticle-enhanced Raman spectroscopy (SHINERS) analysis revealed the adsorbed NO 3 - , NO 2 , and NO species on the electropolished Cu as the intermediates of NH 3 . Low overpotential NO 3 - and NO adsorptions and favorable NO reduction are key to increased NH 3 productivity over Cu samples, which was consistent with the DFT calculation on Cu(100)., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

This perspective paper comprehensively explores recent electrochemical studies on layered transition metal oxides (LTMO) in aqueous media and specifically encompasses two topics: catalysis of the oxygen evolution reaction (OER) and cathodes of aqueous lithium-ion batteries (LiBs). They involve conflicting requirements; OER catalysts aim to facilitate water dissociation, while for cathodes in aqueous LiBs it is essential to suppress water dissociation. The interfacial reactions taking place at the LTMO in these two distinct systems are of particular significance. We show various strategies for designing LTMO materials for each desired aim based on an in-depth understanding of electrochemical interfacial reactions. This paper sheds light on how regulating the LTMO interface can contribute to efficient water splitting and economical energy storage, all with a single material., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Here, we investigate the nonlinear relationship between the content of solid electrolytes in composite electrodes and the irreversible capacity via the degree of nanoscale uniformity of the surface morphology and chemical composition of the solid electrolyte interphase (SEI) layer. Using electrochemical strain microscopy (ESM) and X-ray photoelectron spectroscopy (XPS), changes of the chemical composition and morphology (Li and F distribution) in SEI layers on the electrodes as a function of solid electrolyte contents are analyzed. As a result, we find that the solid electrolyte content affects the variation of the SEI layer thickness and chemical distributions of Li and F ions in the SEI layer, which, in turn, influence the Coulombic efficiency. This correlation determines the composition of the composite electrode surface that can maximize the physical and chemical uniformity of the solid electrolyte on the electrode, which is a key parameter to increase electrochemical performance in solid-state batteries.

The incompatibility of lithium intercalation electrodes with water has impeded the development of aqueous Li-ion batteries. The key challenge is protons which are generated by water dissociation and deform the electrode structures through intercalation. Distinct from previous approaches utilizing large amounts of electrolyte salts or artificial solid-protective films, we developed liquid-phase protective layers on LiCoO 2 (LCO) using a moderate concentration of 0.5∼3 mol kg -1 lithium sulfate. Sulfate ion strengthened the hydrogen-bond network and easily formed ion pairs with Li + , showing strong kosmotropic and hard base characteristics. Our quantum mechanics/molecular mechanics (QM/MM) simulations revealed that sulfate ion paired with Li + helped stabilize the LCO surface and reduced the density of free water in the interface region below the point of zero charge (PZC) potential. In addition, in situ electrochemical surface-enhanced infrared absorption spectroscopy (SEIRAS) proved the appearance of inner-sphere sulfate complexes above the PZC potential, serving as the protective layers of LCO. The role of anions in stabilizing LCO was correlated with kosmotropic strength (sulfate > nitrate > perchlorate > bistriflimide (TFSI - )) and explained better galvanostatic cyclability in LCO cells., Competing Interests: The authors declare no competing financial interest., (© 2023 The Authors. Published by American Chemical Society.)

Organic redox-active molecules are a promising platform for designing sustainable, cheap, and safe charge carriers for redox flow batteries. However, radical formation during the electron-transfer process causes severe side reactions and reduces cyclability. This problem is mitigated by using naphthalene diimide (NDI) molecules and regulating their π-π interactions. The long-range π-stacking of NDI molecules, which leads to precipitation, is disrupted by tethering four ammonium functionalities, and the solubility approaches 1.5 m in water. The gentle π-π interactions induce clustering and disassembling of the NDI molecules during the two-electron transfer processes. When the radical anion forms, the antiferromagnetic coupling develops tetramer and dimer and nullifies the radical character. In addition, short-range-order NDI clusters at 1 m concentration are not precipitated but inhibit crossover. They are disassembled in the subsequent electron-transfer process, and the negatively charged NDI core strongly interacts with ammonium groups. These behaviors afford excellent RFB performance, demonstrating 98% capacity retention for 500 cycles at 25 mA cm -2 and 99.5% Coulombic efficiency with 2 m electron storage capacity., (© 2023 Wiley-VCH GmbH.)

Dependence on lithium-ion batteries for automobile applications is rapidly increasing. The emerging use of anionic redox can boost the energy density of batteries, but the fundamental origin of anionic redox is still under debate. Moreover, to realize anionic redox, many reported electrode materials rely on manganese ions through π-type interactions with oxygen. Here, through a systematic experimental and theoretical study on a binary system of Li 3 NbO 4 -NiO, we demonstrate for the first time the unexpectedly large contribution of oxygen to charge compensation for electrochemical oxidation in Ni-based materials. In general, for Ni-based materials, e.g ., LiNiO 2 , charge compensation is achieved mainly by Ni oxidation, with a lower contribution from oxygen. In contrast, for Li 3 NbO 4 -NiO, oxygen-based charge compensation is triggered by structural disordering and σ-type interactions with nickel ions, which are associated with a unique environment for oxygen, i.e ., a linear Ni-O-Ni configuration in the disordered system. Reversible anionic redox with a small hysteretic behavior was achieved for LiNi 2/3 Nb 1/3 O 2 with a cation-disordered Li/Ni arrangement. Further Li enrichment in the structure destabilizes anionic redox and leads to irreversible oxygen loss due to the disappearance of the linear Ni-O-Ni configuration and the formation of unstable Ni ions with high oxidation states. On the basis of these results, we discuss the possibility of using σ-type interactions for anionic redox to design advanced electrode materials for high-energy lithium-ion batteries., Competing Interests: The authors declare no competing financial interest., (© 2022 The Authors. Published by American Chemical Society.)

Multiscale and multimodal imaging of material structures and properties provides solid ground on which materials theory and design can flourish. Recently, KAIST announced 10 flagship research fields, which include KAIST Materials Revolution: Materials and Molecular Modeling, Imaging, Informatics and Integration (M3I3). The M3I3 initiative aims to reduce the time for the discovery, design and development of materials based on elucidating multiscale processing-structure-property relationship and materials hierarchy, which are to be quantified and understood through a combination of machine learning and scientific insights. In this review, we begin by introducing recent progress on related initiatives around the globe, such as the Materials Genome Initiative (U.S.), Materials Informatics (U.S.), the Materials Project (U.S.), the Open Quantum Materials Database (U.S.), Materials Research by Information Integration Initiative (Japan), Novel Materials Discovery (E.U.), the NOMAD repository (E.U.), Materials Scientific Data Sharing Network (China), Vom Materials Zur Innovation (Germany), and Creative Materials Discovery (Korea), and discuss the role of multiscale materials and molecular imaging combined with machine learning in realizing the vision of M3I3. Specifically, microscopies using photons, electrons, and physical probes will be revisited with a focus on the multiscale structural hierarchy, as well as structure-property relationships. Additionally, data mining from the literature combined with machine learning will be shown to be more efficient in finding the future direction of materials structures with improved properties than the classical approach. Examples of materials for applications in energy and information will be reviewed and discussed. A case study on the development of a Ni-Co-Mn cathode materials illustrates M3I3's approach to creating libraries of multiscale structure-property-processing relationships. We end with a future outlook toward recent developments in the field of M3I3.

Nanostructured LiMnO 2 integrated with Li 3 PO 4 was successfully synthesized by the mechanical milling route and examined as a new series of positive electrode materials for rechargeable lithium batteries. Although uniform mixing at the atomic scale between LiMnO 2 and Li 3 PO 4 was not anticipated because of the noncompatibility of crystal structures for both phases, our study reveals that phosphorus ions with excess lithium ions dissolve into nanosize crystalline LiMnO 2 as first evidenced by elemental mapping using STEM-EELS combined with total X-ray scattering, solid-state NMR spectroscopy, and a theoretical ab initio study. The integrated phase features a low-crystallinity metastable phase with a unique nanostructure; the phosphorus ion located at the tetrahedral site shares faces with adjacent lithium ions at slightly distorted octahedral sites. This phase delivers a large reversible capacity of ∼320 mA h g -1 as a high-energy positive electrode material in Li cells. The large reversible capacity originated from the contribution from the anionic redox of oxygen coupled with the cationic redox of Mn ions, as evidenced by operando soft XAS spectroscopy, and the superior reversibility of the anionic redox and the suppression of oxygen loss were also found by online electrochemical mass spectroscopy. The improved reversibility of the anionic redox originates from the presence of phosphorus ions associated with the suppression of oxygen dimerization, as supported by a theoretical study. From these results, the mechanistic foundations of nanostructured high-capacity positive electrode materials were established, and further chemical and physical optimization may lead to the development of next-generation electrochemical devices., Competing Interests: The authors declare no competing financial interest., (© 2020 American Chemical Society.)

Lithium-oxygen (Li-O 2 ) batteries have been intensively investigated in recent decades for their utilization in electric vehicles. The intrinsic challenges arising from O 2 (electro)chemistry have been mitigated by developing various types of catalysts, porous electrode materials, and stable electrolyte solutions. At the next stage, we face the need to reform batteries by substituting pure O 2 gas with air from Earth's atmosphere. Thus, the key emerging challenges of Li-air batteries, which are related to the selective filtration of O 2 gas from air and the suppression of undesired reactions with other constituents in air, such as N 2 , water vapor (H 2 O), and carbon dioxide (CO 2 ), should be properly addressed. In this review, we discuss all key aspects for developing Li-air batteries that are optimized for operating in ambient air and highlight the crucial considerations and perspectives for future air-breathing batteries.

Pd-catalyzed C-H annulation reactions of halo- and aryl-heteroarenes were developed using readily available o -bromobiaryls and o -dibromoaryls, respectively. A variety of five-membered heteroarenes rapidly provided the corresponding phenanthrene-fused heteroarenes, which led to the identification of phenanthro-pyrazole and thiazole as new, stable -2 V redox couples. The flexible syntheses and tunability of the redox potentials of these azole-fused phenanthrenes over a wide range are expected to facilitate their application as redox-active organic functional materials.

Peripherally substituted antiaromatic naphthorosarins have been synthesized for the first time. The synthesis was accomplished by acid-catalyzed condensation of naphthobipyrrole building blocks with aromatic aldehydes. The naphthobipyrrole building blocks were synthesized by simple oxidative coupling of the corresponding pyrrole substituted aromatics. Solid-state structural analyses of the synthesized naphthorosarins revealed that the presence of meso-2,6-dichlorophenyl- and 5,6-difluoro-substitution substantially alter the geometry and properties of the naphthorosarins. The substituents affect the redox potentials as well and, in turn, the proton-coupled electron-transfer processes leading to the formation of one- and two-electron reduced forms of the corresponding naphthorosarins. One particular naphthorosarin that bears both peripheral fluorine and meso-2,6-dichlorophenyl substituents forms a stable 25 π-electron species upon treating with TFA that was characterized by single-crystal X-ray diffraction analysis. The current study underscores how structural modifications can be used to fine-tune the electronic features of naphthorosarins, including stabilization of odd electron species., (© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

An ongoing challenge with lithium-oxygen (Li-O 2 ) batteries is in deciphering the oxygen evolution reaction (OER) process related to the slow decomposition of the insulating lithium peroxide (Li 2 O 2 ). Herein, we shed light on the behavior of Li 2 O 2 oxidation by exploiting various in situ imaging, gas analysis, and electrochemical methods. At the low potentials 3.2-3.7 V (vs Li/Li + ), OER is exclusive to the thinner parts of the Li 2 O 2 deposits, which leads to O 2 gas evolution, followed by the concomitant release of superoxide species. At higher potentials, OER initiates at the sidewalls of the thicker Li 2 O 2 . The succeeding lateral decomposition of Li 2 O 2 indicates the preferential Li + and charge transport occurring at the sidewalls of Li 2 O 2 . To ameliorate the OER rate, we also investigate an alternative approach of rerouting charge carriers by using soluble redox mediators. Our in situ probes provide insights into the favorable charge-transport routes that can aid in promoting Li 2 O 2 decomposition.

The major challenge facing lithium-oxygen batteries is the insulating and bulk lithium peroxide discharge product, which causes sluggish decomposition and increasing overpotential during recharge. Here, we demonstrate an improved round-trip efficiency of ~80% by means of a mesoporous carbon electrode, which directs the growth of one-dimensional and amorphous lithium peroxide. Morphologically, the one-dimensional nanostructures with small volume and high surface show improved charge transport and promote delithiation (lithium ion dissolution) during recharge and thus plays a critical role in the facile decomposition of lithium peroxide. Thermodynamically, density functional calculations reveal that disordered geometric arrangements of the surface atoms in the amorphous structure lead to weaker binding of the key reaction intermediate lithium superoxide, yielding smaller oxygen reduction and evolution overpotentials compared to the crystalline surface. This study suggests a strategy to enhance the decomposition rate of lithium peroxide by exploiting the size and shape of one-dimensional nanostructured lithium peroxide.

To achieve a high reversibility and long cycle life for lithium-oxygen (Li-O 2 ) batteries, the irreversible formation of Li 2 O 2 , inevitable side reactions, and poor charge transport at the cathode interfaces should be overcome. Here, we report a rational design of air cathode using a cobalt nitride (Co 4 N) functionalized carbon nanofiber (CNF) membrane as current collector-catalyst integrated air cathode. Brush-like Co 4 N nanorods are uniformly anchored on conductive electrospun CNF papers via hydrothermal growth of Co(OH)F nanorods followed by nitridation step. Co 4 N-decorated CNF (Co 4 N/CNF) cathode exhibited excellent electrochemical performance with outstanding stability for over 177 cycles in Li-O 2 cells. During cycling, metallic Co 4 N nanorods provide sufficient accessible reaction sites as well as facile electron transport pathway throughout the continuously networked CNF. Furthermore, thin oxide layer (<10 nm) formed on the surface of Co 4 N nanorods promote reversible formation/decomposition of film-type Li 2 O 2 , leading to significant reduction in overpotential gap (∼1.23 V at 700 mAh g -1 ). Moreover, pouch-type Li-air cells using Co 4 N/CNF cathode stably operated in real air atmosphere even under 180° bending. The results demonstrate that the favorable formation/decomposition of reaction products and mediation of side reactions are hugely governed by the suitable surface chemistry and tailored structure of cathode materials, which are essential for real Li-air battery applications.

In lithium-oxygen (Li-O2) batteries, it is believed that lithium peroxide (Li2O2) electrochemically forms thin films with thicknesses less than 10 nm resulting in capacity restrictions due to limitations in charge transport. Here we show unexpected Li2O2 film growth with thicknesses of ∼60 nm on a three-dimensional carbon nanotube (CNT) electrode incorporated with cerium dioxide (ceria) nanoparticles (CeO2 NPs). The CeO2 NPs favor Li2O2 surface nucleation owing to their strong binding toward reactive oxygen species (e.g., O2 and LiO2). The subsequent film growth results in thicknesses of ∼40 nm (at cutoff potential of 2.2 V vs Li/Li(+)), which further increases up to ∼60 nm with the addition of trace amounts of H2O that enhances the solution free energy. This suggests the involvement of solvated superoxide species (LiO2(sol)) that precipitates on the existing Li2O2 films to form thicker films via disproportionation. By comparing toroidal Li2O2 formed solely from LiO2(sol), the thick Li2O2 films formed from surface-mediated nucleation/thin-film growth following by LiO2(sol) deposition provides the benefits of higher reversibility and rapid surface decomposition during recharge.

Electrical energy storage system such as secondary batteries is the principle power source for portable electronics, electric vehicles and stationary energy storage. As an emerging battery technology, Li-redox flow batteries inherit the advantageous features of modular design of conventional redox flow batteries and high voltage and energy efficiency of Li-ion batteries, showing great promise as efficient electrical energy storage system in transportation, commercial, and residential applications. The chemistry of lithium redox flow batteries with aqueous or non-aqueous electrolyte enables widened electrochemical potential window thus may provide much greater energy density and efficiency than conventional redox flow batteries based on proton chemistry. This Review summarizes the design rationale, fundamentals and characterization of Li-redox flow batteries from a chemistry and material perspective, with particular emphasis on the new chemistries and materials. The latest advances and associated challenges/opportunities are comprehensively discussed.

A perfluorinated alkyl chain grafted to carbon nanotubes is employed in the lithium-oxygen (Li-O2) cell. We demonstrate a highly localized Li-O2 electrochemical reaction in close proximity to the perfluorinated moiety owing to its high O2 affinity. This hydrophobic modification can provide an enhancement in capacity for a very thin microbattery system.

The application of conventional solid polymer electrolyte (SPE) to lithium-oxygen (Li-O2) batteries has suffered from a limited active reaction zone due to thick SPE and subsequent lack of O2 gas diffusion route in the positive electrode. Here we present a new design for a three-dimensional (3-D) SPE structure, incorporating a carbon nanotube (CNT) electrode, adapted for a gas-based energy storage system. The void spaces in the porous CNT/SPE film allow an increased depth of diffusion of O2 gas, providing an enlarged active reaction zone where Li(+) ions, O2 gas, and electrons can interact. Furthermore, the thin SPE layer along the CNT, forming the core/shell nanostructure, aids in the smooth electron transfer when O2 gas approaches the CNT surface. Therefore, the 3-D CNT/SPE electrode structure enhances the capacity in the SPE-based Li-O2 cell. However, intrinsic instability of poly(ethylene oxide) (PEO) of the SPE matrix to superoxide (O2(·-)) and high voltage gives rise to severe side reactions, convincing us of the need for development of a more stable electrolyte for use in this CNT/SPE design.

The lithium-oxygen (Li-O2) electrochemical reaction on nanoporous gold (NPG) is observed using in situ atomic force microscopy (AFM) imaging coupled with potentiostatic measurement. Dense Li2O2 nanoparticles form a film at 2.5 V, which is decomposed at 3.8-4.0 V in an ether-based electrolyte.

A lithium-iodine (Li-I2) cell using the triiodide/iodide (I3(-)/I(-)) redox couple in an aqueous cathode has superior gravimetric and volumetric energy densities (∼ 330 W h kg(-1) and ∼ 650 W h L(-1), respectively, from saturated I2 in an aqueous cathode) to the reported aqueous Li-ion batteries and aqueous cathode-type batteries, which provides an opportunity to construct cost-effective and high-performance energy storage. To apply this I3(-)/I(-) aqueous cathode for a portable and compact 3.5 V battery, unlike for grid-scale storage as general target of redox flow batteries, we use a three-dimensional and millimeter thick carbon nanotube current collector for the I3(-)/I(-) redox reaction, which can shorten the diffusion length of the redox couple and provide rapid electron transport. These endeavors allow the Li-I2 battery to enlarge its specific capacity, cycling retention, and maintain a stable potential, thereby demonstrating a promising candidate for an environmentally benign and reusable portable battery.

Low electrical efficiency for the lithium-oxygen (Li-O2) electrochemical reaction is one of the most significant challenges in current nonaqueous Li-O2 batteries. Here we present ruthenium oxide nanoparticles (RuO2 NPs) dispersed on multiwalled carbon nanotubes (CNTs) as a cathode, which dramatically increase the electrical efficiency up to 73%. We demonstrate that the RuO2 NPs contribute to the formation of poorly crystalline lithium peroxide (Li2O2) that is coated over the CNT with large contact area during oxygen reduction reaction (ORR). This unique Li2O2 structure can be smoothly decomposed at low potential upon oxygen evolution reaction (OER) by avoiding the energy loss associated with the decomposition of the more typical Li2O2 structure with a large size, small CNT contact area, and insulating crystals.

Understanding the lithium-oxygen (Li-O2) electrochemical reaction is of importance to improve reaction kinetics, efficiency, and mitigate parasitic reactions, which links to the strategy of enhanced Li-O2 battery performance. Many in situ and ex situ analyses have been reported to address chemical species of reduction intermediate and products, whereas details of the dynamic Li-O2 reaction have not as yet been fully unraveled. For this purpose, visual imaging can provide straightforward evidence, formation and decomposition of products, during the Li-O2 electrochemical reaction. Here, we present real-time and in situ views of the Li-O2 reaction using electrochemical atomic force microscopy (EC-AFM). Details of the reaction process can be observed at nano-/micrometer scale on a highly oriented pyrolytic graphite (HOPG) electrode with lithium ion-containing tetraglyme, representative of the carbon cathode and ether-based electrolyte extensively employed in the Li-O2 battery. Upon oxygen reduction reaction (ORR), rapid growth of nanoplates, having axial diameter of hundreds of nanometers, length of micrometers, and ~5 nm thickness, at a step edge of HOPG can be observed, which eventually forms a lithium peroxide (Li2O2) film. This Li2O2 film is decomposed during the oxygen evolution reaction (OER), for which the decomposition potential is related to a thickness. There is no evidence of byproduct analyzed by X-ray photoelectron spectroscopy (XPS) after first reduction and oxidation reaction. However, further cycles provide unintended products such as lithium carbonate (Li2CO3), lithium acetate, and fluorine-related species with irregular morphology due to the degradation of HOPG electrode, tetraglyme, and lithium salt. These observations provide the first visualization of Li-O2 reaction process and morphological information of Li2O2, which can allow one to build strategies to prepare the optimum conditions for the Li-O2 battery.

Development of promising battery systems is being intensified to fulfil the needs of long-driving-ranged electric vehicles. The successful candidates for new generation batteries should have higher energy densities than those of currently used batteries and reasonable rechargeability. Here we report that aqueous lithium-iodine batteries based on the triiodide/iodide redox reaction show a high battery performance. By using iodine transformed to triiodide in an aqueous iodide, an aqueous cathode involving the triiodide/iodide redox reaction in a stable potential window avoiding water electrolysis is demonstrated for lithium-iodine batteries. The high solubility of triiodide/iodide redox couples results in an energy density of ~ 0.33 kWh kg(-1), approximately twice that of lithium-ion batteries. The reversible redox reaction without the formation of resistive solid products promotes rechargeability, demonstrating 100 cycles with negligible capacity fading. A low cost, non-flammable and heavy-metal-free aqueous cathode can contribute to the feasibility of scale-up of lithium-iodine batteries for practical energy storage.

Understanding of electrochemical process in rechargeable Li-O2 battery has suffered from lack of proper analytical tool, especially related to the identification of chemical species and number of electrons involved in the discharge/recharge process. Here we present a simple and straightforward analytical method for simultaneously attaining chemical and quantified information of Li2O2 (discharge product) and byproducts using in situ XRD measurement. By real-time monitoring of solid-state Li2O2 peak area, the accurate efficiency of Li2O2 formation and the number of electrons can be evaluated during full discharge. Furthermore, by observation of sequential area change of Li2O2 peak during recharge, we found nonlinearity of Li2O2 decomposition rate for the first time in ether-based electrolyte.

We report a facile synthesis of Fe-N-C catalysts based on the surface functionalization of multi-walled carbon nanotubes (MWCNTs), which show high activity and stability for oxygen reduction reaction (ORR) in acid. Fe-N-MWCNT catalysts, whose ORR mass activities could vary by 3-4 times depending on the choice of Fe precursors, were found to have considerably higher ORR mass activity and higher stability than N-modified MWCNTs (N-MWCNTs). The Fe-N-MWCNT catalyst with a dominant Fe-N(x) moiety (with x ≈ 4) and a surface Fe/C ratio of ∼0.004 exhibits the highest ORR mass activity in acid (∼0.7 mA mg(-1)(Fe-N-MWCNT) at 0.8 V vs. RHE), where the lower mass activity of other Fe-N-MWCNT catalysts can be attributed to lower Fe/C ratios and Fe-N(x) moieties (with x smaller than 4) as revealed from X-ray photoelectron spectroscopy (XPS) and extended X-ray absorption fine structure (EXAFS) spectroscopy. Moreover, the enhanced stability of Fe-N-MWCNTs in comparison to N-MWCNTs can be attributed to less H(2)O(2) production during ORR as determined from rotating ring disk electrode (RRDE) measurements, and higher activity for H(2)O(2) electro-reduction by rotating disk electrode (RDE) measurements. The large surface Fe/C ratio and Fe-N(x) moiety corresponding to high ORR activity and stability of Fe-N-MWCNTs demonstrate that surface functionalization can be very helpful to graft active catalytic sites onto carbon nanostructures, and to provide insights into the ORR mechanism of non-noble metal catalysts (NNMCs) for proton exchange membrane fuel cells (PEMFCs).

The detailed role of iron nanoparticles (NPs) involved with the formation of SiO2 nanotrenches is revealed. The physical movements of iron NPs, such as levitation and adsorption, turn out to be responsible for the initiation of carbothermal reduction (C (carbon nanotube, s) + SiO2(s) <--> SiO(g) + CO(g)), which results in SiO2 nanotrenches that are fully guided by carbon nanotubes. Under the chemical vapor deposition condition with 0.1% of O2 gas, iron NPs are liberally levitated from SiO2/Si substrate then adsorbed on the sidewalls of carbon nanotubes. Depending on the numbers of iron NPs attached to carbon nanotubes, two different types of nanotrenches are determined. When multiple iron NPs are assembled on carbon nanotubes and involved in carbothermal reduction, aligned nanohole type of nanotrenches is produced (Type I). On the contrary, when single iron NPs initiate the carbothermal reduction, nanotrenches having smooth pathways and high shoulders are commonly formed (Type II).

The potential applications of carbon nanotubes are varied. Although it has long been known that solid carbon can reduce SiO2 to its gaseous state at high temperatures, exploiting this reaction to pattern surfaces with carbon nanotubes has never been demonstrated. Here we show that carbon nanotubes can act as the carbon source to reduce (etch) silicon dioxide surfaces. By introducing small amounts of oxygen gas during the growth of single-walled carbon nanotubes (SWNTs) in the chemical vapour deposition (CVD) process, the nanotubes selectively etch one-dimensional nanotrenches in the SiO2. The shape, length and trajectory of the nanotrenches are fully guided by the SWNTs. These nanotrenches can also serve as a mask in the fabrication of sub-10-nm metal nanowires. Combined with alignment techniques, well-ordered nanotrenches can be made for various high-density electronic components in the nanoelectronics industry.

Successful realization of highly crystalline and densely packed Ag2S nanocrystal (NC) films has been achieved by directly converting precursor molecules, Ag(SCOPh), on preheated substrates. When an aliquot of Ag(SCOPh) solution dissolved in trioctylphosphine (TOP) is applied on preheated solid substrates at 160 degrees C, such as SiO2/Si, H-terminated Si, and quartz. Ag2S NC thin films have been formed with instant phase and color changes of the precursor solutions from pale yellow homogeneous solution to black solid films. The average diameter of individual Ag2S NCs forming thin films is ca. 25 nm, as confirmed by examining both isolated Ag2S NCs from thin films and as-made thin film samples by using transmission electron microscopy (TEM) and scanning electron microscopy (SEM), respectively. Powder X-ray diffraction (XRD) pattern shows that the synthesized Ag2S NCs have well-defined monoclinic acanthite phase. Direct precursor conversion process has resulted in densely packed Ag2S NCs with reduced interparticle distances owing to efficient removal of TOP during the reaction. Compared to the devices fabricated by the drop-coating process, Ag2S thin film devices fabricated by direct precursor conversion process have shown a ca. 300-fold increased conductance. Such Ag2S NC devices have also displayed reliable photoresponses upon white light illumination with high photosensitivity (S approximately equal to 1).

Selective formation of metallic Ag and semiconducting Ag(2)S nanocrystals has been achieved via a modified hot-injection process from a single-source precursor molecule, Ag(SCOPh), which can potentially generate both [Ag] and [AgS] fragments simultaneously. When the precursor molecules are injected into a preheated reaction system at 160 degrees C, spherical Ag(2)S nanocrystals are directly obtained even without a molecular activator, such as alkylamines. Mixtures of Ag and Ag(2)S or pure metallic Ag nanocrystals are obtained if the precursor molecules are injected at lower than 160 degrees C or room temperature. These results are attributed to the direct transfer of thermal energies to precursor molecules, which are enough to dissociate S-C as well as Ag-S bonds simultaneously. Detailed characterizations about the produced nanocrystals have been performed using powder X-ray diffraction (XRD), transmission electron microscopy (TEM), as well as energy-dispersive X-ray (EDX) spectrum.

Highly sensitive single-walled carbon nanotube-field effect transistor (SWNT-FET) devices, which detect protein adsorptions and specific protein-protein interactions at 1 pM concentrations, have been achieved. The detection limit has been improved 104-fold compared to the devices fabricated by photolithography. The substantially increased sensitivity is mainly due to the increased Schottky contact area which accommodates relatively more numbers of proteins even at very low concentration. The augmented number of proteins adsorbed on a device induces instant modulation of the work function of metal contact electrodes, which eventually changes the conductance of the device. Such devices have been attained by addressing metal electrodes on network-type SWNTs using a shadow mask on a tilted angle sample stage. The shadow mask allows metals to penetrate underneath the mask efficiently, therefore forming a thin and wide Schottky contact area on SWNT channels.